JACS - 4041

• (2025). Deep-red to near-infrared light-driven radical generation from organoboron compounds via ligand-induced direct excitation catalysis. JACS, 147(44), 41185--41192. (www)

  @article{ , abstract = {We report a catalytic strategy for generating carbon-centered radicals from organoboron compounds under deep-red to near-infrared (DR to NIR) light irradiation via direct excitation of substrate–catalyst complexes. Aza-dipyrromethene (ADP) catalysts form photoactive borate intermediates that enable C–B bond cleavage through ligand-induced photochemical activation. Mechanistic studies support the role of direct excitation. This method allows diverse transformations, including Giese addition, C-heteroatom bond formation, radical–radical coupling, and nickel-catalyzed cross-coupling reactions.}, archive = {J_JACS}, author = {Yusuke Miyamoto and Kanji Muraoka and Sho Murakami and Tadachika Matsudaira and Hirohisa Ohmiya}, doi = {10.1021/jacs.5c17266}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41185--41192}, shortjournal = {J. Am. Chem. Soc.}, title = {Deep-red to near-infrared light-driven radical generation from organoboron compounds via ligand-induced direct excitation catalysis}, volume = {147}, year = {2025}, }
• (2025). Asymmetric, organocatalytic 1,4-addition of pyridinyl acetates with crystallization-enabled diastereoconvergency. JACS, 147(44), 41177--41184. (www)

  @article{ , abstract = {Azaarenyl acetates represent promising building blocks for the synthesis of stereochemically complex scaffolds containing pharmaceutically relevant heterocycles. Current methods that employ azaarenyl acetates as nucleophiles in enantioselective transformations generally rely on metal catalysts and are compatible only with 2-azaarenyl acetates, limiting the diversity of electron-deficient heterocycles that can be installed. We have developed the first enantioselective organocatalytic method for the 1,4-addition of 4-azaarenyl acetates into trisubstituted electrophilic alkenes. The resulting products─possessing three contiguous stereocenters─are obtained in moderate to high diastereo- and enantioselectivities. Mechanistic studies suggest a scenario in which two of the stereocenters are under kinetic control, while the β-keto amide stereocenter undergoes a thermodynamically controlled crystallization-induced diastereomer transformation.}, archive = {J_JACS}, author = {Katelyn M. Kitzinger and Susanna N. Angles and Yuki Kojima and Jeffrey S. Johnson}, doi = {10.1021/jacs.5c17000}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41177--41184}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric, organocatalytic 1,4-addition of pyridinyl acetates with crystallization-enabled diastereoconvergency}, volume = {147}, year = {2025}, }
• (2025). Mechanism-aware deep learning for polar reaction prediction. JACS, 147(44), 41168--41176. (www)

  @article{ , abstract = {Accurately predicting chemical reactions is essential for driving innovation in synthetic chemistry, with broad applications in medicine, manufacturing, and agriculture. Yet reaction prediction remains a complex problem that is both time-consuming and resource-intensive for chemists to solve. Deep learning offers an appealing solution by enabling high-throughput prediction, but most existing models are trained on the US Patent Office data set and treat reactions as recipes or overall transformations─mapping reactants directly to products with limited mechanistic insight. To address this, we introduce PMechRP (Polar Mechanistic Reaction Predictor), trained on the PMechDB data set of polar elementary steps that capture electron flow and mechanistic detail. To broaden coverage and improve generalization, we augment PMechDB with combinatorially generated reactions and train models spanning transformer, graph, and two-stage Siamese architectures. In addition to reaction prediction models, we also develop ArrowFinder, a new model that directly predicts arrow-pushing mechanisms for a set of reactants and products. Our best-performing approach is a hybrid pipeline that combines an ensemble of Chemformer models with a two-stage Siamese framework, leveraging the accuracy of transformers while filtering away “alchemical” products using the two-step network and generating mechanistic annotations using ArrowFinder. This approach achieves strong predictive accuracy while also providing interpretable predictions. We evaluate performance across multiple benchmarks: PMechDB test splits, a curated USPTO subset from the Open Reaction Database, and a human benchmark of mechanistic pathways from an intermediate-level textbook.}, archive = {J_JACS}, author = {Ryan J. Miller and Alexander E. Dashuta and Brayden Rudisill and David Van Vranken and Pierre Baldi}, doi = {10.1021/jacs.5c16838}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41168--41176}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanism-aware deep learning for polar reaction prediction}, volume = {147}, year = {2025}, }
• (2025). Post-transition state bifurcations in reactions that form pimarenyl cation Diastereomers─Implications for terpene biosynthesis. JACS, 147(44), 41160--41167. (www)

  @article{ , abstract = {The role of post-transition state bifurcations in carbocation rearrangements derived from copalyl diphosphate (CPP) and its diastereomers syn -CPP and ent -CPP were investigated using quantum chemical calculations, ab initio molecular dynamics (AIMD) simulations, and potential energy surface (PES) analysis based on principal component analysis (PCA). Proton transfer transition states of pimarenyl cations, which can give rise to multiple products through bifurcating pathways, were the focus. For normal CPP-derived systems, AIMD simulations revealed that Re -face proton transfer leads to a diverse array of products, whereas Si -face proton transfer predominantly follows a single pathway. In contrast, syn -CPP and ent -CPP-derived systems showed reduced product diversity, with bifurcations only observed for the Re -face proton transfer. Orbital alignment analyses highlight the influence of dynamic momentum effects on product distributions. PES analyses further demonstrate that the CPP-derived system possesses the flattest energy landscape. These results highlight how simple stereochemical changes can dramatically alter dynamical outcomes, thereby modulating the challenges faced by enzymes in shaping product selectivity.}, archive = {J_JACS}, author = {Yumeng Cao and Wang-Yeuk Kong and Dean J. Tantillo}, doi = {10.1021/jacs.5c16476}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41160--41167}, shortjournal = {J. Am. Chem. Soc.}, title = {Post-transition state bifurcations in reactions that form pimarenyl cation Diastereomers─Implications for terpene biosynthesis}, volume = {147}, year = {2025}, }
• (2025). Enantioselective redox-neutral radical addition of α-imino esters with sulfonyl hydrazides. JACS, 147(44), 41149--41159. (www)

  @article{ , abstract = {The construction of chiral sp 3 –sp 3 carbon–carbon bonds represents a central challenge in organic synthesis, critically enabling 3D molecular complexity for drug discovery. While transition metal-catalyzed asymmetric alkylation of unsaturated bonds offers a powerful route to these motifs, conventional strategies face inherent limitations: nucleophilic additions require preformed organometallic reagents via an external synthetic sequence, and recent flourishing reductive methods with alkyl halides demand stoichiometric terminal reductants. Herein, we disclose a cobalt-catalyzed, enantioselective redox-neutral radical addition that directly couples bench-stable unactivated alkyl sulfonyl hydrazides with various imines. This strategy eliminates external reductants while accommodating a broad substrate scope, delivering valuable α-amino esters in high yields and enantioselectivities. Crucially, the redox-neutral conditions enable the first asymmetric radical addition of N -TMS iminoesters, providing unprotected α,α-disubstituted amino acids directly without deprotection sequences. Mechanistic studies confirm alkyl radical intermediates in the stereoselective C–C bond formation. This method overcomes key limitations of existing approaches, offering a step-economical route to medicinally relevant chiral building blocks.}, archive = {J_JACS}, author = {Tingting Xia and Zihan Wang and Xiaochen Zhang and Jiangtao Hu and Shengyu Zhang and Yangyang Zhang and Honglei Gu and Xianqing Wu and Wei-Hong Zhu and Jingping Qu and Yifeng Chen}, doi = {10.1021/jacs.5c16138}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41149--41159}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective redox-neutral radical addition of α-imino esters with sulfonyl hydrazides}, volume = {147}, year = {2025}, }
• (2025). Construction of boron-promoted ti active centers in titanosilicates for selective oxidation reactions. JACS, 147(44), 41138--41148. (www)

  @article{ , abstract = {The development of efficient oxidation reactions utilizing titanosilicate/H 2 O 2 catalytic systems holds significant importance for the green production of bulk and fine oxygenated chemicals. Precisely tailoring the microenvironment of Ti active centers in titanosilicates plays a key role in enhancing their catalytic oxidation performance. In the present study, a novel titanium active center was constructed for the first time through the high-temperature treatment of boron-containing titanosilicates under a hydrogen atmosphere. The Ti–O–B bonds in zeotype borosilicotitanate with MWW topology (Ti–B-MWW), confirmed by high-resolution time-of-flight mass spectrometry, undergo cleavage during H 2 treatment, resulting in the formation of “open” Ti species surrounded by tricoordinated boron species. These unique Ti active centers promoted by boron species in the vicinity exhibited enhanced catalytic performance compared to both conventional “open” and “close” Ti active sites in selective oxidation reactions, not only due to the inherent open structure-induced lower H 2 O 2 activation barrier but more importantly to the lower product desorption energy related to adjacent boron. This study demonstrates that the heteroatoms in proximity to Ti active sites significantly influence the catalytic behavior of titanosilicates, offering a new strategy for developing novel zeolite catalysts.}, archive = {J_JACS}, author = {Xianchen Gong and Jingyi Tan and Xiaomin Tang and Jie Tuo and Xintong Li and Chengwei Zhai and Teng Yang and Xianfeng Yi and Yue Ma and Xiaowang Li and Jiabi Ma and Hao Xu and Anmin Zheng and Peng Wu}, doi = {10.1021/jacs.5c15751}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41138--41148}, shortjournal = {J. Am. Chem. Soc.}, title = {Construction of boron-promoted ti active centers in titanosilicates for selective oxidation reactions}, volume = {147}, year = {2025}, }
• (2025). Hydrogen-mediated reductive cross-coupling of aryl iodides with activated aryl and heteroaryl bromides. JACS, 147(44), 41130--41137. (www)

  @article{ , abstract = {Hydrogen-mediated reductive cross-couplings of aryl iodides with activated aryl and heteroaryl bromides are described, along with related homocouplings (Ullmann reactions) and vinylic reductive couplings that occur with cine -substitution. To corroborate key events in the catalytic cycle, Pd-to-Pd transmetalation and cross-selective reductive elimination, dianionic diarylpalladate complexes [Pd(Aryl)(μ-Br)Br] 2 [NPr 4 ] 2 bearing p -fluorophenyl, p -methoxyphenyl and p -nitrophenyl moieties were prepared. Stoichiometric reactions of these complexes in the presence of iodide demonstrate that Pd-to-Pd transmetalation by way of monomeric arylpalladates occurs at a greater rate than reductive elimination and that cross-selective C–C reductive elimination is favored for electronically distinct aryl partners. Hydrogen-mediated reductive cross-coupling of aryl iodides with α-bromostyrene occurs with cine -substitution (as observed in related formate-mediated processes), consistent with carbopalladation of α-bromostyrene by monomeric arylpalladates Pd(Aryl)I 2 [NBu 4 ] that arise upon dissociation of [Pd(Aryl)(μ-I)I] 2 [NBu 4 ] 2 .}, archive = {J_JACS}, author = {Weijia Shen and Yu-Hsiang Chang and Brandon I. Gonzalez and Aidan P. Looby and Jordan J. Dotson and Nicholas A. White and Brad P. Carrow and Michael J. Krische}, doi = {10.1021/jacs.5c15725}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41130--41137}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen-mediated reductive cross-coupling of aryl iodides with activated aryl and heteroaryl bromides}, volume = {147}, year = {2025}, }
• (2025). Peptide-catalyzed asymmetric amination of sulfenamides enabled by DFT-guided catalyst optimization. JACS, 147(44), 41122--41129. (www)

  @article{ , abstract = {The enantioselective synthesis of chiral S(IV) and S(VI) compounds has received heightened interest from the medicinal and synthetic chemistry communities due to the improved potency and selectivity of S -chiral small molecules and agrochemicals relative to classical achiral analogs. Yet, the advancement of stereocontrolled methods to access many of these compounds is still in its infancy, particularly for highly nitrogenated species. In this work, we present a catalytic enantioselective amination of sulfenamides mediated by a peptide-based guanidine catalyst, affording desymmetrized sulfinamidines in good to excellent enantioselectivities. Highlights of the methods are the commercial availability and bench stability of the aminating reagent; the low catalyst loading; and the convenient, open-to-air room temperature setup. Catalyst optimization from a mildly selective hit was guided by DFT-based atomistic modeling, which unveiled the insufficiencies of initial and intermediate catalyst designs. The results of this work highlight an example of computationally guided catalyst optimization in generating novel asymmetric solutions to unsolved problems in asymmetric synthesis, particularly in optimizing highly tunable catalyst designs.}, archive = {J_JACS}, author = {Nicolò Tampellini and Eun Seo Choi and Scott J. Miller}, doi = {10.1021/jacs.5c15618}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41122--41129}, shortjournal = {J. Am. Chem. Soc.}, title = {Peptide-catalyzed asymmetric amination of sulfenamides enabled by DFT-guided catalyst optimization}, volume = {147}, year = {2025}, }
• (2025). Partially ordered mesoporous zeolite beta frameworks as naphtha-selective catalysts in vacuum gas oil hydrocracking. JACS, 147(44), 41109--41121. (www)

  @article{ , abstract = {Designing hierarchical zeolites with ordered mesoporosity remains a major synthetic challenge despite their well-established importance in catalysis and separations. In this study, we examine the spatiotemporal dynamics of zeolite dissolution and reorganization to retrace how transient structural changes during zeolite nucleation influence supramolecular self-assembly. For the first time, we demonstrate that subtle differences in the aluminum (Al) spatial proximity and distribution within various zeolite frameworks critically affect their mesostructuring behavior. Notably, beta zeolite comprising distinct polymorphs with marginally different Al environments has shown an anisotropic dissolution pattern, where polymorph B was selectively fragmented, leaving polymorph A unaffected. Through a postsynthetic mesostructuring approach, polymorph B was preferentially reorganized into a gyroidal cubic ordered mesophase, resulting in partially ordered mesoporous beta zeolite. The prepared zeolites exhibit improved catalytic performance in vacuum gas oil hydrocracking, affording high isoparaffin yields and superior naphtha selectivity. These findings provide a direct link between atomic-scale heterogeneity and mesoscale structural evolution in crystals, offering a new strategy for designing advanced catalytic materials.}, archive = {J_JACS}, author = {Rajesh Kumar Parsapur and Georgian Melinte and Youssef Saih and Edy Abou-Hamad and Vasilios Samaras and Robert Peter Hodgkins and Omer Refa Koseoglu and Mohammad Fuad Aljishi and Anissa Bendjeriou-Sedjerari and Zhiping Lai and Magnus Rueping and Kuo-Wei Huang}, doi = {10.1021/jacs.5c15691}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41109--41121}, shortjournal = {J. Am. Chem. Soc.}, title = {Partially ordered mesoporous zeolite beta frameworks as naphtha-selective catalysts in vacuum gas oil hydrocracking}, volume = {147}, year = {2025}, }
• (2025). Efficient and stable electrocatalytic oxygen evolution from MoTex/Ni(OH)2 heterostructures. JACS, 147(44), 41096--41108. (www)

  @article{ , abstract = {A design methodology is presented here for MoTe x /Ni(OH) 2 heterostructured catalysts that enhance the oxygen evolution reaction (OER) in water electrolysis. This approach relies on the transfer of mechanically exfoliated MoTe 2 nanosheets to Au/Si substrates followed by electrochemical Te dissolution to induce defect-mediated, partial semiconducting (2H) to metallic (1T’) phase transitions. Immersing the resulting MoTe x into a nickel nitrate hydrate solution results in a heterostructure consisting of 2H-MoTe x /Ni(OH) 2 and 1T’-MoTe x /Ni(OH) 2 domains, which enables high stability and improved efficiency for the OER compared to IrO x . Both machine-learning potential and density functional theory calculations searched and evaluated all atomic sites for this materials system, thus revealing the enhancement mechanisms of OER via four-electron transfer processes with lowered free energy barriers in the rate-determining steps.}, archive = {J_JACS}, author = {Junhwi Han and Myeong Kyun Nam and Seunghun Shin and Iaan Cho and Hotae Jeon and Jaewon Heo and Jaehyun Lee and Min Kyung Cho and Daniel J. Preston and Mark C. Hersam and In Soo Kim and Bonggeun Shong and Won-Kyu Lee}, doi = {10.1021/jacs.5c15520}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41096--41108}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient and stable electrocatalytic oxygen evolution from MoTex/Ni(OH)2 heterostructures}, volume = {147}, year = {2025}, }
• (2025). Inverse design of DNA-programmable protein colloidal crystals. JACS, 147(44), 41087--41095. (www)

  @article{ , abstract = {Protein crystals are a promising class of porous materials with applications in catalysis, encapsulation, and structural biology. However, the chemical complexity of proteins renders their crystallization a largely empirical process with variable success. In contrast, DNA-functionalized nanoparticles have been crystallized into ordered superlattices with predictable architectures using highly specific and tunable DNA–DNA interactions. Such programmability, however, has not yet been realized in protein crystals. Herein, we chemically modify protein oligomers with a DNA shell and crystallize the resulting protein–DNA conjugates using the principles of colloidal crystal engineering with DNA. When a new type of DNA design comprising three spacer-18 units and a 4–6 nucleotide sticky end was used, structures with greater crystallinity were produced (as compared to when traditional DNA designs used with inorganic assemblies were employed). Using an inverse design strategy, simple cubic, body-centered cubic (bcc), face-centered cubic (fcc), and cesium chloride (CsCl)-type lattices were synthesized by the judicious choice of DNA sequence and protein type. The resulting crystals exhibit Wulff morphologies, including those of fcc lattices, that were directly observable using optical microscopy; such morphologies are rarely achieved in the context of DNA-guided colloidal crystals and reflect the monodisperse protein building blocks. Furthermore, the annealing rate correlates with crystal growth, enabling the formation of crystals up to 80 μm in size. Given the structural, biological, and chemical diversity of natural and engineered proteins, DNA-directed protein colloidal crystallization is a powerful platform for generating a new class of programmable biomaterials with diverse structures and functionalities.}, archive = {J_JACS}, author = {Zhenyu Han and Young Jun Kim and Chad A. Mirkin}, doi = {10.1021/jacs.5c15424}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41087--41095}, shortjournal = {J. Am. Chem. Soc.}, title = {Inverse design of DNA-programmable protein colloidal crystals}, volume = {147}, year = {2025}, }
• (2025). Activatable fluorescent probes for in vivo and ex vivo dynamic profiling of virus-infected macrophages. JACS, 147(44), 41079--41086. (www)

  @article{ , abstract = {Immune cells are critical for viral clearance, yet they can also be infected by viruses, transforming them into reservoirs that promote viral replication and dissemination. Macrophages, as the primary phagocytic cells, have been found to exhibit contradictory roles. However, due to the lack of analytical methods capable of real-time detection of virus-infected macrophages, the detailed mechanisms underlying macrophage polarization, migration, and dissemination following viral infection remain less understood. In this study, we develop two activatable near-infrared fluorescent probes, ZIP (a single-locked probe) for broadly detecting Zika virus (ZIKV)-infected cells and ZIMP (a dual-locked probe) for specifically identifying ZIKV-infected macrophages. ZIP activates its fluorescence in response to the ZIKV NS3 protease, enabling broad detection of ZIKV-infected cells. ZIMP, in contrast, requires both NS3 protease activity and the presence of caspase-1, which is overexpressed in macrophages, ensuring the selective detection of ZIKV-infected macrophages. Using both probes for in vivo imaging and ex vivo analysis reveals that ZIKV infection induces macrophage polarization toward the M1 phenotype in the lymph nodes of living mice, followed by M1 macrophage-mediated viral transportation to the brain at later time points. Furthermore, ZIMP can be employed to evaluate the efficacy of anti-ZIKV therapeutics treatment. This study highlights the potential of activatable optical probes for in vivo and ex vivo dynamic profiling of virus-infected immune cells, providing new insights into the complexities of viral immunity and antiviral therapeutics screening.}, archive = {J_JACS}, author = {Jie Yu and Yan Zhang}, doi = {10.1021/jacs.5c15321}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41079--41086}, shortjournal = {J. Am. Chem. Soc.}, title = {Activatable fluorescent probes for in vivo and ex vivo dynamic profiling of virus-infected macrophages}, volume = {147}, year = {2025}, }
• (2025). Infrared spectroscopic measurements of excited polaronic states of TiO2(110) rutile and TiO2(101) anatase single crystals. JACS, 147(44), 41067--41078. (www)

  @article{ , abstract = {The long-standing differences in the activity of different phases of a given semiconductor for charge transfer reactions are well-known and have been the subject of many studies in particular for the anatase and rutile phases of TiO 2 (the two most studied oxide semiconductor photocatalysts). The many parameters affecting charge transfer in polycrystalline activity, such as the degree of crystallinity, lattice expansion/contraction, pore sizes, and crystallographic orientations, prevent extraction of fundamental properties that may help in designing a given material. Within this context, polarons of model single crystals of two different phases of TiO 2 , anatase (101) and rutile (110), were monitored by diffuse reflectance infrared spectroscopy at atmospheric pressure in the temperature range between 300 and 623 K, under UV excitation. The linear signal increases with light fluency, and the sign of its response to excited electron and hole traps sheds light on their polaronic nature. The extracted activation energy from the change of the signal intensity with increasing temperature was found to be much smaller for anatase (101), 80–100 meV, when compared to that of rutile (110), 300–330 meV, which might be linked to the differences in their polaronic nature. Moreover, the signal increase and decay upon light excitation/de-excitation at different temperatures were monitored. It was found that the higher the temperature, the faster the signal decay was. The extracted rate constants for the anatase (101) were found to be on the order of 10 –2 s –1 with activation energy close to kT values (15 meV). The fast kinetics observed in the single crystals, in sharp contrast to those routinely observed in their polycrystalline counterparts, may be linked to the absence of particle-to-particle charge hopping, as is the case for polycrystalline semiconductors. Based on the obtained results, the high activity of the anatase phase for hydrogen ion reduction when compared to that of the rutile phase can be linked to their different polaronic nature.}, archive = {J_JACS}, author = {Hicham Idriss}, doi = {10.1021/jacs.5c15244}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41067--41078}, shortjournal = {J. Am. Chem. Soc.}, title = {Infrared spectroscopic measurements of excited polaronic states of TiO2(110) rutile and TiO2(101) anatase single crystals}, volume = {147}, year = {2025}, }
• (2025). Ultrafast encapsulation of bimetallic nanoclusters into zeolites: Linking structural features to catalytic performance. JACS, 147(44), 41056--41066. (www)

  @article{ , abstract = {Encapsulating bimetallic nanoclusters within zeolites integrates the benefits of the porous host with the distinctive geometric and electronic structures of the metal sites. However, achieving precise encapsulation of bimetallic nanoclusters within the nanospace of zeolites while simultaneously tuning their structural features remains a significant challenge. Here, we present a universal methodology that enables the ultrafast, in situ encapsulation of various bimetallic nanoclusters during the rapid zeolite crystallization in minutes. The resulting metal-zeolite composites exhibit unique structural characteristics and tunable interactions within the encapsulated bimetallic nanoclusters. By optimizing their compositions, the zeolite encapsulated with Pt–Ni bimetallic nanoclusters demonstrates exceptional activity and stability in the preferential oxidation of carbon monoxide, while the Pt–Zn encapsulated counterpart exhibits outstanding performance in propane dehydrogenation. This comprehensive synthesis–structure–activity study highlights ultrafast encapsulation as a versatile strategy for fabricating bimetallic-nanocluster-encapsulated zeolites with distinctive structural attributes and enhanced catalytic performance that hold great potential for practical applications.}, archive = {J_JACS}, author = {Tao Yu and Kai Jia and Zhenyuan Zhao and Jie Zhu and Yuki Sada and Hiroki Yamada and Toshiaki Ina and Kaiqi Nie and Mingyuan Shao and Yihao Zhao and Yundong Wang and Haijun Yang and Binhang Yan and Xiao Chen and Jianhong Xu and Zhendong Liu}, doi = {10.1021/jacs.5c15231}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41056--41066}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrafast encapsulation of bimetallic nanoclusters into zeolites: Linking structural features to catalytic performance}, volume = {147}, year = {2025}, }
• (2025). Bioinspired total syntheses of skeletally diverse lycopodium alkaloids. JACS, 147(44), 41046--41055. (www)

  @article{ , abstract = {The phlegmarine skeleton is widely recognized as a key biogenetic intermediate in Lycopodium alkaloids. On this basis, we designed a phlegmarine-derived common intermediate that enables the collective, asymmetric total syntheses of 12 Lycopodium alkaloids with five distinct carbon skeletons. This intermediate was prepared on a decagram scale using commercially available ( R )-pulegone in an eight-step sequence, with a stereoselective Michael addition as a key transformation. Subsequent selective carbon–carbon bond formation of this pivotal intermediate─(C4–C10, C4–C12, C1–C14, and C4–C13)─along with a skeletal rearrangement, delivered five frameworks: the huperzimine, lycodine, lycopodine, and phlegmarine classes, which were represented by (−)-hupserrine A, (−)-β-obscurine, (−)-lycopodine, (−)-cermizine B, and the lyconadin C diastereomer, respectively. Furthermore, we developed the first asymmetric total synthesis of (−)-hupserrine A, which bears a complex [6/6/5/6/7] pentacyclic cage structure and inhibits the 5-HT3A receptor (IC 50 = 10.6 μM).}, archive = {J_JACS}, author = {Yu-Fei Ou and Yuan Jin and Zai-Feng Yuan and Jin He and Xiao-Nian Li and Qin-Shi Zhao}, doi = {10.1021/jacs.5c15169}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41046--41055}, shortjournal = {J. Am. Chem. Soc.}, title = {Bioinspired total syntheses of skeletally diverse lycopodium alkaloids}, volume = {147}, year = {2025}, }
• (2025). Stiffening organic crystals through polymerization using visible light. JACS, 147(44), 41034--41045. (www)

  @article{ , abstract = {Soft organic crystals that combine high strength and toughness are essential for flexible electronics and bioinspired devices, but they often compromise one property for the other. Here, we demonstrate a visible-light–driven, single-crystal-to-single-crystal photopolymerization of 1,1′-dioxo-1 H ,1′ H -[2,2′-biindene]-3,3′-diyl-bis(decanoate) ( B10 ) into a polymeric crystal ( PB10 ) that simultaneously with polymerization enhances its mechanical strength and toughness. Under white-light irradiation (2.5 W cm –2 ), centimeter-long B10 needles exhibit splitting, coiling, and straightening, accompanied by a color change from red to colorless. This transformation is accompanied by a molecular reorganization, where the weak (π···π stacking) interactions are replaced by stronger (C–C) bonds, resulting in a drastic change in mechanical properties. As a result, upon photopolymerization, the PB10 crystals transition from purely elastic to elastic/plastic, with a nearly 228-fold increase in toughness. This polymerization is also accompanied by increases in tensile modulus and a nearly 81-fold increase in tensile toughness. Remarkably, the PB10 crystals exhibit a load-bearing capacity exceeding 1 × 10 5 times their own mass, additionally reflecting the dramatic enhancement in mechanical strength.}, archive = {J_JACS}, author = {Linfeng Lan and Yuxing Zhou and Liang Li and Chenguang Wang and Panče Naumov and Hongyu Zhang}, doi = {10.1021/jacs.5c15122}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41034--41045}, shortjournal = {J. Am. Chem. Soc.}, title = {Stiffening organic crystals through polymerization using visible light}, volume = {147}, year = {2025}, }
• (2025). Turing-type catalytic 2D-metal nanomesh inside silica-bilayer for multicomponent reaction control. JACS, 147(44), 41023--41033. (www)

  @article{ , abstract = {Although Turing-like ordering is common at macroscopic scales, its realization in metal nanostructures has been hindered by the intrinsic tendency of metals toward symmetric growth and coarsening. Here, we report the first synthesis of a few-nanometer-scale Turing-type pattern in a metal catalyst, achieved through a Nano-Molecular Dual confinement (NanoMolD) strategy. A bilayer hollow silica nanoscaffold with a ∼2 nm internal cavity provides spatial confinement, while in situ self-assembly of a surfactant–palladium ion complex modulates precursor diffusion and surface deposition. This synergistic confinement produces an ultrathin two-dimensional palladium nanomesh with periodic, curved “Turing” stripes encased in silica. The 2D nanomesh features a high density of under-coordinated Pd atoms and twin boundaries, forming a unique catalytic architecture. As a result, this catalyst enables multicomponent carbonylative coupling reactions (e.g., Sonogashira, Suzuki–Miyaura, Buchwald–Hartwig, and alcohol coupling) with exceptional efficiency, affording ≥95–99% yields from aryl iodides and appreciable activity with bromides and chlorides. Furthermore, the confined nanomesh facilitates a one-pot sequential semihydrogenation of the intermediate alkynyl ketone to an α, β-unsaturated ketone (chalcone) by simply introducing H 2 , with tunable selectivity governed by the nanostructure. The Turing-type nanomesh is stable, fully recyclable, and demonstrates how nanoscale reaction–diffusion structuring can unlock new capabilities in heterogeneous catalysis.}, archive = {J_JACS}, author = {Yu-Rim Hong and Nitee Kumari and Ankur Maji and Chaeyeon Kim and Sampathkumar Jeevanandham and Amit Kumar and Byeong Su Gu and Min Gyu Kim and Young Joo Lee and Gi-Yeop Kim and Si-Young Choi and Junhyeok No and Hee Cheul Choi and Dongmin Lee and Yongju Yun and In Su Lee}, doi = {10.1021/jacs.5c15063}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41023--41033}, shortjournal = {J. Am. Chem. Soc.}, title = {Turing-type catalytic 2D-metal nanomesh inside silica-bilayer for multicomponent reaction control}, volume = {147}, year = {2025}, }
• (2025). Artificial Mn4SrO4-cluster mimicking the structural changes of the photosynthetic oxygen-evolving center. JACS, 147(44), 41012--41022. (www)

  @article{ , abstract = {The oxygen-evolving center (OEC) of photosystem II (PSII) is characterized by a unique Mn 4 CaO 5 - or Mn 4 SrO 5 -cluster. Understanding the structure–function relationship and the catalytic mechanism of the OEC has been hindered by the lack of a rational model that precisely mimics both the static and dynamic structures of this biological cluster. Herein, we report a series of synthetic Mn 4 SrO 4 -clusters that closely mimic the main metal-oxide core, peripheral coordination sphere, redox properties, and the oxidation states of the four Mn ions in the Sr 2+ -containing OEC. Crystal structural measurements demonstrate that the presence of additional neutral ligands on Sr 2+ of the S 1 state Mn 4 SrO 4 -cluster can significantly modify the geometric conformation of the cluster, whereas the oxidation states and the dominant antiferromagnetic interactions of four Mn ions are largely undisturbed. EPR investigations and DFT calculations on the S 2 state Mn 4 SrO 4 -cluster demonstrate that the presence of additional neutral ligands can significantly affect the magnetic interactions of the cluster, converting the high-spin state giving rise to a g ≈ 4 EPR signal into a low-spin state with a g = 2 multiline EPR signal. Mass spectroscopic measurements show that a Mn 4 SrO 5 -cluster can be generated in solution from the synthetic Mn 4 SrO 4 -cluster. These observations provide chemical insights into the functional role of the redox-inactive metal ion (calcium or strontium), dynamic structural changes, and catalytic mechanism of its biological counterpart.}, archive = {J_JACS}, author = {Changhui Chen and Zaining Wang and Meilin Zhang and Kexin Jia and Feng Pan and Hongjun Fan and Su-Yuan Xie and Jian-Ren Shen and Jihu Su and Bing-Wu Wang and Chunxi Zhang}, doi = {10.1021/jacs.5c14817}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41012--41022}, shortjournal = {J. Am. Chem. Soc.}, title = {Artificial Mn4SrO4-cluster mimicking the structural changes of the photosynthetic oxygen-evolving center}, volume = {147}, year = {2025}, }
• (2025). Skeletal editing of quinolines by single-atom carbon Insertion–Deletion. JACS, 147(44), 41004--41011. (www)

  @article{ , abstract = {In the endeavor to identify a molecule optimally tailored to a specific functional role, the distinction between success and failure often hinges on one or two atoms. Replacing an aromatic carbon with an exogenous one may facilitate the discovery of potential pharmaceuticals; yet, to date, only indirect approaches exist for such C-to-C transformations, most commonly via parallel synthesis. Herein, we report a transformation enabling the direct conversion of two adjacent aromatic carbons remote from the reactive site to two new carbons, thereby reconstructing quinolines. Cyclizative rearrangement of the parent azaarene with an electron-deficient alkyne generates in situ a benzazepine intermediate, which incorporates an isomerizable triene motif priming the subsequent regioselective 6π-azaelectrocyclization and departure of a designated carbon. This method obviates ring opening and recyclization, enabling site-specific editing of azaarenes via single-carbon insertion and deletion. We demonstrate a broad substrate scope encompassing quinolines and associated azaarenes, all undergoing skeletal reconstruction via concurrent 1,2-carbon migration from C3 to C4 and insertion of a new functionalizable C3 carbon. Mechanistic studies validate the pivotal role of the activated intermediate and showcase the utility of this methodology in the late-stage modification of drug molecules.}, archive = {J_JACS}, author = {Di Tian and Lu-Sen Yang and Peng Yuan and Yu-Ping He and Hua Wu}, doi = {10.1021/jacs.5c14766}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {41004--41011}, shortjournal = {J. Am. Chem. Soc.}, title = {Skeletal editing of quinolines by single-atom carbon Insertion–Deletion}, volume = {147}, year = {2025}, }
• (2025). A flexible quadruple-stranded helicate demonstrates a strong binding preference for DNA three-way junctions by induced fit. JACS, 147(44), 40992--41003. (www)

  @article{ , abstract = {Nucleic acid junctions are key to many biological functions from recombination and repair to viral nucleic acid insertion and are an attractive, functional biomolecular target. We describe a quadruple-stranded diplatinum helicate that binds both three-way (3WJ) and four-way DNA junctions (4WJ). This allows us to probe the relative importance of size and shape in junction-binder design. Despite the helicate’s tetragonal symmetry/shape being compatible with the 4WJ, microscale thermophoresis (MST), isothermal calorimetry (ITC), and gel electrophoresis competition experiments demonstrate that this metallo-supramolecule displays a stronger affinity for 3WJs (K d = 12 nM) than for 4WJs (K d > 4 μM) and other DNA structures. The experimental findings are supported by molecular dynamics simulations that reveal the critical role of size. While the open form of the 4WJ is promoted when the helicate is in the cavity, the helicate’s small size means it is unable to maintain π contacts with all four junction base-pairs simultaneously. Although the helicate is slightly too large for the smaller 3WJ cavity, simulations and experiments show that it can open up the cavity (increasing the junction’s hydrodynamic radius) by disrupting a base pair. The flexible helicate also responds to the cavity upon binding by favoring one enantiomer and allowing the helicate to adopt a stable final structure inside the 3WJ that is an induced fit of the two dynamic structures (supramolecule and DNA). This contrasts with previous lock-and-key examples of junction recognition and opens up new possibilities for how to design DNA and RNA junction-binding compounds.}, archive = {J_JACS}, author = {Hugo D. Williams and Samuel J. Dettmer and Sumit Bajpai and Michael J. Hannon}, doi = {10.1021/jacs.5c14580}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40992--41003}, shortjournal = {J. Am. Chem. Soc.}, title = {A flexible quadruple-stranded helicate demonstrates a strong binding preference for DNA three-way junctions by induced fit}, volume = {147}, year = {2025}, }
• (2025). Turn-on conductivity with proton-coupled electron transport in Metal–Organic frameworks. JACS, 147(44), 40981--40991. (www)

  @article{ , abstract = {Proton-coupled electron transfer (PCET) has been studied for decades in the context of molecular reactivity, but its impact on long-range electron transport is barely understood. When defined broadly as ion-coupled charge transport (ICCT), relevant systems include lithium-ion battery electrodes, electrochromic coatings, and myriad electrocatalysts. Despite ample evidence that ion-electron coupling enhances or diminishes the performance of these devices, little is known about the experimental signatures of ICCT and the microscopic factors that govern its mechanism. We expect that ion-electron coupling becomes especially relevant in high-surface-area materials, such as the layered electrodes of intercalation batteries, due to the close proximity of itinerant electrons and electrolytes. Here, we report an electrochemical investigation into a family of metal–organic frameworks (MOFs) that serves as a well-defined platform for understanding the effect of ICCT on both electronic and ionic conductivity. Through photochemical doping of e – –H + pairs and the introduction of solvent guest molecules, the Ti-containing MOFs convert from electronic-only insulators (σ e ≈ 10 –12 S cm –1 ) to mixed ion-electron semiconductors (σ e ≈ 10 –7 S cm –1 , σ ion ≈ 10 –5 S cm –1 ). Direct current and alternating current techniques support the existence of proton–electron coupling and, critically, demonstrate that improved ionic conductivity enhances electronic conductivity. Taken together, these results provide direct evidence that PCET enables long-range charge transport and generalized electrochemical tools and synthetic methods for studying ion-electron coupling in materials broadly.}, archive = {J_JACS}, author = {Erik Svensson Grape and Carl K. Brozek}, doi = {10.1021/jacs.5c14574}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40981--40991}, shortjournal = {J. Am. Chem. Soc.}, title = {Turn-on conductivity with proton-coupled electron transport in Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Tracking lithium intercalation in battery electrodes via their electrochromic properties using operando ellipsometry. JACS, 147(44), 40967--40980. (www)

  @article{ , abstract = {A deep understanding of charge storage mechanisms in lithium-ion battery electrodes is necessary to advance next-generation materials for fast charging and high-power-density applications. Under high-rate conditions, disentangling charge storage contributions (e.g., intercalation, alloying, pseudocapacitance, capacitance, interphase formation, electrolyte degradation, and other processes) is complex, especially for thin film and nanosized materials that typically exhibit surface-dominated behavior. Often overlooked, the electrochromic properties of lithium-ion battery electrodes are innately related to their charge storage properties. In this work, we demonstrate how operando ellipsometry provides detailed insights into charge storage kinetics in battery electrodes. Using a model TiO 2 -anatase thin film, we validate the energy loss function (ELF) derived from the complex dielectric constant as a key indicator for tracking the lithiation state and thus state of charge. Further, we demonstrate that d(ELF)/dV acts as an “opto-voltammogram” that can be used to selectively probe and deconvolute redox reactions, analogous to differential capacity analysis (dQ/dV) or cyclic voltammetry. These findings establish spectroscopic ellipsometry as a powerful technique for optimizing materials in energy storage applications.}, archive = {J_JACS}, author = {Jialin Gu and Adam J. Lovett and Máté Füredi and Thomas Dore and Stefan Guldin and Thomas S. Miller}, doi = {10.1021/jacs.5c14539}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40967--40980}, shortjournal = {J. Am. Chem. Soc.}, title = {Tracking lithium intercalation in battery electrodes via their electrochromic properties using operando ellipsometry}, volume = {147}, year = {2025}, }
• (2025). Triplet sulfur radical pairs stabilized through hund’s rule for ultrafast Lithium–Sulfur batteries. JACS, 147(44), 40958--40966. (www)

  @article{ , abstract = {Sulfur radicals are highly reactive intermediates that can greatly accelerate reaction kinetics in lithium–sulfur batteries. However, the intrinsic instability restricts their applications. Herein, we reveal and validate the formation of ultrastable triplet sulfur radical pairs ([S x · – – S x · – ], x = 2, 3, 4) by combining electron paramagnetic resonance and synchrotron radiations. These radical pairs are produced during the spontaneous decomposition of polysulfide molecules on ferrimagnetic surface, where the sulfur radicals adopt parallel spin alignment and pair into stable triplet states through Hund’s Rule. These radicals enable exceptionally rapid sulfur conversion, delivering a 100-fold kinetic enhancement compared to the traditional polysulfide molecules. Using these triplet radical pairs, the lithium–sulfur battery achieves a remarkable discharge capacity of 728 mAh g –1 , even at an ultrahigh current rate of 8.0 C, with high sulfur loading and lean electrolyte. Significantly, this is the highest capacity under ultrafast charge–discharge rates reported to date.}, archive = {J_JACS}, author = {Huan Li and Rongwei Meng and Lars Thomsen and Shuang Zhong and Chao Ye and Anton Tadich and Shi-Zhang Qiao}, doi = {10.1021/jacs.5c14524}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40958--40966}, shortjournal = {J. Am. Chem. Soc.}, title = {Triplet sulfur radical pairs stabilized through hund’s rule for ultrafast Lithium–Sulfur batteries}, volume = {147}, year = {2025}, }
• (2025). Integrated life cycle assessment guides sustainability in synthesis: Antiviral letermovir as a case study. JACS, 147(44), 40944--40957. (www)

  @article{ , abstract = {The identification of metrics to assess the sustainability of complex chemical synthesis routes has been a topic of interest in recent years. The diversity of life cycle assessment (LCA) approaches for fine chemicals and pharmaceuticals that have been developed face a common challenge: limited availability of production data. This critically affects completeness, accuracy, and reliability. Herein, we describe an iterative closed-loop approach, bridging life cycle assessment and multistep synthesis development. Our comprehensive analysis leverages documented sustainability data augmented by information extrapolated from basic chemicals through retrosynthesis. The LCA results are discussed and evaluated against the more traditional process mass intensity (PMI). We have chosen the synthesis of the commercial antiviral drug Letermovir as a case study: implementation of LCA to the published route in parallel to a de novo synthesis enables us to benchmark, compare, and contrast routes. Identification of bottlenecks in both syntheses revealed negative impacts on the sustainability in asymmetric catalysis as well as metal-mediated couplings, highlighting the continued demand for sustainable catalytic approaches that minimize adverse effects on global warming potential, ecosystem quality, human health, and natural resources. This comprehensive strategy for multilevel sustainability assessment increases the accuracy, facilitates comparisons, and enables targeted optimization of sustainability in organic chemistry.}, archive = {J_JACS}, author = {Sander Folkerts and Maximilian G. Hoepfner and Gonzalo Guillén-Gosálbez and Javier Pérez-Ramírez and Erick M. Carreira}, doi = {10.1021/jacs.5c14470}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40944--40957}, shortjournal = {J. Am. Chem. Soc.}, title = {Integrated life cycle assessment guides sustainability in synthesis: Antiviral letermovir as a case study}, volume = {147}, year = {2025}, }
• (2025). Revealing an unexpected chemical reactivity of boron nitride to H2O and alkane molecules. JACS, 147(44), 40935--40943. (www)

  @article{ , abstract = {Herein, substantial experimental evidence reveals the unexpected chemical reactivity of inert hexagonal boron nitride ( h -BN) to H 2 O, CH 4 , and C 2 H 6 under mild conditions. H 2 O molecules dissociate at B–N edge sites and insert into the B–N bond even under ambient conditions. Detailed spectroscopic characterization shows this process protonates nitrogen sites and hydroxylates boron sites, forming N–H and B–OH groups. Ultimately, the NH 4 + and B(OH) 4 – ions are released into water as the final products of nitrogen protonation and boron hydroxylation. This reactivity is significantly enhanced at the oxygen-doped B–N edges. Theoretical simulations reveal that strong orbital interactions between the H (1s) orbitals of H 2 O and the B (2p)/N (2p) orbitals of the B–N edge produce significant chemical stress at the adsorption sites, promoting the dissociation and subsequent insertion of H 2 O into the B–N bonds. Furthermore, we show that CH 4 and C 2 H 6 can be oxidized to CO and trace CH 3 OH in water over boron nitride at mild temperatures without an additional oxidant. The 18 O isotope-tracing experiment confirms that the oxygen in the boron nitride matrix is responsible for the activation and oxidation of the C–H bond of CH 4 and C 2 H 6 . Simultaneously, the released NH 4 + and B(OH) 4 – ions provide a reaction microenvironment enabling the thermodynamically spontaneous hydration of formed CO to formate. These findings fundamentally challenge the long-standing paradigm of h -BN as a chemically inert material under mild conditions.}, archive = {J_JACS}, author = {Jie Fan and Wen-Cui Li and Yifan Zhang and Weixi Chen and Zhankai Liu and Jichun Jiang and Yuenan Zheng and Lei He and Lei Hua and Dongqi Wang and An-Hui Lu}, doi = {10.1021/jacs.5c14440}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40935--40943}, shortjournal = {J. Am. Chem. Soc.}, title = {Revealing an unexpected chemical reactivity of boron nitride to H2O and alkane molecules}, volume = {147}, year = {2025}, }
• (2025). Molecular engineering of organic prelithiation agents via frontier orbital regulation. JACS, 147(44), 40925--40934. (www)

  @article{ , abstract = {Replenishing the irreversible depletion of the active lithium inventory in lithium-ion batteries is critical for enhancing both energy density and cycling stability in practical applications. Existing prelithiation strategies predominantly address SEI-derived lithium depletion during initial cycles but remain inadequate against subsequent active lithium loss induced by dynamic SEI reconstruction during prolonged cycling. Here, we report a molecular engineering strategy that leverages frontier orbital regulation in organic lithium salts to enable staged, potential-dependent lithium release. By introducing electron-withdrawing or electron-donating functional groups, the HOMO energy levels of molecules are precisely regulated, enabling customized tuning of the decomposition potential for lithium salts. Through this strategy, the reactivity of individual functional groups can be selectively activated. Consequently, a novel multiplatform organic prelithiation agent (Li 4 DOPA) has been synthesized. Comprehensive analyses elucidate potential-dependent decomposition behavior governed by the electronic structure. Benefiting from this molecular-level control and the independent delithiation behavior of distinct functional groups, Li 4 DOPA enables stepwise lithium release when coupled with LiFePO 4 cathodes. The additional lithium compensates for losses in graphite and SiO x /C anodes, ultimately doubling the cycle life. This work establishes generalizable guidelines for developing advanced functional prelithiation agents through targeted frontier orbital engineering.}, archive = {J_JACS}, author = {Chen Li and Xin Chang and Boheng Yuan and Yu-Hao Wang and Xi-Xi Feng and Chao-Fan Gu and Kai Chen and Qinghai Meng and Yu-Guo Guo and Li-Jun Wan}, doi = {10.1021/jacs.5c14171}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40925--40934}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular engineering of organic prelithiation agents via frontier orbital regulation}, volume = {147}, year = {2025}, }
• (2025). Pillar[5]arene-based visual planar chirality switches with variable color expression. JACS, 147(44), 40917--40924. (www)

  @article{ , abstract = {The development of molecular-level chirality control systems that exhibit macroscopic property changes remains a significant challenge, primarily due to the lack of dynamic chirality platforms and efficient molecular designs. Herein, we report two chirality-controlled switches ( P5N- R and P5N- S ) in which planar chirality can be reversibly modulated by solvents, temperature, and guest molecules, with the corresponding color changes. This correlation means that the inclusion of guests into the macrocycle cavity promotes the adoption of a pillar conformation in which the pR -form, P5N- R , is dominant, while the exclusion of guests favors the pS -form with a folded conformation. These different conformations lead to distinct intramolecular hydrogen bonds in P5N- R , altering the electron-donating ability of the amino groups to the benzoquinone unit and causing color changes. Furthermore, P5N- S exhibits similar chirality-controlled and color change behavior. This work demonstrates a new strategy for constructing dynamic chiral switches with macroscopic property changes, which has significant implications for the development of advanced, responsive chiral materials.}, archive = {J_JACS}, author = {Mingrui Xiao and Zhenzhuo Liu and Shiyu Tan and Bohan Zhao and Liya Chen and Zhongwen Liu and Yifei Zhang and Shuai Fang and Li Shao and Yingchun Liu and Bin Hua and Feihe Huang}, doi = {10.1021/jacs.5c14161}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40917--40924}, shortjournal = {J. Am. Chem. Soc.}, title = {Pillar[5]arene-based visual planar chirality switches with variable color expression}, volume = {147}, year = {2025}, }
• (2025). Nickel-catalyzed asymmetric α-alkenylations of acyclic amides that provide tertiary stereocenters. JACS, 147(44), 40910--40916. (www)

  @article{ , abstract = {Carbonyl groups and alkenes are ubiquitous in organic chemistry─present in target molecules as well as versatile handles for conversion into other functional groups. Whereas the coupling of the α position of a carbonyl compound with an alkenyl electrophile represents an attractive approach to uniting these useful functionalities, to date there have been few reports of catalytic asymmetric variants of this bond construction. Most of the progress to date has involved cyclic carbonyl compounds (obviates the issue of controlling the E / Z geometry of the nucleophile) and the generation of quaternary stereocenters (obviates undesired side reactions of the β,γ-unsaturated carbonyl product, such as racemization or isomerization to the more stable α,β-unsaturated carbonyl compound). Herein, we establish that a chiral nickel catalyst can couple acyclic racemic Reformatsky-type reagents (α-zincated amides) with alkenyl halides to generate β,γ-unsaturated amides that bear a tertiary α stereocenter with good enantioselectivity and good yield. The products can be transformed into other useful families of enantioenriched compounds, including intermediates in total synthesis. Mechanistic studies are consistent with a nickel(0)/nickel(II) pathway for asymmetric carbon–carbon bond formation.}, archive = {J_JACS}, author = {Asik Hossain and Gregory C. Fu}, doi = {10.1021/jacs.5c14143}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40910--40916}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-catalyzed asymmetric α-alkenylations of acyclic amides that provide tertiary stereocenters}, volume = {147}, year = {2025}, }
• (2025). Revealing recombination and ultrafast relaxation mechanisms in atomically precise titania nanoclusters. JACS, 147(44), 40900--40909. (www)

  @article{ , abstract = {Understanding dynamics of excited electronic states is critical for optimizing photoactive nanomaterials in numerous technological applications, including those employing semiconducting nanoscale transition-metal oxides. In this work, using a combination of state-of-the-art experimental and computational methods, we provide detailed insights into the recombination and ultrafast relaxation processes in atomically precise size-selected titania (TiO 2 ) n ( n = 1–8) nanoclusters. Femtosecond pump–probe spectroscopy reveals two distinct dynamical regimes: an ultrafast subpicosecond relaxation from the initial excited state down to the lowest excited state (S 1 ), followed by a significantly slower recombination to the ground state (S 0 ) on time scales of tens to hundreds of picoseconds. Ab initio nonadiabatic molecular dynamics simulations accurately reproduce these observed time scales providing a sound theoretical support to the interpretation of the experiments. We find that the nonmonotonic dependence of the corresponding excited-state relaxation and recombination time scales on the nanocluster size emerges from the interplay of electronic energy gaps, nonadiabatic couplings, and densities of states. In larger nanoclusters, larger nonadiabatic couplings between electronic states enhance coherent population transfer within the dense manifold of excited states, facilitating repopulation of higher excited states and, counterintuitively, slowing down the excitation energy relaxation. In contrast, recombination to S 0 depends nonmonotonically on the cluster size: the dynamics is dominated by energy gaps and slows down for larger gaps when n ≤ 4, meanwhile the relaxation accelerates in larger systems ( n ≥ 4) due to increased nonadiabatic couplings. Our findings provide generic mechanistic insights into excited-state dynamics in photoactive materials as exemplified by the important class of size-selected metal oxide nanoparticles.}, archive = {J_JACS}, author = {Miguel Recio-Poo and Chase H. Rotteger and Francesc Illas and Stefan T. Bromley and Ángel Morales-García and Scott G. Sayres and Alexey V. Akimov}, doi = {10.1021/jacs.5c14060}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40900--40909}, shortjournal = {J. Am. Chem. Soc.}, title = {Revealing recombination and ultrafast relaxation mechanisms in atomically precise titania nanoclusters}, volume = {147}, year = {2025}, }
• (2025). A reductive mechanochemical approach enabling direct upcycling of fluoride from polytetrafluoroethylene (PTFE) into fine chemicals. JACS, 147(44), 40895--40899. (www)

  @article{ , abstract = {Polytetrafluoroethylene (PTFE) is a highly versatile material that has found widespread application owing to its exceptionally high chemical resistance and thermal stability. However, these properties mean that PTFE disposal is an energy intensive process, producing fluorinated materials which pose serious concerns regarding toxicity and environmental persistence. Herein we report a straightforward mechanochemical approach for the reductive defluorination of PTFE generating an environmentally benign mixture of elemental carbon and sodium fluoride. The process employs cheap and readily available chunks of sodium metal, proceeding rapidly at room temperature, in the absence of any organic solvent to form sodium fluoride (NaF) in 98% yield. The fluoride generated in the process can be directly upcycled into fine chemicals through in situ mechanochemical fluorination reactions, delivering valuable sulfonyl fluoride and acyl fluoride products in excellent yields.}, archive = {J_JACS}, author = {Matthew E. Lowe and Benjamin M. Gallant and Nathan Davison and Matthew N. Hopkinson and Dominik J. Kubicki and Erli Lu and Roly J. Armstrong}, doi = {10.1021/jacs.5c14052}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40895--40899}, shortjournal = {J. Am. Chem. Soc.}, title = {A reductive mechanochemical approach enabling direct upcycling of fluoride from polytetrafluoroethylene (PTFE) into fine chemicals}, volume = {147}, year = {2025}, }
• (2025). Baited SELEX: Drug-directed selection of aptamers to PSMA for in vivo targeting of prostate cancer xenografts in mice. JACS, 147(44), 40879--40894. (www)

  @article{ , abstract = {We report a selection strategy for linking a drug-pharmacophore to a degenerate DNA library for use in cell- and whole-animal systematic evolution of ligands by exponential enrichment (SELEX) to direct the selection of aptamers to a specific target. This approach enables the discovery of aptamers with both high affinity and high tissue specificity, guided by a tethered small molecule and enhanced by an aptamer. We applied this approach to a critical application in prostate cancer (PCa) by conjugating a fluorescent analogue of the FDA-approved drug Pluvicto to a degenerate N40-DNA library to direct the selection of aptamers against the prostate-specific membrane antigen (PSMA). Seeking antibody-like functionality, we introduce two modified dNTPs─phenolic-dT and naphthyl-dC─to enhance the affinity and serum stability of selected aptamers. After 31 rounds of cell SELEX, followed by one round in a mouse bearing an LNCaP xenograft, next-generation sequencing informed the selection of several aptamers, of which an exemplar shows very high affinity for PSMA ( K d ∼ 0.8 nM). Its affinity depends on both the small-molecule drug and the modified nucleosides. Appreciating the outstanding challenge of identifying agents that differentiate PSMA on tumors from salivary glands, we identify aptamers that selectively bind PSMA-expressing tumors while sparing salivary glands. Use of a PSMA-targeting pharmacophore as a molecular bait represents the first example of SELEX against specific targets expressed on tumors while avoiding binding to the same target expressed on normal tissues. The resulting aptamers represent hybrid biologics that enhance the affinity and tumor specificity of the small-molecule drug-pharmacophore.}, archive = {J_JACS}, author = {Kun Liu and Nicole Robinson and Emirhan Tekoglu and Jerome Lozada and Ivan Pak Lok Yu and Ruyin Astoria Tai and Dogancan Ozturan and Ugur Meric Dikbas and Nathan A. Lack and Michael E. Cox and Miles P. Mannas and Philip Cohen and S. Larry Goldenberg and David M. Perrin}, doi = {10.1021/jacs.5c13307}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40879--40894}, shortjournal = {J. Am. Chem. Soc.}, title = {Baited SELEX: Drug-directed selection of aptamers to PSMA for in vivo targeting of prostate cancer xenografts in mice}, volume = {147}, year = {2025}, }
• (2025). De novo design, directed evolution and computational study of heme-binding helical bundle protein catalysts for biocatalytic enantioselective Ge–H insertion. JACS, 147(44), 40869--40878. (www)

  @article{ , abstract = {De novo designed proteins offer a malleable platform for the development of stereoselective transformations not found in biochemistry. Here, we report the de novo design and directed evolution of helical bundle protein catalysts for enantioselective germylation through Ge–H insertion, a transformation not previously achieved by enzymatic catalysis. Comparative computational analysis revealed that, relative to Si–H insertion, the Ge–H insertion reaction proceeds through an earlier and more flexible transition state, introducing distinct challenges for stereocontrol. Using a fully de novo designed truncated four-helix bundle scaffold as the starting point, directed evolution afforded a quadruple mutant that catalyzes Ge–H insertion with high efficiency, enantioselectivity, and broad substrate scope. Molecular dynamics simulations indicated that beneficial mutations introduced from directed evolution enhanced active-site preorganization and modulated local backbone flexibility, contributing to improved transition-state complementarity with fine-tuned binding pocket size and more stable cofactor positioning regulated by hydrogen bonding interactions. These findings showcase the excellent potential for de novo proteins to achieve stereoselective transformations previously unknown to biocatalysts and underscore the importance of active-site remodeling of de novo protein scaffolds via directed evolution in achieving selective catalysis involving flexible transition states.}, archive = {J_JACS}, author = {Wei Huang and Gessica M. Adornato and Maggie Horst and Turki M. Alturaifi and Kaipeng Hou and Peng Liu and William F. DeGrado and Yang Yang}, doi = {10.1021/jacs.5c13909}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40869--40878}, shortjournal = {J. Am. Chem. Soc.}, title = {De novo design, directed evolution and computational study of heme-binding helical bundle protein catalysts for biocatalytic enantioselective Ge–H insertion}, volume = {147}, year = {2025}, }
• (2025). Programmable assembly of mechanically robust and functional Polymer–Spore biocomposites in organic solvent. JACS, 147(44), 40859--40868. (www)

  @article{ , abstract = {Microbial biocomposites offer genetically programmable and regenerative functionality, but their mechanical tunability remains limited by the mild conditions required for biological activity and viability. Here, we report the programmable self-assembly of Bacillus subtilis spores with benzalcyanoacetate (BCA)-functionalized polymers to form robust composites exhibiting tunable viscoelastic and tensile properties. Surface-exposed cysteines on the spore coat react with BCA motifs, forming dynamic thia-Michael networks with Young’s moduli of >100 MPa. Systematic variation of BCA reactivity and comonomer-dependent polymer dynamics enabled control over stiffness, stress-relaxation behavior, microscale morphology, and covalent biocontainment. Incorporation of engineered spores confers catalytic function that can be regenerated following solvent-triggered disassembly. This work establishes a modular platform for constructing biocomposites that are both mechanically and genetically programmable, bridging the synthetic and biological domains through molecularly defined interfaces.}, archive = {J_JACS}, author = {Masamu Kawada and Ziyu Cui and Justin Chen and Reis Dorit and Jaeho Cho and Seunghyun Sim}, doi = {10.1021/jacs.5c13976}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40859--40868}, shortjournal = {J. Am. Chem. Soc.}, title = {Programmable assembly of mechanically robust and functional Polymer–Spore biocomposites in organic solvent}, volume = {147}, year = {2025}, }
• (2025). Tunable mesoscale chirality in two-dimensional vortex-like assemblies of helically grooved poly(phenylacetylene) derivatives. JACS, 147(44), 40849--40858. (www)

  @article{ , abstract = {Two-dimensional (2D) chiral materials offer exciting opportunities in sensing and catalysis, yet achieving mesoscale chirality in 2D organic assemblies remains challenging. We introduce a bioinspired strategy to fabricate 2D vortex-like platelets with mesoscale chirality from DNA-mimicking helically grooved poly(phenylacetylene) derivatives via interchain twisted coupling. By tuning assembly kinetics including solvent exchange rate and temperature, we program both the handedness and curvature of mesoscopic chirality. Theoretical simulations show that inherent chain helicity dictates twist direction, while assembly conditions govern angular magnitude. Polymers with helical grooves outperform rigid rod-like analogues: their fluted surfaces serve as stereochemical “hotspots”, channeling torsional stress to enable directional coupling across the plane. Dependence of mesoscale chirality on polymer molecular weights further confirms the universality of helical-groove-driven chiral amplification. These vortex platelets exhibit enhanced circularly polarized luminescence (CPL) superior to regular achiral 2D ones. This work offers new insights into both mechanistic understanding of hierarchical chirality transfer and an engineering framework for biomimetic mesoscale chiral materials.}, archive = {J_JACS}, author = {Yihan Huang and Shuming Kang and Siliang Cai and Zhehao Zhang and Peiyao Yu and Xiaoqian Sun and Xinhua Wan and Jie Zhang}, doi = {10.1021/jacs.5c13610}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40849--40858}, shortjournal = {J. Am. Chem. Soc.}, title = {Tunable mesoscale chirality in two-dimensional vortex-like assemblies of helically grooved poly(phenylacetylene) derivatives}, volume = {147}, year = {2025}, }
• (2025). Oxygen vacancy formation in ZnSeTe blue quantum dot light-emitting diodes. JACS, 147(44), 40842--40848. (www)

  @article{ , abstract = {Recent advancements have led to the development of bright and heavy metal-free blue-emitting quantum dot light-emitting diodes (QLEDs). However, consensus understanding of their distinct photophysical and electroluminescent dynamics remains elusive. This work correlates the chemical and electronic changes occurring in a QLED during operation using depth-resolved and operando techniques. The results indicate that oxygen vacancies form in the ZnMgO layer during operation, with important implications on the charge injection and electrochemical dynamics. Taken together, the results suggest a causal relationship between oxygen vacancy formation and operational degradation of the blue-emitting ZnSeTe-based QLEDs.}, archive = {J_JACS}, author = {Shaun Tan and Sujin Park and Seung-Gu Choi and Oliver J. Tye and Ruiqi Zhang and Jonah R. Horowitz and Tanguy Terlier and Heejae Chung and Vladimir Bulović and Jeonghun Kwak and Jin-Wook Lee and Taehyung Kim and Moungi G. Bawendi}, doi = {10.1021/jacs.5c13973}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40842--40848}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxygen vacancy formation in ZnSeTe blue quantum dot light-emitting diodes}, volume = {147}, year = {2025}, }
• (2025). Atropisomeric indene (AtroInd) libraries: Design, catalytic synthesis, and applications. JACS, 147(44), 40833--40841. (www)

  @article{ , abstract = {The development of chiral indenyl metal complexes has been hindered by inefficient synthetic methods, significantly lagging behind the well-established Cp metal complexes. In this study, we present a streamlined and highly efficient synthesis of novel atropisomeric indenes (AtroInds) via asymmetric palladium-catalyzed Suzuki–Miyaura cross-coupling reactions. Leveraging this method, AtroInd libraries, encompassing varying steric and electronic properties, were readily constructed. The resulting AtroInd–Rh(III) complexes were prepared with ease and subjected to comprehensive characterization, revealing exceptional catalytic efficiency in asymmetric catalysis. Computational studies provided profound insights into the reaction pathway and the critical factors governing enantioselectivity, thereby enhancing our mechanistic understanding. This integrated approach not only addresses the prevailing synthetic challenges in the preparation of chiral indenes but also establishes a new paradigm for the design and synthesis of novel ligand libraries through advanced synthetic methodologies.}, archive = {J_JACS}, author = {Yuan Zheng and Jingran Zhang and Jingyi Bai and Minyan Wang and Zhuangzhi Shi}, doi = {10.1021/jacs.5c13866}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40833--40841}, shortjournal = {J. Am. Chem. Soc.}, title = {Atropisomeric indene (AtroInd) libraries: Design, catalytic synthesis, and applications}, volume = {147}, year = {2025}, }
• (2025). Curvature-directed selective C–C bond cleavage driven by electric fields. JACS, 147(44), 40825--40832. (www)

  @article{ , abstract = {Controlling chemical reactivity through molecular strain offers a compelling strategy for precision bond manipulation at the single-molecule level. Here, we show that spatially differentiated curvature in a nonplanar π -conjugated system can program the site of carbon–carbon (C–C) bond cleavage without the need for catalysts or harsh conditions. Using a teardrop-shaped carbon nanohoop ( meta -cycloparaphenylene, m CPP) with an intrinsic curvature gradient, we achieve highly selective C–C bond scission at the most strained site by applying a mild electrical bias (∼1 V) via the scanning tunneling microscopy break-junction (STM-BJ) technique. With a predominant product yield of ∼75%, the process produces linear oligophenylene junctions featuring well-defined Au–C σ contacts. Remarkably, the curved molecular architecture defines a postcleavage transport pathway that inherently exhibits destructive quantum interference (DQI), leading to conductance suppression by over 4 orders of magnitude. These findings introduce molecular curvature as a programmable design element for guiding bond activation and tailoring charge transport in π -electronic systems.}, archive = {J_JACS}, author = {Xuwei Song and Jia-Nan Gao and Kai Song and Hongxiang Xu and Chengjia Jing and Bingchen Liu and Junfeng Lin and Yongfeng Wang and Huan Cong and Daoben Zhu and Yaping Zang}, doi = {10.1021/jacs.5c13861}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40825--40832}, shortjournal = {J. Am. Chem. Soc.}, title = {Curvature-directed selective C–C bond cleavage driven by electric fields}, volume = {147}, year = {2025}, }
• (2025). Immune-induced Antibody–DNA hybrid condensates. JACS, 147(44), 40816--40824. (www)

  @article{ , abstract = {We report here the combined use of Watson–Crick and antibody–antigen interactions to induce phase separation of antibody–DNA hybrid condensates. To achieve this, we have used an antigen-conjugated star-shaped DNA motif (nanostar) in which three arms terminate with single-stranded DNA sticky ends while the fourth arm is end-conjugated with a moiety (i.e., an antigen) that can be recognized by a specific bivalent antibody. Through the concerted action of selective Watson–Crick base-pairing between the sticky ends and bivalent antibody–antigen binding, such antigen-conjugated nanostars phase-separate to form micron-scale hybrid condensates with structural stability provided by both nucleic acids and antibodies. We have demonstrated the specific and orthogonal antibody-induced phase separation of four different antigen-conjugated nanostars (biotin, DIG, DNP and MUC1), each with their corresponding antibody. By adding increasing concentrations of the specific antibody to a fixed concentration of antigen-conjugated nanostars (300 nM), we observe concentration-dependent formation of antibody–DNA condensates, starting at low nanomolar levels of the antibody. The antibody–DNA hybrid condensates are also reversible and can be cyclically formed/dissolved by the cyclic degradation/addition of the specific antibody. We qualitatively (and in some cases quantitatively) reproduce these results with an approach that conjugates theory and simulations of a phase-field model. The introduction of antibody–antigen interactions into the phase separation process of DNA brings these systems closer to natural cellular systems that rely on intricate networks of protein–protein or protein–nucleic acid interactions and allows for greater programmability and versatility that could have applications in sensing and drug delivery.}, archive = {J_JACS}, author = {Sara Scalia and Marco Cappa and Lorenzo Rovigatti and Erica Del Grosso and Francesco Ricci}, doi = {10.1021/jacs.5c13855}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40816--40824}, shortjournal = {J. Am. Chem. Soc.}, title = {Immune-induced Antibody–DNA hybrid condensates}, volume = {147}, year = {2025}, }
• (2025). Y-doped CuS promotes selective electroreduction of CO2 to ethanol. JACS, 147(44), 40807--40815. (www)

  @article{ , abstract = {The carbon dioxide reduction reaction (CO 2 RR) offers a promising route for sustainable energy conversion. However, achieving high selectivity toward targeted C–C products such as ethanol remains a significant challenge. This limitation stems from the structural complexity and design constraints of efficient Cu-based catalysts, as well as uncertainties regarding the nature of active sites. In this study, we present a rare-earth doping strategy in which yttrium (Y) facilitates the formation of amorphous, low-valent Cu species - identified as key contributors to ethanol selectivity. Using this Y–CuS catalyst, we demonstrate direct ethanol synthesis from CO 2 at a current density of 400 mA cm –2 , achieving a Faraday efficiency of 52%. Notably, when the ethanol-producing current density exceeds 200 mA cm –2 , the energy efficiency reaches 23.8%. In situ infrared spectroscopy-mass spectrometry, combined with time-resolved absorption measurements, reveals that Y incorporation into the Cu–S matrix enhances the generation of ethanol-related intermediates by increasing the density of active sites. Complementary in situ X-ray diffraction (XRD) and fluorescence spectroscopy further confirm that the amorphous low-valent Cu species serve as the primary active sites for selective ethanol production, which is further supported by X-ray spectroscopy and ab initio molecular dynamics simulations. Our findings establish a new catalyst design strategy, demonstrating that rare-earth doping can induce the formation of highly active amorphous Cu sites. This approach offers a sustainable and generalizable pathway for efficient CO 2 conversion to ethanol and potentially other value-added products.}, archive = {J_JACS}, author = {Wei Shen and Chen Peng and Qiujin Xia and Yang Hu and Xiaogang Sun and Yizhen Ye and Haodian Xie and Shanshan Wu and Nan Zhang and Li An and Yao Zheng and Shouheng Sun and Pinxian Xi and Chun-Hua Yan}, doi = {10.1021/jacs.5c13850}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40807--40815}, shortjournal = {J. Am. Chem. Soc.}, title = {Y-doped CuS promotes selective electroreduction of CO2 to ethanol}, volume = {147}, year = {2025}, }
• (2025). Borane/Transition Metal–Catalyzed allenylic and allylic alkylation of unactivated 2-alkylbenzoxazoles. JACS, 147(44), 40799--40806. (www)

  @article{ , abstract = {Asymmetric functionalization of unactivated alkyl-substituted azaarenes at the α-position of the alkyl substituent is challenging because deprotonation of the weakly acidic α-C–H bonds requires a strong base. This requirement often impedes effective enantiocontrol by chiral catalysts. As a result, the few reactions that have been reported have narrow substrate scopes. Herein, we report a method for highly diastereo- and enantioselective allenylic alkylation reactions of unactivated 2-alkylbenzoxazoles with conjugated enynes, enabled by synergistic borane/nickel catalysis. The success of this method hinges on catalytic activation of the 2-alkylbenzoxazoles by a triarylborane, which permits deprotonation by triethylamine and thus is crucial for achieving both high yields and diastereo- and enantioselectivities. Extending the utility of synergistic borane/transition metal catalysis, we also demonstrate that a borane/palladium system effectively overcomes the limitations of palladium-catalyzed allylic alkylation reactions of unactivated azaarenes. In particular, previously unreactive acyclic 1,3-disubstituted allylic esters are rendered viable electrophiles, enabling the construction of products bearing two adjacent stereocenters.}, archive = {J_JACS}, author = {Qi-Fei Liu and Qian-Qian Peng and Sheng-Shi Hao and Lu Liu and Fu-Hao Zhang and Zhu-Jun Shi and Jian-Hua Xie and Chong-Ren Ai and Xiao-Chen Wang}, doi = {10.1021/jacs.5c13835}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40799--40806}, shortjournal = {J. Am. Chem. Soc.}, title = {Borane/Transition Metal–Catalyzed allenylic and allylic alkylation of unactivated 2-alkylbenzoxazoles}, volume = {147}, year = {2025}, }
• (2025). De novo design of a metalloprotein with a synthetically inspired dinuclear paddlewheel coordination motif. JACS, 147(44), 40788--40798. (www)

  @article{ , abstract = {A metal-centered design approach was used to design a tetrameric protein assembly, PW1, with a new-to-nature metal center inspired by the structures of transition metal paddlewheel complexes such as di-Cu II tetraacetate. The structure of PW1 matches the design prediction with atomic accuracy, preorganizing four Glu residues to form the desired dinuclear Cu II center. Notably, Cu-PW1 has a reduction potential of −0.085 V at pH 7.0, which is more negative than any natural or engineered Cu redox protein. In addition to Cu II , PW1 can also scaffold Rh II ions in the dinuclear paddlewheel geometry in crystallo as well as trivalent lanthanide ions in a mononuclear fashion. These results demonstrate the feasibility of designing new protein architectures around synthetically inspired, nonbiological metal centers, thus expanding the scope of artificial metalloproteins beyond those constructed around pre-existing protein scaffolds and opening new avenues to discover structure–function relationships outside the constraints of natural evolution.}, archive = {J_JACS}, author = {Alexander M. Hoffnagle and Ryan A. Herold and Chia-Ying Tsai and Angela A. Shiau and R. David Britt and F. Akif Tezcan}, doi = {10.1021/jacs.5c13813}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40788--40798}, shortjournal = {J. Am. Chem. Soc.}, title = {De novo design of a metalloprotein with a synthetically inspired dinuclear paddlewheel coordination motif}, volume = {147}, year = {2025}, }
• (2025). Regulating lithium Intercalation/Plating competition to enhance low-temperature performance of li-ion batteries. JACS, 147(44), 40776--40787. (www)

  @article{ , abstract = {The severe capacity degradation of Li-ion batteries at subzero temperatures stems from the premature onset of lithium plating at graphite anodes, which intrudes into the Li-ion intercalation regime and consumes active lithium. This work deepens the mechanistic understanding of this phenomenon by identifying the critical depth of discharge (DOD) and potential at which lithium plating begins and by revealing that Li-ion intercalation is intrinsically more sensitive to low temperatures than deintercalation. Guided by this insight, we propose and implement a strategy to delay the DOD threshold for the plating onset through interfacial engineering of the solid electrolyte interphase (SEI). An inorganic-rich SEI is constructed using a carbonate-based electrolyte (nff-LB005) containing LiNO 3 , FEC, and LiFSI, which reduces interfacial resistance, mitigates the low-temperature rise in intercalation overpotential, and shifts the plating onset to higher DOD, enabling more complete intercalation before plating. As a result, graphite||Li cells achieve capacities of 320 mAh g –1 at −20 °C and 260 mAh g –1 at −30 °C, while NCM811||graphite full cells retain 98% capacity over 400 cycles at −30 °C. This interfacial-engineering approach offers an effective route to high-energy Li-ion batteries with superior low-temperature performance.}, archive = {J_JACS}, author = {Maozeng Cheng and Aoyuan Chen and Zhenjie Zhang and Chuanchao Sheng and Haoshen Zhou and Ping He}, doi = {10.1021/jacs.5c13810}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40776--40787}, shortjournal = {J. Am. Chem. Soc.}, title = {Regulating lithium Intercalation/Plating competition to enhance low-temperature performance of li-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Noncovalent interactions in density functional theory: All the charge density we do not see. JACS, 147(44), 40763--40775. (www)

  @article{ , abstract = {Exact determination of the electronic density of molecules and materials would provide direct access to accurate bonded and nonbonded interatomic interactions via the Hellman–Feynman theorem. However, density-functional approximations (DFAs)─the workhorse methods for the electronic structure of atomistic systems─only provide approximate and sometimes unreliable electron densities. In this work, we demonstrate that long-range van der Waals (vdW) dispersion interactions can induce significant polarization in the electron density, with the magnitude of effect growing with system size. We evaluate vdW-induced density shifts using newly developed fully coupled and optimally tuned variant of many-body dispersion model (MBD@FCO), benchmarked against accurate coupled-cluster densities. Applied to supramolecular data sets (S12L and L7) and a prototype protein (Fip35-WW), our approach reveals that dispersion-driven polarization alters long-range electrostatic potentials by up to 4 kcal/mol and reshapes noncovalent interaction (NCI) isosurfaces, producing smooth and chemically interpretable interaction regions. These findings demonstrate that dispersion interactions leave a measurable imprint on the electron density, with implications for electrostatics, biomolecular modeling, and density-based chemical analysis. Our results bridge energy-based dispersion models and density-functional theory, paving the way toward dispersion-consistent DFAs and improved machine-learned models based on electron densities.}, archive = {J_JACS}, author = {Almaz Khabibrakhmanov and Matteo Gori and Carolin Müller and Alexandre Tkatchenko}, doi = {10.1021/jacs.5c13706}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40763--40775}, shortjournal = {J. Am. Chem. Soc.}, title = {Noncovalent interactions in density functional theory: All the charge density we do not see}, volume = {147}, year = {2025}, }
• (2025). Development of dual-receptor lysosome-targeting chimeras for protein degradation. JACS, 147(44), 40751--40762. (www)

  @article{ , abstract = {A growing array of lysosome-targeting chimeras (LYTACs) have recently emerged as therapeutic candidates to treat malignancies and other diseases via targeted protein degradation. We established a novel dual lysosome-targeting receptor-dependent protein degradation strategy that leverages the synergistic actions of the C-X-C chemokine receptor 4 (CXCR4) and folate receptor 1 (FOLR1) to degrade extracellular and membrane proteins. Using this strategy, we developed dual-receptor lysosome-targeting chimeras to achieve efficient lysosomal degradation of programmed cell death ligand 1 (PD-L1) and epidermal growth factor receptor (EGFR). The EGFR chimera inhibited the growth of transplanted T790M-mutated drug-resistant EGFR-driven lung cancer tumors by degrading EGFR. This dual-targeting strategy exhibits significantly better protein degradation capabilities compared with single lysosome-targeting chimeras, providing a novel platform for developing drugs targeting cancer.}, archive = {J_JACS}, author = {Kun Wang and Ke Wang and Cong Wang and Hange Yang and Gangzhong Zhou and Peihong Ji and Xudong Sun and Gong Chen and Xuegong Fan and Kuan Hu and Juan Yi and Hailong Zhang and Rui Wang}, doi = {10.1021/jacs.5c13695}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40751--40762}, shortjournal = {J. Am. Chem. Soc.}, title = {Development of dual-receptor lysosome-targeting chimeras for protein degradation}, volume = {147}, year = {2025}, }
• (2025). Super-absorbing quantum-confined cyanine dyes for near-infrared confocal imaging of hierarchical nephron structures. JACS, 147(44), 40739--40750. (www)

  @article{ , abstract = {Bright near-infrared (NIR) dyes are the cornerstones of high-resolution imaging of scattering media and will transform biology, diagnosis, and surgery. Given that NIR fluorescence quantum yields are intrinsically low as dictated by the energy gap law, improving their molar absorptivity is the only alternative strategy to enhance the brightness of NIR fluorophores. Unfortunately, molar absorptivity still remains a gifted rather than an engineerable photophysical property throughout the long course of synthetic dye chemistry. Through an extensive review of the photophysical, structural, and environmental factors governing the molar absorptivity, we envisioned that the site-specific installation of optimized steric groups along the longitudinal axis can significantly enhance the molar absorptivity, along with stability, i.e. , the quantum confinement effect. With an iterative structure–property relationship study of a total of 46 cyanine dyes, both the viability and broad scope of this strategy were established. Unprecedented superabsorbing cyanine dyes (ε > 4 × 10 5 cm –1 M –1 ) are commonplace in this library, and three Cy7/Cy9 dyes even exhibit molar absorptivity higher than 5 × 10 5 cm –1 M –1 . NIR dyes as bright as fluorescein/rhodamine have been made available. This is a milestone in synthetic dye chemistry and paves the way for high-resolution NIR confocal imaging of intricate biological ultrastructures, e.g ., hierarchical nephron structures, and more demanding bioimaging applications.}, archive = {J_JACS}, author = {Yuyang Zhang and Bingya Wang and Qin Yan and Xicun Lu and Xiaodong Zhang and Cheng Yao and Yichen Qi and Mei Yang and Guangbo Ge and Xuhong Qian and Xiao Luo and Youjun Yang}, doi = {10.1021/jacs.5c13660}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40739--40750}, shortjournal = {J. Am. Chem. Soc.}, title = {Super-absorbing quantum-confined cyanine dyes for near-infrared confocal imaging of hierarchical nephron structures}, volume = {147}, year = {2025}, }
• (2025). Heterochiral and heterotypic self-assembly of intrinsically disordered peptides confers peptide supercoils with exceptional proteolytic stability. JACS, 147(44), 40727--40738. (www)

  @article{ , abstract = {Chirality has received extensive exploration in homotypic supramolecular assemblies; however, few heterotypic peptide assemblies employ heterochirality, especially in the context of intrinsically disordered peptides (IDPs). In this work, we show that heterochiral, heterotypic assemblies of IDPs unexpectedly form supercoils of nanofibers. Specifically, conjugating an aromatic motif to IDPs with opposite charge and chirality results in positively and negatively charged IDPs that form supercoils when mixed in a 2:1 ratio. These supercoils significantly modulate the enzymatic stability of l -peptides: they prevent the proteolysis of l -peptides when the d -peptide to l -peptide ratio is 2:1 but promote it when the ratio is 1:2. Moreover, the formation of supercoils enhances the stability of post-translational modification, phosphotyrosine, against a powerful phosphatase. This work presents the first case of heterochiral and heterotypic assemblies of IDPs. It offers a novel and facile approach for designing supramolecular materials made of IDPs with tunable enzymatic stability. These materials promise applications in a variety of in vivo settings, particularly when efficacy depends on enzymatic stability of IDPs.}, archive = {J_JACS}, author = {Yuchen Qiao and Myeonggon Park and Matthew Chu and Grace Wu and Ruipeng Guo and Chen Liu and Hongjian He and Tongyu Li and Lei Tian and Xixiang Zhang and W. Benjamin Rogers and Bing Xu}, doi = {10.1021/jacs.5c13598}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40727--40738}, shortjournal = {J. Am. Chem. Soc.}, title = {Heterochiral and heterotypic self-assembly of intrinsically disordered peptides confers peptide supercoils with exceptional proteolytic stability}, volume = {147}, year = {2025}, }
• (2025). Dinickela-bicyclo[4,4,0]-decadiene complex with a linear heterometallic Mg–Ni–Ni–Mg chain. JACS, 147(44), 40719--40726. (www)

  @article{ , abstract = {Transition metal–diene complexes constitute a fundamental class of organometallic compounds, in which conjugated dienes typically behave as neutral π-donor ligands. While doubly reduced enediyl derivatives have been occasionally documented in the literatures, dinuclear transition metal complexes featuring such bonding motifs have not been explored. Herein, we report a heterometallic complex [( L Mg) 2 Ni 2 (C 4 H 6 ) 2 ] ( L = [(DIPPNCMe) 2 CH] − , DIPP = 2,6- i Pr 2 C 6 H 3 ) featuring a linear Mg–Ni–Ni–Mg bonded chain, which was formed by the reaction of L MgBu·Et 2 O with Ni(cod) 2 (cod: 1,5-cyclooctadiene). Experimental and computational studies reveal two s-trans -butadiene ligands bridging the Ni–Ni bond in a doubly reduced enediyl configuration. This unique bonding arrangement results in a dinickela-bicyclo[4,4,0]-decadiene framework containing a heterocyclic trans -cycloalkene moiety. Treatment of [( L Mg) 2 Ni 2 (C 4 H 6 ) 2 ] with the additional butadiene afforded [( L Mg) 2 Ni 2 (C 4 H 6 ) 3 ], involving three C 4 H 6 ligands bound to nickel centers, in which they behave as two doubly reduced enediyl ligands and one neutral butadiene ligand. In contrast, upon exposure to carbon monoxide (CO), a ligand exchange reaction occurred, yielding [( L Mg) 2 Ni 2 (C 4 H 6 )(CO) 4 ] with one C 4 H 6 ligand, which is considered as a dinickelacyclo-4-hexene supported by Mg-metalloligands.}, archive = {J_JACS}, author = {Yanping Cai and Stella Christodoulou and Laurent Maron and Xin Xu}, doi = {10.1021/jacs.5c13473}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40719--40726}, shortjournal = {J. Am. Chem. Soc.}, title = {Dinickela-bicyclo[4,4,0]-decadiene complex with a linear heterometallic Mg–Ni–Ni–Mg chain}, volume = {147}, year = {2025}, }
• (2025). A 2D double perovskite based on the chiral cystaminium cation exhibiting multiple switches in quadratic nonlinear optical response. JACS, 147(44), 40708--40718. (www)

  @article{ , abstract = {Over the past decade, double halide perovskites with 2D structural architectures have emerged as a promising alternative to lead-based halide perovskites in the field of semiconductors, motivated by the need to reduce the use of toxic metals. In this work, we present an example of a new 2D lead-free compound, (Cyst) 2 AgSbBr 8 , exhibiting switchable nonlinear (SHG, second harmonic generation) optical properties. The use of the cystaminium cation (Cyst 2+ ) which exhibits helical chirality (M and P conformations) helped in inducing phase transitions due to conformational interconversion in the solid state. Four structural phases p 1–4 have been identified in the room temperature (RT/20 °C)–120 °C range. The I (SHG) = f ( T ) curve defines an unprecedented hysteretic behavior with a SHG OFF state at low ( T < 4 °C) and high ( T > 50 °C) temperature, while in the 4 °C–50 °C temperature range, both SHG(OFF) and (ON) states can occur as a result of the existence of the SHG-inactive p 1 phase and the SHG-active p 2 phase. The temperature range around RT for which these two phases are stable is also unprecedented. This allows to store hidden information at RT, which can be erased either by heating ( T > 50 °C) or cooling ( T < 4 °C) leading to all SHG(ON) or SHF(OFF) domains at RT, respectively. Density Functional Theory (DFT) calculations showed a direct band gap for the all phases. Calculations for the relative stability of the different phases confirmed that p 1 is the most thermodynamically stable phase, with p 2 located slightly higher in energy.}, archive = {J_JACS}, author = {Maria Maniadi and Nicolas Mercier and Alexandre Abhervé and Denis Gindre and Elodie Tailleur and Sébastien Pillet and Valérie Dupray and Christos Tyrpenou and George Volonakis}, doi = {10.1021/jacs.5c13444}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40708--40718}, shortjournal = {J. Am. Chem. Soc.}, title = {A 2D double perovskite based on the chiral cystaminium cation exhibiting multiple switches in quadratic nonlinear optical response}, volume = {147}, year = {2025}, }
• (2025). Modulating iridium coordination to control the oxygen evolution reaction pathway. JACS, 147(44), 40697--40707. (www)

  @article{ , abstract = {Tailoring the coordination number of active sites can potentially shift the oxygen evolution reaction (OER) pathway from the traditional adsorbate evolution mechanism (AEM) to the highly active lattice oxygen mechanism (LOM), but effective synthesis approaches are lacking. Herein, we demonstrate a phase transformation strategy to precisely engineer the coordination modes of Ir loaded in zeolitic imidazolate frameworks (ZIFs), which are subsequently converted into two Ir-doped Co 3 O 4 with distinct coordination numbers of Ir (Ir 1 O x –Co 3 O 4 , x = 4, 6) via air calcination. Comprehensive studies reveal that Ir 1 O 6 –Co 3 O 4 , featuring a higher Ir–O coordination number, intensifies the Ir–O covalency, activates the lattice oxygen participation, and reduces the thermodynamic barrier following a dual-metal-site lattice oxygen mechanism (DMSM-LOM), while Ir 1 O 4 –Co 3 O 4 adheres to the AEM pathway. Consequently, Ir 1 O 6 –Co 3 O 4 exhibits a low overpotential of 253 mV at 10 mA cm –2 and superior stability over 200 h, with mass activity approximately 3.4 and 17.3 times greater than those of Ir 1 O 4 –Co 3 O 4 and commercial IrO 2 , respectively. This work not only provides a synthetic strategy for precise coordination number engineering of active sites but also establishes a direct correlation between the coordination environment and the reaction pathway, offering new insights into the rational design of high-performance OER catalysts.}, archive = {J_JACS}, author = {Wenrui Li and Jiajia Zhang and Chenyu Yang and Zhide Geng and Xianchun Chen and Qinghua Liu and Bo Wang and Lu Wang}, doi = {10.1021/jacs.5c13365}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40697--40707}, shortjournal = {J. Am. Chem. Soc.}, title = {Modulating iridium coordination to control the oxygen evolution reaction pathway}, volume = {147}, year = {2025}, }
• (2025). Programmable cancer subtype evaluator via multiply-guaranteed catalytic DNA computing circuit. JACS, 147(44), 40686--40696. (www)

  @article{ , abstract = {Molecular subtype classification of heterogeneous breast cancer is crucial for personalized therapies yet is limited by the low specificity of conventional single-target diagnosis systems. Herein, we developed a compact and versatile catalytic DNA computing (CDC) circuit as a programmable cancer evaluator for efficient dual-microRNA (miRNA) detection, enabling precise breast cancer subtype identification in clinical samples through a sequentially amplified multiplexed molecular imaging technique. Using an innovative and exquisite probe-concatenating and grafting strategy, the compact CDC system was engineered with minimal strand complexity, incorporating only two tandem-caged probes to form two distinct catalytic hairpin assembly (CHA) circuitry modules: pre-CDC and post-CDC modules. These CHA-based modules were sequentially activated by multiple miRNAs, enabling localized cascade signal amplification for the cancer subtype evaluation. Through systematic experimental validation and complementary theoretical simulations, we elucidated the sequential reaction mechanism and discovered the reaction kinetic confinement of the upstream pre-CDC module on the downstream post-CDC module activation. These findings provided valuable insights into the molecular reaction processes and offered critical guidance for designing efficient CDC probes. With its comprehensive multianalyte recognition and synergistic cascade amplification capabilities, the compact CDC circuit enabled the magnified detection of multiple miRNAs within cancer cells. The CDC platform demonstrated exceptional specificity in identifying clinical cancer tissues, making it a robust cancer cell subtype evaluator for breast cancer. Due to its high accuracy and reliability, this molecular evaluator serves as a promising diagnostic tool with potential applications in clinical diagnosis and disease-related molecular mechanism studies.}, archive = {J_JACS}, author = {Ruomeng Li and Xue Gong and Jinhua Shang and Yuqian Jiang and Weizhen Chen and Gaosong Wu and Xiaoqing Liu and Fuan Wang and Jinghong Li}, doi = {10.1021/jacs.5c13399}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40686--40696}, shortjournal = {J. Am. Chem. Soc.}, title = {Programmable cancer subtype evaluator via multiply-guaranteed catalytic DNA computing circuit}, volume = {147}, year = {2025}, }
• (2025). User-friendly, living Coordination–Insertion polymerizations with broad functional group tolerance. JACS, 147(44), 40676--40685. (www)

  @article{ , abstract = {The development of new user-friendly polymerizations for the synthesis of advanced functional materials has the ability to significantly accelerate discovery in materials science. However, it is often difficult to develop robust methodologies that overcome the sensitivities of many polymerization types and enable well-controlled polymerizations of diverse functional monomers. Herein, we introduce (Ad 3 P)Pd(Me)SbF 6 as a bench-stable, single-component catalyst that is capable of living coordination–insertion polymerization of substituted norbornenes conducted in air, at room temperature, and with broad tolerance to over 30 different functional groups. Our studies revealed that the electron-donating phosphine ligand, tri(1-adamantyl)phosphine (Ad 3 P), and a silver salt activating species were pivotal for maintaining well-controlled polymerizations in the presence of coordinating functionalities. We demonstrated the livingness of this catalytic system and generated block copolymers, ultrahigh molecular weight polymers, and functional polymers from a range of substituted norbornenes. Overall, this work enables coordination–insertion polymerization as a user-friendly technique for the direct synthesis of advanced functional materials.}, archive = {J_JACS}, author = {Jesse H. Hsu and Cassandra A. Haynes and Alexandra J. Macbeth and Renee Girbau and Julia E. Borowski and Maeve A. Reilly and Abigail L. Taylor and Cheyenne R. Peltier and Chris Birch and Kevin J. T. Noonan and Geoffrey W. Coates and Brett P. Fors}, doi = {10.1021/jacs.5c13303}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40676--40685}, shortjournal = {J. Am. Chem. Soc.}, title = {User-friendly, living Coordination–Insertion polymerizations with broad functional group tolerance}, volume = {147}, year = {2025}, }
• (2025). Personalized cancer-specific protein-aptamer corona for orthogonal multiplex cancer diagnosis. JACS, 147(44), 40664--40675. (www)

  @article{ , abstract = {Aptamers are powerful synthetic recognition elements for biosensing, yet their application in complex biofluids, such as human serum, is critically limited by enzymatic degradation. To overcome this fundamental challenge, we introduce a novel analytical platform centered on the concept of a personalized protein-aptamer corona (PAC). This strategy leverages the spontaneous formation of a disease-specific protein corona on magnetic nanoparticles, which not only enriches low-abundance biomarkers but also creates a stabilized, nuclease-free nanobio interface for subsequent aptamer recognition. The integration of this PAC concept with an 8-channel orthogonal multiplexed electrochemical (OMEC) chip enables sensitive, amplification-free (PCR-free) signal transduction via alternating current voltammetry. By coupling this platform with machine learning algorithms, we translate complex, multiplexed aptamer binding signatures into a robust diagnostic output. Clinical validation on two independent cancer cohorts demonstrated outstanding performance, achieving an area under the curve of 99.50% for ovarian cancer ( n = 121) and 96.54% for non-small cell lung cancer ( n = 107). This work establishes the PAC-OMEC platform as a versatile and powerful strategy for high-throughput clinical diagnostics, fundamentally addressing the instability of aptamers in native biological samples.}, archive = {J_JACS}, author = {Jinlong Fan and Baichuan Jin and Xin Dai and Ting Fu and Lu Sun and Guangyi Jiang and Weishan Lu and Qixun Chen and Liu Yang and Jianqing Zhu and Yuan Liu and Weihong Tan}, doi = {10.1021/jacs.5c12860}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40664--40675}, shortjournal = {J. Am. Chem. Soc.}, title = {Personalized cancer-specific protein-aptamer corona for orthogonal multiplex cancer diagnosis}, volume = {147}, year = {2025}, }
• (2025). Kupyaphores─Self-assembling diisocyanolipopeptide ZnII ionophores in mycobacterium tuberculosis ZnII/CuI/II homeostasis and antibacterial effects. JACS, 147(44), 40652--40663. (www)

  @article{ , abstract = {Mycobacterium tuberculosis ( Mtb ), the leading cause of infectious disease mortality from a single pathogen, requires essential metal ions to establish infection and persist in the host. Kupyaphores, a suite of recently identified amphiphilic diisocyanolipopeptides, were reported to assist with Zn II acquisition to support a multitude of Zn II -dependent metalloenzymes critical for Mtb ’s survival and pathogenicity. However, compared to well-studied Fe III acquisition systems in Mtb , the mechanisms for Zn II acquisition and homeostasis remain virtually unexplored. Herein, we reveal them as novel metal ionophores in Mtb ’s metal-fluctuating lipidic niche. A concise modular scalable synthesis was developed to assess the critical features required for activity. Synthetic kupyaphores were structurally and functionally validated, respectively, via LCMS and chemical complementation of kupyaphore-deficient (Δ rv0101 ) Mtb . MS, NMR, and IR evidence demonstrated that kupyaphores complex Zn II as a bidentate ligand. Fluorescence competition data indicated Zn II /Cu I/II binding capabilities, by which Mtb entraps excessive metals within o/w-type micelles against host-induced metal intoxication. The inhibition against Gram-positive Staphylococcus aureus and the low human toxicity imply the potential as a novel antibacterial scaffold. Collectively, this work provides insight into the Zn II /Cu I/II homeostasis of Mtb and a chemical basis for the development of mechanistic tools, therapeutic conjugates against Mtb , and antibiotics.}, archive = {J_JACS}, author = {Tsung-Yun Wong and Sachin Sharma and Kritee Mehdiratta and Rashmi S. Bhosale and Kaavya Nimmakayala and Randall K. Wilharm and Arnab Chakraborty and Moyosore Orimoloye and Qiang Liu and Siddhesh S. Kamat and Valérie C. Pierre and Rajesh S. Gokhale and Courtney C. Aldrich}, doi = {10.1021/jacs.5c13262}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40652--40663}, shortjournal = {J. Am. Chem. Soc.}, title = {Kupyaphores─Self-assembling diisocyanolipopeptide ZnII ionophores in mycobacterium tuberculosis ZnII/CuI/II homeostasis and antibacterial effects}, volume = {147}, year = {2025}, }
• (2025). From silent precursor to persistent reporter: Intracellular targeting of a quinone methide for triarylmethyl radicals accumulation. JACS, 147(44), 40643--40651. (www)

  @article{ , abstract = {Real-time monitoring of critical tumor microenvironment parameters, such as intracellular pH, remains challenging yet essential for understanding cancer progression and therapeutic resistance. We recently observed that the trityl radical OX063 undergoes consecutive oxidation to a diamagnetic quinone methide (QM) under superoxide-generating conditions in culture media with high thiol concentrations. This is followed by thiol-mediated reduction to OX063-OH: a structurally modified, pH-sensitive trityl radical in which one carboxyl group is replaced by a hydroxyl moiety. In this study, we developed a method to target this QM adduct within the intracellular compartment by conjugating it to a cell-penetrating peptide for active transport. Inside cells, the QM adduct converts into the free OX063-OH spin probe. This intracellular probe persists over 10-fold longer than when measured in vivo, where it is rapidly cleared by the kidneys. We demonstrate that this trapped intracellular spin probe effectively reports on physiological properties, including intracellular pH and mobility. It provides a signal strength sufficient for in vivo imaging of these intracellular parameters for over 15 h. This technology has potential applications in metabolic diseases (such as lysosomal storage disorder) as well as studying tumor oxygenation. This redox-activated probe establishes a novel strategy for the noninvasive assessment of tumor acidosis, with significant implications for personalized diagnostics and therapy evaluation.}, archive = {J_JACS}, author = {Arthur E. Raizvikh and Sergey S. Ovcherenko and Olga A. Kartina and Dmitry V. Trukhin and Olga Y. Rogozhnikova and Victor M. Tormyshev and Vladimir V. Koval and Elena G. Bagryanskaya}, doi = {10.1021/jacs.5c13124}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40643--40651}, shortjournal = {J. Am. Chem. Soc.}, title = {From silent precursor to persistent reporter: Intracellular targeting of a quinone methide for triarylmethyl radicals accumulation}, volume = {147}, year = {2025}, }
• (2025). Mechanistic insights into the borane-mediated conversion of 5-carboxylcytosine to dihydrouracil in DNA enable an efficient labeling method using alkoxyamines. JACS, 147(44), 40635--40642. (www)

  @article{ , abstract = {TET-assisted pyridine borane sequencing (TAPS) is a powerful method for mapping cytosine modifications, yet the underlying mechanism of conversion of 5-carboxylcytosine (5caC) to dihydrouracil (DHU) remains poorly understood. Here, through both experimental and computational studies, we show that the reaction proceeds via reduction and decarboxylation to give 5,6-dihydrocytidine as the intermediate, which is then slowly hydrolyzed to DHU as the rate-limiting step. We also found that in double-stranded DNA, the reaction can be catalyzed by an adjacent 5caC with high efficiency. The mechanistic discovery of the slow hydrolysis step by water in the conventional TAPS guided us to use more nucleophilic alkoxyamines to improve this protocol, achieving complete conversion within 1 h. This approach, when coupled with a click-chemistry pull-down, enables up to a 47-fold enrichment of 5caC-containing DNA. Our work thus provides fundamental mechanistic insights into a key epigenetic sequencing reaction and translates this knowledge into a new chemical biology tool for the selective labeling of DNA modifications.}, archive = {J_JACS}, author = {Cong Ding and Zipeng Wang and Bing-Wen Li and Jiangtian Shao and Ying Tang and Wei Yang and Xiaocheng Weng and Zhi-Xiang Yu and Xiang Zhou and Yibin Liu}, doi = {10.1021/jacs.5c13154}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40635--40642}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic insights into the borane-mediated conversion of 5-carboxylcytosine to dihydrouracil in DNA enable an efficient labeling method using alkoxyamines}, volume = {147}, year = {2025}, }
• (2025). Highly selective intermolecular cross-coupling reactions via a persistent radical effect on ag(111). JACS, 147(44), 40626--40634. (www)

  @article{ , abstract = {Achieving highly selective cross-coupling between two radicals remains a long-standing challenge due to competing homocoupling pathways. Here, we report a high-yield radical-based cross-coupling reaction on Ag(111), enabled by the persistent radical effect. Using bond-resolving scanning tunneling microscopy (BR-STM), we directly visualize reaction precursors, intermediates, and products at the single bond level. In our model system, we fulfill the stringent requirement of the persistent radical effect: coexisting high concentrations of persistent radicals with low concentrations of transient radicals. As a result, we achieve an unexpectedly high cross-coupling selectivity with yields exceeding 99%. Combining the experimental finding is combined with density functional theory (DFT) calculations, the reaction mechanism is clarified. Moreover, as radical cross-coupling is diffusion-controlled, we elucidate the kinetics of the persistent radical effect through systematic numerical modeling, Monte Carlo simulations, and control experiments on Cu(111).}, archive = {J_JACS}, author = {Huaming Zhu and Junbo Wang and Yong Zhang and Kaifeng Niu and Yajie Zhai and Yi Zhang and Peipei Huang and Haiping Lin and Jianchen Lu and Johanna Rosen and Jonas Björk and Jinming Cai and Lifeng Chi and Qing Li}, doi = {10.1021/jacs.5c13021}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40626--40634}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly selective intermolecular cross-coupling reactions via a persistent radical effect on ag(111)}, volume = {147}, year = {2025}, }
• (2025). Engineering an imine reductase for enantioselective synthesis of atropisomeric amides. JACS, 147(44), 40616--40625. (www)

  @article{ , abstract = {Atropisomeric amides possess unique axial chirality arising from the rotation-restricted C aryl –C amide bond and find broad application in bioactive molecules and asymmetric catalysis. However, catalytic asymmetric methods for their synthesis remain underdeveloped, with no biocatalytic approaches reported. Herein, we report the first efficient biocatalytic strategy for the atroposelective synthesis of atropisomeric amides via dynamic kinetic resolution using engineered imine reductases (IREDs). Structure-guided engineering of an IRED from Kutzneria albida provided a quadruple mutant (IRED-68-M4) capable of catalyzing the stereoconvergent synthesis of diverse napthamides and benzamides in high yields and excellent enantioselectivities (up to 98% yield, >99:1 er). Gram-scale synthesis of an axially chiral napthamide was also demonstrated. Moreover, protein X-ray crystallography and molecular modeling studies revealed the structural basis of the enhanced catalytic performance of the IRED-68-M4 variant.}, archive = {J_JACS}, author = {Zhouchang Yao and Runze Meng and Zitian Zhou and Luyao Yu and Zhiyun Wu and Longqing Tang and Tianzhang Qiao and Ke Li and Ling Huang and Danqing Song and Haigen Fu}, doi = {10.1021/jacs.5c12724}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40616--40625}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering an imine reductase for enantioselective synthesis of atropisomeric amides}, volume = {147}, year = {2025}, }
• (2025). Light-induced Palladium(IV)–Carbon bond homolysis. JACS, 147(44), 40603--40615. (www)

  @article{ , abstract = {Palladium chemistry has been widely studied since the 1950s, particularly for cross-coupling reactions. It facilitates breaking C-X bonds through oxidative addition and forming C–C bonds through reductive elimination. These 2 electrons’ elementary steps are the key features to construct highly elaborated molecules and explain their exceptional versatility. While Pd(0)/Pd(II) catalytic cycles are well understood, the behavior of Pd(IV) alkyl complexes is less studied, particularly due to their instability. Here, we report the synthesis and characterization by X-ray diffraction, solid-state magnetism, and 1 H NMR of several Pd(Alkyl) 4 fragments, which demonstrate unusual stability thanks to a Cp* 2 Yb(bipym) fragment (Cp* is for pentamethylcyclopentadienyl and bipym for 2,2′bipyrimidine). As such, the Cp* 2 Yb(bipym)Pd(Me) 3 (R) (R = Me, 3 Me ; Et, 3 Et ) complexes have a room temperature half-life of more than 17 h, while the one-electron reduction of 3 Me leads to a Pd(Me) 4 fragment, 3 @crypt , which does not degrade over time. This unusual stability allowed us to study the original reactivities of these Pd(Alkyl) 4 fragments other than classical reductive elimination. Thus, we report the first light-induced Pd(IV)–C bond homolysis, which leads to the formation of alkyl radicals. The Cp* 2 Yb(bipym)PdMe 4 complex, 3 Me , reacts under irradiation at 370 nm to form the Cp* 2 Yb(4Me,4H-bipym)PdMe 4 , 4 , and the Cp* 2 Yb(4Me,4H-bipym)PdMe 2 , 5 , in which the methyl radical couples with the bipym radical. The mechanism of this peculiar reaction has been determined by DFT. Similar reactivity with 3 @crypt leads to the formation of a free methyl radical, as shown by EPR reaction trapping.}, archive = {J_JACS}, author = {Linda De Marchi and Maxime Tricoire and Luca Demonti and Oleh Stetsiuk and Angus C. G. Shephard and Lhoussain Khrouz and Salauat R. Kiraev and Olivier Maury and Thayalan Rajeshkumar and Laurent Maron and Grégory Danoun and Grégory Nocton}, doi = {10.1021/jacs.5c12686}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40603--40615}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-induced Palladium(IV)–Carbon bond homolysis}, volume = {147}, year = {2025}, }
• (2025). Hypochlorous acid-gated hydrolysis of a phosphinate ester dye in living cells. JACS, 147(44), 40590--40602. (www)

  @article{ , abstract = {Theranostic fluorescent platforms are capable of the selective delivery of small molecules to target cells with simultaneous optical monitoring. Such technologies promise to significantly reduce off-target effects compared with cytotoxic chemotherapy. However, small-molecule approaches are often hindered by relatively complex designs that are required to incorporate a fluorescent reporter, reactive linker, targeting ligand, and cargo into a single molecule. Herein, we provide the first direct evidence for the ability to gate the delivery of small-molecule cargos from phosphinate ester-containing Nebraska Red ( NR ) dyes in vitro and in living cells. This simplified system integrates the fluorescent reporter, reactive linker, and targeting ligand into one species─a phosphinate ester dye. As a proof-of-principle for delivery of drug-like molecules to cells, we developed NR-HOCl-TFMU , which responds to hypochlorous acid (HOCl), an analyte detected in acute myeloid leukemia (AML). NR-HOCl-TFMU is stable for days prior to reaction with HOCl, leading to phosphinate ester hydrolysis and production of a NIR (near-infrared, NR dye) and blue (cargo) fluorescence signal. NR dye fluorescence is directly proportional to cargo release, and NR-HOCl-TFMU is capable of selectively delivering its drug-like, small-molecule cargo to AML cells in vitro and in a localized tumor model in an HOCl-gated manner. In the long term, we envision the potential use of this technology to afford HOCl-gated delivery systems with selectivity toward HOCl-positive AML cells. More broadly, this approach provides a potentially generalizable strategy for the development of simplified theranostic agents targeted toward small-molecule analytes and enzymatic activities associated with disease.}, archive = {J_JACS}, author = {Yuan Fang and Xinqi Zhou and Julia L. McAfee and Benjamin M. Faulkner and Lauren Lesiak and Yuchen He and Frederik Bro̷ndsted and Hao Fan and Eric D. Donarski and Xiaoyan Hu and B. Jill Venton and Steven Grant and Francine E. Garrett-Bakelman and Cliff I. Stains}, doi = {10.1021/jacs.5c12615}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40590--40602}, shortjournal = {J. Am. Chem. Soc.}, title = {Hypochlorous acid-gated hydrolysis of a phosphinate ester dye in living cells}, volume = {147}, year = {2025}, }
• (2025). Poly(bis(guanidinium)-oxazoline)–Insulin complex exerting long-acting glucose-responsive insulin release in mice and minipigs. JACS, 147(44), 40576--40589. (www)

  @article{ , abstract = {Glucose-responsive insulin formulations, utilizing electrostatic interactions between positively charged polymers and negatively charged insulin, offer significant potential to enhance the therapeutic index of insulin while alleviating the burden of frequent administration. However, their clinical application is limited by concerns on the uncontrolled insulin release, including the dangerous hypoglycemic events. Here, we develop a glucose-responsive insulin formulation for subcutaneous administration, which exhibits exceptional biocompatibility and maintains normoglycemia over 192 h in type 1 diabetic minipigs after a single dose, with negligible hypoglycemia. The formulation comprises recombinant human insulin, tightly binding to bis(guanidinium)-functionalized poly(2-oxazoline) polymers, which are further modified with phenylboronic acid to enable glucose responsive insulin release. Bis-guanidinium strengthens the electrostatic interaction with insulin, thereby preventing uncontrolled insulin release and prolonging the therapeutic effect in vivo. This bis(guanidinium)-functionalized polymer strategy opens new avenues for developing glucose-responsive insulin formulations.}, archive = {J_JACS}, author = {Haodong Zhang and Qian Liang and Weinan Jiang and Qi Chen and Kang Chen and Zihao Cong and Guojian Liu and Jia Shi and Yanxiu Ji and Wenxin Li and Mengyue Dou and Yuwen Wang and Longqiang Liu and Luhang Chen and Donghui Zhang and Yueming Wu and Runhui Liu}, doi = {10.1021/jacs.5c12605}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40576--40589}, shortjournal = {J. Am. Chem. Soc.}, title = {Poly(bis(guanidinium)-oxazoline)–Insulin complex exerting long-acting glucose-responsive insulin release in mice and minipigs}, volume = {147}, year = {2025}, }
• (2025). High-coercivity spin glasses in anisotropic Mo2FeB2-type M1.5Mn1.5B2 (M = mo, w). JACS, 147(44), 40562--40575. (www)

  @article{ , abstract = {Magnetic materials combining spin-glass behavior with hard-magnet coercivity are important for fundamental and applied research. Herein, we report spin-glass behaviors coupled to remarkably large intrinsic coercivity values of 302.4 kA/m ( H c = 3.80 kOe) in Mo 1.5 Mn 1.5 B 2 and 175.1 kA/m ( H c = 2.20 kOe) in W 1.5 Mn 1.5 B 2 . Both phases belong to the Mo 2 FeB 2 -type structure known for enabling excellent structural properties and predicted altermagnetic candidates. Single-phase products were obtained via a compositionally tuned solid-state route that resolves prior phase-purity challenges. Temperature-dependent susceptibility measurements revealed spin-glass behavior below the freezing temperatures T g = 29 K for Mo 1.5 Mn 1.5 B 2 and T g = 43 K (reentrant cluster spin glass) as well as a ferromagnetic (FM) transition at 70 K for W 1.5 Mn 1.5 B 2 . AC susceptibility (χ′) measurements exhibited frequency-dependent peaks that shifted to higher temperatures with increasing frequency, confirming the presence of dynamic spin freezing in both compounds. DFT calculations confirmed the presence of strongly competing FM and antiferromagnetic (AFM) interactions leading to competing FM, AFM and ferrimagnetic (FiM) orderings with a greater spin-exchange energy (Δ E ex = 28–98 meV/f.u.) for FiM/AFM compared to FM in Mo 1.5 Mn 1.5 B 2 and even greater Δ E ex = 53–131 meV/f.u. in W 1.5 Mn 1.5 B 2 . The magnetocrystalline anisotropy energy (MAE) is uniaxial, favoring the c -axis, with MAE = –0.17 meV/f.u. (Mo) and –0.10 meV/f.u. (W), which align well with the large hysteresis found experimentally, while the unexpectedly larger coercivity of Mo 1.5 Mn 1.5 B 2 correlates with its greater AFM interactions. These findings enable the development of Mo 2 FeB 2 -type multifunctional materials, expanding their applications beyond traditional structural material properties.}, archive = {J_JACS}, author = {Shola E. Adeniji and Alexei A. Belik and Takao Mori and Boniface P. T. Fokwa}, doi = {10.1021/jacs.5c12552}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40562--40575}, shortjournal = {J. Am. Chem. Soc.}, title = {High-coercivity spin glasses in anisotropic Mo2FeB2-type M1.5Mn1.5B2 (M = mo, w)}, volume = {147}, year = {2025}, }
• (2025). Discovery of late intermediates in methylenomycin biosynthesis active against drug-resistant gram-positive bacterial pathogens. JACS, 147(44), 40554--40561. (www)

  @article{ , abstract = {The methylenomycins are highly functionalized cyclopentanone antibiotics produced by Streptomyces coelicolor A3(2). A biosynthetic pathway to the methylenomycins has been proposed based on sequence analysis of the proteins encoded by the methylenomycin biosynthetic gene cluster and the incorporation of labeled precursors. However, the roles played by putative biosynthetic enzymes remain experimentally uninvestigated. Here, the biosynthetic functions of enzymes encoded by mmyD , mmyO , mmyF, and mmyE were investigated by creating in-frame deletions in each gene and investigating the effect on methylenomycin production. No methylenomycin-related metabolites were produced by the mmyD mutant, consistent with the proposed role of MmyD in an early biosynthetic step. The production of methylenomycin A, but not methylenomycin C, was abolished in the mmyF and mmyO mutants, consistent with the corresponding enzymes catalyzing the epoxidation of methylenomycin C, as previously proposed. Expression of mmyF and mmyO in a S. coelicolor M145 derivative engineered to express mmr , which confers methylenomycin resistance, enabled the resulting strain to convert methylenomycin C to methylenomycin A, confirming this hypothesis. A novel metabolite (premethylenomycin C), which readily cyclizes to form the corresponding butanolide (premethylenomycin C lactone), accumulated in the mmyE mutant, indicating the corresponding enzyme is involved in introducing the exomethylene group into methylenomycin C. Remarkably, both premethylenomycin C and its lactone precursor were one to two orders of magnitude more active against various Gram-positive bacteria, including antibiotic-resistant Staphylococcus aureus and Enterococcus faecium isolates, than methylenomycins A and C, providing a promising starting point for the development of novel antibiotics to combat antimicrobial resistance.}, archive = {J_JACS}, author = {Christophe Corre and Gideon A. Idowu and Lijiang Song and Melanie E. Whitehead and Lona M. Alkhalaf and Gregory L. Challis}, doi = {10.1021/jacs.5c12501}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40554--40561}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of late intermediates in methylenomycin biosynthesis active against drug-resistant gram-positive bacterial pathogens}, volume = {147}, year = {2025}, }
• (2025). Stereoselective photoenzymatic hydroarylation for the construction of quaternary stereocenters. JACS, 147(44), 40547--40553. (www)

  @article{ , abstract = {Quaternary carbon stereocenters are a crucial component of many bioactive molecules, but they can be challenging to prepare stereoselectively. Olefin hydroarylations are an attractive means for preparing this motif; however, existing methods struggle to set stereocenters on substrates lacking traditional catalyst binding handles. Here, we report a stereoselective photoenzymatic olefin hydroarylation using a repurposed Baeyer–Villiger monooxygenase. Three rounds of iterative site-saturation mutagenesis yielded a photoenzyme capable of preparing valuable tetrahydroquinolines in high yields with excellent enantioselectivity. The engineered variant accepts various arene substituents, highlighting the synthetic utility of this methodology. DFT calculations and control experiments suggest that the protein templates a through-space interaction between the tertiary radical and aromatic group, which attenuates the oxidation potential of the radical, enabling C–C bond formation.}, archive = {J_JACS}, author = {Felix C. Raps and Chufan A. Jin and Alexandra C. Brown and Damien Sorigué and Todd K. Hyster}, doi = {10.1021/jacs.5c12440}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40547--40553}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereoselective photoenzymatic hydroarylation for the construction of quaternary stereocenters}, volume = {147}, year = {2025}, }
• (2025). Fluorescence-detected wavepacket interferometry reveals time-varying exciton relaxation pathways in single light-harvesting complexes. JACS, 147(44), 40537--40546. (www)

  @article{ , abstract = {Photosynthesis relies on efficient energy relaxation within the excited-state manifold of pigment–protein complexes. Since the protein scaffold is rather flexible, the resulting energetic and structural disorder gives rise to a complex excited-state energy level structure that fluctuates on all time scales. Although the impact of such fluctuations on relaxation processes is known, the precise exciton states involved in relaxation as well as the nature of the vibrational modes driving relaxation are under debate. Here, single pigment–protein complexes from a photosynthetic purple bacterium are excited with two identical ultrashort phase-locked pulses, producing two exciton wave packets that can interfere. This leads to a modulation of the emission intensity as a function of the delay time between the pulses that fades out within about ≈100 fs due to fluctuating environments on those time scales. For several single complexes, we find variations in the interference patterns on a time scale of several tens of seconds that reveal fluctuations in the energy relaxation pathways toward the lowest-energy exciton states. This relaxation is driven by temporal variations in the coupling between electronic excitations and low-frequency vibrational modes.}, archive = {J_JACS}, author = {Stephan Wiesneth and Paul Recknagel and Alastair T. Gardiner and Richard J. Cogdell and Richard Hildner and Jürgen Köhler}, doi = {10.1021/jacs.5c12416}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40537--40546}, shortjournal = {J. Am. Chem. Soc.}, title = {Fluorescence-detected wavepacket interferometry reveals time-varying exciton relaxation pathways in single light-harvesting complexes}, volume = {147}, year = {2025}, }
• (2025). Mapping the role of monomer conformation in the amyloid formation of α-synuclein splice variants. JACS, 147(44), 40519--40536. (www)

  @article{ , abstract = {Amyloid formation of the protein α-synuclein (αSyn) is a hallmark of pathogenesis in Parkinson’s disease, multiple system atrophy, and dementia with Lewy bodies. Research has predominantly focused on the 140-amino acid αSyn sequence, yet the SNCA gene can be alternatively spliced to generate several different isoforms, including αSynΔ3, αSynΔ5, and αSynΔ3Δ5. Here, we have used experimental and computational approaches to characterize these splice variants, in addition to the full-length αSyn, in terms of their monomer conformation and amyloid propensity as a function of changes in ionic strength. Kinetic analysis of amyloid formation, flow-induced dispersion analysis, and coarse-grained molecular dynamics simulations reveal a striking correlation between monomer conformation and the rate of secondary nucleation of amyloid formation, and we show that this is governed by both global conformation of the polypeptide chain and local contacts in the hydrophobic core domain and acidic C-terminal domain. By combining changes in amino acid sequences and ionic strength, our analysis reveals the importance of local contacts and long-range electrostatic interactions in driving the kinetics of amyloid formation of αSyn.}, archive = {J_JACS}, author = {Katherine M. Dewison and Alexander I. P. Taylor and David J. Brockwell and Sheena E. Radford}, doi = {10.1021/jacs.5c12366}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40519--40536}, shortjournal = {J. Am. Chem. Soc.}, title = {Mapping the role of monomer conformation in the amyloid formation of α-synuclein splice variants}, volume = {147}, year = {2025}, }
• (2025). Decoding the water harvesting mechanism of MIL-100(Fe) across short- and long-range length scales. JACS, 147(44), 40507--40518. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) hold promise as designer materials for atmospheric water harvesting, due to their unrivaled porosity, chemical tunability, and water affinity. Although an accurate understanding of the pore filling sequence is critical to developing improved MOF water harvesters, obtaining molecular-level details of the evolution of water clusters in MOFs has proven to be experimentally challenging. Here, a novel approach based on X-ray absorption spectroscopy (XAS), X-ray pair distribution function, powder X-ray diffraction, molecular dynamics (MD) simulations and in-depth theoretical XAS calculations is presented to gain quantitative insights into the structural and dynamical properties of water adsorbed within MIL-100(Fe), a prototypical MOF with giant pores. The complementary synchrotron X-ray techniques shed light on the behavior of water confined in MIL-100(Fe) with unprecedented structural sensitivity at the short-, intermediate- and long-range length scales, while the MD and theoretical XAS simulations revealed the order according to which water molecules populate the MOF mesopores and tracked the evolution of the hydrogen-bond network topology as a function of water content. The developed method can provide often elusive information on how the local structure affects the behavior and performance of MOF water harvesters, which is key to the development of rationally optimized MOF systems.}, archive = {J_JACS}, author = {Francesco Tavani and Alessandro Tofoni and Eva Pietropaoli and Dragos Constantin Stoian and Wouter van Beek and Kenneth Marshall and Ida Pettiti and Alessandro Latini and Paola D’Angelo}, doi = {10.1021/jacs.5c12269}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40507--40518}, shortjournal = {J. Am. Chem. Soc.}, title = {Decoding the water harvesting mechanism of MIL-100(Fe) across short- and long-range length scales}, volume = {147}, year = {2025}, }
• (2025). Mining solid-state electrolytes from Metal–Organic framework databases through large language models and representation clustering. JACS, 147(44), 40496--40506. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) are attracting increasing attention as solid-state electrolytes (SSEs) due to their three-dimensional porous diffusion paths for Li + migration. However, their development is hindered by their inherent complexity and the absence of design guidelines. Large language models (LLMs) and machine learning, as emerging artificial intelligence (AI) technologies, can significantly accelerate the development of MOF SSEs by analyzing data and identifying potential materials. Herein, we use LLMs and representation clustering to intelligently mine MOF SSEs from 11,393 candidate MOF materials, subsequently verified by physicochemical characterizations and electrochemical demonstration. Specifically, we adopt an interactive iteration text mining framework based on LLMs to extract information on MOF SSEs, constructing a specialized data set for structural and electrochemical properties of MOF SSEs, with high precision and recall. Each property is projected into a representation space, and representation clustering is performed on samples to mine promising MOF SSEs from a candidate MOF data set. As a typical result, NOTT-400 is successfully identified through the clustering analysis, exhibiting high Li + conductivity (2.23 × 10 –4 S cm –1 ) and a wide electrochemical stability window (0–4.79 V), confirming both the material feasibility and the reliability of the entire AI-driven approach. The AI-assisted mining of novel MOF SSEs, along with their design principles, creates a new paradigm for accelerating materials discovery.}, archive = {J_JACS}, author = {Jinglang Zhang and Jiaxin Li and Guanhua Zhao and Qilong Wang and Yu-Guo Guo and Chunpeng Yang}, doi = {10.1021/jacs.5c12212}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40496--40506}, shortjournal = {J. Am. Chem. Soc.}, title = {Mining solid-state electrolytes from Metal–Organic framework databases through large language models and representation clustering}, volume = {147}, year = {2025}, }
• (2025). Plasma pretreatment of pt single-atom precursors supported on mechanically activated Al2O3: Enhanced performance in propane dehydrogenation. JACS, 147(44), 40481--40495. (www)

  @article{ , abstract = {We investigated the effect of catalyst pretreatment with “cold” plasmas on the catalytic performance of Pt single-atom catalyst (SAC) precursors supported on Al 2 O 3 for the propane dehydrogenation reaction. We found that the catalysts treated with a hydrogen plasma before the conventional calcination/reduction steps showed considerably increased propane conversion without loss of selectivity, whereas exposure to an argon plasma did not result in such an effect. Moreover, the H 2 plasma-treated catalyst showed a lower deactivation rate, suggesting better long-term stability. The structural and chemical evolution of the catalysts studied by TEM, XAS, XPS, and DRIFTS showed that the H 2 plasma: (i) partially reduces singly dispersed Pt 2+ species and promotes Pt clustering; (ii) decreases the amount of Cl remaining after the use of the hexachloroplatinic acid precursor; and (iii) enhances surface defects in the alumina support. We propose that the promotional effect of the H 2 plasma lies in the specific modification of the alumina surface, which in turn alters the metal-support interaction and leads to the formation of a more active Pt/Al 2 O 3 interface during the subsequent oxidation and reduction steps. The results show that nonthermal plasma treatments of single-atom precursors can become a tool for tuning the catalytic performance of highly dispersed metal catalysts.}, archive = {J_JACS}, author = {Jingyi Yang and Eduardo Ortega and Joonbaek Jang and Andrea Martini and Jie Zhu and Janis Timoshenko and Jacopo De Bellis and Ferdi Schüth and Shamil Shaikhutdinov and Beatriz Roldan Cuenya}, doi = {10.1021/jacs.5c12230}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40481--40495}, shortjournal = {J. Am. Chem. Soc.}, title = {Plasma pretreatment of pt single-atom precursors supported on mechanically activated Al2O3: Enhanced performance in propane dehydrogenation}, volume = {147}, year = {2025}, }
• (2025). Quantum defects engineered in chirality pure single-wall carbon nanotubes for enabling ratiometric sensing of insulin. JACS, 147(44), 40466--40480. (www)

  @article{ , abstract = {The Corona Phase Molecular Recognition (CoPhMoRe) method employs fluorescent semiconducting single-wall carbon nanotubes (SWCNTs) wrapped with heteropolymers composed of hydrophobic and hydrophilic groups, thereby creating binding sites on the surface for specific analytes. The C 16 PEG2K Ceramide heteropolymer corona phase of SWCNTs allows selective binding and fluorescent detection of the hormone insulin. Herein, we incorporate quantum defects into the pristine structure of fluorescent SWCNTs to enable ratiometric sensing of analytes with insulin as a test case. SWCNTs are wrapped with C 16 PEG2K Ceramide and subjected to UV irradiation in the presence of 5-iodoracil, inducing sp 3 defects within the sp 2 hybridized carbon atom network of the SWCNTs. This modification results in the emergence of a new emission feature (E 11 * ) alongside the intrinsic E 11 emission. Additionally, we scaled up a method for the isolation of single-chirality SWCNTs, which enhances the efficacy of CoPhMoRe by considerably simplifying the fluorescence spectrum and background emission of the sensor. Our observations show that insulin quenches the fluorescence of such sensors composed of chirality-sorted SWCNTs by an average of 20% more than that of sensors made from unsorted SWCNTs. The use of sorted SWCNTs also significantly improves the fabrication of ratiometric insulin sensors by enabling precise modulation of the E 11 * /E 11 ratio. To quantify the ratiometric sensor response, a new set of metrics is introduced, including the spectral shift and intensity of the E 11 and E 11 * emission features, along with their ratio. Based on these metrics, our findings suggest that a minimum E 11 * /E 11 ratio of 3 is recommended for the transformation of a standard nanosensor into a ratiometric nanosensor via the incorporation of quantum defects into the pristine structure of a single-chirality SWCNT. The results herein underscore new, chemically enabled methods of improving CoPhMoRe sensors by the induction of quantum defects and use of chirality sorted SWCNTs.}, archive = {J_JACS}, author = {Ali A. Alizadehmojarad and Hohyung Kang and Gabriel Sánchez-Velázquez and Xun Gong and Michael S. Strano}, doi = {10.1021/jacs.5c12157}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40466--40480}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantum defects engineered in chirality pure single-wall carbon nanotubes for enabling ratiometric sensing of insulin}, volume = {147}, year = {2025}, }
• (2025). Direct electrosynthesis of c3+ hydrocarbons from CO2 via size-controlled nickel nanoislands on a carbon support. JACS, 147(44), 40454--40465. (www)

  @article{ , abstract = {Direct synthesis of C 3+ hydrocarbons via the electrochemical CO 2 reduction reaction is highly desirable for producing sustainable chemicals. However, this approach remains challenging due to the limited ability of current electrocatalysts to adsorb and couple key reaction intermediates effectively, with promising systems, such as Ni oxyhydroxide-derived catalysts, still exhibiting partial current densities toward C 3+ hydrocarbons <0.9 mA cm –2 . Motivated by the limited activity and control over the active site environment of these systems, we hypothesize that reducing the size of metallic Ni modifies its electronic states and introduces interfacial metal–support sites that promote more balanced *CO adsorption, critical for facilitating C–C coupling beyond C 2 intermediates. Here, we report a plasma-assisted deposition method to synthesize size-controlled metallic Ni nanoislands on a carbon support. Characterization revealed that reducing the nanoisland size (<12 nm) forms undercoordinated, electron-deficient, and strained surfaces with a downshifted d-band center─features associated with weakened *CO binding, favoring intermediate coupling and C 3+ hydrocarbon formation. Nanoislands as small as ∼3.5 nm delivered a 120-fold increase in C 3+ hydrocarbon specific activity relative to large particles (bulk-like Ni). CO stripping voltammetry shows weaker *CO adsorption on isolated nanoislands. While C 3+ partial current densities remain low (∼0.1 mA cm –2 ), these findings identify nanoparticle size and metal–support interactions as key design parameters for advancing CO 2 conversion to long-chain hydrocarbons, offering a foundation for further improvement, as demonstrated by a >20-fold enhancement in the Ni-mass-based activity versus state-of-the-art catalysts.}, archive = {J_JACS}, author = {Maral Vafaie and Roham Dorakhan and Amin Morteza Najarian and Zahra Teimouri and Alexandre Pofelski and Nasim Barati and Ching-Hsuan Chou and Ya-Ching Chang and Sung-Fu Hung and Qian Sun and Zahra Azimi Dijvejin and Robert Ngunjiri and Yuke Li and Ali Shayesteh Zeraati and Kholoud E. Salem and Rui Kai Miao and Sjoerd Hoogland and Drew Higgins and Edward H. Sargent and David Sinton}, doi = {10.1021/jacs.5c12052}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40454--40465}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct electrosynthesis of c3+ hydrocarbons from CO2 via size-controlled nickel nanoislands on a carbon support}, volume = {147}, year = {2025}, }
• (2025). Primary and secondary coordination sphere effects in the cobalt complex-catalyzed electrocatalytic o2 reduction to water. JACS, 147(44), 40440--40453. (www)

  @article{ , abstract = {Molecular cobalt-based complexes generally favor O 2 reduction to H 2 O 2 . However, a full reduction of O 2 to H 2 O is desired for fuel cell applications, which drives the current research in oxygen reduction electrocatalysis. We report a new Co(III) complex based on an N 4 O-coordinating ligand (UMAPA) that electrochemically reduces oxygen to water in the presence of acetic acid in acetonitrile. By combining electrochemistry-coupled electrospray ionization mass spectrometry (EC-ESI-MS), cyclic voltammetry, ultraviolet–visible (UV–vis) spectrophotometry, and rotating ring disk electrode voltammetry analyses, we unraveled the rarely reported integral role of both primary and secondary coordination in a single catalyst. The chronoamperometry EC-ESI-MS experiments allowed us to effectively monitor the catalyst’s activation steps and the formation of the cobalt(III) hydroperoxo intermediate. Consequently, we deciphered how acetic acid and the secondary coordination sphere of the Co(III) complex facilitated the subsequent water-forming steps. Furthermore, we characterized the key Co(III)-hydroperoxo and Co(III)-hydroxo intermediates by using cryogenic ion spectroscopy. Our experiments also showed that the cobalt complex undergoes ligand hydroxylation under oxygen-rich conditions. Interestingly, chronoamperometry EC-ESI-MS showed that the hydroxylated cobalt complex remains active for electrocatalytic oxygen reduction (ORR). We then explored the significance of different coordination configurations of the same ligand around the Co center in ORR. The Co complex with the protonated UMAPA ligand exhibited N 4 coordination and slower preactivation steps than the Co complex with the deprotonated N 4 O-coordinating UMAPA. Surprisingly, the CV experiments revealed that these small changes in the ligand configuration around the Co center result in a drastic change in the ORR activity. EC-ESI-MS was instrumental in determining the molecular-level details of the electrocatalytic ORR catalyzed by the Co complex, which conventional electroanalytical techniques alone cannot provide.}, archive = {J_JACS}, author = {Abhinav Bairagi and Max T. G. M. Derks and Aleksandr Y. Pereverzev and Jana Roithová}, doi = {10.1021/jacs.5c11990}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40440--40453}, shortjournal = {J. Am. Chem. Soc.}, title = {Primary and secondary coordination sphere effects in the cobalt complex-catalyzed electrocatalytic o2 reduction to water}, volume = {147}, year = {2025}, }
• (2025). Self-organization of microcompartments powered by enzyme-driven solutal flows at the Water–Oil interface. JACS, 147(44), 40429--40439. (www)

  @article{ , abstract = {Design of microcompartments capable of self-organization via consumption of energy or fuel to power opposable short-range forces is a step toward realization of adaptive cellular materials capable of intelligent behaviors. Here, we report active microgel compartments (a-MC) containing urease capable of self-organization at the water–oil interface via the regulation of short-range interparticle interactions consisting of urease-powered repulsive solutal flows and attractive capillary forces. The conversion of urea into denser products of ammonia and bicarbonate by urease within the a-MC causes density-driven outward flows leading to repulsive interactions with neighboring a-MCs at the water–oil interface. The modulation of repulsive solutal flows allowed the a-MCs to self-organize into nonclose-packed 2D lattices at high urease activity and 1D chains at low urease activity and high population density. These repulsive solutal flows are fueled by urea, so by limiting the supply of urea, we could achieve disassembly of 2D clusters at high urea concentration and reassembly upon a drop in urea levels. In binary mixtures of active and passive (no urease) microgel compartments, the passive microgel compartments showed increasing orthogonal assembly with a rise in their population density. Immobilization of 2D clusters of a-MCs allowed us to set up long-range collective solutal flows to execute microcompartment cargo logistics and to form fluidic traps for controlling assembly and position of binary/ternary microcompartment clusters for enhanced chemical signaling. Our work presents opportunities for the development of autonomous soft microbots, precision microscale cargo logistics, and intelligent matter.}, archive = {J_JACS}, author = {Pankaj S. Patwal and B. V. V. S. Pavan Kumar}, doi = {10.1021/jacs.5c11877}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40429--40439}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-organization of microcompartments powered by enzyme-driven solutal flows at the Water–Oil interface}, volume = {147}, year = {2025}, }
• (2025). Record superconductivity in a kagome calcium boride at high pressure. JACS, 147(44), 40420--40428. (www)

  @article{ , abstract = {Exotic stoichiometric light-element compounds stabilized by high pressure deliver a plentiful playground in the search for high-temperature superconductors. The experimental discovery of new superconducting phases in this system has been greatly hurdled owing to their complex crystal structures and rich physical phenomena despite numerous theoretical predictions. Here we demonstrate the high-pressure synthesis of a kagome superconductor P 6/ mmm CaB 3 with T c ∼ 22 K, higher than any of the already known kagome superconductors. Based on theoretical calculations, the superconductivity in P 6/ mmm CaB 3 is predominantly driven by the coupling of the vibrations between the B kagome lattice and the p -orbital electrons of B. This research elucidates an unprecedented kagome lattice in the Ca–B system, providing profound insights for the exploration of light-element superconductors.}, archive = {J_JACS}, author = {Kexin Zhang and Jingkun Yu and Simin Li and Yuchen Zhang and Yuzhi Chen and Xiaoli Huang and Tian Cui}, doi = {10.1021/jacs.5c11841}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40420--40428}, shortjournal = {J. Am. Chem. Soc.}, title = {Record superconductivity in a kagome calcium boride at high pressure}, volume = {147}, year = {2025}, }
• (2025). Batch discovery of complex metal superhydrides via an effective machine learning method structured by chemical template concept. JACS, 147(44), 40407--40419. (www)

  @article{ , abstract = {Metal superhydrides, known for their high hydrogen content and polyhedral hydrogen cages, are promising candidates for high-temperature superconductivity. Despite extensive studies on binary metal superhydrides, there remains a large, unexplored chemical space, particularly regarding noninteger hydrogen-to-metal ratios. By integrating the “chemical template effect” with machine learning algorithms, we developed a specialized structure discovery workflow that significantly enhances the efficiency of predicting stable superhydrides. Within the compiled data set used in this work, our method led to the identification of 13 new structural prototypes and 31 stable metal superhydrides, representing a 23% increase in discoveries. The 3D hydrogen clathrates in these compounds are significantly correlated with high superconducting transition temperatures ( T c ), and our approach achieves a remarkable 65% increase. Most of these structures contain over 50 atoms per primitive cell, with the I 4/ m M 10 H 84 prototype having the largest unit cell, containing 94 atoms. Additionally, 19 of the newly identified superhydrides exhibit T c > 100 K, highlighting the potential for higher T c materials within the 3D hydrogen clathrate structures. The method also shows good potential to search for ternary superhydrides on a large scale.}, archive = {J_JACS}, author = {Yuanhui Sun and Austin Ellis and Xin Chen and Maosheng Miao}, doi = {10.1021/jacs.5c11731}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40407--40419}, shortjournal = {J. Am. Chem. Soc.}, title = {Batch discovery of complex metal superhydrides via an effective machine learning method structured by chemical template concept}, volume = {147}, year = {2025}, }
• (2025). Probing the surface chemistry of lithium nitridation. JACS, 147(44), 40398--40406. (www)

  @article{ , abstract = {Chemical synthesis of Li 3 N through lithium nitridation has potential to advance rechargeable battery and nitrogen fixation technology. However, studies of the conditions for forming Li 3 N on the lithium surface via nitrogen gas exposure report contradictory findings, such as the spontaneous reaction of Li with pure N 2 , the impossibility of forming Li 3 N through pure Li and N 2 interaction, the requirement of trace H 2 O to catalyze the reaction, and evidence to the contrary. In this study, ambient pressure X-ray photoelectron spectroscopy (APXPS) was applied to evaluate the in situ chemical evolution of the lithium metal surface under nitrogen gas up to 800 mTorr. At pressures ≤10 mTorr, no Li 3 N was detected. At higher pressures, surface Li 3 N rapidly reacts with trace CO 2 . Additionally, because metallic lithium is readily oxidized by trace gases, the atomic nitrogen concentration of the lithium surface remains below 2%. When nitridation follows oxidation by O 2 gas, CO 2 gas, or H 2 O vapor, surface Li 3 N formation is inhibited. These results suggest that nitrogen gas can diffuse through the oxidized lithium metal surface to react with subsurface metallic lithium.}, archive = {J_JACS}, author = {Ane Etxebarria and Pinar Aydogan Gokturk and Yifan Ye and Philip N. Ross and Ethan J. Crumlin and Miguel Ángel Muñoz-Márquez}, doi = {10.1021/jacs.5c11781}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40398--40406}, shortjournal = {J. Am. Chem. Soc.}, title = {Probing the surface chemistry of lithium nitridation}, volume = {147}, year = {2025}, }
• (2025). Trioctylamine in the synthesis of tris(trimethylsilyl)arsine-based InAs quantum dots prevents the formation of si-based byproducts. JACS, 147(44), 40389--40397. (www)

  @article{ , abstract = {To date, the best reported strategy to synthesize large colloidal indium arsenide (InAs) quantum dots (QDs) with precise control over size and size distribution consists of a seeded-growth synthesis that uses dioctylamine coupled with tris(trimethylsilyl)arsine as arsenic precursor and oleic acid as ligand. Here, we demonstrate through nuclear magnetic resonance studies that, in such an approach, dioctylamine and oleic acid condense at the high temperatures required for synthesis (>250 °C), releasing water as a byproduct. The released water, in turn, leads to the formation of trimethylsilanol, which subsequently condenses to form hexamethyldisiloxane and trimethylsilyl oleate. As a result, dioctylamine-based InAs QDs are contaminated, even after multiple washing steps, by both unbound trimethylsilyl oleate and bound trimethylsilyl-derived species. We further show that these issues can be solved by replacing dioctylamine with a tertiary amine, for example tri-n-octylamine, which prevents the formation of water and leads instead to clean InAs QDs. We also demonstrate that this modified procedure delivers InAs QDs with excellent control over their optical features, with excitonic absorption peaks as narrow as 50 meV (half-width at half-maximum) and peak-to-valley ratios (an important parameter for optoelectronic applications) as high as ∼2, representing a record value for InAs QDs.}, archive = {J_JACS}, author = {Satyaprakash Panda and Lutfan Sinatra and Khursand E. Yorov and Galih R. Suwito and Alexander Bessonov and Marat Lutfullin and Luca Goldoni and Enrico Bergamaschi and Rosaria Brescia and Mirko Prato and Giorgio Divitini and Luca De Trizio and Liberato Manna}, doi = {10.1021/jacs.5c11775}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40389--40397}, shortjournal = {J. Am. Chem. Soc.}, title = {Trioctylamine in the synthesis of tris(trimethylsilyl)arsine-based InAs quantum dots prevents the formation of si-based byproducts}, volume = {147}, year = {2025}, }
• (2025). Rapid intermolecular C–H activation of aromatic substrates at a cationic, electrophilic Molybdenum(VI) nitrido complex: Mechanistic nuance in C–H amination. JACS, 147(44), 40374--40388. (www)

  @article{ , abstract = {When the cationic, octahedral terminal nitrido complex of Mo(VI) supported by a diborate pentadentate ligand is generated in the absence of trapping nucleophiles, it activates the C(sp 2 )–H bonds of simple arenes, forming the cationic imido complexes [[ Ar Mo V ]═NR] + (R = H; PhX, X = H, o,m,p -F). Density Functional Theory computations and experimental studies support a novel mechanism with homolytic aromatic substitution character, wherein electrophilic attack of the arene π system initiates N–C bond formation, but use of electrons from the Mo≡N triple bond completes bond formation through an open-shell singlet transition state that formally reduces the metal center to Mo(V) and imbues the arene ring with radical character. This transition state is enthalpically 15 kcal mol –1 lower in energy than the “Wheland-type” transition state common to electrophilic aromatic substitution paths proposed in related systems. Subsequent intramolecular transfer of the arene hydrogen to the imido nitrogen atom leads to the cationic Mo(IV) anilido complex [[ Ar Mo IV ]-NHPh] + , which reacts with available [[ Ar Mo VI ]≡N] + by a proton-coupled electron transfer step to generate the 1:1 mixture of imido products [[ Ar Mo V ]=NR] + (R = H; C 6 H 4 X, X = H, o,m,p -F). This second phase of the mechanism is supported computationally and by a crossover experiment and is driven by significant coordination-induced bond weakening (CIBW) in the N–H bond of the [[ Ar Mo IV ]-NHPh] + . The novel mechanism of C–H addition to the electrophilic terminal nitrido opens new low energy pathways for the development of systems capable of catalytic nitrogen atom transfer to C–H bonds.}, archive = {J_JACS}, author = {C. Christopher Almquist and Thayalan Rajeshkumar and Wen Zhou and Laurent Maron and Warren E. Piers}, doi = {10.1021/jacs.5c11718}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40374--40388}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid intermolecular C–H activation of aromatic substrates at a cationic, electrophilic Molybdenum(VI) nitrido complex: Mechanistic nuance in C–H amination}, volume = {147}, year = {2025}, }
• (2025). Modulating hydrogen exchange capabilities by heterogenizing pd nanoclusters onto Ni3C multipods for efficiently driving the “Formaldehyde-nitrate” tandem electrochemical system. JACS, 147(44), 40356--40373. (www)

  @article{ , abstract = {Nitrate and formaldehyde, common industrial byproducts and waterborne pollutants, pose serious environmental and health hazards, yet their efficient conversion remains challenging due to sluggish hydrogen (H*) transfer and limited recycling strategies. While recent studies have explored nitrate reduction (NO 3 RR) and formaldehyde oxidation (FOR) coupling, they faced critical limitations such as no H 2 generation, a lack of electricity output, and reliance on Cu-based catalysts prone to deactivation. This work presents Pd nanoclusters on nickel carbide (Pd nc -Ni 3 C) that serve as a noncopper bifunctional catalyst that possesses superior H* exchange capabilities enabling dual-directional catalysis of NO 3 RR and FOR. At the cathode, Pd nc -Ni 3 C achieves an onset potential of +0.27 V vs RHE, and 98% Faradaic efficiency for NH 3 at −0.3 V. At the anode, Pd nc -Ni 3 C achieves an efficient FOR at a low onset potential of 0.04 V and enables a broad oxidation window (0–1.2 V) with high current density (up to 910 mA cm –2 ), outperforming previously reported Cu- and Ni-based systems. Differential electrochemical mass spectra reveal a previously unexplored intermolecular coupling pathway for H 2 evolution, advancing mechanistic insight into the 1-electron formaldehyde oxidation process. By coupling the NO 3 RR and FOR, a high-performance “Formaldehyde–Nitrate” galvanic cell is achieved with an OCV of 0.88 V and peak power density of 7.4 mW cm –2 . Distinctively, this Ni based system simultaneously converts industrial waste into green energy carriers (H 2 , NH 3 ) and value-added chemicals (formate) while producing electricity, offering both environmental and economic benefits.}, archive = {J_JACS}, author = {Zulakha Zafar and Bin Zhao and Rida Javed and Arunpandiyan Surulinathan and Xin Long and M. Bilal Hussain and Ning Chen and Renfei Feng and Yu Zhang and Xian-Zhu Fu and Jing-Li Luo}, doi = {10.1021/jacs.5c11608}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40356--40373}, shortjournal = {J. Am. Chem. Soc.}, title = {Modulating hydrogen exchange capabilities by heterogenizing pd nanoclusters onto Ni3C multipods for efficiently driving the “Formaldehyde-nitrate” tandem electrochemical system}, volume = {147}, year = {2025}, }
• (2025). Chirality-regulated spin-polarization of perovskite nanoplates for photocatalytic CO2 reduction reaction. JACS, 147(44), 40347--40355. (www)

  @article{ , abstract = {Manipulating spin polarizations of photoexcited electrons has been found to play a vital role in enhancing photocatalytic CO 2 conversion by suppressing carrier recombination. In this work, photocatalytic CO 2 reduction conversion efficiencies are significantly enhanced by chirality-regulated spin-polarization of CsPbBr 3 perovskite nanocrystals. We propose the chirality-regulated perovskite thin films by incorporating chiral molecules (MBA:Br) into all-inorganic CsPbBr 3 perovskite nanoplates (NPLs), resulting in (R)- and (S)-2D Ruddlesden–Popper perovskite (RPP)/NPL hybrids. In this configuration, the chiral 2D RPP perovskites offer a significant chiroptical response that promotes the generation of spin-polarized electrons. The chirality-regulated spin-polarization of 2D RPP/NPLs hybrid perovskite thin films has significantly suppressed charge carrier recombination rates, thereby enhancing the efficiency of photocatalytic CO 2 reduction. By harnessing the synergistic effects of induced chirality and the application of an external magnetic field of 0.3 T, the photocatalytic CO 2 reduction efficiencies of the chiral perovskites can be enhanced to be five times that of the pristine CsPbBr 3 perovskite NPLs. The interplay between structure, chirality, spin polarization, and carrier dynamics associated with the enhanced photocatalytic activity of perovskite nanocrystals was systematically analyzed using grazing-incidence wide-angle X-ray scattering (GIWAXS) spectroscopy, magnetic circular dichroism (MCD) spectroscopy, and time-resolved photoluminescence (PL) techniques. Our results pave the way for the manipulation of spin-polarized electrons through chirality-regulated perovskite nanocrystals, significantly enhancing photocatalytic CO 2 reduction efficiencies and highlighting their strong potential for future solar-to-fuel conversion applications.}, archive = {J_JACS}, author = {Cheng-Chieh Lin and Shao-Ku Huang and Wei-Ni Tseng and Chun-Jen Su and Chao-Ching Huang and Chih-Ying Huang and Cheng-Yu Yu and Man-Hong Lai and Jia-Yuan Sun and Yu-Chiang Chao and Hua-Shu Hsu and Chih-Wei Luo and Yu-Ming Chang and Chia-Chun Chen and Chun-Wei Chen}, doi = {10.1021/jacs.5c11357}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40347--40355}, shortjournal = {J. Am. Chem. Soc.}, title = {Chirality-regulated spin-polarization of perovskite nanoplates for photocatalytic CO2 reduction reaction}, volume = {147}, year = {2025}, }
• (2025). Watching polarons dance: Coherent Carrier–Phonon coupling in hematite revealed by transient absorption spectroscopy. JACS, 147(44), 40338--40346. (www)

  @article{ , abstract = {Hematite remains a prominent photoanode candidate for the oxygen evolution reaction in solar water splitting, despite efficiency limitations from rapid trapping of photoexcited electrons and holes. While the formation of polarons, quasiparticles formed by electron–hole interactions with lattice vibrations, is a proposed trapping mechanism, direct evidence of such states has been elusive. Here, we use potential-dependent transient absorption spectroscopy to identify the coherent phonon mode and strong exciton–phonon coupling responsible for exciton–polaron formation after band gap excitation in α-hematite and identify the three underlying d–d transitions that are strongly modulated by this phonon. The equilibrium geometry of exciton–polarons in α-hematite is displaced from the ground state geometry along the vibrational coordinate of an A 1g symmetric Fe–O stretching motion at 225 ± 7 cm –1 , resulting in vibrational coherence with a lifetime of 1.9 ± 0.1 ps. Our comparative ex situ and in situ experiments reveal that the energy and dephasing time of the A 1g mode are remarkably resilient to applied potential and the addition of an Al 2 O 3 overlayer; however, the dephasing time is sensitive to substrate identity. This potential-dependent transient absorption approach establishes a powerful platform for directly probing polaron dynamics in photoelectrochemical systems, opening new pathways to rationally design modified hematite and other transition metal oxide electrodes with enhanced charge transport properties for more efficient solar water splitting.}, archive = {J_JACS}, author = {Cooper R. Johnston and Raiden Speelman and Ashley Arcidiacono and Camille Bridgewater and Lili Rassouli and Xuyan Ma and Isabel Vargas-Hurlston and Jacob Kupferberg and Lauren Martin and Alex B. F. Martinson and Michel Dupuis and Franz M. Geiger and Sarah B. King}, doi = {10.1021/jacs.5c11324}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40338--40346}, shortjournal = {J. Am. Chem. Soc.}, title = {Watching polarons dance: Coherent Carrier–Phonon coupling in hematite revealed by transient absorption spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Metal–Organic frameworks with enhanced electret capability for selective electrostatic separation. JACS, 147(44), 40331--40337. (www)

  @article{ , abstract = {Electrostatic separation plays a pivotal role in bioseparation, energy conversion, and water treatment. Electrostatic polarization is an effective approach for injecting and trapping quasi-permanent charges in electrets, facilitating electrostatic separation. However, it remains challenging to simultaneously enhance charge density and suppress charge dissipation, which are both critical for achieving stable and efficient separation. Herein, we incorporate defect-engineered zeolitic imidazolate frameworks (ZIFs) into the polymer matrix via electrostatic polarization to construct high-performance electrets. Their rigid and ordered frameworks, enriched with abundant functional groups, facilitate the stabilization of reoriented dipoles and the retention of increased charge traps with elevated escape energy barriers following the introduction of structural defects, thereby enhancing the charge density and retention. The resulting composite film with defective ZIF-8 retains 97.4% of its surface potential after 14 days and achieves an exceptional adsorption capability of 487.6 mg/g for electropositive low-density lipoprotein (LDL), with a high LDL/high-density lipoprotein (HDL) selectivity ratio of 63.5 in serum, surpassing those of previously reported materials while also demonstrating excellent biosafety. This defect-induced electret enhancement strategy offers insights into the design of advanced electrostatic adsorbents for applications, such as DNA purification, lithium extraction, and protein separation.}, archive = {J_JACS}, author = {Haiwei Liu and Jie Li and Shuang Zhao and Feiyu Yue and Yuqi Sun and Mengfei Zhu and Shan Wang and Yuanyuan Zhang and Xiao Feng and Bo Wang}, doi = {10.1021/jacs.5c11198}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40331--40337}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal–Organic frameworks with enhanced electret capability for selective electrostatic separation}, volume = {147}, year = {2025}, }
• (2025). Symmetry-shearing chemistry enabled interdigitated 2D covalent organic frameworks with interlayer mortise-and-tenon interlocks for efficient photocatalytic CO2 fixation. JACS, 147(44), 40319--40330. (www)

  @article{ , abstract = {The development of porous organic frameworks with innovative architectures and enhanced structural stability is a central challenge in reticular chemistry. Herein, we report the rational design and synthesis of interdigitated two-dimensional (2D) covalent organic frameworks (ID-COFs) constructed via symmetry-shearing chemistry, incorporating porphyrin-based light-harvesting units and catalytically active magnesium centers into crystalline, porous frameworks. Unlike traditional strictly planar π–π stacked 2D COFs, the resulting ID-COFs feature unique cage-like cavities and mortise-and-tenon interlocked architectures, significantly enhancing both the accessibility of catalytic sites and structural stability. Notably, ID-COF-Mg exhibits excellent photocatalytic performance for the cycloaddition of CO 2 and epoxides under mild conditions. Comprehensive theoretical calculations further reveal that the Mg-porphyrin active centers serve as key electron donors, effectively facilitating the formation of ring-opening intermediates from epoxides. This work not only provides a novel strategy for constructing porous organic frameworks through covalent–supramolecular codriving but also offers an advanced photocatalyst for CO 2 cycloaddition reactions.}, archive = {J_JACS}, author = {Yu Zhao and Yuqing Chen and Yue Yu and Guolong Xing and Linfeng Chen and Fan Xia and Teng Ben}, doi = {10.1021/jacs.5c11188}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40319--40330}, shortjournal = {J. Am. Chem. Soc.}, title = {Symmetry-shearing chemistry enabled interdigitated 2D covalent organic frameworks with interlayer mortise-and-tenon interlocks for efficient photocatalytic CO2 fixation}, volume = {147}, year = {2025}, }
• (2025). Establishing selectivity trends with reactions of thioesterases and semi-synthetic polyketides. JACS, 147(44), 40305--40318. (www)

  @article{ , abstract = {Polyketides are a diverse class of natural products with a wide range of therapeutic properties. They have been widely used in clinical settings as antibiotics, antifungals, anticancer agents, and immunosuppressants. A major subset of these molecules is produced by type I assembly line polyketide synthases (T1ALPKSs), large enzyme complexes that catalyze their stepwise construction. Understanding the selectivity and scope of T1ALPKS domains could greatly expand the diversity of products generated by these synthases and their components. This study explores the reactivity and selectivity of the terminal domains of T1ALPKSs, known as thioesterases (TEs). A panel of 25 wild-type and 10 mutant (Ser→Cys) thioesterases was reacted with semisynthetic substrates. The selectivity with which these TEs form 12- and/or 14-membered macrolactones and one or both of a pair of diastereomeric 14-membered macrolactones was quantified. The results indicate that the selectivity with which wild-type TEs react with unnatural substrates correlates with their parent T1ALPKSs, enabling the assignment of TEs into groups. Additionally, our experiments reveal that mutant (Ser→Cys) TEs often have expanded scopes compared to their wild-type counterparts and that some wild-type TEs are capable of hydrolyzing macrolactones. We demonstrated the synthetic applications of TEs with kinetic resolutions and preparative-scale reactions. This study provides a framework for organizing TEs and predicting their reactivity and selectivity, facilitating future research on structure–activity relationships and supporting directed evolution studies.}, archive = {J_JACS}, author = {Zachary C. Litman and Yuanhuang Chen and David H. Sherman}, doi = {10.1021/jacs.5c11177}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40305--40318}, shortjournal = {J. Am. Chem. Soc.}, title = {Establishing selectivity trends with reactions of thioesterases and semi-synthetic polyketides}, volume = {147}, year = {2025}, }
• (2025). Fast and reliable NMR-based fragment scoring for drug discovery. JACS, 147(44), 40296--40304. (www)

  @article{ , abstract = {Fragment-Based Drug Discovery (FBDD) is a powerful strategy used in the development of new therapeutics. Molecular fragments are screened against a target protein, where interactions are typically characterized by a low affinity. Nuclear Magnetic Resonance (NMR) spectroscopy is well-suited to detect weak protein–ligand interactions and is therefore often used in FBDD. However, while NMR is very effective in initial screening, follow-up NMR experiments to measure binding affinities (i.e., K D values) are labor-intensive and time-consuming. To address this challenge, we have developed an innovative SHARPER NMR fragment scoring technique. The high sensitivity of SHARPER NMR dramatically reduces the data acquisition times, allowing faster and more accurate quantification of fragment K D values from ligand titration curves. To further accelerate fragment scoring, a machine learning model was developed that accurately ranks fragment affinities from only two SHARPER titration points. The resulting integrated method, termed “ML-boosted 1 H LB SHARPER NMR”, produced significant time savings; using a 600 MHz QCI cryoprobe, K D values of up to 144 ligands in a day could be determined under our conditions, compared with only a handful achievable by traditional approaches. The proposed methodology will shorten the transition from hits to lead compounds, accelerating the drug discovery process by rapidly and reliably evaluating fragment binding, providing informed decision-making in the early stages of FBDD.}, archive = {J_JACS}, author = {Ridvan Nepravishta and Juan C. Munoz-Garcia and Kenneth Cameron and Jesús Angulo and Dušan Uhrín}, doi = {10.1021/jacs.5c11092}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40296--40304}, shortjournal = {J. Am. Chem. Soc.}, title = {Fast and reliable NMR-based fragment scoring for drug discovery}, volume = {147}, year = {2025}, }
• (2025). Seawater to sustainable fuel: Sunlight-driven green hydrogen generation with an atomically dispersed photocatalyst. JACS, 147(44), 40282--40295. (www)

  @article{ , abstract = {Green hydrogen is widely regarded as a key to a sustainable future, offering a clean and flexible fuel option for decarbonizing the energy, transport, and industrial sectors. While photocatalytic approaches are known for generating hydrogen directly from water, most existing methods require (over)stoichiometric amounts of sacrificial reagents, which is far from ideal for the production of green hydrogen. To address this challenge, we have developed an atomically dispersed Ni-based photocatalyst that achieves hydrogen evolution rates of up to 270 μmol/g/h (168 mmol/g Ni /h). Remarkably, this photocatalyst also exhibits high photoreactivity under direct sunlight, producing up to 17 μmol/g/h (10.6 mmol/g Ni /h) of hydrogen. Impressively, the catalyst can even generate green hydrogen directly from seawater, up to 144 μmol/g/h, demonstrating significant potential for real-world applications. The photocatalyst is exceptionally stable, remaining active even after 720 h (140 h of irradiation and 580 h resting time) of operation and retaining high performance over more than 15 cycles. Furthermore, comprehensive spectroscopic and structural analyses─including HRTEM, PXRD, ssNMR, XPS, and XAS─provide detailed structural insights and confirm the atomically dispersed nature of the Ni species. In-depth mechanistic studies have elucidated the critical role of atomic dispersion in enabling robust photocatalytic efficiency.}, archive = {J_JACS}, author = {Satyadeep Waiba and Manami Banerjee and Lindsey Frederiksen and Aleksander Jaworski and Susanna Monti and Giovanni Barcaro and Kaan Karaca and Xiufang He and Anna Rokicińska and Thanh Huyen Vuong and Gianvito Vilé and Piotr Kuśtrowski and Jabor Rabeah and David Reyes and Peng Ren and Sergey Bagnich and Anna Köhler and Daniel Hohenberger and Josef Breu and Paul J. Dyson and Shoubhik Das}, doi = {10.1021/jacs.5c11004}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40282--40295}, shortjournal = {J. Am. Chem. Soc.}, title = {Seawater to sustainable fuel: Sunlight-driven green hydrogen generation with an atomically dispersed photocatalyst}, volume = {147}, year = {2025}, }
• (2025). Azaanthraquinone PCET catalysis enables chemoselective decarboxylative functionalization of diverse carboxylic acids. JACS, 147(44), 40272--40281. (www)

  @article{ , abstract = {The advancement of a proton-coupled electron transfer (PCET) strategy holds significance to expand the synthetic applicability and energy efficiency of photoredox chemistry. However, the current implementation of this strategy is typically narrow in terms of the redox potential and reaction efficiency. In this study, a novel PCET catalyst containing an azaanthraquinone skeleton has been developed for the decarboxylative functionalization of a wide range of carboxylic acids, including aromatic and perfluoroalkyl carboxylic acids. By integrating the aza-arene and benzoquinone moieties into a single molecule, this catalyst suppresses the previously problematic back electron transfer (BET) through rapid intersystem crossing from singlet to triplet states and the facilitated electron transfer from the substrate to the excited triplet catalyst via PCET. This catalyst enables a variety of decarboxylative functionalization reactions from challenging substrates, such as benzoic acids and fluoroalkanoic acids, to proceed under mild conditions with high chemoselectivity.}, archive = {J_JACS}, author = {Takeshi Inoue and Daiki Tomiya and Masaaki Fuki and Yasuhiro Kobori and Masahiro Higashi and Kaito Uesaka and Akira Yamakata and Shigehiro A. Kawashima and Kenzo Yamatsugu and Harunobu Mitsunuma and Motomu Kanai}, doi = {10.1021/jacs.5c10807}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40272--40281}, shortjournal = {J. Am. Chem. Soc.}, title = {Azaanthraquinone PCET catalysis enables chemoselective decarboxylative functionalization of diverse carboxylic acids}, volume = {147}, year = {2025}, }
• (2025). Ultrafast nonradiative relaxation limits the efficiency of photoinduced bond homolysis in molecular LMCT photocatalysts. JACS, 147(44), 40264--40271. (www)

  @article{ , abstract = {Ligand-to-metal charge transfer photocatalysts (LMCT PCs) are being increasingly implemented toward construction and functionalization of organic molecules. Leveraging photoinduced metal–ligand bond homolysis, these PCs generate reactive intermediates ranging from halogen radicals to radical cross-coupling partners. Despite their growing synthetic utility, key mechanistic questions remain surrounding both the surprising inefficiency of this photodissociation chemistry and the puzzling success of nonprecious metal photocatalysts despite low energy ligand field states. Herein, femtosecond transient absorption (TA) spectroscopy is implemented to address these mysteries using FeCl 4 – and CeCl 6 2– , which photogenerate Cl• under mild conditions, as model systems. Ultrafast dynamics and complementary TA actinometry indicate that the homolysis efficiency is limited by relaxation to a lower energy excited state within the LMCT excited state manifold at a faster rate than relaxation to ligand field states. These results provide a mechanistic explanation for the low photochemical efficiencies observed in benchtop reactions that have encumbered otherwise proficient PCs.}, archive = {J_JACS}, author = {Rachel Weiss and Bryan Kudisch}, doi = {10.1021/jacs.5c10766}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40264--40271}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrafast nonradiative relaxation limits the efficiency of photoinduced bond homolysis in molecular LMCT photocatalysts}, volume = {147}, year = {2025}, }
• (2025). Operando electrical transport spectroscopy determination of hydration phase diagrams of alkali metal cations in nanoconfined spaces. JACS, 147(44), 40253--40263. (www)

  @article{ , abstract = {The solvation of alkali metal cations (AM + ) in nanoconfined spaces plays a crucial role across a wide range of fields, including biological systems, ion sieving, desalination, and electrochemical energy storage. Achieving a comprehensive understanding of AM + solvation behavior is central for controlling these processes. We exploit operando electrical transport spectroscopy to decipher AM + desolvation dynamics upon intercalation in the nanoconfined space of MXene thin films and establish the corresponding hydration phase diagrams. Our findings show that hydrated Li + cations partially shed their secondary solvation shell when entering MXene interlayers, undergoing further desolvation during negative polarization until only the primary solvation shell remains. Larger cations exhibit a shrinking phase region for the secondary hydration shell. Na + retains only the primary shell at high concentrations while partially retaining its secondary hydration at low concentrations but losing it under negative polarization. K + , in contrast, maintains only the primary hydration shell throughout the entire phase diagram. These phase diagrams elucidate the intricate interplay among cation size, concentration, and electrochemical potential in governing solvation status, offering a foundational framework for the rational design of advanced materials and interfaces in electrochemical devices.}, archive = {J_JACS}, author = {Shuanghao Zheng and Aamir Hassan Shah and Zhong Wan and Yansong Ling and Boxuan Zhou and Jingxuan Zhou and Xiaoyan Liu and Ting-Jung Hsiao and Yu Huang and Xiangfeng Duan}, doi = {10.1021/jacs.5c10627}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40253--40263}, shortjournal = {J. Am. Chem. Soc.}, title = {Operando electrical transport spectroscopy determination of hydration phase diagrams of alkali metal cations in nanoconfined spaces}, volume = {147}, year = {2025}, }
• (2025). Equivalent atrop- and positional isomerism in styrene derivatives prepared by enantioselective 1,3-diarylation. JACS, 147(44), 40244--40252. (www)

  @article{ , abstract = {Isomerism, the ability of a single set of atoms within a molecule to exist in different three-dimensional spatial arrangements connecting through distinct bonding networks, gives rise to distinct physical, chemical, and biological properties from a common set of atomic building blocks. While different forms of isomerism are now well appreciated, a rare phenomenon is the coexistence of multiple equivalent forms of isomerism within a given pair of molecules. Here, we report that a simple combination of palladium and amino acid cocatalysts converts ortho -alkenyl benzaldehydes into substituted styrenes possessing equivalent atrop- and positional isomerism. Mechanistically, the reaction proceeds through successive Mizoroki–Heck arylation promoted by the amino acid cocatalyst. DFT calculations show that the atroposelectivity arises from stereoselective β-H elimination in the second arylation cycle, whereas the formation of Z products with constrained rotation about the chiral axis is driven by the thermodynamic stability of the Z isomer.}, archive = {J_JACS}, author = {Amit Kumar Simlandy and Yiyao Hu and Turki M. Alturaifi and Wen-Ji He and Madeline J. Fitzgerald and Peng Liu and Keary M. Engle}, doi = {10.1021/jacs.5c10118}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40244--40252}, shortjournal = {J. Am. Chem. Soc.}, title = {Equivalent atrop- and positional isomerism in styrene derivatives prepared by enantioselective 1,3-diarylation}, volume = {147}, year = {2025}, }
• (2025). Uric acid monohydrate nanocrystals: An adaptable platform for nitrogen and salt management in reptiles. JACS, 147(44), 40236--40243. (www)

  @article{ , abstract = {Both avian and nonavian reptiles excrete excess nitrogen in solid form─colloquially termed “urates”─as an evolutionary adaptation that aids in water conservation. Yet, there are many open questions regarding the composition, structure, and assembly of these biogenic materials. Here, analyses of urate excretions from ball python ( Python regius ) and 20 other reptile species reveal a clever and highly adaptable system employed to handle both nitrogenous waste and salts. Primitive species excrete urates consisting of 1–10 μm microspheres of turbostratic uric acid monohydrate (UAM) nanocrystals. The nanocrystals’ high surface area and ionizable nature provides a platform to coeliminate substoichiometric concentrations of various salts through surface-ion pairing. In contrast, the granular urates produced by species from more advanced snake lineages are phase mixtures consisting of predominantly ammonium urate hydrate (AUH) and smaller amounts of other crystalline forms. Identification of microspheres as a minor but highly soluble component of these excretions suggests their likely role as reactive precursors to AUH, a hypothesis supported by in vitro experiments. Importantly, this points to a previously unrecognized physiologic function of uric acid, namely the ability to sequester ammonia by transforming it into a solid. The potential implications of this function in other species are discussed.}, archive = {J_JACS}, author = {Alyssa M. Thornton and Timothy G. Fawcett and Amanda K. Rutledge and Gordon W. Schuett and Jennifer A. Swift}, doi = {10.1021/jacs.5c10139}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40236--40243}, shortjournal = {J. Am. Chem. Soc.}, title = {Uric acid monohydrate nanocrystals: An adaptable platform for nitrogen and salt management in reptiles}, volume = {147}, year = {2025}, }
• (2025). Chemically induced ferroic-like phase and collective chemotaxis in an active swarm. JACS, 147(44), 40225--40235. (www)

  @article{ , abstract = {Amplification of weak chemical signals through intracellular cascade networks is crucial for long-range cohesive migration in biological processes, such as embryogenesis and cancer metastasis. While this capability has transformative potential for synthetic systems in precision medicine and adaptive materials, the lack of cascade communication in artificial matter has been a significant barrier. This study demonstrates that a binary active colloid mixture, mediated by a chemical reaction, forms a simple chemical reaction network capable of self-organizing into polarized dynamic swarms, dramatically enhancing chemical amplification. By applying the classical Ising model, we rationalize the self-polarization with increasing chemical activity, drawing an analogy to ferroic materials in the chemically polarized active phase. Under optimal conditions, these “ferrochemical” swarms can amplify weak chemical gradients by over 10 4 times, resulting in exceptional chemical sensitivity and remarkable long-range collective chemotaxis. As a proof of concept, we demonstrate the application of silver-doped active swarms to enhance antibacterial efficacy, showcasing a chemotactic swarm that effectively combats dental biofilm growth on human teeth.}, archive = {J_JACS}, author = {Changjin Wu and Yaxin Huang and Binglin Zeng and Jingyuan Chen and Chun Hung Chu and Mingcheng Yang and Ho Cheung Shum and Jinyao Tang}, doi = {10.1021/jacs.5c10021}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40225--40235}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemically induced ferroic-like phase and collective chemotaxis in an active swarm}, volume = {147}, year = {2025}, }
• (2025). Improving Triplet–Triplet annihilation upconversion output by a triplet mediator approach: Mechanistic insights on homo and hetero-annihilation in three-component systems. JACS, 147(44), 40214--40224. (www)

  @article{ , abstract = {Triplet–triplet annihilation photon upconversion (TTA-UC) is a promising strategy for converting low-energy photons into higher-energy emission, with potential applications in solar energy harvesting, bioimaging, and photocatalysis. A challenge in TTA-UC systems is minimizing the reabsorption of upconverted photons by the annihilator molecules. To address this, we present a mediator-assisted TTA-UC approach utilizing a neutral mediator molecule to facilitate upconversion in the ultraviolet (UV) and visible regions. Our study introduces a general protocol, and through detailed kinetic modeling, we elucidate the underlying mechanism, highlighting the role of hetero-TTA (triplet–triplet annihilation between the mediator and annihilator). Notably, we report the first estimation of a hetero-TTA rate constant, which exceeds the homo-TTA rate by a factor of 2. This work broadens the design space for TTA-UC systems by enabling the use of neutral, noncovalently linked mediators, expanding beyond the conventional reliance on charged or covalently tethered species.}, archive = {J_JACS}, author = {Sunil Kumar Kandappa and Victor Gray}, doi = {10.1021/jacs.5c09906}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40214--40224}, shortjournal = {J. Am. Chem. Soc.}, title = {Improving Triplet–Triplet annihilation upconversion output by a triplet mediator approach: Mechanistic insights on homo and hetero-annihilation in three-component systems}, volume = {147}, year = {2025}, }
• (2025). Motif editing reveals hidden active sites in atomically precise metal nanoclusters for enhanced electrocatalysis. JACS, 147(44), 40205--40213. (www)

  @article{ , abstract = {Metal nanoclusters offer atomically precise platforms for catalysis but often require bulk molecular motifs to achieve cluster stability. Here, we assess how these motifs block access to active sites and quantify trade-offs between structural integrity and catalytic performance. Based on this, we designed a motif-by-motif surface editing strategy to expose catalytic sites with atomic precision while preserving the kernel integrity of the cluster. Using [Au 25 ( p MBA) 18 ] − nanoclusters ( p MBA = para-mercaptobenzoic acid) as a model system, we selectively replace sterically bulky Au 2 ( p MBA) 3 motifs with compact Cu-( p MBA) 3 units, yielding [Au 13 Cu 4 ( p MBA) 12 ] 3– nanoclusters with a symmetric, open-surface architecture. In situ absorption and mass spectrometry reveals a stepwise motif exchange mechanism distinct from conventional coreduction or ligand displacement, which enables surface reconstruction without kernel distortion. The resulting clusters deliver a 180-fold enhancement in hydrogen evolution turnover frequency (18.8 s –1 ), compared to the parent [Au 25 ( p MBA) 18 ] − (0.1 s –1 ), attributed to increased Au 3 facet exposure and improved hydrogen binding, as suggested by spectroscopy and density functional theory. This work offers a generalizable route to programmable surface engineering in metal nanoclusters, contributing to advance in the longstanding paradox between atomic precision and catalytic accessibility.}, archive = {J_JACS}, author = {Zhihe Liu and Moshuqi Zhu and Bo Li and Junmei Chen and Shibo Xi and Yang-Yang Yu and Lu Xia and Lei Wang and De-en Jiang and F. Pelayo García de Arquer and Jianping Xie}, doi = {10.1021/jacs.5c08684}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40205--40213}, shortjournal = {J. Am. Chem. Soc.}, title = {Motif editing reveals hidden active sites in atomically precise metal nanoclusters for enhanced electrocatalysis}, volume = {147}, year = {2025}, }
• (2025). Tuning the f band for enhanced surface redox in strained rare earth oxides. JACS, 147(44), 40196--40204. (www)

  @article{ , abstract = {Reducible rare earth oxides (REO 2– x ) are essential in catalysis due to their 4f band-governed surface redox properties, which influence crucial reactions such as hydrogen dissociation and water formation. However, correlating the 4f band structure with catalytic activity has been a long-standing challenge due to the complexities of manipulating and characterizing 4f electrons. Here, we demonstrate that tensile strain effectively modulates the 4f electronic structure, narrowing the band gap and activating surface oxygen, leading to enhanced redox activity. Using atomically flat ceria ultrathin films under up to a 7% biaxial strain range, we observed a five-fold increase in surface reaction kinetics via time-resolved ambient-pressure X-ray photoelectron spectroscopy. Complementary density functional theory calculations reveal that the tensile strain reduces energy barriers for key catalytic steps by narrowing the 4f–2p band gap. These findings highlight the RE 4f electronic structure as a critical descriptor for catalysis and demonstrate the utility of atomically flat model systems.}, archive = {J_JACS}, author = {Hongyang Su and Jing Chai and Zixuan Guan and Hendrik Bluhm and Ziyun Zhang and Yidan Cao and Zhi Liu and Yuan-Hua Lin and William C. Chueh and Liang Zhang and Di Chen}, doi = {10.1021/jacs.5c08872}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40196--40204}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the f band for enhanced surface redox in strained rare earth oxides}, volume = {147}, year = {2025}, }
• (2025). Interfacial electric fields transform brown carbon formation: Accelerate radical coupling toward strong light-absorbing products. JACS, 147(44), 40182--40195. (www)

  @article{ , abstract = {The formation of brown carbon (BrC) in atmospheric aerosols significantly influences air quality and climate, yet the underlying chemistry governing its interfacial genesis remains poorly understood. Here, we reveal that the intense electric field at the air–water interface of deliquescent nitrite aerosols promotes the oxidation of methoxyphenol, a key biomass burning constituent. The formation of conjugated oligomers, such as C 16 H 14 O 6 and C 15 H 13 NO 7 , exhibits substantial light absorption (mass absorption coefficients ∼4 m 2 g –1 )─a level that surpasses many previously reported pathways. The aging rate can be increased by up to 2 orders of magnitude compared to bulk solutions due to selective radical–radical coupling polymerization. This is driven by promoted intermolecular energy transfer between direction-oriented excited methoxyphenol molecules and reduced energy barriers via stabilized dimer intermediates in the presence of a strong interfacial electric field, as evidenced by high-resolution spectroscopy and quantum calculations. Our study underscores the catalytic role of electric fields in the browning process, reshaping our understanding of atmospheric photochemical aging and highlighting an overlooked driver of BrC formation with far-reaching implications for aerosol reactivity and atmospheric processes.}, archive = {J_JACS}, author = {Yangyang Liu and Kejian Li and Qiuyue Ge and Longqian Wang and Wenbo You and Kedong Gong and Jianpeng Ao and Lifang Xie and Wei Wang and Le Yang and Runbo Wang and Jilun Wang and Licheng Wang and Minglu Ma and Tingting Huang and Tao Wang and Minbiao Ji and Hongbo Fu and Jianmin Chen and Liwu Zhang}, doi = {10.1021/jacs.5c08398}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40182--40195}, shortjournal = {J. Am. Chem. Soc.}, title = {Interfacial electric fields transform brown carbon formation: Accelerate radical coupling toward strong light-absorbing products}, volume = {147}, year = {2025}, }
• (2025). Tuning the quantum-well structure of single-crystal layered perovskite heterostructures. JACS, 147(44), 40171--40181. (www)

  @article{ , abstract = {Single-crystal layered perovskite heterostructures provide a scalable platform for potentially realizing emergent properties recently seen in mechanically stacked monolayers. We report two new layered perovskite heterostructures M 2 (PbCl 2 )(AMCHC) 2 (PbCl 4 )·2H 2 O ( 1_M where M = Na + , Li + ; AMCHC = + NH 3 CH 2 C 6 H 10 COO – ) crystallizing in the chiral, polar space group C 2. The heterostructures exhibit alternating layers of a lead-chloride perovskite and an intergrowth comprising corner-sharing PbCl 4 (η 2 -COO) 2 polyhedra with bridging equatorial chlorides and terminal axial oxygen ligands. Small alkali metal cations and water molecules occupy the cavities between the polyhedra in the intergrowth layer. The heterostructures display wide bandgaps, two closely spaced excitonic features in their optical spectra, and strong second harmonic generation. The calculated band structure of 1_Na features a Type-I quantum-well structure, where the electron–hole correlation function corresponding to the lowest excited state points to electron–hole pairs localized within a single inorganic layer (intralayer excitons), as seen in typical layered halide perovskites. In contrast, calculations show that 1_Li adopts a Type-II quantum-well structure, with electrons and holes in the lowest excited state residing in different inorganic layers (interlayer excitons). Calculations on model complexes suggest that these changes in band alignment, between Type-I and Type-II quantum-well structures, are driven by the placement of the alkali metal and the orientation of the water molecules, changing the electrostatic potential-energy profiles of the heterostructures. Thus, this study sets the stage for accessing different alignments of the perovskite and intergrowth bands in bulk perovskite heterostructures that self-assemble in solution.}, archive = {J_JACS}, author = {Arundhati P. Deshmukh and Yinan Chen and Jamie L. Cleron and Monique Tie and Jiajia Wen and Tony F. Heinz and Marina R. Filip and Hemamala I. Karunadasa}, doi = {10.1021/jacs.5c08391}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40171--40181}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the quantum-well structure of single-crystal layered perovskite heterostructures}, volume = {147}, year = {2025}, }
• (2025). Unraveling the role of the multifunctional groups in the adsorption of l-cysteine on rutile TiO2(110). JACS, 147(44), 40158--40170. (www)

  @article{ , abstract = {Understanding the interaction between biomolecules and oxide surfaces is essential for advancing technologies in photocatalysis, virus inactivation, and self-cleaning materials. This study investigates the adsorption behavior of l -cysteine on the rutile TiO 2 (110) surface using a combined experimental and theoretical approach. By employing X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared reflection absorption spectroscopy (FT-IRRAS), scanning tunneling microscopy (STM), and density functional theory (DFT) calculations, we elucidate the molecular configurations and bonding mechanisms involved in the interaction of cysteine with the TiO 2 surface. The results reveal three distinct adsorption geometries: two bidentate bridging modes involving the carboxylate group and amino group and a configuration involving the interaction of the thiolate group with titanium atoms. Additionally, cysteine molecules form dimers stabilized by disulfide bonds even at low coverage while maintaining a zwitterionic state. Our study highlights, for the first time, the key role of the thiol group in cysteine adsorption on TiO 2 , both for surface direct binding and dimer formation. These findings provide new insights into the fundamental principles of biomolecule–semiconductor interactions with important implications for surface-functionalized materials in catalysis and sensing.}, archive = {J_JACS}, author = {Miguel Blanco Garcia and Daniele Perilli and Chiara Daldossi and Aldo Ugolotti and Martina Giordano and Daniel Silvan Dolling and Michael Wagstaffe and Mona Kohantorabi and Andreas Stierle and Cristiana Di Valentin and Heshmat Noei}, doi = {10.1021/jacs.5c07119}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40158--40170}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the role of the multifunctional groups in the adsorption of l-cysteine on rutile TiO2(110)}, volume = {147}, year = {2025}, }
• (2025). In vivo mRNA delivery to the lung vascular endothelium by dicationic charge-altering releasable transporters. JACS, 147(44), 40146--40157. (www)

  @article{ , abstract = {Endothelial cells (ECs) comprise the pulmonary vascular bed and play a significant role in health and diseases. Consequently, the EC niche represents an attractive therapeutic target for treating a wide range of pulmonary vascular diseases. We have identified a new class of dicationic charge-altering releasable transporters. These single-component transporters selectively deliver mRNA to the lung upon intravenous administration without the use of a targeting ligand. Significantly, the number and spatial array of cationic charges within the repeating units of the CART polymer are found to control both mRNA delivery efficacy and tissue tropism. High-resolution imaging revealed efficient mRNA delivery to endothelial cells in pulmonary arteries, veins, and capillaries. The selective lung tropism of these new CARTs, coupled with the efficient and tunable synthesis of this new family of CART amphiphiles, represents an enabling platform for research and clinical applications.}, archive = {J_JACS}, author = {Mahmoud M. AbdElwakil and Jeffrey Ni and Summer Ramsay-Burrough and Paul Joshua Hurst and Rebecca L. McClellan and Samuel R. Khasnavis and Yuan Jia and Sehar R. Masud and Timothy R. Blake and Adrienne Sallets and Ole A. W. Haabeth and Idit Sagiv-Barfi and Debra K. Czerwinski and Marco Herrera-Barrera and Ronald Levy and Paul A. Wender and Maya E. Kumar and Robert M. Waymouth}, doi = {10.1021/jacs.5c06654}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40146--40157}, shortjournal = {J. Am. Chem. Soc.}, title = {In vivo mRNA delivery to the lung vascular endothelium by dicationic charge-altering releasable transporters}, volume = {147}, year = {2025}, }
• (2025). BiV1–xOy/Noble metal nanoparticle domains with reverse charge transfer improves photoelectrochemical glycerol to dihydroxyacetone conversion. JACS, 147(44), 40136--40145. (www)

  @article{ , abstract = {Photoelectrochemical glycerol oxidation (PecGO) using a BiVO 4 photoanode is a promising strategy for producing high-value-added dihydroxyacetone (DHA), but the selectivity and efficiency are limited to inferior adsorption and activation ability of secondary hydroxyl groups via surface-exposed Bi atoms. Herein, we report a strong metal–support interaction (SMSI) strategy to enrich the surface Bi atom exposure ratio in a BiVO 4 photoanode, while modulating the Bi p -band center through a reverse charge transfer from core/shell like BiV 1– x O y /Au nanoparticle (NP) domains. These BiV 1– x O y /Au NP domains not only increase the adsorption sites of glycerol secondary hydroxyl groups but also reduce the energy barrier for activating secondary hydroxyl groups. As a result, the photoanode with BiV 1– x O y /Au NP domains achieves a photocurrent density of 5.5 mA cm –2 at 1.23 V vs reversible hydrogen electrode, along with a record DHA production rate of 470.5 mmol m –2 h –1 for PecGO that far surpasses other reported values, accompanied by a high selectivity of 75.2%. Furthermore, this SMSI-driven p -band modulation via reverse charge transfer is also applicable with other noble metals such as Pt, Pd, and Ir, offering a universal method to tune the electronic structure of supports beyond the metal NPs themselves and broadening the SMSI applicability across diverse reaction systems.}, archive = {J_JACS}, author = {Zhonghao Wang and Yuan Gao and Yuan Lu and Jun Bum Park and Jeong Hyun Hwang and Tae-Kyung Liu and Zongkun Bian and Yong Xia and Botao Qiao and Kan Zhang and Jong Hyeok Park}, doi = {10.1021/jacs.5c06621}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40136--40145}, shortjournal = {J. Am. Chem. Soc.}, title = {BiV1–xOy/Noble metal nanoparticle domains with reverse charge transfer improves photoelectrochemical glycerol to dihydroxyacetone conversion}, volume = {147}, year = {2025}, }
• (2025). Boosting electrochemical CO2 reduction to formate over la-doped SnO2 via pinning effect and water activation. JACS, 147(44), 40126--40135. (www)

  @article{ , abstract = {Electrochemical reduction of CO 2 to formate over Sn-based catalysts offers an effective carbon-neutral approach for chemical production and renewable energy storage. However, poor selectivity under high current densities persists, primarily due to the instability of Sn–O active sites and slow water dissociation. In this work, a La-doped SnO 2 catalyst is synthesized for efficient CO 2 conversion to formate. Detailed in situ experimental and theoretical studies reveal that La doping induces a pinning effect that effectively stabilizes the Sn–O structure, decreasing the energy barrier for *OCHO conversion. Meanwhile, La species accelerate water activation to provide *H species, and then the moderate *H coverage promotes formate production. As a result, the La-doped SnO 2 exhibits high formate selectivity over a broad potential window from −0.8 to −1.2 V vs reversible hydrogen electrode (RHE), achieving a formate Faradaic efficiency of up to 93.2% with a partial current density of −315.4 mA cm –2 at −1.0 V vs RHE. This work may provide insights into the pinning effect and encourage more design strategies to explore lanthanide element doping for efficient CO 2 electroreduction catalysts.}, archive = {J_JACS}, author = {Yanlin Wang and Guilin Li and Jiaqi Feng and Xue Wang and Qizhou Xue and Aofei Cheng and Boyang Liu and Shaojuan Zeng and Min Wang and Xiangping Zhang}, doi = {10.1021/jacs.5c03978}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40126--40135}, shortjournal = {J. Am. Chem. Soc.}, title = {Boosting electrochemical CO2 reduction to formate over la-doped SnO2 via pinning effect and water activation}, volume = {147}, year = {2025}, }
• (2025). Intracellular peptide N-myristoylation for cancer cell ferroptosis without acquired resistance. JACS, 147(44), 40120--40125. (www)

  @article{ , abstract = {N-Myristoylation, a well-known protein lipidation process, has yet to be explored for in situ peptide lipidation. Here, we report intracellular peptide N-myristoylation for potently inhibiting cancer cells. A self-assembling d -peptide, Gbb-NBD ( 1 ), comprising an N-terminal glycine, a d -dibiphenylalanine backbone, and a C-terminal nitrobenzofurazan, formed nanospheres in aqueous solution and exhibited strong cytotoxicity against cancer cells (GI 50 = 500 nM) while sparing neuronal cells. Live-cell imaging showed that 1 traversed the plasma membrane to the ER, Golgi and mitochondria. NMT inhibition, LC-MS of cell lysates, and click chemistry confirmed the N-myristoylation of 1 . Functional studies showed that blocking NMT activity or modifying the N-terminus suppressed cytotoxicity, establishing N-myristoylation as essential for activity. Mechanistically, immunoblotting, lipidomic profiling, and rescue assays demonstrated that myristoylated 1 disrupted lipid metabolism and induced ferroptotic cell death, notably without the emergence of acquired resistance. In contrast, premyristoylated 1 displayed poor uptake and weak activity, underscoring the importance of in situ lipidation for cellular entry and function. Together, these findings reveal intracellular N-myristoylation of a short peptide as a new approach to drive ferroptosis and highlight its potential for developing membrane-targeting supramolecular therapeutics.}, archive = {J_JACS}, author = {Qiuxin Zhang and Weiyi Tan and Isabela Ashton-Rickardt and William Lau and Linrui Zou and Bing Xu}, doi = {10.1021/jacs.5c15621}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40120--40125}, shortjournal = {J. Am. Chem. Soc.}, title = {Intracellular peptide N-myristoylation for cancer cell ferroptosis without acquired resistance}, volume = {147}, year = {2025}, }
• (2025). Neutral aromatic 2,3-diboranaphthalenes. JACS, 147(44), 40113--40119. (www)

  @article{ , abstract = {Incorporating isosteric boron units into aromatic frameworks provides access to molecules with unusual electronic structures and reactivity. We report the synthesis of 2,3-diboranaphthalenes ( 2 and 4 ), the first neutral diboron analogues of naphthalene featuring an o -diborabenzene core. This electron-rich scaffold exhibits pronounced aromaticity and diverse reactivity. Symmetrical 2 acts as a 6π-aromatic ligand in group 6 metal complexes ( 5 – 7 ) and undergoes double [3 + 2] cycloaddition with CO 2 to afford a fused tetracycle ( 8 ). In contrast, unsymmetrical 4 undergoes electrophile-induced ring contraction ( 9 ) and oxidative skeletal editing with selenium ( 10 ). These findings establish 2,3-diboranaphthalenes as a new class of neutral boron aromatics, broadening the structural and functional space of main-group aromatic systems.}, archive = {J_JACS}, author = {Taisong Zhao and Yuyang Dai and Ping Cui and Chen-Ho Tung and Lingbing Kong}, doi = {10.1021/jacs.5c15558}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40113--40119}, shortjournal = {J. Am. Chem. Soc.}, title = {Neutral aromatic 2,3-diboranaphthalenes}, volume = {147}, year = {2025}, }
• (2025). Concise enantioselective total synthesis of (+)-punctaporonin u. JACS, 147(44), 40106--40112. (www)

  @article{ , abstract = {We report herein the first enantioselective total synthesis of (+)-punctaporonin U, a cage-like pentacyclic sesquiterpene bearing eight contiguous stereocenters. The synthesis features three key transformations: a) a rare cis -selective Mukaiyama-Michael addition of the silyl enol ether derived from 2,2-dimethylcyclobutan-1-one to 4-[( tert -butyldimethylsilyl)oxy]cyclopent-2-en-1-one; b) a domino oxa-Michael addition/aldol reaction/bromination sequence that constructs both a fused five-membered ring and a 1,4-bridged 7-membered ring; c) an intramolecular S N 2 displacement to install the 1,3-bridged tetrahydrofuran ring. The synthesis is accomplished in six steps from 4-[( tert -butyldimethylsilyl)oxy]cyclopent-2-en-1-one, which itself is accessible in five steps from cyclopentadiene.}, archive = {J_JACS}, author = {Paul Gri and Qian Wang and Jieping Zhu}, doi = {10.1021/jacs.5c15423}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40106--40112}, shortjournal = {J. Am. Chem. Soc.}, title = {Concise enantioselective total synthesis of (+)-punctaporonin u}, volume = {147}, year = {2025}, }
• (2025). Probing voltage- and electrolyte-dependent monolayer dynamics with 2D-IR spectroscopy. JACS, 147(44), 40099--40105. (www)

  @article{ , abstract = {Little is known about structural dynamics at electrode surfaces under applied potential. Here, we report 2D-IR spectra of a 4-mercaptobenzonitrile monolayer on a gold electrode, revealing chemical exchange between two subensembles on sub- to tens-of-picoseconds time scales. Dynamics are measured in 100 mM MgCl 2 , LiCl, and KCl at −200 and +300 mV vs Ag/AgCl. At +300 mV, all electrolytes exhibited ≥48 ps exchange, while at −200 mV, the slower exchange component ranged from ≥33 to ≥43 ps. The dynamics correlate with ion concentration, according to radial distribution functions calculated from molecular dynamics simulations, suggesting that local ion densities, regardless of valency or sign, slow dynamics. Results show solvation, electric double layer formation, and monolayer reorientation. This work reveals how electrolyte composition modulates molecular reorientation and hydrogen bonding at functionalized electrodes.}, archive = {J_JACS}, author = {Austin B. Gilbert and Wonjae Jeong and Kyle R. Billings and Aritri Biswas and Matthew J. Ryan and Kijeong Kwac and Minhaeng Cho and Alexei A. Kananenka and Martin T. Zanni}, doi = {10.1021/jacs.5c14718}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40099--40105}, shortjournal = {J. Am. Chem. Soc.}, title = {Probing voltage- and electrolyte-dependent monolayer dynamics with 2D-IR spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Divergent total synthesis of pleurotinoid natural products. JACS, 147(44), 40093--40098. (www)

  @article{ , abstract = {Pleurotinoid natural products have garnered significant attention due to their prominent anticancer and antibacterial activities, as well as their complex structures. Herein, we report a new strategy for the divergent and efficient synthesis of pleurotinoids. The strategy features an intermolecular 1,6-addition/vinylogous Mukaiyama aldol reaction sequence, a rare 4π-electrocyclic ring-opening/vinylogous Michael cascade reaction, diastereoselective Wolff rearrangement ring contraction, facial-selective reduction of terminal allylic alcohols, and late-stage oxidative cyclization.}, archive = {J_JACS}, author = {Jin-Bao Qiao and Jia-Yi Pei and Yuxiang Zhang and Qing-Wei Zhang and Yu-Ming Zhao}, doi = {10.1021/jacs.5c14395}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40093--40098}, shortjournal = {J. Am. Chem. Soc.}, title = {Divergent total synthesis of pleurotinoid natural products}, volume = {147}, year = {2025}, }
• (2025). Side-on n2 binding and reduction by a heterotetrametallic Zr2Co2 cluster. JACS, 147(44), 40087--40092. (www)

  @article{ , abstract = {In multimetallic compounds, N 2 typically bridges late transition metals in an end-on (η 1 :η 1 ) fashion while early transition metals often bind N 2 side-on (η 2 ), with the latter resulting in more significant N–N bond elongation. Herein, N 2 fixation is accomplished by using a well-defined scaffold featuring a heterobimetallic combination of Zr and Co. We report a heterotetrametallic Zr 2 Co 2 cluster in which N 2 is bound side-on to the two Co centers and end-on to Zr in a μ 3 -η 1 :η 2 :η 2 binding mode that defies established paradigms for N 2 binding. The heterometallic approach is shown to facilitate catalytic reductive silylation of N 2 with turnover numbers far exceeding those of reported cobalt catalysts.}, archive = {J_JACS}, author = {Adwitiya Singh and Curtis E. Moore and Christine M. Thomas}, doi = {10.1021/jacs.5c14342}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40087--40092}, shortjournal = {J. Am. Chem. Soc.}, title = {Side-on n2 binding and reduction by a heterotetrametallic Zr2Co2 cluster}, volume = {147}, year = {2025}, }
• (2025). From alkylarenes to α-amino acid derivatives via C-difunctionalization. JACS, 147(44), 40078--40086. (www)

  @article{ , abstract = {Nitrogenation of the carbon–carbon bond is a powerful synthetic strategy for efficiently incorporating the N atom into substrates, showcasing the remarkable step and atom economy in molecular editing processes. However, due to the inherent challenges of cleaving inert C–C bonds, current strategies are restricted to C-monofunctionalization. Herein we report a novel C-difunctionalization strategy of alkylarenes via C–C bond cleavage, providing a unique pathway for the synthesis of unnatural amino acids. This chemistry is a promising strategy for exploring uncharted areas in C–C bond amination, moving beyond traditional C-monofunctionalization to higher-order and gain-of-function-based C-multifunctionalization. The success of this C-difunctionalization approach hinges on an entropy-driven remodeling strategy for skeleton restructuring and precisely controlled chemoselectivity for stepwise carbon editing. This operationally simple reaction provides new avenues for high-value upgrading of petrochemical feedstocks, late-stage modification of complex scaffolds, and abbreviated synthesis of bioactive molecules.}, archive = {J_JACS}, author = {Xi Wang and Jianzhong Liu and Zengrui Cheng and Teng Wang and Jing Peng and Junhong Meng and Yilei Huang and Qi Sun and Ning Jiao}, doi = {10.1021/jacs.5c14247}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40078--40086}, shortjournal = {J. Am. Chem. Soc.}, title = {From alkylarenes to α-amino acid derivatives via C-difunctionalization}, volume = {147}, year = {2025}, }
• (2025). Spin-polarized lasing via ferromagnetic spin filtering in hybrid perovskites. JACS, 147(44), 40071--40077. (www)

  @article{ , abstract = {Metal halide perovskites are rapidly emerging as a promising platform for spin-polarized lasers. However, the weak Zeeman effect of perovskites makes it challenging to realize the magnetic-field induction and manipulation of spin-polarized lasing. Here we introduce a ferromagnetic spin filtering effect in perovskites to achieve spin-polarized lasing. A composite is designed by incorporating ferromagnetic Fe 3 O 4 nanoparticles into an organic–inorganic hybrid perovskite. Under a magnetic field, the Fe 3 O 4 nanoparticle selectively captures electrons with particular spin from the perovskite, resulting in an effective spin polarization for lasing. The magnetic field direction and strength determine the chirality and circular polarization degree of the spin-polarized perovskite lasing. Furthermore, wavelength-tunable spin-polarized lasers are realized by exploiting the composition-tailored bandgaps of hybrid perovskites. Our work establishes a ferromagnetic spin filtering strategy for spin-polarized perovskite lasers.}, archive = {J_JACS}, author = {Penghao Li and Yu Xu and Xinyu Dong and Shizhe Ren and Zhonghao Zhou and Yifan Zhou and Zehua He and Yuhao Xie and Bo Peng and Jiannian Yao and Haiyun Dong and Yong Sheng Zhao}, doi = {10.1021/jacs.5c13764}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40071--40077}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin-polarized lasing via ferromagnetic spin filtering in hybrid perovskites}, volume = {147}, year = {2025}, }
• (2025). Transition-metal-free site-selective β- and γ-C–H borylation of aliphatic amines. JACS, 147(44), 40064--40070. (www)

  @article{ , abstract = {A mild photoinduced transition metal-free method for β- and γ-C(sp 3 )–H borylation of amines has been developed. This protocol features a regioselective intramolecular hydrogen atom transfer (HAT) process to access key amino alkyl radical intermediate employing commercially available, installable/removable iodoaryl tethers. Notably, this method introduces a new iodopyridyl-based hydrogen atom transferring group for abstraction of previously elusive β-C–H bonds of amines. Remarkably, this general and operationally simple method allows activation of primary, secondary, and tertiary C–H sites of a broad range of acyclic and cyclic secondary amines and offers a complementary platform toward regioselective and diastereoselective syntheses of valuable β- and γ-amino boronates. Utility of this protocol has been demonstrated through formal C–H oxidation reaction and other late-stage derivatizations of amines.}, archive = {J_JACS}, author = {Sumon Sarkar and Nitish Kumar Deo and Tong Zhang and Vladimir Gevorgyan}, doi = {10.1021/jacs.5c12618}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40064--40070}, shortjournal = {J. Am. Chem. Soc.}, title = {Transition-metal-free site-selective β- and γ-C–H borylation of aliphatic amines}, volume = {147}, year = {2025}, }
• (2025). Functional group transposition enabled by palladium and photo dual catalysis. JACS, 147(44), 40058--40063. (www)

  @article{ , abstract = {The ability to precisely modify the structure of molecules is a captivating process that has fascinated the synthetic organic and medicinal chemistry communities. To this end, functional group transposition has recently emerged as a powerful strategy to edit molecules and allow for access to novel chemical entities without significantly altering the synthesis routes. Here we disclose an unusual functional group transposition reaction. By using palladium and photo dual catalysis, this radical-induced process enables the transposition between an iodo group and a boryl group to convert iodoarenes appended with an alkylboronate group to arylboronates appended with an alkyl iodide.}, archive = {J_JACS}, author = {Menghua Xu and Chengjun Wu and Ming Chen}, doi = {10.1021/jacs.5c11429}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40058--40063}, shortjournal = {J. Am. Chem. Soc.}, title = {Functional group transposition enabled by palladium and photo dual catalysis}, volume = {147}, year = {2025}, }
• (2025). Monomicelle-encapsulated nanocrystals as versatile building blocks for hydrogen-bonded superlattices with enhanced mechanical properties. JACS, 147(44), 40051--40057. (www)

  @article{ , abstract = {We present a general strategy for constructing mechanically robust superlattices using monomicelle-encapsulated nanocrystals (MENCs) as building blocks. MENCs are created by encapsulating individual nanocrystals within micelles of poly(styrene- co -maleic anhydride), driven by hydrophobic interactions between styrene segments and native surface ligands. Concurrent hydrolysis of maleic anhydride moieties generates carboxyl groups that establish intramicelle hydrogen bonds (H-bonds), stabilizing MENCs in aqueous dispersion. Upon solvent evaporation, MENCs self-assemble into long-range-ordered, three-dimensional superlattices. Crucially, postassembly intermicelle H-bonding spontaneously fuses adjacent MENCs into a continuous, cross-linked architecture. This dual-level H-bonding imparts exceptional structural cohesion, yielding superlattices with elastic moduli of up to 18.73 GPa, far exceeding conventional superlattices stabilized by van der Waals or H-bonding interactions.}, archive = {J_JACS}, author = {Zhebin Zhang and Siyu Wan and Yifan Gao and Xuanyu Lyu and Yutong Gao and Ning Ding and Ziyue Zheng and Dong Yang and Tongtao Li and Angang Dong}, doi = {10.1021/jacs.5c09642}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40051--40057}, shortjournal = {J. Am. Chem. Soc.}, title = {Monomicelle-encapsulated nanocrystals as versatile building blocks for hydrogen-bonded superlattices with enhanced mechanical properties}, volume = {147}, year = {2025}, }
• (2025). Bifunctional iminophosphorane superbases enable the highly enantioselective sulfa-michael addition to fully substituted cyclopropene carboxylic acid derivatives. JACS, 147(44), 40045--40050. (www)

  @article{ , abstract = {The metal-free catalytic enantioselective intermolecular conjugate addition of alkyl thiols to unactivated β-substituted cyclopropene carboxylic acid derivatives has been developed. High enantiomeric excesses and yields were consistently achieved across a broad range of thiol pronucleophiles and fully substituted cyclopropene electrophiles under mild reaction conditions, enabled by a novel tert -leucine-derived amide-containing bifunctional iminophosphorane (BIMP) catalyst. Additionally, lowering the catalyst loading to 5.0 mol % was possible and allowed the reaction to be carried out on a gram scale.}, archive = {J_JACS}, author = {Kang Yuan and Alberto I. Ristache and Szymon M. Kosc and Agamemnon Crumpton and Darren J. Dixon}, doi = {10.1021/jacs.5c07849}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40045--40050}, shortjournal = {J. Am. Chem. Soc.}, title = {Bifunctional iminophosphorane superbases enable the highly enantioselective sulfa-michael addition to fully substituted cyclopropene carboxylic acid derivatives}, volume = {147}, year = {2025}, }
• (2025). Surface science: The foundation of electrocatalysis. JACS, 147(44), 40035--40044. (www)

  @article{ , abstract = {The research community in the electrochemical field is increasingly moving toward device-level investigations in a push to demonstrate practical applicability and widen the adoption of advanced energy conversion and storage technologies. Electrochemical devices, however, are highly complex systems and require a multidisciplinary approach to reveal the fundamental processes and key physical parameters of the materials employed that determine their functional properties. These processes occur in the near-surface region of the electrodes that catalyze electrochemical reactions. Here, we present our view on the critical importance and enduring relevance of a surface science approach to advance knowledge in electrocatalysis, with foundations built on well-defined planar surfaces that could be linked to corresponding nanostructured interfaces.}, archive = {J_JACS}, author = {Alasdair R. Fairhurst and Chaewon Lim and Minki Jun and Benjamin J. Ransom and Filip Mackowicz and Dominik Haering and Vojislav R. Stamenkovic}, doi = {10.1021/jacs.5c10064}, journal = {Journal of the American Chemical Society}, month = {11}, number = {44}, pages = {40035--40044}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface science: The foundation of electrocatalysis}, volume = {147}, year = {2025}, }
• (2025). Autonomous switching of self-propelled motion modes of hinokitiol-fueled elastomer matrices. JACS, 147(43), 40024--40034. (www)

  @article{ , abstract = {Programmable self-propelled motion underpins essential biological functions and serves as a powerful inspiration in the design of dynamic synthetic materials. While significant progress has been made in developing self-propelled systems, most existing strategies rely on external stimuli or the incorporation of coupled oscillatory chemical reactions to achieve mode switching. In contrast, approaches that enable intrinsic switching between motion modes─such as from continuous to oscillatory─without external control remain limited. In this study, we introduce a self-propelled disk utilizing hinokitiol as a surface-active “fuel” within a polystyrene elastomer matrix, floating on the water surface. Hinokitiol-containing disks exhibited spontaneous transitions from continuous to oscillatory movement, distinctly without the need for external inputs. By leveraging the phase transitions of hinokitiol and tuning the mesoscale structure of the polymer scaffold, we succeeded in modulating the duration of continuous motion and frequency of oscillation in the macroscopic motion of the disks. These findings demonstrate that life-like macroscopic motion can be systematically engineered by coordinating the molecular arrangement of fuel species and the mesoscale structures of the surrounding polymer scaffold, presenting a versatile molecular design approach for synthetic self-propelled materials.}, archive = {J_JACS}, author = {Lara Rae Holstein and Masayuki Takeuchi and Nobuhiko J. Suematsu and Atsuro Takai}, doi = {10.1021/jacs.5c17346}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {40024--40034}, shortjournal = {J. Am. Chem. Soc.}, title = {Autonomous switching of self-propelled motion modes of hinokitiol-fueled elastomer matrices}, volume = {147}, year = {2025}, }
• (2025). Ligand evolution-enabled enantioselective C(sp3)–H azidation. JACS, 147(43), 40010--40023. (www)

  @article{ , abstract = {Chiral azides constitute a versatile class of compounds that are ubiquitous in the spectrum of biologically active substances. These compounds serve as valuable precursors for synthesizing various nitrogen-based drug scaffolds, biologically active natural products, and functional molecules. Nevertheless, the inherent high reactivity and elusive nature of azides have limited the reporting of methods for direct asymmetric azidation of carbon–hydrogen (C–H) bonds. Herein, we present a photoinduced copper-catalyzed enantioselective radical α-C(sp 3 )–H azidation of carbonyl compounds via a 1,5-hydrogen atom transfer (HAT) strategy. A novel binary bisphosphine and N , N , N -tridentate anionic chiral ligand system functions both as a photosensitizer and a chiral catalyst for azidation. This practical method exhibits excellent chemo-, regio-, and enantioselectivity in the efficient azidation of the α-carbonyl C–H bond within complex functional group environments. The versatility of this method is further showcased through diverse postazidation manipulations, facilitating the synthesis of non-natural α-amino acid derivatives and the straightforward installation of azide groups in complex bioactive compounds as ligation platforms for click chemistry. DFT studies reveal a remote S H 2 mechanism and demonstrate that the ligand-evolution strategy combining ligand modification and ligand self-assembly is critical for tuning the active chiral space of the catalyst as well as improving the enantioselectivity.}, archive = {J_JACS}, author = {He Zhang and Wei Gu and Jialian Zheng and Jianzhong Lu and Quanzhe Li and Yuzhu Liu and Xiaotian Qi and Guozhu Zhang and Rui Guo}, doi = {10.1021/jacs.5c16924}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {40010--40023}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand evolution-enabled enantioselective C(sp3)–H azidation}, volume = {147}, year = {2025}, }
• (2025). Boosting the brightness of covalent organic frameworks by integration of dual-docking luminogens with aggregation-induced emission effect. JACS, 147(43), 39999--40009. (www)

  @article{ , abstract = {Most covalent organic frameworks (COFs) exhibit minimal or weak emission, even when constructed with highly emissive AIEgens. The fluorescence quenching issues in COFs are typically attributed to nonradiative decay induced by molecular motion or intramolecular charge transfer. As a result, designing emissive COF materials remains a desirable yet challenging task. In this study, we present the construction of highly emissive COFs through the integration of dual-docking AIEgens. Mechanism studies reveal that this integration effectively restricts undesired molecular motion and reduces charge transfer to the imine linkage, thereby enhancing fluorescence generation and improving the crystallinity of the COFs. One benzothiadiazide-based COF, COF-DPQP-BT, exhibits notable brightness with a photoluminescence quantum yield of 36.5% and is successfully utilized for in vivo three-photon fluorescence imaging of brain vasculature in mice, achieving an imaging depth of approximately 1.2 mm. This work provides valuable insights for the design of emissive COFs.}, archive = {J_JACS}, author = {Liang Zhang and Weihang Geng and Xinwen Ou and Shan He and Xiao-Hang He and Wenlang Li and Yantian Jiao and Yi Zhou and Chensen Li and Yingying Chen and Wutong Du and Ziyi Cheng and Ziyi Jin and Jacky W. Y. Lam and Jun Qian and Ben Zhong Tang}, doi = {10.1021/jacs.5c16217}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39999--40009}, shortjournal = {J. Am. Chem. Soc.}, title = {Boosting the brightness of covalent organic frameworks by integration of dual-docking luminogens with aggregation-induced emission effect}, volume = {147}, year = {2025}, }
• (2025). In situ PROTAC synthesis enabled by pathologically activated bioorthogonal catalysis for precision cancer therapy. JACS, 147(43), 39987--39998. (www)

  @article{ , abstract = {Proteolysis-targeting chimeras (PROTACs) have transformed therapeutic interventions by hijacking the ubiquitin–proteasome system. However, their broad application is hindered by inadequate cellular permeability and undesired off-tissue effects. Here, we introduce a modular strategy for the in situ synthesis of PROTACs through pathologically activated bioorthogonal catalysis (ABC-PROTAC), enabling targeted protein degradation specifically in cancer cells. This platform integrates biocompatible, glutathione-activated Click-T-Cu(II) complexes with azido- and acetylene-derived, fragmented PROTAC precursors. These components are encapsulated within AS1411 aptamer-conjugated liposomes to enhance cellular uptake and systemic delivery. Once internalized by nucleolin-overexpressing cancer cells, the Click-T-Cu(II) complexes are activated to catalyze the intracellular assembly of functional PROTACs via click chemistry. This delivery paradigm facilitates efficient degradation of oncoproteins both in vitro and in vivo, resulting in robust antitumor activity with favorable biocompatibility and high selectivity. The modularity of the ABC-PROTAC strategy is demonstrated by utilizing diverse warheads, including small molecules and DNA motifs, to degrade BRD4, PARP1, and NF-κB. Together, this strategy establishes a precise method for targeted protein degradation while minimizing the systemic toxicity associated with conventional PROTACs.}, archive = {J_JACS}, author = {Dilan Ouyang and Rongjin Yang and Yuhang Yao and Fang Jiang and Sijie Song and Yuheng Yang and Edikan A. Ogunnaike and Zhitong Chen and Zhaowei Chen and Huanghao Yang}, doi = {10.1021/jacs.5c15945}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39987--39998}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ PROTAC synthesis enabled by pathologically activated bioorthogonal catalysis for precision cancer therapy}, volume = {147}, year = {2025}, }
• (2025). Synthesis of c3 and c5 oxygenates from the co-electrolysis of carbon monoxide and acetylene on a Cu–Pd catalyst. JACS, 147(43), 39974--39986. (www)

  @article{ , abstract = {The electroreduction of CO 2 (CO 2 RR) and CO (CORR) using renewable electricity provides a sustainable route for decarbonizing chemical manufacturing. However, boosting the production of multi-carbon oxygenates remains challenging. Herein, we report that the co-electroreduction of CO and acetylene (C 2 H 2 ) on an oxide-derived Cu 5 Pd (OD-Cu 5 Pd) catalyst at −1.1 V vs SHE achieves ∼130× higher production of C 3 oxygenates, such as 1-propanol, propionaldehyde, and allyl alcohol, compared to CORR alone. Seven C 5 oxygenates, including 3-pentanone, cyclopentanone, and 1-pentanol, were further identified, none of which have been previously observed in either CORR or CO 2 RR. The remaining balance of the products was mainly ethylene and 1,3-butadiene. The addition of Pd to Cu enhances both CO and C 2 H 2 adsorption, facilitates C–C coupling, and significantly improves the oxygenate yields. At −1.1 V vs SHE, the production rates of C 3 oxygenates on OD-Cu 5 Pd catalyst were doubled, while that of C 5 oxygenates increased by ∼6-fold, as compared to that on unmodified OD-Cu. The oxygenate production rates were further optimized by tuning the applied potential, feedstock stoichiometry, and temperature. Mechanistic studies indicate that the C 3 oxygenates and the C 5 oxygenates with mid-chain oxygen atoms form via CO and C 2 H 2 coupling, while the C 5 oxygenates with terminal oxygen atoms stem from CO reacting with 1,3-butadiene, a C 2 H 2 reduction intermediate. These results present a promising and sustainable strategy for the electrosynthesis of long-chain oxygenates.}, archive = {J_JACS}, author = {Wei Jie Teh and Ben Rowley and Boon Siang Yeo}, doi = {10.1021/jacs.5c15895}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39974--39986}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of c3 and c5 oxygenates from the co-electrolysis of carbon monoxide and acetylene on a Cu–Pd catalyst}, volume = {147}, year = {2025}, }
• (2025). Sulfonated module aggregation for ultrahigh birefringence in aqueous-processable crystals. JACS, 147(43), 39964--39973. (www)

  @article{ , abstract = {Birefringent crystals play a pivotal role in advanced optics owing to their indispensable function in modulating polarized light. Progress in this field has been driven by the evolution of “material genes”, from small π-conjugated monomers to π-oligomers and ultimately to expanded π-motifs. However, the poor aqueous processability inherent to the hydrophobic nature of extended carbon or C–N skeletons remains a significant hurdle for industrial applications. Herein, we propose a sulfonated module aggregation strategy to simultaneously optimize optical anisotropy and enable aqueous processability. Using a mild evaporation method, we synthesized five 1,3,6,8-pyreneterasulfonate (PTS) salts exhibiting large birefringence values ranging from 0.558 to 0.811 @ 546 nm. Notably, Na 2 (4-HPyH) 2 (PTS)·H 2 O [(4-HPyH) = 4-hydroxypyridinium] combines a wide band gap ( E g = 3.05 eV), enhanced aqueous processability, and a record-high birefringence (Δ n = 0.811 @ 546 nm) among all sulfate- and sulfonate-based compounds, establishing it as a highly promising birefringent material. Structurally, the incorporation of [4-HPyH] modules reduces the space available for coordinated and guest water molecules, thereby maximizing the packing density of birefringence-active modules while maintaining ideal alignment of both [4-HPyH] and [PTS] units within the lattice. High-accuracy quantum chemical calculations further reveal a compensation mechanism associated with the ring fusion process─the supralinear polarizability anisotropy effect─which produces a supralinear enhancement of polarizability anisotropy upon aggregation of planar π-modules. This work offers a new paradigm for designing aqueous-processable birefringent crystals and expands the theoretical framework for understanding supralinear enhancement of micro-optical properties via π-module polymerization.}, archive = {J_JACS}, author = {Congcong Jin and Yang Li and Chong-An Chen and Jihyun Lee and Chanhee Ko and Sooyeon Lee and Kang Min Ok}, doi = {10.1021/jacs.5c15741}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39964--39973}, shortjournal = {J. Am. Chem. Soc.}, title = {Sulfonated module aggregation for ultrahigh birefringence in aqueous-processable crystals}, volume = {147}, year = {2025}, }
• (2025). Ultralow ru loading on spinel oxide enhances oxygen coupling for efficient acidic water oxidation. JACS, 147(43), 39953--39963. (www)

  @article{ , abstract = {The development of proton-exchange membrane water electrolysis (PEMWE) technologies urgently demands electrocatalytic systems capable of maintaining exceptional activity and durability under harsh acidic oxygen evolution reaction (OER) conditions. Here, we present ultralow Ru loading on cobalt–manganese oxides (Ru–Co 2 MnO 4.5 ) through a facile synthetic strategy. Ru and Co sites facilitate the direct coupling of the oxygen radicals, thereby exceeding the limitations of the scaling relation and triggering the oxide pathway mechanism. Structural characterizations and theoretical calculations demonstrate that the incorporation of Ru single atoms suppresses both lattice oxygen and metal dissolution while maintaining good coordination environments and crystal structures. Furthermore, Ru single-atom loading enhances the hydroxyl adsorption on the catalyst surface and promotes the OER kinetics. Consequently, the Ru–Co 2 MnO 4.5 catalyst achieves an optimal trade-off between catalytic efficiency and structural durability. In 0.5 M H 2 SO 4 , the Ru–Co 2 MnO 4.5 demonstrates a minimal overpotential of 176 mV at 10 mA cm –2 and exhibits excellent stability during 600 h. In the PEMWE device, the Ru–Co 2 MnO 4.5 catalyst requires merely a voltage of 1.638 V to achieve 1 A cm –2 , with an ultralow Ru loading of 20 μg cm –2 . The system can operate for over 100 h under a high current density of 1 A cm –2 , showcasing its potential in a practical hydrogen production device. This work presents an innovative strategy for advancing the development of high-efficiency and large-scale green hydrogen production systems while elucidating the underlying reaction mechanisms.}, archive = {J_JACS}, author = {Mingxin Cai and Guopu Cai and Ke Liu and Degao Wang and Hongbin Zhao and Peilei He}, doi = {10.1021/jacs.5c15539}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39953--39963}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultralow ru loading on spinel oxide enhances oxygen coupling for efficient acidic water oxidation}, volume = {147}, year = {2025}, }
• (2025). Bright, robust and readily accessible fluorophore family for NIR-II bioimaging. JACS, 147(43), 39936--39952. (www)

  @article{ , abstract = {The scarcity of high-performance fluorophores remains a formidable bottleneck in the rapidly advancing field of NIR-II imaging, as existing candidates suffer from low light absorptivity, poor emission efficiency, and cumbersome synthesis. Herein, we propose a straightforward 2-step cyclization strategy to construct an innovative highly bright NIR-II dye family designated as BM -engineering from readily available materials. BM dyes featured a fully rigid and coplanar skeleton, exhibiting superior molar extinction coefficient (ε DCM = 1.9–3.7 × 10 5 M –1 cm –1 ), high fluorescence quantum yields (Φ F = 10.4–18.0% in DCM), and remarkable photochemical robustness. Notably, BM3 redefines the optical landscape with its exceptional NIR-II optical performance (ε = 3.7 × 10 5 M –1 cm –1 , Φ F = 18.4%), solidifying its status as the brightest NIR-II fluorophore reported to date. Leveraging this advantage, BM3 achieves high-resolution bioimaging at ultralow doses, not only illuminating cerebral vasculature (3 nmol) and lymphatic vessels (75 pmol), but also accurately detecting subtle cerebral capillary damage in ischemia-reperfusion models. More strikingly, BM3 provides the first precise real-time tracking of inflamed lymphatic system triggered by both chemical and bacterial stimuli, unveiling distinct pathophysiological patterns that were previously elusive. Beyond experimental validation, computational analysis further deciphers the intricate relationship between molecular architecture and optical performance, offering new insight into the rational design of next-generation NIR-II fluorophores. This study not only pioneers a streamlined synthesis strategy toward ultrabright NIR-II fluorophores but also expands the frontiers of bioimaging precision and disease diagnostics, unlocking immense potential for biomedical innovations and clinical applications.}, archive = {J_JACS}, author = {Hui Bian and Dandan Ma and Xiaodong Zhang and Yangting Qiu and Xia Wu and Mingyan Jia and Xinfu Zhang and Xiaogang Liu and Youjun Yang and Xiaojun Peng and Juyoung Yoon and Yi Xiao}, doi = {10.1021/jacs.5c15490}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39936--39952}, shortjournal = {J. Am. Chem. Soc.}, title = {Bright, robust and readily accessible fluorophore family for NIR-II bioimaging}, volume = {147}, year = {2025}, }
• (2025). Ni-catalyzed enantioselective arylboration of 1,3-cyclohexadiene. JACS, 147(43), 39926--39935. (www)

  @article{ , abstract = {The development of straightforward and efficient methodologies for synthesizing compounds featuring chiral six-membered ring scaffolds represents a crucial pursuit within the realm of synthetic chemistry. Herein, we report a Ni-catalyzed regio-, enantio-, and diastereoselective arylboration of 1,3-cyclohexadienes employing readily available bis(pinacolato)diboron (B 2 pin 2 ) and aryl iodides, providing convenient access to synthetically valuable chiral boronated 1,4- cis -cyclohexenes with high levels of regio-, enantio-, and diastereoselectivity. Notably, the mild reaction conditions ensure broad functional group compatibility. This has been demonstrated by the broad substrate scope and late-stage functionalizations of bioactive compounds or drug molecules within the reaction system. Moreover, the functionally diverse chiral boronated 1,4- cis -cyclohexene derivatives demonstrate high reactivity in a range of downstream transformations, allowing for the efficient preparation of various enantio-enriched, multisubstituted six-membered ring compounds, thereby underscoring the importance of preserving both the boron moiety and the double bond. Preliminary mechanistic investigations, supported by density functional theory (DFT) calculations, provide insights into the origins of the observed regio- and enantioselectivity.}, archive = {J_JACS}, author = {Wangyang Li and Yanping Zheng and Yunya Gu and Jinhui Xie and Yanying Huang and Qiuling Song}, doi = {10.1021/jacs.5c14738}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39926--39935}, shortjournal = {J. Am. Chem. Soc.}, title = {Ni-catalyzed enantioselective arylboration of 1,3-cyclohexadiene}, volume = {147}, year = {2025}, }
• (2025). Hijacking extracellular targeted protein Degrader–Drug conjugates for enhanced drug delivery. JACS, 147(43), 39912--39925. (www)

  @article{ , abstract = {Antibody-based therapeutics encompass diverse modalities for targeting tumor cells. Among these, antibody–drug conjugates (ADCs) and extracellular targeted protein degradation (eTPD) specifically depend on efficient lysosomal trafficking for activity. A major limitation of ADCs is their reliance on antigens with efficient internalization, while eTPD approaches, although capable of trafficking diverse targets to lysosomes, lack cytotoxic potency. To address this, we developed degrader–drug conjugates (DDCs), leveraging the endocytic and recycling activities of eTPD to enhance lysosomal delivery. We utilized fast internalizers, the low-density lipoprotein receptor (LDLR) and the chemokine receptor (CXCR7), to enhance lysosomal delivery. LDLR-based degraders enabled efficient and selective degradation of diverse extracellular membrane proteins, while DDCs with cytotoxic payload enhanced cytotoxicity compared to conventional ADCs in vitro . This dual modality addresses key challenges of inadequate internalization in conventional ADCs and cytotoxic potency in current eTPD strategies. Our findings demonstrate that DDCs provide additional optionality for developing next-generation antibody therapeutics with broader utility and improved efficacy in cancer treatment.}, archive = {J_JACS}, author = {Fangzhu Zhao and Yan Wu and Kaitlin Schaefer and Yun Zhang and Kun Miao and Zi Yao and Snehal D. Ganjave and Kaan Kumru and Trenton M. Peters-Clarke and Alex Inague and James A. Olzmann and Kevin K. Leung and James A. Wells}, doi = {10.1021/jacs.5c15047}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39912--39925}, shortjournal = {J. Am. Chem. Soc.}, title = {Hijacking extracellular targeted protein Degrader–Drug conjugates for enhanced drug delivery}, volume = {147}, year = {2025}, }
• (2025). Spin-state and reorganization energy considerations for metal-centered photoredox catalysis. JACS, 147(43), 39898--39911. (www)

  @article{ , abstract = {Transition-metal complexes featuring metal-centered excited states have recently emerged as mechanistically distinct platforms for selective photochemistry, including photoredox catalysis. Among these, Co(III) complexes have demonstrated productive photoinduced electron transfer via the 3 T 1 metal-centered state. In contrast, photoreactivity from the 5 T 2 metal-centered state in Fe(II) polypyridyl complexes remains limited. Building on our prior report concerning reactivity associated with the 5 T 2 state in [Fe(tren(py) 3 )] 2+ (tren(py) 3 = tris(2-pyridylmethyliminoethyl)-amine), we introduced stronger-field ligands in an effort to increase excited-state energies of Fe(II) polypyridyl complexes and enhance reactivity. Despite achieving nanosecond-scale excited-state lifetimes and favorable thermodynamic driving forces, no photoreactivity was observed. Reinvestigation of the observations previously reported for [Fe(tren(py) 3 )] 2+ revealed interactions between the metal complex and the substrate in their respective ground states that mimicked dynamic quenching of the chromophore, prompting a reassessment of mechanistic considerations inherent in leveraging reductive chemistry from the 5 T 2 excited state of Fe(II). Our analysis indicates that electron transfer from the 5 T 2 excited state of a low-spin d 6 metal is subject to significant barriers both in terms of reorganization energies and spin conservation that undermines its ability to act as an electron donor for photoredox catalysis. In contrast, ligand fields that are sufficient to stabilize the 3 T 1 excited state have available to them numerous spin-allowed and, in certain cases, near-barrierless pathways to engage in excited-state electron transfer (both oxidative and reductive depending on the identity of the metal). These results highlight the critical role of spin-state changes and their associated reorganization energy requirements in metal-centered photoredox catalysis.}, archive = {J_JACS}, author = {Bekah E. Bowers and Björn Pfund and Hayden F. Beissel and Atanu Ghosh and James K. McCusker}, doi = {10.1021/jacs.5c14935}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39898--39911}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin-state and reorganization energy considerations for metal-centered photoredox catalysis}, volume = {147}, year = {2025}, }
• (2025). Rare-earth-catalyzed selective hydrosilylation of iminocyclopropanes: Efficient access to azasilacyclopentanes. JACS, 147(43), 39890--39897. (www)

  @article{ , abstract = {Catalytic hydrosilylation of iminocyclopropanes (ICPs) may selectively yield intriguing silicon–nitrogen heterocycles. Rare-earth alkyl complexes bearing silyl-binaphthyldiamide ligands have been synthesized and employed as catalysts for the hydrosilylation of ICPs with primary silanes. The catalytic reactions selectively yielded a series of azasilacyclopentanes in excellent yields (93–98%) with high selectivity (>99%) at room temperature. The catalytic reactions could be scaled up to the gram scale with 0.5 mol·% loadings of the catalysts. Notably, the azasilacyclopentanes could undergo facile alcoholysis and hydrolysis to give amine-functionalized siloxanes and silanols. The deuterium labeling and kinetic isotopic effect experiments as well as DFT calculations disclosed a catalytic cascade inter- and intramolecular hydrosilylation mechanism. The catalytic key intermediate silyl-binaphthyldiamine rare-earth hydride has been isolated and structurally characterized.}, archive = {J_JACS}, author = {Xiaoming Xu and Yaxin Feng and Fen Wang and Yuhong Liu and Xiufang Xu and Shou-Fei Zhu and Jianfeng Li and Chunming Cui}, doi = {10.1021/jacs.5c14883}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39890--39897}, shortjournal = {J. Am. Chem. Soc.}, title = {Rare-earth-catalyzed selective hydrosilylation of iminocyclopropanes: Efficient access to azasilacyclopentanes}, volume = {147}, year = {2025}, }
• (2025). Iridium-catalyzed twofold C–H/C–H activation and annulation: Access to anti-kasha emission and photosensitive-phosphorescent materials. JACS, 147(43), 39879--39889. (www)

  @article{ , abstract = {The first example of a multifunctional anti-Kasha emission-photosensitive-phosphorescent material has been synthesized via an efficient twofold C–H/C–H activation and annulation protocol. Both experimental data and theoretical calculations have validated the anti-Kasha emission property of phenothiazinium and phenoxazinium salts. Specifically, the anti-Kasha emission property of phenoxazinium salts enables dual-channel emission intensity ratio imaging for visualizing cellular and intercellular structures, while also endowing them with the capability to specifically target mitochondria in living cells. Furthermore, these newly developed photosensitive-phosphorescent materials have been demonstrated to act as efficient photocatalysts in C–H bond functionalization reactions. In addition, the novel phenothiazinium salts demonstrate photosensitive and phosphorescent properties in PVA (poly(vinyl alcohol)) films: upon light irradiation, they undergo a significant blue shift accompanied by ultralong room-temperature phosphorescence, making them highly promising for applications in encryption and multichannel information storage.}, archive = {J_JACS}, author = {Tao Sun and Jingxian Zhang and Ju Zhang and Xianhui Yang and Danni Yang and Tingting Yang and Bijin Li}, doi = {10.1021/jacs.5c14577}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39879--39889}, shortjournal = {J. Am. Chem. Soc.}, title = {Iridium-catalyzed twofold C–H/C–H activation and annulation: Access to anti-kasha emission and photosensitive-phosphorescent materials}, volume = {147}, year = {2025}, }
• (2025). Crystallization-induced diastereomer transformations of Donor–Acceptor cyclopropanes. JACS, 147(43), 39870--39878. (www)

  @article{ , abstract = {We report the first crystallization-induced diastereomer transformations (CIDTs) of donor–acceptor (D–A) cyclopropanes, providing access to important chiral nonracemic building blocks for stereospecific and stereoselective transformations. Lewis acids rapidly epimerize aniline-substituted D–A cyclopropanes through reversible C–C bond cleavage. Formation of the conjugate acid anilinium salt concurrently slows epimerization and enhances the crystallinity of the cyclopropanes. We present the first example of a temperature-dependent switchable stereoselective crystallization, which enables isolation of either diastereomer with high yield and diastereoenrichment. As a complement to the Lewis acid activation paradigm, solvent-promoted epimerization is demonstrated to enable a spontaneous CIDT of an aniline-substituted D–A cyclopropane in the absence of a Lewis acid. In both approaches, products can be isolated by direct filtration of the reaction mixture without the need for further purification. The latter approach was demonstrated on a multidecagram scale. Through manipulation of the aniline and ester functional handles, this method enables access to diastereo- and enantiopure cyclopropanes and derivatives thereof.}, archive = {J_JACS}, author = {Aidan J. Clarkson and Seth O. Fremin and Jeffrey S. Johnson}, doi = {10.1021/jacs.5c14503}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39870--39878}, shortjournal = {J. Am. Chem. Soc.}, title = {Crystallization-induced diastereomer transformations of Donor–Acceptor cyclopropanes}, volume = {147}, year = {2025}, }
• (2025). Catalytic enantioselective perezone-type [5 + 2] cycloaddition. JACS, 147(43), 39860--39869. (www)

  @article{ , abstract = {Here we report the first catalytic enantioselective Perezone-type [5 + 2] cycloaddition, enabling convenient access to a variety of bicyclo[3.2.1]octanes and other complex carbocycles from readily available quinone ketals and alkenes. Enabled by a new chiral squaramide catalyst, intermolecular C–C bond formation was achieved with excellent enantio- and diastereoselectivities. The highly enantioenriched and densely functionalized products can be transformed into diverse intriguing complex carbocycles that may not be straightforward to access by conventional methods. Mechanistic studies and DFT studies provided important insights into the mechanism, in which substrate solvation is a rate-limiting step, while C–C bond formation is fast and stepwise. Activation of the Lewis acid TESOTf by the chiral hydrogen bond donor catalyst is crucial not only for substrate activation and solvation but also for enantiocontrol via the catalyst-bound chiral counter anion.}, archive = {J_JACS}, author = {Liangliang Yang and Chaoshen Zhang and Jianwei Sun}, doi = {10.1021/jacs.5c14484}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39860--39869}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic enantioselective perezone-type [5 + 2] cycloaddition}, volume = {147}, year = {2025}, }
• (2025). Pt particles on a dynamic TiO2 support in near-ambient Conditions–Disentangling size, pressure, and support effects. JACS, 147(43), 39846--39859. (www)

  @article{ , abstract = {Platinum particles on reducible oxides are known to form complex and highly dynamic catalyst systems at elevated pressures and temperatures, often adopting active structures that differ from those found at room temperature and under ultrahigh vacuum (UHV). Here, we study the oxidation and structural evolution of subnanometer Pt clusters and nanoparticles supported on rutile TiO 2 (110) across an oxygen pressure range from UHV to 0.1 mbar, using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), scanning tunneling microscopy (STM) under UHV and NAP conditions, and low-energy ion scattering (LEIS). Our results reveal distinct differences in oxidation behavior and thermal stability between Pt nanoparticles and clusters, which are further modulated by the support stoichiometry and oxygen pressure. Small Pt clusters become oxidized even at room temperature but are susceptible to accelerated sintering in 0.1 mbar O 2 at elevated temperatures. In contrast, well-crystallized Pt nanoparticles on near-stoichiometric TiO 2 show weaker oxidation. On a reduced, defective TiO 2 support, Pt instead quickly becomes deeply buried by new titania layers, which are formed during support reoxidation. This process appears to result primarily from interactions of the support with the gas phase, unlike the classical, self-limited encapsulation that is induced by the strong metal–support interaction (SMSI). Finally, we address the full complexity of real catalysts in a direct side-by-side comparison of the single-crystalline model system with a Pt-loaded TiO 2 powder catalyst (P25). We conclude that the stoichiometry of the model supports must be carefully chosen and controlled to accurately reproduce the expected state of powder supports during redox reactions.}, archive = {J_JACS}, author = {Florian Kraushofer and Matthias Krinninger and Marina de la Higuera-Domingo and Lorenz Falling and Lukas Strauss and Sebastian Kaiser and Mohammad Salehi and Gaurav Anand and Virginia Pérez Dieste and Monika Blum and Barbara A. J. Lechner}, doi = {10.1021/jacs.5c14353}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39846--39859}, shortjournal = {J. Am. Chem. Soc.}, title = {Pt particles on a dynamic TiO2 support in near-ambient Conditions–Disentangling size, pressure, and support effects}, volume = {147}, year = {2025}, }
• (2025). Mechanistic insights into nitroarene hydrogenation dynamics on pt(111) via in situ tip-enhanced raman spectroscopy. JACS, 147(43), 39838--39845. (www)

  @article{ , abstract = {Mechanistic insights into the molecular-level dynamics of nitroarene hydrogenation on Pt remain limited, largely because most prior studies rely on ex situ , ensemble-averaged measurements, or simulations considered in isolation. Here, we address this gap and demonstrate a novel methodology combining in situ tip-enhanced Raman spectroscopy (TERS) with density functional theory (DFT) modeling to track, at a well-defined single plasmonic junction, the hydrogenation of chloronitrothiophenol (CNTP) on atomically flat Pt(111). In situ TERS captures the dynamic transformation of CNTP → chloroaminothiophenol (CATP) under ambient H 2 exposure with a characteristic time scale of ∼6 s. Complementary DFT modeling maps the reaction energetics, revealing novel mechanistic insights: CNTP desorption is rapid initially (barrier 0.61 eV) but slows down once the Pt(111) surface is at about half-coverage; molecular bending on the half-covered Pt(111) surface is barrierless and exergonic; the first hydrogen addition to CNTP is facile (barrier 0.26 eV), while the second hydrogen addition is kinetically most demanding (barrier 0.83 eV), yielding a time scale of seconds that matches experimental results and identifies the rate-determining step. These findings advance molecular-level understanding of nitroarene hydrogenation on Pt(111) and demonstrate in situ TERS integrated with first-principles DFT modeling as a powerful platform for operando mechanistic studies of heterogeneous catalytic processes at the nanoscale.}, archive = {J_JACS}, author = {Zhen-Feng Cai and Meghna A. Manae and Zi-Xi Tang and Anastasiia Moskalenko and Yao Zhang and Jeremy O. Richardson and Naresh Kumar}, doi = {10.1021/jacs.5c14338}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39838--39845}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic insights into nitroarene hydrogenation dynamics on pt(111) via in situ tip-enhanced raman spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Ultrafast conversion of CO2 into C3–C4 diols in a synergistic electrochemical and AI-assisted biosynthesis system. JACS, 147(43), 39827--39837. (www)

  @article{ , abstract = {Using CO 2 as a feedstock to produce high-value chemicals is attractive but remains far from effective in terms of technical application. In particular, efficient conversion of CO 2 into industrially important C 3+ diols is still challenging. Here, we present a carbon-negative electrochemical-biosynthesis cascade system for synthesizing C 3 –C 4 diols (1,3-propanediol, 1,3-PDO, and 1,3-butanediol, 1,3-BDO) directly from CO 2 at exceptionally high productivities. This integrated platform combines a CuZn-catalyzed electrochemical CO 2 reduction reactor operating at Ampere-level current densities (−1,100 mA cm –2 ) to produce ethanol (close to 1,200 μmol h –1 cm –2 ) with a biocatalytic module for C–C bond extension. A custom-designed J-T membrane prevents ethanol crossover, enabling accumulation to 4.6 g L –1 h –1 , while engineered Thermotoga maritima DERA variants (S233D/F43T) exhibit enhanced catalytic efficiency through a synergistic approach combining AI and rational design, achieving a 1,3-PDO production rate of 1.8 g L –1 h –1 . In situ spectroscopic studies reveal that the presence of key intermediates *CO and *OH, along with the formation of a hydrogen-bonding network, significantly enhances the electrochemical synthesis of ethanol, while molecular dynamics simulations clarify mutation-induced conformational changes in DERA that improve substrate affinity. The system’s versatility is further demonstrated by extending ethanol to 1,3-BDO at 1.0 g L –1 h –1 . This work establishes a scalable paradigm for synthesizing multi-carbon diols from CO 2 , bridging the gap between electrocatalysis and synthetic biology for sustainable manufacturing.}, archive = {J_JACS}, author = {Yonglong Li and Bing Zhang and Yizhou Wu and Tang Tang and Aocong Guan and Qianqing Xu and Linqin Wang and Jianming Liu and Licheng Sun and An-Ping Zeng}, doi = {10.1021/jacs.5c14039}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39827--39837}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrafast conversion of CO2 into C3–C4 diols in a synergistic electrochemical and AI-assisted biosynthesis system}, volume = {147}, year = {2025}, }
• (2025). Entropy-governed zeolite intergrowth. JACS, 147(43), 39818--39826. (www)

  @article{ , abstract = {Entropy, stemming from the second law of thermodynamics, drives the system toward greater disorder. In zeolite design, introducing controlled disorder enhances mass transfer, yet most strategies focus on regulating structure from the perspective of energy, with few efforts devoted to entropy effect control. Here, we propose an entropy strategy by enhancing the translational and rotational confinement of large organic structure-directing agents (OSDAs), leading to an order of magnitude larger change in free energy (1.8 kJ/mol SiO 2 ) than the enthalpy effect. This in turn promotes compensation in the configurational entropy of zeolite structures, leading to the formation of highly disordered intergrown zeolites (e.g., ITH/ITR, MFI/MEL, etc.). Our entropy strategy paves a novel perspective for the intergrowth of zeolites, holding significant guidance for the microscopic mechanisms underlying the formation of zeolite skeletons, including highly disordered porous materials.}, archive = {J_JACS}, author = {Mingyu Zhao and Qinming Wu and Xiao Chen and Hao Xiong and Guo Tian and Litang Yan and Fengshou Xiao and Fei Wei}, doi = {10.1021/jacs.5c14291}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39818--39826}, shortjournal = {J. Am. Chem. Soc.}, title = {Entropy-governed zeolite intergrowth}, volume = {147}, year = {2025}, }
• (2025). Sulfur-bridged dual Fe–N4 sites to boost Lithium–Sulfur battery performance. JACS, 147(43), 39805--39817. (www)

  @article{ , abstract = {Despite the growing interest in d-block single-atom catalysts (SACs) for lithium–sulfur (Li–S) batteries, the localized nature of their 3d orbitals imposes a substantial energy barrier for activating sulfur intermediates during redox reactions. This limitation stems from the low mobility of electrons in 3d orbitals, which hampers effective hybridization with the 2p orbitals of lithium polysulfides (LiPS). Here, we report a single-atom iron catalyst anchored on a nitrogen-doped porous carbon scaffold, featuring a unique axial dual-layer Fe–N 4 structure bridged by a sulfur atom (Fe-SNC), designed to overcome these limitations. The axial configuration, stabilized by the S bridge, enables delocalization of Fe 3d orbitals and promotes dynamic electron transfer between the dual Fe–N 4 layers, thereby enhancing bidirectional Li–S redox kinetics. LiPS adsorption tests, density functional theory (DFT) calculations, symmetric-cell cyclic voltammetry, and potentiostatic deposition/dissolution experiments confirm the superior catalytic activity of Fe-SNC. When applied in Li–S cells, the S@Fe-SNC cathode achieves an initial capacity of 1550 mAh g –1 at 0.1C and 724 mAh g –1 at 3C, retaining 546 mAh g –1 after 1200 cycles at 3C. Under high-sulfur-loading (7.5 mg cm –2 ) and lean-electrolyte conditions ( E / S = 4.7 μL mg –1 ), it reaches excellent areal performance at 8.0 mAh cm –2 . DFT results attribute the high activity to efficient interlayer electron transfer and an asymmetric dynamic spin evolution across the dual Fe–N 4 layers. This asymmetric spin distribution facilitates enhanced d-p orbital hybridization, particularly π-type coupling between Fe 3d xz /yz and S 2p orbitals, thereby improving conductivity, intermediate binding strength, and overall reaction kinetics.}, archive = {J_JACS}, author = {Yapeng Cheng and Jiachen Ma and Canhuang Li and Yao Li and Hao Li and Chaoqi Zhang and Jing Yu and Shichang Cai and Fanglin Wu and Jiawei Zhu and Xiaoyu Bi and Yuchuan Ren and Yanting Xie and Qian Xue and Ren He and Zeyan Li and Ivan Pinto-Huguet and Jordi Arbiol and Jing Lu and Zhengxiao Guo and Haining Zhang and Andreu Cabot}, doi = {10.1021/jacs.5c14250}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39805--39817}, shortjournal = {J. Am. Chem. Soc.}, title = {Sulfur-bridged dual Fe–N4 sites to boost Lithium–Sulfur battery performance}, volume = {147}, year = {2025}, }
• (2025). Understanding electrochemical CO2 reduction selectivity of cu binary alloys from electronic structure descriptors. JACS, 147(43), 39796--39804. (www)

  @article{ , abstract = {We investigate the electrochemical reduction of carbon dioxide (CO 2 RR) using Cu-M (M = Ni, Pd, Ag, Au, Zn, Cr) binary alloys. Through experimental and theoretical analysis, we explore the structural and electronic properties of these alloys and their impact on CO 2 RR product selectivity. Our findings reveal that the d-band center of Cu-M alloys serves as a crucial descriptor, influencing product distribution. As the d-band center increases, more CO is produced, while the formation of C 2 products (ethylene and ethanol) follows a volcano-like trend. We also observe a linear scaling relationship between the d-band center and ethylene/ethanol selectivity, providing opportunities for fine-tuning product selectivity. The observation is explained by theoretical calculations that suggest that the d-band center effectively changes the relative binding of *CCH vs *CHCHOH, thereby controlling product selectivity into ethylene vs ethanol formation. We also find that this d-band center dependence is what makes the *CCH vs *CHCHOH adsorption energy, when properly corrected for alloy composition-dependencies, the most reliable theoretically accessible descriptor for ethylene/ethanol selectivity, while the *O adsorption energy does not show a clear correlation with experimental results. This study enhances our understanding of CO 2 RR catalysis and offers guidelines for designing Cu-based alloy electrocatalysts with improved activity and selectivity for sustainable CO 2 conversion.}, archive = {J_JACS}, author = {Yujin Jung and Hafiz Ghulam Abbas and Soeun Kim and Beomil Kim and Junsic Cho and Sunghoon Han and Hakhyeon Song and Yuta Takaoka and Jun Tae Song and Tatsumi Ishihara and Chang Hyuck Choi and Stefan Ringe and Jihun Oh}, doi = {10.1021/jacs.5c14093}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39796--39804}, shortjournal = {J. Am. Chem. Soc.}, title = {Understanding electrochemical CO2 reduction selectivity of cu binary alloys from electronic structure descriptors}, volume = {147}, year = {2025}, }
• (2025). Dual-site cobalt-doped RuO2/TiO2 electrocatalyst enables stable and cost-efficient acidic oxygen evolution for PEM water electrolysis. JACS, 147(43), 39781--39795. (www)

  @article{ , abstract = {Developing efficient, cost-effective, and durable electrocatalysts for proton exchange membrane water electrolysis (PEMWE) remains a significant challenge, requiring the stabilization and enhancement of catalyst activity under harsh conditions. Here, we present cobalt-doped ruthenium dioxide (Co 0.3 Ru 0.7 O 2 ) on TiO 2 as an electrocatalyst toward an acidic oxygen evolution reaction. The Co 0.3 Ru 0.7 O 2 –TiO 2 achieves an impressive overpotential of 322 mV at 1 A cm –2 and demonstrates stable operation for over 1000 h at 500 mA cm –2 in a PEMWE device. Comprehensive experimental and theoretical calculation results demonstrate that the doping of Co atoms into the rutile RuO 2 lattice optimizes the geometric configuration. Moreover, the lattice-matched interface between Co 0.3 Ru 0.7 O 2 and TiO 2 promotes interfacial electron redistribution and stabilizes active centers under oxidative conditions. This facilitates a dual-site fully parallel oxidation (DFO) pathway in which intermediates are synchronously adsorbed and desorbed at Ru and Co sites, enabling direct O–O coupling. This work highlights the synergistic effect of the Ru–Co dual sites and TiO 2 support in establishing a stable, self-regulating electronic environment that drives efficient intermediate transformation via the DFO mechanism.}, archive = {J_JACS}, author = {Jing Liang and Yuanyuan Zhao and Chenyu Yang and Shandong Zhu and Liang Wang and Ke Xu and Xueliang Mu and Yong Han and Zhi Liu and Zhiwei Zhao and Wei Liu and Fei Li and Zhangquan Peng and Edmund C. M. Tse and Qinghua Liu and Junfeng Gao and Qing Li and Jianfeng Li and Jinxuan Liu}, doi = {10.1021/jacs.5c14137}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39781--39795}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual-site cobalt-doped RuO2/TiO2 electrocatalyst enables stable and cost-efficient acidic oxygen evolution for PEM water electrolysis}, volume = {147}, year = {2025}, }
• (2025). Alternating current-driven diol epimerization via a Deplete–Regenerate strategy. JACS, 147(43), 39770--39780. (www)

  @article{ , abstract = {Epimerization is a powerful strategy for stereochemical editing, granting access to under-represented isomers without altering molecular connectivity. Although photocatalytic methods have recently expanded the epimerization toolkit, electrocatalytic alternatives have remained limited by redox incompatibilities that preclude simultaneous oxidation and reduction under direct current (DC) electrolysis. Here we report a general electrocatalytic epimerization enabled by alternating-current (AC) electrolysis. A deplete–regenerate strategy enables temporal separation of redox events: the thiol mediator is exhaustively oxidized during the anodic half-cycle (depletion prior to substrate activation), and subsequent polarity reversal regenerates the thiol in situ to quench the radical intermediate. This time-domain control allows the oxidative and reductive steps to occur in distinct phases. The method accommodates a broad range of functional groups and is compatible with complex bioactive molecules. Mechanistic investigations (kinetic analysis, cyclic voltammetry, and deuterium labeling) support a model wherein the AC waveform sustains catalytic turnover by resolving the redox incompatibility through this time-separated deplete–regenerate sequence.}, archive = {J_JACS}, author = {Shaolong Qi and Duren Yin and Changqin Huang and Jingyun Huang and Jianchun Wang}, doi = {10.1021/jacs.5c13881}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39770--39780}, shortjournal = {J. Am. Chem. Soc.}, title = {Alternating current-driven diol epimerization via a Deplete–Regenerate strategy}, volume = {147}, year = {2025}, }
• (2025). Achieving record-breaking urea synthesis on Crystalline–Amorphous hybrid via electrochemical-chemical looping. JACS, 147(43), 39761--39769. (www)

  @article{ , abstract = {Electrocatalytic C–N coupling of nitrate and CO 2 represents a paradigm shift in sustainable urea synthesis. We demonstrate that amorphous CuO x -coated crystalline Cu nanowires achieve a record-breaking urea yield rate of 0.89 mol h –1 g –1 via novel electrochemical-chemical looping. Mechanistic investigations reveal a three-step catalytic cycle: (i) electro-reductive generation of Cu 0 and oxygen vacancies (O v ); (ii) O v -mediated nitrate activation via oxygen atom insertion, spontaneously yielding nitrogen-bonded nitrite (*NO 2 ) while oxidizing Cu 0 to catalytically active Cu + ; and (iii) Cu + -catalyzing C–N coupling between *NO 2 and CO 2 to form urea. This pathway circumvents conventional rate-limiting nitrate reduction step, reducing the electron transfer requirement from 16e – to 12e – for urea synthesis. Notably, direct nitrite utilization fails to generate Cu + or nitrogen-bonded intermediates, instead forming oxygen-bonded species with markedly reduced C–N coupling activity–a finding that overturns conventional understanding. Our work establishes new fundamental principles for efficient urea synthesis and provides insights into catalyst design and green chemistry.}, archive = {J_JACS}, author = {Zhong Cheng and Xiaodeng Wang and Dafeng Yan and Xupeng Qin and Dawei Chen and Chu Zhang and Yujie Wang and Yansong Zhou and Chade Lv and Peilian Hou and Kefan Zhang and Peng Jin and Yangyang Zhou and Qinghua Liu and Kaizhi Gu and Xiaoxiao Wei and Chen Chen and Shuangyin Wang}, doi = {10.1021/jacs.5c13721}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39761--39769}, shortjournal = {J. Am. Chem. Soc.}, title = {Achieving record-breaking urea synthesis on Crystalline–Amorphous hybrid via electrochemical-chemical looping}, volume = {147}, year = {2025}, }
• (2025). Synthesis of precisely modified ribonucleic acid to reveal the site-specific effect of modification on message ribonucleic acid translation. JACS, 147(43), 39751--39760. (www)

  @article{ , abstract = {In the past few decades, RNA modifications have significantly promoted the development of mRNA therapy. However, limited knowledge has been revealed on the site-specific effect of the modification, which raised biosafety concerns on mis-modified or overmodified mRNA drugs. Here in this study, we proposed a template-directed strategy for the synthesis of site-specifically modified long ssRNA. Long single-strand RNAs (over 300 nt) with single-base resolution modifications have been successfully prepared, including m 6 A, m 5 C, m 1 Ψ, Ψ, I, Br–dU, Cy3, Cy5, FAM, 2’-F, 2’-OMe, 2’-MOE, 2’-Propargyl, LNA, cET, and PS modifications. Based on this method, the impact of the precisely modified patterns of mRNA on translation has been investigated. We have demonstrated that the modification of m 1 Ψ on specific sites could increase translation fidelity while retaining low immunogenicity. It can be anticipated that our study will provide a guideline for mRNA modification to precisely adjust their functions, which will further promote next-generation mRNA drugs and RNA epigenetics research.}, archive = {J_JACS}, author = {Yufan Pan and Chenyou Zhu and Yuan Zhuang and Xin Li and Rui Xu and Yifan Jiang and Yuanchen Dong and Chuan He and Dongsheng Liu and Xi Zhang}, doi = {10.1021/jacs.5c13616}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39751--39760}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of precisely modified ribonucleic acid to reveal the site-specific effect of modification on message ribonucleic acid translation}, volume = {147}, year = {2025}, }
• (2025). Stiboviologens-decorated Sb4O6 clusters for electrocatalytic proton reduction via coupled electron sponge and proton engine. JACS, 147(43), 39739--39750. (www)

  @article{ , abstract = {Antimony (Sb)-based materials show great promise for hydrogen evolution reaction (HER) catalysis owing to their unique electronic structures and efficient proton–electron transfer capabilities. However, despite their potential, the molecular-level development of Sb-based catalysts has been hindered by significant synthetic challenges, particularly the difficulty in constructing well-defined molecular architectures, such as Sb–porphyrins or clusters. Herein, we report a new synthetic strategy to access two novel stiboviologens-decorated Sb 4 O 6 clusters ( SbVO-Me and SbVO-Ph ) via directed oxidative coupling of stiboviologens. SbVO-Me and SbVO-Ph exhibit excellent redox activity, multielectron transfer capacity, and robust electrochromic behavior. DFT calculations and electrostatic potential mapping analyses reveal a cooperative electron–proton management mechanism: the viologen moiety acts as an “electron sponge,” mediating charge accumulation and delivery, while the tetraantimony hexaoxide (Sb 4 O 6 ) core serves as a “proton engine” to accelerate proton transport. In homogeneous acidic HER catalysis, the system achieves an overpotential of 535 mV with a Faradaic efficiency of 74.5%. Upon immobilization, the heterogeneous system delivers enhanced activity with a reduced overpotential of 182 mV. Mechanistic investigations support a cooperative catalytic pathway involving the viologens and Sb centers. This study introduces stiboviologens as a new class of main-group molecular catalysts, expanding the design landscape for viologen-based redox systems and offering new opportunities in proton-coupled electrocatalysis.}, archive = {J_JACS}, author = {Liang Xu and Jianyue He and Yi Qiao and Zehua Wu and Yawen Li and Guoping Li and Feng Liu and Xin Bo and Yu Fang and Gang He}, doi = {10.1021/jacs.5c13539}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39739--39750}, shortjournal = {J. Am. Chem. Soc.}, title = {Stiboviologens-decorated Sb4O6 clusters for electrocatalytic proton reduction via coupled electron sponge and proton engine}, volume = {147}, year = {2025}, }
• (2025). Photoetching-generated redox pairs in confined layered structure boost single-electron-transfer-mediated photocatalysis. JACS, 147(43), 39732--39738. (www)

  @article{ , abstract = {The single-electron-transfer (SET)-mediated photocatalytic process, as a sustainable and environmentally friendly strategy for synthesizing high-value-added chemicals, faces significant limitations due to rapid quenching of photoexcited electrons and low electron utilization efficiency of photocatalysts. Herein, a redox pair featuring the colocalization of high- and low-valent elements in a group was proposed to realize efficient photoelectron utilization, enabling the storage and release of photogenerated electrons. By taking bismuth oxyiodate (BiOIO 3 ) as a typical model framework, a photoetching strategy was developed to selectively construct iodine redox pairs (I δ+ /IO 3 – ) within the polar soft [IO 3 ] − layers, while maintaining the structural integrity of the [Bi 2 O 2 ] 2+ layers. Through comprehensive theoretical calculations and spectral analyses, it was demonstrated that the as-designed iodine redox pairs (I δ+ /IO 3 – ) significantly modified the electronic structure of BiOIO 3 , with prolonged charge carrier lifetimes and an increase in hot-electron density. This work offers a new strategy to improve the efficiency of electronic utilization and realize electron-mediated high-value-added chemical synthesis.}, archive = {J_JACS}, author = {Junkang Ge and Jun Zhao and Hanghao Ying and Chao Yang and Zhihao Li and Zongpeng Song and Haiou Zhu and Xiaodong Zhang and Yi Xie}, doi = {10.1021/jacs.5c13187}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39732--39738}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoetching-generated redox pairs in confined layered structure boost single-electron-transfer-mediated photocatalysis}, volume = {147}, year = {2025}, }
• (2025). “De novo” construction of planar-chiral ferrocenes via Palladium/Chiral norbornene cooperative catalysis. JACS, 147(43), 39721--39731. (www)

  @article{ , abstract = {Transition-metal-catalyzed asymmetric C–H functionalization has emerged as a powerful strategy for constructing planar-chiral ferrocenes (PCFs). However, current methods typically require preinstallation of a directing group (DG) and are usually limited to monofunctionalization. Herein, we report a “de novo” construction of PCFs via Pd/NBE* cooperative catalysis, employing a unique bulky (C1,C4)-bridgehead-modified chiral norbornene as the cocatalyst as well as the only chiral source. This approach enables the formation of two new chemical bonds in a single step from simple iodoferrocenes. A series of planar-chiral isoquinolone-fused ferrocenes are quickly obtained with up to >99% ee. Mechanistic studies reveal that the ortho -C–H activation step serves as the enantio-determining step, while the reductive elimination is not only the rate-determining step but also plays a pivotal role in further enhancing the enantioselectivity. The synthetic utility is highlighted by diverse transformations of products and the development of a powerful NAD(P)H coenzyme for biomimetic asymmetric hydrogenation of olefins.}, archive = {J_JACS}, author = {Lisha Li and Jinxiang Ye and Liying Zhao and Lan Zhou and Shuang Deng and Dongkai Wang and Yabin Zhang and Hengjiang Cong and Qianghui Zhou and Hong-Gang Cheng}, doi = {10.1021/jacs.5c13420}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39721--39731}, shortjournal = {J. Am. Chem. Soc.}, title = {“De novo” construction of planar-chiral ferrocenes via Palladium/Chiral norbornene cooperative catalysis}, volume = {147}, year = {2025}, }
• (2025). Bioinspired carbonic anhydrase mimics with Zr–OH sites and size-tunable nanopockets for efficient bidirectional catalysis of CO2 hydration. JACS, 147(43), 39708--39720. (www)

  @article{ , abstract = {Carbonic anhydrase (CA)-mimetic enzymes display promising potential in CO 2 -related catalytic applications, whereas currently designed CA mimics are limited to mimicking the active site and nanopockets. Here, we report the de novo design of bioinspired Zr–OH sites and size-tunable nanopockets via Zr-organic framework structures for the efficient catalysis of CO 2 hydration and HCO 3 – dehydration. Competitive coordination modulation enhances Zr–OH site density and accessibility. The high connectivity of the ligand increases the sensitivity of the Zr-organic framework to ligand defects, while its inherently large size provides near-mesoporous-scale nanopockets. This design enables exceptional 4-nitrophenyl acetate hydrolysis performance ( V max = 3.86 μM s –1 and TON = 29.92 × 10 –3 s –1 ), superior to the state-of-the-art CA mimics. Meanwhile, we systematically elucidate the catalytic mechanism of Zr–OH and show that it interacts with CO 2 to form bidentate carbonate intermediates─similar to the catalytic mechanism of natural CA. Furthermore, the Zr-organic framework can also catalyze the dehydration of bicarbonate, which is consistent with the bidirectional character of natural CA. This work provides fundamental insights into the design of atomic sites and the regulation of nanopockets in enzyme mimics, as well as a promising strategy for preparing high-performance CA mimics for CO 2 -related applications.}, archive = {J_JACS}, author = {Wenjie Xu and Chao He and Qian Zhu and Shuang Li and Hao Wu and Yi Wang and Mao Wang and Shudong Sun and Chong Cheng and Changsheng Zhao}, doi = {10.1021/jacs.5c13405}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39708--39720}, shortjournal = {J. Am. Chem. Soc.}, title = {Bioinspired carbonic anhydrase mimics with Zr–OH sites and size-tunable nanopockets for efficient bidirectional catalysis of CO2 hydration}, volume = {147}, year = {2025}, }
• (2025). Molecular insights into the spontaneous generation of CO2 in reaction of CO and HOCl at Air–Water interfaces. JACS, 147(43), 39701--39707. (www)

  @article{ , abstract = {The final step for CO in fossil fuel combustion and tropospheric chemistry is its conversion to CO 2 via ·OH oxidation, which represents a major source of greenhouse gas emissions and has been extensively studied. However, the mechanisms for CO-to-CO 2 transformation beyond ·OH-mediated pathways in the troposphere remain poorly understood. Herein, we identify a novel atmospheric CO 2 generation pathway driven by a heterogeneous reaction between CO and HOCl at air–water interfaces, which operates independently of ·OH. Using ab initio molecular dynamics, we elucidate a stepwise mechanism: (i) coordination of the HO moiety of HOCl with the C atom of CO, forming a HOCO intermediate, followed by (ii) Cl atom transfer to the C center accompanied by simultaneous release of HCl and (iii) dissociation of the formed HCl. The reaction exhibits a remarkably low free-energy barrier (Δ G TS = 13.6 kcal mol –1 ) at approximately 300 K. More importantly, Δ G TS decreases with decreasing temperature. When the temperature decreases to 243 K, the reaction is almost spontaneous (Δ G TS = 1.7 kcal mol –1 ). These findings have further important implications for understanding acid rain formation and O 3 depletion mechanisms.}, archive = {J_JACS}, author = {Fanqi Zeng and Xinlu Yu and Xiaofan Li and Hong-bin Xie and Jingwen Chen and Deming Xia and Joseph S. Francisco}, doi = {10.1021/jacs.5c13341}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39701--39707}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular insights into the spontaneous generation of CO2 in reaction of CO and HOCl at Air–Water interfaces}, volume = {147}, year = {2025}, }
• (2025). Pronounced catalytic enhancement through phase partitioned Metal–Organic framework gas shuttles. JACS, 147(43), 39693--39700. (www)

  @article{ , abstract = {Three-phase catalytic processes, such as hydrogenation, play a vital role in the chemical industry. However, the low solubility of gases in conventional solvents often limits reaction rates due to poor mass transfer. To tackle this challenge, current approaches rely on high pressures, elevated temperatures, or specialized reactor designs─measures that significantly increase capital costs. Here we report the design of a phase partitioned metal–organic framework, U6P@U6, featuring a hydrophobic UiO-66 core that can remain porous in water, and a hydrophilic UiO-66 exterior that ensures colloidal stability. In a model hydrogenation reaction of hydroxymethylfurfural to 2,5-bis(hydroxymethyl)furan catalyzed by Pd-on-carbon, U6P@U6 functions as a permanently porous gas shuttle that can efficiently transport hydrogen from the gas–liquid interface to catalyst surfaces. We show that addition of only 3.7 wt % of U6P@U6 to the reaction mixture resulted in a 350% increase in HMF conversion due to accelerated H 2 mass transfer. This allows for six times the amount of Pd-on-carbon catalyst to be used in the reaction without mass transfer limitations. A mechanistic study reveals that the enhancement of mass transfer results from a 140-fold increase in the diffusion rate of H 2 into the porous particles at the gas–liquid interface compared with that into water.}, archive = {J_JACS}, author = {Shilin Wu and David M. Huang and Siqi Li and Matilda O’Brien and Chunhui Wu and Shuyun Ding and Yinghao Chu and Ningjie Fang and Jack D. Evans and Christian J. Doonan and Tao Li}, doi = {10.1021/jacs.5c13292}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39693--39700}, shortjournal = {J. Am. Chem. Soc.}, title = {Pronounced catalytic enhancement through phase partitioned Metal–Organic framework gas shuttles}, volume = {147}, year = {2025}, }
• (2025). Highly selective and stable covalent organic framework electrocatalysts for sustainable chlorine evolution. JACS, 147(43), 39681--39692. (www)

  @article{ , abstract = {The electrochemical chlorine evolution reaction (CER) is crucial for the chlor-alkali industry but is often hindered by the competing oxygen evolution reaction (OER). The current electrocatalysts for CER have been predominantly metal-based or noble-metal-based materials, such as dimensionally stable anodes (DSAs). Herein, we synthesized a series of metal-free covalent organic frameworks (Tp-Pa-COFs), showing an unexpected CER activity with an overpotential (102 mV) lower than DSA (182 mV) at a current density of 400 mA cm – 2 at 90 °C. The Tp-Pa-COF showed superior CER selectivity (100 ± 4%) and stability (over 200 h) compared to noble metal and non-noble metal catalysts. Through operando characterization and theoretical calculations, we identified carbonyl and amine groups as active sites, where preferential Cl – adsorption breaks the conventional CER-OER scaling relationship. This study highlights the potential of COF-based materials as highly efficient, sustainable alternatives for industrial chlorine production, advancing the development of metal-free electrocatalysts.}, archive = {J_JACS}, author = {Yunbo Dai and Zhangyi Xiong and Haoyu Yin and Chunyu Lai and Xiaole Weng and Zhijie Chen and Le Shi}, doi = {10.1021/jacs.5c13132}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39681--39692}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly selective and stable covalent organic framework electrocatalysts for sustainable chlorine evolution}, volume = {147}, year = {2025}, }
• (2025). Reversible on-demand activation of acid-catalyzed dynamic polymers for gradient-driven reshaping. JACS, 147(43), 39671--39680. (www)

  @article{ , abstract = {Covalent adaptable networks (CANs) unite recyclability and mechanical stability by leveraging externally triggered bond exchange. However, a significant challenge remains in achieving a sharp reversible transition between dynamic and static network states, which broadly limits their applicability. This work introduces a merocyanine photoacid for precise and reversible spatiotemporal control over dynamic bond exchange in thiol–ene photopolymers. When exposed to visible light, the photoacid’s activated spiropyran form enables dynamic network rearrangements through acid-catalyzed transesterification. Switching off the light yields the deactivated merocyanine form and a creep-resistant polymer network. Stress relaxation experiments clearly demonstrate a remarkable difference in mechanical properties resulting from the photoacid’s isomerization state. The rapid isomerization kinetics and fatigue resistance of this system are utilized to generate gradients of active photoacid at the micrometer level. Applied in a novel mold-free reshaping approach, bending radii are predictable based on the introduction of an empirical model. Finally, the successful fabrication of diverse microstructures via multiphoton laser writing highlights the future potential of these reversibly switchable CANs in light-controlled micromechanics.}, archive = {J_JACS}, author = {David Reisinger and Laura Wimberger and Roman Korotkov and Markus Alfreider and Timothy F. Scott and Neil R. Cameron and Cyrille Boyer and Sandra Schlögl}, doi = {10.1021/jacs.5c13227}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39671--39680}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible on-demand activation of acid-catalyzed dynamic polymers for gradient-driven reshaping}, volume = {147}, year = {2025}, }
• (2025). Programmable higher-order topological phases in open-shell Metal–Organic frameworks. JACS, 147(43), 39662--39670. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) offer remarkable structural and functional tunability across chemistry, physics and materials science, yet most MOFs built from closed-shell ligands remain wide-gap insulators, limiting their electronic functionality. Here we introduce a general strategy for imparting programmable topology to MOFs by leveraging open-shell ligands. Integrating radical nanographene linkers─featuring singly occupied molecular orbitals─into cobalt-coordination networks via on-surface synthesis, we create MOFs on Au(111) with emergent electronic states spanning the Fermi level. As a proof of concept, we synthesize Sierpiński-triangle fractal MOFs and directly observe topologically protected corner modes─the hallmarks of higher-order topological phases─using low-temperature scanning tunneling microscopy/spectroscopy. Through precise, molecule-by-molecule tip-induced assembly, we systematically tune the fractal hierarchy and monitor the evolution of topological states, supported by tight-binding simulations that align with experimental data. Our work establishes open-shell ligand chemistry as a versatile route to topological MOFs, paving the way for designer molecular quantum materials with programmable electronic and quantum properties.}, archive = {J_JACS}, author = {Can Li and Ying Wang and Yashi Jiang and Yufeng Liu and Yi Wu and Yan-Jie Han and Zhen-Qiang Chen and Liang Liu and Xiaoxue Liu and Dandan Guan and Yaoyi Li and Hao Zheng and Canhua Liu and Pei-Nian Liu and Jinfeng Jia and Deng-Yuan Li and Shiyong Wang}, doi = {10.1021/jacs.5c13203}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39662--39670}, shortjournal = {J. Am. Chem. Soc.}, title = {Programmable higher-order topological phases in open-shell Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Aqueous Zinc–Organoiodine battery with high kinetics and dense cathodes. JACS, 147(43), 39652--39661. (www)

  @article{ , abstract = {As a promising candidate for sustainable and safe energy storage systems, aqueous zinc-ion batteries have garnered significant attention. Even though organic compounds have advantages, their limited electronic conductivity, solubility of redox intermediates, and low utilization of active groups limit the practical applicability. Here, through the innovative design of a charge-transfer complex between phenazine (PNZ) and iodine (I 2 ), PNZ–I 2 exhibits greatly improved conductivity, enabling fast reaction kinetics and dense cathodes with a mass loading of nearly 60 mg·cm –2 . The formation of N–H···I hydrogen bonds reduces the solubility of intermediates, leading to exceptional long-term cycling stability. At a high current density of 3.0 A·g –1 , the battery retains 92% of its capacity after 4500 cycles. A record-stable aqueous (1.1 Ah) AZIB maintains 70% capacity retention after 700 cycles. The recyclability of PNZ–I 2 after cycling in batteries and low cost are directly related to renewable energy and transformative energy technologies.}, archive = {J_JACS}, author = {Jiahao Guo and Zhuo Zhang and Fulong Zhu and Qilong Yang and Yongzhu Fu and Wei Guo}, doi = {10.1021/jacs.5c13131}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39652--39661}, shortjournal = {J. Am. Chem. Soc.}, title = {Aqueous Zinc–Organoiodine battery with high kinetics and dense cathodes}, volume = {147}, year = {2025}, }
• (2025). Virtual ligand-assisted screening for the generation of ketyl radicals from alkyl ketones via photoexcited palladium catalysis. JACS, 147(43), 39640--39651. (www)

  @article{ , abstract = {Ketyl radicals are versatile radical intermediates that enable diverse C–C-bond-forming reactions. However, their generation from substrates with highly negative potentials such as alkyl ketones via single-electron reduction remains underdeveloped. In this study, we report a new strategy that harnesses the strong reducing power of photoexcited palladium species to provide access to ketyl radicals from alkyl ketones and to promote subsequent C–C-bond-forming reactions. The key to this approach is a computationally guided virtual ligand-assisted screening (VLAS) strategy. Mechanistic investigations revealed that back-electron transfer (BET) is the major factor suppressing reactivity. By systematically evaluating virtual phosphine ligands with varying electronic and steric properties, we established design guidelines for ligands that effectively suppress BET and promote the desired transformations. Using the optimized ligands identified through VLAS, we developed efficient reductive couplings and Heck-type reactions involving both unactivated alkenes and alkynes, which are challenging substrates under conventional SmI 2 -mediated conditions. This work highlights a powerful paradigm that integrates photoexcited transition-metal catalysis with in-silico ligand design, enabling control over single-electron-transfer processes and opening new avenues for radical-based synthetic transformations.}, archive = {J_JACS}, author = {Kosaku Tanaka, III and Ren Yamada and Suvankar Debbarma and Wataru Kanna and Hiroki Hayashi and Wataru Matsuoka and Satoshi Maeda and Tsuyoshi Mita}, doi = {10.1021/jacs.5c13115}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39640--39651}, shortjournal = {J. Am. Chem. Soc.}, title = {Virtual ligand-assisted screening for the generation of ketyl radicals from alkyl ketones via photoexcited palladium catalysis}, volume = {147}, year = {2025}, }
• (2025). Introduction of periodic ketone units on vinyl polymers via a radical alternating copolymerization and postpolymerization modification: Sequence-oriented photodegradation in the bulk state. JACS, 147(43), 39632--39639. (www)

  @article{ , abstract = {The synthesis and the sequence-oriented bulk-state photodegradation of sequence-controlled polymers with a periodic structure bearing acrylamide, ketone, and vinyl ether units is reported. The alternating terpolymers can be synthesized via a radical copolymerization of a silyl-protected 1,3-butadiene bearing a methyl ether group (SBD) with a pentafluorophenyl acrylate (PFA) monomer in an alternating and 1,4-regioselective fashion. This process is followed by the addition of an amine to trigger a cascade aminolysis–desilylation reaction. The pendant alkyl group on the acrylamide unit, which is derived from the added amine, is crucial for determining the physical properties of a series of polymers, particularly the glass-transition temperature ( T g ). Relatively flexible and sufficiently thermally stable polymers with T g values below room temperature could be degraded under UV irradiation in the bulk state. Control experiments revealed that synergistic interactions between the periodically arranged ketone, vinyl ether, and acrylamide units were essential for promoting the photodegradation.}, archive = {J_JACS}, author = {Keita Kuroda and Makoto Ouchi}, doi = {10.1021/jacs.5c13090}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39632--39639}, shortjournal = {J. Am. Chem. Soc.}, title = {Introduction of periodic ketone units on vinyl polymers via a radical alternating copolymerization and postpolymerization modification: Sequence-oriented photodegradation in the bulk state}, volume = {147}, year = {2025}, }
• (2025). Hydrogen-bonded dimer dissociation under MOF nanoconfinement enables thermal transition tailoring of medium-chain fatty acids. JACS, 147(43), 39623--39631. (www)

  @article{ , abstract = {Significant modulation of phase transition temperatures ( T tr ) in organic phase-change materials (PCMs) remains a long-standing challenge due to their intrinsically stable intermolecular interactions. We provide direct evidence that metal–organic framework (MOF) nanoconfinement and host–guest interactions dissociate hydrogen-bonded dimers of medium-chain fatty acids into monomeric species. These monomers engage in site-selective hydrogen bonding with the μ 3 -O sites in UiO-66, reconstructing thermodynamic pathways of medium-chain fatty acids and enabling significant T tr control. Specifically, the melting point of lauric acid (C 12 ) confined in UiO-66 is reduced from 44 to 2 °C, and that of capric acid (C 10 ) is reduced from 28 to −18 °C, exceeding the modulation by conventional porous hosts. In contrast, longer-chain fatty acids, such as myristic acid (C 14 ) and palmitic acid (C 16 ), retain dimeric structures and exhibit limited change in T tr , revealing a chain-length-dependent, selective molecular recognition within the MOF pores. Our findings demonstrate a supramolecular approach to modulate phase-transition behavior by controlled dissociation of hydrogen-bonded dimers under nanoconfinement, offering a molecular-level strategy for designing advanced thermal energy storage materials.}, archive = {J_JACS}, author = {Kunyi Leng and Rei Yoshii and Akihiro Suguno and Genki Hatakeyama and Xuejing He and Yusuke Nishiyama and Teppei Yamada}, doi = {10.1021/jacs.5c13043}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39623--39631}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen-bonded dimer dissociation under MOF nanoconfinement enables thermal transition tailoring of medium-chain fatty acids}, volume = {147}, year = {2025}, }
• (2025). Multiconfigurational ground state of a diradicaloid characterized at the atomic scale. JACS, 147(43), 39616--39622. (www)

  @article{ , abstract = {We report the tip-induced generation and scanning probe characterization of a singlet diradicaloid, consisting of two phenalenyl units connected by an sp-hybridized C 4 chain on an ultrathin insulating NaCl surface. The bond-order contrast along the C 4 chain measured by atomic force microscopy and mapping of charge-state transitions by scanning tunneling microscopy, in conjunction with multiconfigurational calculations, reveal that the molecule exhibits a many-body ground state. Our study experimentally demonstrates the manifestation of strong electronic correlations in the geometric and electronic structures of a single molecule.}, archive = {J_JACS}, author = {Elia Turco and Lara Tejerina and Gonçalo Catarina and Andres Ortega-Guerrero and Nils Krane and Leo Gross and Michal Juríček and Shantanu Mishra}, doi = {10.1021/jacs.5c13039}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39616--39622}, shortjournal = {J. Am. Chem. Soc.}, title = {Multiconfigurational ground state of a diradicaloid characterized at the atomic scale}, volume = {147}, year = {2025}, }
• (2025). Coexistence of liquid- and solid-like ion transport in Metal–Organic frameworks. JACS, 147(43), 39610--39615. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) are emerging as unique (pseudo)solid-state electrolytes that enable transport of technologically relevant cations such as Li + , Na + , K + , Mg 2+ , Zn 2+ , and Sr 2+ . As solids, they should be subject to the compositional and structural engineering approaches that are common to traditional solid-state electrolytes. Yet, they also contain liquid within their pores. As such, cations may benefit from sampling both solid and liquid-like transport regimes. Here, we show that Li + , Na + , K + , Mg 2+ , Zn 2+ , and Sr 2+ ions are mobile in the cation-exchangeable anionic MOF [Cu 3 (μ 3 -OH)(pyrazole-4-carboxylate) 3 ] − , with conductivity values spanning from 4.3 × 10 –6 for Zn 2+ to 1.7 × 10 –3 S/cm for K + . Experiments aimed at probing the effects of solvated ion radii, interaction with the host framework, charge carrier concentration, and vacancy sites on ionic conductivity and activation energy for individual ions demonstrate that, indeed, transport of ions in MOFs should be thought of as a combination of direct interaction with the framework as well as liquid-like transport in the pores.}, archive = {J_JACS}, author = {Alice Y. Su and Stefano Canossa and Julius J. Oppenheim and Zhentao Yang and Mircea Dincă}, doi = {10.1021/jacs.5c12979}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39610--39615}, shortjournal = {J. Am. Chem. Soc.}, title = {Coexistence of liquid- and solid-like ion transport in Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Boosting CO2 photoreduction through dispersing quantum dots in viscous polymer networks. JACS, 147(43), 39599--39609. (www)

  @article{ , abstract = {Natural photosynthesis, which achieves high photo-to-chemical conversion efficiency, operates in a highly viscous environment rich in biopolymers that effectively promote charge separation. Inspired by this biological strategy, we explored artificial photoreduction of CO 2 within viscous polymer networks. Specifically, quantum dots (QDs)─functioning as both light-harvesting antennas and catalytic centers─were embedded into physically cross-linked poly(vinyl alcohol) (PVA) gel networks. Under visible-light irradiation, QDs embedded in PVA gel networks exhibited markedly enhanced activity for CO 2 -to-CO conversion, achieving ≈94.9 mmol per gram of QDs per hour (mmol g –1 h –1 )─among the highest values reported for QD-based photocatalytic systems. Mechanistic studies suggested that S 2– capped QDs interact with the semicrystalline PVA networks via hydrogen bonding, which facilitates hole trapping of the photogenerated charges on the QDs. Furthermore, coembedding plasmonic Au nanocrystals (NCs) with QDs in the same gel networks enabled the coupling of proton reduction with CO 2 reduction, leading to the efficient production of syngas (CO and H 2 ) with high conversion rates (84.7 mmol g –1 h –1 for CO and 248.1 mmol g –1 h –1 for H 2 ). Importantly, the syngas composition can be precisely tuned by varying the QD-to-Au NC ratio, offering potential integration with the Fischer–Tropsch process for the production of liquid fuels.}, archive = {J_JACS}, author = {Jurong Dong and Zhijie Yang and Hui Li and Yuewen Li and Jingjing Wei}, doi = {10.1021/jacs.5c13007}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39599--39609}, shortjournal = {J. Am. Chem. Soc.}, title = {Boosting CO2 photoreduction through dispersing quantum dots in viscous polymer networks}, volume = {147}, year = {2025}, }
• (2025). Spin glass behavior and giant magnetoresistance via aliovalent Fe/Ni alloying in amorphous tetrathiafulvalene-tetrathiolate coordination polymers. JACS, 147(43), 39590--39598. (www)

  @article{ , abstract = {The discovery of materials with programmable combinations of charge transport and magnetic properties is a major goal in synthetic chemistry. Molecular materials, such as coordination polymers (CPs), are emerging candidates in this field due to their synthetic modularity. While there are many conductive or magnetic CPs, single-component examples with both properties are still emerging. Here we demonstrate how alloying paramagnetic Fe(III) centers into a highly conductive Ni-based CP results in novel amorphous materials with high conductivity and giant magnetoresistance. Aliovalent doping with paramagnetic Fe centers engenders spin-glass transitions, while Ni and the strong π-stacking interactions of tetrathiafulvalene-2,3,6,7-tetrathiolate (TTFtt) ligands support conductivity. Ni 0.69 Fe 0.31 TTFtt has σ ≈ 200 S/cm and a 1.8 K magnetoresistance of −52% at 5 T, among the largest for any coordination solid. This work demonstrates not only how magnetic properties can be rationally incorporated into conductive CPs, but also an unexpected potential for amorphous materials in spintronic applications.}, archive = {J_JACS}, author = {Chen-Yu Lien and Jie-Hao Chen and Anna O. Schouten and Grant R. Wilkinson and Di Wang and Jan Hofmann and Maia E. Czaikowski and Barbara Lavina and Alexander S. Filatov and Karena W. Chapman and Andrew P. Higginbotham and Dmitri V. Talapin and David A. Mazziotti and Henry S. La Pierre and Shrayesh N. Patel and John S. Anderson}, doi = {10.1021/jacs.5c12985}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39590--39598}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin glass behavior and giant magnetoresistance via aliovalent Fe/Ni alloying in amorphous tetrathiafulvalene-tetrathiolate coordination polymers}, volume = {147}, year = {2025}, }
• (2025). Red-light-driven C(sp2)–H sulfonylation of anilines using a recyclable benzothiadiazole-based covalent organic framework. JACS, 147(43), 39582--39589. (www)

  @article{ , abstract = {The limitations of traditional high-energy (NUV or blue) photocatalysis, such as limited penetration in reaction media, off-target reactivity, and health hazards, have spurred the development of seminal red-light-mediated transformations. Despite recent advances, most homogeneous red-light photocatalysts suffer from poor recyclability, and recyclable heterogeneous systems remain underexplored. Herein, we report a red-light-driven C(sp 2 )–H sulfonylation of anilines using a highly stable benzothiadiazole-based covalent organic framework (Tp-BT COF) as an efficient, recyclable photocatalyst. The reaction proceeds under exceptionally mild conditions, affording sulfonylated products in good to excellent yields with minimal catalyst loading. Notably, the Tp-BT COF retains its catalytic activity over six consecutive cycles. Comparative studies with structurally related COFs highlight the critical role of the BT core in red-light absorption and the superior performance of the AA stacking mode. This work underscores the potential of rationally designed photoactive COFs for sustainable red-light photocatalysis.}, archive = {J_JACS}, author = {Saúl Alberca and Akshay M. Nair and Paula Escamilla and Pedro Ferreira and Manuel Souto and Martín Fañanás-Mastral}, doi = {10.1021/jacs.5c12697}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39582--39589}, shortjournal = {J. Am. Chem. Soc.}, title = {Red-light-driven C(sp2)–H sulfonylation of anilines using a recyclable benzothiadiazole-based covalent organic framework}, volume = {147}, year = {2025}, }
• (2025). Ultraslow relaxation of toroidal state in ferrotoroidal dysprosium complex. JACS, 147(43), 39572--39581. (www)

  @article{ , abstract = {Molecular systems are emerging candidates for quantum information science (QIS) due to their unique quantum behaviors and structural tunability, opening avenues for next-generation quantum technologies. While molecular nanomagnets (MNMs) have emerged as promising spin-based qubit candidates, achieving long coherence times and feasible readouts remains challenging. Among molecular nanomagnets, single-molecule toroics (SMTs) stand out as a particularly promising class, offering magnetically silent ground states, along with the unique ability to modulate their intrinsic chirality. Realizing toroidal states in molecular systems remains a significant hurdle, with the design and stabilization of ferrotoroidal (FT) moments posing an even greater level of complexity. Moreover, the anticipated slow relaxation of toroidal states has not been explicitly demonstrated, limiting their viability in molecular quantum devices. In this work, we report a tridecanuclear [Ga 7 Dy 6 (N-mdea) 6 (ClCH 2 COO) 6 (NO 3 ) 6 (OH) 12 (H 2 O) 6 ]·3Cl ( 1 ) complex, which exhibits an FT ground state. Remarkably, this complex shows slow relaxation of the toroidal states, experimentally observed for the first time, with a quantum tunneling of magnetization (QTM) relaxation time of ∼3.5 × 10 8 s (∼11 years), far surpassing the relaxation times reported for state-of-the-art Dy(III) based single-molecule magnets. The robust FT ground state in complex 1 is unequivocally established by μSQUID and corroborated by ab initio calculations, marking a major advance in the field of SMTs. This ultraslow relaxation, arising from quenched many-body tunneling processes, lays the foundation for integrating toroidal states into quantum technologies and offers a new design paradigm for molecular complexes in QIS.}, archive = {J_JACS}, author = {Deepanshu Chauhan and Sagar Paul and Dipanti Borah and Appu Sunil and Wolfgang Wernsdorfer and Maheswaran Shanmugam and Gopalan Rajaraman}, doi = {10.1021/jacs.5c12742}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39572--39581}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultraslow relaxation of toroidal state in ferrotoroidal dysprosium complex}, volume = {147}, year = {2025}, }
• (2025). Alkyne dihydroboration via in situ-formed nickel cluster catalysis: Reordering group addition by multinuclear nature. JACS, 147(43), 39561--39571. (www)

  @article{ , abstract = {Understanding the roles and dynamic evolution of active species represents a crucial yet challenging frontier in catalysis research, particularly in systems involving in situ -formed nanoclusters. Owing to the multimetallic nature of soluble nanoclusters, elucidating their distinct catalytic mechanisms, which differ fundamentally from those of conventional homogeneous molecular catalysts or heterogeneous surfaces, has emerged as a critical scientific priority, though this field remains largely unexplored. Herein, we demonstrate a nickel-catalytic system that achieves the regioselective double hydroboration of unsymmetrical internal alkynes with pinacolborane (HBpin), enabling efficient synthesis of sterically congested quaternary 1,1-diboryl alkanes. Mechanistic studies reveal that the catalytic activity originates from in situ -generated Ni nanoclusters, which uniquely activate multiple HBpin simultaneously and enable geminal (H, H) and (B, B) addition to alkynes. This proposed gem -addition mechanism diverges fundamentally from classical sequential double hydroboration pathways mediated by monometallic centers, highlighting the advantages of polynuclear architectures in unlocking unprecedented reactivity and catalytic pathways.}, archive = {J_JACS}, author = {Yuyang Su and Kaidong Shen and Pingsen Shi and Chenrui Liu and Shuo Song and Hong Yi and Aiwen Lei and Yingchao Liu and Heng Wang and Xiaopeng Li and Qiquan Luo and Chang Xu and Xiaoming Wang}, doi = {10.1021/jacs.5c12842}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39561--39571}, shortjournal = {J. Am. Chem. Soc.}, title = {Alkyne dihydroboration via in situ-formed nickel cluster catalysis: Reordering group addition by multinuclear nature}, volume = {147}, year = {2025}, }
• (2025). Self-assembly of artificial topological nanostructures for enhanced bioorthogonal activation and drug penetration for cancer immunotherapy. JACS, 147(43), 39547--39560. (www)

  @article{ , abstract = {Bioorthogonal-based prodrug activation strategy holds great potential in reducing the severe side effects of chemotherapy and has been widely applied in the development of in situ personalized cancer vaccines. However, current strategies mainly focus on the caging and release of cytotoxic drugs, while the simultaneous enhancement of drug accumulation and penetration within tumors remains underexplored. Here, we modularly design a tetrazine (Tz)-modified peptide (TMP) capable of cascade responsiveness to the tumor microenvironment and biomarkers, leading to the in situ self-assembly of an artificial topological nanostructure (ATNs) catalytic system on the tumor cell surface. This system significantly increases the local concentration of bioorthogonal handles (Tz), thereby improving the activation efficiency of the prodrugs trans-cyclooctene (TCO)-doxorubicin (Dox) and TCO-imiquimod (IMQ). We demonstrated that activated Dox induced immunogenic cell death (ICD) by releasing tumor-associated antigens (TAAs), while activated IMQ further amplified immune stimulation, leading to tumor ablation. Additionally, ATNs inhibit tumor cell migration, regulate tumor tissue permeability, and ultimately promote the penetration of the activated drugs. In vivo results demonstrated that the ATNs catalytic system enhanced drug penetration by 7.8-fold in tumor tissues and exhibited excellent safety and selectivity, leading to markedly improved survival outcomes. Moreover, this system also showed promising therapeutic effects in preventing tumor recurrence. We postulate that the synergistic integration of in situ self-assembly and bioorthogonal catalysis offers great potential for the safe and effective development of in situ cancer vaccines and holds promise as a universal prodrug delivery platform for cancer therapy.}, archive = {J_JACS}, author = {Yuhan Dong and Zhaode Mu and Yijie Wu and Hui Hu and Jianli Zuo and Yanzhi Li and Shuai Wang and Zhipeng Wang and Lijuan Bai and Hongwen Liang}, doi = {10.1021/jacs.5c12835}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39547--39560}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-assembly of artificial topological nanostructures for enhanced bioorthogonal activation and drug penetration for cancer immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Insights into the dynamical sodium occupancy evolution and rate-limiting steps in hard carbon. JACS, 147(43), 39537--39546. (www)

  @article{ , abstract = {Accurate understanding of the sodium-storage mechanisms and behaviors is essential for advancing hard carbon (HC) anodes, yet significant controversies persist regarding the sloping and low-voltage-plateau sodiation processes. This work leverages quantitative in situ NMR with Raman spectroscopy and electrochemical analysis to achieve a critical quantified understanding. The approach definitely identifies a transition of Na + from intercalation/adsorption sites to quasi-metallic sodium clusters within closed pores in the early stage of the plateau and subsequently cluster-grow alongside adsorption/intercalation-reoccupy during the late plateau. Notably, our results demonstrate that adsorbed Na + maintains a significantly higher mobility than intercalated Na + during the transition. This transition exhibits strong correlation with decreasing diffusion coefficient during the process, critically governing the rate performance of HC. This understanding clearly explains the enhanced plateau kinetics of HC by introducing abundant defects and closed pores and enlarging carbon layers, which provide a fast transition pathway into quasi-metallic sodium. As a result, our strategically designed HC material achieves a high reversible capacity of 413.2 mAh g –1 at 30 mA g –1 and an exceptional rate capability of 253.0 mAh g –1 at 1500 mA g –1 . These fundamental insights into Na + release and the transition-storage mechanism provide a critical foundation for the rational design of high-performance HC materials.}, archive = {J_JACS}, author = {Ying Ge and Yanling Qiu and Jianxin Han and Shahid Mirza and Hao Liu and Guiming Zhong and Qiong Zheng and Zhangquan Peng and Xianfeng Li}, doi = {10.1021/jacs.5c12673}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39537--39546}, shortjournal = {J. Am. Chem. Soc.}, title = {Insights into the dynamical sodium occupancy evolution and rate-limiting steps in hard carbon}, volume = {147}, year = {2025}, }
• (2025). Zirconium carbide clusters stabilized within carbon cages. JACS, 147(43), 39527--39536. (www)

  @article{ , abstract = {Zirconium-based endohedral metallofullerenes (EMFs) were first detected in the gas phase in 1992, but their bulk synthesis has remained elusive over the past three decades. Herein, we present the first successful synthesis of Zr-based EMFs, addressing this longstanding challenge in fullerene chemistry. By utilizing an optimized synthesis strategy with zirconium carbide as the metal source, we obtained three Zr-based carbide clusterfullerenes, namely, Zr 2 C 2 @ D 3 h (5)-C 78 , Zr 2 C 2 @ I h (7)-C 80 , and Zr 3 C 2 @ I h (7)-C 80 . Single-crystal X-ray diffraction analyses revealed that the Zr 2 C 2 clusters adopt a planar rhombic configuration bridged by a (C≡C) 2– unit, while the Zr 3 C 2 cluster exhibits a rare trifoliate geometry with a bridging (C–C) 6– unit. The coordination modes in these Zr-based clusters are different from those observed in conventional organozirconium complexes, highlighting the unique coordination environments within fullerene cages. Combined experimental and theoretical studies further reveal the electronic structures of the Zr-based EMFs as (Zr 2 C 2 ) 6+ @(C 2 n ) 6– (2 n = 78, 80) and (Zr 3 C 2 ) 6+ @( I h (7)-C 80 ) 6– . This breakthrough in the synthesis of Zr-based EMFs not only offers new insights into the mechanisms of arc-discharge reaction and the formation of EMFs but also provides a substantial guideline for the encapsulation of new elements into fullerene cages, establishing a foundation for the design and synthesis of novel EMFs.}, archive = {J_JACS}, author = {Yi Shen and Laura Abella and Yang-Rong Yao and Qingyu Meng and Rongrong Luo and Bei Li and Zixin Wu and Josep M. Poblet and Antonio Rodríguez-Fortea and Ning Chen}, doi = {10.1021/jacs.5c12573}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39527--39536}, shortjournal = {J. Am. Chem. Soc.}, title = {Zirconium carbide clusters stabilized within carbon cages}, volume = {147}, year = {2025}, }
• (2025). 1D silver organochalcogenide semiconductors: Color tunable luminescence, polarized emission, and long-range exciton diffusion. JACS, 147(43), 39516--39526. (www)

  @article{ , abstract = {Metal organochalcogenides (MOCs) represent a promising class of organic–inorganic hybrid semiconductors with unique light-matter interactions. Their hybrid nature enables extensive structural and optoelectronic tunability via ligand engineering. In this study, we systematically modulated the electronic properties of ligands using Cl and Me functional groups, achieving precise control over the optoelectronic properties of Ag-based MOCs. Structural analysis revealed that these MOCs adopt a one-dimensional (1D) chain structure with organic ligands surrounding a Ag-chalcogen core. Density functional theory (DFT) calculations demonstrated that MOCs exhibit characteristics of 1D semiconductors with strongly dispersive conduction and valence bands aligned along the crystal rod directions. Experimentally, the MOCs displayed bright luminescence, with peaks centered between 560 and 690 nm. The substitution of Cl with Me groups in the benzene ligands induced a red shift in both absorption and photoluminescence, corroborated by experimental and theoretical analyses. Further optical measurements indicated that the emission from the MOCs is strongly polarized along the chain directions. Notably, Se-based MOCs exhibited enhanced exciton diffusivity along the chain axis with a diffusion length of 130 nm, which is among the highest reported for covalent systems. The observed trend in carrier diffusivity among individual compounds is attributed to differences in the effective masses of the carriers, as determined by DFT calculations. Our findings offer valuable insights into the systematic structural and property tuning of hybrid semiconductors and highlight the unique characteristics of the 1D MOC family.}, archive = {J_JACS}, author = {Tomoaki Sakurada and Nithin Pathoor and Takuma Matsumoto and Rattapon Khamlue and Petcharaphorn Chatsiri and Jan Valenta and Tadashi Kawamoto and Shun Omagari and William A. Tisdale and Watcharaphol Paritmongkol and Yeongsu Cho and Martin Vacha}, doi = {10.1021/jacs.5c12551}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39516--39526}, shortjournal = {J. Am. Chem. Soc.}, title = {1D silver organochalcogenide semiconductors: Color tunable luminescence, polarized emission, and long-range exciton diffusion}, volume = {147}, year = {2025}, }
• (2025). Precise dual-metal pairs enable ultrafast structural response for CO2-to-ethylene photoconversion. JACS, 147(43), 39505--39515. (www)

  @article{ , abstract = {Dual-metal sites have shown great potential for high catalytic performance, owing to their synergistic effects. However, randomly distributed dual-metal sites and unidentified coordination environments make it challenging to investigate charge transfer dynamics and elucidate actual catalytic mechanisms. Herein, we report a judicious strategy to construct precisely distributed dual-metal pairs through anchoring single atoms in vacancy-rich metal–organic frameworks (MOFs), enabling ultrafast structural response for CO 2 photoreduction to ethylene. Using oxygen vacancy-rich Mil-125(Ti)-NH 2 loaded with Cu atoms as an example, low-dose real-space imaging and X-ray absorption spectra reveal the well-defined distribution of Cu–Ti dual-metal pairs, resulting in rapid charge transfer from Ti to neighboring Cu within 3.0 ps. Remarkably, a high solar-to-chemical efficiency of 0.62% with a superior electron-based selectivity of 78.3% for ethylene production from CO 2 and H 2 O is achieved. Mechanistic investigation unveils that the unique Cu–Ti bimetallic pairs induce strong d-p hybridization with *CHOCO intermediates and undergo structural self-regulation under excitation, thereby facilitating C–C coupling to proceed spontaneously. The generality of precise dual-metal pairs for the ethylene synthesis is also realized by other MOF-based catalysts. This work enlightens a meticulous strategy to attain identified dual-metal catalytic sites and bridges the discrepancy between experimental study and theoretical insight.}, archive = {J_JACS}, author = {Wentao Song and Bo Song and Yuhang Liang and Yi Zhou and Bo Wang and Wanguo Gao and Yao Wu and Xia Ling and Yong Liu and Ruquan Ye and Qian He and Tze Chien Sum and Yingfang Yao and Zhiqun Lin and Zhigang Zou and Bin Liu}, doi = {10.1021/jacs.5c12465}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39505--39515}, shortjournal = {J. Am. Chem. Soc.}, title = {Precise dual-metal pairs enable ultrafast structural response for CO2-to-ethylene photoconversion}, volume = {147}, year = {2025}, }
• (2025). Mixed Ionic–Covalent bonds achieve durable acidic water oxidation. JACS, 147(43), 39494--39504. (www)

  @article{ , abstract = {The widespread deployment of proton exchange membrane (PEM) water electrolysis is hindered by the instability of oxygen evolution reaction (OER) catalysts under acidic conditions, stemming from coupled degradation mechanisms: lattice oxygen overoxidation (driven by high metal–oxygen (M–O) covalency) and acid-induced metal leaching/collapse. Here, we introduce an electronegativity-guided Li- and Ru-doped spinel Co 3 O 4 (LRCO) catalyst featuring mixed Li–O (ionic) and Ru/Co–O (covalent) bonding. This design simultaneously stabilizes lattice oxygen via strong Li–O anchoring and modulates metal valence states through Ru–O–Co electron sharing, preventing overoxidation. Operando studies reveal a potential-dependent mechanism where Ru donates electrons to Co at low potentials, forming active Ru species, and electron redistribution prevents Ru overoxidation at high potentials. Crucially, Li–O bonds effectively suppress oxygen vacancy formation throughout, and Ru–O coordination remains stable, even at high potentials. LRCO achieves a record-low overpotential of 141 mV at 10 mA cm –2 with >3,300 h stability. Integrated PEM electrolyzers operated >720 h at 1 A cm –2 , achieving a key milestone toward next-decade industry targets.}, archive = {J_JACS}, author = {Shicheng Zhu and Ruoou Yang and Yingying Xu and Xintong Li and Zhaoyang Shi and Lin Yu and Youwen Liu and Huiqiao Li and Tianyou Zhai}, doi = {10.1021/jacs.5c12381}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39494--39504}, shortjournal = {J. Am. Chem. Soc.}, title = {Mixed Ionic–Covalent bonds achieve durable acidic water oxidation}, volume = {147}, year = {2025}, }
• (2025). Reinventing chemiluminescence through redox-driven self-assembly. JACS, 147(43), 39482--39493. (www)

  @article{ , abstract = {Chemiluminescence (CL) typically derives from harvesting the energy released during the cleavage of covalent bonds, wherein molecular substrates are irreversibly consumed to generate electronically excited states. In contrast, regenerative CL seeks to bypass substrate decomposition by using reversible redox processes to produce emissive states, an approach that is largely limited to polypyridyl complexes of Ru(II) and Cr(III). Here, we report a fundamentally distinct chemiluminescence mechanism in which the exergonic reduction of Pt(IV) complexes powers the spontaneous formation of emissive Pt(II) aggregates. Notably, light emission arises not from discrete molecular species but from the self-assembled state, whose electronic structure features a lowered excited-state energy ( E 0,0 ) conducive to radiative decay. The emission spectrum observed during chemical reduction matches that of photoexcited aggregates, confirming that the emissive state is intrinsic to the aggregated Pt(II) architecture. This chemiluminescence occurs without external photoexcitation, and its intensity and persistence depend on the nature of the reductant, ranging from transient flashes to sustained afterglow. These findings unveil a new energy transduction pathway in CL: emission driven by redox-triggered self-assembly, expanding the conceptual and chemical space of chemiluminescence beyond classical molecular luminophores and toward dynamic, structure-responsive materials.}, archive = {J_JACS}, author = {Dario Alessi and Luca Morgan and Elisa Pelorosso and Mirco Scaccaglia and Piermaria Pinter and Alessandro Aliprandi}, doi = {10.1021/jacs.5c12281}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39482--39493}, shortjournal = {J. Am. Chem. Soc.}, title = {Reinventing chemiluminescence through redox-driven self-assembly}, volume = {147}, year = {2025}, }
• (2025). Li atomic diffusivity: A key descriptor for critical current density and cycling stability in alloy anodes for all-solid-state lithium batteries. JACS, 147(43), 39475--39481. (www)

  @article{ , abstract = {Alloy anodes hold promise for achieving dendrite-free all-solid-state lithium batteries (ASSLBs) by regulating lithium deposition behavior, leading to enhanced critical current density (CCD) and cycling stability. However, existing alloy anodes in ASSLBs fall short of practical requirements (CCD > 10 mA cm –2 ), and key factors determining CCD remain unclear. Here, we propose a diffusion-controlled Li deposition model in which CCD critically depends on the competition between surface attachment and diffusion of incoming atoms. Multimodal characterizations validate that Li atomic diffusivity in the alloy anode is a key descriptor for the CCD and cycling stability of ASSLBs. Leveraging this insight, LiGa is chosen as the optimized alloy anode due to its high Li atomic diffusivity (∼3 × 10 –7 cm 2 s –1 ), which enables a record-high CCD exceeding 50 mA cm –2 and stable solid electrolyte-anode interface at a high current density of 3 mA cm –2 . ASSLBs pairing the LiGa anode with the LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode and using Li 6 PS 5 Cl (LPSCl) solid electrolyte exhibit remarkable long-term cycling stability of 1000 cycles with 80% capacity retention under 25 °C and a stacking pressure of 1 MPa, outperforming state-of-the-art alloy anode-based counterparts. This work establishes a unified descriptor for the control of Li deposition, advancing practical ASSLB development.}, archive = {J_JACS}, author = {Guoyong Xue and Jie Lu and Zhe-Tao Sun and Chenji Hu and Ruilong Liu and Chu Lu and Wei Wei and Yi Cui and Yixiao Zhang and Xi Liu and Ziyang Ning and Shou-Hang Bo and Linsen Li and Chuying Ouyang and Kai Wu and Liwei Chen}, doi = {10.1021/jacs.5c12252}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39475--39481}, shortjournal = {J. Am. Chem. Soc.}, title = {Li atomic diffusivity: A key descriptor for critical current density and cycling stability in alloy anodes for all-solid-state lithium batteries}, volume = {147}, year = {2025}, }
• (2025). Competing magnetic states in the possible altermagnet candidate GdAlGe. JACS, 147(43), 39464--39474. (www)

  @article{ , abstract = {Altermagnetism, a newly discovered magnetic order, combines zero net magnetization with nonrelativistic spin splitting of electronic bands. Its ability to utilize the advantages of both antiferromagnets and ferromagnets is highly promising for spintronic applications. Currently, the merge of altermagnetism and weak ferromagnetism in a single material excites significant interest as it provides additional control mechanisms over material properties. However, the role of dimensionality in this interplay is yet to be explored. Here, we study magnetism and electron transport in epitaxial films of the candidate altermagnet GdAlGe ranging from bulk-like to a single monolayer. The films exhibit the anomalous Hall effect and negative magnetoresistance. In contrast to altermagnetic GdAlSi, the candidate altermagnet GdAlGe demonstrates an admixture of the ferromagnetic state whose contribution increases as the system approaches the 2D limit. The coexistence of the magnetic states induces technologically important intrinsic exchange bias. The present work underpins future studies and applications of nanoscale altermagnets.}, archive = {J_JACS}, author = {Oleg E. Parfenov and Dmitry V. Averyanov and Ivan S. Sokolov and Alexey N. Mihalyuk and Ivan A. Yakovlev and Oleg A. Kondratev and Alexander N. Taldenkov and Andrey M. Tokmachev and Vyacheslav G. Storchak}, doi = {10.1021/jacs.5c12194}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39464--39474}, shortjournal = {J. Am. Chem. Soc.}, title = {Competing magnetic states in the possible altermagnet candidate GdAlGe}, volume = {147}, year = {2025}, }
• (2025). Kinetically programmed signaling cascades for molecular detection. JACS, 147(43), 39452--39463. (www)

  @article{ , abstract = {Upon external stimulation, living cells activate a series of precisely programmed signaling cascade reactions that efficiently convert multiple stimuli into relevant output signals, thereby maintaining physiological homeostasis. These naturally evolved molecular networks have recently inspired the development of new chemical strategies in fields ranging from synthetic biology to molecular computing, drug delivery, and biosensing systems. While some studies have begun to explore how programming the thermodynamics of these bioinspired chemical systems can optimize their performance, the impact of programming their kinetics remains largely unexplored. Here, we leveraged the modularity and programmability of DNA chemistry to develop a simple DNA-based signaling cascade to measure the concentration of specific molecules and investigated how programming its kinetics affects its performance. This signaling cascade comprises four modules (input, receptor, processor, and output) and three molecular interactions for which we have characterized all intrinsic rate constants. Through simulations and experiments, we demonstrated that careful kinetic programming can significantly enhance the rate, gain, and sensitivity of the signaling cascade output. We further illustrated the versatility and modularity of this cascade by adapting it for the detection of four different molecules ( small molecules and proteins). We also showed that it can be readily adapted into a rapid, one-step, inexpensive electrochemical sensor enabling therapeutic drug monitoring (TDM) at home directly from a drop of blood. We believe that similar kinetically programmed signaling cascades could be developed for a wide range of chemical applications, allowing complex, multistep workflows to be streamlined into rapid, single-step reactions.}, archive = {J_JACS}, author = {Guichi Zhu and Dominic Lauzon and Carl Prévost-Tremblay and Arnaud Desrosiers and Bal-Ram Adhikari and Alexis Vallée-Bélisle}, doi = {10.1021/jacs.5c12059}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39452--39463}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetically programmed signaling cascades for molecular detection}, volume = {147}, year = {2025}, }
• (2025). Hydrogen bond reconstruction maneuver in eutectic electrolyte enables ultralong-lifespan zinc-ion batteries. JACS, 147(43), 39440--39451. (www)

  @article{ , abstract = {Eutectic electrolytes (EEs) serve as a kind of ionic liquid-analogue electrolytes, newly emerging due to their low cost, high stability, biodegradability, nonflammability, and easy preparation properties. The commonly used quaternary ammonium salts play the role of acceptors to form hydrogen bonds (HBs), while the inorganic anions are mostly anchored. Herein, a new type of choline-chloride-based EE was prepared by reshaping the HB donor–acceptor identity to unconstrain chloride anions. Multiple spectral characterizations combined with theoretical analysis confirm the existence of reconstructed HBs and the formation of an anion-dominated solvation structure. Consequently, an organic–inorganic hybrid solid electrolyte interphase film was created on the Zn surface, realizing dendrite-free Zn anodes and achieving an ultralong lifespan of 18175 h (∼2.07 years) of highly reversible Zn plating/stripping performance at a current density of 0.5 mA cm –2 , even a super high cumulative capacity of 42 Ah cm –2 at 20 mA cm –2 . Furthermore, the assembled Zn || AC@I 2 pouch cell shows stable rate and cycling electrochemical properties. This research sheds new light on developing EEs for high-safety and practical zinc-ion batteries.}, archive = {J_JACS}, author = {Xuemei Zhang and Qiang Tang and Hang Luo and Yanling Xu and Sicheng Miao and Shuyang Zhou and Changhaoyue Xu and Ye Jia and Qiujie He and Jianan Peng and Liang He and Yingze Song and Yun Zhang and Wenlong Cai}, doi = {10.1021/jacs.5c12021}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39440--39451}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen bond reconstruction maneuver in eutectic electrolyte enables ultralong-lifespan zinc-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Rational design of conductive MOF-based diatomic electrocatalysts for selective ammonia synthesis. JACS, 147(43), 39430--39439. (www)

  @article{ , abstract = {Diatomic catalysts (DACs) have recently attracted emerging attention beyond single-atom catalysts (SACs) in achieving targeted catalytic performance, yet their rational design and synthesis remain challenging. Here, we demonstrate the feasibility of designing DACs for highly selective ammonia synthesis from nitrate by developing a water-stable conductive metal–organic framework (cMOF) with a tunable Cu and Ni node (Cu x Ni y -DBCO) used as a platform catalyst. The well-defined diatomic structure of the cMOFs and adjustable metal components enable systematic identification of active diatomic species and elucidation of the underlying nitrate reduction mechanism. Based on this understanding, we successfully design and synthesize a targeted DACs catalyst (Cu 98.5 Ni 1.5 -DBCO) to exhibit unit of selectivity accompanied with ammonia yields of over 200 mg h –1 mg cat –1 (3.5 mmol h –1 cm –2 ) at a current density of >750 mA cm –2 . A Zn–NO 3 – battery incorporating this optimized DACs as the cathode delivers a power density of 35.6 mW cm –2 , highlighting the potential of conductive MOFs in developing target DACs for industrial electrocatalysis.}, archive = {J_JACS}, author = {Qinglin Li and Chunmei Jia and Qianxiao Wang and Xiangyang Guo and Kun Qi and Jinfeng Liu and Wenjun Fan and Lin Luo and Jiangnan Li and Jun Long and Jianping Xiao and Fuxiang Zhang}, doi = {10.1021/jacs.5c11655}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39430--39439}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design of conductive MOF-based diatomic electrocatalysts for selective ammonia synthesis}, volume = {147}, year = {2025}, }
• (2025). Covalent organic frameworks via in situ monomer release for humid CO2 uptake. JACS, 147(43), 39419--39429. (www)

  @article{ , abstract = {Achieving high crystallinity and porosity in covalent organic frameworks (COFs) remains a major challenge, particularly for robust azine-linked systems, where limited bond reversibility hinders framework ordering. While several strategies have improved the crystallinity in imine-linked COFs, analogous advances in azine-linked frameworks are still lacking. Here, we present a kinetic modulation strategy based on the in situ slow release of hydrazine via the trifluoroacetic acid (TFA)-mediated hydrolysis of a tetrazine precursor during the COF synthesis. Using this approach, we successfully synthesized two crystalline azine-linked COFs incorporating either a nonplanar bicarbazole or a planar pyrene core. This method enhances structural order, as evidenced by narrowed full width at half-maximum (FWHM) values in PXRD and higher surface areas compared to the COFs prepared with direct hydrazine hydrate addition. Time-resolved UV–vis and PXRD analyses elucidate the role of reaction kinetics in framework evolution. Notably, the resulting COFs exhibit S-shaped water vapor adsorption isotherms with minimal uptake below 40% relative humidity (RH), reflecting their hydrophobic backbones. More importantly, CO 2 uptake remains largely unaffected at 40% RH, and dynamic breakthrough experiments confirm that H 2 O does not interfere with CO 2 adsorption under these conditions. This work establishes a generalizable route for crystallinity enhancement in kinetically trapped COFs and offers promising materials for gas separation under humid environments.}, archive = {J_JACS}, author = {Arnab Sadhukhan and Shanmuk Srinivas Ravuru and Agnibha Das and Ekta Nehra and Satyadip Paul and Golam Rosul Khan and Matthew A. Addicoat and Yusuke Nishiyama and Snehasis Daschakraborty and Arvind Rajendran and Rahul Banerjee}, doi = {10.1021/jacs.5c11733}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39419--39429}, shortjournal = {J. Am. Chem. Soc.}, title = {Covalent organic frameworks via in situ monomer release for humid CO2 uptake}, volume = {147}, year = {2025}, }
• (2025). Retrosynthetic design of dinuclear copper enzymes for Azide–Alkyne cycloaddition via clickable noncanonical amino acids. JACS, 147(43), 39408--39418. (www)

  @article{ , abstract = {Copper-catalyzed azide–alkyne cycloaddition (CuAAC) has enabled numerous synthetic and biological applications, driven by advances in the synthesis and optimization of copper-binding ligands. However, to the best of our knowledge, no bottom-up protein-based ligands have been specifically developed to catalyze this reaction. Here, we present a retrosynthetic protein design that leverages the introduction, duplication, and diversification of metal-chelating amino acid residues via a clickable noncanonical amino acid and CuAAC-mediated post-translational modification. A naturally occurring homodimer, dTDP-4-keto-6-deoxy-D-hexulose 3,5-epimerase, was engineered to structurally mimic the molecular framework of well-known CuAAC ligands, featuring multidentate triazole-containing motifs with four nitrogen donor atoms capable of accommodating two copper-binding sites. Remarkably, one protein construct R79TP exhibits CuAAC activity toward exogenous alkyne and azide substrates at rates exceeding that of a benchmark ligand, likely via a dinuclear mechanism. This work highlights the potential of genetically encoded precursors for multidentate ligand in proteins, expands the molecular complexity achievable in metalloenzyme engineering, and provides mechanistic insights and potential for copper-mediated bioorthogonal catalysis.}, archive = {J_JACS}, author = {Yunjong Lee and Jaewon Moon and Kyu Jin Son and Jaehee Lee and Seoungjun Ha and Woon Ju Song}, doi = {10.1021/jacs.5c11725}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39408--39418}, shortjournal = {J. Am. Chem. Soc.}, title = {Retrosynthetic design of dinuclear copper enzymes for Azide–Alkyne cycloaddition via clickable noncanonical amino acids}, volume = {147}, year = {2025}, }
• (2025). Magnetocaloric effect in a microporous material using a rare-earth-free, hybrid perovskite. JACS, 147(43), 39401--39407. (www)

  @article{ , abstract = {Magnetic refrigeration using the magnetocaloric effect (MCE), where the temperature of a material changes as a magnetic field is applied, is a promising technology to increase the energy efficiency of commodity gas liquefaction at cryogenic temperatures. Currently, the most commonly studied materials for this application utilize rare-earth elements in nonporous forms. The continued development of magnetocaloric materials could benefit from (1) the discovery of materials with high surface areas capable of condensing substantial quantities of gas using minimal energy inputs and (2) the use of cheap and abundant precursors instead of utilizing rare-earth metals. We show here that microporous copper-halide perovskites, which form a layered structure with accessible crystalline voids between copper-halide sheets, demonstrate large entropy changes upon applying a magnetic field at temperatures relevant for H 2 condensation. This is the first demonstration of the magnetocaloric effect for a transition-metal-based porous material. Furthermore, tuning the halide composition gives fundamental insight into how to control both the ferromagnetic transition temperature and the magnetic entropy change within this class of materials.}, archive = {J_JACS}, author = {Connor W. Dalton and Tian Wang and Gregory Morrison and Hans-Conrad zur Loye and Xiaosong Li and Douglas A. Reed}, doi = {10.1021/jacs.5c11644}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39401--39407}, shortjournal = {J. Am. Chem. Soc.}, title = {Magnetocaloric effect in a microporous material using a rare-earth-free, hybrid perovskite}, volume = {147}, year = {2025}, }
• (2025). Substituting cyclohexyl with phenyl at phosphorus makes a NiP2N2 molecular catalyst active for hydrogen evolution in alkaline conditions at low overvoltage. JACS, 147(43), 39391--39400. (www)

  @article{ , abstract = {Among the large family of mononuclear bis-diphosphine nickel catalysts with pendant amines, the so-called NiCyArg complex, with a cyclohexyl group at the phosphine and an arginine substituted amine, has attracted attention for catalyzing H 2 oxidation and production reversibly in aqueous solutions, with a significant bias in favor of H 2 oxidation. Here, we analyze the voltammetric responses of this complex and an analogue where the cyclohexyl group was replaced with a phenyl group. Our analysis helps distinguish the molecular and kinetic distinct determinants of rate, directionality and reversibility of NiP 2 N 2 redox molecular catalysts of H + /H 2 conversion. The NiPhArg complex described in this work is a bidirectional, reversible catalyst over a large range of pH. It is strongly biased in the direction of reductive catalysis, and still active for proton reduction at pH 9. It could become useful in applications where H 2 evolution should be catalyzed in aqueous solutions under mild conditions and at low overpotential.}, archive = {J_JACS}, author = {Antoine Jacob-Villedieu and Sriram Katipamula and Achille Marchand and Bertrand Reuillard and Vincent Artero and Vincent Fourmond and Bruno Faure and A. Jalila Simaan and Christophe Léger}, doi = {10.1021/jacs.5c11615}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39391--39400}, shortjournal = {J. Am. Chem. Soc.}, title = {Substituting cyclohexyl with phenyl at phosphorus makes a NiP2N2 molecular catalyst active for hydrogen evolution in alkaline conditions at low overvoltage}, volume = {147}, year = {2025}, }
• (2025). Local-global synergistic pore space partition in Metal–Organic frameworks for boosting CO2 capture and conversion. JACS, 147(43), 39379--39390. (www)

  @article{ , abstract = {How to rationally maximize host–guest interactions or the density of binding sites within metal–organic framework (MOF) pores is critical to their promising adsorption and catalysis performance but still challenging. In this work, a local-global synergistic pore space partition (LGS-PSP) strategy is proposed to integrate ligand-mediated local partition with interpenetration-driven global partition, enabling precise design and efficient utilization of MOF pore space. Forty-four MOF examples featuring six types of pore-space partitioned modes ( psit-d , psit-d/u , psit-u , psit-i , psit-d-i , and psit-u-i ) derived from merely one parent sit framework, along with their tunable and boosting CO 2 adsorption and photocatalytic ability, clearly demonstrate the power of the LGS-PSP strategy. Detailed single-crystal structure analysis indicates that the translation/rotation of ligands and frameworks can dynamically regulate the microenvironment of the local pores and the interpenetration mode of the global network, realizing a dynamic and controllable alignment of local and global pore engineering with the pore environment. Remarkably, the dual-partitioned SNNU-196-Ni MOF with ultramicropores and uniformly dispersed Lewis-basic and acidic sites promoted the CO 2 adsorption capacity by 206%, and the photocatalytic conversion efficiency in the carboxylation cyclization of propargylic amines and CO 2 was nearly 100% under visible light irradiation.}, archive = {J_JACS}, author = {Shu-Cong Fan and Yong-Peng Li and Jia-Wen Wang and Chen-Chen Xing and Zi-Yuan Liu and Wenyu Yuan and Ying Wang and Quan-Guo Zhai}, doi = {10.1021/jacs.5c11494}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39379--39390}, shortjournal = {J. Am. Chem. Soc.}, title = {Local-global synergistic pore space partition in Metal–Organic frameworks for boosting CO2 capture and conversion}, volume = {147}, year = {2025}, }
• (2025). A stable radical in cationic dinuclear rare-earth triple-decker complexes featuring switchable magnetic properties. JACS, 147(43), 39367--39378. (www)

  @article{ , abstract = {In quantum information processing, the implementation of qu d its─multilevel qubits where d is the number of levels─has been a major challenge that, if resolved, could lead to the acceleration of certain computational tasks. Spin transport measurements demonstrate that tris(phthalocyaninato)-dinuclear rare-earth(III) molecules offer a promising platform for nuclear spin qudits with an increased Hilbert space. However, the absence of radicals in these systems has so far hindered studies on the coupling between lanthanide ions and conduction electrons. In this study, we report the synthesis of (phthalocyaninato)bis(porphyrinato)-dinuclear rare-earth(III) complexes functionalized with thiomethyl groups. The tailored oxidation of the neutral complexes facilitated their conversion to air-stable radicals. CASSCF calculations and static magnetic measurements revealed a radical–lanthanide exchange coupling constant of J Ln–Rad = −0.45 cm –1 . Dynamic magnetic measurements demonstrated a shift in the magnetic properties due to exchange interaction, namely from field-induced single-molecule magnets (SMMs) to zero-field SMMs. The findings of this study, along with the strong bonding affinity of thiomethyl groups to gold electrodes, highlight the potential of these molecules as novel materials for the implementation of nuclear spin qudits with an increased Hilbert space.}, archive = {J_JACS}, author = {Joe Komeda and Sören Schlittenhardt and Asato Mizuno and Eufemio Moreno-Pineda and Yaorong Chen and Olaf Fuhr and Jordan L. Appleton and Athanassios K. Boudalis and Svetlana Klyatskaya and Mario Ruben}, doi = {10.1021/jacs.5c11362}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39367--39378}, shortjournal = {J. Am. Chem. Soc.}, title = {A stable radical in cationic dinuclear rare-earth triple-decker complexes featuring switchable magnetic properties}, volume = {147}, year = {2025}, }
• (2025). Construct open lipid nano-membranes with controllable lateral behavior. JACS, 147(43), 39359--39366. (www)

  @article{ , abstract = {Understanding the in-membrane behaviors of membrane proteins requires precise control over lipid bilayers, yet such precision remains challenging due to their dynamic and amphiphilic nature. Here, a universal strategy is developed to construct open lipid membranes, which are defined as lipid bilayers confined within open DNA nanobarrels based on DNA origami, exhibiting programmable geometry and lateral fluidity. The open membranes exhibit high stability by optimizing the spatial distribution of the leading cholesterols and the lipid ratio. Through the engineering of complementary DNA interactions and shape-matching features, spatially defined membrane fusion can be achieved. Compared with the traditional closed scaffold systems, this strategy has allowed lipid diffusion across adjacent compartments within the same membrane. Such a membrane fusion process brings membrane-associated model proteins into proximity, thereby enhancing confined enzymatic reactions and benefiting the understanding of the dynamic interaction of the membrane proteins within the lipid bilayer. This platform provides a versatile system for investigating membrane protein organization, interaction dynamics, and functional coordination in controlled lipid contexts.}, archive = {J_JACS}, author = {Guizhi Dong and Jiafang Piao and Wei Yuan and Chuangyuan Zhao and Xiao Li and Rui Xu and Dongsheng Liu and Yuanchen Dong}, doi = {10.1021/jacs.5c11355}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39359--39366}, shortjournal = {J. Am. Chem. Soc.}, title = {Construct open lipid nano-membranes with controllable lateral behavior}, volume = {147}, year = {2025}, }
• (2025). Polar triptycene-based nonmetal organic frameworks show enhanced hydrogen adsorption. JACS, 147(43), 39351--39358. (www)

  @article{ , abstract = {Porous nonmetal organic frameworks (N-MOFs) are an emerging class of porous materials that can have desirable properties such as stability for iodine capture, proton conductivity, and xenon/ krypton separation. Here, we present the first experimental evidence of polymorphism in porous N-MOFs through the identification of two stable porous phases of a triptycene framework (T.Cl-α and T.Cl-β). We also report single-crystal structures for two isostructural porous N-MOFs (T.Cl-α and T.Br-α). All three polymorphs are porous to carbon dioxide and nitrogen, and T.Cl-α exhibits a remarkable hydrogen uptake of 7.2 mmol g –1 at 77 K and 1 bar. This hydrogen sorption far exceeds most other porous crystals and compares favorably with many MOFs under the same condition. The hydrogen uptake for T.Cl-α is anomalously high for its relatively modest pore volume (0.198 cm 3 g –1 from N 2 isotherms at 77 K), which we attribute to London-dispersion interactions and geometric confinement within subnanometer pores.}, archive = {J_JACS}, author = {Megan O’Shaughnessy and Hang Qu and Xue Wang and Jacob B. Holmes and Lyndon Emsley and Joseph Glover and Roohollah Hafizi and Graeme M. Day and Andrew I. Cooper}, doi = {10.1021/jacs.5c11317}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39351--39358}, shortjournal = {J. Am. Chem. Soc.}, title = {Polar triptycene-based nonmetal organic frameworks show enhanced hydrogen adsorption}, volume = {147}, year = {2025}, }
• (2025). Switchable rhodamines for molecular electronics. JACS, 147(43), 39340--39350. (www)

  @article{ , abstract = {Rhodamines are widely used in bioimaging as fluorogenic sensors that reversibly switch between homoconjugated lactone (dark) and conjugated zwitterionic (bright) states in response to external stimuli. Here we transpose the lactone–zwitterion equilibrium ( K L–Z ) concept from fluorescence microscopy to molecular electronics to create the first rhodamine-based single-molecule conductance switch. Installing thioanisole end groups onto rhodamines enables their study in scanning tunneling microscope break-junction (STM-BJ) measurements. We use optical absorbance, STM-BJ, and density functional theory studies to show that trifluoroacetic acid (TFA) triggers switching between insulating and conducting states in rhodamine molecular junctions with an on/off conductance ratio of 46, which is among the highest reported switching factors for chemically responsive single-molecule junctions. Control studies with a permanently conjugated methyl ester derivative supports that the switching mechanism describes spirolactone interconversion between closed and open states. We demonstrate reversible acid/base switching over three cycles and also show we can drive conductance switching with lithium ion or sonication as external stimuli. Given the known sensitivity of rhodamine electronic structure to minor synthetic modifications, this work establishes rhodamines as an exciting yet untapped platform for the design of functional molecular electronics.}, archive = {J_JACS}, author = {Lan D. Pham and Matthew O. Hight and Grace Wang and Ashley E. Pimentel and Lamia Haque and Timothy A. Su}, doi = {10.1021/jacs.5c11150}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39340--39350}, shortjournal = {J. Am. Chem. Soc.}, title = {Switchable rhodamines for molecular electronics}, volume = {147}, year = {2025}, }
• (2025). Recovery of high-voltage oxygen redox activity by eliminating residual oxygen dimers. JACS, 147(43), 39330--39339. (www)

  @article{ , abstract = {Oxygen-redox layered oxides are promising electrode materials with the potential for superior energy density; however, their real-world employment is hindered by severe electrochemical irreversibility. The fundamental origin of this irreversibility has been difficult to pinpoint due to the complex evolution of both the structure and redox centers during cycling. Herein, we reveal that oxygen redox irreversibility is governed by the formation and persistence of oxygen dimer states and, for the first time, demonstrate the reversible recovery of the intrinsic high-voltage oxygen redox plateau (∼4.5 V vs Li/Li + ), which is typically lost after initial charge. Our in-depth tracking of oxygen dimer behavior establishes a direct correlation between the recoverability of the high-voltage plateau and the residual concentration of oxygen dimers in the electrode material. Furthermore, we identify sluggish dimer dissociation kinetics as the root cause of the irreversible loss of high-voltage oxygen redox activity. More importantly, we demonstrate that these kinetically trapped oxygen dimers can be eliminated by facilitating electron transfer from transition metal to oxygen dimers via redox reshuffling at a moderately elevated temperature, thereby fully restoring the high-voltage oxygen redox activity. These findings clarify the role of oxygen dimer kinetics in redox irreversibility and provide valuable insights toward achieving voltage-hysteresis-free anionic redox in oxygen redox electrodes.}, archive = {J_JACS}, author = {Youngsin Kim and Hyuk-Joon Kim and Dae Soo Jung and Okkyun Seo and Akhil Tayal and Hojoon Lim and Saki Imada and Jooha Park and Sung-Pyo Cho and Youngjun Jeon and Jihyeon Kim and Donggun Eum and Seongmin Kang and Byungwook Kang and Kyoungoh Kim and Hongjin Ahn and Jonghun Park and Ho-Young Jang and Sung-O Park and Joohyeon Noh and Chaelin Lee and Jong Deok Lee and Kun-hee Ko and Hyunsoung Jin and Kisuk Kang}, doi = {10.1021/jacs.5c11310}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39330--39339}, shortjournal = {J. Am. Chem. Soc.}, title = {Recovery of high-voltage oxygen redox activity by eliminating residual oxygen dimers}, volume = {147}, year = {2025}, }
• (2025). Multivalency enables signal processing at single protein level. JACS, 147(43), 39321--39329. (www)

  @article{ , abstract = {Synthetic signal processing in cells can be achieved through complex networks of molecules or simpler, single-molecule-based mechanisms. The latter approach stands out for its reduced genetic load and ease of delivery. Multivalent protein binders are such single-molecule signal processors that exhibit distinct behaviors when interacting with cells presenting various antigen profiles. However, a quantitative and precise method to design multivalent interactions in the context of cell surface binding is still lacking. Here, we developed Multivalent Antigen Sensing Simulator (MASS) to guide the design of such multivalent proteins. We verified the model through in vitro and cell binding experiments, showing the predictive accuracy of our model in designing multivalent binders to sense cell surface antigen identities and elicit selective killing. Our model also accurately captured, which was verified via experiments, the nonmonotonic interplay between valency and monovalent affinity in designing multivalent binders that sense cell surface antigen densities. Our work suggests practical guidelines in designing multivalent proteins that could simultaneously sense both antigen identities and densities and enables fast and precise in silico prescreening of multivalent protein binders.}, archive = {J_JACS}, author = {Xiaoyu Wu and Yuanqi Jia and Tong Zhang and Zhehao Xiong and Zihang Ye and Ge Yu and Yingjie Lei and Zhuo Mao and Vicky Qu and Bobo Dang and Ziyao Xu and Zibo Chen}, doi = {10.1021/jacs.5c11096}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39321--39329}, shortjournal = {J. Am. Chem. Soc.}, title = {Multivalency enables signal processing at single protein level}, volume = {147}, year = {2025}, }
• (2025). Two flavoenzymes convert fungal polyketide-nonribosomal peptide to cis-2-butene-1,4-dial-type carcinogen via olefin dihydroxylation and C–C bond cleavage. JACS, 147(43), 39310--39320. (www)

  @article{ , abstract = {Postmodification steps by multiple oxidation enzymes are an effective strategy for converting the polyketide-nonribosomal peptide (PK-NRP) core backbone to structurally distinctive natural products, where decoration steps occurring on conjugated polyenes (olefin ≥3) of the PK-NRP core backbones are relatively scarce. In this study, we identified two flavoenzymes from the frt cluster in Fusarium reticulatum : (1) a FAD-dependent monooxygenase FrtD catalyzes olefin dihydroxylation of a five-conjugated polyene PK-NRP precursor ( 8 ) to yield vicinal diols ( 1a / 1b ); (2) a secretion-type berberine bridge enzyme-like oxidase FrtB is then responsible for converting 1a to cis- 2-methyl-2-butene-1,4-dial ( 17 ) and three conjugated polyene α,β-unsaturated ketone ( 12 ), the process of which includes dehydrogenation, C–C bond cleavage, and isomerization. Most importantly, 17 was characterized as a new cis -2-butene-1,4-dial-type carcinogen from Fusarium sp. due to its ability to bind amino acids and induce DNA damage. Our work reveals the unusual functions of flavoenzymes and discovers a new mycotoxin metabolite from Fusarium sp., which poses potential health risks that require further attention in the future.}, archive = {J_JACS}, author = {Jin-Mei Zhang and Guan-Yin Yuan and Min-Xiu Shi and Yi Zou}, doi = {10.1021/jacs.5c11221}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39310--39320}, shortjournal = {J. Am. Chem. Soc.}, title = {Two flavoenzymes convert fungal polyketide-nonribosomal peptide to cis-2-butene-1,4-dial-type carcinogen via olefin dihydroxylation and C–C bond cleavage}, volume = {147}, year = {2025}, }
• (2025). Allosteric modulation toward nonionic covalent organic framework nanosheets. JACS, 147(43), 39298--39309. (www)

  @article{ , abstract = {Nonionic covalent organic framework nanosheets (nCOFNs) are new-generation building blocks for diverse applications. However, the solution-phase synthesis of highly crystalline, large-sized nCOFNs remains particularly challenging, as it requires the simultaneous regulation of chemical interactions for intralayer framework construction and physical interactions for interlayer stacking. Allostery, a ubiquitous natural process for regulating the structure and activity of biomacromolecules, awaits exploration in synthetic functional materials. Herein, we showcase an allosteric modulation strategy for the solution-phase synthesis of β-ketoenamine-linked nCOFNs. The secondary amine, as an allosteric modulator, facilitates enol-keto tautomerization reversibility, affording allosteric activation for in-plane assembly, while its steric hindrance affords allosteric inhibition for out-of-plane assembly. The modulator with a high N exposure factor and moderate-size side groups can achieve an optimal balance between two allosteric effects. Consequently, a series of high-quality nCOFNs with high crystallinity and aspect ratios exceeding 1000 can be mildly synthesized under ambient conditions with yields of up to 82%. The excellent solution processability of nCOFNs enables their facile assembly into membranes that exhibit ultrahigh methanol permeance of 127 L m –2 h –1 bar –1 , superior durability in continuous filtration for over 1000 h, and high efficiency in purifying high-value pharmaceuticals. Furthermore, we demonstrate the practical application potential by assembling nCOFNs into large-area flat-sheet (∼430 cm 2 ) and hollow fiber membranes.}, archive = {J_JACS}, author = {Hao Deng and Ying Wang and Yanqiu Lu and Zhong Gao and Yong Zhu and Bohui Lyu and Ziting Zhu and Kaiyu Wang and Febrian Hillman and Sui Zhang and Runnan Zhang and Zhongyi Jiang}, doi = {10.1021/jacs.5c11087}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39298--39309}, shortjournal = {J. Am. Chem. Soc.}, title = {Allosteric modulation toward nonionic covalent organic framework nanosheets}, volume = {147}, year = {2025}, }
• (2025). Efficient and selective photocatalytic conversion of low-concentration CO2 to CO using mn-complex catalysts. JACS, 147(43), 39284--39297. (www)

  @article{ , abstract = {For the practical application of photocatalytic CO 2 reduction systems, it should be important that the catalyst directly reduces low concentrations of CO 2 in photocatalytic systems consisting of only Earth-abundant elements. Despite the development of numerous photocatalytic CO 2 reduction systems, CO 2 utilization at low CO 2 concentrations has not been thoroughly investigated. Although fac -[Mn I (diimine)(CO) 3 L] n + -type complexes are among the most abundant transition-metal complexes and have been studied as CO 2 reduction catalysts in electrocatalytic systems, their application in photocatalytic reactions has been limited by the formation of photochemically unstable Mn(0) dimers. Thus, the photocatalytic activities of systems using Mn complexes as catalysts have not been evaluated at low CO 2 concentrations. In this work, we synthesized a novel Mn(I) complex by introducing one sterically bulky mesityl group at the 6-position of the 4,4′-dimethyl-2,2′-bipyridine (dmb) ligand and used it as a catalyst in photocatalytic reactions. In the presence of trifluoroethanol (TFE) and diisopropylethylamine, the Mn complex captures CO 2 to form the corresponding carbonate ester complex ( MnMes-CO 2 TFE ), and the addition of an organic photosensitizer ( 4DPAIPN ) enables the selective reduction of CO 2 to CO. MnMes-CO 2 TFE demonstrated excellent catalytic durability, owing to the complete suppression of Mn dimer formation in the photocatalytic reactions. The turnover number (TON) of CO formation reached a maximum of 8770 based on the MnMes-CO 2 TFE used, and the quantum yield of CO formation reached 40%. Furthermore, MnMes-CO 2 TFE exhibited high selectivity and catalytic rates for CO production, even at low CO 2 concentrations (1–10%), attributed to the efficient CO 2 capture reaction.}, archive = {J_JACS}, author = {Kei Kamogawa and Hiroki Koizumi and Osamu Ishitani}, doi = {10.1021/jacs.5c10694}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39284--39297}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient and selective photocatalytic conversion of low-concentration CO2 to CO using mn-complex catalysts}, volume = {147}, year = {2025}, }
• (2025). Mechanistic elucidation and stereochemical consequences of alternative binding of alkenyl substrates by engineered arylmalonate decarboxylase. JACS, 147(43), 39271--39283. (www)

  @article{ , abstract = {The cofactor-free arylmalonate decarboxylase (AMDase) is a valuable biocatalyst for synthesizing α-aryl and α-alkenyl alkanoic acids with excellent stereoselectivity. We engineered a new hydrophobic pocket in ( S )-selective AMDase mutants, creating AMDase ICPLLG with enhanced activity. For the investigation of the mechanism, we synthesized isotope-labeled, pseudochiral 2-methyl-2-vinyl malonate via an auxiliary-based asymmetric route using a chiral imidazolidinone to enable stereoselective bis-alkylation of malonates. Our results reveal striking substrate-dependent stereochemical behavior: AMDase ICPLLG decarboxylates prochiral aromatic malonates with retention of configuration at the α-carbon. The critical Cys residue adds a proton from the same face of the substrate as the leaving carboxylate. Interestingly, the same mutant decarboxylates the corresponding alkenyl malonate with inversion of configuration, i.e., with protonation from the opposite face. Kinetic isotope effect measurements and QM/MM metadynamics calculations suggest that alkenyl malonates adopt an alternative binding mode and undergo decarboxylation via a borderline concerted mechanism instead of a stepwise mechanism. This new pathway changes the stereochemical preference. We exploited this strategy to decarboxylate sterically hindered alkenyl malonates (substrates not converted by wild-type AMDase) with high stereoselectivity. The engineered hydrophobic pocket in ( S )-selective AMDase mutants expands the substrate scope for synthesizing enantiomerically pure α-aryl and α-alkenyl butanoic acids. This work demonstrates a new approach (a mechanistic change) to engineer the substrate range and stereoselectivity of enzymes.}, archive = {J_JACS}, author = {Elske van der Pol and Thomas Schlatzer and Gyula Hoffka and Bruno Di Geronimo and Johannes Eder and Anna K. Schweiger and Marianna Karava and Dominik Gross and Roland C. Fischer and Daniel Kracher and Romas Kazlauskas and Kenji Miyamoto and Shina Caroline Lynn Kamerlin and Rolf Breinbauer and Robert Kourist}, doi = {10.1021/jacs.5c10721}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39271--39283}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic elucidation and stereochemical consequences of alternative binding of alkenyl substrates by engineered arylmalonate decarboxylase}, volume = {147}, year = {2025}, }
• (2025). Dendrite-free high-capacity alkali metal batteries by two-dimensional confinement of desolvated ions. JACS, 147(43), 39259--39270. (www)

  @article{ , abstract = {Alkali metal anodes (Li, Na, and K) hold great promise for energy storage due to their high specific capacities and low reduction potentials. However, the deposition of alkali metals is frequently disrupted by a simultaneous desolvation process, leading to dendrite growth and rapid capacity decay. In this work, we present a general strategy to achieve dendrite-free, high-capacity alkali metal batteries by utilizing the two-dimensional (2D) confinement of desolvated ions. 2D transition metal disulfides (TMDSs) are employed as interlayers with high adsorption energy for alkali metal ions, effectively facilitating the rapid separation of the desolvation process from metal deposition. The desolvated ions, characterized by high diffusivity, are confined within the 2D channels of TMDSs, enabling planar alkali metal deposition without interference from the desolvation process. Furthermore, the TMDS interlayers avoid side reactions between solvents and metals during deposition, resulting in a thin solid electrolyte interphase that promotes fast ion diffusion. This approach enables dendrite-free K metal batteries capable of plating/stripping at 10 mAh cm –2 and cycling at 36 C for over 3000 cycles. Our strategy provides a novel pathway to advance high-energy metal batteries, significantly enhancing their performance and longevity.}, archive = {J_JACS}, author = {Mingze Ma and Ning Lu and Yu Yao and Fangxin Ling and Fei Wang and Zhiyu Lu and Junhao Wang and Zhen Li and Junyi Dai and Weikang Dong and Ruilin Bai and Hai Yang and Zhiwen Zhuo and Zixu He and Shuhong Jiao and Yu Shao and Shaoming Fang and Yue Lin and Yu Qiao and Hanyu Huo and Yan Yu}, doi = {10.1021/jacs.5c10623}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39259--39270}, shortjournal = {J. Am. Chem. Soc.}, title = {Dendrite-free high-capacity alkali metal batteries by two-dimensional confinement of desolvated ions}, volume = {147}, year = {2025}, }
• (2025). Tuning core flexibility and curvature in azine-linked covalent organic frameworks for attomolar-level impedimetric sensing of glucose. JACS, 147(43), 39247--39258. (www)

  @article{ , abstract = {Glucose serves as a key biomarker of metabolic health, requiring continuous and reliable monitoring. Nonenzymatic impedimetric sensors have emerged as a promising alternative to enzymatic glucose sensors, which dominate current clinical practice. However, their sensitivity is limited by weak molecular recognition and inefficient charge transport at the sensing interface. In this study, we tuned the core flexibility and curvature of azine-linked covalent organic frameworks (COFs) by substituting the central triazine ring in the C 3 symmetric building unit with a nitrogen atom. This modification maximized glucose–framework interactions, thereby enhancing signal transduction and detection sensitivity. The results confirmed the sensitivity and selectivity of the COFs toward glucose, with a linear response over a wide concentration range [1 aM–5 mM], surpassing previously reported glucose sensors. The sensors achieved a subattomolar limit of detection (LOD), with excellent stability and reproducibility compared to traditional enzymatic sensors, offering a simpler and more practical alternative for integration into wearable and implantable devices. Experimental findings are supported by molecular simulations, which reveals the mechanism of sensing and charge transfer dynamics. This work establishes a versatile design strategy for enzyme-free designed-to-purpose transducers, opening new pathways for ultrasensitive and selective molecular detection.}, archive = {J_JACS}, author = {Nada Elmerhi and Sara Awni Alkhatib and Sushil Kumar and José Ignacio Martínez and Nabila Yasmeen and Najat Maher Aldaqqa and Blaž Belec and Anna-Maria Pappa and Dinesh Shetty}, doi = {10.1021/jacs.5c10578}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39247--39258}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning core flexibility and curvature in azine-linked covalent organic frameworks for attomolar-level impedimetric sensing of glucose}, volume = {147}, year = {2025}, }
• (2025). Deciphering spin-governed dual emissions in TTM diradicaloids: Unraveling the interplay of singlet and triplet fluorescence pathways. JACS, 147(43), 39232--39246. (www)

  @article{ , abstract = {The photophysical mechanisms governing luminescent diradicals, particularly the interplay between their singlet and triplet emissions, remain incompletely understood. Herein, we report three luminescent radicals, monoradical MTA and diradical DTA and DTA( t -Bu) 2 , based on a tris(2,4,6-trichlorophenyl)methyl (TTM) scaffold. Experimental results and DFT calculations demonstrated the dual emission mechanism of two diradicaloids with distinct S 1 → S 0 (first excited singlet state to singlet ground state) and T 1 → T 0 (first excited triplet state to triplet ground state) fluorescent radiative pathways, while monoradical MTA shows only doublet emission with a D 1 → D 0 (first excited doublet state to doublet ground state) fluorescent radiative pathway. Varying-temperature electron spin resonance measurements revealed the singlet ground state and thermal accessible triplet ground state of DTA and DTA( t -Bu) 2 , with Δ E S–T values of −0.33 and −0.35 kcal/mol, respectively. Boltzmann population analysis based on the Δ E S–T values reveals the coexistence of singlet and triplet states at 298 K, with the S 0 state predominating at 63.6% for DTA and 64.4% for DTA( t -Bu) 2 , while the corresponding T 0 state populations are 36.4% and 35.6%, respectively. Moreover, two diradicaloids exhibit maximum magnetoluminescence phenomena near 100 K, reflecting the synergistic interplay of thermal energy and magnetic-field-induced S 0 → T 0 spin conversion. Notably, temperature-dependent photoluminescent experiments of two diradicaloids unveiled the dual emission behavior of two diradicaloids: cooling from 298 to 78 K progressively suppressed triplet fluorescence at ∼690 nm while it enhanced weak singlet fluorescence in the near-infrared region beyond 900 nm. External heavy-atom effects of two diradicaloids also demonstrated intramolecular intersystem crossing from T 1 to S 1 . Furthermore, theoretical excited-state conformation analysis on two diradicaloids revealed their distinct structural preservation during T 1 → T 0 transitions compared to S 1 → S 0 transitions, which is also confirmed by the smaller reorganization energy, weaker high-frequency vibrations, and smaller radiative transition rate constant. Our work establishes a comprehensive understanding of spin-governed dual fluorescence in TTM diradicaloid systems, providing critical design principles for developing high-spin luminescent materials with tunable spin-controlled emission properties.}, archive = {J_JACS}, author = {Zekun Tong and Shuo Zhang and Weiwei Niu and Tingxi Yu and Xinfang Zhang and Penglei Yao and Jinfeng Wang and Yibo Han and Guangwu Li and Shaoqiang Dong}, doi = {10.1021/jacs.5c10608}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39232--39246}, shortjournal = {J. Am. Chem. Soc.}, title = {Deciphering spin-governed dual emissions in TTM diradicaloids: Unraveling the interplay of singlet and triplet fluorescence pathways}, volume = {147}, year = {2025}, }
• (2025). Topological derivative strategy for large-pore three-dimensional covalent organic frameworks. JACS, 147(43), 39223--39231. (www)

  @article{ , abstract = {The pursuit of three-dimensional covalent organic frameworks (3D COFs) with ultralarge pores faces fundamental challenges from structural interpenetration. We address this limitation through a topology-driven design strategy that transforms edge-transitive scu nets into two distinct derivative frameworks─ mmm and jcg ─via symmetry-controlled monomer selection. This approach yields contrasting pore evolution behaviors: while mmm series COFs (JUC-693 to JUC-695) show unpredictable pore size fluctuations (2.6 → 3.9 → 1.2 nm) due to complex interpenetration patterns, jcg series frameworks (JUC-696 to JUC-698) exhibit controlled expansion up to a record of 5.1 nm pore diameter in JUC-698. Comprehensive characterization, including macromolecular encapsulation studies with vitamin B12 and myoglobin, confirms the structural integrity and accessibility of these engineered pores. Our findings establish topology-directed design as a powerful tool for overcoming interpenetration barriers in porous materials development.}, archive = {J_JACS}, author = {Haorui Zheng and Hui Li and Jie Ji and Fengqian Chen and Yiji Wang and Jinquan Suo and Jialong Song and Dan Zhao and Valentin Valtchev and Shilun Qiu and Qianrong Fang}, doi = {10.1021/jacs.5c10534}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39223--39231}, shortjournal = {J. Am. Chem. Soc.}, title = {Topological derivative strategy for large-pore three-dimensional covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Efficient assembly of functional RNA by in situ phosphate activation and loop-closing ligation. JACS, 147(43), 39212--39222. (www)

  @article{ , abstract = {How ribozymes might have emerged prior to the evolution of an efficient RNA replicase remains an open question. A potential solution involves the nonenzymatic ligation of RNA oligomers that are short enough to have been replicated by nonenzymatic chemistry. However, the high concentrations of metal ions that facilitate ligation are incompatible with primitive protocells. In addition, the mode of oligoribonucleotide 5′-phosphate activation is unclear, and in an aqueous environment the competing hydrolysis of such activated intermediates limits ligation efficiency. In this study, we have investigated the template-independent assembly of structured RNAs via loop-closing ligation using a potentially prebiotic in situ phosphate activation approach. We demonstrate that the 5′-phosphate of oligonucleotides can be activated through an N -methylimidazole-intercepted phospho-Passerini reaction, enabling subsequent loop-closing ligation to efficiently form hairpin structures. Remarkably, this reaction proceeds in the absence of divalent metal ions and remains effective even at low millimolar concentrations of the activating reagent. We identify a novel pathway leading to a phosphorimidazolium species, mediated by an N -imidoyl- N ′-methylimidazolium intermediate. Furthermore, we show that two successive in situ activation/loop-closing ligations enable the assembly of a functional RNA Flexizyme with a near-quantitative yield. Our findings provide insight into potential mechanisms for the prebiotic origin of functional RNAs and offer a viable strategy for the chemical synthesis of long RNA molecules.}, archive = {J_JACS}, author = {Jian Zhang and Aleksandar Radakovic and Filip Bošković and Harry R. M. Aitken and Long-Fei Wu and Jack W. Szostak}, doi = {10.1021/jacs.5c10478}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39212--39222}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient assembly of functional RNA by in situ phosphate activation and loop-closing ligation}, volume = {147}, year = {2025}, }
• (2025). Programmable artificial-cellular membrane dynamics via ring-closing metathesis. JACS, 147(43), 39204--39211. (www)

  @article{ , abstract = {Lateral phase-separated structures in cellular membranes serve as functional domains in various membrane-mediated biological processes. Controlling phase-separation dynamics through catalysis could enable the assembly of smart vesicles that exhibit life-like phenomena. Herein, we present the first example of dynamic control of lateral phase separation via a catalytic reaction: ring-closing olefin metathesis (RCM). This catalytic reaction occurs near the membrane by engineering the surface of lipid membranes with a biotin-streptavidin-based artificial metalloenzyme (ArM). We designed a substrate that, following RCM, releases decanoic acid, which could be spontaneously incorporated into the lipid bilayer, resulting in the disappearance of lipid domains within the membrane. Genetic optimization of the ArM led to a 3-fold increase in catalytic activity, ultimately leading to the budding of a larger lipid domain.}, archive = {J_JACS}, author = {Rei Hamaguchi and Damian Alexander Graf and Kazushi Kinbara and Thomas R. Ward}, doi = {10.1021/jacs.5c10187}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39204--39211}, shortjournal = {J. Am. Chem. Soc.}, title = {Programmable artificial-cellular membrane dynamics via ring-closing metathesis}, volume = {147}, year = {2025}, }
• (2025). Lattice energy partitions in crystals of flexible molecules and the 40% limit. JACS, 147(43), 39192--39203. (www)

  @article{ , abstract = {Flexible molecules change their conformations to optimize intermolecular interactions in the solid-state ─a process that comes at an intramolecular energy cost. The interplay between these opposing forces leads to beautifully balanced and elegant crystal structures. Yet, the relationship between intramolecular energy penalties and intermolecular stabilization has not been fully explored, largely because it requires models capable of accurately capturing components with distinct physical origins. In this work, we employ state-of-the-art hybrid DFT models to probe these interactions and quantify their energetic contributions to crystal lattice energies. After benchmarking 18 computational methods, we identify PBE-MBD/B2PLYPD as the method best reproducing experimental polymorph stabilities with mean absolute deviations of just 2.3 kJ·mol –1 across 17 polymorphic pairs. Using this model, we compute and analyze lattice energy partitions for 125 crystal structures spanning a diverse set of flexible compounds. Our analysis reveals a striking empirical trend─the “40% limit”─which shows that up to 40% of the intermolecular stabilization energy can compensate for intramolecular energy penalties associated with conformational variations. Furthermore, the probability of a higher-energy conformation being observed in the solid-state decreases as a function of the intra-to-intermolecular energy ratio and becomes negligible at the 40% mark. These findings are significant: they define the energetic limits of conformational flexibility in the solid-state and the intra-to-intermolecular energy ratios provide a quantitative tool to predict structures. They can be used to guide the conformational phase space sampling for crystal structure prediction, to rank hypothetical structures according to their crystallizability, or to anticipate difficulties of nucleation and crystal growth in crystal forms of flexible compounds.}, archive = {J_JACS}, author = {Amrita Chattopadhyay and Adam R. Hill and Sarah E. Wright and Gregory J. O. Beran and Aurora J. Cruz-Cabeza}, doi = {10.1021/jacs.5c09997}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39192--39203}, shortjournal = {J. Am. Chem. Soc.}, title = {Lattice energy partitions in crystals of flexible molecules and the 40% limit}, volume = {147}, year = {2025}, }
• (2025). Manipulating interfacial charge distribution for water reduction. JACS, 147(43), 39181--39191. (www)

  @article{ , abstract = {Heterogeneous electrocatalysis often involves a complex interplay of the non-Faradaic process and the Faradaic process at the electrode/electrolyte interface, with the reaction kinetics typically exhibiting an exponential dependence on applied bias. However, the indivisible nature of bias hinders independent understanding and fine-tuning of each process. Synergistically regulating these two processes containing multiple reaction steps via one single, yet unified mediator remains a formidable challenge. Here, precise manipulation of the interfacial charge distribution is proposed to tackle this critical challenge. Through lattice strain engineering in NiCo 2 S 4 , the optimal amount matching between non-Faradaic charges and Faradaic charges is yielded during alkaline hydrogen evolution reaction (HER). As a result, the restriction of electrostatic potential on the water molecule reorganization process is alleviated, and the positive contribution of chemical potential to the water molecule dissociation process is concurrently strengthened. Furthermore, the moderate e g orbital filling is evidenced as the essential origin of a substantial increase in Faraday charges, the relationship between which is in the volcanic form. This interfacial charge redistribution enabled a synergistic optimization route of kinetic multisteps that can be further extended to other heterogeneous electrocatalytic reactions beyond HER.}, archive = {J_JACS}, author = {Jing Wu and Xin Wang and Wenhao Zheng and Yu Sun and Yong Xie and Zhen Tian and Wenjia Zhang and Guowei He and Zhuojian Liang and Zhuo Kang and Yue Zhang}, doi = {10.1021/jacs.5c09493}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39181--39191}, shortjournal = {J. Am. Chem. Soc.}, title = {Manipulating interfacial charge distribution for water reduction}, volume = {147}, year = {2025}, }
• (2025). Electronic states modulation of BiVO4 with transition metal-substituted polyoxometalates to activate lattice oxygen mechanism for efficient water oxidation. JACS, 147(43), 39169--39180. (www)

  @article{ , abstract = {Oxygen evolution reaction (OER) is the bottleneck of photoelectrochemical (PEC) water splitting. Activating the lattice oxygen mechanism (LOM) can break the limitation of the slow O–O coupling and accelerate the water oxidation kinetics. However, the current methods for activating LOM are limited and it is crucial to develop new strategies to induce LOM. Herein, we have modified BiVO 4 with transition metal-substituted silicotungstate (X 3 SiW 9 , X = Co, Ni, Cu) to form X 3 SiW 9 –BiVO 4 photoanodes, triggering the LOM by surface modification for the first time. X 3 SiW 9 can modulate the electronic structure of BiVO 4 , resulting in an upward shift of the O 2 p energy band position relative to the metal 3 d energy band, increasing the overlap of the metal and oxygen orbital energy levels, and enhancing covalency between metal and oxygen, which facilitates the activation of the lattice oxygen, thus triggering the LOM and significantly improving the OER activity of BiVO 4 . The enhancement of the OER activity depends on the influence of X 3 SiW 9 on the electronic state. Among them, Co 3 SiW 9 has the greatest influence on the electronic state of BiVO 4 . Therefore, Co 3 SiW 9 –BiVO 4 exhibits the highest photocurrent density of 4.13 mA cm –2 at 1.23 V RHE , four times higher than that of BiVO 4 (1.02 mA cm –2 ). This work modifies the photoanode with transition metal-substituted polyoxometalates to modulate the energy levels of metal and oxygen to activate LOM for significantly enhanced OER activity, which provides new strategies and perspectives on the design and application of polyoxometalates for efficient OER in PEC water splitting.}, archive = {J_JACS}, author = {Zhaohui Li and Faheem Abbas and Fangfang Feng and Kaiqin Gao and Yanli Liu and Zifeng Wu and Ze Zhang and Xionghui Fu and Yi Zhu and Yuanming Zhang and Yongge Wei}, doi = {10.1021/jacs.5c09257}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39169--39180}, shortjournal = {J. Am. Chem. Soc.}, title = {Electronic states modulation of BiVO4 with transition metal-substituted polyoxometalates to activate lattice oxygen mechanism for efficient water oxidation}, volume = {147}, year = {2025}, }
• (2025). Conversion of a heme-dependent dehydratase to a piperazate synthase reveals the role of the heme propionate group in N–N bond-formation. JACS, 147(43), 39160--39168. (www)

  @article{ , abstract = {Enzymes that form nitrogen–nitrogen bonds are employed in natural product biosynthesis and the nitrogen cycle. Piperazate synthase forms the cyclic hydrazine l -piperazic acid from l - N 5 -OH-ornithine, using heme as a cofactor. In this work, we discover sequence-related enzyme NohD that instead reacts with l - N 5 -OH-ornithine to release ammonia, and we solve its structure to 1.4 Å resolution. We then employ structure-guided site-directed mutagenesis to endow variants of NohD with piperazate synthase activity. Crystal structures of the NohD variants reveal how the heme propionate changes conformation, positioning it upward toward the amino nitrogen, where it is likely to activate the amine for N–N bond-formation. This study highlights a key structural requirement for N–N bond-formation and sets the stage for the development of new N–N-bond-forming catalysts.}, archive = {J_JACS}, author = {Melanie A. Higgins and Nana Mirotadze and Xinjie Shi and Elesha R. Hoffarth and Yi-Ling Du and Katherine S. Ryan}, doi = {10.1021/jacs.5c08886}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39160--39168}, shortjournal = {J. Am. Chem. Soc.}, title = {Conversion of a heme-dependent dehydratase to a piperazate synthase reveals the role of the heme propionate group in N–N bond-formation}, volume = {147}, year = {2025}, }
• (2025). Mechanistic insights into enhanced capacity and pure-phase formation in fe-based mixed phosphate cathodes. JACS, 147(43), 39151--39159. (www)

  @article{ , abstract = {Fe-based mixed phosphate Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 is a promising sodium-ion battery cathode due to its structural stability and cost-effectiveness, yet its capacity is limited by impurity phases and insufficient Fe redox activity. We introduce an electroactive coefficient (η = C/I ), where C is the number of redox couples and I is the number of transferred ions per formula unit, as a design metric for high-capacity cathodes. Analysis reveals that Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 has a suboptimal η (0.72), prompting a V-doping strategy to enhance multielectron transfer, raising η to 0.85. V doping also triggers a high-spin-to-low-spin transition in Fe 2+ , shortening Fe–O bonds and increasing the Fe-vacancy formation energy, thus suppressing impurities. The optimized Na 3.6 Fe 2.6 V 0.4 (PO 4 ) 2 P 2 O 7 achieves a record capacity of 124.6 mAh g –1 at 0.1 C. This work elucidates phase-pure cathode formation and establishes a universal design principle for high-capacity electrodes.}, archive = {J_JACS}, author = {Wande Song and Nan Chen and Jinpeng Wang and Weibo Hua and Bohan Zhang and Shuoqing Zhao and Xing Ming and Zexiang Shen and Gang Chen and Fei Du}, doi = {10.1021/jacs.5c08636}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39151--39159}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic insights into enhanced capacity and pure-phase formation in fe-based mixed phosphate cathodes}, volume = {147}, year = {2025}, }
• (2025). Interplay between β-chitin nanocrystal supramolecular architecture and water structuring: Insights from three-dimensional atomic force microscopy measurements and molecular dynamics simulations. JACS, 147(43), 39134--39150. (www)

  @article{ , abstract = {Chitin, a highly abundant natural biopolymer, holds significant promise as a renewable resource; however, the structural organization and hydration properties of its β-crystalline form remain poorly understood, which limits our understanding of its fundamental characteristics. A thorough understanding of the three-dimensional (3D) supramolecular arrangement of chitin nanocrystals (NCs) in aqueous environments is crucial for realizing their full potential. Here, we employed atomic force microscopy (AFM) in combination with molecular dynamics simulations to elucidate the surface structure of individual β-chitin NCs at the single-fiber level under varying pH conditions. In situ AFM imaging reveals a highly ordered crystalline architecture with unprecedented molecular detail and demonstrates that water intercalation expands the lattice along the b -axis. 3D-AFM further revealed heterogeneous, pH-dependent hydration shells, forming an intricate 3D hydrogen bonding network around β-chitin NCs, thereby establishing substantial energetic barriers to direct interactions of external ions and molecules with the chitin surface and might lead to selective biomolecular interactions. Notably, α-chitin NCs exhibit stronger hydration forces than β-chitin NCs, reflecting distinct reactivities. Understanding the molecular assembly of β-chitin chains and their interactions with water across different pH values is critical for elucidating relevant biological processes and optimizing chitin decrystallization strategies. These findings advance our mechanistic understanding of the molecular assembly of water-intercalated β-chitin NCs, thereby enabling their efficient use in renewable products and supporting the rational design of functional and sustainable bionanomaterials.}, archive = {J_JACS}, author = {Ayhan Yurtsever and Kazuho Daicho and Fabio Priante and Keisuke Miyazawa and Mohammad Shahidul Alam and Kazuki Miyata and Akinori Yabuki and Noriyuki Isobe and Tsuguyuki Saito and Adam S. Foster and Takeshi Fukuma}, doi = {10.1021/jacs.5c08484}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39134--39150}, shortjournal = {J. Am. Chem. Soc.}, title = {Interplay between β-chitin nanocrystal supramolecular architecture and water structuring: Insights from three-dimensional atomic force microscopy measurements and molecular dynamics simulations}, volume = {147}, year = {2025}, }
• (2025). Optimizing CO2-loaded aqueous amine solutions for higher electrocatalytic CO2 reduction activity. JACS, 147(43), 39123--39133. (www)

  @article{ , abstract = {The activity of aqueous-based carbon dioxide reduction (CO 2 R) reactions is often limited by the solubility of CO 2 . The addition of amines can increase the total dissolved carbon in water through the formation of bicarbonate and carbamate species, which has been used to a great effect to capture CO 2 from dilute streams. In this study, we explore the effect of 12 primary and secondary amines of varying Brønsted basicity, steric profile, and hydrogen-bonding capabilities on the aqueous CO 2 R to CO activity of a molecular Ni(cyclam)Cl 2 catalyst with a Hg electrode. Addition of some of the amines results in greater activity and selectivity for CO production compared to equivalent aqueous solutions without added amines. Under optimal conditions (0.4 M 3-amino-propionitrile), there is an over sevenfold increase in partial current density and greater selectivity for CO compared to equivalent conditions with no amine. Interestingly, the increase in activity did not correlate to any single property across the 12 amines. To elucidate the effect of the amine additives on catalysis, we used vapor–liquid equilibrium modeling (VLE), 13 C NMR spectroscopy, and computational analysis to determine the carbon speciation of the solutions. These results indicate that for amines without ethylalcohol functionalities, CO 2 R activity correlates with carbamate concentration, which is in turn governed by amine basicity and steric effects. However, this correlation does not persist for amines with ethylalcohol functionalities, which can form more stable carbamates through intramolecular-hydrogen bonding. These studies demonstrate that amine additives can enhance aqueous CO 2 R activity and selectivity and describe amine properties that lead to these higher performance metrics.}, archive = {J_JACS}, author = {Ab Qayoom Mir and Avishek Banerjee and Ferdawss Ihiri and Shawn Chiu and Anastassia N. Alexandrova and Carlos Morales-Guio and Jenny Y. Yang}, doi = {10.1021/jacs.5c07783}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39123--39133}, shortjournal = {J. Am. Chem. Soc.}, title = {Optimizing CO2-loaded aqueous amine solutions for higher electrocatalytic CO2 reduction activity}, volume = {147}, year = {2025}, }
• (2025). Synthesis-aware materials redesign via large language models. JACS, 147(43), 39113--39122. (www)

  @article{ , abstract = {We propose a novel framework that leverages large language models (LLMs) to transform synthetically infeasible inorganic crystal structures into synthetically feasible ones. Unlike previous studies on synthesis predictions, which focus primarily on estimating synthesizability, our method provides actionable solutions for redesigning unsynthesizable materials into synthesizable ones. By integrating an invertible structural representation and an iterative fine-tuning strategy, our framework not only predicts synthetic feasibility but also modifies unsynthesizable materials into viable candidates. As a result, we demonstrate that LLMs can effectively modify materials of various types, enhancing their synthesizability and increasing the likelihood of successful synthesis. As an indirect experimental validation, we demonstrate that 34 materials among the top 100 redesigned (but originally unsynthesizable) structures have indeed been experimentally reported in the literature. This approach addresses a critical gap between design and synthesis in materials science, and enables the discovery of experimentally realizable compounds by employing the “learn-and-regenerate” strategy in LLMs.}, archive = {J_JACS}, author = {Jaehwan Choi and Seongmin Kim and Yousung Jung}, doi = {10.1021/jacs.5c07743}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39113--39122}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis-aware materials redesign via large language models}, volume = {147}, year = {2025}, }
• (2025). Size-dependent restructuring of supported platinum cluster catalysts. JACS, 147(43), 39103--39112. (www)

  @article{ , abstract = {Supported metal clusters have reactivities that depend on their nuclearity and structure. Herein, we present a strategy for precisely controlling the nuclearity of platinum clusters and demonstrate their size-dependent restructuring behavior and catalytic properties. The clusters are located on isolated CeO x nanoislands on high-area SiO 2 , and the isolation facilitates control of the migration of the platinum. Thus, in an H 2 atmosphere, the clusters are stably confined to the nanoislands, whereas in a CO atmosphere, they migrate out of the nanoislands, grow, and are thereafter confined again to the nanoislands. During CO oxidation catalysis, these platinum clusters undergo restructuring. Clusters with average diameters of 0.7 nm are quickly deactivated as O 2 causes oxidative fragmentation to form single atoms. In contrast, 1.5 nm clusters maintain their nuclearity, with only partial surface oxidation, being more active as catalysts than both the 0.7 nm clusters and those with 2.2 nm diameters. These results provide new insights into the dynamic restructuring of catalytically active metal clusters and how to construct and stabilize supported metal cluster catalysts with optimized properties.}, archive = {J_JACS}, author = {Xu Li and Nan Zhang and Di Wu and Yuan Ji and Jingyi Zhang and Jiankang Zhao and Yizhen Chen and Bruce C. Gates and Jingyue Liu and Chuan Xia}, doi = {10.1021/jacs.5c07056}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39103--39112}, shortjournal = {J. Am. Chem. Soc.}, title = {Size-dependent restructuring of supported platinum cluster catalysts}, volume = {147}, year = {2025}, }
• (2025). Superconducting sn-intercalated TaSe2: Structural diversity obscured by routine characterization techniques. JACS, 147(43), 39093--39102. (www)

  @article{ , abstract = {Using Sn-intercalated TaSe 2 as a model system, we demonstrate the presence of structural heterogeneity captured by single-crystal X-ray diffraction (SCXRD) and scanning transmission electron microscopy (STEM) that eludes the routine characterization techniques of powder X-ray diffraction, Raman spectroscopy, and electronic transport measurements. From a single growth composition (1:1:2 Sn:Ta:Se), we obtained crystals diverse in stoichiometry and structure, with near-continuous intercalation for Sn x TaSe 2 from 0 ≲ x ≲ 1. Using SCXRD, we found global structural diversity, identifying three new structure types: Sn 0.18 TaSe 2.0 /Sn 0.08 TaSe 1.96 ( R 3 m ), Sn 0.16 TaSe 2.0 ( P 6 3 / mmc ), and Sn 1.2 TaSe 1.9 ( Fmm 2). Using STEM, we observed local structural diversity, manifested as regions of highly variable stacking within a single crystal. In contrast, powder X-ray diffraction did not resolve all observed global structures. Raman spectroscopy was unable to distinguish between different structures or compositions in the standard measurement range. Electronic transport measurements showed consistent superconductivity and charge density wave behavior irrespective of Sn-intercalation amount. Our results indicate that routine approaches to characterization of intercalated transition metal dichalcogenides may be inadequate for capturing the diversity of this family of materials, highlighting the need for high-resolution structural characterization when examining the properties of van der Waals-layered compounds.}, archive = {J_JACS}, author = {Brenna C. Bierman and Gillian Nolan and Hongrui Ma and Ying Wang and Pinshane Huang and Daniel A. Rhodes}, doi = {10.1021/jacs.5c06808}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39093--39102}, shortjournal = {J. Am. Chem. Soc.}, title = {Superconducting sn-intercalated TaSe2: Structural diversity obscured by routine characterization techniques}, volume = {147}, year = {2025}, }
• (2025). Electrochemical stability and reduction mechanism of LLZO interfaces in li batteries from first principles. JACS, 147(43), 39080--39092. (www)

  @article{ , abstract = {We investigate the electrochemical stability of tetragonal, cubic, and doped Li 7 La 3 Zr 2 O 12 (LLZO) in a Li battery by performing both energy level alignment across the Li-LLZO interface and grand-canonical phase analysis in unison. We employ density-functional theory (DFT) as well as GW many-body perturbation theory for more accurate electronic energy levels. We explicitly enumerate interface structures of minimal lattice mismatch, determine energy level alignment for each interface using the average electrostatic potential as the reference, and combine the results with canonical thermodynamic averaging. We further study the effects of Ta and Nb doping of LLZO systems in the effort to explain the limited electrochemical stability observed in experiments over extended periods of contact or during cycling. We show that, compared to the more expedient vacuum-slab model, direct level alignment through the interfaces can substantially sway the predicted stability margins against electron transfer. We show that regardless of doping, LLZO at nominal composition should be electrochemically stable against Li. However, we identify formation of intermediate electronic states in the bulk of doped LLZO during lithiation as an intrinsic source of instability of doped LLZO against Li in a battery setting. These states localize onto the dopant atoms and fall below the Li Fermi level, effectively allowing electrons to be admitted at a positive voltage. Electron transfer onto of the dopant atoms would ultimately lead to phase separation, completing reductive decomposition of LLZO. A holistic pathway from electron spillover to LLZO degradation is thus established.}, archive = {J_JACS}, author = {Junsoo Park and Stephen R. Xie and Zhigang Wu and John W. Lawson}, doi = {10.1021/jacs.5c05770}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39080--39092}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical stability and reduction mechanism of LLZO interfaces in li batteries from first principles}, volume = {147}, year = {2025}, }
• (2025). Magnetic ground state discrimination of a polyradical nanographene using nickelocene-functionalized tips. JACS, 147(43), 39072--39079. (www)

  @article{ , abstract = {Molecular magnets are a promising class of materials with exciting properties and applications. However, a profound understanding and application of such materials depend on the accurate detection of their electronic and magnetic properties. Despite the availability of experimental techniques that can sense the magnetic signal, the exact determination of the spin ground states and spatial distribution of the exchange interaction of strongly correlated single-molecule magnets remain challenging. Here, we demonstrate that scanning probe microscopy with a nickelocene-functionalized probe can distinguish between nearly degenerate multireference ground states of single-molecule π-magnets and map their spatial distribution of the exchange interaction. This method expands the already outstanding imaging capabilities of scanning probe microscopy for characterizing the chemical and electronic structures of individual molecules, paving the way for the study of strongly correlated molecular magnets with unprecedented spatial resolution.}, archive = {J_JACS}, author = {Diego Soler-Polo and Oleksandr Stetsovych and Manish Kumar and Benjamin Lowe and Ana Barragán and Zhiqiang Gao and Andrés Pinar Solé and Hao Zhao and Elena Pérez-Elvira and Goudappagouda and David Écija and Akimitsu Narita and Pavel Jelínek and José I. Urgel}, doi = {10.1021/jacs.5c11722}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39072--39079}, shortjournal = {J. Am. Chem. Soc.}, title = {Magnetic ground state discrimination of a polyradical nanographene using nickelocene-functionalized tips}, volume = {147}, year = {2025}, }
• (2025). Synthesis and characterization of a π-extended clar’s goblet. JACS, 147(43), 39067--39071. (www)

  @article{ , abstract = {Concealed non-Kekulé polybenzenoid hydrocarbons have no sublattice imbalance yet cannot be assigned a classical Kekulé structure, leading to an open-shell ground state with potential applications in organic spintronics. They constitute an exceedingly small fraction of the total number of polybenzenoid hydrocarbons that can be constructed for a given number of benzenoid rings, and their synthesis remains challenging. The archetype of such a system is the Clar’s goblet (C 38 H 18 ), a diradical proposed by Erich Clar in 1972 and recently synthesized on a Au(111) surface. Here, we report the synthesis of a π-extended Clar’s goblet (C 76 H 26 ), a tetraradical concealed non-Kekulé polybenzenoid hydrocarbon, by a combined in-solution and on-surface synthetic approach. By low-temperature scanning tunneling microscopy and atomic force microscopy, we characterized individual molecules adsorbed on a Cu(111) surface. We provide insights into the electronic properties of this elusive molecule, including the many-body nature of its ground and excited states, by mean-field and multiconfigurational quantum chemistry calculations.}, archive = {J_JACS}, author = {Shantanu Mishra and Manuel Vilas-Varela and Igor Rončević and Fabian Paschke and Florian Albrecht and Leo Gross and Diego Peña}, doi = {10.1021/jacs.5c07588}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39067--39071}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis and characterization of a π-extended clar’s goblet}, volume = {147}, year = {2025}, }
• (2025). Synthesis of acyclic all-carbon quaternary stereocenters through nickel-catalyzed enantioselective C(sp3)–H amination. JACS, 147(43), 39060--39066. (www)

  @article{ , abstract = {The catalytic enantioselective construction of acyclic all-carbon quaternary stereocenters via C(sp 3 )–H functionalization represents a fundamental challenge in synthetic chemistry primarily due to the steric congestion and enhanced conformational mobility of these motifs. While noble metals have demonstrated efficacy in such desymmetrizations, the development of sustainable catalytic systems based on earth-abundant 3d metals remains rare. Herein, we report a nickel-catalyzed asymmetric C(sp 3 )–H amination using a commercially available, air-stable Ni(II) catalyst and a sterically tuned chiral BINOL-derived ligand. The reaction enables the direct desymmetrization of prochiral gem -dimethyl groups, providing access to a wide range of enantioenriched β-amino acid derivatives bearing all-carbon quaternary stereocenters in high yields and with excellent enantioselectivity (up to >99% ee). The utility of this transformation is highlighted by the late-stage functionalization of pharmaceutical scaffolds and versatile downstream elaboration of the resulting quaternary stereocenters, establishing a robust platform for sustainable synthesis of these valuable structural motifs.}, archive = {J_JACS}, author = {Jia-Hao Chen and Tian-Yu Jiang and Qi-Jun Yao and Ya-Lan Feng and Ming-Yu Zhong and Fan-Rui Huang and Bing-Feng Shi}, doi = {10.1021/jacs.5c16651}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39060--39066}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of acyclic all-carbon quaternary stereocenters through nickel-catalyzed enantioselective C(sp3)–H amination}, volume = {147}, year = {2025}, }
• (2025). Temporary molybdenum η6-coordination enables selective and general dearomative 1,2-hydrofunctionalization of benzenes. JACS, 147(43), 39052--39059. (www)

  @article{ , abstract = {Despite molybdenum’s sustainable profile and broad utility in organic synthesis, its use in high-value arene dearomative functionalizations remains markedly underexplored. Herein, we report a general and efficient dearomative 1,2-hydrofunctionalization of nonactivated arenes via transient molybdenum η 6 -coordination. This method operates under mild conditions and exhibits broad substrate scope and high regioselectivity, thus providing convenient access to valuable functionalized 1,3-cyclohexadienes. The molybdenum activation allows precise ring-selective dearomatization within complex polyaromatic systems and facilitates late-stage modification of drug molecules. Its synthetic utility is further demonstrated through the total synthesis of (±)-infectocaryone and formal syntheses of (±)-juvabione and (±)-lycorane. Notably, the molybdenum-based system demonstrates unique reactivity and superior selectivity compared to conventional chromium analogues, highlighting its distinct capability for selective dearomative functionalization.}, archive = {J_JACS}, author = {Jia-Yi Qiu and Jun-Jie Zhi and Qin He and Ming-Yang Wang and Wei-Long Zeng and Chu-Qiao Li and Wei Li}, doi = {10.1021/jacs.5c15942}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39052--39059}, shortjournal = {J. Am. Chem. Soc.}, title = {Temporary molybdenum η6-coordination enables selective and general dearomative 1,2-hydrofunctionalization of benzenes}, volume = {147}, year = {2025}, }
• (2025). Cascade mechanochemical transformation of a benzobarrelane polymer. JACS, 147(43), 39047--39051. (www)

  @article{ , abstract = {Designing and understanding the reactivity of individual force-responsive molecules, mechanophores, has been a central topic in polymer mechanochemistry. However, we envision that when certain molecular structures are closely coupled along a polymer backbone, new mechanochemical reactivity that is absent from individual molecules may arise. Herein, we describe a polymer consisting of benzobarrelane repeat units that are connected via backbone alkenes, where force-induced bond scission triggers a radical cascade reaction to transform the polymer backbone structure. Despite the lack of weak covalent bonds or significant ring strain in the benzobarrelane polymer, it achieved similar degrees of mechanochemical transformation as our previously reported polyladderene systems consisting of highly strained repeat units. In contrast, no mechanochemical reaction was observed in benzobarrelane units that are distant from one another along the backbone: the mechanochemistry of barrelane requires immediately connected barrelane units. This work demonstrates the possibility of eliciting novel reactivities by creating cooperative chemical pathways across otherwise inert individual units.}, archive = {J_JACS}, author = {Daniel C. Lee and Erica J. Flear and Rui Xu and Ke Zheng and Todd J. Martínez and Yan Xia}, doi = {10.1021/jacs.5c14494}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39047--39051}, shortjournal = {J. Am. Chem. Soc.}, title = {Cascade mechanochemical transformation of a benzobarrelane polymer}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of annotinolide b via sequential quinoline dearomatization. JACS, 147(43), 39042--39046. (www)

  @article{ , abstract = {We report the first total synthesis of the complex cyclobutane-containing Lycopodium alkaloid annotinolide B. Our approach leverages a sequential quinoline dearomatization strategy that enables the transformation of this readily accessible heteroaromatic precursor to a tricyclic N -acyl dihydropyridone intermediate. Extensive studies aimed at forging the signature cyclobutane revealed a β-silyl acrylate to be essential for the success of a key [2 + 2] photocycloaddition reaction. Further functional group transformations and a final one-pot methylation/lactonization sequence furnish annotinolide B in 20 steps.}, archive = {J_JACS}, author = {Bhawyanth Duvvuru and Myles W. Smith}, doi = {10.1021/jacs.5c14142}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39042--39046}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of annotinolide b via sequential quinoline dearomatization}, volume = {147}, year = {2025}, }
• (2025). Chiral lithium amides as key reagents in enantioselective synthesis of 2-alkylpyridines with multiple stereocenters. JACS, 147(43), 39036--39041. (www)

  @article{ , abstract = {A direct enantioselective conjugate addition of 2-alkylpyridines enables efficient construction of complex functionalized pyridinyl scaffolds with contiguous stereocenters. This method leverages chiral lithium amides as traceless stereodirecting auxiliaries, operating through defined aggregation of organolithium intermediates to achieve excellent enantio- and diastereocontrol.}, archive = {J_JACS}, author = {Dyllan P. Ly and Leroy Lu and Priya Kandiyal and Armen Zakarian}, doi = {10.1021/jacs.5c13977}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39036--39041}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral lithium amides as key reagents in enantioselective synthesis of 2-alkylpyridines with multiple stereocenters}, volume = {147}, year = {2025}, }
• (2025). Metal- and CO-free carbonylation of alkyl iodides. JACS, 147(43), 39031--39035. (www)

  @article{ , abstract = {We report a new method for the carbonylation of alkyl iodides under photochemical conditions. The process relies on a simple aryl formate reagent, synthesized in one step from readily available chemicals and capable of releasing CO along with a phenolate species in the presence of a mild base. The photoactivity of this phenolate is harnessed to activate alkyl iodides via single-electron transfer and generate alkyl radicals that add to CO and ultimately offer access to carboxylic acids and amides. This new, user-friendly procedure overcomes the typical need for CO gas and/or metal catalysts in carbonylation chemistry while being highly efficient and versatile to accommodate a variety of functional groups.}, archive = {J_JACS}, author = {Emilien Le Saux and Maurus Mathis and Giorgia Panizzolo and Bill Morandi}, doi = {10.1021/jacs.5c13505}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39031--39035}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal- and CO-free carbonylation of alkyl iodides}, volume = {147}, year = {2025}, }
• (2025). Anfinsen redux: Ribonuclease folding in the single-molecule regime. JACS, 147(43), 39026--39030. (www)

  @article{ , abstract = {Ribonuclease A (RNase A) has long been known to spontaneously refold to its native conformation and recover catalytic activity following denaturation. Yet, the molecular heterogeneity of its folding pathway has remained unclear due to ensemble averaging in traditional bulk measurements. Here, we use single-molecule enzymology (SME) to monitor the catalytic recovery of urea-denatured RNase A at the single-molecule level. We directly observe that individual RNase A molecules exhibit either fast or slow refolding kinetics, indicating distinct renaturation pathways that implicate slow prolyl peptide bond isomerization. These findings establish the utility of SME in revealing hidden heterogeneity in protein folding pathways.}, archive = {J_JACS}, author = {Arek V. Melkonian and Evans C. Wralstad and Ronald T. Raines and David R. Walt}, doi = {10.1021/jacs.5c13815}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39026--39030}, shortjournal = {J. Am. Chem. Soc.}, title = {Anfinsen redux: Ribonuclease folding in the single-molecule regime}, volume = {147}, year = {2025}, }
• (2025). Electron ptychography images hydrogen atom superlattices and 3D inhomogeneities in palladium hydride nanoparticles. JACS, 147(43), 39020--39025. (www)

  @article{ , abstract = {When hydrogen atoms occupy interstitial sites in metal lattices, they form metal hydrides (MH x ), whose structural and electronic properties can differ significantly from those of the host metals. Determining where the hydrogen is located within the MH x is crucial for predicting and understanding the resultant unique physical and electronic properties of the hydride. Yet, directly imaging hydrogen within a host material remains a major challenge due to its weak signal in conventional X-ray and electron imaging techniques. Here, we employ electron ptychography, a scanning transmission electron microscopy (STEM) technique, to image the three-dimensional (3D) distribution of H atoms in palladium hydride (PdH x ) nanocubes, one of the most studied and industrially relevant MH x materials. We observe an unexpected one-dimensional superlattice ordering of hydrogen within the PdH x nanocubes and 3D hydrogen clustering in localized regions within the PdH x nanocubes, revealing spatial heterogeneity in metal hydride nanoparticles previously inaccessible by other methods.}, archive = {J_JACS}, author = {Zixiao Shi and Qihao Li and Himani Mishra and Desheng Ma and Héctor D. Abruña and David A. Muller}, doi = {10.1021/jacs.5c13741}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39020--39025}, shortjournal = {J. Am. Chem. Soc.}, title = {Electron ptychography images hydrogen atom superlattices and 3D inhomogeneities in palladium hydride nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Catalytic enantioselective Diels–Alder reaction of dienes with acyclic and α,β- and β,β-disubstituted enones. JACS, 147(43), 39011--39019. (www)

  @article{ , abstract = {Despite the wealth of methods to enantioselectively catalyze Diels–Alder reactions of α,β-unsaturated carbonyl dienophiles, until today, not a single example with an acyclic enone that is either β,β- or α,β-disubstituted has been reported. Herein, we disclose a general Brønsted acid-catalyzed enantioselective Diels–Alder reaction of various aliphatic acyclic disubstituted enones with hydrocarbon dienes featuring diverse steric and electronic properties. The established method has been employed to synthesize several enantiopure targets, including well-known fragrance components such as arborone and the damascones.}, archive = {J_JACS}, author = {Jan Samsonowicz-Górski and Santanu Ghosh and Nobuya Tsuji and Markus Leutzsch and Georg Breitenbruch and Nils Nöthling and Philip Kraft and Benjamin List}, doi = {10.1021/jacs.5c13725}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39011--39019}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic enantioselective Diels–Alder reaction of dienes with acyclic and α,β- and β,β-disubstituted enones}, volume = {147}, year = {2025}, }
• (2025). Asymmetric total syntheses of hetidine-type c20-diterpenoid alkaloids: Spirasines v and VI, spiradine d, and the proposed structures of spirafines II and III. JACS, 147(43), 39004--39010. (www)

  @article{ , abstract = {Herein we describe a divergent strategy toward the asymmetric total syntheses of five hetidine-type C 20 -diterpenoid alkaloids, namely, spirasines V and VI, spiradine D, and the proposed structures of spirafines II and III. Crucial transformations include an Enders asymmetric addition, an oxidative dearomatization induced Diels–Alder cycloaddition, and a MHAT-initiated transannular radical cyclization. The heterocyclic rings were assembled by an efficient reductive cyclization sequence at a late stage. Our approach has enabled the total syntheses of these natural products in 17–20 steps from commercially available starting materials with high enantio- and diastereocontrol.}, archive = {J_JACS}, author = {Fengjie Yao and Yufei Wu and Yidian Sheng and Kuan Yu and Peirong Rao and Jun Xuan and Hanfeng Ding}, doi = {10.1021/jacs.5c13564}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {39004--39010}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric total syntheses of hetidine-type c20-diterpenoid alkaloids: Spirasines v and VI, spiradine d, and the proposed structures of spirafines II and III}, volume = {147}, year = {2025}, }
• (2025). Light-driven paramagnetic tags for efficient pseudocontact shifts measurements in protein NMR spectroscopy. JACS, 147(43), 38998--39003. (www)

  @article{ , abstract = {Pseudocontact shifts (PCSs) are essential for studies of protein structures and dynamics. However, structural calculations typically require multiple tags or labeling at multiple sites, which can be both time-consuming and expensive. In this study, we demonstrate that two independent sets of PCSs can be obtained using an azobenzene-based paramagnetic probe. Upon photoisomerization, the magnetic field around the protein is redistributed, resulting in a distinct NMR spectrum and enabling the acquisition of a new set of structural constraints. This light-driven spatial motion of the paramagnetic center eliminates the need for additional mutations or chemical activators to induce magnetic transitions, paving the way for the development of tensor-switchable paramagnetic tags.}, archive = {J_JACS}, author = {Zhaofei Chai and Qiong Wu and Kai Cheng and Weixuan Wang and Jiawen Chen and Xiaoli Liu and Yujun Xie and Zhen Li and Ling Jiang and Conggang Li}, doi = {10.1021/jacs.5c13482}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {38998--39003}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-driven paramagnetic tags for efficient pseudocontact shifts measurements in protein NMR spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Reversible enzymatic switching of the oxidation state of a EuIII/II complex controls relaxivity. JACS, 147(43), 38992--38997. (www)

  @article{ , abstract = {We show that europium trisbipyridyl cryptate exhibits an electrochemically reversible Eu III/II redox couple at −360 mV vs the standard hydrogen electrode (SHE) and is susceptible to reduction or oxidation by a range of redox enzymes or biological small molecule redox agents. Modulation of the europium oxidation state can be used to achieve dramatic changes in the T 1 relaxation time of bulk water in solutions containing these complexes: in the reduced form, the complex exhibits high relaxivity (3.08 mM –1 s –1 at 499.9 MHz) comparable with that of commercial MRI contrast media, while the oxidized form has negligible relaxivity, illustrating the scope for application in imaging reducing environments in biological systems.}, archive = {J_JACS}, author = {Euan T. Sarson and Saul M. Cooper and Adam C. Sedgwick and Amy-Grace Berger and Sophie A. Twigger and Ester M. Hammond and Kylie A. Vincent and Stephen Faulkner}, doi = {10.1021/jacs.5c13447}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {38992--38997}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible enzymatic switching of the oxidation state of a EuIII/II complex controls relaxivity}, volume = {147}, year = {2025}, }
• (2025). Interstellar formation of the elusive phosphanyloxyphosphane (H2POPH2) and phosphanylphosphinous acid (H2PPHOH) via nonequilibrium chemistry: Precursors to the phosphate backbone of nucleotides. JACS, 147(43), 38987--38991. (www)

  @article{ , abstract = {The P–O–P moiety plays a central role in inorganic and biological systems and is considered to be a critical precursor to the phosphate backbone of nucleotides. However, the isolation of the simplest prototype, phosphanyloxyphosphane (H 2 POPH 2 ), has remained elusive due to its high susceptibility to hydrolysis. Here, we report the first preparation of phosphanyloxyphosphane and its isomer phosphanylphosphinous acid (H 2 PPHOH) in low-temperature phosphine (PH 3 )–carbon dioxide (CO 2 ) ices upon exposure to galactic cosmic ray proxies in the form of energetic electrons. These isomers were isolated and identified in the gas phase using tunable vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry combined with isotopic labeling studies. Our findings not only suggest that the hitherto undetected phosphanyloxyphosphane and phosphanylphosphinous acid can be synthesized in phosphine-rich extraterrestrial ices but also advance our fundamental understanding of the formation of P–O–P and P–P–O linkages via nonequilibrium chemistry under astrophysical conditions.}, archive = {J_JACS}, author = {Jia Wang and Bing-Jian Sun and Alexandre Bergantini and Zesen Wang and Andrew M. Turner and Agnes H. H. Chang and Ralf I. Kaiser}, doi = {10.1021/jacs.5c12481}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {38987--38991}, shortjournal = {J. Am. Chem. Soc.}, title = {Interstellar formation of the elusive phosphanyloxyphosphane (H2POPH2) and phosphanylphosphinous acid (H2PPHOH) via nonequilibrium chemistry: Precursors to the phosphate backbone of nucleotides}, volume = {147}, year = {2025}, }
• (2025). Photocatalyst-regulated trifluoromethoxylation of aryl halides under silver promotion. JACS, 147(43), 38979--38986. (www)

  @article{ , abstract = {Trifluoromethoxylated aromatics are crucial in pharmaceuticals and agrochemicals, yet their synthesis remains challenging. While aryl halides offer advantages such as commercial availability and facile regioselectivity control, their direct trifluoromethoxylation has remained unachievable, even with transition-metal catalysis. Here, we report the first trifluoromethoxylation of aryl halides, enabled by a photocatalytic strategy via aryl cationic radical intermediates. A key advancement is the use of silver salts, which unlocks the participation of electronically neutral and electron-withdrawing aryl halides. Moreover, this method demonstrates exceptional chemoselectivity for aryl chlorides and bromides.}, archive = {J_JACS}, author = {Jingya Zhou and Longhui Chen and Ziang Miao and Jinjin Li and Yu-Xin Luan and Li Chen and Pingping Tang}, doi = {10.1021/jacs.5c11167}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {38979--38986}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalyst-regulated trifluoromethoxylation of aryl halides under silver promotion}, volume = {147}, year = {2025}, }
• (2025). Proton reduction with a cobalt-doped thiomolybdate cluster: A structural and functional model of co-doped MoS2. JACS, 147(43), 38973--38978. (www)

  @article{ , abstract = {A heterometallic thiomolybdate cluster, Cp* 3 CoMo 2 S 4 (Cp* = 1,2,3,4,5-pentamethylcyclopentadienide) has been synthesized and identified as a molecular electrocatalyst for proton reduction in dimethylformamide. Compared with its homometallic congener (Cp* 3 Mo 3 S 4 ), cobalt incorporation improves activity by lowering the overpotential for proton reduction, consistent with the contrasting catalytic performance of MoS 2 and its Co-doped derivative. Isolation of the reduced form of Cp* 3 CoMo 2 S 4 and subsequent reactivity studies provide insight into the reaction pathway. These findings establish Cp* 3 CoMo 2 S 4 as a molecular model for extended sulfide materials.}, archive = {J_JACS}, author = {Kamaless Patra and Leyla R. Valerio and Zhou Lu and Kaye Kuphal and William W. Brennessel and Ellen M. Matson}, doi = {10.1021/jacs.5c09888}, journal = {Journal of the American Chemical Society}, month = {10}, number = {43}, pages = {38973--38978}, shortjournal = {J. Am. Chem. Soc.}, title = {Proton reduction with a cobalt-doped thiomolybdate cluster: A structural and functional model of co-doped MoS2}, volume = {147}, year = {2025}, }
• (2025). A sodium iron phosphate nanocatalyst-regulated high-mobility ion reservoir enables tumor-selective immunotherapy. JACS, 147(42), 38958--38972. (www)

  @article{ , abstract = {Sodium ion (Na + )-mediated pyroptosis has emerged as a promising strategy in ion interference therapy (IIT) for tumor treatment. However, conventional Na + delivery systems suffer from off-target leakage and osmotic toxicity in normal tissues. Herein, we present the construction of a peroxidase-mimicking ion reservoir based on sodium iron phosphate (NFPP) nanocatalysts, which enables rapid and tumor-selective Na + outflow through pH-gated nanocatalytic activation. NFPP maintains an “OFF” state in normal cells due to the minimal ion release induced by the catalytic inactivation. Crucially, in tumor cells, the peroxidase-like catalytic activity of NFPP is activated by the more acidic lysosome environment than that within normal cells, transitioning NFPP to an “ON” state. The optimal activity boosts the Na + outward migration, resulting in intracellular Na + overload that triggers the pyroptosis pathway. Conversely, the rapid Na + flux amplifies the peroxidase-like catalytic activity, thus reinforcing oxidative stress and exacerbating pyroptosis. The NFPP nanoplatform can further provoke robust immune responses and provide long-term protection against tumor relapse and metastasis. This work pioneers a design strategy for constructing nanocatalysis-regulated high-mobility ion reservoirs to overcome limitations in precise ion modulation for selective tumor immunotherapy.}, archive = {J_JACS}, author = {Zitong Zhu and Huan Wang and Mengmeng Liu and Yanjun Ji and Anjun Song and Jinsong Ren and Xiaogang Qu}, doi = {10.1021/jacs.5c16505}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38958--38972}, shortjournal = {J. Am. Chem. Soc.}, title = {A sodium iron phosphate nanocatalyst-regulated high-mobility ion reservoir enables tumor-selective immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Discovery and biosynthetic interrogation of a cobalt-containing terpene-polyketide-nonribosomal peptide tribrid with anticoronavirus activity. JACS, 147(42), 38951--38957. (www)

  @article{ , abstract = {The structural complexity of natural products arises from the complexity of their biosynthetic pathways and directly contributes to their biological activities. Guided by this principle, we screened 500 microbial extracts using high-throughput screening to identify structurally novel inhibitors of coronavirus main protease, 3CL pro . We discovered and structurally characterized a new scaffold, cobaltribin, the only isolated cobalt-containing natural product except vitamin B12 cobalamins. We further analyzed cobaltribin analogs to expand this unique class of anticoronavirus compounds. Furthermore, evidence from our bioinformatic, isotope labeling, and gene deletion analyses suggested that cobaltribin is a tribrid natural product resulting from an unprecedented terpene-polyketide (PK)-nonribosomal peptide (NRP) trihybridized biosynthesis. Notably, cobaltribin inhibits live severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) replication in infected Vero E6 cells without toxicity to the host, demonstrating its promise as a therapeutic candidate against SARS-CoV-2.}, archive = {J_JACS}, author = {Dan Xue and Qihao Wu and Lukuan Hou and Conor Pulliam and Mingming Xu and Michael D. Madden and Joshua Madu and Ying Li and Shufeng Liu and Daping Fan and Tim S. Bugni and Tony Wang and Jie Li}, doi = {10.1021/jacs.5c16450}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38951--38957}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery and biosynthetic interrogation of a cobalt-containing terpene-polyketide-nonribosomal peptide tribrid with anticoronavirus activity}, volume = {147}, year = {2025}, }
• (2025). Kinetic resolution for 1,4-spin-center shift-based reduction of azaarene-functionalized secondary and tertiary allylic alcohols. JACS, 147(42), 38942--38950. (www)

  @article{ , abstract = {The spin-center shift (SCS) represents a highly effective strategy in the field of photoredox catalysis for the generation of radical intermediates. Owing to intrinsic mechanistic constraints, the reaction pathway primarily entails a 1,2-radical translocation event, concomitant with a two-electron ionic shift. In contrast, remote SCS events are exceedingly rare, and when observed, they typically exploit C═C bonds within aromatic systems, where aromatization serves as an important thermodynamic driving force for this challenging transformation. Here, we present a proof-of-concept demonstrating that simple olefins can function as effective C═C units to facilitate the elusive 1,4-SCS process. Under cooperative photoredox and chiral Brønsted acid catalysis, a broad range of racemic azaarene-functionalized secondary and tertiary allylic alcohols undergo highly efficient kinetic resolution through 1,4-SCS-based reduction. This chiral acid-mediated pathway promotes the selective removal of γ-alcohols in one enantiomer, furnishing the complementary enantiomer in satisfactory yield with good to excellent enantioselectivity. The synthetic and pharmaceutical value of these enantioenriched azaarene derivatives─together with the challenges in accessing them by conventional methods─highlights the impact of this approach. By introducing an unprecedented π-system platform for remote SCS, this work represents a conceptual advance that opens new avenues for SCS-driven synthetic transformations.}, archive = {J_JACS}, author = {Xiangbin Bai and Jialu Yao and Mengbo Zhang and Qing Peng and Wenxian Li and Xiaowei Zhao and Yanli Yin and Zhiyong Jiang}, doi = {10.1021/jacs.5c15917}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38942--38950}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetic resolution for 1,4-spin-center shift-based reduction of azaarene-functionalized secondary and tertiary allylic alcohols}, volume = {147}, year = {2025}, }
• (2025). Copper-catalyzed asymmetric C–H sulfilimination of arenes via HAT-primed C–S Radical–Radical coupling. JACS, 147(42), 38931--38941. (www)

  @article{ , abstract = {As an important class of chiral-at-sulfur products, sulfilimines play an important role in diverse fields as functional molecules. Reported herein is the efficient synthesis of sulfilimines via oxidative C–H sulfilimination of (hetero)arenes with sulfenamides under copper catalysis. In particular, the sulfilimination of indoles and naphthols proceeded under mild conditions in excellent regio- and enantioselectivity with air or organic peroxide as the oxidant, and the configurational lability of the sulfilimine products further highlighted the challenge of this catalytic system. Experimental and computational mechanistic studies revealed a dual hydrogen atom transfer (HAT) pathway, and the C–S formation occurs via an outer-sphere HAT-primed radical–radical coupling with concerted arene HAT and C–S bonding in an eight-membered ring transition state.}, archive = {J_JACS}, author = {Yishou Wang and Yucai Mu and Xin Han and Jichao Xiao and Genping Huang and Fen Wang and Xiao-Xi Li and Xingwei Li}, doi = {10.1021/jacs.5c15479}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38931--38941}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper-catalyzed asymmetric C–H sulfilimination of arenes via HAT-primed C–S Radical–Radical coupling}, volume = {147}, year = {2025}, }
• (2025). Atomically precise copper cluster for highly chemoselective carbenoid insertion into the N–H bond of aliphatic amine. JACS, 147(42), 38922--38930. (www)

  @article{ , abstract = {Due to the strong coordination effect between aliphatic amines and transition metal catalysts, the activity of the catalyst is inhibited by aliphatic amines’ strong Lewis basicity, leading to poor chemoselectivity and a significant challenge to the N–H insertion reaction. Here, we report a highly stable copper cluster (Cu 3 NC (NHC) ) with dynamic catalytic sites for the first time that is used to efficiently and chemoselectively catalyze the N–H insertion reaction of aliphatic amines. Pyridine groups as dynamic ligands and aliphatic amines could compete for coordination to prevent catalyst deactivation due to passivation. The dissociated dynamic ligands could regulate the steric effect of the catalyst to achieve highly selective alkylation of primary amines. Moreover, the reaction afforded high chemoselectivity between the C═C bond and the N–H bond by forming a Cu 3 NC (NHC) -carbenoid intermediate. TON of the N–H insertion reaction has reached 79200. The reaction could be applied in pharmaceutical synthesis and late-stage functionalization. Mechanistic studies and density functional theory demonstrate that this process of generating Cu 3 NC (NHC) -carbenoid was both kinetically and thermodynamically favorable and that this process may not be the rate-limiting step. This investigation highlights the broad application prospects of metal nanoclusters in the field of organic catalysis, providing a new idea for the development of cluster chemistry.}, archive = {J_JACS}, author = {Teng Jia and Miao-Miao Zhang and Rui Liu and Cai-Fang Sun and Jie Ai and Zheng Wang and Yu Lan and Shuang-Quan Zang}, doi = {10.1021/jacs.5c15400}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38922--38930}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomically precise copper cluster for highly chemoselective carbenoid insertion into the N–H bond of aliphatic amine}, volume = {147}, year = {2025}, }
• (2025). Cleavable hydrophobic anchors optimize immunomodulatory effects of oligonucleotides. JACS, 147(42), 38907--38921. (www)

  @article{ , abstract = {Oligonucleotides (ODNs) are useful in a wide variety of biomedical applications, spanning diagnostics, and therapeutics but are susceptible to nuclease degradation and exhibit poor cellular uptake. Strategies that involve phosphorothioate (PS) backbone modifications and hydrophobic group conjugations have been used to enhance the stability and bioavailability of ODNs. However, improved ODN cellular delivery has not always correlated well with enhancing therapeutic efficacy, particularly in the context of immune modulation. Herein, we propose a theory to explain why this is the case and subsequently present a strategy based upon it to incorporate cleavable linkages between functional ODNs and hydrophobic moieties to simultaneously enhance cellular uptake and improve ODN functionality. Specifically, we synthesized nuclease-cleavable lipid-modified ODNs with phosphodiester (PO)–phosphorothioate (PS) backbone hybrids (POPS). Importantly, these POPS-ODNs exhibit enhanced cellular uptake and functional efficacy compared to their fully PS-modified counterparts. ODN cellular uptake and immunomodulation efficacy were further increased by incorporating POPS-ODNs within a liposomal spherical nucleic acid (SNA) architecture. Our findings highlight the critical balance between enhancing cellular uptake and maintaining therapeutic effectiveness in modified ODN designs, offering insights for optimizing their application in biomedical research and therapeutic development.}, archive = {J_JACS}, author = {Taokun Luo and Young Jun Kim and Alex Cushing and Yinglun Ma and Zhenyu Han and Ryan E. Johnson and Mia J. P. Pascall and Chad A. Mirkin}, doi = {10.1021/jacs.5c15110}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38907--38921}, shortjournal = {J. Am. Chem. Soc.}, title = {Cleavable hydrophobic anchors optimize immunomodulatory effects of oligonucleotides}, volume = {147}, year = {2025}, }
• (2025). Unlocking difluorocarbene as a fluorocarbanion and a fluorocarbon radical precursor for sequential catalytic coupling. JACS, 147(42), 38897--38906. (www)

  @article{ , abstract = {Here we report an unprecedented mechanism involving the thermolytic homolysis of difluoroalkylpalladium species, which can be directly generated in situ from palladium difluorocarbene, yielding difluoroalkyl radicals. This discovery bridges the gap between difluorocarbene and fluorocarbon radical, enabling difluorocarbene to function as both a fluorocarbanion and a fluorocarbon radical precursor. By exploiting the synthetic versatility of difluorocarbene to sequentially form various active intermediates, including palladium(II) difluorocarbene, difluoroalkylpalladium species, and difluoroalkyl radicals, this strategy provides a synthetically versatile paradigm for the modular construction of difluoroalkylated arenes. The approach leverages readily available components, including aryl iodides, alkenes, and the industrial chemical ClCF 2 H, opening a new avenue for the precise introduction of the difluoromethylene group.}, archive = {J_JACS}, author = {Shi-Ping Sun and Tong Mu and Xue-Ying Zhang and Xia-Ping Fu and Hai-Yang Zhao and Yanxia Zhang and Xiao-Song Xue and Xingang Zhang}, doi = {10.1021/jacs.5c15052}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38897--38906}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking difluorocarbene as a fluorocarbanion and a fluorocarbon radical precursor for sequential catalytic coupling}, volume = {147}, year = {2025}, }
• (2025). Double disguise: Camouflaging photocages for bioorthogonally controlled conditional activation. JACS, 147(42), 38889--38896. (www)

  @article{ , abstract = {Photocages provide excellent spatiotemporal control over biological processes; however, strategies to restrict their activation to specific conditions remain limited. In this work, we demonstrate that our recently introduced photocages based on the aminofluorone (rhodol) choromophore can be rendered completely inactive through a single substitution on the oxygen auxochrome. These ‘camouflaged’ photocages are entirely colorless, preventing photouncaging in their disabled state. Bioorthogonal removal of the camouflaging group restores the photoactivity of the cages, introducing an additional layer of control for photoassisted delivery systems. We further demonstrate this concept of substitution-dependent, bioorthogonally regulated photoactivation in a cellular context, where both a bioorthogonal reagent and light were required to release a potent topoisomerase inhibitor, SN38.}, archive = {J_JACS}, author = {Orsolya Ember and Krisztina Németh and Dóra Kern and Attila Kormos and Péter Kele and Márton Bojtár}, doi = {10.1021/jacs.5c15005}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38889--38896}, shortjournal = {J. Am. Chem. Soc.}, title = {Double disguise: Camouflaging photocages for bioorthogonally controlled conditional activation}, volume = {147}, year = {2025}, }
• (2025). A biomimetic procedure for the synthesis of 1,2-cis C-vinyl furanosides from unprotected aldoses. JACS, 147(42), 38879--38888. (www)

  @article{ , abstract = {C -glycosides are valuable analogs of O - and N -glycosides with broad pharmaceutical relevance. While most synthetic approaches to C -glycosides rely on protected glycosyl donors, there is growing interest in methods that utilize unprotected native sugars, particularly for synthesizing C -furanosides, which are thermodynamically less favored than their pyranosyl counterparts. Inspired by enzymatic biosynthesis, we report a biomimetic “open-and-close” strategy for the synthesis of 1,2- cis C -vinyl furanosides from unprotected aldoses. This process involves a morpholine-mediated Petasis reaction between aldoses and vinyl boronic acids, converting cyclic hemiacetals into linear polyhydroxy amines with high 1,2- anti selectivity. Subsequent difluorocarbene-induced deaminative cyclization efficiently forms the furanose ring with high chemoselectivity and diastereoselectivity. The method exhibits broad substrate scope, accommodating various vinyl boronic acids as well as native mono- and disaccharides, and is amenable to scale-up under mild, aqueous-compatible conditions. Downstream derivatizations of the vinyl group afford 1,2- cis C -alkyl furanosides, offering efficient access to otherwise challenging molecular architectures.}, archive = {J_JACS}, author = {Dongyang Sun and Xuerui Dou and Fen Wang and Jiawei Wu and Wenbo Wang and Gang He}, doi = {10.1021/jacs.5c14877}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38879--38888}, shortjournal = {J. Am. Chem. Soc.}, title = {A biomimetic procedure for the synthesis of 1,2-cis C-vinyl furanosides from unprotected aldoses}, volume = {147}, year = {2025}, }
• (2025). Computationally aided design of ionizable cholesteryl lipids for lipid nanoparticles to modulate hepatic mRNA accumulation. JACS, 147(42), 38865--38878. (www)

  @article{ , abstract = {mRNA therapeutics are emerging as a revolutionary therapeutic modality, providing a versatile platform for the treatment and prevention of a broad spectrum of diseases. Nonviral nanoparticle-based delivery systems, particularly lipid nanoparticles (LNPs), are essential for their successful clinical translation. However, the currently FDA-approved four-component lipid nanoparticle (LNP) formulations primarily accumulate in the liver due to apolipoprotein E/Low-Density Lipoprotein Receptor (ApoE/LDLR)-mediated uptake by hepatic cells following systemic administration, which significantly limits extrahepatic mRNA delivery and restricts its broader therapeutic applications. Herein, we present a computationally assisted design approach to identify and optimize ionizable cholesteryl (iChol) lipids with extrahepatic delivery properties while formulating a three-component LNP system. Using DiffDock-L-assisted design, we rationally integrated two key components of LNPs, cholesterol and ionizable lipid, into a single chemical entity and developed a novel class of ionizable cholesteryl (iChol) lipids that exhibit attenuated interactions with ApoE. These iChol lipids, along with phospholipids and PEGylated lipids, can self-assemble into stable three-component lipid nanoparticles (Tc-LNPs). The Tc-LNPs exhibit decreased ApoE adsorption compared to conventional four-component LNP counterparts. Importantly, the Tc-LNPs show reduced hepatic accumulation via modulating ApoE/LDLR-mediated endocytosis in hepatocytes and improved spleen enrichment compared to commercially available LNPs. Additionally, this approach is applicable to other ionizable lipids, including the commercially available ALC-0315 lipid, paving a new way for accelerating the development of extrahepatic delivery LNPs and potentially expanding the applications of mRNA-based therapeutics.}, archive = {J_JACS}, author = {Yilong Teng and Yuxuan Guo and Zhixiang Liu and Maoping Tang and William Stewart and Xiaoyang Xu and Xue-Qing Zhang}, doi = {10.1021/jacs.5c14870}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38865--38878}, shortjournal = {J. Am. Chem. Soc.}, title = {Computationally aided design of ionizable cholesteryl lipids for lipid nanoparticles to modulate hepatic mRNA accumulation}, volume = {147}, year = {2025}, }
• (2025). One-step synthesis of cyanated quinoxaline regioisomers enables n-type polymers with record ambient-processed thermoelectric performance. JACS, 147(42), 38851--38864. (www)

  @article{ , abstract = {Advancements in organic electronics critically depend on the development of high-performance n-type π-conjugated polymers. However, electron-depleted polymers of this kind exhibiting facile synthesis, excellent processability and good air stability remain rare due to limitations in accessing building blocks meeting these requirements. Here we develop two novel, structurally simple and yet π-extended and highly electron-deficient cyanated building blocks: 2,3-quinoxalinedicarbonitrile ( QxCN ) and 6,7-quinoxalinedicarbonitrile ( CNQx ). These units are synthesized in a single-step from low-cost precursors via regioselective cyanation of the weak acceptor quinoxaline. Copolymerization with thiophene-flanked diketopyrrolopyrrole affords two acceptor–acceptor type copolymers TDPP-QxCN and TDPP-CNQx , respectively, exhibiting significantly deeper LUMO levels (∼−3.9 eV) compared to the noncyanated polymer analogue TDPP-Qx (−3.35 eV). In-depth spectroscopic, theoretical, and microstructural analyses reveal that cyanation at the 6,7-positions in TDPP-CNQx suppresses minority carrier effects associated with intramolecular charge transfer in TDPP-QxCN , while promoting excellent conformational adaptability that drives efficient self-assembly into a highly crystalline film with a favorable balance of ordered and disordered domains. This microstructural organization ensures rapid electron transport and efficient dopant diffusion, leading to large field-effect mobilitiesfor TDPP-CNQx (up to 1.3 cm 2 V –1 s –1 ) and unprecedented n-doping efficiency even under air-processed conditions. Consequently, n-doped TDPP-CNQx films exhibit a high n-type electrical conductivity (44.50 S cm –1 ), excellent power factor (65.16 μW m –1 K –2 ), and ultralow thermal conductivity (0.10 W m –1 K –1 ), collectively culminating in a record thermoelectric figure of merit (ZT = 0.20) for solution/ambient-processed films. This performance also surpasses nearly all vacuum-processed counterparts, positioning CNQx as a highly promising building block for next-generation organic electronics.}, archive = {J_JACS}, author = {Sergio Gámez-Valenzuela and Suxiang Ma and Yanlin Wei and Yani Lu and Changjing Xu and Kui Feng and Sang Young Jeong and Hong Wang and Han Young Woo and Antonio Facchetti and Xugang Guo}, doi = {10.1021/jacs.5c14816}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38851--38864}, shortjournal = {J. Am. Chem. Soc.}, title = {One-step synthesis of cyanated quinoxaline regioisomers enables n-type polymers with record ambient-processed thermoelectric performance}, volume = {147}, year = {2025}, }
• (2025). Synergistic programming of macrophages by hybrid glycocalyx-inspired nanoparticles for adoptive cell therapy. JACS, 147(42), 38838--38850. (www)

  @article{ , abstract = {Adoptive cell transfer has emerged as a promising approach for cancer immunotherapy. However, the transfer of macrophages is limited by their high plasticity, which can switch the pro-inflammatory phenotype (M1-like) to the anti-inflammatory state (M2-like) in an immunosuppressive microenvironment. Inspired by natural glycocalyx and its indispensable functions on immune response and communication, here we report an approach of hybrid glycocalyx-inspired nanoparticles that integrates (oligo)mannoside-modified glycopolymers with iron oxide to program primary macrophages into a persistent M1-like phenotype in which glycocalyx-inspired nanoparticles and iron oxide act as the extracellular and intracellular stimulatory signals, respectively. Importantly, with the synergistically enhanced immunoactivation of dual signals, the programmed macrophages are able to resist the immunosuppressive microenvironment and exhibit significantly enhanced tumoricidal effects both in vitro and in vivo. We further demonstrate that adoptive transfer of macrophages programmed by hybrid glycocalyx-inspired nanoparticles also improves the tumor microenvironment and increases T cell responses. These results, using glycocalyx mimetics as macrophage encoders, highlight an alternative approach for the development of adoptive cell immunotherapies.}, archive = {J_JACS}, author = {Lin Yin and Xuyang Xu and Yiwei Shi and Xiangyun Xu and Xiaomei Liu and Jieyi An and Qiqige Du and Long Li and Guosong Chen}, doi = {10.1021/jacs.5c14740}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38838--38850}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic programming of macrophages by hybrid glycocalyx-inspired nanoparticles for adoptive cell therapy}, volume = {147}, year = {2025}, }
• (2025). Photoelectrochemical catalyzed site-selective tryptophan β-position functionalization. JACS, 147(42), 38827--38837. (www)

  @article{ , abstract = {Site-specific bioconjugation methods offer exceptional uniformity in producing protein/peptide conjugates, thereby improving pharmacological properties. However, developing site-selective chemical modifications directly on natural amino acids, especially at the β-position, remains challenging. Here, we present a novel photoelectrochemical strategy for site-selective tryptophan β-position functionalization. Employing a 2,3-dichloro-5,6-dicyano- p -benzoquinone (DDQ)/ tert -butyl nitrite (TBN) catalyst system under blue LED irradiation and electrochemical conditions, we achieved C(sp 3 )-H functionalization for activating the tryptophan β-position with nucleophiles. This resulted in a variety of conjugated peptides and proteins with outstanding selectivity. The in situ generation of the C-centered Trp-skatolyl cation by this protocol allows its reaction with nucleophiles to produce diverse functionalized products. Offering mild, eco-friendly conditions and enhanced selectivity, this method emerges as a promising tool for peptide and protein modification in pharmaceutical applications.}, archive = {J_JACS}, author = {Ci-Yang Sun and Yu-Yu Chen and Hung-Chi Chen and Hung-Li Li and Chien-Wei Chiang}, doi = {10.1021/jacs.5c14517}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38827--38837}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoelectrochemical catalyzed site-selective tryptophan β-position functionalization}, volume = {147}, year = {2025}, }
• (2025). NiH-catalyzed homobenzylic hydroalkylation of aryl alkenes using sulfoxonium ylides. JACS, 147(42), 38817--38826. (www)

  @article{ , abstract = {We present here the first example of NiH-catalyzed homobenzylic hydroalkylation of aryl alkenes mediated by a nickel carbene radical, achieving the elusive β-selectivity with excellent regiocontrol. Mechanistic investigations suggest that this transformation is enabled by the preferential engagement of NiH with bench-stable sulfoxonium ylides, whose unique chelation properties promote carbene activation prior to alkene insertion. The resulting nickel carbene radical is proposed to undergo selective β-addition, followed by intramolecular metal hydride transfer and protodemetalation. The reaction exhibits broad scope across aryl, heteroaryl, and complex bioactive alkene derivatives, as well as diverse sulfoxonium ylides. This work establishes a new mechanistic platform for NiH catalysis, expanding the synthetic repertoire for site-selective alkene functionalization.}, archive = {J_JACS}, author = {Qing Wang and Hoonchul Choi and Xiang Lyu and Dongwook Kim and Sukbok Chang}, doi = {10.1021/jacs.5c14594}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38817--38826}, shortjournal = {J. Am. Chem. Soc.}, title = {NiH-catalyzed homobenzylic hydroalkylation of aryl alkenes using sulfoxonium ylides}, volume = {147}, year = {2025}, }
• (2025). Controlled synthesis of ultralow-defect poly(vinylidene fluoride) via organocatalyzed low-temperature polymerization. JACS, 147(42), 38807--38816. (www)

  @article{ , abstract = {Polyvinylidene fluoride (PVDF), distinguished for its exceptional electroactivity, holds considerable promise for applications in flexible and wearable electronics. However, its performance is limited by intrinsic chain defects during radical addition. We demonstrate that temperature critically governs defect formation and exploit this insight to develop a wide-temperature-range (−40 to 50 °C), organocatalyzed photoredox polymerization to enable controlled PVDF synthesis. The synergy of low-temperature propagation and reductive initiation not only suppressed chain defects to 1.8% by enforcing regioselective head-to-tail addition but also shifted chain-end connections from the VDF tail (CH 2 ) to the more active head (CF 2 ). The defect control promoted the formation of the β-phase, achieving a dielectric constant 40% higher than conventional PVDFs (12.7 vs 9). Moreover, this method unlocks PVDF’s potential as a modular building block, enabling on-demand access toward previously unattainable structural diversity. This work overcomes a long-standing bottleneck in electroactive polymer design, opening avenues to tailor primary structures for advanced flexible electronics.}, archive = {J_JACS}, author = {Xing Guo and Jinglin Yi and Chengda Zhou and Zexi Zhang and Mao Chen}, doi = {10.1021/jacs.5c14385}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38807--38816}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlled synthesis of ultralow-defect poly(vinylidene fluoride) via organocatalyzed low-temperature polymerization}, volume = {147}, year = {2025}, }
• (2025). Controlled synthesis of lipoate homopolymers via reversible Addition–Fragmentation chain transfer polymerization. JACS, 147(42), 38796--38806. (www)

  @article{ , abstract = {Polylipoates (PLp), derived from α-lipoic acid, are promising polymers for developing biocompatible, stimuli-responsive, and fully (closed-loop) recyclable materials. However, their synthesis is hindered by two key challenges: the high propensity of lipoate propagating radicals to undergo backbiting during polymerization, and the tendency for polymers to spontaneously depolymerize due to a low ceiling temperature. In this study, we demonstrate that reversible addition–fragmentation chain transfer (RAFT) polymerization overcomes these challenges and can be used to synthesize PLp homopolymers with a high degree of control. This was confirmed by a linear relationship between molecular weight ( M n ) and monomer conversion, as well as first-order polymerization kinetics, characteristics not achievable with conventional radical polymerization. By adjusting the RAFT agent feed ratio, the M n of homopolymer PLps was precisely controlled with an M n ranging from 3.6 to 62.6 kg mol –1 . RAFT polymerization provided stable end-groups that effectively suppressed the spontaneous depolymerization of PLp. Polymers synthesized using RAFT agents remained intact for over 2 weeks in both solution and bulk, while those prepared under traditional radical conditions showed substantial degradation. Moreover, the trithiocarbonate end-group enabled light-triggered, on-demand depolymerization back to the original monomer. RAFT was also successfully extended to the synthesis of degradable block copolymers. Together, these results demonstrate that RAFT offers a simple, accessible, and proven strategy to address key challenges in PLp synthesis and long-term stability.}, archive = {J_JACS}, author = {Kenny Lee and Shiwei Han and Parker T. Morris and Christopher M. Bates and Craig J. Hawker and Cyrille Boyer}, doi = {10.1021/jacs.5c14377}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38796--38806}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlled synthesis of lipoate homopolymers via reversible Addition–Fragmentation chain transfer polymerization}, volume = {147}, year = {2025}, }
• (2025). Photochemical generation and characterization of alanine imine: A key intermediate in prebiotic amino acid formation. JACS, 147(42), 38785--38795. (www)

  @article{ , abstract = {Simple imino acids have received sparse consideration as reactive intermediates in the formation of amino acids under prebiotic or astrochemical conditions. Under cryogenic matrix isolation conditions, 2-azidopropionic acid decomposes after ultraviolet (UV) irradiation to dinitrogen and 2-iminopropionic acid, namely, alanine imine, which is the proposed key intermediate in biologically relevant alanine transaminase reactions. Three conformers of alanine imine were spectroscopically characterized by Fourier transform infrared (FT-IR) and ultraviolet–visible (UV/vis) spectroscopy in solid argon at 3.5 K. One high-energy conformer can be selectively prepared by the near-IR induced excitation of an OH-overtone vibration. In the dark, this conformer undergoes H-tunneling CO-bond rotamerization. In aqueous solution, 2-azidopropionic acid decomposes to glyoxylic and pyruvic acid after hydrolysis of the formed imine intermediates as identified by 1 H NMR spectroscopy. Under more acidic conditions and prolonged irradiation, the intermediary formed imino acids are reduced to their glycine and alanine amino acid equivalents, respectively.}, archive = {J_JACS}, author = {Vladimir D. Drabkin and Christian Thiehoff and María Eugenia Sandoval-Salinas and Viktor Paczelt and Rachel Crespo-Otero and André K. Eckhardt}, doi = {10.1021/jacs.5c14327}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38785--38795}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemical generation and characterization of alanine imine: A key intermediate in prebiotic amino acid formation}, volume = {147}, year = {2025}, }
• (2025). Copper-catalyzed asymmetric nitrenoid transfer to access fused δ-lactams via HFIP-assisted aziridination and cascade cyclization. JACS, 147(42), 38772--38784. (www)

  @article{ , abstract = {Aza-steroids and terpenoid alkaloids are prominent entities of biorelevant ring-fused azacycles with significant pharmaceutical applications. Despite their importance, synthetic approaches to these complex molecules remain a great challenge due to the lack of strategic routes to the multiple contiguous chiral centers, particularly in the case of thermodynamically unstable cis -ring frameworks. Herein, we report a Cu-catalyzed asymmetric cascade cyclization of arylalkenyl dioxazolones to access ring-fused δ-lactams. It is initiated to form a bicyclic N -acylaziridine intermediate to involve a concerted transition state, allowing an asynchronous C–N bond formation on the open-shell singlet surface. This key reactivity is enabled by 1,1,1,3,3,3-hexafluoropropan-2-ol (HFIP), which stabilizes the reactive Cu-acylnitrenoid intermediate via inner-sphere hydrogen bonding. The resulting N -acylaziridine undergoes HFIP-promoted regio- and diastereoselective ring-opening with pendant arene or heteroarene nucleophiles to deliver condensed δ-lactam products with excellent anti -selectivity.}, archive = {J_JACS}, author = {Suhyeon Kim and Eleonora Tufano and Matteo Barilli and Emanuele Casali and Younghoon Kim and Dongwook Kim and Tommaso Massimini and Giuseppe Zanoni and Sukbok Chang}, doi = {10.1021/jacs.5c14319}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38772--38784}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper-catalyzed asymmetric nitrenoid transfer to access fused δ-lactams via HFIP-assisted aziridination and cascade cyclization}, volume = {147}, year = {2025}, }
• (2025). Charge-transfer states enable spin-selective formation of quartet state qudits in luminescent radical-chromophore dyads. JACS, 147(42), 38762--38771. (www)

  @article{ , abstract = {Luminescent tris(2,4,6-trichlorophenyl)methyl (TTM) radicals are promising doublet emitters that have been used to generate spin-optical interfaces in molecular electron spin qudits. In particular, photoexcitation of covalent TTM-chromophore dyads can generate quartet spin states that can be detected via photoluminescence. However, the mechanism of quartet spin initialization is complicated by competing charge-transfer (CT) and energy-transfer (EnT) pathways between the radical and the chromophore. Here, we demonstrate the role of CT intermediates by engineering a covalent dyad of TTM and naphthalene-(1,4:5,8)-bis(dicarboximide) (NDI), a well-known electron acceptor chromophore. Transient absorption spectroscopy indicates that photoexcitation of TTM results in ultrafast electron transfer from 2* TTM to NDI, which kinetically outcompetes EnT. Electron paramagnetic resonance spectroscopy reveals that charge recombination proceeds via spin–orbit charge-transfer intersystem crossing to generate 3* NDI, followed by spin mixing with 2 TTM to form the quartet state. This process uniquely spin-polarizes the quartet state, providing fundamental design principles to purify the initial wave function for quantum information processing.}, archive = {J_JACS}, author = {Yizhe Chen and Jonathan R. Palmer and Brian T. Phelan and Kathryn R. Peinkofer and Matthew D. Krzyaniak and Ryan M. Young and Michael R. Wasielewski}, doi = {10.1021/jacs.5c14244}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38762--38771}, shortjournal = {J. Am. Chem. Soc.}, title = {Charge-transfer states enable spin-selective formation of quartet state qudits in luminescent radical-chromophore dyads}, volume = {147}, year = {2025}, }
• (2025). Atomic coordination editing achieves ultraproductive single-atom catalysts with ultralow loadings. JACS, 147(42), 38752--38761. (www)

  @article{ , abstract = {Fabrication of noble-metal-based catalysts combining ultralow loadings with industrial-grade performance remains a grand challenge. Here, we report a facile strategy to synthesize ppm-level loaded Ir 1 single-atom catalysts (SACs) that can break scaling-relation limitations, achieving exceptional propane dehydrogenation (PDH) performance. Simple H 2 IrCl 6 impregnation on carbon followed by NH 3 pyrolysis yields a catalyst that achieves ∼33% propane conversion and ∼92% propylene selectivity. It demonstrates a remarkable propylene time-space yield of 14976 mol C 3 H 6 mol Ir –1 h –1 with an ultralow deactivation constant (0.00191 h –1 ), outperforming Ir nanoparticles and most reported noble-metal catalysts. Advanced characterizations and density functional theory calculations disclose that NH 3 pyrolysis induces in situ substitution of Cl by N species to generate an Ir–O 2 N 2 active motif, where dual N/O coordination simultaneously drives the PDH reaction and prevents metal aggregation. This approach provides a blueprint for developing industrial-viable SACs that reconcile atom-economy with process-intensity demands, as validated across multiple noble-metal systems.}, archive = {J_JACS}, author = {Liru Cao and Fenfei Wei and Yang Chen and Xiaoli Pan and Hongchen Cao and Yang Su and Yang Zhao and Dali Chen and Yicong Chai and Lulu Chen and Jian Lin and Sen Lin and Xiaodong Wang and Xianzhi Fu and Tao Zhang}, doi = {10.1021/jacs.5c14188}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38752--38761}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic coordination editing achieves ultraproductive single-atom catalysts with ultralow loadings}, volume = {147}, year = {2025}, }
• (2025). Carbene zipper reaction for cascade π-extension. JACS, 147(42), 38743--38751. (www)

  @article{ , abstract = {The unique electronic, thermal, and mechanical properties of nanographenes structured with polycyclic aromatic hydrocarbons (PAHs) can be finely tuned via modulation of the π-length, π-width, π-shape, π-edge, and π-curvature topology. However, the programmable construction of such architectures remains a formidable challenge, drastically hindering the systematic exploration of structure–property relationships in graphene-based materials. In this study, a cascade π-extension strategy has been established for the precise synthesis of PAHs through a copper-catalyzed domino carbene transfer process, enabling determinate structural control with tunable lengths, facilitating the construction of versatile twisted π-systems with local aromaticity variations.}, archive = {J_JACS}, author = {Hongxu Lv and Leiyang Bai and Xuefeng Jiang}, doi = {10.1021/jacs.5c14209}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38743--38751}, shortjournal = {J. Am. Chem. Soc.}, title = {Carbene zipper reaction for cascade π-extension}, volume = {147}, year = {2025}, }
• (2025). Synthesis of metallostannylenes from transition metal polyhydride complexes. JACS, 147(42), 38732--38742. (www)

  @article{ , abstract = {Syntheses of high-valent open-chain metallostannylene hydride complexes from transition metal polyhydride complexes and aryl-substituted amidostannylenes are reported. The reaction of ( Me BDI Dipp )IrH 4 ( Me BDI Dipp = (Dipp)NC(Me)CH(Me)CN(Dipp); Dipp = 2,6-diisopropylphenyl) with DMPSnN(SiMe 3 ) 2 (DMP = C 6 H 3 -2,6-Mes 2 , Mes = mesityl) gives access to metallostannylene ( Me BDI Dipp )IrH 3 SnDMP ( 1 ) with HN(SiMe 3 ) 2 as the byproduct. Similarly, treatment of Cp*IrH 4 (Cp* = η 5 -C 5 Me 5 ) with DMPSnN(SiMe 3 ) 2 leads to the formation of Cp*IrH 3 SnDMP ( 2 ). In contrast to 1 , 2 cleanly reacts with a second equivalent of DMPSnN(SiMe 3 ) 2 , allowing for the synthesis of bis(metallostannylene) Cp*IrH 2 (SnDMP) 2 ( 3 ). Additionally, the synthesis and characterization of two new amidostannylenes DMPSn[N(Dipp)(SiMe 3 )] ( 4 ) and TripSn[N(Dipp)(SiMe 3 )] ( 5 ; Trip = 2,4,6-triisopropylphenyl) is presented. While the reaction of Cp*IrH 4 with 4 represents an alternative route to 2 , treatment of ( Me BDI Dipp )IrH 4 with 5 yields the amidostannylene complex ( Me BDI Dipp )(H) 2 Ir═Sn(Trip){N(Dipp)(SiMe 3 )} ( 6 ) with concomitant release of H 2 , rendering stannylene coordination a reaction pathway that competes with Sn–N bond cleavage and metallostannylene formation. Within the broader context of transition metal–main group element compounds, metallostannylene formation is characterized as a formal deprotonation of the transition metal polyhydride complex by the amidostannylene. Notably, the ambiphilicity of amidostannylenes, which distinguishes them from tetravalent amidostannanes, appears to be essential for efficient Ir–Sn bond formation.}, archive = {J_JACS}, author = {Marcel Bamberg and Thomas Gasevic and Jose Martinez Fernandez and Tyler G. Saint-Denis and T. Don Tilley}, doi = {10.1021/jacs.5c14064}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38732--38742}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of metallostannylenes from transition metal polyhydride complexes}, volume = {147}, year = {2025}, }
• (2025). Dynamic shape modulation of deflated and adhered lipid vesicles. JACS, 147(42), 38720--38731. (www)

  @article{ , abstract = {Lipid membrane-bounded organelles often possess intricate morphologies with spatially varying curvatures and large membrane surface areas relative to internal volume (small reduced volumes). These features are thought to be essential for protein sorting and vesicle trafficking, but challenging to reproduce in vitro . Here, we show that weakly adhered giant unilamellar vesicles (GUVs) can be osmotically deflated to reduced volumes as low as 0.1, similar to what is found in flattened, disc-shaped organelles such as Golgi cisternae and ER sheets. Using shape analysis with the Canham-Helfrich model, we determine mechanical parameters including adhesion strength, membrane tension, and pressure of individual vesicles. We find that the rate of shape flattening during deflation is governed by a normalized adhesion strength that combines vesicle size, adhesion energy, and bending rigidity. For highly flattened disc-like vesicles, we identify a geometric relationship that allows the adhesion strength to be estimated solely from the vesicle’s aspect ratio, size, and bending rigidity. These results provide a quantitative experimental platform for bottom-up studies of membrane shaping mechanisms and shape-dependent phenomena, such as curvature-mediated protein sorting.}, archive = {J_JACS}, author = {Gianna Wolfisberg and Jaime Agudo-Canalejo and Pablo C. Bittmann and Eric R. Dufresne and Robert W. Style and Aleksander A. Rebane}, doi = {10.1021/jacs.5c13925}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38720--38731}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic shape modulation of deflated and adhered lipid vesicles}, volume = {147}, year = {2025}, }
• (2025). Chemical construction of molecular truss lattices with tunable topologies. JACS, 147(42), 38711--38719. (www)

  @article{ , abstract = {Engineering connectivity at the nanoscale enables unprecedented mechanical metamaterials with exotic properties. However, nanomanufacturing 3D lattices with molecular connectivity and tunable topologies is challenging. Here, we select a supramolecular material named metal–organic framework (MOF) as the prototype, where molecules are employed as nodes and beams to construct nanosized truss lattices. An MOF named PCN-700 featuring a well-defined body-centered cubic structure is synthesized, of which the molecular connectivity, topology, and internal stress can be precisely tuned via postsynthetic installation of organic linkers with variable lengths. Herein, the topology is regulated with subnanometer resolution, affording lightweight materials with tunable elastic moduli (8.9–17.4 GPa) without apparent density changes, confirmed by atomic force microscopy indentation. The study of the compressive behaviors from nanonewton to millinewton regimes establishes a connection between the intrinsic chemical structures and the mechanical properties, where the molecular connectivity determines the lattice deformation mode. Raman spectra and ab initio calculations indicate that the PCN-700 can accommodate compressive deformation through the rotation of molecular planes within the organic ligands, contributing to the integral stiffness. The insights presented here will not only uncover MOFs’ application potentials in mechanics but also inspire chemical design and precision engineering of mechanical metamaterials at the nanoscale.}, archive = {J_JACS}, author = {Kun-Yu Wang and Yinding Chi and Claudia Pereyra Huelmo and Yaoye Hong and Zongsu Han and Kailin Chen and Christine Huang and Yaojun Zeng and Kunhao Yu and Ottman A. Tertuliano and Christopher B. Murray and Shu Yang}, doi = {10.1021/jacs.5c13591}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38711--38719}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemical construction of molecular truss lattices with tunable topologies}, volume = {147}, year = {2025}, }
• (2025). Photochemical and thermal concerted 1,3-sigmatropic rearrangements of a π-extended methylenecyclopropane. JACS, 147(42), 38700--38710. (www)

  @article{ , abstract = {The reversible interconversion between methylenecyclopropane (MCP) and trimethylenemethane (TMM) has been extensively studied, yet precise control over their spin states remains challenging. Here, we designed and synthesized a propeller-shaped π-extended MCP derivative and its corresponding TMM derivative with anthroxyl moieties. The MCP derivative was isolated as a stable compound, and upon photoirradiation, it generated the triplet-state TMM derivative, which reverted to the MCP derivative without decomposition. In contrast, thermal excitation induced a unique carbon–carbon bond fluxionality within the MCP core via a concerted 1,3-sigmatropic rearrangement rather than a stepwise diradical pathway. These findings demonstrate that external stimuli such as light and heat enable spin-state control and dynamic bond fluxionality, providing new insights into organic stimuli-responsive materials.}, archive = {J_JACS}, author = {Shunsuke Konrai and Ma-aya Takano and Manabu Abe and Hiroyasu Sato and Ryohei Kishi and Takashi Kubo and Tomohiko Nishiuchi}, doi = {10.1021/jacs.5c13563}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38700--38710}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemical and thermal concerted 1,3-sigmatropic rearrangements of a π-extended methylenecyclopropane}, volume = {147}, year = {2025}, }
• (2025). Integrated solvation chemistry enables high energy li metal batteries. JACS, 147(42), 38691--38699. (www)

  @article{ , abstract = {Rational electrolyte design for high-energy Li metal batteries (LMBs) demands the simultaneous suppression of solvent reactivity and the promotion of anion reduction. However, existing approaches often fall short due to inadequate control over the solvation structure, leading to excessive free solvent and anion species and continual side reactions. Here, we propose a solvation integration strategy that confines both solvent molecules and anions within the first solvation sheath, thereby minimizing their reactivity. As a proof of concept, we employ lithiophilic (trifluoromethoxy)fluorobenzene (TFMFB) to tune Li + solvation by enhancing the affinity of solvents toward Li + , ensuring favorable Li + kinetics. Simultaneously, lipophilic (trifluoromethyl)cyclohexane (FMCH) forms an outer-layer kinetic barrier that inhibits solvent/anion desolvation. This inner-lithiophilic and outer-lipophilic configuration creates synergistic confinement, significantly enhancing oxidation stability and enabling robust interfacial chemistry. As a result, an anode-free Cu∥LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) pouch cell utilizing the tailored solvation-integrated electrolyte (SIE) achieves 80% capacity retention after 120 cycles. Furthermore, the aggressive 10 Ah Li∥LiNi 0.9 Co 0.05 Mn 0.05 O 2 (NCM955) pouch cell with an ultralean electrolyte (1.1 g Ah –1 ) delivers an ultrahigh energy density of 568 Wh kg –1 . This solvation integration concept provides a promising guideline for the electrolyte design toward practical high-energy LMBs.}, archive = {J_JACS}, author = {Yuntong Ma and Haikuo Zhang and Shihao Duan and Baochen Ma and Shuoqing Zhang and Ling Lv and Long Chen and Tao Zhou and Yong Li and Rui Guo and Ruhong Li and Tao Deng and Xiulin Fan}, doi = {10.1021/jacs.5c13371}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38691--38699}, shortjournal = {J. Am. Chem. Soc.}, title = {Integrated solvation chemistry enables high energy li metal batteries}, volume = {147}, year = {2025}, }
• (2025). Structure-guided design of a bioactive covalent small molecule targeting a riboswitch. JACS, 147(42), 38684--38690. (www)

  @article{ , abstract = {Small molecule ligands targeting structured RNA elements hold promise for modulating RNA function, serving as chemical probes and potential therapeutics. In this study, the characterization of phenylglyoxal-based covalent probe designed to target unpaired guanine residues in structured RNAs is reported. A structure-guided design strategy was employed to modify covalently unpaired guanines critical for flavin mononucleotide (FMN) binding to the FMN riboswitch. Covalent modification occurs at the designed site and modulates riboswitch function in a cellular reporter system, highlighting the potential of covalent mechanisms of action for bioactive RNA ligands.}, archive = {J_JACS}, author = {Chungen Li and Xueyi Yang and Kyle A. Dickerson and Patrick R. A. Zanon and Noah A. Springer and Jielei Wang and Yilin Jia and Nikhil C. Munshi and Robert T. Batey and Matthew D. Disney}, doi = {10.1021/jacs.5c13219}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38684--38690}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure-guided design of a bioactive covalent small molecule targeting a riboswitch}, volume = {147}, year = {2025}, }
• (2025). Reversible single-crystal-to-single-crystal isomerization of the azo photoswitch. JACS, 147(42), 38677--38683. (www)

  @article{ , abstract = {The reversible E ⇄ Z photoisomerization of azo molecules is of fundamental significance for the development of photoresponsive materials, but it is typically hindered in crystals due to restricted molecular motion. A longstanding challenge has been the achievement of single-crystal-to-single-crystal (SCSC) isomerization, in which isomerization occurs in bulk molecular crystals while preserving the perfect single-crystalline order. In this work, SCSC E ⇄ Z isomerization of an azobispyrazole molecule is directly observed by single-crystal X-ray diffraction. The crystal lattice similarity between the E and Z single crystals favors such a transformation. The single crystal structures of two key intermediate states are captured, revealing a three-step transformation process. The process involves not only conformation change and isomerization but also molecular motions including interlayer gliding and molecular distance adjustment that proceed with minimal displacements. This discovery redefines the long-held perception that azo isomerization inevitably disrupts single crystallinity, thereby opening new avenues for the development of light-responsive crystalline materials and devices.}, archive = {J_JACS}, author = {Tongtong Dang and Yixin He and Xuanchi Yu and Zhao-Yang Zhang and Lingling Li and Tao Li}, doi = {10.1021/jacs.5c12874}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38677--38683}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible single-crystal-to-single-crystal isomerization of the azo photoswitch}, volume = {147}, year = {2025}, }
• (2025). Competitive cation exchange and etching processes in metal sulfide nanoparticles from Anion/Ligand cooperativity and exogenous cations. JACS, 147(42), 38667--38676. (www)

  @article{ , abstract = {Cation exchange reactions enable the construction of sophisticated multimaterial architectures within nanoparticles, with certain regions capable of being etched to create void spaces and sculpted morphologies. However, the chemical reactivity that leads to etching often remains unknown and therefore uncontrollable, making it an undesirable side reaction rather than a reaction that can be harnessed for nanostructure design. Here, we report the discovery that spectator anions and exogenous cations that are assumed to be innocent during nanoparticle cation exchange reactions instead drive an etching process that is competitive with exchange. Attempts to exchange some of the Cu + cations in roxbyite Cu 1.8 S nanorods with Ga 3+ using GaCl 3 proceed as expected, but when the same reaction is applied to heterostructured ZnS–Cu 1.8 S, CdS–Cu 1.8 S, and CuInS 2 –Cu 1.8 S nanorods, Ga 3+ exchange does not occur, but instead the Cu 1.8 S regions are etched. Through a comprehensive series of experiments, we identified three reaction components that work cooperatively to favor etching over exchange: Cl – anions from GaCl 3 or another chloride salt, trioctylphosphine that is present to help drive the cation exchange reaction, and the presence of exchangeable metal cations in solution that can originate from the non-Cu 1.8 S regions of the heterostructured nanorods. These insights reveal that nanoparticle cation exchange and etching exist on a continuum and that these competitive processes can be harnessed to control and tune nanostructural features.}, archive = {J_JACS}, author = {Joseph M. Veglak and Nicholos A. Benson and Raymond E. Schaak}, doi = {10.1021/jacs.5c13174}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38667--38676}, shortjournal = {J. Am. Chem. Soc.}, title = {Competitive cation exchange and etching processes in metal sulfide nanoparticles from Anion/Ligand cooperativity and exogenous cations}, volume = {147}, year = {2025}, }
• (2025). Beyond composition: Optimizing ion transport in solid-state composite polymer electrolytes through pathway engineering. JACS, 147(42), 38657--38666. (www)

  @article{ , abstract = {Composite polymer electrolytes (CPEs), composed of a polymer matrix and inorganic nanoparticles, are promising for solid-state batteries. While most studies focus on compositional factors such as filler type and polymer structure, mesoscale connectivity between polymer coordination sites represents a crucial, yet underexplored, factor influencing ion transport. Here, using coarse-grained Monte Carlo simulations, we explored how coordination site connectivity governs transport. The polymer chain connectivity is quantified as a proxy for coordination site connectivity, and we found that repulsive nanoparticles enhance chain connectivity, particularly at high weight ratio and strong repulsion. Structural analysis shows that this enhancement extends throughout the polymer. These predictions were validated experimentally using CPEs composed of poly(ethylene oxide) and silica nanoparticles of tunable surface chemistry. CPE with strong repulsive silica nanoparticles exhibited improved room-temperature ionic conductivity by up to 5-fold and a significant reduction in effective activation energy under a suboptimal condition. Our findings demonstrate that connectivity restructuring critically enhances ionic transport, offering a new design paradigm for CPEs based on mesoscale connectivity control.}, archive = {J_JACS}, author = {Jianrui Zhang and Yuzhu Tian and Xin Jia and Shujiang Ding and Hao Bin Wu and Yaqiong Su}, doi = {10.1021/jacs.5c13014}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38657--38666}, shortjournal = {J. Am. Chem. Soc.}, title = {Beyond composition: Optimizing ion transport in solid-state composite polymer electrolytes through pathway engineering}, volume = {147}, year = {2025}, }
• (2025). Customizable aperture geometry in Metal–Organic frameworks for kinetic hydrocarbon separation. JACS, 147(42), 38647--38656. (www)

  @article{ , abstract = {Precise control of aperture dimensions is crucial in adsorptive separations of hydrocarbons, as it directly affects key parameters such as selectivity, capacity, diffusion, and recyclability. The development of metal–organic frameworks (MOFs) has enabled the fine-tuning of local pore environments to address important hydrocarbon separations. However, customizing the aperture geometry to tune the kinetic separation performance remains challenging. Here, we deploy a mixed-linker synthesis strategy, combining long and short linkers on fcu net Zr-MOFs with equilateral triangular apertures to construct isoreticular multivariate MOFs, NU-415 and NU-416, with tailored isosceles triangular apertures suitable for the separation of hexane isomers. Sorption, liquid batch separation, and X-ray diffraction measurements demonstrate significantly improved selectivity, capacity, stability, and recyclability of NU-415 and NU-416 compared with Zr-muconate and MOF-801. Notably, both NU-415 and NU-416 achieve uptake capacities of 2.2 mmol g –1 in 1 min with an n -hexane to 2,2-dimethylbutane selectivity over 200 in an equimolar ternary mixture at ambient conditions, comparable to leading reported materials. Mechanistic studies confirm that separation performance is predominantly governed by significant kinetic differences rather than by thermodynamics. The successful customization of aperture geometry not only enables superior linear to monobranched hexane selectivity in NU-415 but also demonstrates the mixed-linker synthesis strategy as a promising solution for precise and predictable pore architecture control in MOFs.}, archive = {J_JACS}, author = {Shengyi Su and Haomiao Xie and Bang Hou and Xianhui Tang and Kent O. Kirlikovali and Zi-Ming Ye and Nathan C. Gianneschi and Omar K. Farha}, doi = {10.1021/jacs.5c13078}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38647--38656}, shortjournal = {J. Am. Chem. Soc.}, title = {Customizable aperture geometry in Metal–Organic frameworks for kinetic hydrocarbon separation}, volume = {147}, year = {2025}, }
• (2025). Uncovering the true active sites in Ni–N–C catalysts for CO2 electroreduction. JACS, 147(42), 38636--38646. (www)

  @article{ , abstract = {Understanding and designing active sites in single-atom catalysts (SACs) requires going beyond static models to capture their dynamic evolution under realistic electrochemical conditions. Here, we develop an integrated theoretical framework that accounts for operational conditions, by combining grand canonical density functional theory (GC-DFT) with machine-learning-accelerated sampling, to uncover structure–activity–stability relationships in Ni–N–C SACs for the CO 2 reduction reaction (CO 2 RR). A library of NiN x C 4– x ( x = 0–4) motifs─representing coordination defects likely formed during high-temperature synthesis─was systematically evaluated. Under working conditions, these sites were found to undergo hydrogenation, and NiN 3 C 1_ H 1 was identified as the most probable active site. At reducing potentials, hydrogen adsorbs spontaneously at C–Ni bridge sites rather than Ni top sites, while subsurface hydrogen facilitates bent CO 2 adsorption crucial for activation. High CO 2 RR selectivity toward CO arises from site separation: Ni centers drive CO 2 RR, while the hydrogen evolution reaction (HER) occurs at the C–Ni bridge or N sites and from thermodynamic suppression of HER at moderate hydrogen coverage. At more negative potentials, a shift in the CO 2 RR rate-determining process (RDP) and Ni out-of-surface displacement induced by coadsorption of H and H 2 O jointly reduce activity and selectivity. Thus, both the high CO 2 RR selectivity of Ni–N–C catalysts and its reversal with more negative potentials can be rationalized by accounting for hydrogenated surfaces. This highlights the necessity of modeling realistic; in situ conditions. This framework provides generalizable insights into the dynamic behavior of active sites in SACs, offering guidance for the rational design of active and robust catalysts for a wide range of electrochemical reactions.}, archive = {J_JACS}, author = {Yulan Han and Yu Wei and Anubhav Goswami and Anastassia Alexandrova}, doi = {10.1021/jacs.5c12847}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38636--38646}, shortjournal = {J. Am. Chem. Soc.}, title = {Uncovering the true active sites in Ni–N–C catalysts for CO2 electroreduction}, volume = {147}, year = {2025}, }
• (2025). Discovery and mechanism of a diiron enzyme in ethylidene azetidine formation. JACS, 147(42), 38627--38635. (www)

  @article{ , abstract = {Azetidine is a strained four-membered N -heterocycle that has important applications in medicinal chemistry and organic synthesis. Despite its relevance to human health and agriculture, azetidine biosynthesis remains largely unexplored. Herein, the DUF6202 family enzyme PolF is shown to utilize a diiron center and O 2 to catalyze sequential desaturation and azetidination of l -isoleucine to yield the ethylidene azetidine moiety during the biosynthesis of polyoxin. Crystallographic analysis of PolF in complex with iron (or manganese) and l -isoleucine (or an alkene intermediate) reveals that it is a heme oxygenase-like diiron oxidase with a new iron-binding motif. Trapping an O 2 -bound intermediate in crystallo along with a distinctive iron-to-protein ratio observed under anoxic and aerobic environments indicates that binding of the second iron occurs in an O 2 -dependent manner. Mössbauer and stopped-flow optical absorption spectroscopy together with deuterium kinetic isotope effect measurements demonstrate that a μ-peroxodiiron(III) species is likely responsible for C–H bond activation. Mass Spectrometry analysis reveals that the decay of the μ-peroxodiiron(III) species is accompanied by the formation of a desaturated intermediate. Bioinformatic analysis identifies ca. 200 PolF homologues indicative of new biosynthetic pathways for azetidine-containing natural products.}, archive = {J_JACS}, author = {Yaoyao Shen and Yu-Cong Zheng and Philip M. Palacios and Kuo Wang and Ailiena O. Maggiolo and Yisong Guo and Wei-chen Chang}, doi = {10.1021/jacs.5c12910}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38627--38635}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery and mechanism of a diiron enzyme in ethylidene azetidine formation}, volume = {147}, year = {2025}, }
• (2025). Ir(III) pincer complex with solo coordinatively active site as a surrogate for half-sandwich catalysts: Enabling asymmetric acylnitrenoid transfer and Structure–Activity relationship studies. JACS, 147(42), 38615--38626. (www)

  @article{ , abstract = {Metal-acylnitrenoid-enabled asymmetric C(sp 3 )–H amidation has emerged as a highly effective synthetic strategy for accessing enantioenriched amides and chiral amines. While state-of-the-art transition metal catalysts typically feature a half-sandwich scaffold, the exploration of novel catalyst scaffolds remains intriguing. We herein introduce a new class of Ir(III) pincer complexes, which exhibit exceptional modularity and tunability in both steric and electronic properties. They have been demonstrated to function as highly efficient precatalysts (with loadings as low as 0.01 mol %) for C(sp 3 )–H amidation, enabling the synthesis of enantioenriched γ-lactams and octahydroindole derivatives. The remarkable robustness of these iridium complexes has been confirmed through treatments with strong acid and base, as well as heating and catalyst recovery experiments. Structure–activity relationship studies provided valuable insights into the underlying mechanisms driving the success of these Ir(III) complexes.}, archive = {J_JACS}, author = {Yun-Peng Chu and Zhen-Hui Xu and Jing Zhao and Chuanyong Wang and Constantin G. Daniliuc and Jiajia Ma}, doi = {10.1021/jacs.5c12730}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38615--38626}, shortjournal = {J. Am. Chem. Soc.}, title = {Ir(III) pincer complex with solo coordinatively active site as a surrogate for half-sandwich catalysts: Enabling asymmetric acylnitrenoid transfer and Structure–Activity relationship studies}, volume = {147}, year = {2025}, }
• (2025). Accelerated fatty acid oxidation occurs at the Water–Air interface of sea spray microdroplets. JACS, 147(42), 38609--38614. (www)

  @article{ , abstract = {The oxidation of organic molecules, such as fatty acids, in seawater microdroplets generated by breaking waves is an important source of secondary organic aerosols and impacts the global climate. While the oxidation of fatty acids in sea spray aerosols (SSAs) has traditionally been attributed to photochemical reactions, this study reports a spontaneous nonphotochemical oxidation mechanism that occurs in seawater microdroplets. Notably, we observed marked increases in the oxidation rate (3186- to 11093-fold) for the naturally abundant fatty acids docosahexaenoic acid, oleic acid, and palmitic acid, with the primary oxidation products being hydroxylated. Integrated computational simulations and mass spectrometry analyses of reaction paths and intermediates suggest that this rapid oxidation is triggered by the simultaneous accumulation of fatty acids and the spontaneous generation of hydroxy radicals (•OH) at the microdroplet water–air interface. Our study revealed an overlooked path of fatty acid oxidation, shedding light on organic carbon cycles at the ocean–atmosphere interface.}, archive = {J_JACS}, author = {Shuxuan Chen and Xiaojiao Li and Ye-Guang Fang and Xiaochen Liu and Yu Yao and Baoliang Chen and Joseph S. Francisco and Chongqin Zhu and Chiheng Chu}, doi = {10.1021/jacs.5c12716}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38609--38614}, shortjournal = {J. Am. Chem. Soc.}, title = {Accelerated fatty acid oxidation occurs at the Water–Air interface of sea spray microdroplets}, volume = {147}, year = {2025}, }
• (2025). Synergistic Rh/La codoping enables trap-mediated charge separation in layered perovskite photocatalysts. JACS, 147(42), 38599--38608. (www)

  @article{ , abstract = {Two-dimensional layered perovskite oxides have emerged as promising photocatalysts for solar-driven hydrogen evolution. Although doping has been widely employed to enhance photocatalytic performance, its role in modulating the electronic structure and the local chemical environment of these materials remains poorly understood. Here in this study, we investigate the codoping of Rh and La into exfoliated nanosheets of the Dion–Jacobson perovskite KCa 2 Nb 3 O 10 to enhance photocatalytic hydrogen evolution reaction (HER) activity. A substantial increase in H 2 evolution rate, from 12.3 to 69.0 μmol h –1 , was achieved at an optimal doping level of 0.2 wt % Rh and 1.3 wt % La. Comprehensive structural and spectroscopic analyses, including synchrotron techniques and high-resolution microscopy, revealed that Rh 3+ substitutes Nb 5+ to introduce shallow 4 d acceptor states that mediate charge separation, while La 3+ substitutes Ca 2+ , compensates for aliovalent charge imbalance, and modulates local lattice distortions and oxygen vacancy formation. This codoping strategy enhances charge carrier lifetime and separation efficiency through a trap-mediated mechanism. The observed volcano-shaped activity trend highlights a narrow compositional window, where electronic and structural factors are optimally balanced. These findings establish a mechanistic foundation for defect engineering in layered perovskites and offer a pathway for the rational design of photocatalysts.}, archive = {J_JACS}, author = {Mengqi Duan and Shuai Guo and Wentian Niu and Hangjuan Ren and Thomas Dittrich and Dongpei Ye and Lucy Saunders and Sarah Day and Veronica Celorrio and Diego Gianolio and Peixi Cong and Robert S. Weatherup and Robert Taylor and Songhua Cai and Yiyang Li and Shik Chi Edman Tsang}, doi = {10.1021/jacs.5c12425}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38599--38608}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic Rh/La codoping enables trap-mediated charge separation in layered perovskite photocatalysts}, volume = {147}, year = {2025}, }
• (2025). Enzyme-like enantioselectivity in GTM chiral zeolite catalysts upon preactivation of ge sites. JACS, 147(42), 38585--38598. (www)

  @article{ , abstract = {Extra-large-pore Ge-containing GTM chiral zeolite catalysts have recently proved useful asymmetric catalysts, with chirality emerging from their chiral confined nanospace. However, so far these exceptional materials have suffered from low framework stability in the presence of water and moderate catalytic enantioselectivity in the ring-opening of chiral trans -stilbene oxide with 1-butanol used as a test reaction. Here, we report that these chiral zeolite catalysts can be easily stabilized upon exposure of the calcined material to 1-butanol, providing stability against water and, most importantly, prompting a preactivation of the chiral active sites that boosts their enantioselective properties, reaching unprecedented enantiomeric excesses up to 88% where one enantiomer reacts 16 times more than the other. A range of physicochemical studies, including in situ Fourier transform infrared (FTIR) and X-ray absorption spectroscopy, indicates that framework Ge sites increase their coordination environment upon interaction with 1-butanol molecules, which after a thermal treatment above 100 °C remain irreversibly bound to Ge as a consequence of a condensation and dehydration reaction, providing a route to easily functionalize these materials. These preactivated GTM asymmetric catalysts act similarly to enzymes by controlling the confinement of the chiral reactants in particular orientations through coordination with Ge and development of H-bonds with nearby hydroxyl groups, thus attaining enantioselective catalytic activities close to those reached by enzymatic systems but with the crucial advantage associated with heterogeneous catalysts and, notably, the possibility of preparing both enantiomeric versions of the catalyst by using an easily accessible alkaloid.}, archive = {J_JACS}, author = {Ramón de la Serna and Jaime Jurado-Sánchez and Carlos Márquez-Álvarez and M. Asunción Molina and Lucy Costley-Wood and Andrew M. Beale and Diego Gianolio and Joaquín Pérez-Pariente and Luis Gómez-Hortigüela}, doi = {10.1021/jacs.5c12567}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38585--38598}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzyme-like enantioselectivity in GTM chiral zeolite catalysts upon preactivation of ge sites}, volume = {147}, year = {2025}, }
• (2025). Nonlinear optical properties of mechanically interlocked nanohoops. JACS, 147(42), 38571--38584. (www)

  @article{ , abstract = {The design of molecular systems that harness spatial topology to modulate light–matter interactions is a powerful and emerging approach in modern photonics, opening up new possibilities for advanced technologies. In this study, we present the first comprehensive theoretical and experimental investigation of the nonlinear optical (NLO) properties of nanohoop catenanes, which are mechanically interlocked molecular architectures. Specifically, we explored systems based on [9]cycloparaphenylene with 2,2′-bipyridyl (Bipy[9]CPP), [12]cycloparaphenylene with 1,2,3-triazole (Tz[12]CPP), and the nanohoop[2]catenane [9+12] incorporating both units. Herein, we explore how noncovalent topological modifications influence the photophysical behavior of these systems. Using classical and entangled two-photon absorption (TPA and ETPA) spectroscopy, femtosecond transient absorption (fsTA), and time-dependent density functional theory (TD-DFT) calculations, we show that mechanical interlocking introduces strong noncovalent interactions between the rings and the formation of new interlocked-state-specific electronic transitions. Through these measurements and calculations, we find that interlocking leads to the formation of charge-transfer states and nonlinear absorption behavior not present in the individual components. These findings underscore that spatial topology─not just molecular identity or covalent connectivity─can give rise to emergent electronic behavior useful for applications in quantum imaging, optical switching, and other advanced photonic technologies.}, archive = {J_JACS}, author = {Juan S. Sandoval and Yuqiu Lei and Bishal Saha and Noah A. Grinde and Ramesh Jasti and Theodore Goodson, III}, doi = {10.1021/jacs.5c12623}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38571--38584}, shortjournal = {J. Am. Chem. Soc.}, title = {Nonlinear optical properties of mechanically interlocked nanohoops}, volume = {147}, year = {2025}, }
• (2025). Tailored electronic Metal–Support interaction boosts hydrogen release from organic carriers. JACS, 147(42), 38562--38570. (www)

  @article{ , abstract = {The support plays a pivotal role in heterogeneous catalysis by not only providing stable binding sites for nanoparticles but also modulating their morphology and electronic properties. In this study, we systematically investigated the electronic effects on the catalytic dehydrogenation of dodecahydro-N-ethylcarbazole─a promising liquid organic hydrogen carrier─using well-defined palladium nanoparticles (Pd NPs) supported on various metal oxides. Our findings reveal that the catalytic behavior of Pd NPs is strongly influenced by charge transfer interactions, which are dictated by the energy gap between the Pd Fermi level and the valence band maximum of the support material. This interfacial electron transfer governs the electronic metal–support interaction, leading to a volcano-shaped correlation between the H 2 production rate and the electronic state of Pd. Moreover, our study highlights that different stages of the dehydrogenation process require distinct electronic states. Leveraging these insights, we designed a high-performance catalyst comprising ultrafine Pd NPs supported on a binary metal oxide. The resulting Pd/Ce-TiO 2 catalyst outperformed previously reported systems by facilitating stepwise dehydrogenation through a tandem mechanism.}, archive = {J_JACS}, author = {Fan Luo and Zhiyao Liang and Wentong Jing and Yingjie Lai and Jiajun Huang and Xiongkai Tang and Lei Li and Zhe Yang and Ruixuan Qin and Nanfeng Zheng}, doi = {10.1021/jacs.5c12538}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38562--38570}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailored electronic Metal–Support interaction boosts hydrogen release from organic carriers}, volume = {147}, year = {2025}, }
• (2025). Responsive plasmonic reporters decrypt nanoparticle-induced single membrane protein degradation. JACS, 147(42), 38549--38561. (www)

  @article{ , abstract = {Nanoparticle-mediated degradation of proteins of interest has recently emerged as a powerful tool in biomedical research and the pharmaceutical industry. Nevertheless, the limited understanding of dynamic processes poses challenges in further improving the efficacy. Herein, we develop responsive plasmonic nanoprobe systems capable of discrimination between membrane protein monomer and dimerization states, enabling the direct observation of membrane protein degradation during nanoparticle endocytosis. The nanoprobes are engineered with precisely controlled aptamer modifications through asymmetric spherical nucleic acid functionalization to ensure low-valence protein binding. Upon ligand stimulation, protein dimerization triggers proximity-induced DNA hybridization between nanoprobe and protein complexes, resulting in distinctive plasmonic coupling signals. Using the cellular mesenchymal to epithelial transition factor (Met) as a model protein, we demonstrate differential endocytosis kinetics between monomeric and dimeric states, with dimers exhibiting enhanced endocytic efficiency. Further investigation into downstream protein expression and cellular responses reveals an enhanced phosphorylated Met (p-Met) degradation process by the aggregation state, providing insights into the relationship between protein oligomerization and nanoparticle-mediated degradation efficiency. These findings offer valuable theoretical foundations for designing targeted protein degradation platforms based on nanoparticles.}, archive = {J_JACS}, author = {Jin Wang and Jing Tan and Zhao Zhang and Xiuxiu Wang and Jing Zhao and Jie Li and Chen Wang}, doi = {10.1021/jacs.5c12343}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38549--38561}, shortjournal = {J. Am. Chem. Soc.}, title = {Responsive plasmonic reporters decrypt nanoparticle-induced single membrane protein degradation}, volume = {147}, year = {2025}, }
• (2025). Pretargeted mitochondrial delivery of organoarsenicals for cancer immunotherapy. JACS, 147(42), 38534--38548. (www)

  @article{ , abstract = {Mitochondrial targeting of organoarsenic compounds shows potential for cancer therapy, but current delivery approaches face significant challenges such as poor tumor selectivity and systemic toxicity, leading to dose-limiting side effects and reduced therapeutic efficacy. In this study, we present a subcellular pretargeted delivery strategy designed to selectively and efficiently accumulate organoarsenic therapeutics within tumor cell mitochondria. This approach leverages P-TCO-TPP, an alkaline phosphatase (ALP)-responsive small-molecule probe containing a phosphate-caged near-infrared merocyanine fluorophore, trans-cyclooctene (TCO), and triphenylphosphonium (TPP) groups. This enables the in situ self-assembly of mitochondria-targeting nanoparticles upon ALP-mediated dephosphorylation. These mitochondria-localized nanoparticles then rapidly capture tetrazine-arsenic conjugates (Tz-As) via bioorthogonal inverse electron demand Diels–Alder (IEDDA) reaction, resulting in a >5-fold increase in mitochondrial arsenic accumulation. This, in turn, leads to mitochondrial proteins labeling, thioredoxin reductase inhibition, severe mitochondrial dysfunction, and immunogenic cell death in tumor cells. Notably, this strategy achieves strong antitumor efficacy with minimal toxicity in both subcutaneous cervical HeLa and orthotopic breast 4T1 tumor models. Furthermore, combining this strategy with anti-PD-L1 immunotherapy induces complete 4T1 tumor regression in 40% of mice, extended survival, and nearly prevents pulmonary metastasis. This subcellular pretargeted strategy offers a robust platform for precision mitochondrial drug delivery, enhancing therapeutic potential of various cytotoxic agents in cancer immunotherapy.}, archive = {J_JACS}, author = {Run Wang and Yuyang Tian and Xuliang Lu and Leyi Fang and Yinxing Miao and Daqing Fang and Yingxia Li and Hong Liu and Deju Ye}, doi = {10.1021/jacs.5c12201}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38534--38548}, shortjournal = {J. Am. Chem. Soc.}, title = {Pretargeted mitochondrial delivery of organoarsenicals for cancer immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Hierarchical design of COFs via NHC-grafting for selective gold recovery from E-waste: Experimental and MD analyses. JACS, 147(42), 38516--38533. (www)

  @article{ , abstract = {In this study, a highly crystalline imine-linked covalent organic framework (COF) was synthesized via Schiff base condensation, followed by postsynthetic modification (PSM) to introduce N-heterocyclic carbene (NHC) ligands. The two-step PSM involved reduction of imine bonds to secondary amines and the subsequent covalent attachment of NHCs, while preserving the COF’s crystallinity and porosity. Structural analyses confirmed successful functionalization and high stability of the modified COF. The resulting NHC-functionalized COF demonstrated strong affinity and high selectivity toward Au ions, making it a promising adsorbent for efficient gold recovery from complex e-waste matrices. XPS analysis confirmed the selective adsorption of Au(III) ions and their reduction to Au(I) via electron donation from NHC sites, enabling efficient and selective uptake from solution through coordination interactions within the COF matrix. Adsorption analysis demonstrated that Au(III) uptake by COF–NHC follows a PSO-Freundlich model, characterized by rapid adsorption kinetics and heterogeneous surface binding. Molecular dynamics simulations revealed that carbon functional groups within the postsynthetically modified COF play a crucial role in stabilizing and potentially reducing gold ions, underscoring the framework’s effectiveness for selective gold recovery from e-waste.}, archive = {J_JACS}, author = {Amir Khojastehnezhad and Anna Bisio and Seyed Faridedin Rafie and Maziar Jafari and Zhiyuan Peng and Mohammad K. Shehab and Nidal Abu-Zahra and Omar K. Farha and Mohamed Siaj}, doi = {10.1021/jacs.5c12234}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38516--38533}, shortjournal = {J. Am. Chem. Soc.}, title = {Hierarchical design of COFs via NHC-grafting for selective gold recovery from E-waste: Experimental and MD analyses}, volume = {147}, year = {2025}, }
• (2025). Mechanistic dissymmetry between crystal growth and dissolution drives ratcheted chiral amplification. JACS, 147(42), 38508--38515. (www)

  @article{ , abstract = {Complete chiral amplification of the solid phase arises when mixtures of self-sorting enantiopure crystals undergo cycles of crystal growth and dissolution under solution-phase racemizing conditions. However, despite extensive studies and widespread use, the mechanism underlying such crystallization-induced deracemization remains insufficiently understood, hindering its optimization and broader application. Here, we experimentally dissect the individual contributions of crystal growth and dissolution and use a mass-balance to expose crystal dynamics. Regardless of the racemization rate, we always find a dissymmetry between the growth and the dissolution of the enantiomer populations. These experiments suggest that a fundamental difference between the mechanisms of crystal growth and dissolution enables a ratchet effect that drives chiral amplification. These insights advance our understanding of chiral crystallization mechanisms and provide guidance for optimizing crystallization-induced deracemizations, particularly by separately optimizing growth and dissolution steps to maximize the chiral amplification and deracemization efficiency.}, archive = {J_JACS}, author = {Sjoerd W. van Dongen and Jin Maeda and Bernard Kaptein and Pascal Cardinael and Adrian Flood and Gerard Coquerel and Willem L. Noorduin}, doi = {10.1021/jacs.5c12199}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38508--38515}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic dissymmetry between crystal growth and dissolution drives ratcheted chiral amplification}, volume = {147}, year = {2025}, }
• (2025). Simultaneous reduction and oxidation of NO2 on water microdroplets provides previously unknown pathways to the formation of HONO and HNO3. JACS, 147(42), 38500--38507. (www)

  @article{ , abstract = {HONO and HNO 3 are important atmospheric species, yet their formation pathways in the atmosphere remain uncertain. In this study, we report the simultaneous formation of HONO and HNO 3 at the air–water interface of water microdroplets in the presence of trace amounts of NO 2 . Water microdroplets were generated either in ambient air or in a glovebox where the gas content could be precisely controlled. The products generated by the microdroplets and surrounding gas were directly analyzed with mass spectrometers. Our results indicated that NO 2 gas could be reduced by an electron to form NO 2 – , which was further protonated to yield HONO, or could be oxidized by a hydroxyl radical (·OH) to form HNO 3 . Electrons and ·OH were produced by a strong electric field that facilitated OH – dissociation at the air–water interface of the microdroplets. Tandem mass spectrometry, isotope labeling, and chemical ionization methods confirmed the formation of neutral HONO and HNO 3 . Our results provide a previously unknown pathway for the formation of HONO and HNO 3 in the troposphere.}, archive = {J_JACS}, author = {Huan Chen and Xu Yuan and Jianze Zhang and Xiangyu Chen and Joseph S. Francisco and Yifan Meng and Xinxing Zhang}, doi = {10.1021/jacs.5c12051}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38500--38507}, shortjournal = {J. Am. Chem. Soc.}, title = {Simultaneous reduction and oxidation of NO2 on water microdroplets provides previously unknown pathways to the formation of HONO and HNO3}, volume = {147}, year = {2025}, }
• (2025). Synthesis of crystalline calcium bicarbonate. JACS, 147(42), 38492--38499. (www)

  @article{ , abstract = {Bicarbonate reactions, especially those involving calcium, play prominent roles in the carbon cycle and biochemical processes, contributing to the largest carbon pool on Earth. However, although they were hypothesized over two centuries ago, all attempts to isolate calcium bicarbonate Ca(HCO 3 ) 2 , both in nature and in the laboratory, as well as other bicarbonates of multivalent metals as pure compounds, have failed and invariably resulted in the formation of carbonates. In this study, we synthesized Ca(HCO 3 ) 2 crystals by modifying the bonding environment to increase the stability of the bicarbonate ions and determined their crystal structure. Ca(HCO 3 ) 2 crystals with direct calcium–bicarbonate bonds share an identical rhombohedral crystal structure with calcite. We further determined that the polarization of calcium-bonded bicarbonate ions in polarization-favorable environments (e.g., water solvation) inhibits the isolation of Ca(HCO 3 ) 2 , as it polarizes the hydroxy group to destabilize the calcium–bicarbonate ion pairing, which is a prerequisite for Ca(HCO 3 ) 2 crystallization. These findings, particularly the first-ever resolved crystal structure of Ca(HCO 3 ) 2 , provide fundamental insight into metal–bicarbonate interactions and the formation of ionic compounds, advancing the ability to direct CO 2 -involved reactions.}, archive = {J_JACS}, author = {Kangren Kong and Guohong Cai and Zaiqiang Ma and Yinlin Shen and Biao Jin and Pohua Chen and Yu Yin and Junliang Sun and Zhaoming Liu and Ruikang Tang}, doi = {10.1021/jacs.5c12101}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38492--38499}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of crystalline calcium bicarbonate}, volume = {147}, year = {2025}, }
• (2025). Rational design and synthesis of a Metal–Organic framework featuring Cu(I)–Carbon bonds for enhanced artificial photosynthesis. JACS, 147(42), 38484--38491. (www)

  @article{ , abstract = {The development of a stable and highly efficient artificial photosynthetic system without the need for additional electron sacrificial agents has long been a pursuit but remains highly challenging. Here, we designed and synthesized a novel metal–organic framework (MOF), Cu-TEPA (TEPA = tris(4-ethynylphenyl)amine), by connecting triphenylamine and Cu(I) ions via metal–carbon (M–C) bonds for artificial photosynthesis. Cu-TEPA showed excellent stability in pH = 0 or 14 aqueous solutions for over 12 h. Interestingly, using water as the electron donor, Cu-TEPA demonstrated remarkable performance in the overall artificial photosynthetic reaction, achieving a CO yield of 86.0 μmol g –1 h –1 with nearly 100% selectivity and an O 2 evolution rate of 43.9 μmol g –1 h –1 , maintaining performance after five cycles. Mechanistic studies reveal that triphenylamine acts as both a photosensitizer and water oxidation catalyst, while Cu(I) reduces CO 2 to CO. Therefore, the superior performance of Cu-TEPA can be attributed to the excellent photosensitivity of triphenylamine, the high catalytic activity of Cu(I), and the more stable and conductive M–C bonds between the organic ligands and metal ions.}, archive = {J_JACS}, author = {Hui-Ying Chen and Zhen-Hua Zhao and Ning-Yu Huang and Jia-Run Huang and Pei-Qin Liao}, doi = {10.1021/jacs.5c11801}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38484--38491}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design and synthesis of a Metal–Organic framework featuring Cu(I)–Carbon bonds for enhanced artificial photosynthesis}, volume = {147}, year = {2025}, }
• (2025). Ligand-controlled stereodivergent α-vinylation and α-arylation of peptide backbones. JACS, 147(42), 38475--38483. (www)

  @article{ , abstract = {The stereoselective modulations of peptide backbone α-carbons at internal sites present a longstanding synthetic challenge. To the best of our knowledge, transition metal-catalyzed C–C cross-coupling chemistry has not been employed to address this issue. Herein, we report that a racemic α-C-tosyl glycinyl unit (TsG), readily installed at a defined site within the peptide backbone, serves as an excellent electrophile for Ni-catalyzed reductive vinylation and arylation with vinyl and aryl triflates or halides, delivering α-C(sp 2 )-modified peptides with outstanding diastereoselectivity. Catalyst control dominates stereoselectivity, enabling stereodivergent modification at internal peptide backbone sites by tuning ligand chirality─a rare achievement compared with most contemporary studies focusing primarily on N -terminal α-carbons. The peptide scope was broad, encompassing decapeptides and cyclic pentapeptides. This study is expected to inspire broad interest in late-stage peptide backbone modification through cross-coupling strategies.}, archive = {J_JACS}, author = {Jie Hu and Shengjie Su and Haodong Zhang and Haohao An and Yunrong Chen and Hegui Gong}, doi = {10.1021/jacs.5c11836}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38475--38483}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand-controlled stereodivergent α-vinylation and α-arylation of peptide backbones}, volume = {147}, year = {2025}, }
• (2025). Balanced CO/OH intermediates for efficient and CO-resilient electrocatalytic methanol oxidation via pt supported on la-doped α-MoC. JACS, 147(42), 38465--38474. (www)

  @article{ , abstract = {The electrocatalytic methanol oxidation reaction (MOR) over Pt-based catalysts is critical for renewable energy applications. However, its performance is often hampered by CO poisoning and the inefficient utilization of active sites. Regulating the kinetic balance of the CO and OH intermediates through microenvironmental control has emerged as an effective strategy to mitigate these limitations. Here, we present a Pt catalyst supported on lanthanum-doped molybdenum carbide (La-MoC), which leverages the exceptional water-dissociation capability of α-MoC to supply abundant OH species, while precisely controlling the surface coverage through La doping and Pt loading. This dual microenvironmental modulation establishes an optimal ratio between CO on Pt and OH on MoC, thereby accelerating CO oxidation and maximizing reaction kinetics. The resulting Pt/La-MoC catalyst exhibits a remarkable mass activity of 8.58 A mg Pt –1 (3.6× higher than commercial Pt/C), excellent stability (92% activity retention after 120 h in 0.1 M KOH and 80% activity retention after 30 h in 1 M KOH), and a low CO oxidation onset potential (∼0.2 V vs RHE). In situ spectroscopic and electrochemical studies confirm that the synchronized cycling of CO and OH intermediates promotes rapid CO removal and active-site regeneration. This work provides a rational design concept centered on intermediate balance, offering new insights into the dynamics of surface reactions in electrocatalysis.}, archive = {J_JACS}, author = {Weiqin Wei and Xingjie Peng and Qingqing Zhou and Maolin Wang and Haoyi Tang and Junzhong Xie and Shuheng Tian and Wu Zhou and Xiao Ren and Ding Ma}, doi = {10.1021/jacs.5c11866}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38465--38474}, shortjournal = {J. Am. Chem. Soc.}, title = {Balanced CO/OH intermediates for efficient and CO-resilient electrocatalytic methanol oxidation via pt supported on la-doped α-MoC}, volume = {147}, year = {2025}, }
• (2025). Donor–Acceptor stenhouse adducts as intrinsically photoswitchable dynamic covalent bonds. JACS, 147(42), 38452--38464. (www)

  @article{ , abstract = {Combining dynamic covalent bonds with photoswitches allows the kinetics and thermodynamics of exchange to be controlled with light. However, this two-component strategy introduces synthetic and compatibility challenges. Here, we present a single-component strategy using donor–acceptor Stenhouse adducts (DASAs) as both the photoswitch and the dynamic covalent bond. DASAs isomerize from “open” to “closed” forms with light and heat, respectively. We discovered that open DASA isomers undergo dynamic covalent exchange of their amine donor via two pathways, reversible dissociation and conjugate transamination. Exchange can then be arrested upon irradiation to form the closed DASA isomer, offering a handle to gate dynamic behavior. Consequently, incorporating DASAs as cross-linkers in PDMS-based networks yields covalent adaptable networks (CANs) with viscoelastic behavior that can be tuned by light. We also identify degradation pathways that limit the reversibility of this system under extended heating. Overall, DASA exchange represents a synthetically accessible platform for photocontrolled soft materials. More broadly, this work introduces DASAs as a new class of intrinsically photoswitchable dynamic covalent bonds and lays the foundation for the discovery of other stimuli-gated dynamic bonds that combine reactivity and responsiveness in a single molecular unit.}, archive = {J_JACS}, author = {Emmanuel A. Garcia Villatoro and Shoki Matsushima and Jonathan H. Sklar and Julia A. Kalow}, doi = {10.1021/jacs.5c11859}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38452--38464}, shortjournal = {J. Am. Chem. Soc.}, title = {Donor–Acceptor stenhouse adducts as intrinsically photoswitchable dynamic covalent bonds}, volume = {147}, year = {2025}, }
• (2025). Calochorturils: Chiral bowl-shaped cavitands obtained by anisotropic tangential substitution. JACS, 147(42), 38443--38451. (www)

  @article{ , abstract = {Substitution of the extended tribenzo-cyclononatriene transforms an achiral cavitand into a chiral host molecule. Calculations of the continuous chirality measure (CCM) predict that tangential substitution induces greater distortion of the unsubstituted bowl-shaped cavitand than radial substitution. We achieved the new cavitands through regioselective synthesis and named them Calochorturils (CTs) after the chiral C 3 -symmetric Calochortus venustus tulip. Resolving them into optically pure enantiomers using chiral HPLC enabled their characterization by optical rotation and circular dichroism spectroscopy. Their absolute configuration was determined by X-ray crystallography of an enantiomerically pure triply etherified CT with ( S )-BINOL. A comparison of CCM calculations for several solid-state CT derivatives with gas-phase models shows satisfactory agreement. The racemization rate constant for the bowl-to-bowl inversion, k rac = 7.1 × 10 –6 s –1 , corresponds to an activation free energy barrier of ΔG # = 115.1 kJ mol –1 . Notably, the CT skeleton is configurationally more stable than the CTV framework, with a 27 h half-life at 334 K in chloroform, compared with 8 h of CTV. Thus, CT derivatives can be handled in solution at room temperature without a significant loss of optical purity.}, archive = {J_JACS}, author = {Sadhna Shah and Venkata S. R. Ganga and Yu-Xiang Huang and Natalia Fridman and Inbal Tuvi-Arad and Yi-Tsu Chan and Ofer Reany and Ehud Keinan}, doi = {10.1021/jacs.5c11855}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38443--38451}, shortjournal = {J. Am. Chem. Soc.}, title = {Calochorturils: Chiral bowl-shaped cavitands obtained by anisotropic tangential substitution}, volume = {147}, year = {2025}, }
• (2025). Nature-inspired glycosylation strategy enabled hydrosoluble polyhydric thioalkylated ferrocene derivatives for pH-neutral aqueous redox flow batteries. JACS, 147(42), 38435--38442. (www)

  @article{ , abstract = {Organic molecules have been regarded as promising alternatives in aqueous redox flow batteries, with the aim of reducing reliance on mineral resources. Enhancing the solubility and stability of organic species is essential and requires strategic functional group refinement and molecular structure optimization. However, there are relatively few solubilization strategies of naturally water-solubilizing groups in ARFBs. Sugars, i.e., carbohydrates, ubiquitous in nature and indispensable as nutrients, possess an exceptional hydrophilic property and offer a sustainable pathway for molecular functionalization. Herein, we present a thioglucose functionalization strategy to synthesize highly soluble ferrocene derivatives via convenient thioetherification reactions under mild conditions. Under the hydrophilic effect of abundant highly polar hydroxyl moieties, the as-synthesized glycosyl-functionalized thioalkylated ferrocene derivative, namely, Fc-(Thio-Glc) 2 , exhibits high water solubility (1.3 M in 1.0 M KCl solution) and favorable electrochemical properties. Molecular dynamics simulations manifest the effects of hydrogen bond networks on the molecular configuration and solvation behavior. Ex situ spectroscopic analyses confirmed the high reversibility and long-term operation stability of Fc(Thio-Glc) 2 . Consequently, the pH-neutral ARFBs assembled with the 0.5 M Fc(Thio-Glc) 2 catholyte achieve a capacity retention of 99.995% per cycle or 99.82% per day. This study highlights the tremendous potential of a bioinspired molecular engineering strategy in advancing safe, stable, and sustainable ARFBs toward large-scale energy storage applications.}, archive = {J_JACS}, author = {Guochun Ding and Tianyu Shen and Pengbo Zhang and Zuoao Wu and Qianchuan Yu and Yuzhu Liu and Sheng Wen and Jie Wei and Zuoxiu Tie and Yichao Yan and Zhong Jin}, doi = {10.1021/jacs.5c11833}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38435--38442}, shortjournal = {J. Am. Chem. Soc.}, title = {Nature-inspired glycosylation strategy enabled hydrosoluble polyhydric thioalkylated ferrocene derivatives for pH-neutral aqueous redox flow batteries}, volume = {147}, year = {2025}, }
• (2025). Ion-specific interfacial electric fields on water microdroplets for tuning menshutkin reactions. JACS, 147(42), 38428--38434. (www)

  @article{ , abstract = {High interfacial electric fields (EFs) on water microdroplets can drastically accelerate chemical reactions; however, how dissolved ions can alter these fields and associated reaction kinetics remain elusive. By combining microdroplet experiments, molecular dynamics (MD) simulations, and quantum chemical calculations, here we studied the ion-specific effects in the pyridine–iodomethane Menshutkin reaction, a reaction that can be accelerated by the EF at the air–water interface of microdroplets. Experimental results reveal that monovalent anions regulate reaction yields in accordance with the Hofmeister series (HCOO – > F – > Cl – > NO 3 – > BF 4 – ≈ SCN – > ClO 4 – > PF 6 – ). Theoretical analyses show that the strength of the EF depends on the interplay between the interfacial affinity of ions and hydration energy: cations with high interfacial affinity and strong hydration capacity amplify interfacial EFs and accelerate reaction rates, whereas anions adsorb to the interface competitively, weakening EFs and suppressing reactivity. This work deciphers how ion-specific interfacial microenvironments govern chemical reactivity in microdroplet systems, providing a basis for the rational design of new EF accelerated microdroplet reactions.}, archive = {J_JACS}, author = {Jianze Zhang and Ziyuan Liu and Chenghui Zhu and Shixuan Wang and Shuang Zhu and Chongqin Zhu and Xinxing Zhang}, doi = {10.1021/jacs.5c11766}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38428--38434}, shortjournal = {J. Am. Chem. Soc.}, title = {Ion-specific interfacial electric fields on water microdroplets for tuning menshutkin reactions}, volume = {147}, year = {2025}, }
• (2025). Turning 2D MOFs into mixed ionic-electronic conductors via side chain engineering. JACS, 147(42), 38419--38427. (www)

  @article{ , abstract = {Despite the wide-ranging use of metal–organic frameworks (MOFs) as either electronic or ionic conductors, mixed electron–ion conductivity in MOFs remains largely unexplored. Here, we report a new methodology for designing new mixed ionic-electronic conductors (MIECs) by tethering ionophilic ethylene glycol (EG) functional groups onto an electrically conductive MOF (cMOF), yielding M 3 (HIR 3 -TAT) 2 (M = Ni, Cu; TAT = triazatruxene; R = n Bu, 1EG, 2EG; referred to as M-R). Leveraging systematic physicochemical variability in the pore microenvironment while preserving in-plane conjugation of the functionalizable TAT core, we orthogonally tune and enhance electronic conjugation through the crystalline framework (in-plane and out-of-plane) and ionic transport through defined abundant pore channels. Upon LiTFSI incorporation, Ni-1EG exhibits the highest room-temperature ionic conductivity (1.1 × 10 –4  S/cm) in the series─nearly an order of magnitude higher than Ni- n Bu (4.18 × 10 –5  S/cm), which features a hydrophobic side chain of the same length─while preserving the electronic conductivity (∼5 × 10 –4  S/cm). Consistent with previous reports, the added steric bulk in Ni-2EG reduces electronic conductivity to 2.7 × 10 –4 S/cm, though the drop is minimal compared to aliphatic side chains of similar length. Counterintuitively, despite improved polarity, ionic conductivity significantly decreases in Ni-2EG, to 2.58 × 10 –6 S/cm, likely due to pore blockage, with electronic conductivity largely remaining unchanged at 2.7 × 10 –6 S/cm. This study unlocks the potential of cMOFs as tunable platforms for the decoupled control of ionic and electronic transport via side chain engineering. It opens doors to the unexplored design space of single-phase porous crystalline MIECs with orthogonal integration of functionalities tailored for emerging applications in chemistry, physics, and materials science.}, archive = {J_JACS}, author = {Heejung Roh and Alice Y. Su and Changhwan Oh and Julius J. Oppenheim and Heather J. Kulik and Aristide Gumyusenge and Mircea Dincă}, doi = {10.1021/jacs.5c11806}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38419--38427}, shortjournal = {J. Am. Chem. Soc.}, title = {Turning 2D MOFs into mixed ionic-electronic conductors via side chain engineering}, volume = {147}, year = {2025}, }
• (2025). High pressure and compositionally directed route to a hexagonal GeSn alloy class. JACS, 147(42), 38413--38418. (www)

  @article{ , abstract = {Despite their electronic dominance, cubic diamond structured Si and Ge, are optoelectronically deficient. Recent work indicates, however, that a volume-expanded hexagonal Ge modification can exhibit intensely sought, superior optoelectronic characteristics. If larger Sn could form a hexagonal solid solution with Ge, this would achieve this expansion. But this was not expected because Ge and Sn are unreactive at ambient conditions, Sn does not have an ambient hexagonal symmetry, and only cubic or tetragonal binary modifications could be prepared under any conditions including thin film processing. This state of affairs is categorically changed here by subjecting Ge and Sn to pressures of 9 and 10 GPa and temperatures up to 1500 K using large-volume press methods. Synchrotron angle-dispersive X-ray diffraction, precession electron diffraction and chemical analysis using electron microscopy reveal ambient pressure recovery of hexagonal 2H, 4H and 6H Ge–Sn solid solutions ( P 6 3 / mmc ). Formation of this new binary materials landscape is correlated with Sn uptake, with the hexagonal symmetry being accessible below 21 atom % Sn and the cubic diamond symmetry at or above this value. The findings form fertile routes to advanced materials, by in tandem creating reactivity with pressure and directing production of needed crystal symmetries with composition, as well as opportunity to tune properties based on crystal symmetry, composition, and stacking sequence for optoelectronic applications.}, archive = {J_JACS}, author = {George Serghiou and Hans Josef Reichmann and Gang Ji and Laurence Nigay and Jonathan P. Wright and Daniel J. Frost and Gus Calder}, doi = {10.1021/jacs.5c11716}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38413--38418}, shortjournal = {J. Am. Chem. Soc.}, title = {High pressure and compositionally directed route to a hexagonal GeSn alloy class}, volume = {147}, year = {2025}, }
• (2025). Ultradurable regenerative propane dehydrogenation catalyst by fluorination-induced confining and positioning. JACS, 147(42), 38404--38412. (www)

  @article{ , abstract = {In the chemical industry, an elaborated design of catalysts for propane dehydrogenation (PDH) should be capable of high propane conversion and propylene selectivity, strong resistance to sintering and coke deposition, and easy regeneration. Here, we report a unique design of fluorinated siliceous MFI zeolite-clothed PtSn for PDH, where the fluorination induces the formation of “holes” in all-silica molecular sieves and the position of ultrasmall PtSn nanoclusters as a result of high activity, selectivity, and especially remarkable resistance to sintering during PDH over 5000 h. The present catalyst displays a near-thermodynamic-limited propane conversion and 94% propylene selectivity in pure propane, respectively, under industrially relevant conditions. Impressively, the coked catalyst can be simply regenerated by H 2 treatment at the same temperature for PDH, avoiding the complicated, poisonous, and corrosive oxychlorination process in the conventional method for regeneration, which will contribute to the extensive application of the industrial PDH process. Detailed investigations demonstrate that the strong synergy between F-modified PtSn nanoclusters and MFI zeolite can promote the selective PDH to propylene and stabilize PtSn nanoclusters against sintering and coke deposition. The unique design of the catalyst and the enhanced performance will provide a feasible strategy to solve the current difficulties in the industrial PDH process.}, archive = {J_JACS}, author = {Yuting He and Shiyun Xiong and Zhongliang Huang and Guodong Qi and Xiaoqing Li and Xiaozhi Liu and Jun Xu and Dong Su and Zhiwei Hu and Wei-Hsiang Huang and Chih-Wen Pao and Shuangli Yang and Mingshu Chen and Yong Xu and Xiaoqing Huang}, doi = {10.1021/jacs.5c11524}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38404--38412}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultradurable regenerative propane dehydrogenation catalyst by fluorination-induced confining and positioning}, volume = {147}, year = {2025}, }
• (2025). Bridged-backbone strategy enables asymmetric synthesis of highly functionalized oxabicyclo[3.3.1]nonanes with anti-osimertinib-resistant NSCLC activity. JACS, 147(42), 38390--38403. (www)

  @article{ , abstract = {The synthesis of highly functionalized oxa[3.3.1]-bridged bicycles remains challenging because of ring strain and the presence of multiple stereocenters. Herein, we report a Brønsted acid-catalyzed bridged-backbone strategy enabling the efficient and asymmetric synthesis of oxabicyclo[3.3.1]nonanes featuring a furochromene motif and three contiguous stereocenters. This method offers excellent enantioselectivity, good regioselectivity, a broad substrate scope, exceptionally mild reaction conditions, and scalability. Notably, it enables the first asymmetric syntheses of the bridged polycyclic natural products myrtucyclitone C and myrtucommulone J, along with the diastereoselective asymmetric synthesis of myrtucommuacetalone. Mechanistic insights derived from quantum mechanical calculations elucidate the origin of the observed selectivities. Furthermore, this strategy led to the discovery of a compound exhibiting potent in vitro and in vivo activity against osimertinib-resistant non-small-cell lung cancer (NSCLC). This compound operates through a unique mechanism involving stearoyl-CoA desaturase 1 (SCD1) inhibition and subsequent induction of ferroptosis, offering a promising avenue for the development of oxabicyclo[3.3.1]nonane-based therapeutics to overcome osimertinib resistance.}, archive = {J_JACS}, author = {Chao Yang and Xueping Lei and Xian-Bo Chen and Ni-Ping Li and Boyin Li and Yu-Xin He and Shi-Lin Lin and Ming Chen and Tian-Hong Zhang and Yong-Heng Wang and Hao Gao and Chuang-Chuang Li and Min-Jing Cheng and Wen-Cai Ye and Lei Wang}, doi = {10.1021/jacs.5c11520}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38390--38403}, shortjournal = {J. Am. Chem. Soc.}, title = {Bridged-backbone strategy enables asymmetric synthesis of highly functionalized oxabicyclo[3.3.1]nonanes with anti-osimertinib-resistant NSCLC activity}, volume = {147}, year = {2025}, }
• (2025). Shaping the glycan landscape: Hidden relationships between linkage and ring distortions induced by carbohydrate-active enzymes. JACS, 147(42), 38376--38389. (www)

  @article{ , abstract = {Carbohydrate-active enzymes (CAZymes) catalyze glycan remodeling by forming and cleaving glycosidic bonds. An often-observed aspect of their catalytic mechanisms, particularly in glycosidases, is monosaccharide ring distortion that brings the substrate from a stable solution conformation to a reactive state. To what extent this distortion is promoted by steric constraints in the enzyme’s binding pocket or by more elusive dynamical effects associated with the glycan conformational flexibility is still a matter of debate. In our work, we quantify the conformational phase-space changes experienced by glycans upon CAZyme binding by means of enhanced-sampling molecular dynamics simulations. Our results reveal a novel correlation between torsional degrees of freedom along the glycosidic bonds and the pucker degrees of freedom within the mannose ring at the −1 subsite of glycan M5G0 upon binding to the Golgi α-mannosidase II enzyme. Key factors driving this torsional phase-space reshaping and the associated transition from solution 4 C 1 to O S 2 / B 2,5 reactive pucker states include tight interactions with a protonated aspartic acid and a Zn 2+ ion in the catalytic site. Comparative studies with ER α-mannosidase I show a different mechanism, where torsional conformations and ring distortion of the M9 glycan substrate are not correlated. By validating against previous computational and experimental studies, we theoretically predict the influence of amino acid mutations and altered glycan compositions on the conformational transition mechanisms. Our findings provide new insights into CAZyme specificity and effectiveness, laying the groundwork for the design of selective inhibitors targeting glycosylation-related diseases.}, archive = {J_JACS}, author = {Isabell Louise Grothaus and Paul Spellerberg and Carme Rovira and Lucio Colombi Ciacchi}, doi = {10.1021/jacs.5c11504}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38376--38389}, shortjournal = {J. Am. Chem. Soc.}, title = {Shaping the glycan landscape: Hidden relationships between linkage and ring distortions induced by carbohydrate-active enzymes}, volume = {147}, year = {2025}, }
• (2025). CO reduction to ethylene and cyclopropane via a trappable ruthenium methylidene. JACS, 147(42), 38365--38375. (www)

  @article{ , abstract = {Ruthenium complexes based on cis -[Ru(bpy) 2 (CO) 2 ] 2+ (bpy is 2,2′-bipyridine) can reduce CO 2 and CO to C 1 products including methanol, but access to products containing C–C bonds has been elusive. A reaction pathway to convert CO into multicarbon products ethylene and cyclopropane is presented here, along with mechanistic studies elucidating the key intermediates in C–C bond formation. The ruthenium hydroxymethyl complex [Ru(bpy′) 2 (CO)(CH 2 OH)] + (bpy′ = 5,5′-dimethyl-2,2′-bipyridine) undergoes protonolysis to generate the ethylene complex [Ru(bpy′) 2 (CO)(C 2 H 4 )] 2+ even at −80 °C, with free ethylene released upon warming to room temperature. Experimental evidence implicates a highly electrophilic methylidene complex [Ru(bpy′) 2 (CO)(CH 2 )] 2+ as the key intermediate. The methylidene was successfully trapped with nitriles and pyridine, forming adducts (ylide complexes) that each have a unique reactivity profile. With an appropriate nitrile, the adduct can be characterized at low temperature before warming generates ethylene. A more stable pyridine adduct [Ru(bpy′) 2 (CO)(CH 2 pyridine)] 2+ was crystallographically characterized. Even ethylene itself is sufficiently nucleophilic to react with the electrophilic methylidene, revealing a route from CO to the C 3 hydrocarbon cyclopropane. The methods for controlling the reactivity of hydroxymethyl and methylidene complexes toward C–C bond formation can inform the development of CO and CO 2 reduction catalysts.}, archive = {J_JACS}, author = {Allison M. Smith and Stephen J. Tereniak and Haley Cox and Mehmed Z. Ertem and Marsha D. Massey and Cynthia K. Schauer and Alexander J. M. Miller}, doi = {10.1021/jacs.5c11327}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38365--38375}, shortjournal = {J. Am. Chem. Soc.}, title = {CO reduction to ethylene and cyclopropane via a trappable ruthenium methylidene}, volume = {147}, year = {2025}, }
• (2025). In situ probing two radicals in halogenation couplings from photoanodic single-atom catalysis. JACS, 147(42), 38354--38364. (www)

  @article{ , abstract = {Photoelectrocatalysis (PEC) has emerged as a transformative heterogeneous protocol for oxidative organocatalytic synthesis, offering remarkable yield, selectivity, and stability. However, its mechanistic advantages over conventional methods remain unclear, largely due to the limitations of current techniques in uncovering the complexity of PEC systems. In this study, as a state-of-the-art advancement, a single-atom nickel oxide anchored BiVO 4 photoanode was developed for the halogenation of (hetero)arenes, with the bromination of anisole serving as a model reaction, achieving 88% yield and 94% selectivity. Notably, a suite of in situ techniques, including in situ Raman spectroscopy and online atmospheric pressure glow discharge mass spectrometry, was adapted to PEC systems to identify active sites and capture reactive intermediates in real time, respectively. These data, combined with time-resolved Fourier transform infrared spectroscopy and density functional theory simulations, revealed a diradical coupling mechanism driving the halogenation process. Furthermore, the photoanode demonstrated remarkable long-term stability for the bromination of anisole over 160 h, with nearly stoichiometric hydrogen evolution at the cathode, emphasizing its advantages for sustainable synthesis and green energy in practical scale-up applications. This work integrates multiple innovative in situ spectroscopic techniques, providing a universal method to uncover the inherent advantages of the PEC system in organic transformations.}, archive = {J_JACS}, author = {Tao Yuan and Yuanxing Fang and Jiaxin Su and Shun Zhao and Rong Qian and Zhenli Zhu and Xinchen Wang}, doi = {10.1021/jacs.5c11269}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38354--38364}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ probing two radicals in halogenation couplings from photoanodic single-atom catalysis}, volume = {147}, year = {2025}, }
• (2025). Strategic fermi level engineering of Donor–Acceptor self-assembled monolayer toward ultrahigh paired-pulse facilitations in photosynaptic transistors. JACS, 147(42), 38341--38353. (www)

  @article{ , abstract = {Given the rapid advancement of artificial intelligence and the demand for low-power computing, photosynaptic transistors have emerged as promising candidates by integrating sensing, memory, and processing to mimic biological synapses. However, simultaneously realizing high paired-pulse facilitation (PPF) and low energy consumption in an artificial synapse, as biological ones, remains challenging. This property should be achieved by balancing the high carrier density while maintaining a low conductivity in the photoresponsive/charge-trapping electret; however, these prerequisites are mutually contradictory. To achieve this goal, a series of electron acceptors, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F 4 TCNQ), tris(pentafluorophenyl)borane (BCF), and their Lewis-paired F 4 BCF, are introduced to the orderly anchored and segregated pyrene self-assembled monolayers for Fermi level modulation of the charge-trapping electret. The high electron deficiency of F 4 BCF induces strong donor–acceptor interaction with pyrene, lowering its Fermi level and stabilizing charges through charge transfer. This molecular design strategy yields a record-high PPF ratio of 293% and an ultralow energy consumption of 2.96 × 10 –19 J, supporting low-power and multilevel memory characteristics analogous to those of biological synapses. Finally, the demonstrated image preprocessing highlights its potential for neuromorphic visual computing. This study highlights the effectiveness of Lewis-paired acceptor engineering as a powerful molecular strategy for modulating the Fermi level. By combining the segregated anchored SAM electret, a decent balance between high carrier density and low conductivity is achieved, thereby realizing the highest PPF ratio and the lowest energy consumption simultaneously among the reported systems. This outperformance underscores its potential for next-generation low-power optoelectronic neuromorphic devices.}, archive = {J_JACS}, author = {Ya-Shuan Wu and Wei-Cheng Chen and Yi-Sa Lin and Cheng-Liang Liu and Yan-Cheng Lin and Wen-Chang Chen}, doi = {10.1021/jacs.5c11235}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38341--38353}, shortjournal = {J. Am. Chem. Soc.}, title = {Strategic fermi level engineering of Donor–Acceptor self-assembled monolayer toward ultrahigh paired-pulse facilitations in photosynaptic transistors}, volume = {147}, year = {2025}, }
• (2025). An electron Donor–Acceptor complex-driven strategy enables initiation of photoiniferter RAFT polymerization from amines, carboxylic acids, and alcohols. JACS, 147(42), 38331--38340. (www)

  @article{ , abstract = {Here, we report a unified approach for the photoiniferter RAFT polymerization technique allowing the utilization of organic molecules with the most ubiquitous functional groups (amines, carboxylic acids, and alcohols) as initiators without significant limitations in substrate complexity providing close to complete α-end functionalization of synthesized polymers. Our catalytic system relies on a combination of visible light-induced electron donor–acceptor complex-driven initiation mechanism and photocontrolled radical polymerization to provide polymers with controlled molar mass, low dispersity, and targeted α-end functionality. Through this method, a wide range of diverse amines and carboxylic acids, including biorelevant and drug-like substrates, were effectively attached to polyacrylate backbone. In addition to that, we have developed a reagent for effective initiation from complex amines and alcohols, which also provides a new dimension for the construction of conjugates with potentially biocleavable bridge between the α-end and polymer chain.}, archive = {J_JACS}, author = {Andrei A. Leushukou and Vladislav A. Badyoukov and Maksim I. Hulnik and Sergei V. Kostjuk}, doi = {10.1021/jacs.5c11213}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38331--38340}, shortjournal = {J. Am. Chem. Soc.}, title = {An electron Donor–Acceptor complex-driven strategy enables initiation of photoiniferter RAFT polymerization from amines, carboxylic acids, and alcohols}, volume = {147}, year = {2025}, }
• (2025). Excited state dynamics of CO2 reduction catalyst under vibrational strong coupling. JACS, 147(42), 38320--38330. (www)

  @article{ , abstract = {Molecular polaritons, formed by coupling molecular electronic or vibrational transitions to photonic modes in microcavities, have gained interest for their potential to influence chemical dynamics. Here, we investigate the effects of vibrational strong coupling (VSC) on solvation-induced time-dependent Stokes shifts using transient infrared (IR) transmission spectroscopy. The electronic excited-state dynamics of the Re(bpy-COOH)(CO) 3 Cl complex (ReC0A) is monitored via angle-resolved time-dependent transmission spectra of vibrational polaritons following 400 nm excitation inside a Fabry–Perot cavity. Our results reveal distinct infrared polaritonic signatures of the CO dynamical Stokes shift, which we interpret using simulations based on a time-dependent excited-state absorption model. We observed negligible change of the solvation-induced vibrational dynamic Stokes shift of the CO modes under VSC. We also investigate the perturbed free induction decay in the cavity and its connection to polariton dynamics. This setup allows us to probe and test potential fundamental VSC effects on molecular processes relevant to the reactivity and charge transfer.}, archive = {J_JACS}, author = {Tao Jin and Sara T. Gebre and Christopher J. Miller and Clifford P. Kubiak and Raphael F. Ribeiro and Tianquan Lian}, doi = {10.1021/jacs.5c11060}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38320--38330}, shortjournal = {J. Am. Chem. Soc.}, title = {Excited state dynamics of CO2 reduction catalyst under vibrational strong coupling}, volume = {147}, year = {2025}, }
• (2025). Biomimetic interface with dynamic disulfide bonds boosts durable photoconversion of diluted CO2. JACS, 147(42), 38311--38319. (www)

  @article{ , abstract = {The integration of molecular catalysts into covalent organic frameworks (COFs) provides a promising route for solar-driven conversion of low-concentration CO 2 into value-added fuels and chemicals. However, the intrinsic rigidity of conventional COFs greatly impedes the adaptive incorporation of molecular catalysts and disrupts directional charge migration, which inevitably limits their photocatalytic activity and operational durability under dilute CO 2 conditions. Herein, we report a biomimetic strategy of incorporating dynamic disulfide bonds into COFs for enabling adaptive anchoring of [Co(bpy) 3 ] 2+ (bpy = 2,2′-bipyridine) and promoting interfacial electronic coherence to significantly improve CO 2 photocatalytic efficiency and stability. The resulting disulfide-rich TFBP-APDS COFs achieve a CO evolution rate of 10.6 mmol g –1 h –1 with a high selectivity of 94.5%, which is 2.4 times higher than its disulfide-free analogue TFBP-BD (4.4 mmol g –1 h –1 ; 78.9% selectivity). Combined spectroscopic and theoretical analyses reveal that the dynamic disulfide linkages enhance adaptive Co–S interaction with [Co(bpy) 3 ] 2+ and strengthen interfacial electronic coupling, thereby facilitating efficient and directional charge transfer across the COF framework. In a homemade integrated flow-type photocatalytic microreactor, TFBP-APDS achieves a CO production rate of 5.1 mmol g –1 h –1 under simulated flue gas conditions (15% CO 2 ) and maintains operation for 300 h without performance loss.}, archive = {J_JACS}, author = {Ruijin Zeng and Chenglong Sun and Zheng Lin and Yanli Li and Chenhui Zhou and Shipeng Zhang and Lu Li and Shaojun Guo}, doi = {10.1021/jacs.5c10865}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38311--38319}, shortjournal = {J. Am. Chem. Soc.}, title = {Biomimetic interface with dynamic disulfide bonds boosts durable photoconversion of diluted CO2}, volume = {147}, year = {2025}, }
• (2025). Unravelling the effects of anions on the vicinal H-bonding network near an electrode and activity of single-atom electrocatalysts. JACS, 147(42), 38301--38310. (www)

  @article{ , abstract = {While extensive research has been devoted to studying the electrochemical performance of single-atom catalysts (SACs), the impact of electrolyte anions on their electrochemical activity remains largely unexplored. We performed multiscale molecular dynamics (MD) simulations to examine how anions affect the vicinal hydrogen-bonding network and associated water dissociation dynamics at the SAC electrode/electrolyte interface. Constant-potential MD simulations demonstrate the presence of two distinct hydrogen bond gap regions at the interface and that hydrogen bond connectivity may be highly sensitive to the anion type and electrode potential. In particular, at the interface, differences in anion adsorption strength can lead to opposite trends in hydrogen bond connectivity. Another key insight obtained from ab initio MD simulations is that anions act as active modulators rather than passive bystanders. Nonspecific anion adsorption tends to modulate water activation due to the asymmetry in the local hydrogen-bonding environment. Overall, molecular-level insights into the effects of anions at the SAC electrode/electrolyte interface will lead to new electrolyte engineering strategies to optimize electrochemical performance.}, archive = {J_JACS}, author = {Kaiwei Wan and Yunxiao Cui and Joseph S. Francisco and Xinghua Shi and Xiao Cheng Zeng}, doi = {10.1021/jacs.5c11019}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38301--38310}, shortjournal = {J. Am. Chem. Soc.}, title = {Unravelling the effects of anions on the vicinal H-bonding network near an electrode and activity of single-atom electrocatalysts}, volume = {147}, year = {2025}, }
• (2025). Unlocking polyanion-type materials through high-entropy effect for aqueous potassium-ion batteries. JACS, 147(42), 38291--38300. (www)

  @article{ , abstract = {Exploration of electrode materials for aqueous batteries has predominantly followed the established principles and design strategies derived from organic electrolyte-based systems. However, this conventional approach faces inherent limitations. Although V-based polyanion materials (e.g., Na 3 V 2 (PO 4 ) 3 ) are compelling for organic electrolyte-based alkali metal ion batteries, their applications in aqueous K-ion batteries remain untapped, probably due to the limited cation electroactivity and uncontrollable dissolution. Herein, we unlock reversible and stable aqueous K + storage in V-based polyanion materials via a high-entropy strategy. Unlike the phase-transition mechanism in traditional polyanionic electrodes, in situ spectroscopic characterizations reveal a solid-solution process in the entropy-tuned polyanionic electrode, facilitated by reduced steric hindrance during K + uptake. Time-of-flight secondary ion mass spectrometry and density functional theory simulations further confirm the suppressed Na + /K + -migration barrier and solubility of the entropy-tuned polyanionic cathodes. As a result, the high-entropy V-based polyanion cathodes are demonstrated promising for aqueous K-ion batteries, even in dilute aqueous electrolytes, achieving an ultrahigh initial Coulombic efficiency of 98.7%, rate capability at 36C, and impressive cycling durability up to 3500 cycles. This work uncovers the charge storage gap between organic and aqueous electrolyte-based systems and provides insights into activating the electroactivity of other materials in an aqueous environment.}, archive = {J_JACS}, author = {Bingqiu Liu and Qi Zhang and Xiaoyu Yu and Yutong Feng and Zhuo Yang and Wanhai Zhou and Dan Xie and Chengyu Li and Yongjin Chen and Lu Li and Chungang Wang and Dongliang Chao}, doi = {10.1021/jacs.5c11011}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38291--38300}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking polyanion-type materials through high-entropy effect for aqueous potassium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). A multi-pronged approach to the determination of cation distribution, site selectivity, and chemical ordering in “High entropy” spinel oxides. JACS, 147(42), 38283--38290. (www)

  @article{ , abstract = {“High entropy” oxides (HEOs) are complex, multifunctional materials that have provided a paradigm shift on the design of technologically important materials. With their high number of chemical substituents, they offer a wide chemical space to explore compared with traditional solid solutions and common semiconductors. They also exhibit magnetic uniformity seldom associated with highly disordered materials. The versatility of HEOs and their excellent emergent properties have made these materials potential candidates for use as anodes in lithium-ion batteries, electrocatalysts in water splitting, and spintronic materials. However, the compositional complexity of these materials makes them challenging to understand at a fundamental level. This work represents a milestone in our understanding of “high entropy” materials, owing to our use of a multipronged approach: high-resolution synchrotron X-ray diffraction, resonant X-ray diffraction, X-ray absorption spectroscopy, and X-ray and neutron total scattering techniques. Our comprehensive characterization reveals key insights regarding the site selectivity and chemical ordering in a “high entropy” spinel oxide fabricated via a conventional solid-state reaction. Cr, Ni, and Mn have been found to strongly prefer an octahedral environment, while Co has been shown to predominantly occupy tetrahedral sites. Evidence of Ni clustering is reported for the first time.}, archive = {J_JACS}, author = {Sikhumbuzo M. Masina and Gugulethu C. Nkala and Mathias A. Kiefer and Chi L. Cao and Liam A. V. Nagle-Cocco and Yongezile Mhlana and Kevin H. Stone}, doi = {10.1021/jacs.5c10967}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38283--38290}, shortjournal = {J. Am. Chem. Soc.}, title = {A multi-pronged approach to the determination of cation distribution, site selectivity, and chemical ordering in “High entropy” spinel oxides}, volume = {147}, year = {2025}, }
• (2025). Development of a ligand for cu-catalyzed amination of base-sensitive (Hetero)aryl chlorides. JACS, 147(42), 38275--38282. (www)

  @article{ , abstract = {We report a new N 1 , N 2 -diarylbenzene-1,2-diamine ligand, L6 , that supports a copper catalyst capable of coupling base-sensitive aryl chlorides and amines that were previously unsuccessful substrates for Cu-catalyzed C–N coupling. A detailed structure–activity relationship study, combined with density functional theory (DFT) calculations, was used to uncover two key structural features that contribute to the efficacy of the catalyst derived from L6 . First, steric repulsion caused by a methyl substituent induces a conformational change that opens up additional space for ligand deprotonation and oxidative addition. Second, the trifluoromethyl groups create electrostatic interactions between the ligand and aryl chloride substrates that facilitate oxidative addition via through-space ligand–substrate interaction.}, archive = {J_JACS}, author = {Han-Jun Ai and Binh Khanh Mai and Cecilia Liu and Peng Liu and Stephen L. Buchwald}, doi = {10.1021/jacs.5c10910}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38275--38282}, shortjournal = {J. Am. Chem. Soc.}, title = {Development of a ligand for cu-catalyzed amination of base-sensitive (Hetero)aryl chlorides}, volume = {147}, year = {2025}, }
• (2025). Spatial conformation of ionizable lipids regulates endosomal membrane disruption. JACS, 147(42), 38265--38274. (www)

  @article{ , abstract = {The delivery efficiency of biologics via lipid nanoparticles (LNPs) is critically dependent on the incorporation of ionizable lipids. The subtle structural changes to these lipids led to dramatic variations in cytosolic delivery efficiency. However, beyond the p K a values of tertiary amines in ionizable lipids, our understanding of the structure–activity relationships (SARs) between ionizable lipid spatial conformations and their endosomal escape efficacies remains limited. Here, we constructed a library of 18 bioreducible ionizable lipids with varying numbers of alkyl tails, ranging from two to four. We found that three-tailed ionizable lipids exhibited robust endosomal disruption and cytosolic delivery efficiency compared to those of their counterparts with similar p K a values. Molecular dynamics simulations and 31 P NMR spectroscopy show that the three-tailed ionizable lipid adopts a characteristic cone-shaped structure, which upon interaction with endosomal phospholipids promotes the formation of inverted hexagonal phases and facilitates endosomal membrane disruption. These results underscore that the number of alkyl tails in ionizable lipids must be precisely tuned, as excessive tail branching may not linearly correlate with improved endosomal disruption. Our research contributes to the mechanistic comprehension of ionizable lipids, highlighting that the spatial configuration serves as a critical design parameter governing intracellular biologic transport.}, archive = {J_JACS}, author = {Yu Zhao and Zhiyuan Qu and Markéta Paloncýová and Zeyu Wang and Benson Weng and Yuchen Zhao and Lihan Liu and Donghui Song and Douglas Wich and Michal Otyepka and Qiaobing Xu}, doi = {10.1021/jacs.5c10908}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38265--38274}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatial conformation of ionizable lipids regulates endosomal membrane disruption}, volume = {147}, year = {2025}, }
• (2025). Real-time untargeted monitoring of intracellular metabolism in live cells using 1H NMR and extracellular signal suppression. JACS, 147(42), 38254--38264. (www)

  @article{ , abstract = {Nuclear magnetic resonance (NMR) spectroscopy is ideally suited for observing atomic-level phenomena in living cells. However, the measurement of intracellular signals using untargeted, highly sensitive 1 H NMR is impeded by the simultaneous detection of overwhelming signals from the extracellular media. To circumvent this limitation, we developed extracellular signal suppression (ExSS)-NMR, an in-cell NMR approach that enables the untargeted, real-time detection of intracellular 1 H NMR signals. This is primarily accomplished using a T 2 relaxation compound (α-Fe 2 O 3 nanorods) that suppresses extracellular signals (348× at 600 MHz; 15,737× at 900 MHz) with no detectable reduction in cell viability. We present here the potential of this approach for: high temporal resolution (1 min time increments) metabolomics, mitochondrial function/dysfunction monitoring, native-state lipid droplet characterization, and xenobiotic uptake in HepG2 cells. We also report its suitability for use with adherent human cell lines established from the brain, breast, and prostate, indicating its potential for deriving novel insights from an array of cell types.}, archive = {J_JACS}, author = {Drew R. Ekman and Quincy Teng}, doi = {10.1021/jacs.5c10909}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38254--38264}, shortjournal = {J. Am. Chem. Soc.}, title = {Real-time untargeted monitoring of intracellular metabolism in live cells using 1H NMR and extracellular signal suppression}, volume = {147}, year = {2025}, }
• (2025). The Boroxine–Boronic acid equilibrium. JACS, 147(42), 38237--38253. (www)

  @article{ , abstract = {The equilibrium between boroxines and boronic acids is a major component of their physicochemical properties, key to many of their applications, and a complicating factor in the analysis of their purity and stoichiometry. While the equilibrium is well-known and extensively applied, there is a dearth of information on the mechanism and kinetics of the multistep process that underpins the overarching hydrolytic sequence. The kinetics of the interconversion of arylboronic acids and arylboroxines in aqueous THF have now been studied in detail by 1 H/ 19 F NMR and UV–vis spectroscopy, including titrations, stopped-flow kinetics, magnetization transfer, 1 H/ 2 H solvent kinetic isotope effects, numerical simulations of reaction kinetics and equilibria, and DFT calculations using explicit solvation approaches. The study has identified two acyclic anhydride intermediates in a three-step interconversion of boroxines and boronic acids. Water acts as a reagent and as a catalyst in each of these steps, and the hydrogen-bond acceptor properties of the solvent strongly affect the overarching hydrolytic equilibrium. A spreadsheet for estimating boroxine–boronic equilibrium speciation is provided. In addition, competing equilibria of boroxines with boric acid generate hydroxyboroxines, and direct associative transfer of Ar–B units occurs between boroxines and boronic acids, bypassing the hydrolysis. These findings have implications for the use of boronic acids and boroxines as reagents, catalysts, sensors, and pharmaceuticals, and in the design and application of boroxine-based materials, polymers, and dynamic architectures.}, archive = {J_JACS}, author = {Chen Li and Lia Sotorrios and Patrick J. Boaler and Valentas Olikauskas and Matteo Amico and Andrés García-Domínguez and Andrew G. Leach and Guy C. Lloyd-Jones}, doi = {10.1021/jacs.5c10835}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38237--38253}, shortjournal = {J. Am. Chem. Soc.}, title = {The Boroxine–Boronic acid equilibrium}, volume = {147}, year = {2025}, }
• (2025). A-cation-dependent Structure–Optical property relationships of halide perovskite heterostructures with complex interfaces. JACS, 147(42), 38225--38236. (www)

  @article{ , abstract = {Halide perovskite heterostructures offer promising interfacial interactions for energy conversion, yet challenges in synthesizing structurally well-defined systems limit detailed investigations into structure–property relationships. Here, we report the synthesis of compositionally controlled 3D/3D and 3D/2D halide perovskite heterostructures using evaporation crystallization–polymer pen lithography (EC-PPL) and single-particle analysis of their properties. By systematically varying A-site-cation combinations and crystal dimensions, we show that heterointerfaces induce local lattice distortions that modulate vibrational dynamics and electron–phonon coupling. These interfacial effects result in significantly extended carrier lifetimes compared to compositionally similar pure phases. Raman spectroscopy, temperature-dependent photoluminescence, and power-dependent emission analysis reveal that localized structural modulations at the interface govern exciton–phonon interactions. These effects are magnified in smaller crystals due to increased interfacial contributions. Our findings highlight the critical role of interface-driven lattice control in tuning the optoelectronic properties of halide perovskites and provide design principles for engineering heterostructures in next-generation optoelectronic devices.}, archive = {J_JACS}, author = {Donghoon Shin and Yongjin Shin and David D. Xu and M. Iqbal Bakti Utama and Tong Cai and Zihao Ye and EunBi Oh and Jun Li and Deokjae Choi and Mark C. Hersam and James M. Rondinelli and Chad A. Mirkin}, doi = {10.1021/jacs.5c10848}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38225--38236}, shortjournal = {J. Am. Chem. Soc.}, title = {A-cation-dependent Structure–Optical property relationships of halide perovskite heterostructures with complex interfaces}, volume = {147}, year = {2025}, }
• (2025). Mapping the various li+ jump pathways in Li10GeP2S12: From ultraslow exchange to high-temperature diffusion. JACS, 147(42), 38215--38224. (www)

  @article{ , abstract = {The solid electrolyte Li 10 GeP 2 S 12 is known to exhibit exceptionally fast Li + diffusion within its tetragonal crystal structure. Experimentally, however, the various Li + hopping processes remain incompletely understood. In this study, we employed 7 Li spin-alignment echo (SAE) NMR and complementary NMR techniques to resolve lithium-ion dynamics in LGPS over nearly 12 orders of magnitude in jump rates, from ultraslow local exchange at 90 K to fast long-range diffusion close to room temperature. Our data reveal a sequence of dynamic regimes and activation energies that reflect the dimensional evolution of Li + transport, from localized 1D hopping to full 3D diffusion. The SAE NMR decay rates, which directly reflect slow Li + jump rates, on the order of one jump every three seconds (0.32(2) s –1 ) at 90 K, reveal two distinct dynamic regimes with activation energies of 0.09 and 0.18 eV, suggesting a transition from 1D to 2D diffusion. At higher temperatures, a third regime emerges, characterized by an activation energy of 0.28 eV, detected by NMR relaxation and SAE NMR. This regime likely corresponds to 3D Li + transport, and the measured rates are in excellent agreement with those from pulsed field gradient NMR, quasi-elastic neutron scattering, and theoretical predictions.}, archive = {J_JACS}, author = {Annika Marko and Katharina Hogrefe and Lukas Schweiger and Florian Stainer and Jana Königsreiter and Jonas Spychala and Jakob Schwaiger and Paul Heitjans and Bernhard Gadermaier and H. Martin R. Wilkening}, doi = {10.1021/jacs.5c10283}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38215--38224}, shortjournal = {J. Am. Chem. Soc.}, title = {Mapping the various li+ jump pathways in Li10GeP2S12: From ultraslow exchange to high-temperature diffusion}, volume = {147}, year = {2025}, }
• (2025). Constructing dynamic Rhδ+–Ov–Ti interfacial sites for highly efficient and stable photothermal catalytic methane dry reforming. JACS, 147(42), 38204--38214. (www)

  @article{ , abstract = {Photothermal catalytic dry reforming of methane (DRM) is a promising process for converting two greenhouse gases into syngas. However, it still suffers from poor reactivity and coke-induced instability. Here, we report a Rh-embedded SrTiO 3 with stable interfacial sites (Rh δ+ –O v –Ti) induced by strong electronic metal–support interactions, which enables highly efficient and stable DRM. In situ characterizations and theoretical calculations confirm that these interfacial sites act as intrinsic active centers for the adsorption and activation of CH 4 and CO 2 molecules via the CH 3 O* pathway, without coking. Furthermore, the local charge redistribution and oxygen vacancy (O v ) regeneration enable the dynamic evolution of the Rh δ+ –O v –Ti interfacial sites during DRM. Consequently, a syngas yield of 7.6/9.6 mol g Rh –1 h –1 for H 2 /CO production and durability of 100 h were achieved with the Rh/SrTiO 3 catalyst under light irradiation. More importantly, this embedding strategy can be universally applied to synthesize other anticoking catalysts for photothermal DRM and other structure-sensitive reactions.}, archive = {J_JACS}, author = {Hailong Xiong and Zehui Dai and Cenfeng Fu and Xiaomin Ji and Yueyue Dong and Min Ge and Ran Long and Yingpu Bi and Yujie Xiong}, doi = {10.1021/jacs.5c10497}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38204--38214}, shortjournal = {J. Am. Chem. Soc.}, title = {Constructing dynamic Rhδ+–Ov–Ti interfacial sites for highly efficient and stable photothermal catalytic methane dry reforming}, volume = {147}, year = {2025}, }
• (2025). Photobiocatalytic radical hydroalkylation with C(sp3)–H bonds enabled by engineered imine reductase and redox buffering. JACS, 147(42), 38195--38203. (www)

  @article{ , abstract = {Photobiocatalytic systems that leverage nicotinamide- or flavin-dependent oxidoreductases have enabled diverse hydro-functionalization of alkenes. However, these typically rely on preactivated radical precursors and native reducing equivalents (e.g., reduced nicotinamide adenine dinucleotide phosphate (NADPH)). Direct hydroalkylation using abundant C–H substrates remains attractive yet highly challenging. Here, we report a photobiocatalytic “redox buffering” strategy that repurposes imine reductase (IRED) to catalyze the hydroalkylation of enamides with commercial alkanes. Cooperative external peroxide and synthetic photocatalyst activate C(sp 3 )–H bonds via hydrogen atom transfer (HAT), while engineered IRED with its native NADPH precisely orchestrates subsequent C-radical addition to enamides and stereodetermining HAT steps. This synergistic integration of an external oxidant with the native reductant, coupled with the merging of photoredox and biocatalysis, unlocks unnatural enzyme functionalities, producing enantioenriched amines (with up to >99% ee, low to 0.02 mol % of IRED).}, archive = {J_JACS}, author = {Bin Chen and Ran Ge and Jinhai Yu and Ruiqi Zhu and Qin Zhu and Jiawei Zhang and Mingfeng Cao and Xiaoqiang Huang}, doi = {10.1021/jacs.5c10377}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38195--38203}, shortjournal = {J. Am. Chem. Soc.}, title = {Photobiocatalytic radical hydroalkylation with C(sp3)–H bonds enabled by engineered imine reductase and redox buffering}, volume = {147}, year = {2025}, }
• (2025). Metabolic hijacking by engineered probiotics reprograms tumor metabolism and immune microenvironment for self-reinforcing photodynamic immunotherapy. JACS, 147(42), 38180--38194. (www)

  @article{ , abstract = {Metabolic hijacking disrupts tumor redox homeostasis and reprograms immune-metabolic crosstalk. Nevertheless, existing approaches lack integrated coordination between metabolic perturbation and immunogenic activation to achieve self-reinforcing photodynamic-immunotherapy synergy. Here, we designed an upconversion nanoparticle (UCNP)-bacteria hybrid system that depletes glycine while generating the photosensitizer protoporphyrin IX (PpIX) in tumors. We reprogrammed E. coli 1917 probiotics to express glutamyl-tRNA reductase A and malate synthase B to synthesize 5-aminolevulinic acid, which tumor cells convert into PpIX. Microfluidic-chip screening optimized bacteria to utilize glycine as their sole carbon source, while UCNP-DNA through G4-hairpin and bacterial aptamers binds to bacteria, responding to tumor miRNA-21 to form G-quadruplexes that trap PpIX and amplify PDT. This dual metabolic system disrupts tumor self-protection against ROS by glycine depletion and enriches photosensitizers by functionalized-UCNPs, enabling self-reinforcing PDT. Additionally, it promotes ROS-mediated immunogenic cell death, dendritic cell activation, and M1 macrophage polarization, exhibiting robust antitumor growth and metastasis.}, archive = {J_JACS}, author = {Shurong Qin and Qi Wang and Zhuangwei Zhang and Junhui Gu and Guanzhong He and Fei Zeng and Ruiyue Chen and Bangshun He and Yuzhen Wang and Meng Wang and Yujun Song}, doi = {10.1021/jacs.5c10242}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38180--38194}, shortjournal = {J. Am. Chem. Soc.}, title = {Metabolic hijacking by engineered probiotics reprograms tumor metabolism and immune microenvironment for self-reinforcing photodynamic immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Enhancing c2+ product faradaic efficiency in CO2 reduction using fluorine-stabilized superhydrophobic copper (δ+). JACS, 147(42), 38169--38179. (www)

  @article{ , abstract = {Oxide-derived (OD) Cu catalysts are recognized for their effectiveness in producing C 2+ products, but often revert to their metallic state, reducing selectivity due to the loss of their positive oxidation state. Here, we report a novel strategy to incorporate fluorine (F) into Cu 2 O nanospheres using hydrofluoric acid (HF). While halogen acids have traditionally been employed to etch metals and create cavities for confinement effects, this work goes a step further by inserting F ions into the lattice. Among all halogens, F provided the best lattice stability and was thus selected for catalyst testing. F incorporation was found to stabilize the Cu (δ+) oxidation state, achieving an impressive Faradaic efficiency (FE) of 91.9 ± 2.03% for C 2+ products, predominantly ethylene (67%), at a current density of 250 mA cm –2 . High-field 1D and 2D 19 F magic-angle spinning (MAS) solid-state nuclear magnetic resonance (ssNMR) spectroscopy provided definitive evidence of F substitution at oxygen vacancies and the formation of a surface layer of HF. Water contact angle (WCA) measurements revealed enhanced hydrophobicity, with the 3 M HF-treated Cu 2 O exhibiting superhydrophobicity (WCA = 161°), which effectively suppressed hydrogen evolution (HER). In situ Raman spectroscopy confirmed prolonged stability of the Cu 2 O phase in the F-incorporated catalyst, while in situ ATR-FTIR spectroscopy with isotopic labeling elucidated the mechanistic pathway for ethylene production. Additionally, density functional theory (DFT) calculations offered mechanistic insights into ethylene formation, while Bader charge analysis revealed the electronic role of F incorporation in Cu 2 O, thereby providing insight into its enhanced selectivity.}, archive = {J_JACS}, author = {Geetansh Chawla and Nilutpal Dutta and Siddhi Kediya and Debabrata Bagchi and Anu Pulparambil and Andrew G. M. Rankin and Sayan Das and Subhajit Chakraborty and G. N. Manjunatha Reddy and Sebastian C. Peter}, doi = {10.1021/jacs.5c10233}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38169--38179}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing c2+ product faradaic efficiency in CO2 reduction using fluorine-stabilized superhydrophobic copper (δ+)}, volume = {147}, year = {2025}, }
• (2025). Cation competition experiments during electrochemical CO2 reduction as a probe of the film-modified copper microenvironment. JACS, 147(42), 38158--38168. (www)

  @article{ , abstract = {Alkali metal electrolyte cations affect product activity and selectivity in electrochemical CO 2 reduction (CO 2 R); however, the precise mechanisms of action are not fully understood. By performing cation competition experiments with LiHCO 3 and CsHCO 3 during CO 2 R with bare and an organic film-modified Cu electrode, we deconvolute cation-dependent electric-field and nonelectric-field effects and their impact on CO 2 R performance. Attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) experiments reveal that organic additive films do not change cation accumulation at the electrochemical interface. Instead, through time-resolved ATR-SEIRAS experiments, we find that additive films alter the transport and interfacial concentrations of CO 2 and CO, a CO 2 R intermediate. This lowers the required [Cs + ] to achieve improved CO 2 R without changing the intrinsic reaction kinetics. Additionally, we find that even small amounts of Cs + significantly disrupt the interfacial water structure, which we infer is key to the promotion of CO 2 R to CO and/or CO reduction to C–C coupled products. Together, this study yields spectroscopic evidence for the mechanism of improved CO 2 R selectivity with organic film-modified electrodes and decouples electric-field and nonelectric-field cation effects in CO 2 R.}, archive = {J_JACS}, author = {Madeline H. Hicks and Nicholas B. Watkins and Sebastian Castro and Theodor Agapie and Jonas C. Peters}, doi = {10.1021/jacs.5c10155}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38158--38168}, shortjournal = {J. Am. Chem. Soc.}, title = {Cation competition experiments during electrochemical CO2 reduction as a probe of the film-modified copper microenvironment}, volume = {147}, year = {2025}, }
• (2025). Nanoscale Core–Shell catalysts for h2 production by methane decomposition: Supported nickel nanoparticles ensheathed in metal oxides. JACS, 147(42), 38141--38157. (www)

  @article{ , abstract = {Catalytic methane decomposition provides a potentially viable route to low-cost, CO x -free H 2 from this abundant source. A remaining challenge is to facilitate the needed low-temperature C–H bond activation with high catalytic activity and stability. We now report the design and synthesis of supported Ni catalysts that address these limitations; they consist of silica-supported Ni nanoparticles ensheathed in nanoscale TiO 2 shells, forming an embedded core–shell structure that provides catalyst stability, maintaining a H 2 site-time yield of 3.6 mol/g Ni /h at a space velocity of 24000 mL g cat –1 ·h –1 at 550 °C for 6 h on stream in a flow reactor. In contrast, a comparable catalyst without the sheath deactivated after only 2.5 h, being characterized by a Ni-extracting tip-growth mechanism of coproduct carbon nanotube formation that destroyed the catalyst. An advantage of the ensheathed catalyst is that it facilitates a Ni-sparing base-growth mechanism. Infrared and Raman spectra, combined with other catalyst characterization data and calculations at the level of density functional theory, show that the TiO 2 sheaths barely hinder the C–H bond cleavage and carbon nanotube formation on the underlying nickel, while providing the advantages stated above. We postulate that these results provide guidance for the synthesis of catalysts for low-temperature H 2 production and related reactions requiring C–H bond activation.}, archive = {J_JACS}, author = {Qiangqiang Xue and Shuairen Qian and Kang Hui Lim and Melvin Xin Jie Wee and Kaiqi Nie and Shuwen Cheng and Xiaohan Chen and Prae Chirawatkul and Bernt Johannessen and Binhang Yan and Zongyou Yin and Yujun Wang and Guangsheng Luo and Bruce C. Gates and Sibudjing Kawi}, doi = {10.1021/jacs.5c10017}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38141--38157}, shortjournal = {J. Am. Chem. Soc.}, title = {Nanoscale Core–Shell catalysts for h2 production by methane decomposition: Supported nickel nanoparticles ensheathed in metal oxides}, volume = {147}, year = {2025}, }
• (2025). Establishing the field-flow competition model to decipher the nonmonotonic interfacial li+ dynamic process for stabilizing the high-voltage Cathode–Electrolyte interface. JACS, 147(42), 38128--38140. (www)

  @article{ , abstract = {Deciphering the evolution of the interfacial solvation structure represents a critical frontier in unlocking high-performance lithium-ion batteries. While the solvation chemistry of bulk electrolytes has been extensively characterized, the dynamic behavior of interfacial species under electric and concentration fields, as well as its governing role in cathode–electrolyte interphase (CEI) formation, remains elusive. Here, we employ in situ electrochemical spectroscopy to uncover a multistage nonmonotonic evolution of the interfacial Li + population, which exhibits an “enrichment–depletion–re-enrichment” trend. We introduce a field-flow competitive regulation model wherein the interfacial electric field drives Li + migration away from the interface, while the delithiation-induced Li + inflow replenishes the interfacial concentration. This mechanistic framework correlates interfacial solvation configurations with operational parameters (field strength, current density, solvent polarity) and ultimately dictates CEI composition through a phase-controlled solvation stage. Leveraging these insights, we developed a potential-modulated activation protocol to bypass the deleterious Li + /anion-depletion phase, enabling the construction of a mechanically robust CEI. This approach significantly enhances the cycling stability of high-voltage cathodes. By uncovering the principles of dynamic interfacial solvation engineering, this work provides a foundation for the rational design of electrode/electrolyte interfaces in advanced energy storage systems.}, archive = {J_JACS}, author = {Haiyan Luo and Xiangyu Ji and Hongxin Lin and Baodan Zhang and Kang Wang and Zixin Wu and Junhao Wang and Yilong Chen and Jian-Feng Li and Yeguo Zou and Guang Feng and Yu Qiao and Haoshen Zhou and Shi-Gang Sun}, doi = {10.1021/jacs.5c10013}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38128--38140}, shortjournal = {J. Am. Chem. Soc.}, title = {Establishing the field-flow competition model to decipher the nonmonotonic interfacial li+ dynamic process for stabilizing the high-voltage Cathode–Electrolyte interface}, volume = {147}, year = {2025}, }
• (2025). HNO dimerization as a chemical reference standard for N2O isotopomer ratio: Ab initio calculations, formation kinetics, and frequency comb spectroscopy. JACS, 147(42), 38110--38127. (www)

  @article{ , abstract = {The 15 N-site preference of N 2 O, δ 15 N SP = [ 14 N 15 NO]/[ 15 N 14 NO] – 1 ≈ δ 15 N α – δ 15 N β = SP, quantifies the relative enrichment of 15 N at the central (α) versus terminal (β) position in nitrous oxide and serves as a robust isotopic fingerprint for tracing N 2 O sources and formation pathways. One such pathway involves dimerization of nitroxyl (HNO), which can occur directly or enzymatically. The direct dimerization of HNO in aqueous solution has been suggested to proceed via acid-base equilibria, forming cis -hyponitrite or cis -hyponitrous acid intermediates that decompose to N 2 O. Measuring δ 15 N SP (N 2 O) from HNO dimerization would not only test the postulated formation pathway but also offer an easily reproducible chemical reference standard for isotopic studies. Using high-precision mid-infrared frequency comb spectroscopy, we determine the 15 N-site preference by analyzing the absorption ratio of multiple rovibrational line pairs of the α and β isotopomers. At pH = 0.62, δ 15 N SP (N 2 O) decreases with synthesis temperature from 36.6‰ at T = 278 K to 23.4‰ at T = 336 K, in very good agreement with prediction based on a kinetic equilibrium model of the strongly pH-dependent cis -hyponitrous acid/ cis -hyponitrite acid-base system. These results confirm N 2 O formation via the cis pathway is dominated─at the low synthesis pH─by the decomposition of the neutral cis -hyponitrous acid. Alternative formation of N 2 O from trans -hyponitrite, predicted to yield δ 15 N SP ≈ −7‰, can be excluded. Our work, combining high-precision spectroscopic measurements with first-principles ab initio and transition state theory calculations, is the first step toward establishing the chemical synthesis of N 2 O from HNO dimerization under acidic conditions as an absolute δ 15 N SP reference.}, archive = {J_JACS}, author = {Ibrahim Sadiek and Adrian Hjältén and Gernot Friedrichs and Aleksandra Foltynowicz}, doi = {10.1021/jacs.5c09983}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38110--38127}, shortjournal = {J. Am. Chem. Soc.}, title = {HNO dimerization as a chemical reference standard for N2O isotopomer ratio: Ab initio calculations, formation kinetics, and frequency comb spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Construction of kondo chains by engineering porphyrin π-radicals on au(111). JACS, 147(42), 38100--38109. (www)

  @article{ , abstract = {Quantum manipulation of molecular radical spins provides a crucial platform for exploring emergent phenomena in many-body systems. Here, we combine surface-confined synthesis with scanning tunneling microscopy (STM) tip-induced dehydrogenation to achieve atom-precise engineering of quasi-one-dimensional porphyrin-based Kondo chains (1–7 units) on Au(111). High-resolution STS measurements and low-energy effective modeling collectively demonstrate that π-radicals at each fused-porphyrin unit form Kondo singlets screened by conduction electrons. Adjacent singlets develop direct coherent coupling via quantum-state-overlap-enabled electron tunneling. Crucially, chiral symmetry in the effective model governs zero-mode distribution─present in odd-length chains yet absent in even-length chains─which dictates pronounced odd–even quantum effects in STS spectra of finite chains. Furthermore, the number of parallel porphyrin chains nonmonotonically tunes the competition between the Kondo effect and spin exchange, showing opposing trends in strength and demonstrating that both wave function overlap and the SOMO–LUMO gap collectively govern these interactions. This work simultaneously resolves the dimensional dependence of many-body correlations in confined quantum systems and pioneers approaches for quantum-critical manipulation in molecular spin architectures.}, archive = {J_JACS}, author = {Yan Zhao and Kaiyue Jiang and Peng-Yi Liu and Jie Li and Ruoning Li and Xin Li and Xinchen Fang and Anjing Zhao and Yutong Zhu and Hongxiang Xu and Ting Chen and Dong Wang and Xiaodong Zhuang and Shimin Hou and Kai Wu and Song Gao and Qing-Feng Sun and Yajie Zhang and Yongfeng Wang}, doi = {10.1021/jacs.5c09846}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38100--38109}, shortjournal = {J. Am. Chem. Soc.}, title = {Construction of kondo chains by engineering porphyrin π-radicals on au(111)}, volume = {147}, year = {2025}, }
• (2025). Phosphate boosts catalytic hydrodeoxygenation by facilitating Proton/Electron transfer at the Metal–Support interface. JACS, 147(42), 38089--38099. (www)

  @article{ , abstract = {Catalytic hydrogenation and deoxygenation of oxygenated compounds play an essential role in the synthesis. Despite the development of numerous hydrodeoxygenation (HDO) reactions, many reactions still rely on stoichiometric reducing agents, resulting in undesirable byproducts and a low atomic efficiency. H 2 has emerged as an environmentally friendly alternative, but its efficient utilization remains challenging under mild conditions. In this study, the straightforward phosphate modification of Pt/TiO 2 led to a remarkable ∼250-fold enhancement in the sulfoxide HDO activity. Owing to the presence of the Ti–PO 4 –Pt interface, the Pt/Ti(HPO 4 ) 2 catalyst exhibited an impressive ∼280 times higher productivity than pristine Pt/TiO 2 , surpassing other homogeneous and heterogeneous catalysts by orders of magnitude. The critical roles of coordinatively unsaturated Ti 3+ sites, interfacial phosphate, and platinum were elucidated at the atomic scale, highlighting the significance of facilitated proton/electron transfer at the interface. This work offers a promising strategy for sustainable catalytic hydrogenation processes with broad applicability in organic synthesis.}, archive = {J_JACS}, author = {Pengyao You and Liming Wu and Yazhou Zhang and Gang Fu and Lansun Zheng and Ruixuan Qin and Nanfeng Zheng}, doi = {10.1021/jacs.5c09850}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38089--38099}, shortjournal = {J. Am. Chem. Soc.}, title = {Phosphate boosts catalytic hydrodeoxygenation by facilitating Proton/Electron transfer at the Metal–Support interface}, volume = {147}, year = {2025}, }
• (2025). Homologous imide bonds to build polymer-covalent organic framework electrolytes for efficient ion transport. JACS, 147(42), 38078--38088. (www)

  @article{ , abstract = {A critical challenge for the safe operation of next-generation lithium (Li) metal batteries lies in the development of the key enabler of solid electrolytes. Herein, a polymer-covalent organic framework (COF) electrolyte with homologous imide bonds was designed and developed for safe and stable solid-state Li metal batteries. The imide-bonded COFs with ordered channels function as Li + selective gates and conduction bridges, facilitating efficient ion transport while maintaining structural stability. Meanwhile, the fluorinated polyimide (FPI) polymer enriched with imide bonds contributes to the mechanical robustness, flexibility, and interfacial compatibility with Li metal electrodes, mitigating dendrite growth and improving long-term cycling stability. Owing to the synergistic effect between the COF and polymer, the polymer-COF delivers an ionic conductivity of 3.3 × 10 –4 S cm –1 with a transference number of 0.82 and a wide electrochemical stability window. Besides, the polymer-COF solid electrolyte displays stable Li plating/stripping behavior over 2000 h, benefiting from superior interfacial compatibility. The applications of polymer-COF solid electrolytes in Li//LiNi 0.8 Co 0.1 Mn 0.1 O 2 batteries further demonstrate that high Coulombic efficiency (>99.0%) and long life (>200 cycles) can be achieved. This design opens new routes to develop room-temperature solid electrolytes for high-performance solid batteries.}, archive = {J_JACS}, author = {De-Hui Guan and Xiao-Xue Wang and Lin Li and Guan-Nan Chen and Guan-Yu Qiao and Ji-Jing Xu}, doi = {10.1021/jacs.5c09639}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38078--38088}, shortjournal = {J. Am. Chem. Soc.}, title = {Homologous imide bonds to build polymer-covalent organic framework electrolytes for efficient ion transport}, volume = {147}, year = {2025}, }
• (2025). Depth-resolved probing of native solid electrolyte interphase formation and dynamics in li metal batteries by cryogenic X-ray photoelectron spectroscopy. JACS, 147(42), 38069--38077. (www)

  @article{ , abstract = {Solid electrolyte interphase (SEI) critically governs lithium (Li) battery performance. Yet, understanding the native SEI remains challenging due to the lack of techniques capable of depth profiling of the interphase layer under electrolyte conditions (wet-SEI). In this work, cryogenic X-ray photoelectron spectroscopy (cryo-XPS) coupled with argon gas cluster ion beam (GCIB) sputtering was developed to extensively investigate the vitrified wet-SEI of Li metal batteries without chemical damage. First, the combined cryo-XPS and GCIB platform captures the full composition of the native SEI in the presence of electrolyte, which comprises organic polymeric hydrocarbons and inorganic species like LiC x , LiF, LiO x , and Li 2 CO 3 . These results are significantly distinct from conventional XPS characterizations of dry-SEI (i.e., SEI without electrolyte) showing a depletion of inorganic species and thus highlight the strength of this hybrid approach in revealing the real motif of the native SEI. Second, a graded SEI architecture has been revealed with electrochemical decomposition products (LiF and Li 2 CO 3 ) dominating the electrolyte-facing region, and chemically derived species (LiO x and LiC x ) accumulating at the electrode-facing region. Lastly, this approach is capable of scrutinizing the dynamic evolution of SEI during Li deposition, unravelling a compositional shift from electrochemical SEI to a graded complex SEI architecture, with a thickness increase from the nanometer- to micrometer-scale. Therefore, depth-resolved cryo-XPS serves as a promising methodology for elucidating the dynamic heterogeneous chemical signatures across evolving solid–liquid interfaces in electrocatalysis and energy storage processes.}, archive = {J_JACS}, author = {Shenghong Wang and Shiwen Li and Xiaoqin Chen and Qianwen Yin and Wang Zhang and Yanxiao Ning and Guohui Zhang and Qiang Fu}, doi = {10.1021/jacs.5c09519}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38069--38077}, shortjournal = {J. Am. Chem. Soc.}, title = {Depth-resolved probing of native solid electrolyte interphase formation and dynamics in li metal batteries by cryogenic X-ray photoelectron spectroscopy}, volume = {147}, year = {2025}, }
• (2025). A chemical mechanistic path leads the way to cellular argpyrimidine. JACS, 147(42), 38055--38068. (www)

  @article{ , abstract = {Argpyrimidine (APY) is a methylglyoxal-derived advanced glycation end-product (AGE) that has been associated with multiple diseases. As APY forms without an enzyme, it remains exceptionally difficult to pinpoint where APY is likely to be found, both on individual proteins and in cells. In this study, we used a peptide model system and mass spectrometry analysis to investigate the chemical mechanism through which APY arises from methylglyoxal (MGO), a biologically relevant glycating agent. Consistent with other proposed APY formation mechanisms, our results identify AGE species with a mass change of [M + 144], presumably including tetrahydropyrimidine (THP), as a direct precursor to APY. However, our results rule out previously proposed reductone or oxidative decarboxylation mechanisms. Instead, we show that a formal oxidation step is not required, and that formate is released instead of CO 2 . We further show the potential for a nearby residue such as Tyr to assist in the APY formation mechanism by acting as a general base. These experiments also reveal that phosphorylated Tyr or Ser residues can also promote equivalent levels of APY formation, despite introducing additional negative charges that we previously showed to impede glycation. Guided by these mechanistic insights and a newly defined role for phosphorylated residues on glycation substrates, we performed quantitative bottom-up proteomics analysis for MGO-treated cells. Gene ontology and functional annotation clustering analyses for APY-modified proteins suggested a correlation with phosphorylation-related terms (e.g., kinase activity or protein phosphorylation), which was validated using synthetic phosphopeptide substrates. Collectively, these data define a chemical mechanistic path to APY and suggest significant crosstalk between cellular phosphorylation and glycation events including APY formation.}, archive = {J_JACS}, author = {Vo Tri Tin Pham and Suprama Datta and Amy C. Sterling and Stefan M. Hansel and Rebecca A. Scheck}, doi = {10.1021/jacs.5c09369}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38055--38068}, shortjournal = {J. Am. Chem. Soc.}, title = {A chemical mechanistic path leads the way to cellular argpyrimidine}, volume = {147}, year = {2025}, }
• (2025). Superlattice of self-assembled silver-thiolates: The formation of unique sublayers induced by mixed N-alkyl chains. JACS, 147(42), 38043--38054. (www)

  @article{ , abstract = {A new type of superlattice has been found in blended metal–thiolate crystals, AgSC n H 2 n + 1 and AgSC m H 2 m  + 1 ( n , m = 6–18, n < m , n and m are even), with various chain length mismatches (η = ( m – n )/ n ), precipitated from a mixture of hot solutions of individual thiolates. The superlattice consists of alternating sublayers of crystalline thiolate lamellae and chain-end regions with distinct properties. Diffraction patterns suggest that the superlattice stacks are highly periodic and well registered. Carbons from these two alternating sublayers are exposed to different chemical environments, as shown by nuclear magnetic resonance measurements. The chain-end region exhibits a new material state that is ordered but behaves like an amorphous state in calorimetric measurements, without a chain-melting transition. Its thickness, estimated from X-ray diffraction and calorimetric analysis, coincides with the chain length difference between −C n H 2 n  + 1 and −C m H 2 m  + 1 ligands, presumably indicating that the chain-end regions consist of surplus parts of the longer alkyl chains protruding from adjacent lamellar layers. Mixed thiolates exhibit a melting point depression of the crystalline lamellae in comparison with the individual components. Triggered by the existence of the unique nonmelting layer, this effect is described by the Gibbs–Thomson model. The synthetic procedure yields good-quality crystals with η up to 1 over a wide range of mixing ratios, which is employed as a control parameter to continuously tune the structure of the superlattice.}, archive = {J_JACS}, author = {Jie Zhao and Zichao Ye and Zhuonan Ji and Andre Sutrisno and Kisung Kang and Mikhail Y. Efremov and Jian-Min Zuo and André Schleife and Leslie H. Allen}, doi = {10.1021/jacs.5c09452}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38043--38054}, shortjournal = {J. Am. Chem. Soc.}, title = {Superlattice of self-assembled silver-thiolates: The formation of unique sublayers induced by mixed N-alkyl chains}, volume = {147}, year = {2025}, }
• (2025). Macroscopic uniform 2D moiré superlattices with controllable angles. JACS, 147(42), 38033--38042. (www)

  @article{ , abstract = {Moiré superlattices, engineered through precise stacking of van der Waals (vdW) layers, hold immense promise for exploring strongly correlated and topological phenomena. However, these applications have been held back by the common preparation method: tear-and-stack of Scotch tape exfoliated monolayers, which suffer from low efficiency and reproducibility, twist angle inhomogeneity, interfacial contamination, and micrometer sizes. Here, we report an effective strategy to construct highly consistent mixed-dimensional and twisted bilayer vdW moiré structures with high production throughput, near-unity yield, pristine interfaces, precisely controlled twist angles, and macroscopic scale (up to centimeters) with enhanced thermal stability. We demonstrate the versatility across various vdW materials, including transition metal dichalcogenides, graphene, and hBN. The expansive size and high quality of moiré structures enable reciprocal-space high-resolution mapping of the superlattices and back-folded moiré mini band structures with low energy electron diffraction (LEED) and angle-resolved photoemission spectroscopy (ARPES). In particular, we identify the backfolded bands at the K point of twisted transition metal dichalcogenide moiré structures. This technique will have broad applications in both fundamental studies and the mass production of twistronic devices.}, archive = {J_JACS}, author = {Gregory Zaborski, Jr. and Paulina E. Majchrzak and Samuel Lai and Amalya C. Johnson and Qile Li and Ashley P. Saunders and Ziyan Zhu and Yujun Deng and Donghui Lu and Makoto Hashimoto and Zhi-Xun Shen and Fang Liu}, doi = {10.1021/jacs.5c09131}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38033--38042}, shortjournal = {J. Am. Chem. Soc.}, title = {Macroscopic uniform 2D moiré superlattices with controllable angles}, volume = {147}, year = {2025}, }
• (2025). Mechanistic insights into the light-driven difunctionalization of alkenes with a sulfonyl-based reagent: A catalyst-free approach. JACS, 147(42), 38021--38032. (www)

  @article{ , abstract = {Visible-light-mediated difunctionalization of nonactivated alkenes offers a sustainable and efficient strategy for constructing diverse molecular frameworks relevant to medicinal chemistry, polymer science, and synthesis of fine chemicals. While established approaches─such as photoredox catalysis, energy transfer (EnT), and ligand-to-metal charge transfer (LMCT)─have demonstrated success, they typically require external photocatalysts to achieve high reactivity. Alternatively, electron donor–acceptor (EDA) complexes have been explored, but these methods often rely on specially designed substrates, limiting the scope of this reaction. To overcome these limitations, we present a DFT-guided approach for identifying suitable radicals for light-mediated difunctionalization of nonactivated alkenes, eliminating the requirement of auxiliary catalysts or reagents. Our DFT calculations elucidate general reaction mechanisms and provide insights into regioselectivity. Additionally, time-dependent DFT (TD-DFT) calculations are employed to simulate UV–vis spectra and analyze the orbitals involved in key photoinduced transitions, guiding the selection of appropriate light sources. We further investigated the electrophilic and nucleophilic properties of the generated radicals to predict the regioselectivity of their additions. This study provides a framework for designing atom-economical difunctionalization reactions without relying on photocatalysts or substrate-specific EDA complexes and opens new avenues for further development in this area.}, archive = {J_JACS}, author = {Rakesh Maiti and Aritra Nath and Ana B. R. Guimarães and Sergey Bagnich and Anna Köhler and Feliu Maseras and Shoubhik Das}, doi = {10.1021/jacs.5c08562}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38021--38032}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic insights into the light-driven difunctionalization of alkenes with a sulfonyl-based reagent: A catalyst-free approach}, volume = {147}, year = {2025}, }
• (2025). Regiodivergent access to α- and β-amino acids via solvent-controlled rh-catalyzed carboamidation of β,γ-unsaturated carboxylic acids. JACS, 147(42), 38008--38020. (www)

  @article{ , abstract = {Non-natural α- and β-amino acids are pivotal building blocks in medicinal chemistry and bioactive molecule discovery. Herein, we report a rhodium-catalyzed, solvent-directed, regiodivergent carboamidation of β,γ-unsaturated alkenyl carboxylic acid for the programmable synthesis of both α- and β-amino acids. This strategy leverages β,γ-unsaturated alkenyl carboxylic acids, organoboronic acids, and dioxazolones as readily available substrates, achieving broad substrate scope with high efficiency (average yield 60%) and excellent functional group tolerance. The solvent system (HFIP vs THF) serves as a simple switch to precisely control regioselectivity (α:β up to >20:1 or β:α up to >20:1), bypassing traditional protecting-group manipulations. Notably, this protocol enables concise two-step synthesis of N -Ac sitagliptin and rapid access to diverse peptidomimetics, showcasing its potential in streamlining the development of pharmaceuticals and bioactive probes. DFT calculations reveal distinct energy barriers for the rate-determining steps of the two pathways in HFIP and THF, rationalizing the solvent-controlled selectivity.}, archive = {J_JACS}, author = {Xiaoyan Jia and Shuo Zhang and Yue Zeng and Zhewei Li and Ganchun Wu and Ming Lei and Liangbin Huang}, doi = {10.1021/jacs.5c08142}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {38008--38020}, shortjournal = {J. Am. Chem. Soc.}, title = {Regiodivergent access to α- and β-amino acids via solvent-controlled rh-catalyzed carboamidation of β,γ-unsaturated carboxylic acids}, volume = {147}, year = {2025}, }
• (2025). Unexpected impacts of CO2/H2O adsorption order on the mixed-gas adsorption capacity of a Metal–Organic framework. JACS, 147(42), 37999--38007. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) have been examined extensively for CO 2 capture, and the influence of water coadsorption on these processes is particularly relevant, as CO 2 capture generally occurs in humid gas streams. To investigate CO 2 /H 2 O coadsorption, binary adsorption isotherms of CO 2 and H 2 O were measured on MOF-808-TFA (TFA = trifluoroacetic acid). When water was preadsorbed on MOF-808-TFA, and a subsequent CO 2 adsorption isotherm was measured, the CO 2 adsorption was slightly reduced, as expected. However, when CO 2 was adsorbed first and then an H 2 O adsorption isotherm was measured, no significant H 2 O adsorption capacity was observed. The near complete loss of water adsorption capacity was observed even when only a trace amount of CO 2 was preadsorbed. The results show that unexpected, nonstate function adsorption equilibria can result from dynamic MOF behaviors and defect sites, which may lead to counterintuitive adsorption data compared to traditional materials.}, archive = {J_JACS}, author = {Jon Hastings and Zhiwei Wang and Jiayang Liu and Filip Formalik and Haomiao Xie and Thomas Lassitter and Omar K. Farha and Randall Q. Snurr and Joseph T. Hupp and T. Grant Glover}, doi = {10.1021/jacs.5c08171}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37999--38007}, shortjournal = {J. Am. Chem. Soc.}, title = {Unexpected impacts of CO2/H2O adsorption order on the mixed-gas adsorption capacity of a Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). An immunocompatible conductive polymer for long-term bioelectronic implants. JACS, 147(42), 37985--37998. (www)

  @article{ , abstract = {Tissue-electronic interfaces are vital for neural implants, health monitoring devices, and augmented reality applications; however, the host immune reaction against the electrodes profoundly impacts their durability, precision, and overall fidelity. Building a highly immunocompatible yet conductive interface for implantable electrodes remains a significant challenge. Here, by screening PEDOT derivatives functionalized with diverse immunoregulatory moieties, we identified PEDOT-TMO as a candidate combining superior immunocompatibility with robust conductivity for long-term bioelectronic implants. PEDOT-TMO/PSS coatings exhibit substantially mitigated acute inflammation and chronic fibrotic response following subcutaneous implantation in mice compared to conventional PEDOT/PSS, while preserving its original electrochemical properties. During extended in vivo brain implantation trials in freely moving rat models, we observed that the immunocompatible conductive polymer-coated silicon electrode can reliably record electrophysiological signals for at least 8 weeks, demonstrating significantly better performance compared to PEDOT/PSS-coated and bare electrodes. Notably, the PEDOT-TMO/PSS interface substantially reduced the expression of S100A9 in surrounding brain tissue. Pharmacological inhibition of S100A9 similarly attenuated tissue responses to brain implants, suggesting a target for neuroinflammation inhibition. The new type of immunocompatible conductive polymer reported here holds promise in enhancing and extending the long-term function in a range of bioelectronic devices by attenuating local immune responses to functional bioelectrodes.}, archive = {J_JACS}, author = {Xianchi Zhou and Zihao Zhu and Wenbin Dai and Wenzhong Cao and Zuolong Liu and Kexin Chen and Yu Yan and Fan Zhang and Shaomin Zhang and Fan Jia and Youxiang Wang and Jian Ji and Peng Zhang}, doi = {10.1021/jacs.5c07902}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37985--37998}, shortjournal = {J. Am. Chem. Soc.}, title = {An immunocompatible conductive polymer for long-term bioelectronic implants}, volume = {147}, year = {2025}, }
• (2025). Cerium dimer anion and the contribution of 4f electrons to lanthanide Metal–Metal bonds. JACS, 147(42), 37977--37984. (www)

  @article{ , abstract = {Direct metal–metal bonding between lanthanide atoms has been challenging to observe. We report on the first spectroscopic characterization of the cerium dimer anion (Ce 2 – ) and its neutral analog (Ce 2 ) in the gas phase, achieved using photoelectron and ultrafast spectroscopy combined with high-level quantum chemistry calculations. The electron affinity of Ce 2 is 0.24 eV, from which a dissociation energy of 2.21 eV is derived for Ce 2 – . The wave-packet dynamics upon photodetachment are studied and yield vibrational frequencies for electronically excited Ce 2 . Ce 2 – exhibits a conventional metal–metal triple bond with minimal contribution from 4f electrons. However, evidence of 4f-electron participation in bonding is identified for the low-energy excited states only 0.1 eV higher. The results challenge the assumption of inert 4f electrons in metal–metal bonding, and we propose a promising strategy for forming stable lanthanide–lanthanide bonds involving significant 4f-electron contributions.}, archive = {J_JACS}, author = {Jiaye Jin and Nikita Kavka and Tatsuya Chiba and Max Grellmann and Shiying Wang and Marcel Jorewitz and Kit H. Bowen and Roland Mitric and Knut R. Asmis}, doi = {10.1021/jacs.5c07348}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37977--37984}, shortjournal = {J. Am. Chem. Soc.}, title = {Cerium dimer anion and the contribution of 4f electrons to lanthanide Metal–Metal bonds}, volume = {147}, year = {2025}, }
• (2025). From spheres to cones: Structural instabilities and acidity at conical regions in trivalent metal ion nanoclusters. JACS, 147(42), 37965--37976. (www)

  @article{ , abstract = {We computationally demonstrate that subnanometer aqueous clusters containing a single trivalent metal ion (Fe 3+ , Lu 3+ , or La 3+ ) can exhibit charge-induced structural instability. These clusters dynamically evolve across their potential energy landscape, adopting triangular, elongated two-point, single-point, and more spherical configurations often with distinct conical surface protrusions. The manifestation of this instability differs from that observed in mesoscopic and microscopic droplets containing macroions, where stable “star-like” structures form, characterized by a specific number of conical protrusions that varies with the droplet size. We find that the orientation of the H 2 O molecules surrounding the metal ion is influenced not only by the electric field of the trivalent ion but also by the local conical protrusions. To further investigate the local acidity in the conical protrusions, a model system consisting of an aqueous nanocluster containing three H 3 O + ions was simulated using ab initio molecular dynamics. Within the conical regions of the cluster, protons exhibit mobility across several water molecules forming cyclic structures, in contrast to the more localized proton delocalization observed in the compact body of the cluster. These findings suggest that local geometry can significantly modulate acidity in highly charged nanoclusters, with potential implications for understanding charge-transfer and ionization mechanisms in techniques such as electrospray ionization mass spectrometry. Additionally, the structural motifs and solvent organization reported here provide a molecular-level framework that can complement interpretations from infrared spectroscopic data.}, archive = {J_JACS}, author = {Jihong Shi and Han Nguyen and Mateo Pescador Arboleda and Styliani Consta}, doi = {10.1021/jacs.5c06879}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37965--37976}, shortjournal = {J. Am. Chem. Soc.}, title = {From spheres to cones: Structural instabilities and acidity at conical regions in trivalent metal ion nanoclusters}, volume = {147}, year = {2025}, }
• (2025). Metal electronics mediate steric and coordination number effects on Palladium(II) C–X reductive elimination. JACS, 147(42), 37949--37964. (www)

  @article{ , abstract = {Reductive elimination is the key bond-forming elementary step in many transition metal-catalyzed reactions relevant to the synthesis of pharmaceuticals, materials and fine chemicals. Metal electronics, ancillary ligand sterics and metal complex coordination number have been identified as the primary factors which affect the rate of reductive elimination, but their relative importance has not been quantified. By studying a new class of palladacycles using kinetics, electrochemistry, DFT calculations and tools from causal inference, we reexamine the canonical model and find that a direct effect of coordination number on rate is unlikely. To address this contradiction, we propose an updated understanding based on mechanistic considerations, which accounts for our findings, the canonical understanding, and other observations in literature. Path coefficients calculated using mediation analysis allow the quantification of the effects of electronics, sterics and coordination number on the rate. Overall, we find that electronics and changes in coordination number exert the greatest influence on the rate, with the latter primarily acting through altering metal electronics. Finally, using this new-found knowledge, we were able to use the structures of complexes reported in the literature to calculate appropriate DFT descriptors and build a model capable of predicting the rate of reductive elimination for C–N, C–S and C–O bond formation with reasonable accuracy.}, archive = {J_JACS}, author = {Michael K. Bogdos and Sven Roediger and Florian Ruepp and Nathalie A. V. Rowlinson and Patrick Müller and Fabio Masero and Jan Hübscher and Bill Morandi}, doi = {10.1021/jacs.5c06124}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37949--37964}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal electronics mediate steric and coordination number effects on Palladium(II) C–X reductive elimination}, volume = {147}, year = {2025}, }
• (2025). Iridium-catalyzed, regio- and stereoselective silylation of primary and secondary C(sp3)–H bonds in primary amines. JACS, 147(42), 37940--37948. (www)

  @article{ , abstract = {The functionalization of amines at C–H bonds beyond the α-position could generate valuable difunctional products, but such transformations with readily accessible amine derivatives remain underdeveloped. We report the iridium-catalyzed, regio- and stereoselective silylation of primary and secondary C( sp 3 )–H bonds in primary amine derivatives to afford silapyrrolidines and 1,2-amino alcohols after oxidation. The use of sulfonamides as protecting groups on the alkyl amines enables alkylation of the resulting sulfonamide with halomethylsilanes and subsequent silylation of the C( sp 3 )–H bonds with broad scope. This reaction also enables the functionalization of both primary and secondary C( sp 3 )–H bonds with high regioselectivity and stereoselectivity. Reactions with iridium complexes of new chiral nitrogen-based ligands occur with high enantioselectivity.}, archive = {J_JACS}, author = {Takahiro Suto and Chris La and John F. Hartwig}, doi = {10.1021/jacs.5c05764}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37940--37948}, shortjournal = {J. Am. Chem. Soc.}, title = {Iridium-catalyzed, regio- and stereoselective silylation of primary and secondary C(sp3)–H bonds in primary amines}, volume = {147}, year = {2025}, }
• (2025). Granzyme B-targeting quenched activity-based probes for assessing tumor response to immunotherapy. JACS, 147(42), 37926--37939. (www)

  @article{ , abstract = {Molecular imaging of immune activation holds tremendous potential for the development of novel immunotherapies. In particular, chemical probes capable of detecting immune responses before changes in tumor size occur can guide early therapeutic strategies. Here, we present a quenched activity-based probe targeting granzyme B as a biomarker of antitumor immunity. Through optimization of the peptide recognition element and functional chemical warhead, we have developed an optical imaging probe, Cy5-IEPCya PhP -QSY21, which rapidly reacts with granzyme B at substoichiometric concentrations and enables efficient, selective labeling of the active enzyme in a complex proteome. With high specificity and minimal background signal, this probe produces granzyme B-induced near-infrared fluorescence signals in the tumors of living mice shortly after injection. Both in vivo and ex vivo fluorescence signals correlate with granzyme B expression and activity, and the population of CD8+ cells in tumor tissues. Moreover, it demonstrates the potential to track tumor response to immunotherapy. Thus, this study offers a chemical tool for assessing immune-mediated anticancer activity using noninvasive optical imaging.}, archive = {J_JACS}, author = {Muhammad Kazim and Arghya Ganguly and Sebastian M. Malespini and Lai Thang and Nimit L. Patel and Caleb Kim and Kalyani Thakur and Joseph D. Kalen and Claudia Calcagno and Simone Difilippantonio and Euna Yoo}, doi = {10.1021/jacs.5c04392}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37926--37939}, shortjournal = {J. Am. Chem. Soc.}, title = {Granzyme B-targeting quenched activity-based probes for assessing tumor response to immunotherapy}, volume = {147}, year = {2025}, }
• (2025). A crystalline monomeric diboryl diazene. JACS, 147(42), 37919--37925. (www)

  @article{ , abstract = {Azo compounds (R─N═N─R′) are a foundational class of nitrogen-containing molecules. In contrast to the bench-stability of many azo derivatives, monomeric diboryl diazenes (R 2 BN═NBR 2 ) have long eluded isolation and were presumed to exist only as polymeric materials or fleeting intermediates. Here, we report the synthesis, characterization, and reactivity of an isolable monomeric diboryl diazene, Mes 2 BN═NBMes 2 ( 2 , Mes = mesityl), featuring a nearly linear, cumulenic B═N═N═B core. Lewis basic substrates, including N-heterocyclic carbene (NHC), quinones, and fluorenone, induce N 2 extrusion from 2 to release Mes 2 B• radicals that are captured by an NHC or diverted to organoboron derivatives. By contrast, ammonia and ethylamine engage 2 via B,N cooperative N–H bond activation, affording aminoborane and transient diazene N 2 H 2 without radical formation. Collectively, these results establish diboryl diazenes as versatile main group platforms that enable controllable access to boryl radicals and provide insights into N 2 reduction chemistry.}, archive = {J_JACS}, author = {Fengbo Huang and Xin-Feng Wang and Baixu Ma and Lizhi Tao and Lingbing Kong and Liu Leo Liu and Qiuming Liang}, doi = {10.1021/jacs.5c14754}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37919--37925}, shortjournal = {J. Am. Chem. Soc.}, title = {A crystalline monomeric diboryl diazene}, volume = {147}, year = {2025}, }
• (2025). An inverse electron-demand Diels–Alder approach to selective activity-based sensing of acetaldehyde in living cells. JACS, 147(42), 37912--37918. (www)

  @article{ , abstract = {Acetaldehyde (AA) is a reactive aldehyde primarily produced in cells as a metabolic intermediate during ethanol oxidation. Excess AA, often resulting from impaired AA detoxification, leads to aberrant DNA, protein, and/or lipid damage and increases risk of diseases such as cancer, hepatitis, and cirrhosis. Traditional methods for detecting biological AA often require sample destruction or extensive processing, which compromise spatiotemporal resolution, or do not exhibit sufficient selectivity for this two-carbon metabolite over other competing aldehydes and reactive carbon species in living systems. To overcome these limitations, we now report the design, synthesis, and biological applications of a fluorescent probe platform for acetaldehyde-specific activity-based sensing. The first-generation reagent Acetaldehyde Probe-1 (AAP-1) utilizes an AA-triggered inverse electron-demand Diels–Alder (IEDDA) reaction to enable selective detection of physiologically relevant levels of this two-carbon aldehyde in aqueous solution and in live cells, with minimal interference from competing biological analytes, including highly similar aldehydes like formaldehyde (FA) and methylglyoxal (MGO). Furthermore, AAP-1 enables visualization of endogenous AA pools generated during ethanol metabolism in a human liver cancer cell line, highlighting the potential of this chemical activity-based sensing strategy for studying two-carbon biology in living systems.}, archive = {J_JACS}, author = {Yuxuan Li and Gen Li and Erin L. Li and Jaehee Kim and Christopher J. Chang}, doi = {10.1021/jacs.5c14058}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37912--37918}, shortjournal = {J. Am. Chem. Soc.}, title = {An inverse electron-demand Diels–Alder approach to selective activity-based sensing of acetaldehyde in living cells}, volume = {147}, year = {2025}, }
• (2025). Hydride transfer reactivity of an open-shell [Fe3H]− cluster. JACS, 147(42), 37907--37911. (www)

  @article{ , abstract = {We report herein the synthesis and reactivity of the high-spin iron-hydride cluster [K(C 222 )][( tbs L)Fe 3 (μ 3 –H)]. Direct hydride transfer reaction attempts led to cluster reduction to afford the anionic cluster [( tbs L)Fe 3 ] − , whereas metathesis using phenylsilane and an alkoxide-bound cluster (e.g., [( tbs L)Fe 3 (μ 3 –OMe)] − ) afforded the targeted hydride-bearing cluster [K(C 222 )][( tbs L)Fe 3 (μ 3 –H)]. The hydride cluster was verified using both solution (e.g., NMR, cyclic voltammetry) and solid-state techniques (e.g., 57 Fe Mössbauer, X-ray crystallography). The anionic hydride was shown to be reactive with unsaturated small molecule substrates (e.g., aldehydes, isonitriles, alkynes) to afford their cooperatively bound reduction products. Furthermore, the anionic hydride cluster was shown to be a viable catalyst for hydrosilylation of aldehyde substrates, converting benzyl and alkyl aldehydes to their corresponding silylethers.}, archive = {J_JACS}, author = {Lisa N. Awaitey and Iván E. Arvizo and Shao-Liang Zheng and Theodore A. Betley}, doi = {10.1021/jacs.5c13885}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37907--37911}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydride transfer reactivity of an open-shell [Fe3H]− cluster}, volume = {147}, year = {2025}, }
• (2025). Synthesis of sterically congested carbonyl compounds via an ipso-selective sulfonium rearrangement. JACS, 147(42), 37899--37906. (www)

  @article{ , abstract = {Despite the success of metal-catalyzed cross-coupling strategies to assemble a variety of C–C bonds, the synthesis of sterically congested α-arylated carbonyl compounds remains a difficult task. Herein, we present an ipso -rearrangement approach relying on electron redistribution in sulfonium intermediates. This modular method enables the synthesis of a variety of α-arylated carbonyl compounds and is orthogonal to traditional metal-catalyzed cross-coupling strategies. More importantly, it demonstrated remarkable robustness toward steric hindrance and allowed us to efficiently forge congested C–C bonds.}, archive = {J_JACS}, author = {Immo Klose and Christian Knittl-Frank and Nicolas G.-Simonian and Boris Maryasin and Daniel Kaiser and Nuno Maulide}, doi = {10.1021/jacs.5c13777}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37899--37906}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of sterically congested carbonyl compounds via an ipso-selective sulfonium rearrangement}, volume = {147}, year = {2025}, }
• (2025). Aminoacyl-tRNA specificity of a ligase catalyzing non-ribosomal peptide extension. JACS, 147(42), 37893--37898. (www)

  @article{ , abstract = {Peptide aminoacyl-transfer ribonucleic acid ligases (PEARLs) are amide-bond-forming enzymes that extend the main chain of peptides by using aminoacyl-tRNA (aa-tRNA) as a substrate. In this study, we investigated the substrate specificity of the PEARL BhaB C Ala from Bacillus halodurans , which utilizes Ala-tRNA Ala . By leveraging flexizyme, a ribozyme capable of charging diverse acids onto a desired tRNA, we generated an array of aa-tRNAs in which we varied both the amino acid and the tRNA to dissect the substrate scope of BhaB C Ala . We demonstrate that BhaB C Ala catalyzes peptide extension with noncognate proteinogenic and noncanonical amino acids, hydroxy acids, and mercaptocarboxylic acids when attached to tRNA Ala . For most of these, the efficiency was considerably reduced compared to Ala, indicating that the enzyme recognizes the amino acid. By variation of the different parts of the tRNA, enzyme specificity was shown to also depend on the acceptor stem and the anticodon arm of the tRNA. These findings establish the molecular determinants of PEARL specificity and provide a foundation for engineering these enzymes for broader applications in peptide synthesis.}, archive = {J_JACS}, author = {Dinh T. Nguyen and Josseline S. Ramos-Figueroa and Alexander A. Vinogradov and Yuki Goto and Mayuresh G. Gadgil and Rebecca A. Splain and Hiroaki Suga and Wilfred A. van der Donk and Douglas A. Mitchell}, doi = {10.1021/jacs.5c12610}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37893--37898}, shortjournal = {J. Am. Chem. Soc.}, title = {Aminoacyl-tRNA specificity of a ligase catalyzing non-ribosomal peptide extension}, volume = {147}, year = {2025}, }
• (2025). Deoxygenative C(sp3)–N(sp3) cross-coupling enabled by nickel metallaphotoredox catalysis. JACS, 147(42), 37885--37892. (www)

  @article{ , abstract = {Metallaphotoredox catalysis has emerged as a powerful platform for generating high-energy radicals from native functionalities. This approach integrates radical reactivity with transition metal catalysis to enable controlled bond formation. However, the synthesis of tertiary amines remains a significant challenge due to their redox sensitivity under photoredox conditions and the inherent difficulty of C( sp 3 )–N( sp 3 ) reductive elimination. Herein, we describe a deoxygenative C–N cross-coupling between alcohols and N -hydroxylamine esters to form tertiary amines. Oxidation of the tertiary amine products is kinetically suppressed under optimized conditions, while a sterically demanding ancillary ligand promotes reductive elimination. This methodology displays broad substrate scope, accommodating diverse functional groups, heterocycles, and pharmaceutical derivatives.}, archive = {J_JACS}, author = {Ruizhe Chen and Taehyun Kim and Noah B. Bissonnette and Robert T. Martin and Joseph R. Martinelli and Albert Cabré and David W. C. MacMillan}, doi = {10.1021/jacs.5c10915}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37885--37892}, shortjournal = {J. Am. Chem. Soc.}, title = {Deoxygenative C(sp3)–N(sp3) cross-coupling enabled by nickel metallaphotoredox catalysis}, volume = {147}, year = {2025}, }
• (2025). Metal-free reduction of nitrous oxide via PIII/PV═O cycling: Mechanistic insights and catalytic performance. JACS, 147(42), 37879--37884. (www)

  @article{ , abstract = {The catalytic reduction of nitrous oxide (N 2 O) has been achieved through metal-free P III /P V ═O catalysis. Kinetic analysis revealed that the oxygen transfer reaction to the phosphetane is rate determining. Computational investigations support a reaction mechanism in which the phosphetane catalyst preferentially interacts with the nitrogen terminus of N 2 O, leading to the formation of a P–N═N–O intermediate in the cis configuration. Natural population analysis indicates stabilizing interactions between the occupied nonbonding oxygen orbitals and the antibonding orbitals of the phosphetane backbone, facilitating the oxygen atom transfer. Following nitrogen extrusion, the active phosphetane species is regenerated via silane-mediated reduction. The catalytic activity was quantitatively assessed by monitoring the nitrogen evolution through gas chromatography (GC) analysis.}, archive = {J_JACS}, author = {Rundong Zhou and Viktorija Medvarić and Thomas Werner and Jan Paradies}, doi = {10.1021/jacs.5c06190}, journal = {Journal of the American Chemical Society}, month = {10}, number = {42}, pages = {37879--37884}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal-free reduction of nitrous oxide via PIII/PV═O cycling: Mechanistic insights and catalytic performance}, volume = {147}, year = {2025}, }
• (2025). Correction to “Determination of uranium central-field covalency with 3d4f resonant inelastic X-ray scattering”. JACS, 147(41), 37876--37878. (www)

  @article{ , archive = {J_JACS}, author = {Timothy G. Burrow and Nathan M. Alcock and Myron S. Huzan and Maja A. Dunstan and John A. Seed and Blanka Detlefs and Pieter Glatzel and Myrtille O. J. Y. Hunault and Jesper Bendix and Kasper S. Pedersen and Michael L. Baker}, doi = {10.1021/jacs.5c14044}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37876--37878}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Determination of uranium central-field covalency with 3d4f resonant inelastic X-ray scattering”}, volume = {147}, year = {2025}, }
• (2025). An amino-trans-dihydrido Cobalt(III) catalyst for asymmetric hydrogenation reactions. JACS, 147(41), 37864--37875. (www)

  @article{ , abstract = {The development and fundamental chemistry of an amino- trans -dihydrido Co(III) catalyst for asymmetric hydrogenation (AH) reactions are described in this work. With an enantiopure tetradentate ( S,S )-amino-ene(amido)diphosphine ligand defining the equatorial plane, axial trans -dihydrido coordination donors are incorporated into a cobalt(III) center with an octahedral coordination geometry. This cobalt complex serves as a novel amino- trans -dihydrido cobalt(III) catalyst ( C1 ) for AH of ketones and esters. The introduction of these dihydrido ligands to C1 occurs in the precatalyst activation process, which involved substituting the bidentate acetylacetonato ( acac ) ligand in the amino-ene(amido)diphosphine Co(III) acac precatalyst ( PC1 ) with trans -located dihydride ligands derived from dihydrogen gas. The molecular structure of C1 was characterized using 1 H and 31 P{ 1 H} nuclear magnetic resonance (NMR) spectroscopy, and a comparative analysis of calculated 31 P NMR chemical shifts versus the experimental values was conducted to further confirm the molecular structure of C1 . C1 exhibited an unexpectedly high turnover frequency (TOF) of up to 9.9 s –1 and an enantiomeric excess (e.e.) of up to 99% in the AH of a wide range of ketone substrates under mild conditions. This efficiency, particularly for diaryl ketone substrates, was 66–90 times greater than those achieved with precious metal (ruthenium and iridium) catalysts and 8 503 times greater than those reported for cobalt catalysts chelated with other chiral ligands. The practical synthetic application of this cobalt catalyst was demonstrated through the synthesis of ( R )-inabenfide, a plant growth regulator, with 95% e.e., at the 50 g scale. Kinetic studies determined that the H 2 activation by a cobalt catalyst was the turnover-limiting step. For reactions conducted in toluene at 303 K, with [ C1 ] = (0.36–1.52) × 10 –4 M, [ketone] = (0.95–1.89) M, and H 2 pressure = 50–70 bar, the rate law was rate = k [ C1 ][H 2 ], with k = (0.74–3.84) × 10 5 M –1 h –1 , Δ H ⧧ = 7.8 kcal mol –1 , and Δ S ⧧ = −35.9 cal mol –1 K –1 . Density functional theory (DFT) calculations revealed that the enantio-determining step of the ketone reduction by C1 has a minimum energy barrier of 7.0 kcal mol –1 . Analysis of the catalyst structure and performance revealed that the trans -located hydride ligand at C1 activates the catalyst for the hydrogenation of ketone substrates, while the NH functionality enables an outer-sphere H 2 heterolytic splitting pathway that proceeds through a low-energy barrier. This active catalyst also catalyzed the hydrogenation of more challenging esters under mild conditions.}, archive = {J_JACS}, author = {Zeming Wang and Minhao Li and Weiwei Zuo}, doi = {10.1021/jacs.5c15142}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37864--37875}, shortjournal = {J. Am. Chem. Soc.}, title = {An amino-trans-dihydrido Cobalt(III) catalyst for asymmetric hydrogenation reactions}, volume = {147}, year = {2025}, }
• (2025). An enantioselective nucleophilic aromatic tele-substitution. JACS, 147(41), 37854--37863. (www)

  @article{ , abstract = {This work presents the first leaving-group-directed aminocatalytic enantioselective nucleophilic aromatic tele -substitution on the tropone scaffold. The integration of an appropriate leaving group on tropone enables the nucleophilic aromatic substitution with carbon nucleophiles under mild reaction conditions, a reaction which has previously only been reported under harsh reaction conditions. An efficient and highly enantioselective approach for the remote installation of quaternary all-carbon stereocenters via tele -substitution is reported. Mild reaction conditions are achieved by employing a primary amine catalyst with α-branched aldehydes affording enantioenriched tropones in up to 96% yield and up to 97% ee. The tele -substitution pathway is elucidated by a series of both qualitative and quantitative deuterium-labeling studies and different substitution patterns on the tropone scaffold. DFT calculations reveal that the geometry of the enamine governs the stereochemical outcome. H-Bonding, π–π interaction, and a cation-π interaction were found to be crucial in the stereodetermining step.}, archive = {J_JACS}, author = {Valdemar J. Enemærke and Anne Kristensen and Louise G. Rost and Esben Skovsgaard and Karl Anker Jørgensen}, doi = {10.1021/jacs.5c14328}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37854--37863}, shortjournal = {J. Am. Chem. Soc.}, title = {An enantioselective nucleophilic aromatic tele-substitution}, volume = {147}, year = {2025}, }
• (2025). Biosynthesis of the 5-isoxazolidinone-containing hexacyclic structure of parnafungin. JACS, 147(41), 37842--37853. (www)

  @article{ , abstract = {Parnafungins A–D ( 1 – 4 ) are fungal natural products that inhibit eukaryotic poly(A)-polymerase and were first discovered by Merck & Co., Inc., through a Candida albicans Fitness Test (CaFT) screening program. The biological activity of parnafungins is a result of the unique fused hexacyclic structure highlighted by a 5-isoxazolidinone (5ILD) N -heterocycle. In this work, we characterize the complete biosynthetic pathway of parnafungins through heterologous reconstitution and enzymatic assays. Nearly half of the 26-gene biosynthetic gene cluster of parnafungin is responsible for the production of a known polyketide natural product, blennolide C. Starting from the blennolide C fragment, a three-enzyme cascade involving CoA-ligase ParJ, P450 ParO, and DUF829 ParD catalyzes the formal biaryl cross-coupling between blennolide C and anthranilate. Subsequent oxidative cyclization generates a phenanthridine product that is then reduced by atypical short-chain reductase ParT. N -Hydroxylation by flavin-dependent monooxygenase ParB and subsequent lactonization catalyzed by a homologue of dienenolactone hydrolase ParF form the 5ILD ring and complete the biosynthesis of 1 and 2 . Methylation of 1 forms parnafungin C ( 3 ), and lastly epoxidation forms parnafungin D ( 4 ). Together, our work revealed the chemical logic and enzymology in extending the biosynthetic pathway of a well-characterized natural product, blennolide C, to introduce considerable additional structural diversity that affords parnafungins with unique biological activity.}, archive = {J_JACS}, author = {Zuodong Sun and Karl M. Yost and Gerald F. Bills and Yi Tang}, doi = {10.1021/jacs.5c14217}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37842--37853}, shortjournal = {J. Am. Chem. Soc.}, title = {Biosynthesis of the 5-isoxazolidinone-containing hexacyclic structure of parnafungin}, volume = {147}, year = {2025}, }
• (2025). Transitory topochemical tailoring of a van der waals superconductor. JACS, 147(41), 37833--37841. (www)

  @article{ , abstract = {Topochemical intercalation is widely used to access metastable phases with novel electronic properties, but the reverse reaction (deintercalation) typically restores the original state, limiting practical use. Here, we present a topochemical approach that employs a sacrificial intercalant that thermally decomposes to irreversibly lock in the new electronic state. Using 2-aminobutane as the sacrificial intercalant, we convert the van der Waals (vdW) material 1T-TiSe 2 into a superconductor and the vdW superconductor 2H-NbSe 2 into a nonsuperconducting metal, while preserving the ability to exfoliate the resulting crystals. We find that this transitory intercalation increases the electron density in both materials and partially suppresses the CDW in TiSe 2 . By tuning the thermolysis temperature, we can systematically vary the carrier density in TiSe 2 , enabling us to map its phase diagram. The superconductivity in TiSe 2 is retained in exfoliated flakes, although with a lower critical temperature. This transitory topochemical strategy enables access to new electronic states with precisely tuned carrier densities that are otherwise inaccessible through direct solid-state synthesis.}, archive = {J_JACS}, author = {Xiaoyu Song and Ziyu Liu and Eric F. Seewald and Asish K. Kundu and Daniel Muñoz-Segovia and Myung-Geun Han and Scott R. Docherty and Daniel G. Chica and Julian P. Ingham and Jiayi Li and Junsik Mun and Madisen Holbrook and Qifeng Jiang and Jordan Cox and Jeffrey McNeill and Yimei Zhu and Colin Nuckolls and Andrew J. Millis and Elio Vescovo and Raquel Queiroz and Cory R. Dean and Abhay N. Pasupathy and Xavier Roy}, doi = {10.1021/jacs.5c14254}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37833--37841}, shortjournal = {J. Am. Chem. Soc.}, title = {Transitory topochemical tailoring of a van der waals superconductor}, volume = {147}, year = {2025}, }
• (2025). How electrolyte pH affects the oxygen reduction reaction. JACS, 147(41), 37819--37832. (www)

  @article{ , abstract = {Electrolyte pH is known to affect catalytic activity and selectivity for the oxygen reduction reaction (ORR). But a clear understanding of why ORR rates respond more strongly to pH over certain catalysts than others has not been developed. Here, we propose that pH effects on the ORR result from electric field induced changes in the binding energies of intermediates involved in kinetically relevant elementary steps. For strongly binding metals (Pt, Ir, Ru, and Pd), whose rates are limited by the proton-coupled electron transfer (PCET) step to form *OOH or remove adsorbed OH (*OH), ORR rates are weakly affected by electrolyte pH. This behavior is observed because the binding energies of the reaction intermediates in these steps are minimally affected by electric field strength. The weak pH dependence is most pronounced for Pt, which shows essentially identical rates in acidic and alkaline electrolytes. For weakly binding metals (Au, Ag), whose rates are limited by non-PCET O 2 adsorption, ORR rates increase significantly when moving from acidic to alkaline electrolytes. This strong pH dependence results from the stabilization of adsorbed O 2 by the increasingly negative electric field present at the catalyst surface under alkaline conditions. We argue that modifying electrolyte pH does not change the rate-determining elementary step for the ORR, but does decrease the apparent activation barrier for O 2 adsorption over weakly binding catalysts. These arguments are substantiated by a combination of experimental kinetic studies and atomistic simulations.}, archive = {J_JACS}, author = {Jay T. Bender and Rohan Yuri Sanspeur and Nicolas Bueno Ponce and Angel E. Valles and Alyssa K. Uvodich and Delia J. Milliron and John R. Kitchin and Joaquin Resasco}, doi = {10.1021/jacs.5c14208}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37819--37832}, shortjournal = {J. Am. Chem. Soc.}, title = {How electrolyte pH affects the oxygen reduction reaction}, volume = {147}, year = {2025}, }
• (2025). Dynamic evolution from single-atom catalysts to active nanograins for CO2 reduction. JACS, 147(41), 37808--37818. (www)

  @article{ , abstract = {Understanding dynamic catalyst evolution, particularly Cu-based single-atom catalysts, faces tremendous challenges of tracking rapid and nanoscale evolution and uncontrolled catalyst reoxidation during post-reaction air exposure. Although ex situ / in situ studies have indirectly indicated the structural reconstruction of single-atom catalysts, direct probing of single-atom catalyst evolution requires time-resolved nanoscale operando methods. Here, we present direct experimental evidence of dynamic evolution from single-atom catalysts to Cu nanostructures rich in active nanograins, based on a conductive metal–organic framework-based Cu single-atom catalyst (Cu-SAC). Operando synchrotron-based high-energy-resolution X-ray spectroscopy and IR absorption spectroscopy quantitatively tracked the structural and molecular fingerprints during single-atom-to-nanograin evolution. Cu-SAC supported on nanocarbon (Cu-SAC-NC) with nearly 100% metallic Cu nanograins achieved a 5-fold increase in multicarbon Faradaic efficiency (C 2+ FE), relative to the Cu-SAC control group with less than half metallic Cu nanograins. Cu-SAC-NC, with superior electronic conductivity provided by the nanocarbon, facilitated the formation of dense copper carbonyl (Cu–CO) intermediates, leading to a larger fraction of active metallic Cu nanograins for effective C–C coupling and significantly enhanced C 2+ selectivity. Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) directly captured real-time movies of dynamic structure evolution from isolated Cu single atoms to metallic Cu nanograins under the CO 2 RR. Operando electrochemical four-dimensional (4D) STEM reveals the complex polycrystalline Cu nanostructures rich in metallic nanograin boundaries, serving as catalytically active sites. This study paves the way for the design of a new generation of single-atom catalysts based on their operando active structures instead of pristine structures.}, archive = {J_JACS}, author = {Juhyung Choi and Sungin Kim and Ji Yong Choi and Sejin Park and Kwanghwi Je and Shikai Liu and Jiahong Jiang and Shaojinlin Yang and Christopher J. Pollock and Rafael Guzman-Soriano and Kathryn Bairley and Bayu I. Z. Ahmad and Phillip J. Milner and Erik H. Thiede and Yun Jeong Hwang and Jihye Park and Yao Yang}, doi = {10.1021/jacs.5c14123}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37808--37818}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic evolution from single-atom catalysts to active nanograins for CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). Single-crystal-to-single-crystal synthesis of an adaptive two-dimensional polymer with dynamic pores. JACS, 147(41), 37798--37807. (www)

  @article{ , abstract = {The synthesis of defect-free, large-area two-dimensional (2D) polymers with dynamic functionality remains a formidable challenge. Here, we report a transformative approach to 2D polymer synthesis via heat-induced topochemical azide–alkyne cycloaddition (TAAC), enabling the single-crystal-to-single-crystal (SCSC) formation of a novel 2D polymer. Unlike conventional rigid 2D frameworks, our design incorporates flexible linkers, imbuing the resulting polymer with dynamic and adaptive pores. We demonstrate reversible guest uptake and exchange, providing unprecedented atomic-resolution insights into host–guest interactions and framework conformational changes. Furthermore, the successful exfoliation of these crystalline 2D polymers into robust, free-standing sheets highlights their practical utility. This work establishes a powerful platform for designing next-generation adaptive materials with precisely controlled molecular recognition and transport capabilities.}, archive = {J_JACS}, author = {Haripriya Balan and Shajiya Shahanas and Kana M. Sureshan}, doi = {10.1021/jacs.5c13942}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37798--37807}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-crystal-to-single-crystal synthesis of an adaptive two-dimensional polymer with dynamic pores}, volume = {147}, year = {2025}, }
• (2025). Molecular orientation controls triplet exciton dynamics in organic molecules coupled to lanthanide-doped nanoparticles. JACS, 147(41), 37788--37797. (www)

  @article{ , abstract = {Hybrid organic–inorganic materials, which combine the unique properties of organic semiconductors (OSCs) and inorganic nanoparticles, show great promise for optoelectronic applications. Understanding structure–function relationships in these nanohybrids is crucial for understanding the mechanisms governing their excited state dynamics, particularly those controlling triplet excitons, which are key to their performance. While previous studies focused primarily on triplet energy transfer (TET) across the interface, we study the full triplet exciton dynamics in OSCs coupled with various lanthanide-doped nanoparticles (LnNPs), with an emphasis on the impact of molecular orientation. We examine three anthracene carboxylic acid (ACA) isomers, differing in the position of the carboxylic acid group (1-, 2-, and 9-position) on the anthracene core. These isomers all exhibit similar triplet dynamics and low triplet yields (∼10%) when uncoordinated, but adopt distinct binding geometries on the LnNP surface, making them ideal for studying how coordination geometry influences triplet exciton dynamics. Using time-resolved optical spectroscopy, we observe significant variations in triplet generation rates, yields, lifetimes, and TET rates between the ACA isomers upon coordination onto the LnNPs. Triplet generation rates and yields are consistently highest in 1-ACA (up to 86%) and lowest in 2-ACA. TET rates are fastest for 9-ACA (up to 1.1 × 10 8 s –1 ) and slowest for 2-ACA. Notably, in the absence of TET, triplet exciton lifetimes exceed 0.1 ms for all LnNP@ACA nanohybrids. These results quantitatively describe how positional isomerism governs the triplet exciton dynamics in LnNP@OSC nanohybrids and highlight the pivotal role of molecular orientation in mediating interfacial photophysics.}, archive = {J_JACS}, author = {Lars van Turnhout and Alasdair Tew and Simon A. Dowland and Ebin Sebastian and Zhao Jiang and Rakesh Arul and Zhongzheng Yu and Akshay Rao}, doi = {10.1021/jacs.5c13962}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37788--37797}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular orientation controls triplet exciton dynamics in organic molecules coupled to lanthanide-doped nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Au–Mn bond formal metathesis with Ar–F via synergistic bimetallic activation. JACS, 147(41), 37779--37787. (www)

  @article{ , abstract = {Selective C–F activation with gold-complex has been esteemed as a long-standing issue owing to a kinetically unfavorable oxidative addition elementary reaction. Herein, we report a synergistic bimetallic Au–Mn bond formal metathesis with aromatic C(sp 2 )–F bond, establishing a versatile platform for the synthesis of polyfluorophenyl-substituted Au(I) complexes. A wide range of structurally diverse L–Au(I)–Ar Fn complexes (37 examples, up to 98% yield) have been readily constructed. Mechanistic studies together with DFT calculations support that the key C–F bond cleavage proceeds via thermodynamically and kinetically feasible Au–Mn bimetallic cooperative activation, rather than direct oxidative addition toward either Au or Mn metal center. Notably, these aryl gold(I) complexes exhibit broad biological functions, including anticancer and/or anti-inflammatory efficacy, facilitating promising candidate drug discovery for pharmaceutical development. This bimetallic strategy should open new avenues to achieve unique reactivity profiles and novel mechanistic pathways.}, archive = {J_JACS}, author = {Siyu Xia and Weina Zhong and Tingrui Li and Zhongren Xu and Jie Han and Wukun Liu and Weipeng Li and Chengjian Zhu and Jin Xie}, doi = {10.1021/jacs.5c13893}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37779--37787}, shortjournal = {J. Am. Chem. Soc.}, title = {Au–Mn bond formal metathesis with Ar–F via synergistic bimetallic activation}, volume = {147}, year = {2025}, }
• (2025). The interplay between luminescence dissymmetry factor and quantum yield: Symmetric and asymmetric hydrogen bonding. JACS, 147(41), 37771--37778. (www)

  @article{ , abstract = {Unraveling the luminescence–structure relationship in metal-free chiral perovskites remains challenging, particularly for achieving both a strong circularly polarized luminescence (CPL) and high photoluminescence quantum yield (PLQY). Here, we attempt to decode this hidden linkage by constructing the isomorphic polymorph-based metal-free chiral perovskite through the rational design of the A-site cation. The distinct steric hindrance between meta - and ortho -ammonium sites in 2-methylpiperazine-1,4-diium provides two possibilities for forming the hydrogen bond, which could control the crystallization pathways. Therefore, two different metal-free chiral perovskite polymorphs (A and B) with symmetric or asymmetric hydrogen bonding were obtained, which exhibit a remarkable difference in PLQY (36.51% vs 1.85%) and photoluminescence dissymmetry factor (| g lum |, 0.032 vs 0.066). The highly luminescent polymorph A demonstrates stronger intermolecular coupling mediated by the symmetric hydrogen bonding, which effectively suppresses the nonradiative decay through rigidification of the octahedral framework, thereby enhancing the PLQY. In contrast, the asymmetric hydrogen bonding in polymorph B induces a greater structural distortion, which enhances the electron–phonon coupling and consequently reduces the PLQY. However, this asymmetric hydrogen bonding promotes efficient chirality transfer, leading to an increase of | g l u m |. Our work provides a molecular-level understanding of symmetric and asymmetric hydrogen bonding to determine the crystal packings and exciton dynamics, and thus the luminescence dissymmetry factor and quantum yield.}, archive = {J_JACS}, author = {Zhaoyu Wang and Xin Zeng and Wenkai Zhao and Yunchao Miao and Haolin Lu and Hebin Wang and Tianyin Shao and Xinyi Niu and Sehrish Gull and Tianjiao Qiao and Bing Sun and Xinfeng Liu and Hao-Li Zhang and Yongsheng Chen and Guankui Long}, doi = {10.1021/jacs.5c13847}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37771--37778}, shortjournal = {J. Am. Chem. Soc.}, title = {The interplay between luminescence dissymmetry factor and quantum yield: Symmetric and asymmetric hydrogen bonding}, volume = {147}, year = {2025}, }
• (2025). Temperature-controlled cyclic polyester molecular weights in ring-expansion polymerization. JACS, 147(41), 37761--37770. (www)

  @article{ , abstract = {Ring-expansion polymerization of cyclic esters is a feasible approach to synthesize cyclic polyesters; however, controlling the molecular weight of cyclic polyesters is still a formidable challenge. In this work, the molecular weight of cyclic polyester can be easily controlled by regulating the polymerization rate and cyclization rate during a chain-growth polymerization process by adjusting the polymerization temperature. The molecular weights of cyclic polyesters (poly(salicylic phenyl glycolide)), ranging from 32.2 to 189.0 kg/mol, are controlled well because of an inverse relationship between the natural logarithms of molecular weights and temperatures. The molecular weights of cyclic polymers remain similar throughout polymerization, regardless of the different conversions at a fixed temperature. The cyclic structures of the polyesters are confirmed by gel permeation chromatography, mass spectrometry, and atomic force microscopy. Due to the incorporation of phenyl groups in the polymer side and main chains, the glass transition temperature can be as high as 116.6 °C.}, archive = {J_JACS}, author = {Jinxing Jiang and Ge Yao and Yaqin Cui and Luya Cao and Yadong Zhang and Kun Yuan and Xiaobo Pan and Yu Tang and Jincai Wu}, doi = {10.1021/jacs.5c13840}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37761--37770}, shortjournal = {J. Am. Chem. Soc.}, title = {Temperature-controlled cyclic polyester molecular weights in ring-expansion polymerization}, volume = {147}, year = {2025}, }
• (2025). Direct deaminative halogenation at hindered tertiary centers. JACS, 147(41), 37751--37760. (www)

  @article{ , abstract = {General strategies for direct deaminative halogenation of α-tertiary amines─including those relevant to three-dimensional scaffolds─have remained an unsolved challenge in synthetic chemistry, primarily due to the difficulty of direct cleavage of C–N bonds at congested tertiary carbon centers. We report a radical-mediated deaminative halogenation platform that overcomes these limitations using commercially available O-diphenylphosphinyl hydroxylamine. By modulating reaction conditions, we redirect the inherent hydrogenation pathway toward halogen-atom transfer, enabling the efficient halogenation of sterically hindered substrates. This practical, one-pot transformation enables efficient chlorination, bromination, and iodination of structurally diverse amines while maintaining excellent functional group compatibility. The power of this methodology is also showcased by the straightforward preparation of valuable aryl-halide isosteres, including halogenated derivatives of bicyclo[1.1.1]pentane, bicyclo[2.2.1]heptane, bicyclo[2.2.2]octane, 2-azabicyclo[2.1.1]hexane, and cubane. Combining a broad substrate scope with operational simplicity and scalability, this advance provides a robust platform for late-stage molecular diversification and opens new avenues for the development of next-generation chlorine-containing drug candidates.}, archive = {J_JACS}, author = {Zhangkai Cui and Panpan Ma and Qi Sun and Ken Lin and Pengcheng Tang and Saizhou Wang and Hongjian Lu}, doi = {10.1021/jacs.5c13592}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37751--37760}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct deaminative halogenation at hindered tertiary centers}, volume = {147}, year = {2025}, }
• (2025). Visible-light-induced bond homolysis in titanacyclopentadienes for the catalytic cyclodimerization of internal alkynes. JACS, 147(41), 37741--37750. (www)

  @article{ , abstract = {Ligand-to-metal charge transfer (LMCT) processes offer significant potential in photochemical synthesis but remain comparatively underdeveloped, relative to metal-to-ligand charge transfer (MLCT) pathways. Titanium organyls are particularly promising in this context, enabling the direct generation of carbon-centered radicals. However, reports on their photochemistry have remained scarce. Herein, we present the visible-light-induced homolytic cleavage of a Ti–C bond in a titanacyclopentadiene complex supported by a bulky pyridine-diamido ligand. The resulting biradicaloid undergoes a selective skeletal rearrangement via a H atom shift to form a titanacyclopentene. This stoichiometric transformation was translated into a novel catalytic cyclodimerization of internal alkynes. With 2-butyne, the unusual dimer 1,2,3-trimethyl-4-methylenecyclobutene, a strained and readily functionalizable small ring, was obtained quantitatively. Mechanistic investigations of this previously unreported catalytic transformation including quantum chemical calculations, single-turnover experiments, quantum yield determination by actinometry, and reaction kinetics reveal key features of the underlying reactivity and indicate that visible-light-induced Ti–C bond homolysis is the rate-determining step. Overall, our findings demonstrate that the combination of a sterically demanding ligand, which suppresses alkyne cyclotrimerization, with visible-light-induced bond homolysis offers a new entry point into catalytic alkyne oligomerization chemistry.}, archive = {J_JACS}, author = {Maxi L. Heldner and Tobias Körner and Corinna Czernetzki and Patrick T. Geppert and Agnieszka Nowak-Król and Gabriele Hierlmeier}, doi = {10.1021/jacs.5c13492}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37741--37750}, shortjournal = {J. Am. Chem. Soc.}, title = {Visible-light-induced bond homolysis in titanacyclopentadienes for the catalytic cyclodimerization of internal alkynes}, volume = {147}, year = {2025}, }
• (2025). Postsynthetic triazolate functionalization of Ni2Cl2BTDD: Creation of supplementary CO2 adsorption sites and exceptional CO2 selectivity. JACS, 147(41), 37732--37740. (www)

  @article{ , abstract = {Postsynthetic modification (PSM) offers a versatile approach to tune metal–organic frameworks (MOFs) by introducing functional groups or exchanging bridging ligands while preserving open metal sites (OMSs). Nevertheless, generating additional adsorption sites via PSM remains challenging. Herein, we report a new PSM strategy that creates supplementary sorption sites within a robust MOF framework. We synthesized triazolate-exchanged Ni 2 (triazolates) x Cl 2– x BTDD (BTDD = bis(1H-1,2,3-triazolo[4,5- b ],[4′,5′-i])dibenzo[1,4]dioxin), where bridging chlorides in the parent Ni 2 Cl 2 BTDD were successfully replaced with triazolate ligands. Rietveld refinement of synchrotron X-ray diffraction confirmed that triazolates bridge adjacent Ni(II) centers through 1,2-nitrogen atoms without obstructing the OMSs. This structural modification substantially enhanced CO 2 adsorption owing to newly formed binding sites and cooperative interactions between triazolate moieties and BTDDs. Among the modified frameworks, Ni_dmtz incorporating 3,5-dimethyl-1,2,4-triazolate (dmtz) showed a remarkable improvement: CO 2 uptake increased 5.2-fold at 0.15 bar and 2.6-fold at 1 bar compared to the parent framework, while also displaying enhanced stability under humid conditions. Notably, the Ideal Adsorbed Solution Theory (IAST) selectivity for CO 2 /N 2 (15/85 v/v) reached 456,000, significantly surpassing most reported MOFs. Grand Canonical Monte Carlo simulations revealed the presence of a third adsorption site in Ni_dmtz, where CO 2 interacts with the methyl-substituted triazolate in addition to conventional ligand pocket sites. This study highlights a simple yet effective PSM approach to design multifunctional sorbents and provides valuable insights into the rational development of MOFs for efficient CO 2 capture.}, archive = {J_JACS}, author = {Ju Hyoung Kim and Hongryeol Yun and Chan Gu Kim and Namju Kim and Yurim Yang and Saeeun Yoo and Dohyun Moon and Dongwon Kim and Chang Seop Hong}, doi = {10.1021/jacs.5c13450}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37732--37740}, shortjournal = {J. Am. Chem. Soc.}, title = {Postsynthetic triazolate functionalization of Ni2Cl2BTDD: Creation of supplementary CO2 adsorption sites and exceptional CO2 selectivity}, volume = {147}, year = {2025}, }
• (2025). Logical exploration of cinnamoyl-containing nonribosomal peptides via metabologenomic targeting and regulator overexpression. JACS, 147(41), 37719--37731. (www)

  @article{ , abstract = {A targeted method for discovering cinnamoyl-containing nonribosomal peptides (CCNPs), a unique class of bioactive compounds, was devised by using cinnamoyl isomerase, a key enzyme in the biosynthesis of the cinnamoyl moiety, as a genome mining probe. A total of 39 hit strains were obtained, including 35 from polymerase chain reaction-based screening of the in-house bacterial library (2.5% of 1400 strains) targeting the cinnamoyl isomerase-encoding gene and 4 from the genome mining of online databases. Sequence similarity networking and phylogenetic analyses of the isomerase amplicons (∼530 bp) classified the CCNPs into three major substructure-based groups (Z-, E-, and M-type CCNPs) and revealed distinct clade–structure relationships (13 clades). To overcome the challenge of silent biosynthetic gene clusters, we activated these clusters by overexpressing conserved cluster-situated LuxR regulators combined with extensive culture optimization. CCNP production was metabolomically detected in the bacterial extracts by using the characteristic UV absorption and MS/MS fragments of cinnamoyl moieties. CCNP production was observed in 20 of the 39 hit strains, resulting in the isolation of 6 new CCNPs, including oxy-skyllamycin B ( 2 ), gwanacinnamycin ( 3 ), and luxocinnamycins A–D ( 4–7 ), with high structural novelty. Their structures were elucidated using comprehensive spectroscopic analyses and multiple-step chemical derivatizations, and the putative biosynthetic pathways were bioinformatically proposed. Gwanacinnamycin ( 3 ) exhibited significant antimycobacterial activity, whereas luxocinnamycin A ( 4 ) displayed moderate antiproliferative activity against stomach cancer cells. Our findings highlight a targeted metabologenomic approach combined with transcriptional regulator overexpression as a logical and efficient platform for the discovery of bioactive compounds from nature.}, archive = {J_JACS}, author = {Sangwook Kang and Thanh-Hau Huynh and Jung Min Kim and Bo Eun Heo and Sung Chul Jang and Chae Won Ock and Jayho Lee and Yejin Song and Joon Soo An and Ben Shen and Seung Bum Kim and Jichan Jang and Sang Kook Lee and Yeo Joon Yoon and Dong-Chan Oh}, doi = {10.1021/jacs.5c13143}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37719--37731}, shortjournal = {J. Am. Chem. Soc.}, title = {Logical exploration of cinnamoyl-containing nonribosomal peptides via metabologenomic targeting and regulator overexpression}, volume = {147}, year = {2025}, }
• (2025). Dinuclear magnesium-catalyzed hydroboration: Unveiling Metal–Ligand cooperative activation of polar unsaturated bonds. JACS, 147(41), 37708--37718. (www)

  @article{ , abstract = {Metal–ligand cooperation (MLC) has emerged as a cornerstone strategy for catalytic small molecule activation across both synthetic and biological chemistry. While MLC has driven significant progress in catalytic hydroboration, most known systems rely on MLC-mediated activation of the H–B bond to generate metal hydride intermediates. In contrast, catalytic hydroboration via direct MLC activation of polar unsaturated bonds remains largely unexplored, despite its potential for expanding substrate scope and achieving novel selectivity. Here, we report a dinuclear magnesium complex [Mg]-1 , supported by dianionic ligands capable of dearomatization-rearomatization MLC at each metal center. This complex exhibits unconventional MLC behavior, preferentially activating ketones over HBpin to form a magnesium-ketone adduct [Mg]-2 . This selectivity diverges from that of analogous Ruthenium(II) complexes bearing the same ligand framework, which preferentially activate HBpin over ketones to yield ruthenium hydride species. These findings underscore the distinctive MLC reactivity of main-group metal systems compared to transition metal analogues. Kinetic studies and DFT calculations reveal that the rate-determining step involves hydride transfer from HBpin to the ketone within the magnesium–ketone adduct, enabled by synergistic activation across both Mg centers. The catalyst demonstrates broad utility, enabling the hydroboration of over 70 polar unsaturated substrates, including challenging classes such as nitro compounds. Notably, it also mediates selective 1,4-hydroboration of quinoline derivatives, a transformation rarely achieved with main-group catalysts.}, archive = {J_JACS}, author = {Hengxu Li and Mingjie Fan and Qiang Liu}, doi = {10.1021/jacs.5c13113}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37708--37718}, shortjournal = {J. Am. Chem. Soc.}, title = {Dinuclear magnesium-catalyzed hydroboration: Unveiling Metal–Ligand cooperative activation of polar unsaturated bonds}, volume = {147}, year = {2025}, }
• (2025). Force-triggered thermodynamically uphill disulfide reduction through sulfur oxidation state control. JACS, 147(41), 37701--37707. (www)

  @article{ , abstract = {In addition to thermal energy, current, and light, mechanical forces activate chemical reactions, often steering reaction pathways that result in products different from those obtained under thermodynamic control. Single-molecule mechanochemistry experiments have probed how the forced activation of a single covalent bond results in accelerated scission of both homolytic and heterolytic bonds, and the ring-opening of strained mechanophores in long polymers. Due to its mechanistic simplicity, the concerted S N 2 thiol–disulfide nucleophilic substitution has been successfully used as a model system to interrogate how the nucleophilicity of an attacking organic, low-oxidation state thiol determines the force dependency of the thiol/disulfide exchange rate. Inorganic sulfur-oxyanions are comparatively much less reactive. Whether mechanical forces can activate the rupture of a protein disulfide by sulfur-oxyanions featuring higher oxidation states remains unknown. Here we employ single-molecule force-clamp spectroscopy, complemented by density functional theory (DFT) calculations and colorimetric assay measurements, to show that the thermodynamically nonfavored reduction of a disulfide bond by inorganic oxyanions can be activated by mechanical force. Occurring within the core of a protein with a physiological mechanical role, the force-unlocked reactivity has a direct impact on protein elasticity.}, archive = {J_JACS}, author = {Marc Mora and Georgia Cohen and William Cranton and Olaia Anton and Amy E. M. Beedle and Guillaume Stirnemann and Sergi Garcia-Manyes}, doi = {10.1021/jacs.5c13084}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37701--37707}, shortjournal = {J. Am. Chem. Soc.}, title = {Force-triggered thermodynamically uphill disulfide reduction through sulfur oxidation state control}, volume = {147}, year = {2025}, }
• (2025). A post-translational Histidine–Histidine cross-link enhances enzymatic oxygen reduction activity with greater pH adaptability. JACS, 147(41), 37688--37700. (www)

  @article{ , abstract = {Cross-linked protein residues exist as enzyme cofactors to enable or enhance catalytic activities. Despite their importance in nature, the chemical identity of the cross-links is limited to certain amino acid combinations, whose function and the formation mechanism remain insufficiently understood due to the difficulty in isolating native enzymes without the cross-links. Herein, we report the formation and characterization of both His-Tyr and His-His cross-links under oxidative enzymatic turnover conditions in L29H/F33Y/F43H Mb, a structural and functional model of heme-copper oxidase (HCO). The connectivity of the cross-link was characterized as N ε2 (His29)-C δ2 (His43) by mass spectrometry (LC-MS/MS) and nuclear magnetic resonance (NMR). Interestingly, formation of the cross-link significantly enhances the oxygen reduction activity of the enzyme at neutral or basic pH with higher product specificity. X-ray crystallography has identified a novel Tyr-His cross-link through a Tyr-O-His linkage. Our mechanistic studies indicate the involvement of high-valent heme-iron and the neighboring tyrosine in an oxidative self-processing pathway to generate the cross-link. This work serves as a new example while providing insights into the enzyme cross-link formation, allowing the design of artificial biocatalysts containing these novel cross-links with higher activity and pH adaptability.}, archive = {J_JACS}, author = {Yiwei Liu and Avery C. Vilbert and Barshali Ghosh and Robert P. Young and Eric D. Merkley and Arnab Mukherjee and Lisa Phan and Casey Van Stappen and Ambika Baghi-Damodaran and Kyle D. Miner and Joshua N. Adkins and John R. Cort and Yi Lu}, doi = {10.1021/jacs.5c12710}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37688--37700}, shortjournal = {J. Am. Chem. Soc.}, title = {A post-translational Histidine–Histidine cross-link enhances enzymatic oxygen reduction activity with greater pH adaptability}, volume = {147}, year = {2025}, }
• (2025). An isolated lithium ortho-carboranyl cuprate complex for the synthesis of multiple-carborane-substituted arenes from (Hetero)Aryl bromides and chlorides. JACS, 147(41), 37677--37687. (www)

  @article{ , abstract = {Carborane-substituted arenes have emerged as versatile building blocks in medicinal chemistry, materials science, and coordination chemistry owing to the unique three-dimensional aromaticity, exceptional stability, and bioisosteric properties of carboranes. However, the existing synthetic routes to carborane-substituted arenes via C–C bond formation often rely on complex and laborious in situ procedures using aryl iodides, thus severely limiting the scope of their practical applications. Here, we report the isolation and characterization of a lithium bis( o -carboran-1-yl)cuprate complex ( Li/Cu-1 ) that enables the efficient “dump-and-stir” synthesis of carborane-substituted arenes from readily available aryl bromides and chlorides. Remarkably, isophthalonitrile functions as a ligand for the Li center in Li/Cu-1 , leaving the Cu center available for the oxidative addition to aryl halides. This represents a paradigm shift from traditional approaches using pyridines as ligands for Cu centers. Our method provides access to a diverse array of unprecedented molecules, including multiple-carborane-substituted or carborane-fused arenes, thereby converting a hitherto difficult transformation in synthetic chemistry into a practical and scalable process.}, archive = {J_JACS}, author = {Yusei Hisata and Daina Morishita and Yoichi Hoshimoto}, doi = {10.1021/jacs.5c13004}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37677--37687}, shortjournal = {J. Am. Chem. Soc.}, title = {An isolated lithium ortho-carboranyl cuprate complex for the synthesis of multiple-carborane-substituted arenes from (Hetero)Aryl bromides and chlorides}, volume = {147}, year = {2025}, }
• (2025). Tuning the degradability profiles of polyesters with indium-catalyzed incorporation of poly(ε-thiocaprolactone) blocks. JACS, 147(41), 37667--37676. (www)

  @article{ , abstract = {There are no examples of high molecular weight (>100 000 g/mol) poly(ε-thiocaprolactone) (PtCL), and the mechanism of ε-thiocaprolactone (tCL) polymerization with organometallic complexes has not been investigated. In this work, we demonstrate the synthesis of the highest reported molecular weight PtCL ( M n = 109 000 g/mol) by using a cationic indium thiolate catalyst formed in situ via the addition of benzyl mercaptan. The mechanism of the polymerization is thoroughly investigated and the reaction coordinate is elucidated via computational calculations; the polymerization propagates through a coordination–insertion mechanism. If the PtCL is not isolated during the polymerization, the resulting indium-PtCL macromolecule can be used as an initiator to form copolymers with poly(lactide) (PLA) and poly(ε-caprolactone) (PCL). Incorporating 10% PtCL in these polymers alters their degradation behavior: the hydrolytic degradation period of PLA is reduced by nearly half, while PCL becomes more resistant to hydrolysis.}, archive = {J_JACS}, author = {Joseph Chang and Chatura Goonesinghe and Hootan Roshandel and Takeo Iwase and Ana Luisa Granja and Sophia Zhang and Kimia Hosseini and Kritika Sharma and Padmapriya Srinivasan and Jason Wai-Lok Poon and Maria Ezhova and Hyuk-Joon Jung and Paula L. Diaconescu and Parisa Mehrkhodavandi}, doi = {10.1021/jacs.5c12988}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37667--37676}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the degradability profiles of polyesters with indium-catalyzed incorporation of poly(ε-thiocaprolactone) blocks}, volume = {147}, year = {2025}, }
• (2025). An experimental benchmark for the barrier height of an on-surface reaction: Hydrogen oxidation on pt(332). JACS, 147(41), 37658--37666. (www)

  @article{ , abstract = {Developing predictive theories for the rates of reactions between surface-bound molecules is a central challenge to understanding many important phenomena including: heterogeneous catalysis, electrocatalysis, nanofabrication, and corrosion. To meet this challenge, chemically accurate benchmarks to test theoretically derived reaction rates and barrier heights are essential, but few exist. Here, we determine from experiment an accurate zero-point-energy corrected barrier height, 0.76 ± 0.03, for the reaction O* + H* → OH* occurring at atomic Pt B-type step sites, the rate limiting step of hydrogen oxidation on Pt. This experimental benchmark agrees with density functional theory (DFT) predictions made at the level of the generalized gradient approximation (GGA) for five different functionals, exhibiting a mean absolute error (MAE) of 25 meV. This is far better agreement than commonly expected for this level of theory. We speculate that this level of agreement may be a common feature for reactions that involve only species adsorbed on surfaces.}, archive = {J_JACS}, author = {Florian Nitz and Stefan Hörandl and Michael Schwarzer and Theofanis Kitsopoulos and Daniel J. Auerbach and Alec M. Wodtke}, doi = {10.1021/jacs.5c12862}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37658--37666}, shortjournal = {J. Am. Chem. Soc.}, title = {An experimental benchmark for the barrier height of an on-surface reaction: Hydrogen oxidation on pt(332)}, volume = {147}, year = {2025}, }
• (2025). Genetically engineered biomimetic nanoparticles for synergistic activation of glioma-associated macrophages against glioblastoma. JACS, 147(41), 37641--37657. (www)

  @article{ , abstract = {Glioma-associated macrophages (GAMs) are central mediators of immune evasion and therapeutic resistance in glioblastoma multiforme (GBM) due to their tumor-promoting M2 phenotype and loss of phagocytic activity toward tumor cells. Activating GAMs represent an attractive therapeutic strategy against GBM, but it is hindered by the lack of effective therapies and insufficient drug exposure. Herein, an engineered biomimetic delivery system (SIRPα@BSA/PTX) is developed by enveloping albumin-bound paclitaxel (BSA/PTX) with a genetically engineered melanoma cell membrane expressing SIRPα variants to activate GAMs for improved GBM therapy. SIRPα@BSA/PTX efficiently penetrates the blood–brain barrier (BBB) to accumulate in GBM by leveraging the brain tropism of the melanoma cell membrane. Subsequently, SIRPα variants on the cell membrane, along with PTX in the inner core, synergistically enhance the repolarization and phagocytic abilities of GAMs. In vivo studies show that SIRPα@BSA/PTX significantly suppresses tumor growth and recurrence in orthotopic and postoperative murine GBM models and achieves 100% mouse survival when combined with immune checkpoint inhibitors. Transcriptome analysis of clinical GBM patient samples treated with SIRPα@BSA/PTX also reveals remarkable immune activation signatures, suggesting the great potential of nanoenabled macrophage-based immunotherapy for brain tumors.}, archive = {J_JACS}, author = {Jia-Qi Luo and Ji Zhang and Hui-Han Yu and Yu-Xuan Li and Zhong-Hong Zhou and Yuyou Duan and Jin-Zhi Du and Jun Wang}, doi = {10.1021/jacs.5c12775}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37641--37657}, shortjournal = {J. Am. Chem. Soc.}, title = {Genetically engineered biomimetic nanoparticles for synergistic activation of glioma-associated macrophages against glioblastoma}, volume = {147}, year = {2025}, }
• (2025). Stapling of β-glucans increases antibody binding. JACS, 147(41), 37634--37640. (www)

  @article{ , abstract = {Higher-order structures are essential for the function of biological macromolecules. Tuning the conformational space of peptides by stapling improves their pharmacological properties. The three-dimensional (3D) structures of glycans are much less well understood than those of peptides and oligonucleotides, and willful modulation of oligosaccharide structures to improve binding to proteins has not been described to date. Herein, we describe stapling of β-(1,3)-glucans to tune their conformation, aiming to mimick the naturally occurring triple helix. The stapled glycans are prepared by automated glycan assembly, followed by linker construction and ring-closure assisted by solid-phase peptide synthesis. Thereby, staples of different lengths, polarities, and topologies can be readily introduced. Molecular dynamics simulations served to evaluate the effect of stapling on the conformational space. Glycan microarray experiments revealed that stapled glycans bound significantly more tightly to monoclonal mouse and rabbit antibodies than did linear glycans. Controlling the conformational space of short oligosaccharides creates opportunities for synthetic glycans in drug and vaccine development.}, archive = {J_JACS}, author = {Jiří Ledvinka and Richard Kullmann and Emelie E. Reuber and Thomas Weikl and Manuel G. Ricardo and Peter H. Seeberger}, doi = {10.1021/jacs.5c12690}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37634--37640}, shortjournal = {J. Am. Chem. Soc.}, title = {Stapling of β-glucans increases antibody binding}, volume = {147}, year = {2025}, }
• (2025). Kinetically controlled seed-mediated synthesis of colloidal copper nanotetrahedra with intricate internal structure. JACS, 147(41), 37622--37633. (www)

  @article{ , abstract = {The controlled synthesis of non-noble metal nanocrystals, such as Cu, with well-defined shapes and internal structures remains a major challenge in nanochemistry, primarily due to the limited mechanistic understanding of their nucleation and growth pathways. Here, we report a heterometallic seed-mediated synthesis of monodisperse, size-tunable Cu truncated bitetrahedra (TBT) and tetrahedra using preformed Au nanocrystals as seeds. Systematic variation of the Au seed concentration enables precise control over nanocrystal size, while rapid reduction kinetics and sustained Cu monomer supply facilitate the evolution of TBT intermediates into well-defined Cu tetrahedra. Electron microscopy analyses reveal that the penta-twinned Au seeds induce asymmetric Cu overgrowth and initiate the formation of central twin boundaries in TBT. Four-dimensional scanning transmission electron microscopy of individual Cu tetrahedra at various tilt angles uncovers twinned layers on three facets and 5-fold axes along three edges. These structural features are rarely observed in previously reported noble-metal tetrahedra. The resulting Cu nanocrystals exhibit sharp, size-dependent localized surface plasmon resonance peaks in the visible range and demonstrate excellent activity in surface-enhanced Raman scattering. Near-field plasmon excitation mapping using electron energy-loss spectroscopy, supported by electromagnetic simulations, confirms distinct plasmon modes at individual Cu tetrahedra. This work highlights the potential of heterometallic twinned seeds for directing the synthesis of low-symmetry Cu nanocrystals and opens new opportunities for the design of non-noble-metal nanocrystals with tailored optical and catalytic properties.}, archive = {J_JACS}, author = {Soojin Jeong and Mingjian Wu and Rebecca X. Skalla and Bianca Paranzino and Alexander Kichigin and Baixu Zhu and Alex N. Butrum-Griffith and Xun Zhan and Yaxu Zhong and Chenyu Yan and Philipp Pelz and Colin Ophus and Stefanie Rechberger and Yi Wang and Jun Chen and Akira Yasuhara and Yoshitaka Aoyama and Mayu Kakefuda and Katherine A. Willets and Erdmann Spiecker and Xingchen Ye}, doi = {10.1021/jacs.5c12614}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37622--37633}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetically controlled seed-mediated synthesis of colloidal copper nanotetrahedra with intricate internal structure}, volume = {147}, year = {2025}, }
• (2025). Electrosynthesis of agrochemicals via alternating-current-driven selective, continuous dehalogenation. JACS, 147(41), 37611--37621. (www)

  @article{ , abstract = {Dehalogenation is a critical transformation in chemical synthesis but remains limited by catalyst deactivation and low selectivity in industrial processes. Here, we report an alternating current (AC) electrolysis strategy for the selective, continuous dechlorination of picloram to aminopyralid, a widely used herbicide. Conventional electrolysis, currently used in industrial aminopyralid electrosynthesis, suffers from structural degradation of the Ag catalyst and the in situ formation of reactive species (ClO – , NH 3 , and NO 2 – ), leading to reduced product yields (<30%) and increased side-product formation. By contrast, AC electrolysis sustains catalytically active, defect-rich Ag surfaces through periodic redox cycling and minimizes the accumulation of ClO – and NO 2 – , thereby suppressing side reactions. The optimized AC protocol achieves a yield of >85% aminopyralid with >90% conversion, enabling uninterrupted operation in a flow system for over 50 days. This work not only advances the industrial electrosynthesis of aminopyralid but also highlights AC electrolysis as a broadly applicable platform for enhancing selectivity and catalyst durability in electrocatalytic transformations.}, archive = {J_JACS}, author = {Diptangshu Datta Mal and Nikita Redkar and Kaida Liu and Hyoju Park and Ellis Rae Kennedy and Sungin Kim and Wenqi Li and Yao Yang and Yue Qi and Matthew Neurock and Long Luo}, doi = {10.1021/jacs.5c12620}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37611--37621}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrosynthesis of agrochemicals via alternating-current-driven selective, continuous dehalogenation}, volume = {147}, year = {2025}, }
• (2025). Unravelling the influence of the local structure on the ultralow thermal conductivity of the Bismuthinite–Aikinite series, Cu1–x□xPb1–xBi1+xS3. JACS, 147(41), 37598--37610. (www)

  @article{ , abstract = {Understanding the relationship between crystal structure, bonding and thermal transport is critical for the discovery of materials with ultralow thermal conductivities. Materials in the bismuthinite–aikinite series, Cu 1– x □ x Pb 1– x Bi 1+ x S 3 (0 ≤ x ≤ 1), in which a Bi 3+ cation and a vacancy (□) are progressively substituted by a Pb 2+ and a Cu + cation, exhibit ultralow thermal conductivities (∼0.5 W m −1 K –1 for x < 1). Here, we investigate the effect of decreasing the Pb 2+ and Cu + content on the crystal structure and properties of Cu 1– x □ x Pb 1– x Bi 1+ x S 3 ( x = 0, 0.33, 0.6 and 0.83). These materials exhibit two-channel thermal transport, with non-propagating phonons being the dominant contribution. Neutron diffraction data reveal that intermediate compositions crystallize in the krupkaite structure ( x = 0.5, P 2 1 ma ), instead of the end-member aikinite structure ( x = 0, Pnma ). Pair distribution function (PDF) analysis reveals that the disordering of vacancies and cations deviates significantly from that expected for a statistical distribution and that, at a local level, copper-rich and copper-poor regions occur. Reducing the Pb 2+ and Cu + content results in lattice softening, which may be attributed to the increased concentration of vacancies in copper-poor regions. Moreover, the persistence of short Pb 2+ –Cu + distances in the copper-rich regions is likely to facilitate the cooperative interaction between lone pairs and rattling Cu + cations that leads to phonon scattering. These findings provide crucial insights into the effect of the local structure on the phonon transport and highlight the potential of local-structure design to achieve high thermoelectric performance in crystalline solids.}, archive = {J_JACS}, author = {Paz Vaqueiro and Anna Herlihy and Mahmoud Elgaml and Shriparna Mukherjee and David A. Keen and David J. Voneshen and Anthony V. Powell}, doi = {10.1021/jacs.5c12526}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37598--37610}, shortjournal = {J. Am. Chem. Soc.}, title = {Unravelling the influence of the local structure on the ultralow thermal conductivity of the Bismuthinite–Aikinite series, Cu1–x□xPb1–xBi1+xS3}, volume = {147}, year = {2025}, }
• (2025). Heterogeneous integration of single-crystalline organic semiconductor microstructures via capillary condensation. JACS, 147(41), 37587--37597. (www)

  @article{ , abstract = {Single-crystalline organic emissive semiconductors, featuring high photoluminescence quantum efficiency, intrinsic optical microcavities, and high charge carrier mobility, hold great promise for integrated photonics applications. However, realizing practical integrated photonics requires the deterministic patterning of multicomponent single-crystalline organic semiconductors with high resolution and unidirectional crystallographic orientation, which remains an ongoing challenge. Here, we report a nanoconfined recrystallization strategy that enables the integrated patterning of multicomponent, single-crystalline organic microstructures. By precisely regulating site-specific capillary condensation within top-pillar-confined spaces, we achieve selective rewetting of printed polycrystalline semiconductors, leading to the formation of discrete multicomponent nanoconfined liquid bridges without cross-contamination. Controlled nucleation and directional growth under regulated evaporation conditions yielded well-defined single-crystalline microstructures with a uniform size and pure crystallographic orientation. These multicomponent heterogeneous microstructures achieve a minimum feature size and interfeature spacing of 2 μm, representing a significant advancement over conventional patterning methods. These high crystalline structures demonstrate excellent optical microcavity characteristics, achieving an ultralow lasing threshold of 0.49 μJ cm –2 and quality factor ( Q ) as high as 1.1 × 10 4 . Leveraging this platform, we fabricated 2 in. full-color organic single-crystalline microlaser arrays with pixel densities exceeding 2000 PPI (pixels per inch) and a color gamut coverage of 104% of the Rec. 2020.}, archive = {J_JACS}, author = {Fengmian Li and Junchuan Yang and Yuyan Zhao and Ke He and Xiao Wei and Jiangang Feng and Hanfei Gao and Jing Li and Ning Guo and Tianchen Li and Tenglong Li and Yifei Cheng and Zhenglian Qin and Yuchen Qiu and Zhiyuan He and Lei Jiang and Yuchen Wu}, doi = {10.1021/jacs.5c12461}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37587--37597}, shortjournal = {J. Am. Chem. Soc.}, title = {Heterogeneous integration of single-crystalline organic semiconductor microstructures via capillary condensation}, volume = {147}, year = {2025}, }
• (2025). Controlling selectivity in electrochemical conversion of organic mixtures through dynamic control of electrode microenvironments. JACS, 147(41), 37576--37586. (www)

  @article{ , abstract = {Organic electrosynthesis using renewable electricity offers a sustainable approach to chemical manufacturing. Among its promising applications, the selective transformation of complex organic mixtures presents a valuable opportunity to eliminate costly separation processes and directly convert heterogeneous feedstocks to valuable products. However, controlling selectivity in reaction mixtures remains challenging due to competing reaction pathways and varying reactivities among substrates. Here, we demonstrate how selectivity in mixed organic electrosynthesis can be systematically controlled through a balance of reaction kinetics and mass transport limitations. Using acrylonitrile and crotononitrile mixtures as a model substrate mixture, we established quantitative relationships between substrate compositions, current densities, and product distributions that reveal distinct kinetically limited and mass transport-limited reaction regimes that control selectivity. We further demonstrated how pulsed electrolysis can be used to strategically control these reaction regimes to drive selectivity toward specific products. These insights create opportunities for developing adaptive and dynamic chemical manufacturing processes capable of handling complex feedstocks.}, archive = {J_JACS}, author = {Ricardo Mathison and Elina Rani and Amelia M. Rose and Fjona Prendi and Casey K. Bloomquist and Miguel A. Modestino}, doi = {10.1021/jacs.5c12445}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37576--37586}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlling selectivity in electrochemical conversion of organic mixtures through dynamic control of electrode microenvironments}, volume = {147}, year = {2025}, }
• (2025). Photoredox fe-catalyzed aminoalkylation toward sterically hindered chiral β-amino acids. JACS, 147(41), 37565--37575. (www)

  @article{ , abstract = {β-Amino acids represent a vital class of structural motifs in natural products and pharmaceuticals, motivating sustained research efforts in organic synthesis and peptidomimetics. Despite the development of numerous methods for the preparation of β-amino acids, sterically hindered variants continue to pose challenges for their synthesis. In this context, an alternative approach via carboxyalkylation of prevalent tertiary amine scaffolds offers a promising yet underexplored strategy for the streamlined synthesis of β-amino acid derivatives. Herein, we report the development of an iron-porphyrin/photoredox dual catalytic system for the C(sp 3 )–C(sp 3 ) cross-coupling of tertiary amines and α-halo acyl compounds, enabling the efficient assembly of sterically hindered β-amino acid frameworks. Mechanistic studies disclosed that the iron catalyst participates in the single-electron oxidation with α-carbonyl radical to generate a ferric enolate intermediate, thereby facilitating Mannich-type addition to afford the desired β-amino acid derivatives. Furthermore, the utilization of chiral auxiliaries enabled efficient stereocontrol over the aminoalkylation process, providing a platform for synthesizing a broad array of chiral β-amino acid derivatives.}, archive = {J_JACS}, author = {Tianze Zhang and Pengwei Gu and Hanmin Huang}, doi = {10.1021/jacs.5c12328}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37565--37575}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoredox fe-catalyzed aminoalkylation toward sterically hindered chiral β-amino acids}, volume = {147}, year = {2025}, }
• (2025). Synergistic optimization of electronic and thermal properties in single-stage GeTe thermoelectric devices. JACS, 147(41), 37555--37564. (www)

  @article{ , abstract = {Thermoelectric generators offer a promising route for converting low-grade waste heat into electricity; however, their practical deployment remains limited by their low conversion efficiency (η). Herein, we report a monolithic, single-stage, 7-pair device based on lead-free GeTe alloys that achieves a remarkable η of 14.1% and a power density of 2.19 W cm –2 at a temperature difference of 460 K. This breakthrough stems from the synergistic integration of ordered-disordered state modulation and multiband engineering. Specifically, multiband evolution suppresses intervalley scattering while promoting valence-band convergence, optimizing the balance between the carrier effective mass and mobility to elevate the weighted mobility and average power factor. The concurrent introduction of abundant lattice defects and localized disorder drives the lattice thermal conductivity toward the amorphous limit. Consequently, achieving a maximum ZT of 2.6 at 703 K with an average ZT of 1.7 across 303–803 K is realized. This study establishes a promising design paradigm for high-performance lead-free thermoelectric technologies.}, archive = {J_JACS}, author = {Jianglong Zhu and Ruiheng Li and Xiaobo Tan and Qiang Sun and Gehong Su and Siqi Huo and Pingan Song and Min Hong and Ran Ang}, doi = {10.1021/jacs.5c11936}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37555--37564}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic optimization of electronic and thermal properties in single-stage GeTe thermoelectric devices}, volume = {147}, year = {2025}, }
• (2025). Controllable reductive alkylation of monodentate phosphine ligands under iron catalysis. JACS, 147(41), 37544--37554. (www)

  @article{ , abstract = {Unsymmetrical aryldialkylphosphine ligands, characterized by their electron-rich and sterically hindered nature, play a pivotal role in the fine-tuning of transition-metal catalysts during catalytic processes. However, their synthesis remains challenging via conventional approaches. Herein, we report an iron-catalyzed reductive cross-coupling of aryldialkylphosphine ligands with alkyl bromides under mild conditions and successfully extend this strategy to diarylalkylphosphines. Utilizing a well-designed iron/diboron catalytic system that promotes the selective cleavage of C(alkyl)–P bonds via the alkyl substituent exchange, this method enables the efficient transformation of readily available monophosphines into structurally diverse tertiary phosphine ligands. The protocol accommodates late-stage functionalization of bioactive phosphines and offers a versatile platform for the diversification of sterically hindered ligands, including Buchwald-type scaffolds, thereby highlighting its utility in transition-metal-catalyzed coupling reactions. Mechanistic studies suggest that borylation of the C(alkyl)–P bond governs the selective C–P bond cleavage, driving the reductive alkylation of phosphines. These findings not only deepen our understanding of iron-catalyzed reductive coupling processes but also inspire the development of new carbon–heteroatom bond-forming strategies using iron/diboron catalysis.}, archive = {J_JACS}, author = {Qingyun Wu and Shasha Geng and Adong Qiao and Siyu Wang and Jinping Yuan and Yun He and Zhang Feng}, doi = {10.1021/jacs.5c12288}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37544--37554}, shortjournal = {J. Am. Chem. Soc.}, title = {Controllable reductive alkylation of monodentate phosphine ligands under iron catalysis}, volume = {147}, year = {2025}, }
• (2025). Vitrification and cold crystallization of a one-dimensional perovskite-like compound enabled by reorganizable coordination bonds and a configurationally restricted cation. JACS, 147(41), 37534--37543. (www)

  @article{ , abstract = {Understanding glass formation and transformation remains a fundamental challenge in materials science. Here, we report the first example of vitrification and multifactor-triggered cold crystallization in a one-dimensional (1D) perovskite-like coordination polymer, (4-methylmorpholinium)[Cd(SCN) 3 ]. By introducing cleavable and reorganizable Cd–S/N coordination bonds, we enable glass formation via melt-quenching, a process previously unachievable in 1D perovskite-like compounds. Comprehensive structural and spectroscopic analyses as well as molecular dynamics simulations, especially in-depth solid-state NMR analysis, reveal that reversible coordination bond reorganization and the restricted configurational freedom of the methylmorpholinium cation drive the glass–crystal transition. Combined dynamic and isothermal DSC studies demonstrate that cold crystallization proceeds via instantaneous nucleation and 1D crystal growth, driven by the confined rearrangement of the 4-methylmorpholinium cation. These findings establish a new vitrification mechanism based on dynamic coordination bonds, providing molecular-level insight into phase transitions in low-dimensional hybrid organic–inorganic perovskites or perovskite-like compounds and offering new strategies for glass-forming hybrid materials.}, archive = {J_JACS}, author = {Zi-Yi Du and Miao Xie and Wei-Yu Hu and Qing Wang and Wenbing Yuan and Chun Wu and Haiming Liu and Takayoshi Nakamura and Chun-Ting He and Rui-Kang Huang and Xiao-Ming Chen}, doi = {10.1021/jacs.5c12026}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37534--37543}, shortjournal = {J. Am. Chem. Soc.}, title = {Vitrification and cold crystallization of a one-dimensional perovskite-like compound enabled by reorganizable coordination bonds and a configurationally restricted cation}, volume = {147}, year = {2025}, }
• (2025). Precise synthesis of racemate-based one-handed helical polymers as recyclable homogeneous chiral catalysts for multiple asymmetric reactions. JACS, 147(41), 37521--37533. (www)

  @article{ , abstract = {Developing chiral catalysts from racemic materials while retaining the merits of both homogeneous and heterogeneous catalysts is a highly desirable yet formidable challenge to date. In this work, we synthesized optically active, one-handed helical polycarbenes from racemic monomers using chiral Pd(II) catalysts. The living polymerization of enantiomeric diazo acetate monomers ( L - and D -1 ) bearing tert -butyloxycarboryl-protected L -prolinol ester using chiral Pd(II)/L R ,or ,S catalysts coordinated with R - or S -bidentate phosphine ligand showed high enantioselectivity ( k fast / k s low = 142). Interestingly, the living polymerization of racemic D / L -1 shows high helix-sense selectivity and affords left- and right-handed helices by using Pd(II)/L R ,and, S catalysts, respectively. Removing the tert -butyloxycarboryl-protected groups on prolinol esters, the racemate-based helical polycarbenes bearing amine pendants showed excellent catalytic activity and enantioselectivity in asymmetric Aldol reaction, Michael addition, and Domino oxa-Michael/Aldol condensation. All of the reactions gave the target products in high yields (>78%) with enantiomeric excess ( ee ) up to 99%. Surprisingly, enantioselectivity is solely determined by the backbone helicity, regardless of the pendant chirality; thus, enantiomeric products are easily obtained using helical polymer-based catalysts in opposite handedness. The polymer catalysts could be recovered from the homogeneous reaction solution via solvent precipitation and were recycled at least 5 times while maintaining excellent activity and enantioselectivity, confirming that these racemate-based helical polymers have the merits of both homogeneous and heterogeneous catalysts.}, archive = {J_JACS}, author = {Run-Tan Gao and Jia-Xin Yu and Qi-Hui Ti and Ming-Yang Mo and Na Liu and Zong-Quan Wu}, doi = {10.1021/jacs.5c12015}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37521--37533}, shortjournal = {J. Am. Chem. Soc.}, title = {Precise synthesis of racemate-based one-handed helical polymers as recyclable homogeneous chiral catalysts for multiple asymmetric reactions}, volume = {147}, year = {2025}, }
• (2025). Band-gap tunability in anharmonic perovskite-like semiconductors driven by polar Electron–Phonon coupling. JACS, 147(41), 37506--37520. (www)

  @article{ , abstract = {The ability to finely tune optoelectronic properties in semiconductors is crucial for the development of advanced technologies, ranging from photodetectors to photovoltaics. In this work, we propose a novel strategy to achieve such tunability by utilizing electric fields to excite low-energy polar optical phonon modes, which strongly couple to electronic states in anharmonic semiconductors. We conducted a high-throughput screening of over 10,000 materials, focusing on centrosymmetric compounds with imaginary polar phonon modes and suitable band gaps, and identified 310 promising candidates with potential for enhanced optoelectronic tunability. From this set, three perovskite-like compounds─Ag 3 SBr, BaTiO 3 , and PbHfO 3 ─were selected for in-depth investigation based on their contrasting band gap behavior with temperature. Using first-principles calculations, ab initio molecular dynamics simulations, tight-binding models, and anharmonic Fröhlich theory, we analyzed the underlying physical mechanisms. Our results show that polar phonon distortions can induce substantial band gap modulations at ambient conditions, including reductions of up to 70% in Ag 3 SBr and increases of nearly 23% in BaTiO 3 , relative to values calculated at zero temperature, while PbHfO 3 exhibits minimal change. These contrasting responses arise from distinct electron–phonon coupling mechanisms and orbital hybridization at the band edges. This work establishes key design principles for harnessing polar lattice dynamics to engineer tunable optoelectronic properties, paving the way for adaptive technologies such as wavelength-selective optical devices and solar absorbers.}, archive = {J_JACS}, author = {Pol Benítez and Ruoshi Jiang and Siyu Chen and Cibrán López and Josep-Lluís Tamarit and Edgardo Saucedo and Bartomeu Monserrat and Claudio Cazorla}, doi = {10.1021/jacs.5c11968}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37506--37520}, shortjournal = {J. Am. Chem. Soc.}, title = {Band-gap tunability in anharmonic perovskite-like semiconductors driven by polar Electron–Phonon coupling}, volume = {147}, year = {2025}, }
• (2025). Determination of the generation efficiency and reductive reactivity of the upconverted hot electrons from mn-doped quantum dots under weak visible light. JACS, 147(41), 37497--37505. (www)

  @article{ , abstract = {Hot electrons generated via Mn-mediated Auger upconversion in Mn-doped quantum dots (QDs) have been shown to be highly effective for reduction reactions that require high reduction potentials and long-range electron transfer. Due to their high energy, these electrons can drive reduction reactions in the solution phase through multiple pathways, including interfacial hot electron transfer on the QD surface and reduction by presolvated and solvated electrons within the solvent. Despite their demonstrated ability to drive challenging reactions, the efficiency of generating upconverted hot electrons under continuous-wave (cw) visible light excitation remains largely unknown. Here, we quantified the quantum yield of hot electron generation from Mn-doped CdSSe/ZnS QDs under continuous white light (455 nm) in aqueous media using the reductive dechlorination of monochloroacetate (MCA) as a hot electron-selective reaction. We found that the quantum yield for hot electron upconversion can reach 35–40% at an excitation intensity of ∼0.1 W/cm 2 , highlighting the high efficiency of Mn-doped QDs as a source of hot electrons. Furthermore, we observed a dependence of the product yield on the photoexcitation history, suggesting a possible excitation-induced surface charge affecting the local concentration of reactants near the QDs, thereby altering the reaction kinetics. These findings provide important insights into the design of more efficient Mn-doped QD structures and reaction conditions for hot electron-enabled photocatalysis using visible light-driven hot electron sources.}, archive = {J_JACS}, author = {Connor Orrison and Ian C. Schulze and Zefan Zhang and Dallas Freitas and Ian Murray and Xin Yan and Christian Hilty and Dong Hee Son}, doi = {10.1021/jacs.5c12004}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37497--37505}, shortjournal = {J. Am. Chem. Soc.}, title = {Determination of the generation efficiency and reductive reactivity of the upconverted hot electrons from mn-doped quantum dots under weak visible light}, volume = {147}, year = {2025}, }
• (2025). Strain-induced quinoidal character in a carbon nanoring embedding anthracene units. JACS, 147(41), 37488--37496. (www)

  @article{ , abstract = {We report a carbon nanoring, [2.2]cyclo(9,10)anthrylene-paraphenylene ([2.2]CAPP), featuring alternating anthracene and phenylene units within a [4]cycloparaphenylene (CPP) framework. The molecule was synthesized via a six-step metal-free route and structurally characterized by single-crystal X-ray diffraction. The high ring strain induces significant distortion in the anthracene units, resulting in a quinoidal electronic structure with a suppressed aromaticity. Despite possessing a 16π-electron conjugation pathway, no global antiaromaticity was observed. This work demonstrates that strain engineering in carbon nanorings enables control over the aromaticity and open-shell character through rational molecular design.}, archive = {J_JACS}, author = {Tomohiko Nishiuchi and Yuta Makihara and Takashi Kubo}, doi = {10.1021/jacs.5c11812}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37488--37496}, shortjournal = {J. Am. Chem. Soc.}, title = {Strain-induced quinoidal character in a carbon nanoring embedding anthracene units}, volume = {147}, year = {2025}, }
• (2025). Single-atom separation of gas in oriented zeolite membranes. JACS, 147(41), 37480--37487. (www)

  @article{ , abstract = {A single atom, with maximized atomic utilization and a tailored electronic structure, serves as a promising selective site for achieving ultrahigh selectivity in separation membranes. However, single-atom synthesis within membrane pores with the required chemical specificity for separation remains challenging. Here, we demonstrate single-atom gas separation using Ni single atoms confined in the 10-membered ring channels of (h0h)-oriented MFI zeolite membranes, which serve as intrinsic ultraselective sites for CO 2 . At an ultralow Ni loading of 0.037 wt %, the membrane achieves an ultrahigh H 2 /CO 2 separation factor of 596, along with excellent H 2 permeability of 1924 Barrer, while maintaining stable operation for over 200 h. This performance compares favorably with that of state-of-the-art membranes. Mechanistic studies reveal that hybridization of Ni–O orbitals preferentially interacts with CO 2 , in contrast to the weak physisorption of H 2 . This work establishes an atomic-level recognition mechanism in nanoporous architectures and offers new design principles for energy-critical gas separations.}, archive = {J_JACS}, author = {Xiaoming Yu and Tongwen Yu and Minghui Chu and Kun Li and Yichun Cai and Ming Xue and Haijiao Xie and Weishen Yang}, doi = {10.1021/jacs.5c11935}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37480--37487}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-atom separation of gas in oriented zeolite membranes}, volume = {147}, year = {2025}, }
• (2025). Covalent probes reveal small-molecule binding pockets in structured RNA and enable bioactive compound design. JACS, 147(41), 37460--37479. (www)

  @article{ , abstract = {The SARS-CoV-2 frameshift stimulation element (FSE) is a critical RNA structure that is essential for viral replication and represents a promising target for antiviral intervention. Here, Chemical Cross-Linking and Isolation by Pull-down (Chem-CLIP) covalent target validation and binding site mapping was applied, to identify small-molecule binding pockets within the FSE and ultimately develop a ligandability map. These studies employed ∼ 190 Chem-CLIP fragments, including the fluoroquinolone merafloxacin, previously shown to interact with this element. Covalent mapping defined merafloxacin’s binding pocket at a nucleotide-level resolution and revealed interactions that, along with structure-based design, efficient one-pot on-plate synthesis and competitive displacement assays, enabled the development of bioactive compounds with antiviral activity. Complementary chemical probing with dimethyl sulfate (DMS) in the presence of a bioactive ligand, coupled to Deconvolution of RNA Alternative Conformations (DRACO), revealed that compound binding increased the reactivity of specific nucleotides with DMS, indicative of changes in local RNA folding. These results highlight the importance of combining Chem-CLIP and DMS profiling to differentiate direct ligand binding from ligand-induced changes in RNA structure. In addition, in silico pocket analysis of FSE structures derived from cryogenic-electron microscopy (cryo-EM) studies identified four recurring cavities, including the experimentally determined merafloxacin and Chem-CLIP fragments binding pockets. Altogether, the findings advance our understanding of RNA–ligand interactions and support a strategy to design and discover small molecules that bind RNA structures.}, archive = {J_JACS}, author = {Sandra Kovachka and Jielei Wang and Amirhossein Taghavi and Yilin Jia and Taro Asaba and Karen C. Wolff and Mason Martin and Xueyi Yang and Samantha M. Meyer and Sabine Ottilie and Mina Heacock and Zhong Cheng and Case W. McNamara and Gurudutt Dubey and Arnab K. Chatterjee and Sumit Chanda and José Gallego and Jessica L. Childs-Disney and Matthew D. Disney}, doi = {10.1021/jacs.5c11898}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37460--37479}, shortjournal = {J. Am. Chem. Soc.}, title = {Covalent probes reveal small-molecule binding pockets in structured RNA and enable bioactive compound design}, volume = {147}, year = {2025}, }
• (2025). Post-synthetic modification-induced structural transformations of 413 and 814 metalla-links via sequential oxidation of dibenzothiophene moieties. JACS, 147(41), 37449--37459. (www)

  @article{ , abstract = {Investigating stimulus-responsive structural transformations of complex mechanically interlocked molecules (MIMs) is key to better understanding the dynamic behaviors of biological macromolecules. Herein, we integrated oxidation-reactive dibenzothiophene moieties into organic frameworks, which self-assembled with binuclear half-sandwich organometallic clips of varying lengths, achieving selective construction of a linear [3]catenane (4 1 3 metalla-link) and an exceptionally rare closed four-link chain (CFLC, 8 1 4 metalla-link), the latter representing a synthetically challenging, highly interlocked topology. Topological transformation of the linear [3]catenane into a metalla-macrocycle was driven by substantial steric repulsion induced by bulky sulfone groups upon full oxidation with 3-chloroperoxybenzoic acid. By contrast, the CFLC exhibited remarkable topological stability against oxidative modifications, consistently preserving 8 1 4 link topology throughout the sequential oxidation process despite in situ structural transformations, yielding sulfoxide- and sulfone-containing CFLC derivatives. All nonoxidized and oxidized supramolecular assemblies were comprehensively characterized using single-crystal X-ray diffraction, high-resolution electrospray ionization mass spectrometry, and nuclear magnetic resonance spectroscopy. This work unveils a new pathway for postsynthetic modification of MIMs and provides critical insights into chemically driven transformations of complex, higher-order interlocked architectures, with significant potential to mimic nature’s sophisticated, dynamic molecular systems.}, archive = {J_JACS}, author = {Shu-Jin Bao and Yan Zou and Guo-Xin Jin}, doi = {10.1021/jacs.5c11669}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37449--37459}, shortjournal = {J. Am. Chem. Soc.}, title = {Post-synthetic modification-induced structural transformations of 413 and 814 metalla-links via sequential oxidation of dibenzothiophene moieties}, volume = {147}, year = {2025}, }
• (2025). Deactivation of interfacial recombination center for thermally stable perovskite solar cells. JACS, 147(41), 37437--37448. (www)

  @article{ , abstract = {We report here on deactivation of the recombination center at the perovskite/Spiro-MeOTAD interface for thermally stable perovskite solar cells (PSCs). Investigation into the chemical reactivity of oxidized Spiro-MeOTAD (Spiro-MeOTAD •+ ) reveals that the Spiro-MeOTAD •+ -induced interfacial recombination center is a key factor contributing to lowering open-circuit voltage ( V OC ) and thereby power conversion efficiency (PCE) of PSCs under thermal stress. To deactivate the recombination center via suppressing chemical reactivity, a functional molecule of 3-aminopropyltriethoxysilane (APTES) is inserted between the perovskite film and the Spiro-MeOTAD-based hole transporting layer (HTL). The alkoxy head in APTES is found to coordinate with the perovskite, and the amino tail reacts with the triphenylamine moiety of Spiro-MeOTAD •+ , which effectively captures the excess oxidized Spiro-MeOTAD. As a result, the nonradiative recombination of perovskite is deactivated and the oxidation level of HTL is modulated, leading to a significant increase in V OC from 1.032 to 1.19 V after introducing APTES, along with a certified PCE of 25.6%. Thermal stability tests at 85 °C for 1000 h following the ISOS-D2I protocol show that 82% of the initial PCE is retained by the deactivation approach.}, archive = {J_JACS}, author = {Xin Liang and Sanwan Liu and Tiankai Zhang and Matthias J. Grotevent and Guiming Fu and Jae-Min Jang and Chae-Yeon Lee and Seong-Ho Cho and Yong Ming and Chandan Chandru Gudal and Sang Yoon Kim and Chan-Hwa Chung and Tae-il Kim and Jun-Yeob Lee and Feng Gao and Moungi G. Bawendi and Nam-Gyu Park}, doi = {10.1021/jacs.5c11581}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37437--37448}, shortjournal = {J. Am. Chem. Soc.}, title = {Deactivation of interfacial recombination center for thermally stable perovskite solar cells}, volume = {147}, year = {2025}, }
• (2025). Effective ammonia production from nitrogen and water under ambient conditions through proton-coupled in situ radiolytic electron transfer. JACS, 147(41), 37428--37436. (www)

  @article{ , abstract = {Ammonia (NH 3 ) is a vital component for sustaining global food supplies and fuel production, but its industrial production via the Haber–Bosch process remains energetically demanding and carbon-intensive. Here, we report an electron-beam-activated NH 3 synthesis strategy that utilizes only atmospheric N 2 and water as feedstocks under ambient conditions. This approach achieves an industrially relevant rate of 83.6 μmol g –1  s –1 with a substantially improved energy efficiency of 0.53 MJ/mol, which surpasses most laboratory-scale technologies and is comparable to that of the Haber–Bosch process. Time-resolved operando spectroscopic experiments, combined with theoretical calculations, reveal that this distinct activation mode enables rapid N 2 →NH 3 conversion through a proton-coupled transfer of an in situ generated energetic hydrated electron. Furthermore, techno-economic analysis and life-cycle assessment demonstrate that the operational simplicity and exceptional throughput of the present N 2 fixation approach could promote nitrogen circularity in the sustainable chemical industry.}, archive = {J_JACS}, author = {Changjiang Hu and Junyi Zhao and Ruisi Chang and Hui Dong and Zhiwen Jiang and Xiang Li and Shinichi Yamashita and Pengfei Zheng and Degao Wang and Qing Huang and Xiaoping Ouyang and Yuxiang Bu and Shuao Wang and Jun Ma}, doi = {10.1021/jacs.5c11505}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37428--37436}, shortjournal = {J. Am. Chem. Soc.}, title = {Effective ammonia production from nitrogen and water under ambient conditions through proton-coupled in situ radiolytic electron transfer}, volume = {147}, year = {2025}, }
• (2025). Efficient, versatile, and durable electrocatalytic nitroaromatic-to-arylamine reduction via heteroatom-site hydrogen-atom transfer. JACS, 147(41), 37414--37427. (www)

  @article{ , abstract = {The selective reduction of nitroaromatics to arylamines affords key intermediates for the industrial production of diverse chemical stocks and materials. The current reduction strategies generally work under harsh conditions, including high temperature, high pressure, and the use of hazardous hydrogen gas, leading to substantial challenges in sustainability and energy efficiency. To this end, direct electrocatalytic nitroaromatic reduction (with water-originated green hydrogen source) is a promising solution to these issues; however, their industrial applications are limited by the low selectivity, low current density, and poor stability of the catalytic electrodes. Here, we report a universally applicable, efficient, and selective electrocatalytic nitroaromatic-to-arylamine reduction approach utilizing highly stable self-standing Ru 1 Cu alloy electrodes. Superior performance (e.g., >99% selectivity, >99% yield, and >99% Faradaic efficiency for p -nitrophenol-to- p -aminophenol) can be achieved under mild working conditions and industrial-level current densities, which can be upheld over a wide range of working potentials (∼500 mV), pH values (0–14), and substrate concentrations (12.5–250 mM), and further extended to broad scope of nitroaromatics substrates and drugs. Moreover, we demonstrate the durable operation of electrolysis for over 1000 h in a flow reactor and kilogram-level production of p -aminophenol. Mechanistic investigations revealed that the superior catalytic performance originated from a switch from the PCET pathway to the HAT pathway as a result of the ensemble effect in Ru 1 Cu, enabling a heteroatom-site bimolecular microkinetic model with significantly promoted activation of surface hydrogen species (*H) and balanced surface bimolecular reaction kinetics.}, archive = {J_JACS}, author = {Pan Ran and Fenfei Wei and Beiyao Xiang and Aoqian Qiu and Bailin Tian and Xinrui Xu and Luhan Dai and Haowen Zhang and Fangyuan Wang and Yamei Sun and Yang Lv and Xixi Hu and Daiqian Xie and Mengning Ding}, doi = {10.1021/jacs.5c11419}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37414--37427}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient, versatile, and durable electrocatalytic nitroaromatic-to-arylamine reduction via heteroatom-site hydrogen-atom transfer}, volume = {147}, year = {2025}, }
• (2025). Gelatinase-responsive short peptide conjugate as a precision therapy against methicillin-resistant staphylococcus aureus. JACS, 147(41), 37398--37413. (www)

  @article{ , abstract = {Methicillin-resistant Staphylococcus aureus (MRSA) is resistant to most antibiotics, posing a major challenge to effective treatment. To address this, a gelatinase-responsive short peptide has been synthesized, selectively targeting pathogenic MRSA while sparing beneficial bacteria in the microflora. The therapeutic peptide, Py-FFRPLGVRGKKQK ( Py-FGGK ; Py: Pyrene), comprises a fiber-forming Py-FFR sequence, a gelatinase-cleavable linker (PLGVRG), and a heparan sulfate (HS)-binding motif (KKQK). HS is found ubiquitously on the MRSA-infected site. Py was used as a fluorescent marker apart from favoring self-aggregation through π-stacking interactions. Reverse-phase HPLC studies showed a serum half-life of ∼4.5 h, and isothermal calorimetry confirmed moderate binding with heparin sulfate (HPS) (3.08 ± 0.2 × 10 4 M –1 ), a pharmaceutical analogue of HS. Cationic lysine-derivatives in Py-FGGK , helped in specific binding to HS at the MRSA-infected site, followed by gelatinase-mediated cleavage at the G–V site, releasing the active component Py-FFRPLG ( Py-FG ), which self-assembled into amyloid fibrils via aggregation of the bis-phenylalanine moieties on the MRSA surfaces causing remarkable antibacterial activity. Py-FGGK is highly effective in biofilm disruption, leakages of cellular constituents, in situ ROS generation, killing biofilm-embedded cells, and favoring cellular migration in NIH/3T3 Cells that help wound healing. The significance of each synthon in Py-FGGK is demonstrated by control studies using various model peptides with appropriate structural variations. Biocompatibility of Py-FGGK as a potential therapeutic agent is ensured through hemolysis assay and insignificant mortality toward live HEK293 and WI38 cells. Its efficacy in wound healing and recovery of MRSA-infected female albino Wistar rats is also demonstrated.}, archive = {J_JACS}, author = {Snehanka Bose and Samya Sen and Taniya Mariyam and Aniket Jana and Nabanita Mukherjee and Uttam Pal and Batakrishna Jana and Surajit Ghosh and Amitava Das}, doi = {10.1021/jacs.5c11249}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37398--37413}, shortjournal = {J. Am. Chem. Soc.}, title = {Gelatinase-responsive short peptide conjugate as a precision therapy against methicillin-resistant staphylococcus aureus}, volume = {147}, year = {2025}, }
• (2025). Prevalent room-temperature phosphorescence in natural nuts. JACS, 147(41), 37385--37397. (www)

  @article{ , abstract = {Room-temperature phosphorescence (RTP) has extensive applications in various fields such as data encryption, chemical sensing, optoelectronic displaying, and time-resolved bioimaging, yet most materials are fossil fuel-based. Recently, an increasing interest has emerged with respect to natural organic RTP. However, the cases are rare and the structure–property relationships remain poorly understood. Here, natural nuts with prevalent RTP characters were unveiled with comprehensive elucidation on the molecular origins, representing an alternative reservoir of sustainable and clean RTP materials. The nuts generally show seconds-long afterglow at ambient conditions, relying heavily on excitation wavelengths and nut composition. RTP of intrinsic nutrients including aromatic vitamins, aromatic nucleobases, and aromatic amino acids dispersed in nonaromatic natural media at low contents (as low as the ppm level) covers the entire RTP spectra of nuts, spanning <400 to >700 nm. Different aromatic nutrients require varied excitation energies and are capable of showing distinct RTP colors. Thus, biomatrices and diverse aromatic nutrients should rationalize excitation-dependent broad-band nut RTP synergistically, both of which should not be overlooked. Furthermore, nut RTP can be facilely modulated by trace polyaromatic phosphors, facilitating color-tunable 3D afterglow for multilevel information storage. This work considerably expands the scope of natural RTP based on abundant sources and provides new insights into the underlying mechanism, opening a broad avenue for applying sustainable luminescent materials that can be produced at a large scale and low cost.}, archive = {J_JACS}, author = {Ruizhi Yang and Hao Su and Jiajun Song and Chendong Xie and Biao Chen and Xueyu Li and Jun Jiang and Guoqing Zhang and Yi Luo and Xuepeng Zhang and Ben Zhong Tang}, doi = {10.1021/jacs.5c10814}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37385--37397}, shortjournal = {J. Am. Chem. Soc.}, title = {Prevalent room-temperature phosphorescence in natural nuts}, volume = {147}, year = {2025}, }
• (2025). Bambusuril small-molecule ionic isolation lattices for exciton coupled dimers and dicationic fluorophores. JACS, 147(41), 37372--37384. (www)

  @article{ , abstract = {Ionic self-assembly of molecular fluorophores is a promising avenue to program properties into optical materials. Controllable optical energies, lifetimes, exciton hopping and energy transfer have been engineered in small-molecule, ionic isolation lattices (SMILES) by using preferred binding stoichiometries that pair singly charged complexes (−1) with singly charged fluorophores (+1) to isolate them on lattice sites. We hypothesize that these rules can be generalized if charge balance can be expanded from one anion and one cation to pair of each ion, i . e ., from 1:1 to 2:2. If true, opportunities emerge to instead bring two cations together as discrete isolated dimers potentially turning on new optical states. We tested these ideas by exchanging cyanostar receptors for bambusuril receptors known to host two chloride anions. When charge matched with two monocationic cyanines in a 2:2 ratio, the crystal structure reveals π-stacked dimers form into isolated emitters that pack charge-by-charge with (bambusuril)·(chloride) 2 complexes. New red-shifted emission at 615 nm from cyanine–cyanine dimers and DFT calculations agree with Kasha’s theory of exciton coupling as offset H-dimers. The bambusuril can also host single anions leading to isolation of single cyanines with monomer emission at 507 nm. In addition, we also discovered a SMILES material using dicationic fluorophores (+2) in the form of styryldipyrylium and a new packing stoichiometry with bambusuril. Stoichiometry, anion identity and charge define crystal engineering rules of bambusuril SMILES. Thus, we add valence control to the rules for isolation of discrete dye dimers and inclusion of discrete dicationic dyes in emissive SMILES materials.}, archive = {J_JACS}, author = {Andrew H. Olsson and Vikrant Tripathy and Nobuyuki Yamamoto and Junichi Usuba and Jeno S. Leavitt and Elizabeth A. Kambas and Katherine L. VanDenburgh and Krishnan Raghavachari and Grace G. D. Han and Bo W. Laursen and Amar H. Flood}, doi = {10.1021/jacs.5c11141}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37372--37384}, shortjournal = {J. Am. Chem. Soc.}, title = {Bambusuril small-molecule ionic isolation lattices for exciton coupled dimers and dicationic fluorophores}, volume = {147}, year = {2025}, }
• (2025). Chemoenzymatic synthesis of asymmetric bisecting bi-, tri-, and tetra-antennary N-glycans. JACS, 147(41), 37357--37371. (www)

  @article{ , abstract = {N -Acetylglucosaminyltransferase-III (GnT-III) is a glycosyltransferase that can install a β1,4-linked N -acetylglucosamine (GlcNAc) residue at the central β-mannoside of N -glycans. The resulting so-called bisecting GlcNAc is not further extended by glycosyl transferases and has been implicated in a wide range of biological processes. The molecular mechanism by which bisection modulates the biosynthesis of N -glycans and influences molecular recognition is not well understood, which is due to a lack of well-defined N -glycans with and without bisection. We describe a chemoenzymatic methodology that can readily provide a wide range of asymmetrical bisecting bi-, tri-, and tetra-antennary N -glycans. It was found GnT-III can act on bi-, tri-, and tetra-antennary N -glycans and can also accept N -glycans having a β1,2GlcNTFA or GlcN 3 moiety at the α1,3- or α1,6-antenna making it possible to prepare panels of asymmetrical N -glycans with and without bisection and having different patterns of sialylation and fucosylation. Enzyme kinetic experiments showed GnT-III preferentially modifies biantennary glycans. The compounds were printed as a glycan microarray, which was screened for lectin binding. It was found that some lectins preferentially bind to bisecting glycans, whereas others do not tolerate or are not affected by this modification. We investigated receptor specificities of human H1N1 and H3N2 influenza viruses and animal H5N1 viruses that pose a pandemic threat, including a virus that has become endemic in cattle. The H1N1 and H3N2 viruses did not tolerate bisection, whereas it did not affect H5N1 viruses. A/bovine had the broadest receptor specificity, providing a rationale for its wide host range.}, archive = {J_JACS}, author = {Balasaheb K. Ghotekar and Seema K. Bhagwat and Pradeep Chopra and Thomas Buckley and Geert-Jan Boons}, doi = {10.1021/jacs.5c11009}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37357--37371}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemoenzymatic synthesis of asymmetric bisecting bi-, tri-, and tetra-antennary N-glycans}, volume = {147}, year = {2025}, }
• (2025). Ligand-controlled Alkylation–Heck–C(sp3)–H annulation cascade for a divergent synthesis of cyclobutane- and cyclopropane-containing heterocycles. JACS, 147(41), 37347--37356. (www)

  @article{ , abstract = {The ability to harness divergent reactivity and selectively dictate product outcomes from simple precursors has been a longstanding challenge in organic chemistry. Specifically, the realization of this goal in C–H functionalization remains a considerable challenge due to the inherent difficulties in achieving precise regioselective control in the presence of multiple, stereoelectronically similar C–H bonds. Herein, we report a two-component C(sp 3 )–H annulation cascade reaction that effectively unites ortho -bromophenols or ortho -bromoanilines with allylic alkyl bromides and provides direct access to two different heterocyclic scaffolds via precise ligand-controlled reactivity. Our newly developed transformation proceeds via an initial alkylation followed by a regioselective Heck carbopalladation and is terminated by a regiodivergent C(sp 3 )–H annulation of a γ-methylene or a δ-methyl C–H bond. Moreover, this C–H annulation platform provides a divergent access to spirocyclic cyclobutane or fused cyclopropane scaffolds that are frequently featured in natural products or medicinally relevant molecules. This cascade transformation possesses a broad substrate scope with respect to the aryl as well as alkyl halide components, showcased by the preparation of >60 heterocyclic products with excellent regiocontrol.}, archive = {J_JACS}, author = {Wan-Xu Wei and Yangjin Kuang and Martin Tomanik}, doi = {10.1021/jacs.5c11047}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37347--37356}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand-controlled Alkylation–Heck–C(sp3)–H annulation cascade for a divergent synthesis of cyclobutane- and cyclopropane-containing heterocycles}, volume = {147}, year = {2025}, }
• (2025). Coacervate droplets drive organocatalyzed aqueous C–C bond formation via interfacial activation. JACS, 147(41), 37337--37346. (www)

  @article{ , abstract = {Compartmentalization is central to the regulation of biochemical reactions in living systems, with membraneless organelles formed by liquid–liquid phase separation (LLPS) offering dynamic environments that influence biochemical reactivity. Inspired by this principle, coacervate microdroplets have emerged as promising synthetic analogues for modulating both enzymatic and nonenzymatic reactions in water. Here, we report that coacervates can actively promote aqueous N-heterocyclic carbene (NHC) organocatalysis, enabling base-free carbon–carbon (C–C) bond formation via the Stetter reaction. Using a newly designed amphiphilic thiazolium precatalyst, we show that model polyelectrolyte coacervates not only sequester organic droplets containing the Stetter reactants, creating a unique coacervate/organic droplet interface, but also directly facilitate carbene generation. Remarkably, this activation arises from a strong electrostatic interaction between the thiazolium salt and the polyanion, which spontaneously coacervate together to form catalytically active droplets. These coacervates act as sacrificial reaction compartments, dissolving upon carbene formation while driving C–C bond formation in the absence of added base, highlighting the capacity of coacervates to restructure and respond dynamically during catalysis. Together, our results uncover a previously unrecognized mode of organocatalyst activation within LLPS-based materials, expanding the functional scope of phase-separated systems and suggesting broader potential for leveraging multiphase systems to modulate reactivity through emergent interfacial phenomena in water.}, archive = {J_JACS}, author = {Kevin Peyraud-Vicré and Charline Dechamps and Nicolas Martin and Valérie Desvergnes}, doi = {10.1021/jacs.5c10731}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37337--37346}, shortjournal = {J. Am. Chem. Soc.}, title = {Coacervate droplets drive organocatalyzed aqueous C–C bond formation via interfacial activation}, volume = {147}, year = {2025}, }
• (2025). Unraveling the molecular pathways for structure “Making” and “Breaking” by ions in water. JACS, 147(41), 37328--37336. (www)

  @article{ , abstract = {Aqueous anions play a crucial role in chemical and biological processes. They are traditionally classified as “structure makers” or “structure breakers” based on their impact on the viscosity of electrolyte solutions. Until now, this behavior has been assumed to stem from a single restructuring mechanism of the hydrogen (H) bonding network of water, that could align with macroscopic properties. Correlated Vibrational Spectroscopy (CVS) measurements reveal that this is not the case. Rather, anions modify water–water H-bonds through multiple distinct pathways, with frequency shifts correlating with charge transfer, and intensity changes quantifying variations in the number of interacting/orientationally cross-correlated H-bonds. The different ways through which anions impact water structure can be explained in terms of Hard–Soft-Acid–Base theory. Hard anions only affect water H-bonds through electrostatics. By contrast, soft anions weaken the H-bonds via charge transfer but simultaneously increase their concentration. The two effects for soft anions nearly cancel each other out in terms of structure breaking/making, resulting in macroscopic behavior that is similar to hard anions in spite of dramatically different molecular-level effects.}, archive = {J_JACS}, author = {Mischa Flór and Viktor Vorobev and Varun Mandalaparthy and Nico F. A. van der Vegt and Paul S. Cremer and Sylvie Roke}, doi = {10.1021/jacs.5c10984}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37328--37336}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the molecular pathways for structure “Making” and “Breaking” by ions in water}, volume = {147}, year = {2025}, }
• (2025). DNA condensation-inspired assembly of DNA nanotubes into reversible superstructures: A base pairing-orthogonal way to create rings, bundles, or vast networks. JACS, 147(41), 37317--37327. (www)

  @article{ , abstract = {By offering exquisite programmability, sequence-specific DNA self-assembly is the foundation of structural DNA nanotechnology but necessitates custom-designed DNA strands. Finding assembly principles orthogonal to base pairing is thus desirable not only to organize DNA in a sequence-independent manner but also to bring additional levels of control over preformed DNA self-assembled structures. Here, we report that self-assembled DNA nanotubes, upon the addition of DNA-condensing multivalent cations, including the naturally occurring polyamines spermidine and spermine, spontaneously condense to form higher-order structures including well-defined micrometer-sized rings and 30 to 60 nm wide bundles, in which DNA strands are parallelly packed with an interspacing ranging from 2.5 to 3 nm. In the semidilute regime, a new organization into vast tridimensional networks is observed for a specific range of charge ratios, prior to the formation of highly clustered bundles. We demonstrate that the process is electrostatically driven, conferring a ubiquitous character to this assembly principle. We report in particular a pivotal role of the counterion valency (the higher it is, the lower the charge ratio required), emphasizing the role of DNA neutralization through the entropically driven exchange between DNA counterions and the condensing agents. We also show an important role of DNA concentration for controlling the individual or interconnected nature of the formed structures as well as favoring the nanotube assembly. We finally devise methods for additional control, such as superstructure disassembly upon monovalent ion addition or photocontrol using a photosensitive DNA-condensing agent.}, archive = {J_JACS}, author = {Laura Bourdon and Xiang Zhen Xu and Laurent J. Michot and Mathieu Morel and Sergii Rudiuk and Ayako Yamada and Damien Baigl}, doi = {10.1021/jacs.5c10921}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37317--37327}, shortjournal = {J. Am. Chem. Soc.}, title = {DNA condensation-inspired assembly of DNA nanotubes into reversible superstructures: A base pairing-orthogonal way to create rings, bundles, or vast networks}, volume = {147}, year = {2025}, }
• (2025). Ligand architecture control geometry, self-sorting, and postsynthetic modification in anthracene-based organometallic assemblies. JACS, 147(41), 37306--37316. (www)

  @article{ , abstract = {Although various skeletons of organic ligands have been applied to achieve the structural diversity of metallasupramolecular assemblies, limited approaches are available for organometallic cluster-based assemblies. Herein, we present how the architecture of anthracene-based ligands dictated the structure and properties of organometallic cluster-based assemblies. The combination of Pt 3 -cluster node [(Tr 2 Pt 3 )(CH 3 CN) 3 ][BF 4 ] 2 (Tr = cycloheptatrienyl ring) with disubstituted-anthracene ligands ( L1 – L3 ) selectively synthesize the first (Tr 2 Pt 3 ) 8 L 12 -type cubic assembly 1 and cylindric assembly 2 by altering coordination parameters of ligands and noncovalent interactions (π–π stacking and C–H···π interactions). Lengthening L3 with functional linkers gives rise to an unprecedented (Tr 2 Pt 3 ) 2 L 3 -type self-penetrated assembly 3 with the assistance of π···π stacking interactions between three consecutive stacked anthracene skeletons. Interestingly, synergistically weakening such π···π stacking among anthracene skeletons but increasing it between Pt 3 -cluster nodes produces a triple helicate assembly 4 . The ligand architecture also affects the postsynthetic modification (PSM) reactivity of these Pt 3 -cluster node-based supramolecular assemblies. While triple helicate 5 underwent PSM smoothly upon irradiation without photosensitizers, other assemblies remained photochemically inert under similar conditions. Systematic self-sorting investigations show how marginal differences in ligands can selectively lead to narcissistic and social behaviors in complex systems. The results offer valuable design principles and emphasize the critical role that ligand architecture plays in constructing novel organometallic cluster-based assemblies.}, archive = {J_JACS}, author = {Sha Bai and Lu-Wen Zhang and Yu-Tong Zhang and Ying-Feng Han}, doi = {10.1021/jacs.5c10725}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37306--37316}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand architecture control geometry, self-sorting, and postsynthetic modification in anthracene-based organometallic assemblies}, volume = {147}, year = {2025}, }
• (2025). C–H bond activation via photolysis of a mn nitride ligand radical complex. JACS, 147(41), 37299--37305. (www)

  @article{ , abstract = {We report the thermal and photoactivation of a solution-stable Mn nitride ligand radical complex [Mn V (Sal NMe2• )N] + , which facilitates N–N bond homocoupling to generate N 2 , a reaction commonly observed in Mn VI nitrides. Theoretical calculations suggest that the nitride is ambiphilic, facilitating the N–N bond formation. Notably, photoactivation of the Mn V ligand radical at room temperature enables rapid C–H bond activation, leading to the formation of C–N insertion products, excluding dihydroanthracene where a desaturation product is observed. This study presents a rare example of photochemically driven intermolecular N atom transfer to a C–H bond mediated by a first-row Mn terminal nitride complex, made possible by the unique stability and turn-on reactivity of the oxidized ligand radical electronic structure.}, archive = {J_JACS}, author = {Samyadeb Mahato and Omar Castro-Sandoval and Vanessa Cheung and Ryan M. Clarke and Saeid Kamal and Loren Kaake and Olivier Jarjayes and Fabrice Thomas and Tim Storr}, doi = {10.1021/jacs.5c10538}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37299--37305}, shortjournal = {J. Am. Chem. Soc.}, title = {C–H bond activation via photolysis of a mn nitride ligand radical complex}, volume = {147}, year = {2025}, }
• (2025). Inhibiting isomerization via confinement in Ice–Water interfaces enhances stereoselectivity in [2 + 2] cycloaddition. JACS, 147(41), 37290--37298. (www)

  @article{ , abstract = {Cyclobutanes serve as fundamental motifs in natural products, bioactive substrates, and pharmaceuticals. Despite numerous efforts to synthesize cyclobutane products, particularly through light-driven [2 + 2] cycloaddition, significant challenges persist, such as the rapid cis / trans isomerization of olefin substrates and the thermodynamic difficulty in synthesizing syn- cyclobutane derivatives, which limit their widespread application across various fields. Here, by introducing a confined ice–water interface to mediate the [2 + 2] photocycloadditions, we not only efficiently inhibit reactant isomerization but also achieve the syn- cyclobutane products ( syn- dimer > 95%) without the need for additional chemical auxiliary reagents. The specific proportional relationship of reaction kinetics and the active ice surface area reveals the unique catalytic role of the ice surface in [2 + 2] cycloaddition reactions. Theoretical simulations and experimental studies demonstrate that at the ice–water interface, solute molecules tend to adsorb on the ice surface and form molecular pairs in a prereactive arrangement. Compared to molecular monomers, these molecular pairs exhibit a higher energy barrier for photoisomerization and tend to align in a syn- configuration, thereby inhibiting isomerization and facilitating stereoselective [2 + 2] cycloaddition. This work highlights the potential of ice-assisted photochemical methods in advancing sustainable and environmentally friendly chemical synthesis.}, archive = {J_JACS}, author = {Shi-Peng Wan and Dan Wang and Jiahui Wu and Shizhong Zhang and Xiaofei Chen and Chuanbiao Zhang and Jie Liu and Xin Zhou and Zhiyuan He and Jianjun Wang}, doi = {10.1021/jacs.5c10587}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37290--37298}, shortjournal = {J. Am. Chem. Soc.}, title = {Inhibiting isomerization via confinement in Ice–Water interfaces enhances stereoselectivity in [2 + 2] cycloaddition}, volume = {147}, year = {2025}, }
• (2025). Thiocrown ether: Reversing SN1 to SN2 pathways in 1,2-cis phosphoryl glycosylation. JACS, 147(41), 37280--37289. (www)

  @article{ , abstract = {Glycosyl phosphosaccharides, a ubiquitous and crucial family of complex carbohydrates, widely occur in living organisms. Considering the importance in various physiological and pathophysiological processes, the synthesis of glycosyl phosphosaccharides is a key scientific issue in carbohydrate chemistry. However, their preparation presents two major challenges: achieving high stereoselectivity in phosphorylated glycosides and maintaining the stability of labile phosphoester linkages. Here, we redesigned the classical Koenigs–Knorr glycosylation reaction to efficiently synthesize 1,2- cis phosphorylated glycosides, using 1,7,13-trithio-18-crown-6 as a rationally designed additive. The key to this strategy is that the thiocrown ether could reverse the reaction mechanism from S N 1 to S N 2 pathways by modulating the interaction between silver and glycosyl chloride donors. This method enables phosphoryl glycosylation to proceed at room temperature without the use of acid or base. The feasibility of this strategy is demonstrated by the synthesis of 54 complex glycosyl phosphosaccharides with high efficiency and stereoselectivity, the gram-scale production of UDP-6-N 3 -Glc, and the synthesis of a tetrasaccharide diphosphate derived from Haemophilus influenzae type C.}, archive = {J_JACS}, author = {Ru Xia and Xinyue Fu and Shengzhou Ma and Wenli Xiao and M. V. Krishna Rao and Peihao Zhao and Liuqing Wen and Jiabin Zhang}, doi = {10.1021/jacs.5c10568}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37280--37289}, shortjournal = {J. Am. Chem. Soc.}, title = {Thiocrown ether: Reversing SN1 to SN2 pathways in 1,2-cis phosphoryl glycosylation}, volume = {147}, year = {2025}, }
• (2025). Electrochemical C–H functionalization and defunctionalization of polystyrene. JACS, 147(41), 37272--37279. (www)

  @article{ , abstract = {Covalent modification of simple commodity polymers by C–H functionalization is an efficient way to access new structure–property characteristics and a promising strategy for repurposing plastic waste. We developed an electrochemical method for preparing sulfonium polyelectrolytes by C–H functionalization of polystyrene (PS) from simple thianthrenes. This methodology affords access to structurally diverse polysulfonium products with a controllable degree of functionalization and tunable properties. Modular access to new thianthrenium-functionalized PS materials in this fashion enabled detailed structure–property studies, which revealed that the thianthrenium polymers exhibit high thermal stability, multiphase behavior, and photochemical reactivity that introduces photoacid generator functionality and the ability to undergo defunctionalization.}, archive = {J_JACS}, author = {Roxanne A. Naumann and Maribel A. Clerk and Ritchie E. Hernandez and Nathan A. Romero}, doi = {10.1021/jacs.5c10490}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37272--37279}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical C–H functionalization and defunctionalization of polystyrene}, volume = {147}, year = {2025}, }
• (2025). Magnetic sorting of chiral pharmaceuticals using Fe3O4–Cellulose acetate phthalate nanosplitters. JACS, 147(41), 37265--37271. (www)

  @article{ , abstract = {Natural polymers have been used as stereoselective crystallization inhibitors benefiting from their intrinsic hierarchical chirality. However, the chirality of their constituent unit is intrinsically immutable due to the natural biosynthetic origin of biopolymers, fundamentally limiting their versatility, as they cannot be synthetically inverted to target the opposite enantiomer. Herein, we designed a magnetic nanosplitter by grafting cellulose acetate phthalate onto Fe 3 O 4 nanoparticles to selectively interact with the crystals of one enantiomer, enabling them to form magnetized crystals that can be efficiently separated from their racemic conglomerate with an external magnetic field. This approach enabled the resolution of racemic nimodipine, simultaneously yielding considerable quantities of magnetic S -crystals and nonmagnetic R -crystals. It should be mentioned that using pristine natural polymer derivatives can only obtain crystals of one enantiomer, the less pharmacologically active R -crystals. Further structural investigation revealed that the chain length of the polymer and the size of Fe 3 O 4 nanoparticles significantly influence the resolution of the nanosplitters. When containing cellulose acetate phthalate with a molecular weight above 20 kDa and Fe 3 O 4 cores sized between 5 and 14 nm, the optimal performance has been achieved, producing S - and R -enantiomers with 82 ee % and 92 ee %, respectively, and a combined yield of 40%. This work pioneers a magnetically driven separation strategy that can be seamlessly integrated into automated chiral separation platforms.}, archive = {J_JACS}, author = {Yingze Liu and Yifu Chen and Jie Zhang and Xinhua Wan}, doi = {10.1021/jacs.5c10439}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37265--37271}, shortjournal = {J. Am. Chem. Soc.}, title = {Magnetic sorting of chiral pharmaceuticals using Fe3O4–Cellulose acetate phthalate nanosplitters}, volume = {147}, year = {2025}, }
• (2025). Zn microenvironment engineering for aryl-c(sp2) cleavage to phenols and tertiary amines. JACS, 147(41), 37255--37264. (www)

  @article{ , abstract = {Cleaving inert aryl-C(sp 2 ) bonds present a fundamental catalytic challenge due to their intrinsic robustness, yet it is essential for valorizing lignin into value-added chemicals. Current strategies predominantly convert aromatic rings to phenols at the expense of side-chain carbon utilization, compromising the atom economy. We report zinc coordination microenvironment engineering to achieve efficient aryl-C(sp 2 ) cleavage in phenolic substrates with transformable side chains (e.g., ketones and alkenes), concurrently yielding phenols and tertiary amines. A nitrogen-coordinated zinc catalyst (ZnNC-900) delivered 90.0% phenol and 82.7% N,N-dimethylethylamine from 4-methoxyacetophenone. Significantly, this catalytic system demonstrates broad activity toward multiple native lignin sources, with bamboo lignin processing on a 5.0 g scale affording 1.04 g of alkyl-free phenolics (20.8 wt %) and 0.67 g of N,N-dimethylethylamine (13.4 wt %). Mechanistic studies via spectroscopy and DFT calculations demonstrate that the zinc microenvironment dictates the reaction pathway. Specifically, the ZnNC-900 catalyst, featuring zinc coordinated by three pyrrolic-N atoms and one pyridinic-N atom, reduces the energy barrier by 0.71 eV relative to ZnNC-600 (which exclusively has pyridinic-N coordination). This work provides a catalytic strategy to overcome the limitations of low atom economy, harsh conditions, and narrow substrate scope in lignin valorization.}, archive = {J_JACS}, author = {Lulin Wang and Yike Huang and Yu Xin and Tianjiao Wang and Sen Luan and Minghua Dong and Bin Zhang and Xiaojun Shen and Qinglei Meng and Buxing Han and Huizhen Liu}, doi = {10.1021/jacs.5c10429}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37255--37264}, shortjournal = {J. Am. Chem. Soc.}, title = {Zn microenvironment engineering for aryl-c(sp2) cleavage to phenols and tertiary amines}, volume = {147}, year = {2025}, }
• (2025). Chelation-driven dissolution and single-crystal growth of hybrid metal organochalcogenide semiconductors by polydentate amines. JACS, 147(41), 37242--37254. (www)

  @article{ , abstract = {The ability to grow single crystals is critical to modern society, particularly forming the foundation of the semiconductor industry that drives transformative innovations. While inorganic semiconductors are typically grown using melt-based methods, and organic semiconductors via solution processing, these approaches are often unsuitable for hybrid organic–inorganic semiconductors, which tend to exhibit low thermal stability and high solvent resistance. Here, we report a general solution-based strategy to overcome this challenge by exploiting polydentate amine solvents to dissolve and recrystallize previously intractable metal organochalcogenides (MOCs)─an emerging family of hybrid semiconductors, with potentials for robust luminescence, strong exciton binding energy, and electronic anisotropy. Using silver phenylselenide as a model system, we show that chelation-driven solubility in amines enables the growth of up to 1.02 cm × 0.54 cm single crystals with enhanced spectral purity, and that this strategy is general across MOC derivatives with diverse organic and chalcogen components. Recrystallization from these solvents yields high-quality single crystals of 15 MOCs, including eight previously unreported structures and three adopting noncentrosymmetric or polar space groups. Mechanistic studies reveal that dissolution proceeds via fragmentation into neutral, nanoscale polymeric units rather than ionic dissociation. These findings not only deepen the understanding of MOC solubility but also establish a broadly applicable platform for accessing single crystals of hybrid semiconductors. Together with the observation that several MOCs adopt 2D layered and noncentrosymmetric architectures, this work positions MOCs as a new family of next-generation, solution-processable semiconductors and opens avenues for crystallizing other insoluble hybrid materials.}, archive = {J_JACS}, author = {Rattapon Khamlue and Petcharaphorn Chatsiri and Tomoaki Sakurada and Jesadaporn Chotimook and Pimpan Leangtanom and Pongkamon Prayongkul and Thassanant Atithep and Jintara Padchasri and Pinit Kidkhunthod and Martin Vacha and Pichaya Pattanasattayavong and Watcharaphol Paritmongkol}, doi = {10.1021/jacs.5c10260}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37242--37254}, shortjournal = {J. Am. Chem. Soc.}, title = {Chelation-driven dissolution and single-crystal growth of hybrid metal organochalcogenide semiconductors by polydentate amines}, volume = {147}, year = {2025}, }
• (2025). Triggering photoluminescence in high-nuclear silver nanoclusters via extra silver atom incorporation. JACS, 147(41), 37231--37241. (www)

  @article{ , abstract = {Photoluminescence (PL) in silver (Ag) nanoclusters (NCs) is intrinsically linked to their structural architecture, yet their low quantum yield at room-temperature hinders practical applications. Although various strategies have been explored to enhance the PL efficiency of Ag NCs, their effectiveness in high-nuclear Ag NCs remains largely uncertain. Here, we demonstrate a 77-fold enhancement in room-temperature PL quantum yield by modulating both radiative and nonradiative decay pathways in high-nuclear Ag NCs. A comparative study of two anion-templated Ag NCs, differing by a single Ag atom in the outermost shell, reveals that this substitution lowers structural symmetry, thereby increasing the radiative decay rate. This structural modification is facilitated by the alterations in ligands and their coordination environment, which simultaneously suppress atomic fluctuations and reduce the nonradiative decay component. Furthermore, theoretical investigations corroborate these findings, indicating that the incorporation of an additional Ag atom modifies the electronic distribution, thereby influencing the PL characteristics and ultimately altering the emission mechanism. These insights provide a deeper understanding of the structure–property relationship in high-nuclear Ag NCs and offer a rational strategy for enhancing their luminescence efficiency for potential applications.}, archive = {J_JACS}, author = {Aoi Akiyama and Sakiat Hossain and Sourav Biswas and Takafumi Shiraogawa and Pei Zhao and Mana Nakamoto and Daiji Ogata and Tokuhisa Kawawaki and Yoshiki Niihori and Junpei Yuasa and Masahiro Ehara and Yuichi Negishi}, doi = {10.1021/jacs.5c10289}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37231--37241}, shortjournal = {J. Am. Chem. Soc.}, title = {Triggering photoluminescence in high-nuclear silver nanoclusters via extra silver atom incorporation}, volume = {147}, year = {2025}, }
• (2025). Hydrogen-based reduction boosts sustainable iron production from red mud. JACS, 147(41), 37223--37230. (www)

  @article{ , abstract = {Extracting iron from red mud─a caustic waste formed during the refinement of bauxite into alumina─provides a promising pathway toward the sustainable treatment of the unwanted byproduct and the supply of an important resource, but existing approaches raise environmental concerns and are financially unattractive. Here, we describe a plasma-enhanced chemical vapor reduction process that allows for efficient extraction of iron from red mud by using hydrogen as the reducing agent. This process, powered by electricity, can generate iron at temperatures down to 900 °C, with a high grade up to 71% and an iron recovery rate of 88.1%, showing advantages over conventional hydrometallurgy and pyrometallurgy methods in terms of cost and environmental footprint. The achieved performance can be attributed to the energetic hydrogen radicals generated in situ that make the iron reduction thermodynamically favorable. Our results suggest a promising path for economically viable and emission-free extraction of iron from red mud.}, archive = {J_JACS}, author = {Wen-Long Liang and Yu-Cai Zhang and Ye-Cheng Li and Yuan-Qin Chang and Min-Rui Gao}, doi = {10.1021/jacs.5c10175}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37223--37230}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen-based reduction boosts sustainable iron production from red mud}, volume = {147}, year = {2025}, }
• (2025). High-throughput discovery illuminates design principles and limits for long-lived charged species in organic electrolytes. JACS, 147(41), 37211--37222. (www)

  @article{ , abstract = {The chemical stability of charged molecules in all-organic redox flow batteries (RFBs) is required for the prolonged operation of these devices. Molecular engineering and electrolyte optimization are used to mitigate parasitic reactions and extend the lifetimes of the charge carriers. However, how much can structural variation extend the lifetime? To probe this query, we designed a high-throughput kinetic study of the radical cation of N -methylphenothiazinium, guided by statistical sampling and learning algorithms. Using Argonne’s autonomous discovery facility, we conducted over 6,000 kinetic experiments with robotic sample preparation, parallel kinetic measurements, and machine learning inputs, testing 188 solvent molecules selected from a space of over 540 candidates from 11 chemical classes. Algorithmic selections guided us to stable solvent candidates, which were further tested in high concentration with and without supporting electrolyte. Our findings reveal the inherent difficulty of exceeding the current state of the art through solvent variation. The desired stability is statistically rare and poorly predictable. Among the many tested, only three solvents significantly outperformed our baseline, acetonitrile─and none by more than a factor of 3─suggesting a general challenge in achieving the necessary techno-economic targets. We suggest that self-discharge through solvent homolysis is the cause of the observed limitations. Several structural motifs contribute to >1,000 h half-life stability including molecular simplicity, symmetry, oxidation complement, and strategic fluorination. Importantly, this workflow establishes effective assays for diagnosing and predicting oxidative stress for highly stable liquid electrolytes in all batteries.}, archive = {J_JACS}, author = {Lily A. Robertson and Ilya A. Shkrob and Ryan Lewis and Logan Ward and Rafael Vescovi and Benjamin T. Diroll}, doi = {10.1021/jacs.5c10140}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37211--37222}, shortjournal = {J. Am. Chem. Soc.}, title = {High-throughput discovery illuminates design principles and limits for long-lived charged species in organic electrolytes}, volume = {147}, year = {2025}, }
• (2025). Main-chain ketone installation in polyethylene chains: A metal-free strategy toward photodegradable plastics. JACS, 147(41), 37204--37210. (www)

  @article{ , abstract = {Polyethylene with in-chain isolated ketones is an attractive target for achieving photodegradability while maintaining polyolefin material properties. This work reports a method to functionalize post-consumer polyethylene through radical C–H activation to install TEMPO functionalities and subsequent oxidation to obtain in-chain isolated ketones without compromising the polymer molecular weights. This process does not require metals, catalysts, or expensive reagents and allows tunable ketone incorporation up to 3 mol %. The thermal and mechanical properties were investigated to demonstrate that the ketone-containing polyethylene could potentially work as a photodegradable alternative of existing polyethylene. Photodegradation of the ketone-containing polyethylene reveals a clear decrease in molecular weights and suggests random installation of functionalities. This approach enables the conversion of post-consumer polyethylene into ketone functionalized materials through simple chemical transformations.}, archive = {J_JACS}, author = {Shilin Cui and Zhipeng Lu and Jaqueline C. Lopez and Moritz Kränzlein and Christopher J. Kim and Song Lin and Anne M. LaPointe and Geoffrey W. Coates}, doi = {10.1021/jacs.5c09943}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37204--37210}, shortjournal = {J. Am. Chem. Soc.}, title = {Main-chain ketone installation in polyethylene chains: A metal-free strategy toward photodegradable plastics}, volume = {147}, year = {2025}, }
• (2025). An axle-cycle induction strategy for the synthesis of chiral [2]Rotaxanes. JACS, 147(41), 37196--37203. (www)

  @article{ , abstract = {Chiral rotaxanes have attracted considerable attention due to their distinctive properties resulting from their unique mechanically interlocked structures. However, the construction of chiral rotaxanes based on the dynamic racemic pillar[5]arene ( DMP5A ) by induction remains uncharted territory. In this study, we provide a method for synthesizing chiral rotaxanes based on DMP5A via an axle-cycle induction strategy. Amino acid derivatives serve as both chiral axles and chiral inducers for DMP5A , enabling the diastereoselective construction of chiral [2]rotaxanes. This axle-cycle induction strategy not only offers a synthetic method for DMP5A -based chiral rotaxanes with stereochemical control but also provides a foundation for chiral stationary-phase high-performance liquid chromatography (HPLC)-free (CSP-free) synthesis of mechanically interlocked molecules.}, archive = {J_JACS}, author = {Ranran Wang and Conghao Shi and Wang Xie and Yang Zhou and Shirong Ban and Guangzhou Xu and Juli Jiang and Zhigang Ni and Xiaoqi Wang and Xiancai Lu and Yong Liang and Leyong Wang}, doi = {10.1021/jacs.5c10122}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37196--37203}, shortjournal = {J. Am. Chem. Soc.}, title = {An axle-cycle induction strategy for the synthesis of chiral [2]Rotaxanes}, volume = {147}, year = {2025}, }
• (2025). Accurate prediction of mechanical property of organic crystals using molecular dynamics-based nanoindentation simulations. JACS, 147(41), 37186--37195. (www)

  @article{ , abstract = {Developing reliable methods to predict the mechanical response of organic crystals is essential due to their growing recognition as soft, compliant, lightweight, and ultrafast smart dynamic materials that have applications ranging from pharmaceuticals to biomaterials. Traditional experimental methods, such as nanoindentation, come with practical convenience such as simplicity and efficacy; however, they are restrictive with regard to the surface quality and are subject to other experimental constraints such as the availability of suitable samples and accessibility of as-grown crystal faces. Computational approaches, including quantum mechanics and classical molecular dynamics (MD), offer an alternative approach that is independent of the sample, yet they are known to vary greatly in their predictive accuracy. To account for this shortfall of predictive tools, in this study, we systematically benchmark three major computational methods, including density functional theory (DFT), MD-based approaches based on deformation, and direct nanoindentation simulations, against experimental Young’s moduli. Our results show that the MD-simulated process of indentation conforms most favorably with the experiments and has the lowest mean absolute error. The intermolecular interactions, crystal size, indenter spacing, and unloading rates are identified as the key factors that determine the stiffness, as given by the modulus. Our findings underscore the importance of incorporating both thermal effects and experimental conditions into computational models for improved predictive accuracy and highlight the potential of nanoindentation simulations as a reliable tool for the assessment of the mechanical properties and, possibly, also for the design of organic crystals with predetermined mechanical properties and dynamic behavior.}, archive = {J_JACS}, author = {Sara M. Elgengehi and Durga Prasad Karothu and Weiwei He and Rabindranath Paul and Serdal Kirmizialtin and Panče Naumov}, doi = {10.1021/jacs.5c09944}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37186--37195}, shortjournal = {J. Am. Chem. Soc.}, title = {Accurate prediction of mechanical property of organic crystals using molecular dynamics-based nanoindentation simulations}, volume = {147}, year = {2025}, }
• (2025). Highly OH– conductive membranes enabled by 2D-hydrogen bonding networks within layered confined nanofluidic channels. JACS, 147(41), 37176--37185. (www)

  @article{ , abstract = {Membranes that combine high OH – conductivity (>10 –2 S cm –1 ) with long-term stability remain urgently needed for energy-related devices. Herein, we present a general confined structure-controlled strategy to fabricate highly stable layered double hydroxide (LDH)-based membranes with high conductivity (450 mS cm –1 in 30 wt % KOH solution at 25 °C) enabled by tuning OH – transport through 2D- and 3D-hydrogen-bonding networks in layered confined nanofluidic channels. By controlling the interlayer spacing of LDH, distinct hydrogen bonding networks can be achieved, and the directional OH – transport in the layered confined channels can be accelerated efficiently in a 2D-hydrogen-bonding network. The designed membranes exhibit <1% mass degradation after more than 10,000 h in a 30 wt % KOH solution at 80 °C and work efficiently for use in alkaline water electrolyzers (∼1.7 V for over 4,000 h at 300 mA cm –2 ), anion exchange membrane water electrolyzers (∼1.65 V for over 2,000 h at 250 mA cm –2 ), and alkaline zinc–iron flow batteries (∼500 cycles at 260 mA cm –2 with energy efficiency >78%). This work shows that a membrane with both high OH – conductivity and stability is possible, offering a new and evolutionary option for alkaline-based energy-related devices.}, archive = {J_JACS}, author = {Jialin Li and Xiaomin Tang and Liping Zhi and Lixin Liang and Dongguo Li and Zhiqiang Liu and Anmin Zheng and Zhizhang Yuan and Xianfeng Li}, doi = {10.1021/jacs.5c09800}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37176--37185}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly OH– conductive membranes enabled by 2D-hydrogen bonding networks within layered confined nanofluidic channels}, volume = {147}, year = {2025}, }
• (2025). Ni–Zn dual-atom sites enable synergistic parallel pathways for efficient photosynthesis of H2O2 with long-term stability. JACS, 147(41), 37167--37175. (www)

  @article{ , abstract = {The photocatalytic coupling of oxygen reduction (ORR) and water oxidation (WOR) pathways presents a sustainable strategy to supplant the energy-intensive anthraquinone process for H 2 O 2 production. However, persistent challenges in radical-mediated catalyst degradation ( • O 2 – / • OOH/ • OH) and suboptimal charge dynamics continue to plague conventional photocatalytic systems. Herein, we anchored dual-atom Ni–Zn sites onto polymeric carbon nitride (PCN) to prepare an efficient photocatalyst ( Ni 1 Zn 1 -PCN ) for photocatalytic H 2 O 2 production. Interestingly, using oxygen and water as feedstocks, Ni 1 Zn 1 -PCN achieves a record yield of 1205.4 μmol g –1 h –1 with unprecedented operational stability (>376 h, TON = 2659.6), outperforming best reported catalysts. Mechanism studies revealed that the dual-atom Ni–Zn site could induce charge transfer excitation of the support PCN to suppress electron–hole recombination. In addition, the electronic interaction/modulation in the dual-active sites reduces the activation energy barriers of the WOR and the ORR, thereby achieving a high overall photocatalytic efficiency. This work marks a step forward in the development of efficient and durable photocatalytic H 2 O 2 synthesis, offering significant potential for industrial-scale renewable energy applications.}, archive = {J_JACS}, author = {Jia-Run Huang and Hui-Ying Chen and Hao-Lin Zhu and Pei-Qin Liao and Xiao-Ming Chen}, doi = {10.1021/jacs.5c09202}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37167--37175}, shortjournal = {J. Am. Chem. Soc.}, title = {Ni–Zn dual-atom sites enable synergistic parallel pathways for efficient photosynthesis of H2O2 with long-term stability}, volume = {147}, year = {2025}, }
• (2025). Photoredox/Ni-catalytic synthesis of cis-vinyl iodides from acetylene. JACS, 147(41), 37157--37166. (www)

  @article{ , abstract = {The stereoselective synthesis of cis -vinyl iodides represents a long-standing challenge in organic synthesis, with Stork–Zhao olefination remaining the benchmark methodology since its inception in 1989. Herein, we report a synergistic photoredox/nickel dual-catalytic system that enables the efficient cis -carboniodination of acetylene, affording cis -vinyl iodides with exceptional selectivity and 100% atom economy. Mechanistic studies reveal that the cis -insertion of an aryl-nickel intermediate into acetylene is pivotal for stereocontrol, while photoexcitation of the redox catalyst facilitates the generation of transient vinyl-Ni(III) species, thereby promoting reductive elimination to form the C–I bond with high fidelity. Furthermore, this protocol is extendable to the synthesis of vinyl ethers via tandem C–O coupling when alcohols are introduced into the reaction system. This operationally simple yet mechanistically sophisticated strategy not only offers a sustainable and atom-economical approach to cis -vinyl iodides and ethers but also establishes a versatile platform for the difunctionalization of acetylene under mild conditions.}, archive = {J_JACS}, author = {Kangkui Li and Yue Huang and Xianyang Long and Dong Zhu and Yang Chen and Shifa Zhu}, doi = {10.1021/jacs.5c08849}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37157--37166}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoredox/Ni-catalytic synthesis of cis-vinyl iodides from acetylene}, volume = {147}, year = {2025}, }
• (2025). Correlated calorimetric and potentiometric titration elucidates quantitative lithium cation coordination thermodynamics. JACS, 147(41), 37144--37156. (www)

  @article{ , abstract = {Understanding the thermodynamics of interactions within the coordination environment of Li + ions is critical for rational electrolyte design. Drawing a physical analogy to ligand–receptor binding in biological systems, in this work, we introduce a combined isothermal titration calorimetry (ITC) and potentiometric titration (PT) framework to quantitatively determine the Gibbs free energy (Δ G ), enthalpy (Δ H ), and entropy (Δ S ) associated with solvent displacement─an exemplar coordination sphere reaction that powerfully reports on the underlying energetics─in nonaqueous Li-based electrolytes. The physical understanding behind the solvent displacement scheme is first validated with Raman spectroscopy, such that the heat measured during ITC is confirmed to arise predominantly from differential changes in coordinated solvent as the bulk electrolyte composition is systematically modified. A statistical binding model is then developed to interpret the thermodynamic data and parametrize single-site displacement enthalpy and equilibrium constants in a set of exemplar dual-solvent electrolytes. The framework is tested across systems with both dissimilar (DMSO:acetonitrile or DMSO:PC) and structurally similar (EC:PC) solvents, revealing how subtle differences in solvent–cation interaction enthalpy and entropy govern coordination preferences. These results provide new experimental insight into the driving forces behind microscopic coordination sphere changes and offer a powerful approach to guide electrolyte formulation.}, archive = {J_JACS}, author = {Dhyllan A. Skiba and Aaron M. Melemed and Betar M. Gallant}, doi = {10.1021/jacs.5c08751}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37144--37156}, shortjournal = {J. Am. Chem. Soc.}, title = {Correlated calorimetric and potentiometric titration elucidates quantitative lithium cation coordination thermodynamics}, volume = {147}, year = {2025}, }
• (2025). Visualizing the three-dimensional arrangement of hydrogen atoms in organic molecules by coulomb explosion imaging. JACS, 147(41), 37133--37143. (www)

  @article{ , abstract = {Structure-sensitive methods based on femtosecond light or electron pulses are now making it possible to measure how molecular structures change during light-induced processes. Despite significant progress, high-fidelity imaging of nuclear positions remains a challenge even for relatively small molecular systems and, notably, regarding the positions of hydrogen atoms. As demonstrated in recent work, X-ray-induced Coulomb explosion imaging (CEI) may overcome this obstacle, as its sensitivity does not depend on the mass of the imaged atoms. The photoinduced ring opening of the heterocyclic molecule 2(5 H )-thiophenone has attracted recent interest. Here, we show that CEI offers a powerful route to imaging the peripheral H atoms in this molecule and thus, more generally, to tracking detailed nuclear motions (e.g., isomerizations) in organic molecules on ultrafast time scales. Specifically, we record momentum-space Coulomb explosion images that report on the three-dimensional positioning of all nuclei within the molecule, for instance, distinguishing H atoms in C–H bonds that lie within or are directed out of the plane defined by the heavy atoms. The prospect of imaging peripheral H atoms to probe photochemical dynamics is explored by coupling ab initio molecular dynamics with classical Coulomb explosion simulations, thereby differentiating potential photoproduct isomers, including those whose structures primarily differ in the position of the hydrogens.}, archive = {J_JACS}, author = {Alice E. Green and Keyu Chen and Surjendu Bhattacharyya and Felix Allum and Sergey Usenko and Michael N. R. Ashfold and Thomas M. Baumann and Kurtis D. Borne and Mark Brouard and Michael Burt and Basile F. E. Curchod and Benjamin Erk and Ruaridh J. G. Forbes and Lea M. Ibele and Rebecca A. Ingle and Huynh Van Sa Lam and Xiang Li and Kang Lin and Tommaso Mazza and Joseph W. McManus and Michael Meyer and Terence Mullins and Joao Pedro Figueira Nunes and Daniel E. Rivas and Aljoscha Roerig and Arnaud Rouzée and Philipp Schmidt and John Searles and Björn Senfftleben and Henrik Stapelfeldt and Rico Mayro P. Tanyag and Florian Trinter and Anbu Selvam Venkatachalam and Enliang Wang and Emily M. Warne and Peter M. Weber and Thomas J. A. Wolf and Till Jahnke and Artem Rudenko and Rebecca Boll and Daniel Rolles}, doi = {10.1021/jacs.5c08730}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37133--37143}, shortjournal = {J. Am. Chem. Soc.}, title = {Visualizing the three-dimensional arrangement of hydrogen atoms in organic molecules by coulomb explosion imaging}, volume = {147}, year = {2025}, }
• (2025). Photoelectrochemical hydride generation with oxide-coated silicon. JACS, 147(41), 37123--37132. (www)

  @article{ , abstract = {Photoelectrochemical generation of a potent organic hydride donor at silicon is demonstrated. Two different oxide-coated p-type silicon photoelectrodes reduced 1,2,3,5,6-pentamethyl-1 H -benzo[ d ]imidazol-3-ium hexafluorophosphate, [PMBI][PF 6 ], to its corresponding imidazole hydride, PMBIH, in the presence of a proton source. Under 1 sun illumination, in acetonitrile with 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) buffer, the p-Si photoelectrodes convert PMBI + to PMBIH with good Faradaic efficiencies (FEs): 78% FE at −2.3 V vs Fc +/0 for Si|TiO 2 and 83% FE at −2.6 V vs Fc +/0 for Si|SiO 2 (where Si|SiO 2 represents silicon coated with an oxide layer). Generally, the Si|TiO 2 catalyzed the reaction at milder potentials than Si|SiO 2 , but the Si|SiO 2 had better selectivity for PMBIH generation over H 2 evolution than Si|TiO 2 . In light of prior studies of these photoelectrodes, the differences in selectivity and onset potential suggest a difference in mechanism, likely an outer-sphere electron transfer (ET) mechanism at the SiO 2 surface and potentially a proton-coupled ET process at the TiO 2 surface. To help understand reaction efficiency and identify areas of improvement, a thermochemical model for understanding net hydride transfer from the semiconductor to an acceptor in solution was developed. We find that the reactions in the present system are quite downhill. The high overpotentials (even while maintaining selectivity over H 2 evolution) emphasize the need for improved catalysts. This approach to evaluate the thermodynamics of net hydride transfer should be broadly valuable for electrochemical and photoelectrochemical processes.}, archive = {J_JACS}, author = {Hannah S. Nedzbala and Rebecca E. Powers and Annie S. Knapp and Hyuenwoo Yang and Ryan J. Gentile and Pierpaolo Vecchi and John C. Dickenson and Jake T. Sirlin and Carrie L. Donley and Kenneth O. Chua and Paul J. Griffin and Andressa V. Müller and Renato N. Sampaio and Megan N. Jackson and Javier J. Concepcion and Gerald J. Meyer and James F. Cahoon and Gregory N. Parsons and Alexander J. M. Miller and Jillian L. Dempsey and James M. Mayer}, doi = {10.1021/jacs.5c08666}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37123--37132}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoelectrochemical hydride generation with oxide-coated silicon}, volume = {147}, year = {2025}, }
• (2025). Strained-induced morphological reconstruction of RuO2(110) thin-film electrocatalysts. JACS, 147(41), 37115--37122. (www)

  @article{ , abstract = {Strain is a widely used strategy for electrocatalyst engineering. Overstraining, however, can lead to unintentional materials transformation. We investigate the impact of strain on the surface morphology of a rutile RuO 2 (110) film grown on a symmetry-matching rutile TiO 2 (110) substrate. When the film thickness exceeds 9 nm, the RuO 2 surface relaxes by forming step edges that expose the {011} plane. Density functional theory (DFT) calculation shows that the (011) facet is among the lower energy surfaces of rutile RuO 2 , suggesting that this formation incurs minimal energetic penalties. In situ atomic force microscopy (AFM) shows that the film maintains the (110) structure of the terrace during electrochemistry. Inductively coupled plasma–mass spectrometry (ICP-MS) further reveals the insensitivity of the Ru dissolution to strain. Our findings show a strain-relieving pathway via surface reconstruction in RuO 2 (110) and provide an example of a strain-relieving mechanism that does not affect dissolution.}, archive = {J_JACS}, author = {Jacob Som and Austin J. Reese and Luka Mitrovic and R. Soyoung Kim and Shay McBride and Swapnil S. Nalawade and Shyam Aravamudhan and Geoffroy Hautier and Junko Yano and Darrell G. Schlom and Jin Suntivich}, doi = {10.1021/jacs.5c08607}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37115--37122}, shortjournal = {J. Am. Chem. Soc.}, title = {Strained-induced morphological reconstruction of RuO2(110) thin-film electrocatalysts}, volume = {147}, year = {2025}, }
• (2025). Mechanistic interrogation of a PQQ and rare earth-dependent artificial metalloenzyme. JACS, 147(41), 37104--37114. (www)

  @article{ , abstract = {Pyrroloquinoline quinone (PQQ)-binding proteins are found in diverse species and play key roles in the central metabolism of many methylotrophic bacteria, acting as redox-active cofactors in their alcohol dehydrogenase (ADH) enzymes. These enzymes also require a Lewis acidic metal ion to activate PQQ, and the 2011 discovery of lanthanide (Ln 3+ )-dependent ADH enzymes sparked a surge of interest in understanding their functional properties. However, key questions remain regarding the mechanism, metal ion-dependence, and electron transport processes of these enzymes. We report mechanistic, structural, and computational studies on an artificial metalloenzyme (ArM) containing a biomimetic active site that binds Ln 3+ , PQQ, and catalyzes benzyl alcohol dehydrogenation. These studies provide insights into the potential structure–function relationships present in natural MDHs. Examining the relative reactivities of substituted benzyl alcohol substrates revealed a kinetic isotope effect of 2.9 ± 0.4 and a linear free energy relationship consistent with one of the two mechanistic pathways widely proposed to operate in ADHs. Preparing ArMs with metal ions spanning the rare earth series, we observed decreasing reactivity with increasing Lewis acidity, a pattern consistent with that of natural ADH assays. In contrast to patterns observed in natural ADH assays, addition of ammonia had no effect on catalysis. Finally, investigating the role of a conserved active site residue through X-ray diffraction and molecular dynamics simulations, revealed a PQQ/substrate access channel critically regulated by this site. Together, these studies bear new insights into the mechanism, metal ion-dependence, and conformational dynamics associated with PQQ and rare earth-dependent enzymes.}, archive = {J_JACS}, author = {Mohd Taher and Peter J. Thompson and Carlos Nava-Matadamas and Austin T. Bruchs and Jennifer Bridwell-Rabb and Lisa Olshansky}, doi = {10.1021/jacs.5c08540}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37104--37114}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic interrogation of a PQQ and rare earth-dependent artificial metalloenzyme}, volume = {147}, year = {2025}, }
• (2025). Marine natural product chagosendine c induces cuproptosis in colorectal cancer cells by targeting FDX1. JACS, 147(41), 37089--37103. (www)

  @article{ , abstract = {Colorectal cancer (CRC) treatment is hampered by high recurrence rates and drug resistance. Cuproptosis, a copper-induced cell death mechanism, offers a new therapeutic approach. Here, we identified a marine natural product, chagosendine C (CHC), which kills tumor cells by increasing the intracellular copper ion concentration. CHC and related metal coordination homodimer alkaloids were rapidly synthesized and purified for further pharmacological study. In vitro , CHC significantly inhibited HCT116 and RKO CRC cell growth, induced G1 phase arrest and cell death, and overcame oxaliplatin resistance. In vivo , CHC suppressed colorectal tumor growth in mice at 40 mg/kg without obvious toxic effects. Mechanistically, CHC induces cuproptosis by targeting FDX1, increasing intracellular copper ions and ROS levels in tumor cells, and leading to cell death. Thus, CHC presents a novel CRC treatment strategy, showing strong antitumor activity and potential to overcome oxaliplatin resistance with promising clinical prospects.}, archive = {J_JACS}, author = {Xiaoyu Tao and Hongru Wang and Qun Wang and Chengji Wang and Chang-Wei Shao and Yang Jin and Dianping Yu and Hongmei Hu and Qing Zhang and Mengting Xu and Xiangxin Geng and Hanchi Xu and Linyang Li and Ruling Shen and Yue-Wei Guo and Xu-Wen Li and Sanhong Liu and Weidong Zhang}, doi = {10.1021/jacs.5c07917}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37089--37103}, shortjournal = {J. Am. Chem. Soc.}, title = {Marine natural product chagosendine c induces cuproptosis in colorectal cancer cells by targeting FDX1}, volume = {147}, year = {2025}, }
• (2025). When are dopant d-states free-atom-like? periodic trends and confinement effects in single-atom alloys. JACS, 147(41), 37079--37088. (www)

  @article{ , abstract = {The free-atom-like character of dopant d -states is a defining feature of single-atom alloys (SAAs), contributing to their exceptional selectivity and activity in heterogeneous catalysis. Based on reliable density functional theory (DFT) calculations for the full series of 4 d transition metal (TM) dopants embedded in various hosts, we provide a unified perspective on when dopants exhibit this characteristic and how it can be tuned. Only late TM dopants exhibit the narrow, free-atom-like d -bands typically associated with SAAs, whereas early TM dopants display significantly broader d -bands that approach the width of host metal d -bands. This variation is not driven by increased dopant–host d -state mixing, which remains minimal across the series. Instead, we attribute the observed periodic trend to differences in the spatial extent of the localized dopant states and their overlap with surrounding host atoms, as well as to avoided hybridization associated with d -state filling. We further corroborate that dopant confinement, quantified by the number and proximity of surrounding host atoms, is as a key factor: more confined dopants exhibit broader d -bands, whereas less confined dopants feature narrower d -bands. Reduced dopant confinement also stabilizes high-spin configurations, enhancing spin polarization for certain 4 d elements. Together, these findings offer fundamental insights into the origins of the unique electronic structure of SAAs. Building on these findings, we establish design principles for tuning dopant d -band shape and spin and illustrate how such modifications impact catalytic selectivity. The developed guidelines are also encapsulated in a machine learning model that predicts d -band widths, facilitating the rational design of SAAs.}, archive = {J_JACS}, author = {Fabian Berger and Angelos Michaelides}, doi = {10.1021/jacs.5c07771}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37079--37088}, shortjournal = {J. Am. Chem. Soc.}, title = {When are dopant d-states free-atom-like? periodic trends and confinement effects in single-atom alloys}, volume = {147}, year = {2025}, }
• (2025). β-fluorovinylsulfonamide as a highly reactivity- and structure-tunable electrophile for covalent targeting of proteins. JACS, 147(41), 37065--37078. (www)

  @article{ , abstract = {Covalent targeting of proteins with small molecule probes is a powerful approach for analyzing and manipulating biological functions. Recent advancements in the design of target selective covalent ligands further expand the scope of accessible proteins in this approach. Here we report β-fluorovinylsulfonamide (FVS) as a versatile electrophile for the design of covalent ligands. FVS irreversibly reacts with cysteine residues in proteins to afford stable vinyl sulfide adducts. The reactivity of FVS is maintained with the introduction of various substituents at the β-position, allowing for fine-tuning of the electrophilic reactivity and flexible molecular design of FVS-based covalent ligands. These reaction properties were leveraged in the development of highly selective covalent ligands for RSK2 and BTK. FVS compounds are also able to react with lysine residues in proteins to form enamine-type reversible covalent adducts, which are susceptible to hydrolysis under neutral aqueous conditions. This lysine reactivity of FVS led to the discovery of FVS compound 53 as a reversible covalent ligand for PFKL, which selectively reacts with K677 of PFKL and allosterically upregulates PFKL activity in living cells.}, archive = {J_JACS}, author = {Shunsuke Watanabe and Keisuke Tokunaga and Yudai Tanaka and Yuya Hirose and Emi Mishiro-Sato and Keiko Kano and Kaori Sasaki-Tabata and Yuri Kato and Motohiro Nishida and Naoya Shindo and Akio Ojida}, doi = {10.1021/jacs.5c07422}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37065--37078}, shortjournal = {J. Am. Chem. Soc.}, title = {β-fluorovinylsulfonamide as a highly reactivity- and structure-tunable electrophile for covalent targeting of proteins}, volume = {147}, year = {2025}, }
• (2025). Live-cell monitoring and omics analysis of Liquid–Solid transitions of biomolecular condensates. JACS, 147(41), 37056--37064. (www)

  @article{ , abstract = {Biomolecular condensates, or so-called membraneless organelles, transition from liquid into more solid-like states over time, contributing to the development of pathological conditions. The present study proposes a simple method using photoactive yellow protein (PYP) and its specific fluorescent covalent ligands to distinguish between the liquid and solid states of protein condensates in live cells. The method, compatible with fluorescence-activated cell sorting (FACS), correlates the stiffness of specific protein condensates with their accessibility to PYP ligands, enabling quantitative multicolor monitoring of condensate solidification. We applied this technique to 12 phase-separating proteins and their mutants, finding that TDP-43, particularly its A315T mutant linked to familial amyotrophic lateral sclerosis, most readily forms solid aggregates. Furthermore, this FACS-compatible strategy enabled the isolation of distinct cell populations based on condensate states, allowing for subsequent proteomic and transcriptomic analyses. Our findings demonstrate that condensate solidification is accompanied by the upregulated expression of extracellular matrix proteins, suggesting a previously unrecognized link between solid aggregate formation and extracellular matrix hardening.}, archive = {J_JACS}, author = {Asmaa M.A.S. Farrag and Koshiro Ota and Hideaki Yoshimura and Misao Takemoto and Takuma Mitarai and Takuya Kamikawa and Masahiro Abo and Vaibhav Pal Singh and Changyi Cui and Lu Zhou and Fumiyoshi Ishidate and Takahiro Fujiwara and Shin-ichi Sato and Yuichiro Hori and Takeaki Ozawa and Kazuya Kikuchi and Motonari Uesugi}, doi = {10.1021/jacs.5c07340}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37056--37064}, shortjournal = {J. Am. Chem. Soc.}, title = {Live-cell monitoring and omics analysis of Liquid–Solid transitions of biomolecular condensates}, volume = {147}, year = {2025}, }
• (2025). Mixed-valence aryloxido-bridged dilanthanide complexes with lanthanide-dependent electron delocalization. JACS, 147(41), 37045--37055. (www)

  @article{ , abstract = {Mixed-valence lanthanide complexes of the type (Cp iPr5 ) 2 Ln 2 I 3 (Cp iPr5 = pentaisopropylcyclopentadienyl; Ln = Gd, Tb, Dy, Ho, Er) featuring Ln–Ln bonding interactions can exhibit strongly coupled high-moment ground states with a large axial magnetic anisotropy. Here, we report the synthesis, structures, and magnetic properties of the aryloxido-bridged mixed-valence dilanthanide complexes (Cp iPr5 ) 2 Ln 2 (OAr tt ) 3 ( 1-Ln , Ln = Gd, Dy; – OAr tt = 3,5-bis( tert -butyl)phenoxide anion). The solid-state structures of the two complexes are distinct, with 1-Dy exhibiting a nearly symmetric structure and a short Dy–Dy bond of 3.265(1) Å, suggesting valence delocalization, while 1-Gd has an asymmetric structure with each Gd atom in a distinct coordination environment, indicative of valence localization. Static magnetic susceptibility data confirm that 1-Gd is valence localized, with only very weak antiferromagnetic exchange between the Gd II and Gd III centers at low temperatures. In contrast, magnetic susceptibility data for 1-Dy reveal strong magnetic coupling to give a large angular momentum ground state with magnetic blocking below 40 K. Solid-state Raman spectra for 1-Dy are indicative of Dy–Dy bonding that persists up to ambient temperatures. Computational analyses suggest that the bonding interaction in 1-Dy becomes highly polarized in the presence of slight structural asymmetry and that this effect becomes more pronounced at higher temperatures, as supported by variable-temperature single-crystal X-ray diffraction data. Detailed exploration of the vibronic coupling is consistent with vibronic-driven valence localization at elevated temperatures in 1-Dy .}, archive = {J_JACS}, author = {K. Randall McClain and Hyunchul Kwon and Yasmin Whyatt and Matthew P. Erodici and Andrea Mattioni and Katie R. Meihaus and Benjamin G. Harvey and Nicholas F. Chilton and Jeffrey R. Long}, doi = {10.1021/jacs.5c05894}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37045--37055}, shortjournal = {J. Am. Chem. Soc.}, title = {Mixed-valence aryloxido-bridged dilanthanide complexes with lanthanide-dependent electron delocalization}, volume = {147}, year = {2025}, }
• (2025). The mechanism of mineral nucleation and growth in a mini-ferritin. JACS, 147(41), 37030--37044. (www)

  @article{ , abstract = {Iron is an enigmatic element. While necessary for life, as Fe(II) it also catalyzes formation of reactive oxygen species. To mitigate this, cellular life has evolved the ferritin protein superfamily, which includes the 24 subunit ferritins and bacterioferritins, and 12 subunit mini-ferritins (DPS). Each catalyze the oxidation of Fe(II) to ferric oxyhydroxide, which is then sequestered within the hollow protein shell. While there is a wealth of structural information on unmineralized ferritins, high resolution information on iron loaded ferritins is lacking, and the mechanism of iron mineralization is poorly understood. To address this, we followed iron loading in a mini-ferritin by cryo-EM. We determined a 1.86 Å structure in the unmineralized state, as well as a 1.91 Å structure of an early, iron loading state in which the mini-ferritin catalyzes nucleation of ferric oxyhydroxide at the acidic 3-fold pores. Mechanistically, a conserved crucible of precisely positioned glutamates and unsaturated main chain carbonyls are employed as a template to catalyze nucleation. A 2.4 Å structure at a later time point was also determined, revealing the role of a second constellation of main-chain carbonyls on the interior surface that subsequently supports crystalline mineral growth, that then proceeds into the center of the particle. Notably, the visualized mineral is consistent with one of two competing structural descriptions for ferrihydrite. This study provides the first pseudoatomic level observation of controlled mineral nucleation and growth in any member of the ferritin superfamily, and informs general mechanisms of nucleation and biomineralization.}, archive = {J_JACS}, author = {Colin C. Gauvin and Monika Tokmina-Lukaszewska and Hitesh Kumar Waghwani and Sterling C. McBee and Trevor Douglas and Brian Bothner and C. Martin Lawrence}, doi = {10.1021/jacs.5c05464}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37030--37044}, shortjournal = {J. Am. Chem. Soc.}, title = {The mechanism of mineral nucleation and growth in a mini-ferritin}, volume = {147}, year = {2025}, }
• (2025). Revealing the low-temperature phase of FAPbI3 using a machine-learned potential. JACS, 147(41), 37019--37029. (www)

  @article{ , abstract = {Formamidinium lead iodide (FAPbI 3 ) is a material of interest for its potential in solar cell applications, driven by its remarkable optoelectronic properties. However, the low-temperature phase of FAPbI 3 remains poorly understood, with open questions surrounding its crystal structure, octahedral tilting, and arrangement of formamidinium (FA) cations. Using our trained machine-learned potential in combination with large-scale molecular dynamics (MD) simulations, we provide a detailed investigation of this phase, uncovering its structural characteristics and dynamical behavior. Our analysis reveals the octahedral tilt pattern and sheds light on the rotational dynamics of FA cations in the low-temperature phase. Strikingly, we find that the FA cations become frozen in a metastable configuration, unable to reach the thermodynamic ground state. By comparing our simulated results with experimental nuclear magnetic resonance (NMR) and inelastic neutron scattering (INS) spectra, we demonstrate good agreement, further validating our findings. This phenomenon mirrors experimental observations and offers a compelling explanation for the experimental challenges in accessing the true ground state. These findings provide critical insights into the fundamental physics of FAPbI 3 and its low-temperature behavior, advancing our understanding of this important material.}, archive = {J_JACS}, author = {Sangita Dutta and Erik Fransson and Tobias Hainer and Benjamin M. Gallant and Dominik J. Kubicki and Paul Erhart and Julia Wiktor}, doi = {10.1021/jacs.5c05265}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37019--37029}, shortjournal = {J. Am. Chem. Soc.}, title = {Revealing the low-temperature phase of FAPbI3 using a machine-learned potential}, volume = {147}, year = {2025}, }
• (2025). Total syntheses of giraldine i and heterophyllisine. JACS, 147(41), 37012--37018. (www)

  @article{ , abstract = {Aconitine and related norditerpenoid alkaloids are chemically and biologically significant natural products that represent a formidable synthetic challenge. Here, we report the first total syntheses of aconitine-type alkaloid giraldine I and lactone-type alkaloid heterophyllisine. Key strategies include (1) early stage installation of the C4 all-carbon quaternary stereocenter and nitrogen atom via allene hydrocyanation, (2) skeletal editing through hydrodealkenylative fragmentation/Mannich cyclization to build the A/B/E/F tetracyclic scaffold, (3) a Claisen rearrangement/ring-closing metathesis (RCM) sequence followed by transannular pinacol coupling to form the characteristic C/D rings of aconitines, and (4) a bioinspired and regioselective Baeyer–Villiger oxidation to access the lactone-type alkaloid.}, archive = {J_JACS}, author = {Chuang Li and Fei Lu and Ningwei Wang and Cheng Zhang and Guanrui He and Wenli Lei and Jing Liu and Jiamin Wang and Xiao-Yu Liu and Yong Qin}, doi = {10.1021/jacs.5c14513}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37012--37018}, shortjournal = {J. Am. Chem. Soc.}, title = {Total syntheses of giraldine i and heterophyllisine}, volume = {147}, year = {2025}, }
• (2025). Two-photon light-activatable fluorophores for organelle imaging in living cells and tissue-level imaging. JACS, 147(41), 37005--37011. (www)

  @article{ , abstract = {Precise spatiotemporal control of bioactive molecule release within cells is crucial for understanding cellular processes. Two-photon photocaging provides a noninvasive powerful method for deep-tissue activation. This work introduces a series of organelle-targeted, two-photon photoactivatable fluorophores (PAFs) based on 4-nitrobiphenyl derivatives, designed for mitochondria, endoplasmic reticulum, and lysosome targeting. These PAFs exhibit high brightness and photostability under both one- and two-photon excitation. Organelle specificity was achieved by conjugating organelle-targeted motifs to PAFs, with low cytotoxicity, excellent membrane permeability, and specific organelle localization in different cells. Ex vivo , these PAFs enabled deep-tissue imaging (up to 100 μm) in mouse liver, kidney, and heart via two-photon excitation, while in vivo , they supported high-resolution, three-dimensional structural imaging of subcutaneous tumors with minimal background. The findings highlight the potential of these PAFs for high-resolution, organelle, and deep-tissue imaging, offering a versatile platform for studying subcellular dynamics with applications in biomedical research.}, archive = {J_JACS}, author = {Zhuang Ma and Zhangcheng Fu and Boxuan Hou and Xueying Zeng and Junqiao Wang and Ying Tan and Yuyang Jiang and Naihan Xu and Chunyan Tan}, doi = {10.1021/jacs.5c14442}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {37005--37011}, shortjournal = {J. Am. Chem. Soc.}, title = {Two-photon light-activatable fluorophores for organelle imaging in living cells and tissue-level imaging}, volume = {147}, year = {2025}, }
• (2025). Enantioselective β-C–H arylation of α-fluoroalkyl cyclopropane and cyclobutane carboxylic acids. JACS, 147(41), 36999--37004. (www)

  @article{ , abstract = {Fluoroalkyl-substituted small-membered rings are highly valuable scaffolds in drug discovery; nevertheless, there exists no general method to prepare them enantioselectively. Herein, we report a highly enantioselective β-C–H arylation of simple and readily available α-fluoroalkyl cyclopropane and cyclobutane carboxylic acids via C–H activation. This transformation enabled by chiral monoprotected- N -amino sulfonamide (MPASA) ligand is compatible with a broad range of aryl iodides, affording an efficient route to diverse small-membered rings with all-carbon quaternary centers bearing fluoroalkyls, which have been difficult to access to date. The synthetic utility of the arylation product was demonstrated by converting the carboxylic acid into alcohol and amine, which may be used to prepare new analogues of bioactive compounds. Preliminary mechanistic studies were also conducted, giving initial insights into catalyst speciation and the stability of this reaction.}, archive = {J_JACS}, author = {D. Quang Phan and Jin-Quan Yu}, doi = {10.1021/jacs.5c13423}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36999--37004}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective β-C–H arylation of α-fluoroalkyl cyclopropane and cyclobutane carboxylic acids}, volume = {147}, year = {2025}, }
• (2025). Deoxygenative cyanofunctionalization of aldehydes and ketones enabled by electrochemical reduction. JACS, 147(41), 36992--36998. (www)

  @article{ , abstract = {The deoxygenative difunctionalization of carbonyls converts readily available carbonyl compounds into value-added gem -difunctionalized building blocks. We report an electrochemical carbonyl umpolung approach for the deoxygenative cyanofunctionalization of aldehydes and ketones, affording various α-functionalized nitriles. Further derivatization of these products provides a versatile and modular platform for geminal disubstitution of carbonyl oxygens.}, archive = {J_JACS}, author = {Yi Wang and Bofei Wang and Song Lin}, doi = {10.1021/jacs.5c13173}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36992--36998}, shortjournal = {J. Am. Chem. Soc.}, title = {Deoxygenative cyanofunctionalization of aldehydes and ketones enabled by electrochemical reduction}, volume = {147}, year = {2025}, }
• (2025). The Singlet–Triplet gap of pyruvic acid. JACS, 147(41), 36987--36991. (www)

  @article{ , abstract = {Understanding the gas-phase photochemistry of pyruvic acid is crucial to assessing its role and evolution in the atmosphere and relies on knowledge of the relative energy gaps between the atmospherically relevant excited electronic states of the molecule. However, accurate determination of these gaps, particularly between the lowest excited singlet and triplet states, has remained elusive due to the challenge of directly interrogating triplet states of the isolated molecule. In this work, we combine anion photoelectron spectroscopy and computational photochemistry to determine that the adiabatic S 1 -T 1 energy gap of pyruvic acid is 0.29 ± 0.04 eV. This study provides a reference value for the singlet–triplet energy gap of pyruvic acid and validates an approach that combines theory and experiment to determine energy gaps for volatile organic compounds of atmospheric interest.}, archive = {J_JACS}, author = {E. Michi Burrow and Javier Carmona-García and Connor J. Clarke and Basile F. E. Curchod and Jan R. R. Verlet}, doi = {10.1021/jacs.5c13075}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36987--36991}, shortjournal = {J. Am. Chem. Soc.}, title = {The Singlet–Triplet gap of pyruvic acid}, volume = {147}, year = {2025}, }
• (2025). Crystalline aryliminophosphinyl radical: A phosphorus congener of aryldiazenyl radicals. JACS, 147(41), 36980--36986. (www)

  @article{ , abstract = {Aryldiazenyl radicals (Ar–N═N·), bearing a terminal dinitrogen unit, are important reactive intermediates in organic transformations but typically short-lived due to rapid nitrogen extrusion. Herein, we report the synthesis, and structural and spectroscopic characterization of a robust aryliminophosphinyl radical Ar–N═P·, stabilized by a sterically demanding aryl substituent. It represents the first isolable heavier congener of aryldiazenyl radicals and the first phosphorus-centered radical featuring a pseudomonosubstituted phosphorus atom. Electron paramagnetic resonance spectroscopy and theoretical calculations revealed that the spin density is primarily localized on the phosphorus center with partial delocalization onto the nitrogen atom. Furthermore, we investigated its chemical property, revealing its phosphorus-centered radical reactivity and N–P unit associated redox reactivity. Notably, reduction of the radical with potassium graphite yielded an unprecedented anionic iminophosphanorcaradiene salt.}, archive = {J_JACS}, author = {Xu Wang and Yizhen Chen and Xinyi Li and Lei Xu and Gengwen Tan}, doi = {10.1021/jacs.5c12959}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36980--36986}, shortjournal = {J. Am. Chem. Soc.}, title = {Crystalline aryliminophosphinyl radical: A phosphorus congener of aryldiazenyl radicals}, volume = {147}, year = {2025}, }
• (2025). Paired pulsed decarboxylative hydroxylation designed by online Electrochemistry–Mass spectrometry. JACS, 147(41), 36975--36979. (www)

  @article{ , abstract = {We present a novel strategy for optimizing paired pulsed electrosynthesis by real-time monitoring of redox processes at the electrode interface using voltammetry–electrospray ionization mass spectrometry (VESI-MS). VESI-MS provides molecular insight into interfacial events, enabling the rational design of voltage pulses and synchronization of redox reactions, facilitating the discovery of new alternating current (AC) electrochemical transformations. We apply this approach to develop a selective decarboxylative hydroxylation by coupling oxygen reduction with the oxidative decarboxylation of a carboxylic acid. The pilot study with 2-phenylpropionic acid yields 1-phenylethanol with excellent selectivity using only molecular oxygen, KPF 6 , water, and carbon electrodes. This work opens new possibilities for the design of pulsed electrosynthetic reactions.}, archive = {J_JACS}, author = {Adarsh Koovakattil Surendran and Jana Roithová}, doi = {10.1021/jacs.5c12895}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36975--36979}, shortjournal = {J. Am. Chem. Soc.}, title = {Paired pulsed decarboxylative hydroxylation designed by online Electrochemistry–Mass spectrometry}, volume = {147}, year = {2025}, }
• (2025). (Salen)Metal-catalyzed β-glucuronidation of alcohols, phenols, and anilines. JACS, 147(41), 36969--36974. (www)

  @article{ , abstract = {β-Glucuronidation is an important metabolic pathway for a variety of chemicals, including drugs and endogenous substances. We report here that simple (salen)cobalt and (salen)chromium complexes catalyze the β-glucuronidation of alcohols, phenols, and anilines via stereospecific opening of 1,2-anhydroglucuronate electrophiles. The optimized protocol is mild and pH-neutral, enabling the β-glucuronidation of complex pharmaceuticals and natural products bearing acid-sensitive and Lewis-basic functionalities. Kinetic studies reveal a first-order kinetic dependence on catalyst concentration, which stands in contrast to the (salen)metal-catalyzed opening of simple epoxides where second-order rate dependence on the catalyst has been observed consistently.}, archive = {J_JACS}, author = {Peyton D. Beyer and Eric N. Jacobsen}, doi = {10.1021/jacs.5c12693}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36969--36974}, shortjournal = {J. Am. Chem. Soc.}, title = {(Salen)Metal-catalyzed β-glucuronidation of alcohols, phenols, and anilines}, volume = {147}, year = {2025}, }
• (2025). Rapid activation of amino acids with cyanide and hypochlorite. JACS, 147(41), 36963--36968. (www)

  @article{ , abstract = {Cyanogen chloride (NCCl) produced from the reaction of – CN with HOCl has previously been shown to afford activation of ribonucleotides. We now report that NCCl reacts with primary aliphatic amino acids to rapidly produce N -carbamoyl dipeptides in excellent yields (89–98%). Studies with l -alanine suggest that racemization of the amino acids does not occur significantly during the reaction. Quantum chemical (DFT) calculations predict that the mechanism proceeds via activated 2-amino-5(4 H )-oxazolone intermediates, which undergo amino acid nucleophilic attack. NCCl can also be generated in situ from glycine and HOCl, enabling the “sacrificial activation” of glycine to form N -carbamoyl diglycine. At 70 °C, selective peptide bond hydrolysis yields N -carbamoyl glycine, which is a known peptide precursor. The findings herein build upon prior work involving NCCl in prebiotic ribonucleotide synthesis and activation, highlighting its potential as a general chemical activator for the prebiotic condensation of life’s molecular building blocks.}, archive = {J_JACS}, author = {Luke K. Marshall and Ruiqin Yi and Joshua J. Brown and Albert C. Fahrenbach}, doi = {10.1021/jacs.5c12639}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36963--36968}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid activation of amino acids with cyanide and hypochlorite}, volume = {147}, year = {2025}, }
• (2025). Site-specific profiling of RNA-binding proteins enabled by isotopic signature-enhanced mass spectrometry. JACS, 147(41), 36956--36962. (www)

  @article{ , abstract = {RNA-binding proteins (RBPs) ubiquitously regulate RNA throughout their lifespan, being extensively involved in cellular metabolism and genetic evolution. Therefore, comprehensive identification of the RNA-protein interactions, especially their interfaces with site-specific resolution, is significant to elucidate the intricate biological activities governed by RNA. Nevertheless, it remains challenging for data-dependent acquisition (DDA)-based proteomics to identify the RNA-cross-linked peptides in depth due to the low abundance and negative charge of modified peptides. To address such limitations, we developed an innovative method named “isoRIC” for profiling RNA-binding proteomes with site-specific resolution, which combines the metabolic labeling of isotopic nucleotides for photo-cross-linking of RNA-binding proteins and the real-time targeted LC-MS/MS analysis of RNA-cross-linked peptides. This method shows a dramatic improvement of sensitivity in identifying RNA-cross-linked peptides with low abundance as compared to the DDA-based proteomic approaches, enabling the discovery of novel RNA-binding proteins and precise mapping of RNA–protein binding interfaces at single amino acid resolution. We applied isoRIC in the context of pathogenic mutations and post-translational modifications to highlight the critical role of RNA-binding sites in modulating the RNA-binding ability.}, archive = {J_JACS}, author = {Yicheng Liu and Guogeng Jia and Chengxi Li and Tianyu Feng and Weidi Xiao and Chu Wang}, doi = {10.1021/jacs.5c11224}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36956--36962}, shortjournal = {J. Am. Chem. Soc.}, title = {Site-specific profiling of RNA-binding proteins enabled by isotopic signature-enhanced mass spectrometry}, volume = {147}, year = {2025}, }
• (2025). Enantioselective synthesis of atropisomeric 3-arylindoles via cobalt-catalyzed electroreductive cross-coupling. JACS, 147(41), 36947--36955. (www)

  @article{ , abstract = {Cobalt-catalyzed enantioselective electroreductive cross-coupling of aryl iodides and indole bromides has been developed. This strategy is characterized by mild reaction conditions, high enantioselectivities, and a broad substrate scope. Notably, this approach effectively addresses the challenges associated with indole substrates that do not possess electron-withdrawing substituents at the 2-position, a limitation that remains unresolved in other strategies.}, archive = {J_JACS}, author = {Shi-Shuo Xu and Jian-Feng Guo and Cong Ma and Ping Fang and Tian-Sheng Mei}, doi = {10.1021/jacs.5c11094}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36947--36955}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective synthesis of atropisomeric 3-arylindoles via cobalt-catalyzed electroreductive cross-coupling}, volume = {147}, year = {2025}, }
• (2025). Alkenyl- and aryl-borane nucleophiles in enantioselective iridium-catalyzed allylic substitution of vinyl epoxides. JACS, 147(41), 36940--36946. (www)

  @article{ , abstract = {The catalytic asymmetric Petasis reaction represents a practical approach for synthesizing highly valuable chiral amine building blocks. However, despite the potential that this reactivity provides, the extension of the mechanistic framework to alternative electrophilic fragments is noticeably underdeveloped. We report herein the first Ir-catalyzed allylation of alkenyl, aryl, and alkynyl boranes with racemic vinyl epoxides or vinyl aziridines via an enantioselective 1,4-boronate rearrangement. Mechanistic studies reveal that the high levels of stereoselectivity arise due to tandem dynamic kinetic resolution and kinetic resolution processes, with computational analysis suggesting that a stabilizing interaction between the alkenyl boronate π-system and the electrophile facilitates the key transition state. The utility of this methodology is demonstrated in a concise, enantioselective two-step synthesis of the phytotoxin ( R )-pyricuol.}, archive = {J_JACS}, author = {Jiangwei Wen and Lushuai Zhang and Chengyu He and Su-min Song and Jasper L. Tyler and Robert S. Paton and Varinder K. Aggarwal}, doi = {10.1021/jacs.5c10680}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36940--36946}, shortjournal = {J. Am. Chem. Soc.}, title = {Alkenyl- and aryl-borane nucleophiles in enantioselective iridium-catalyzed allylic substitution of vinyl epoxides}, volume = {147}, year = {2025}, }
• (2025). Revealing dynamic structural changes in platinum-group-metal nanoparticles during the catalytic hydrogen evolution reaction. JACS, 147(41), 36934--36939. (www)

  @article{ , abstract = {Despite the crucial role of structural dynamics in catalytic reactions, the influence of nanoparticle (NP) size and elemental composition on these dynamics under electrochemical conditions is often overlooked. Herein, we present the first systematic operando investigation of the size- and element-dependent structural and electronic dynamics of platinum-group-metal (PGM) NPs (Pt, Pd, Rh, and Ru) during the hydrogen evolution reaction (HER) under both acidic and alkaline conditions. By combining operando powder X-ray diffraction and X-ray absorption spectroscopy, we revealed that the smaller the NPs, the more significant the structural changes, indicating surface adsorbate-induced dynamics. Notably, we also found that the constant lattice expansion in Pt, Pd, and Rh NPs occurred on a slow time scale (several tens of seconds). The electronic states of these NPs were more reductive than their standard zerovalent states owing to interactions with hydrogen. However, the Ru NPs remained oxidized even during the HER, indicating distinct electronic changes in the PGMs. These findings reveal previously unrecognized dynamics, providing a comprehensive understanding of how size and composition influence the structural and electronic changes of PGM NPs in realistic electrochemical reaction environments. This study establishes a foundational framework for operando catalyst investigations and opens new avenues for the rational design of size- and element-optimized HER catalysts.}, archive = {J_JACS}, author = {Yuto Maruta and Hirotaka Ashitani and Shogo Kawaguchi and Toshiaki Ina and Osami Sakata and Yoshiki Kubota and Tomokazu Yamamoto and Takaaki Toriyama and Yasukazu Murakami and Megumi Mukoyoshi and Hiroshi Kitagawa and Kohei Kusada}, doi = {10.1021/jacs.5c10453}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36934--36939}, shortjournal = {J. Am. Chem. Soc.}, title = {Revealing dynamic structural changes in platinum-group-metal nanoparticles during the catalytic hydrogen evolution reaction}, volume = {147}, year = {2025}, }
• (2025). A uniquely structured heteronuclear cluster cage with anion-templated pentagons and hexagons. JACS, 147(41), 36929--36933. (www)

  @article{ , abstract = {Constructing structurally sophisticated molecules with interesting properties is the goal of supramolecular chemistry. Herein, two heterometallic clusters, formulated respectively as [Gd 136 Ni 84 L 106 (μ 6 -C 2 O 4 ) 12 (μ 5 -NO 3 ) 12 (μ 3 -OH) 176 (μ-OH) 26 (μ 4 -C 2 O 4 ) 3 (H 2 O) 106 ]Cl 120 ·49H 2 O·90MeOH ( Gd 136 Ni 84 , H 2 L = N -methyliminodiacetic acid) and [Tb 136 Ni 84 L 106 (μ 6 -C 2 O 4 ) 12 (μ 5 -NO 3 ) 12 (μ 3 -OH) 176 (μ-OH) 26 (H 2 O) 114 ]Cl 126 ·50H 2 O·130MeOH ( Tb 136 Ni 84 ), were obtained by the cohydrolysis of Ln 3+ (Ln = Gd, Tb) and Ni 2+ in the presence of H 2 L and triethylamine. The essentially isostructural cationic cluster cages are constructed by coexisting pentagons and hexagons whose formation is respectively templated by nitrate and oxalate ions. Rather than the desired buckminsterfullerene structure, the clusters are of a truncated tetrahedral structure due to the unique disposition of the polygonal building units that are structurally distinct from those in a regular fullercage. Cluster Gd 136 Ni 84 maintains its structural integrity in solution as evidenced by the results of mass spectroscopic and electron microscopic studies. Its isothermal magnetic entropy change is 43.91 J·kg –1 ·K –1 at 3.0 K and 7.0 T, placing it among the high-performing lanthanide-containing clusters possibly useful for magnetic cooling.}, archive = {J_JACS}, author = {Weiming Huang and Qingsong Yang and Wanmin Chen and Qixia Bai and Zhe Zhang and Pingshan Wang and Zhiping Zheng}, doi = {10.1021/jacs.5c09924}, journal = {Journal of the American Chemical Society}, month = {10}, number = {41}, pages = {36929--36933}, shortjournal = {J. Am. Chem. Soc.}, title = {A uniquely structured heteronuclear cluster cage with anion-templated pentagons and hexagons}, volume = {147}, year = {2025}, }
• (2025). Correction to “Room-temperature superprotonic conductivity beyond 10–1 s cm–1 in a Co(II) coordination polymer”. JACS, 147(40), 36928. (www)

  @article{ , archive = {J_JACS}, author = {Shyam Chand Pal and Debolina Mukherjee and Yasaswini Oruganti and Byoung Gwan Lee and Dae-Woon Lim and Bikram Pramanik and Arun K. Manna and Madhab C. Das}, doi = {10.1021/jacs.5c13994}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36928}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Room-temperature superprotonic conductivity beyond 10–1 s cm–1 in a Co(II) coordination polymer”}, volume = {147}, year = {2025}, }
• (2025). Residue-resolved liquid-state hyperpolarized NMR of peptide condensate surfaces. JACS, 147(40), 36920--36927. (www)

  @article{ , abstract = {Understanding how biomolecular condensates interact with their environment requires atomic-level insights into their surface composition. However, conventional Nuclear Magnetic Resonance (NMR) spectroscopy lacks the sensitivity to probe solvent-exposed regions in large, phase-separated peptide systems, where surface moieties are sparse relative to bulk residues. Here, we introduce hyperpolarized liquid-state surface-specific NMR spectroscopy, a technique that visualizes solvent-accessible residues in large biomolecular condensates. In combination with unconventional sample handling instrumentation and hyperpolarization-specific data processing, we report high-resolution hyperpolarized surface NMR spectra with spectral qualities that do not fall short of cutting-edge high-field methods yet have substantially boosted sensitivity. Targeting the biotechnologically widely used elastin-like polypeptide (ELP) nanoscale complexes, we demonstrate residue-resolved detection of the water interface of mega Dalton-sized peptide condensates with sensitivity enhancements reaching 2 orders of magnitude. Our method reveals glycine residues at the coacervate surface while hydrophobic core residues remain suppressed, providing direct evidence for glycine-rich surface segregation in these biomaterials. These findings resolve long-standing questions about ELP surface architecture and open an avenue for a solution-state analog to surface-enhanced solid-state NMR. The presented advance might thus foster detailed investigations of soft-matter interfaces in protein condensates, synthetic coacervates, and bioengineered materials.}, archive = {J_JACS}, author = {Dörte Brandis and Ertan Turhan and Milan Zachrdla and Dennis Kurzbach}, doi = {10.1021/jacs.5c15053}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36920--36927}, shortjournal = {J. Am. Chem. Soc.}, title = {Residue-resolved liquid-state hyperpolarized NMR of peptide condensate surfaces}, volume = {147}, year = {2025}, }
• (2025). Rhodium-catalyzed homogeneous asymmetric hydrogenation of naphthylamine derivatives. JACS, 147(40), 36911--36919. (www)

  @article{ , abstract = {The precise control of chemo-, regio- and enantioselectivity in the transition-metal-catalyzed hydrogenation of naphthylamine derivatives has remained a long-standing challenge, stemming from their inherent high aromaticity and the potential for catalyst poisoning by amine groups. Herein, we report the first highly efficient homogeneous hydrogenation of naphthylamine derivatives, enabled by a chiral tethered rhodium-diamine complex. This method provides direct and practical access to a broad range of valuable chiral 1,2,3,4-tetrahydronaphthylamine derivatives from readily available naphthylamine feedstocks. Its extensive synthetic utility is further demonstrated by the concise synthesis of several chiral drugs and bioactive molecules.}, archive = {J_JACS}, author = {Shu-Xin Zhang and Lin Zuo and Zeyu Li and Yan-Mei He and Wei Hao and Qing-Hua Fan}, doi = {10.1021/jacs.5c14310}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36911--36919}, shortjournal = {J. Am. Chem. Soc.}, title = {Rhodium-catalyzed homogeneous asymmetric hydrogenation of naphthylamine derivatives}, volume = {147}, year = {2025}, }
• (2025). Vitamin d3 activation by cytochrome p450 enzymes: Differences between bacterial and human calcitriol biosynthesis. JACS, 147(40), 36898--36910. (www)

  @article{ , abstract = {Vitamin D 3 (VD 3 ) is an important natural product with functions in the human body related to bone growth and homeostasis. In the body, vitamin D 3 is converted into the hormone calcitriol by successive activation of the C 25 –H and C 1 –H groups by two cytochrome P450 isozymes that each catalyze a regioselective C–H hydroxylation step. By contrast, in bacteria, both reactions happen in the same P450 isozyme, but the product after the first hydroxylation step does not escape into solution. To understand the differences between human and bacterial VD 3 activation, we performed molecular dynamics and quantum mechanics studies of these enzymes. Molecular dynamics simulations on the four P450 structures for human and bacterial isozymes with VD 3 and 25-hydroxy-VD 3 bound show that the human P450 enzyme for the first hydroxylation step has a small and narrow cavity around the heme, which only fits an aliphatic chain, and hence can only perform C 25 -hydroxylation. On the other hand, the bacterial P450 has a more open and spherical substrate binding pocket where the substrate fits in both orientations. Consequently, 25-hydroxy-VD 3 will bind for a long period of time in the bacterial P450 isozyme that can trigger a second reaction cycle with molecular oxygen. Subsequently, QM calculations on cluster models show that all reaction steps happen through a rate-determining hydrogen atom abstraction. However, the human P450 isozyme reacts with faster kinetics than the bacterial isozyme through better and tighter positioning of the substrate, which highlights the role of the second coordination sphere for enzyme-catalyzed reactions.}, archive = {J_JACS}, author = {Yi Zhang and Yuanxin Cao and Sam P. de Visser}, doi = {10.1021/jacs.5c13857}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36898--36910}, shortjournal = {J. Am. Chem. Soc.}, title = {Vitamin d3 activation by cytochrome p450 enzymes: Differences between bacterial and human calcitriol biosynthesis}, volume = {147}, year = {2025}, }
• (2025). Overriding norrish type II to access cyclopropanols. JACS, 147(40), 36890--36897. (www)

  @article{ , abstract = {The propensity for photoexcited aryl ketones to undergo 1,5-hydrogen atom transfer (HAT) reactions is a fundamental process in organic synthesis and polymer degradation. Since its discovery in 1958, Norrish–Yang photocyclization has become a prominent method to access cyclobutanols under mild photoirradiative conditions. Despite its successful extension to larger ring systems, access to medicinally relevant 3-membered rings remains limited due to the strong kinetic preference for 1,5-HAT over 1,4-HAT. In this work, we demonstrate the first photocyclization of β-boryl aryl ketones to cyclopropanols. Our strategy relies on solvent-controlled selective population of the π,π* triplet state over the n,π* triplet state, with the former preferentially undergoing 1,4-boryl group transfer over 1,5-HAT. This protocol proceeds under mild irradiative conditions with excellent functional group tolerance, providing access to a broad range of highly valuable cyclopropanol scaffolds.}, archive = {J_JACS}, author = {James W. Pearson and Samantha L. Dudra and Anthony F. Palermo and Benjamin S. Y. Chiu and Julie Dang and Alexis L. Gabbey and Bridget A. B. Henson and Teh Ren Hou and Negin Nabavi and Sophie A. L. Rousseaux}, doi = {10.1021/jacs.5c13001}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36890--36897}, shortjournal = {J. Am. Chem. Soc.}, title = {Overriding norrish type II to access cyclopropanols}, volume = {147}, year = {2025}, }
• (2025). Methylation and alkylation of pyridines at the meta position using aldehydes or aldehyde surrogates. JACS, 147(40), 36882--36889. (www)

  @article{ , abstract = {The installation of methyl groups can significantly enhance the drug potency, motivating the development of diverse methylation strategies. C–H methylation is particularly attractive, yet a broadly applicable method for meta -C–H methylation of pyridines─the most common N -heterocyclic pharmacophore─remains elusive. Herein, we report a method for meta -methylation of pyridines that utilizes dihydropyridines, generated in situ, in conjunction with benzotriazolylmethanol or paraformaldehyde as the methylating agent, enabling the construction of a diverse array of meta -methyl-substituted pyridines with excellent selectivity for monomethylation. Moreover, the method can be readily extended to meta -alkylation using aldehydes as alkyl sources. Density functional theory calculations, control experiments, and kinetic studies were performed to elucidate the reaction mechanisms, in which the cooperation of the borane catalyst with the base was crucial for the deoxygenation step. Given the impact of methyl groups on molecular potency and the prevalence of pyridine pharmacophores, we anticipate that this method may offer a powerful handle for accessing new drug candidates.}, archive = {J_JACS}, author = {Zhi-Hao Chen and Lu Liu and Yun-Bo Wang and Heng Luo and Zi-Lu Tang and Xin-Yue Zhou and Xiao-Chen Wang}, doi = {10.1021/jacs.5c13428}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36882--36889}, shortjournal = {J. Am. Chem. Soc.}, title = {Methylation and alkylation of pyridines at the meta position using aldehydes or aldehyde surrogates}, volume = {147}, year = {2025}, }
• (2025). Pd-catalyzed O-arylation of phenols mediated by a weak, soluble organic base: Methodology, mechanism, and compatibility with enabling technologies. JACS, 147(40), 36870--36881. (www)

  @article{ , abstract = {The low nucleophilicity of phenols represents a major obstacle to the Pd-catalyzed synthesis of diaryl ethers. This inherent challenge is typically exacerbated by the reliance of C–O couplings on an insoluble, inorganic base: the resulting reaction heterogeneity leads to irreproducibility across scales and between laboratories, and incompatibility with common enabling technologies. In this Article , we report the development and mechanistic interrogation of an homogeneous, Pd-catalyzed C–O coupling between phenols and aryl triflates that uses a weak, soluble tertiary amine as base. We show that the choice of ligand, aryl electrophile, and base is crucial if side reactions and catalyst poisoning are to be avoided, and productive catalysis achieved. Investigation of reaction kinetics and linear free energy relationships has revealed the identity of both the catalyst resting state and the turnover-limiting step. The combined mechanistic insight allows qualitative a priori prediction of reaction outcome as a function of substrate electronics, and provides an intuitive guide as to how diaryl ether targets should be disconnected. The resulting methodology exhibits broad substrate scope, with yields reproducible across both preparative ‘singleton’ scales and high throughput formats. The homogeneous nature of the couplings allows their safe execution under microwave heating, with elevated temperatures allowing for short reaction times even in the presence of air, and their facile translation to scale-up in continuous flow.}, archive = {J_JACS}, author = {Martyna I. Ostrowska and James A. Morris and Liam T. Ball}, doi = {10.1021/jacs.5c13469}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36870--36881}, shortjournal = {J. Am. Chem. Soc.}, title = {Pd-catalyzed O-arylation of phenols mediated by a weak, soluble organic base: Methodology, mechanism, and compatibility with enabling technologies}, volume = {147}, year = {2025}, }
• (2025). Europium(II) ynolate complex: Synthesis, bonding, and reactivity. JACS, 147(40), 36862--36869. (www)

  @article{ , abstract = {Anionic ketenes [RCCO] − exhibit two resonance forms: ketenyl anions and ynolate anions. While ketenyl complexes have been isolated and characterized, crystalline ynolate complexes remain elusive. Herein, we report the first lanthanide ynolate complex, namely, the europium ynolate complex. A σ-bond metathesis reaction of Me 3 Si(H)CN 2 with a europium(II) hydrido or alkyl complex yields a europium(II) nitrilimine, which reacts with CO to provide a europium(II) ynolate complex. Single-crystal X-ray diffraction and DFT calculations confirm the dominance of the ynolate resonance form, showing two orthogonal π orbitals between the C–C unit and a significant negative charge (−0.83) on the oxygen atom. Reactivity studies demonstrate C-centered trapping products with trimethylsilyl trifluoromethanesulfonate, benzophenone, isothiocyanate, and carbodiimide. Mechanistic DFT analysis of the carbodiimide reaction reveals a gradual shift from ynolate to ketenyl anion, enhancing reactivity for [2 + 2] cyclization.}, archive = {J_JACS}, author = {Qingqing Wen and Ruyi Li and Xiaojuan Liu and Qian Peng and Yaofeng Chen}, doi = {10.1021/jacs.5c13427}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36862--36869}, shortjournal = {J. Am. Chem. Soc.}, title = {Europium(II) ynolate complex: Synthesis, bonding, and reactivity}, volume = {147}, year = {2025}, }
• (2025). Cobalt-catalyzed enantioselective hydroalkylation of oxa- or azabicyclic alkenes. JACS, 147(40), 36851--36861. (www)

  @article{ , abstract = {Bridged bicyclic structures, exemplified by rigid oxa- and azabicyclic alkanes, are pivotal scaffolds in drug design and natural product synthesis due to their three-dimensional architecture and inherent ring strain. Functionalization of readily available bicyclic alkenes provides a potential pathway to synthesizing molecules with complex cyclic structures. However, strained bicyclic alkenes exhibit thermodynamic reactivity driven by strain energy release, which predominantly favors ring-opening pathways. In contrast, ring-retentive hydroalkylation─a direct method for synthesizing complex bridged bicyclic architectures─remains underdeveloped. Here, we present a cobalt-catalyzed enantioselective hydroalkylation strategy for bicyclo[2.2.1]alkenes that enables ring-retentive addition while constructing tertiary carbon stereocenters within oxa- or azabicyclic frameworks. Mechanistic investigations revealed that the hydrometalation of alkenes serves as the selectivity-determining step, where noncovalent interactions between the catalyst and substrate govern stereoisomeric differentiation. The protocol demonstrates broad compatibility with diverse alkyl iodides and bicyclo[2.2.1]alkenes, facilitating late-stage functionalization of bioactive molecules and enabling the efficient synthesis of antifungal agents with potent activity.}, archive = {J_JACS}, author = {Xu-Yang Liu and Jia-Wang Wang and Deguang Liu and Jun Liu and Can Zhao and Yao Chen and Peng-Jie Yang and Zi-Li Ren and Quan Gao and Yan Li and Xi Lu and Haiqun Cao and Yao Fu}, doi = {10.1021/jacs.5c13397}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36851--36861}, shortjournal = {J. Am. Chem. Soc.}, title = {Cobalt-catalyzed enantioselective hydroalkylation of oxa- or azabicyclic alkenes}, volume = {147}, year = {2025}, }
• (2025). Pretzelanes with planar chirality and guest recognition capabilities. JACS, 147(40), 36843--36850. (www)

  @article{ , abstract = {Developing efficient approaches to synthesize robust large-sized macrocycles with a guest recognition ability represents one of the major focuses in the field of host–guest chemistry. Here, we obtained a series of macrocycles each containing no less than 100 nonhydrogen atoms in high or close to quantitative yield by leveraging catenation as the ligation reaction in the ring closure step. Each of these macrocycles, in the form of pretzelanes, consists of a catenane core whose two interlocked macrocycles are interconnected by a bridging unit. Their pseudoquantitative yields arise from the marriage of dynamic nature of the hydrazone bonds that allows error correction and a hydrophobic effect that drives catenation. Within each pretzelane, the bridging unit breaks planar symmetry, imparting intrinsic planar chirality. When the bridge is sufficiently rigid, it restricts the intramolecular pirouetting of one macrocycle relative to the other, preventing racemization of the enantiomers. Moreover, the rigid bridging and catenane components create a preorganized cavity capable of accommodating various hydrophobic guests. When an anthracene derivative is encapsulated within the pretzelane cavity featuring a viologen bridge, the latter can quench the excited state of the guest, protecting it from UV-stimulated oxidation to 9,10-anthraquinone.}, archive = {J_JACS}, author = {Songna Zhang and Yuxi Wei and Qiong Chen and Yongwei Qian and Guangcheng Wu and Chenqi Ge and Feihe Huang and Hao Li}, doi = {10.1021/jacs.5c13338}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36843--36850}, shortjournal = {J. Am. Chem. Soc.}, title = {Pretzelanes with planar chirality and guest recognition capabilities}, volume = {147}, year = {2025}, }
• (2025). Dual Proton–Electron conductivity in 2D azaborine Metal–Organic frameworks. JACS, 147(40), 36837--36842. (www)

  @article{ , abstract = {Dual proton–electron conductors are highly sought after for applications in electronics and energy storage. Whereas two-dimensional metal–organic frameworks (MOFs) (2D MOFs) with high electrical conductivity are now numerous, introducing conduits for ion transport in these is challenging. Herein, we report the synthesis of two new mixed electron–proton conductors, M 3 TABC 2 (M = Cu, Zn; TABC = hexahydroxy-1,5,9-triaza-2,6,10-trihydroxyboracoronene), made from a new conjugated azaborine ligand with mobile protons. Cu 3 TABC 2 and Zn 3 TABC 2 show high electronic conductivities of 6.0 × 10 –2 S/cm and 2.2 × 10 –4 S/cm, and ionic conductivities of 1.6 ± 0.1 × 10 –5 S/cm and 1.9 ± 0.4 × 10 –5 S/cm, respectively. Overall, this work demonstrates the incorporation of mobile protons into aromatic ligands as a strategy for enabling mixed conductivity in 2D MOFs.}, archive = {J_JACS}, author = {Alice Y. Su and Julius J. Oppenheim and Mircea Dincă}, doi = {10.1021/jacs.5c13331}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36837--36842}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual Proton–Electron conductivity in 2D azaborine Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Generalized A(n)BC recombination model in semiconductors with multilevel defects. JACS, 147(40), 36825--36836. (www)

  @article{ , abstract = {The ABC model has been widely used to describe the carrier recombination rate, in which the rate of defect-assisted recombination is assumed to depend linearly on excess carrier density Δ n , leading to a constant recombination coefficient A . However, for multilevel defects that are prevalent in semiconductors, when Δ n varies, we find that the carrier capture and emission of defects can change the defect density distribution in different charge states, which makes the A coefficient depend on Δ n and become a function A ( n ). Therefore, the recombination rate should depend nonlinearly on Δ n . However, in many recent computational studies on multilevel defects, only carrier capture was considered, while carrier emission from defect levels was neglected, causing incorrect charge-state distribution and misleading linear dependence of the rate on Δ n , especially for multilevel defects with shallow levels. Taking V Ga -O N in wurtzite GaN and Pb I in perovskite CsPbI 3 as examples, our calculations showed that neglecting carrier emission can cause the recombination rate to be underestimated by more than 8 orders of magnitude when Δ n is 10 15 cm –3 . Our findings suggest that recent studies on carrier recombination assisted by multilevel defects should be revisited with carrier emission considered, and the widely used ABC model should be reformulated into the A ( n ) BC model.}, archive = {J_JACS}, author = {Shanshan Wang and Menglin Huang and Su-Huai Wei and Xin-Gao Gong and Shiyou Chen}, doi = {10.1021/jacs.5c13336}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36825--36836}, shortjournal = {J. Am. Chem. Soc.}, title = {Generalized A(n)BC recombination model in semiconductors with multilevel defects}, volume = {147}, year = {2025}, }
• (2025). Perovskite/CIGS tandem solar cells with over 1000 h operational stability through interconnection stress relief. JACS, 147(40), 36815--36824. (www)

  @article{ , abstract = {Perovskite/CIGS thin-film tandem solar cells offer a promising solution for lightweight and cost-effective photovoltaic technologies. However, their practical deployment is hindered by unsatisfied long-term operational stability. In this study, we identify perovskite films deposited on smoothed CIGS substrates exhibit tensile stress, which weakens bonding interactions, induces chemical structural instability, lowers defect formation energy and ion migration activation energy, impeding long-term operation of tandem devices under photothermal stress. Rough CIGS substrates featured with corrugated surface morphology effectively alleviating harmful tensile stresses. As a result, photothermal tolerance and optoelectronic properties are enhanced in corresponding perovskite films. The monolithic perovskite/CIGS tandem devices achieve a certified stabilized efficiency exceeding 28%, along with a notably extended T 80 lifetime of 1123 h under maximum power point tracking with full-spectrum AM 1.5G illumination. Additionally, these devices demonstrate enhanced operational stability at an elevated temperature of 60 °C and under thermal cycling tests (from room temperature to 65 °C) in a N 2 -filled glovebox. This work underscores the essential role of interconnection contact engineering in enhancing the long-term stability of perovskite-based devices.}, archive = {J_JACS}, author = {Fengtao Pei and Shuping Lin and Jiahong Tang and Xingye Huang and Yu Han and Qi Sun and Shiju Lin and Hao Wang and Zhongyang Zhang and Xinmeng Zhuang and Kailin Li and Cheng Zhu and Yihua Chen and Tinglu Song and Teng Cheng and Yuanyuan Cui and Ying Zhang and Huiqing Hou and Wentao Zhou and Yuze Lin and Boyan Li and Shaoxin Hong and Huanping Zhou and Xueyun Wang and Yuanyuan Zhou and Dalong Zhong and Qi Chen and Yan Jiang}, doi = {10.1021/jacs.5c13264}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36815--36824}, shortjournal = {J. Am. Chem. Soc.}, title = {Perovskite/CIGS tandem solar cells with over 1000 h operational stability through interconnection stress relief}, volume = {147}, year = {2025}, }
• (2025). Structural analysis of valine residues in silk fibroin by solid-state NMR. JACS, 147(40), 36805--36814. (www)

  @article{ , abstract = {The silk fibroin produced by the silkworm Bombyx mori has a highly repetitive sequence, composed mainly of repeats of GAGAGS or GAGAGA, with some of the A/S residues being replaced by Y or V. Silk fiber is approximately 60% composed of crystalline regions, separated by less structured regions, generally described as amorphous. The crystalline regions are widely thought to be composed mainly of GAGAGS and GAGAGA repeats, and the role of the YV-repeats is not well understood. Because of the heterogeneous nature of silk fiber, it has been difficult to relate structural features to sequence. Here, we use solid-state NMR to study the conformation of valine residues in silk fiber, and in liquid silk before spinning, and we show that the valines have an identical secondary structure distribution to the alanines. This implies that the YV-repeats are part of the crystalline regions and function to demarcate their boundaries, and that the amorphous regions are formed from both AS and YV-repeats.}, archive = {J_JACS}, author = {Misaki Mizushima and Takashi Mizuno and Mitsuru Toda and Mike P. Williamson and Yu Suzuki}, doi = {10.1021/jacs.5c13210}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36805--36814}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural analysis of valine residues in silk fibroin by solid-state NMR}, volume = {147}, year = {2025}, }
• (2025). Unveiling the synergistic and perforation-dominant self-assembly mechanisms of supramolecular chiral helical microtoroids. JACS, 147(40), 36793--36804. (www)

  @article{ , abstract = {Supramolecular assemblies with chiral helical structures play pivotal roles in biological systems, molecular sensing, chiral nanomaterials, and optoelectronic devices. Understanding the formation mechanisms of such chiral assemblies is essential for the rational design and precise control of their morphologies and functions. However, the complex noncovalent interactions and multiscale assembly pathways pose significant challenges to unveiling the underlying mechanisms. Herein, we introduce a generic patchy-ellipsoid-chain model that enables efficient coarse-grained molecular dynamics simulations to elucidate the assembly kinetics of supramolecular chiral helical microtoroids. Our simulations reveal that the formation of chiral helical microtoroids arises from the synergistic interplay of molecular chirality, directional noncovalent interactions, and solvophobic effects, proceeding through two distinct kinetic pathways: perforation and cyclization. Notably, the perforation pathway predominates due to energetically favorable π–π stacking interactions. This work provides both a robust modeling framework and mechanistic insights into supramolecular chiral self-assembly, offering rational strategies for the design of tailored supramolecular chiral structures.}, archive = {J_JACS}, author = {Li-Li Han and Yu-Wei Sun and Zhan-Wei Li}, doi = {10.1021/jacs.5c12969}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36793--36804}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling the synergistic and perforation-dominant self-assembly mechanisms of supramolecular chiral helical microtoroids}, volume = {147}, year = {2025}, }
• (2025). Photoredox-catalyzed cyclopropanation via ligated boryl radical-mediated nonstabilized carbene formation. JACS, 147(40), 36781--36792. (www)

  @article{ , abstract = {The [2 + 1] cycloaddition of carbenes with alkenes is widely regarded as one of the most straightforward strategies for synthesizing cyclopropanes, which are ubiquitous motifs in pharmaceuticals. A significant challenge in cyclopropanation reactions is managing the high reactivity and inherent safety risks associated with the use of diazo compounds, particularly alkyl-substituted variants, as carbene precursors. Leveraging metallaphotoredox catalysis, we report the development of a method for ligated boryl radical-mediated generation of nonstabilized metal carbenes directly from aliphatic aldehydes. Employing B 2 cat 2 as the activating agent for the carbonyl group, this approach enables the direct use of alkyl aldehydes as nonstabilized carbene precursors, eliminating the need for substrate prefunctionalization. This protocol features mild conditions, broad substrate scope (>88 examples), and good functional group tolerance, demonstrating its applicability in diverse cyclopropanation and σ-bond insertion reactions. Preliminary mechanistic studies have been also performed to elucidate the reaction pathway.}, archive = {J_JACS}, author = {Rong-Bin Liang and Chao Yang and Wujiong Xia and Lin Guo}, doi = {10.1021/jacs.5c12677}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36781--36792}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoredox-catalyzed cyclopropanation via ligated boryl radical-mediated nonstabilized carbene formation}, volume = {147}, year = {2025}, }
• (2025). Design, synthesis, and application of a type of chiral spirocyclic naphthylamines. JACS, 147(40), 36774--36780. (www)

  @article{ , abstract = {A family of new spirocyclic chiral mono- and diamine structures has been designed together with their de novo asymmetric synthesis, featuring a short sequence from simple substrates. This study complements the previous limited exploration of the counterparts of well-established 1,1′-spirobiindane-7,7′-diol (SPINOL) and its modified analogs. The convenient enantioselective synthesis of 2,2′,3,3′-tetrahydro-1,1′-spirobi-[phenalene]-9,9′-diamine (SPHENAM) and 9′-amino-2,2′,3,3′-tetrahydro-1,1′-spirobi[phenalen]-9-ol (NOSPHEN) represents a notable advantage over the limited spirocyclic precedents of this type, which were uniformly derived from their spiro parents. Two synthetic routes, both featuring catalyst-controlled enantioselective induction, have been designed, leading to the convenient construction of a large library of both C 2 -symmetric and non- C 2 -symmetric derivatives of 2,2′,3,3′-tetrahydro-1,1′-spirobi[phenalene]-9,9′-diol (SPHENOL), all with high efficiency and enantiomeric excess. Preliminary studies have demonstrated their superior performance as backbones of diverse effective chiral catalysts and ligands, illustrating their potential in asymmetric synthesis.}, archive = {J_JACS}, author = {Ronghua Zhang and Minghui Zhu and Jianwei Sun}, doi = {10.1021/jacs.5c12568}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36774--36780}, shortjournal = {J. Am. Chem. Soc.}, title = {Design, synthesis, and application of a type of chiral spirocyclic naphthylamines}, volume = {147}, year = {2025}, }
• (2025). Potential pulsing-induced fe undercoordination in NiFe (Oxy)Hydroxide enhances electrochemical oxygen evolution. JACS, 147(40), 36763--36773. (www)

  @article{ , abstract = {Undercoordinated metal centers serve as key catalytic sites for the oxygen evolution reaction (OER) in water electrolysis. However, their inherent instability under oxidative conditions leads to rapid deactivation, limiting practical applications. Here, we demonstrate that reductive potential pulsing (RPP) is an effective strategy for generating and sustaining highly active undercoordinated Fe species in NiFe (oxy)hydroxide (NiFeOOH) during prolonged OER operation. Implementing this approach in an anion exchange membrane water electrolyzer enables a remarkable 40% enhancement in current density, achieving stable operation at 0.7 A/cm 2 for 180 h. A key insight from operando X-ray absorption characterization reveals that the OER activity of NiFeOOH is directly correlated with dynamically modulated Fe coordination, while the chemical state of Ni remains largely unchanged during OER and RPP processes. Beyond providing new insights into the long-standing debate over NiFeOOH active sites, this study introduces a practical approach to enhancing both activity and stability, with potential applicability to other electrochemical systems.}, archive = {J_JACS}, author = {Zhi-Peng Wu and Shouwei Zuo and Ruitao Wu and Cailing Chen and Xiaojuan Zhao and Yuanfu Ren and Xiangyun T. Xiao and Jing Zhang and Javier Ruiz-Martínez and Zhi-Pan Liu and Huabin Zhang and Yu Han}, doi = {10.1021/jacs.5c12507}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36763--36773}, shortjournal = {J. Am. Chem. Soc.}, title = {Potential pulsing-induced fe undercoordination in NiFe (Oxy)Hydroxide enhances electrochemical oxygen evolution}, volume = {147}, year = {2025}, }
• (2025). Germanium-mediated catalysis via Ge(II)/Ge(III)/Ge(IV) or Ge(II)/Ge(IV) redox cycling. JACS, 147(40), 36752--36762. (www)

  @article{ , abstract = {Main group elements have recently emerged as promising candidates for redox catalysis, challenging the traditional reliance on transition metals. Despite heavy group 14 elements, such as germanium, possessing variable oxidation states that suggest their redox catalytic potential, their practical applications have been limited. In this study, we present the synthesis of a carbodiphosphoranyl germanium(II) compound and investigate its redox catalytic application. This organogermanium(II) species exhibits excellent catalytic performance in promoting the transfer hydrogenation of azoarenes and imines under mild conditions. Mechanistic studies revealed two distinct catalytic platforms based on Ge II /Ge III /Ge IV and Ge II /Ge IV redox cycles at a single germanium center. These results enable us to achieve the catalytic hydrogenation of azoarenes mediated by frustrated radical pairs (FRPs), as well as the catalytic chemoselective dearomatization of N -heteroarenes undergoing a Ge II /Ge IV redox process. Our work demonstrates the capacity of main group catalysts to facilitate diverse challenging chemical transformations through regulating the catalytic modes.}, archive = {J_JACS}, author = {Yihan Zhou and Zhuchunguang Liu and Huan Mu and Hanjiao Chen and Xinran Fu and Bo Xiao and Weichao Xue and Jiliang Zhou and Zhaowen Dong}, doi = {10.1021/jacs.5c12407}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36752--36762}, shortjournal = {J. Am. Chem. Soc.}, title = {Germanium-mediated catalysis via Ge(II)/Ge(III)/Ge(IV) or Ge(II)/Ge(IV) redox cycling}, volume = {147}, year = {2025}, }
• (2025). Conformation and dynamics of monomeric, phase-separated, and cross-linked resilin biomaterials. JACS, 147(40), 36734--36751. (www)

  @article{ , abstract = {Resilin is an elastomeric protein found in insects that provides flexibility and locomotive function in numerous biological contexts. Recombinant resilin and resilin-derived proteins share resilin’s capacity for liquid–liquid phase separation (LLPS) and formation of materials with high elasticity and biocompatibility, making it a promising candidate for regenerative medicine and tissue engineering applications. While prior research has focused on domain 1 of resilin, the role of domain 3 (D3) in resilin self-assembly and material properties is not well understood. Here, we used nuclear magnetic resonance, electron paramagnetic resonance, and small-angle X-ray scattering to study the conformation, dynamics, and intermolecular interactions of D3 as a monomer, in the phase-separated state, and as a cross-linked gel. We show that D3 remains unusually dynamic and is primarily disordered in all three states. In elucidating the mechanism of D3 LLPS, we find a complex set of electrostatic and π-based interactions complemented by the hydrophobic effect that finely tune the solution sensitivity of D3 and its capacity for LLPS. Overall, these results highlight the complex mechanisms governing resilin LLPS with implications for utilizing resilin-derived sequence features in the rational design of self-assembling biomaterials.}, archive = {J_JACS}, author = {James B. Otis and Joerg Reichenwallner and Sean E. Reichheld and Aaron Au and Christopher M. Yip and Oliver P. Ernst and Simon Sharpe}, doi = {10.1021/jacs.5c12305}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36734--36751}, shortjournal = {J. Am. Chem. Soc.}, title = {Conformation and dynamics of monomeric, phase-separated, and cross-linked resilin biomaterials}, volume = {147}, year = {2025}, }
• (2025). Advancing chemoenzymatic synthesis and covalent immobilization of a comprehensive ganglio-glycosphingolipid library enables functional multiplex bead assays. JACS, 147(40), 36717--36733. (www)

  @article{ , abstract = {Ganglio-series glycosphingolipids (ganglio-GSLs) are biologically important glycolipids comprising a glycan of a ganglio-series nature and a lipid called ceramide. The glycan component often contains one or more sialic acid residues. Accesses to structurally defined ganglio-GSLs remain limited due to their structural complexity and synthetic challenges, hindering both functional studies and therapeutic applications. To overcome the challenges, we report herein a scalable chemoenzymatic total synthesis strategy for the construction of the most comprehensive library of ganglio-GSLs to date. A chiral pool approach was developed for synthesizing simple glycosylsphingosines with desired sphingosine lengths (d18:1 or d20:1) from inexpensive d -xylose. Complex glycosylsphingosines were prepared using enzyme assembly synthetic map (EASyMap)-guided streamlined one-pot multienzyme (OPME) and stepwise OPME (StOPMe) glycosylation strategies facilitated by designing mutants with improved catalytic efficiencies for two key glycosyltransferases (CjCgtA and human ST6GALNAC5). Ganglio-GSLs containing a terminal primary amino group were then prepared by chemical acylation, enabling their covalent immobilization on magnetic beads to form a novel comprehensive ganglio-GSL-bead library encompassing 0-, a-, b-, and c-series ganglio-GSLs including structures containing up to five sialic acid residues with different (α2–3/6/8) sialyl linkages. Multiplex binding assays revealed that ganglio-GSLs exhibit distinctive interactions with glycan-binding proteins including plant lectins, antiganglioside antibodies, bacterial toxins, galectins, and human and mouse siglecs. The integration of streamlined chemoenzymatic total synthesis strategies, glycosyltransferase engineering, covalent immobilization of GSL analogs, and a multiplex assay platform enables synthesis and high-throughput studies of previously difficult-to-obtain ganglio-GSLs. It is broadly applicable to help advance glycobiology and develop GSL-based diagnostics and therapeutics.}, archive = {J_JACS}, author = {Arin Gucchait and Jingxin Fu and Libo Zhang and Anand Kumar Agrahari and Zimin Zheng and Xiaohong Yang and Hai Yu and Xiaoxiao Yang and Ajit Varki and Xi Chen}, doi = {10.1021/jacs.5c12312}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36717--36733}, shortjournal = {J. Am. Chem. Soc.}, title = {Advancing chemoenzymatic synthesis and covalent immobilization of a comprehensive ganglio-glycosphingolipid library enables functional multiplex bead assays}, volume = {147}, year = {2025}, }
• (2025). Anionic lipids regulate the light-harvesting complex 1-reaction center photocycle in purple bacteria. JACS, 147(40), 36706--36716. (www)

  @article{ , abstract = {Photosynthetic purple bacteria can capture and convert sunlight with a remarkable, nearly 100% quantum efficiency. The light-harvesting complex 1-reaction center (LH1-RC) core complex is the membrane complex fundamentally responsible for solar energy conversion. LH1-RC has a highly conserved surrounding lipid composition known to favor anionic lipids for an unknown function. In this work, we compared experimentally the rate of LH1-to-RC energy transfer in detergent, membrane nanodiscs with varying lipid compositions, purified membrane fragments, and live cells. The energy transfer rate indicated that RC turnover decreased in neutral lipids, yet was partially restored in anionic lipids, revealing an unexpected lipid dependence. In complementary molecular dynamics simulations, the anionic lipid cardiolipin showed electrostatic interactions with LH1-RC that may mediate quinone exchange, providing a mechanism for the observed lipid dependence. Overall, these results revealed that anionic lipids facilitate LH1-RC redox cycling, identifying a functional role for membrane composition in photosynthetic solar energy conversion.}, archive = {J_JACS}, author = {Olivia C. Fiebig and Graham P. Schmidt and Neetu Singh Yadav and Dihao Wang and Muath Nairat and Helen Tang and Yi Ji and Valérie Prima and James N. Sturgis and Josh V. Vermaas and Dvir Harris and Gabriela S. Schlau-Cohen}, doi = {10.1021/jacs.5c12301}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36706--36716}, shortjournal = {J. Am. Chem. Soc.}, title = {Anionic lipids regulate the light-harvesting complex 1-reaction center photocycle in purple bacteria}, volume = {147}, year = {2025}, }
• (2025). Highly stable heterometallic catalysts for polyester depolymerization and polymerization at high temperatures. JACS, 147(40), 36697--36705. (www)

  @article{ , abstract = {Chemical depolymerization to monomer is a valuable tool in the quest to prevent the accumulation of single-use plastic, especially poly(ethylene terephthalate), PET, in the environment. However, the protic nucleophiles and high temperatures usually required in this process make the development of rationally designed, stable catalysts very challenging. Herein, we report a series of heterobimetallic catalysts, combining Zn(II) and Mg(II) with K(I) and Na(I) to form “ate” complexes that are stable in air and at high temperatures, which can be applied in the depolymerization of PET and poly(lactide), PLA. The catalysts present outstanding stability and remain active after 4 successive PET additions over several days on the bench. Reaction studies reveal the influence of the metal coordinated in the inner pocket of the ligand upon the activity of the metal coordinated in the outer pocket, with different heterobimetallic catalysts being found to be optimal for the depolymerization of PET and PLA respectively. Their potential for application in industrially relevant bulk polymerization of rac -lactide is also demonstrated and provides key insights for rational heterometallic catalyst design in the (de)polymerization of PET and PLA.}, archive = {J_JACS}, author = {Natalia V. Reis and Yali Zhou and Bige Bati and Ying Wang and Gary S. Nichol and Jennifer A. Garden and Andrew P. Dove}, doi = {10.1021/jacs.5c12243}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36697--36705}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly stable heterometallic catalysts for polyester depolymerization and polymerization at high temperatures}, volume = {147}, year = {2025}, }
• (2025). Molecular models of layered ternary Cu2MoS4 reveal sulfur-based h2 evolution pathway. JACS, 147(40), 36686--36696. (www)

  @article{ , abstract = {Highly crystalline ternary copper–molybdenum sulfide (Cu 2 MoS 4 ) has been demonstrated to promote the electro/photocatalytic hydrogen evolution reaction (HER). Theoretical calculations have suggested that Cu 2 MoS 4 outperforms molybdenum disulfide (MoS 2 ) because of its more moderate free energy of hydrogen adsorption, Δ G H* . However, the elucidation of intermediates involved in this process remains challenging, rendering the mechanistic details and specific role of Cu in improving activity uncertain. Herein, we describe the isolation and characterization of [NEt 4 ][Tp*MoS 3 (CuSPh) 2 ] (Tp* = tris(3,5-dimethylpyrazolyl)borate), a molecular model of Cu 2 MoS 4 capable of promoting electrocatalytic HER. Mechanistic investigations by DFT and multireference variational 2-electron reduced density matrix (v2RDM)-CASSCF implicate a sulfur-based hydrogen evolution pathway in which the bridging μ 2 -sulfides are rendered more basic by one-electron reduction, which populates a Mo-4d/S-3p based orbital with significant electron delocalization on the two μ 2 -sulfides. Reduction and protonation of two adjacent Mo(μ 2 -S) moieties leads to H 2 elimination with an accessible energy barrier of +20.2 kcal/mol. This pathway contrasts recent studies of stilbene hydrogenation by [Mo 3 S 4 Cl 3 (ImNH 2 ) 3 ] + , in which formation of the corresponding one-electron reduced μ 2 -SH species via H 2 splitting leads to spin density being shared across the Mo III centers. These results provide an atomistic perspective into the role of Cu in modulating the μ 2 -S p K a and facilitating HER via a formal Mo VI/IV cycle with significant electron delocalization between Mo, Cu, and μ 2 -S.}, archive = {J_JACS}, author = {Lauren T. Feden and Shatha Alabbad and Manuraj Kallumkal and Jan-Niklas Boyn and Gwendolyn A. Bailey}, doi = {10.1021/jacs.5c12079}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36686--36696}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular models of layered ternary Cu2MoS4 reveal sulfur-based h2 evolution pathway}, volume = {147}, year = {2025}, }
• (2025). Bio-inspired deconjugative isomerization of borylated dienoates. JACS, 147(40), 36677--36685. (www)

  @article{ , abstract = {The evolutionary success of (poly)ene isomerization paradigms in generating molecular diversity is manifest throughout biosynthesis. Algorithms to relocate short π-systems, often against a thermochemical bias, with simultaneous regio- and stereocontrol, are a feat of precision that remains challenging to translate to a laboratory setting. The divergent biosynthesis of vitamin D and tachysterol from previtamin D, leveraging positional or geometric isomerization, is a powerful exemplar. Inspired by this venerable blueprint, a deconjugative isomerization of borylated dienoates has been developed under the auspices of photochemical activation. Alleviating ground-state thermochemical restrictions through light-induced reactivity enables facile bifurcation of the diene and carbonyl chromophores: this occurs by a geometric isomerization/[1,5]-hydrogen shift sequence that emulates previtamin D photobiology. Broad functional group tolerance is observed, allowing the process to be leveraged in complex settings that would otherwise require multistep approaches. It is envisaged that the operationally simple, enabling nature of this strategy, coupled with the traceless nature of the boron handle, will stimulate interest in poly(ene) relocation strategies and begin to reconcile the paucity of synthetic methods with their ubiquity in biosynthesis.}, archive = {J_JACS}, author = {Amélia Messara and Byeongseok Kweon and Ferdinand Woge and Constantin G. Daniliuc and Christian Mück-Lichtenfeld and Ryan Gilmour}, doi = {10.1021/jacs.5c11995}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36677--36685}, shortjournal = {J. Am. Chem. Soc.}, title = {Bio-inspired deconjugative isomerization of borylated dienoates}, volume = {147}, year = {2025}, }
• (2025). Polyelemental nanoparticle synthesis enabled by noncontact metallothermic reactions. JACS, 147(40), 36669--36676. (www)

  @article{ , abstract = {Combinatorial synthesis, when coupled with high-throughput screening, accelerates materials discovery. However, the vast design space and synthetic challenges of nanomaterials present considerable barriers, and their structure–function relationships often differ from those of bulk materials. Here, we introduce an approach that combines “noncontact metallothermic reactions” with polymer pen lithography (PPL) and scanning probe block copolymer lithography (SPBCL) to enable the creation of libraries containing millions of nanoscale features. We successfully demonstrated the synthesis of diverse metal combinations spanning p-, d-, and f-block elements using nine representative ones (i.e., Al, Sc, Ti, V, Cr, Mn, Fe, Ga, La). We study the reaction pathway using Al 0.95 Sc 0.05 as a model system and validate the method’s scalability by preparing a 2 × 2 cm 2 chip made of glassy carbon, a common electrode material used for electrocatalysis, and characterizing representative compositions. This approach enables the efficient synthesis and exploration of complex material compositions, not attainable by existing methods, in a substrate general manner (SiN x , glassy carbon, and amorphous SiO 2 ) that will advance the systematic discovery of novel nanomaterials.}, archive = {J_JACS}, author = {Zhe Wang and Jin Huang and Chaojian Chen and Zihao Ye and Chad A. Mirkin}, doi = {10.1021/jacs.5c12003}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36669--36676}, shortjournal = {J. Am. Chem. Soc.}, title = {Polyelemental nanoparticle synthesis enabled by noncontact metallothermic reactions}, volume = {147}, year = {2025}, }
• (2025). Mode-specific coherent interference of vibrational sum-frequency generation imaging: An approach to differentiate lung tumors through collagen interfibrillar distances. JACS, 147(40), 36657--36668. (www)

  @article{ , abstract = {Chemical imaging holds great promise for chemical, materials, and biological applications. However, its contrast often relies on subtle spectral differences arising from molecular-level changes. Here, we introduce label-free chemical imaging based on bond-specific coherent interference, which is highly sensitive to nanoscopic structural variations in collagen fibers. We demonstrated this idea using vibrational sum-frequency generation (VSFG) microscopy to identify lung tumors by detecting collagen I structural remodeling. Hyperspectral VSFG images reveal dramatic differences in the NH and CH x stretch regions between metastatic and tumor-free lung tissues. Based on these differences, key spectral signatures, such as the intensity ratio of NH S /CH 2,Ss and CH S /CH 2,Ss modes, were established to reliably distinguish metastatic tumor and tumor-free tissues with high fidelity. Theoretical modeling based on structural knowledge from Electron Microscopy indicates that distinctive interferences between VSFG vibrational modes make the intensity ratio directly related to interfibrillar distances at the 20–50 nm level. These findings suggest that collagen fibrils are more densely packed in tumors, corroborating the enhanced stiffness observed in tumor tissues. This result establishes an interference-based imaging mechanism that enhances chemical contrast and enables nanoscale structural readouts without labels. This method not only preserves sample integrity but also provides a powerful platform for fundamental biophysical studies and holds strong potential for future applications in oncology and pathology.}, archive = {J_JACS}, author = {Bin Yang and Jianyu Ren and Chun-Chieh Yu and Zixuan Wang and Minghui Cao and Shizhen Emily Wang and Wei Xiong}, doi = {10.1021/jacs.5c11862}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36657--36668}, shortjournal = {J. Am. Chem. Soc.}, title = {Mode-specific coherent interference of vibrational sum-frequency generation imaging: An approach to differentiate lung tumors through collagen interfibrillar distances}, volume = {147}, year = {2025}, }
• (2025). Gas–Liquid decoupling transport by self-draining in the anode of anion exchange membrane fuel cells. JACS, 147(40), 36650--36656. (www)

  @article{ , abstract = {The gas–liquid decoupling transport represents a fundamental challenge in anode catalytic layers of anion exchange membrane fuel cells (AEMFCs), where water exhibits a paradoxical duality: as an essential transport medium for hydroxide ions (OH – ), yet as a kinetic-limiting product requiring immediate expulsion. Herein, we report a biomimetic capillary-driven water management strategy to achieve gas–liquid decoupling transport by engineering a hierarchically porous carbon nanofiber layer (CNL) as a self-draining anode catalytic layer (SD-ACL). The SD-ACL achieves anisotropic mass transport through structurally decoupled pathways: promoting rapid through-plane gas transport with a hydrophobic porous network while driving spontaneous in-plane water drainage via capillary action. As a result, the SD-ACL-fabricated membrane electrode assemble (MEA) achieved a high peak power density of 1150.3 mW cm –2 at high humidity with excellent durability, which was 2.3 times higher than that of the traditional one. Moreover, the SD-ACL could enhance nonprecious metal-anode-based AEMFCs by 57.5%, offering a promising strategy to achieve high-performance platinum-group metal-free (PGM-free) AEMFC technology.}, archive = {J_JACS}, author = {Guangyao Zhao and Zebi Chen and Xiaoyun Song and Qimei Yang and Jian Wang and Wei Ding and Zidong Wei}, doi = {10.1021/jacs.5c11489}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36650--36656}, shortjournal = {J. Am. Chem. Soc.}, title = {Gas–Liquid decoupling transport by self-draining in the anode of anion exchange membrane fuel cells}, volume = {147}, year = {2025}, }
• (2025). Symmetry breaking induced by chiral phosphonic acids in a 2D tin-halide perovskite. JACS, 147(40), 36642--36649. (www)

  @article{ , abstract = {The ability to induce and modulate chirality in metal halide perovskite semiconductors (MHPs) using chiral additives expands the compositional design space and offers a means of tuning chiroptical properties. Motivated by the ability of phosphonic acids to interact with metal ions, we designed three chiral phosphonic acids (CPAs) to impose chirality in otherwise achiral 2D MHP, phenylammonium tin iodide (PA 2 SnI 4 ). We found that both the position of the phosphonic acid relative to the bond between the two naphthalene rings (i.e., the chiral axis) and the distance between the phosphonic acid and the binaphthyl chiral units significantly impact the transfer of structural chirality into the MHP lattice. The compound with a phosphonic acid directly bound to one of the naphthalene rings at the carbon adjacent to the chiral axis resulted in the largest circular dichroism dissymmetry factor of the three phosphonic acids. Furthermore, optical pump-terahertz probe measurements reveal an increase in the charge carrier mobility in the MHPs following the addition of CPAs. This dual functionality of CPAs in inducing chirality and improving charge transport properties in MHPs is promising for chiral-optoelectronic applications.}, archive = {J_JACS}, author = {Margherita Taddei and Junxiang Zhang and Md Azimul Haque and Colin McLeod and Steven P. Harvey and Yifan Dong and Laura T. Schelhas and Stephen Barlow and Jeffrey L. Blackburn and Joseph M. Luther and Seth R. Marder and Matthew C. Beard}, doi = {10.1021/jacs.5c11860}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36642--36649}, shortjournal = {J. Am. Chem. Soc.}, title = {Symmetry breaking induced by chiral phosphonic acids in a 2D tin-halide perovskite}, volume = {147}, year = {2025}, }
• (2025). Covalent organic frameworks with localized high polarity via defect engineering for interfacial regulation of aqueous zinc batteries. JACS, 147(40), 36626--36641. (www)

  @article{ , abstract = {Aqueous zinc batteries are promising energy storage systems, but face significant challenges, including zinc dendrite growth, electrochemical corrosion, and poor reversibility for large-scale applications. Herein, we design a defective fluorinated covalent organic framework (FCOF) with localized high polarity based on a truncated monomer strategy. Controllable defect design in the FCOF framework produces polar amino groups with enhanced Zn 2+ trapping ability. Meanwhile, an additional transport pathway was formed at the well-designed defect sites, which reduced the migration energy barriers. The Zn 2+ diffusion coefficient of the optimal defective FCOF separators (FCOF-30, with 30% defect content) was calculated to be 9.83 × 10 –10 cm s –1 (2 times higher than FCOF). At 10 mA cm –2 (5 mAh cm –2 ), the symmetric cell using FCOF-30 exhibited excellent Zn 2+ deposition/stripping behavior with 1200 h cycling stability. This defect engineering concept provided in-depth insights into the ion transport regulation for the electrochemical energy storage applications.}, archive = {J_JACS}, author = {Shaochong Cao and Tianlin Zhou and Yongshuai Liu and Wenyi Lu and Aiwen Zhang and Shan He and Pengshu Yi and Longli Ma and Zhu Liu and Fengkai Zuo and Liang Cao and Zhouhong Ren and Mingxin Ye and Huayi Fang and Jianfeng Shen}, doi = {10.1021/jacs.5c11813}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36626--36641}, shortjournal = {J. Am. Chem. Soc.}, title = {Covalent organic frameworks with localized high polarity via defect engineering for interfacial regulation of aqueous zinc batteries}, volume = {147}, year = {2025}, }
• (2025). Triazolate-functionalized zirconium nitride for air-fed H2O2 production with industrial-level current density. JACS, 147(40), 36618--36625. (www)

  @article{ , abstract = {The electrochemical two-electron oxygen reduction reaction (2e – ORR) offers a green and energy-efficient pathway for hydrogen peroxide (H 2 O 2 ) production, yet reliance on high-purity oxygen significantly limits scalability. Here, we report a triazolate-modified zirconium nitride catalyst (T-ZrN) that enables efficient and durable H 2 O 2 electrosynthesis directly from atmospheric air. The T-ZrN catalyst achieves a high H 2 O 2 yield of 55.6 mol·h –1 ·g –1 and a Faradaic efficiency of 93.2%, while maintaining stable operation over 540 h at an industrial-level current density of 800 mA·cm –2 . Economic analysis reveals a production cost of 70 wt % H 2 O 2 as low as $0.10 kg –1 , highlighting its commercial potential. This work presents a viable strategy for cost-effective and decentralized H 2 O 2 manufacturing advancing sustainable chemical production technologies.}, archive = {J_JACS}, author = {Jiahao Liu and Zhaorui Zhang and Xiaoli Wang and Chenshuai Han and Minghui Yang}, doi = {10.1021/jacs.5c11803}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36618--36625}, shortjournal = {J. Am. Chem. Soc.}, title = {Triazolate-functionalized zirconium nitride for air-fed H2O2 production with industrial-level current density}, volume = {147}, year = {2025}, }
• (2025). Impact of carbene ligands on the properties and reactivity of diazoboranes. JACS, 147(40), 36604--36617. (www)

  @article{ , abstract = {While diazo compounds and organic azides have been extensively studied over the past two centuries, their boron analogs, diazoboranes, were only successfully isolated last year, and their properties remain largely unexplored. This study presents a systematic investigation of the synthesis, properties, and reactivity of diazoboranes. In this work, the diazoborane library is expanded to eight species by varying the carbene ligands coordinated to boron, allowing the identification of key correlations between ligand electronic properties and diazoborane behavior. The results demonstrate that increasing carbene π-acidity weakens the B–N bond while strengthening the N–N bond, significantly decreasing thermal stability. Kinetic studies reveal that less π-acidic carbenes promote a second-order decay mechanism, leading to dibora-azine formation, whereas more π-acidic carbenes favor first-order dinitrogen dissociation, facilitating borylene generation. Electrochemical studies indicate that redox potentials also correlate with carbene π-acidity. Three representative reactivity studies are presented in which the same substrate reacts with different diazoboranes to yield either different products or the same product via different reaction mechanisms. These insights provide a generalizable framework for tuning diazoborane properties, facilitating their use in cycloaddition chemistry and small-molecule activation.}, archive = {J_JACS}, author = {Chonghe Zhang and Agustin Valles and Junyi Wang and Noah D. McMillion and Christopher C. Cummins and Robert J. Gilliard, Jr}, doi = {10.1021/jacs.5c11090}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36604--36617}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of carbene ligands on the properties and reactivity of diazoboranes}, volume = {147}, year = {2025}, }
• (2025). Explainable recommendation engines to predict complex intermetallics: Synthesis and characterization of Gd10RuCd3, a neutron absorption material. JACS, 147(40), 36589--36603. (www)

  @article{ , abstract = {The search for a neutron absorption material was aided by materials informatics tools that comprise the developed recommendation engines. A new member in the ternary RE 10 MCd 3 series, Gd 10 RuCd 3 , was predicted and synthesized as an experimental validation. The recommendation engine is based on partial least-squares-discriminant analysis (PLS-DA) crystallographic site processing to classify the site preference of elements in compounds crystallizing in the Y 10 RuCd 3 -type structure and upon projecting other elements onto Principal Component map, the titled compound emerged as the top candidate. The distinguishing feature of the developed recommendation engine is in the three explainable methods utilized in the predictive framework: unrestricted, conservative, and cluster methods. Predictions are visualized with convenient property projection tools. The prediction was validated by high-temperature synthesis. The structure was confirmed with single-crystal and powder X-ray diffraction. The cold-water-quenched samples quenched at 800 °C have a smaller unit cell volume than the samples quenched at 600 °C annealing temperature. Transport property measurements show an unusually low thermal conductivity (5–7 W·m –1 K –1 ) and a trend change indicates a possible structure transition between 600 and 800 °C. The unusual low thermal conductivity was predicted with a machine-learning model that focuses on thermoelectric property prediction. DFT analysis reveals the presence of a 0D electride phenomenon. The neutron cross section and absorption based on the constituent elements put our material within the top 0.4% of neutron absorbers. The negative thermal expansion and high mass absorption suggest Gd 10 RuCd 3 as an attractive neutron absorption material.}, archive = {J_JACS}, author = {Brook Xhabrahimi and Emil I. Jaffal and Danila Shiryaev and Nikhil K. Barua and Madison Donohoe and Natalia Pozdnyakova and Mariam Ismail and Balaranjan Selvaratnam and Ehsan Niknam and Holger Kleinke and Anton O. Oliynyk}, doi = {10.1021/jacs.5c11646}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36589--36603}, shortjournal = {J. Am. Chem. Soc.}, title = {Explainable recommendation engines to predict complex intermetallics: Synthesis and characterization of Gd10RuCd3, a neutron absorption material}, volume = {147}, year = {2025}, }
• (2025). Photoredox catalysis with spin magnetic field effects: A scheme for chiral resolution. JACS, 147(40), 36579--36588. (www)

  @article{ , abstract = {Quantities that break both mirror symmetry and time-reversal symmetry, such as the orbital angular momentum, are known to connect molecular chirality with an applied magnetic field. This concept has led to observations such as magneto-chiral dichroism and chirality-induced spin selectivity (CISS). However, being small, these effects often require additional amplification procedures such as flow chemistry to achieve bulk enantioseparation. In this work, we demonstrate how the magnetic field effect on photogenerated radical pairs, which also breaks time-reversal symmetry, can be harnessed for enantiopurification. Fundamental to this process is the collective decay of the singlet and triplet radical-pair states made possible by an applied magnetic field. Because opposite enantiomers exhibit spin–orbit coupling matrix elements of opposite signs, the singlet and triplet decay channels interfere constructively in one enantiomer. Meanwhile, molecules of the other enantiomer are funnelled into the first enantiomer through excited-state chirality inversion, achieving (dynamic kinetic) chiral resolution. Using an axially chiral binaphthyl derivative and a borane photosensitizer as prototype, we predict an appreciable enantiomeric excess (e.e.) of 90% to be possible at steady state, attained within hundreds of milliseconds when irradiated by a laser. Importantly, our analytical results showcase regimes of perfect enantioselectivity (100% e.e.), accessible by further chemical optimization of the photosensitizer for which general strategies are discussed. Overall, this work illustrates a so-far untapped but powerful control knob for photoredox catalysis based on spin chemistry principles.}, archive = {J_JACS}, author = {Yong Rui Poh and Arghadip Koner and Michael Reitz and Joel Yuen-Zhou}, doi = {10.1021/jacs.5c11502}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36579--36588}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoredox catalysis with spin magnetic field effects: A scheme for chiral resolution}, volume = {147}, year = {2025}, }
• (2025). Metal–Metal bonding influences hydride reactivity in [Sn–Rh]3+ and [Sn–Ni]2+ bimetallics. JACS, 147(40), 36570--36578. (www)

  @article{ , abstract = {Heavier group 14 metal hydrides serve as key intermediates in catalytic transformations, such as hydroboration. Regenerating such intermediates via a clean hydride source like dihydrogen could provide catalytic processes with a more economical alternative to, e.g., silanes and hydridoborane reagents. Herein, we report our efforts toward this goal using a [Sn–Rh] 3+ bimetallic system with the formal Rh I center acting as a potential dihydrogen activator. Targeting the introduction of a hydride ligand to the bimetallic core, our reactivity studies have revealed a preference for the hydride ligand to be bound to the Rh center, instead of the Sn center. Examination of the electronic structures of these complexes via theoretical and experimental methods has revealed the electron acceptor nature of the Rh center within the bimetallic core and offers an explanation for the localization of the hydride between metal centers.}, archive = {J_JACS}, author = {Benyu Zhou and Samantha N. MacMillan and Kyle M. Lancaster}, doi = {10.1021/jacs.5c11577}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36570--36578}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal–Metal bonding influences hydride reactivity in [Sn–Rh]3+ and [Sn–Ni]2+ bimetallics}, volume = {147}, year = {2025}, }
• (2025). UCl3-type crystalline oxychloride electrolytes for all-solid-state lithium-ion batteries. JACS, 147(40), 36557--36569. (www)

  @article{ , abstract = {Halide solid-state electrolytes are promising for next-generation all-solid-state lithium-ion batteries due to their high ionic conductivity and wide electrochemical windows. While most research focuses on close-packed crystal structures, nonclose-packed frameworks─exemplified by UCl 3 -type structures─offer unique advantages in enhancing lithium-ion transport via reduced diffusion barriers. Here, we report a new family of UCl 3 -type crystalline oxychloride electrolytes, Li 0.388+ x La 0.475 Ta 0.238 Cl 3– x O x (0 ≤ x ≤ 0.388, LLTCO), synthesized via rapid high-energy shake milling. The material with an optimized composition ( x = 0.15) exhibits high ionic conductivity above 2 mS cm –1 at 30 °C, oxidative stability exceeding 5 V vs Li/Li + , and excellent mechanical compressibility. Moreover, the LLTCO-based Li–Li symmetric cells show a long cycle life, indicating their strong capacity to suppress lithium dendrite formation. Spectroscopy analyses reveal the successful incorporation of oxygen, which preferentially substitutes Cl – around Ta 5+ sites without compromising crystallinity, even at a high oxygen content. The oxygen incorporation further promotes the formation of Li environments with fast dynamics, accounting for the enhanced conductivity. All-solid-state batteries utilizing the optimized oxychloride electrolyte in conjunction with Ni-rich cathodes demonstrate enhanced reversible capacities compared to their undoped counterparts. This work highlights the benefits of nonclose-packed UCl 3 -type oxychloride electrolytes, offering new design strategies for high-performance all-solid-state batteries.}, archive = {J_JACS}, author = {Junlong Yang and Shiwei Chen and Qiong Yuan and Guangsu Tan and Qinzhe Liu and Shaoyu Yang and Yanxin Deng and Yingbo Zhao and Wei Liu and Yi Yu and Yanming Cui and Jian Wang and Shou-Hang Bo and Chao Xu}, doi = {10.1021/jacs.5c11480}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36557--36569}, shortjournal = {J. Am. Chem. Soc.}, title = {UCl3-type crystalline oxychloride electrolytes for all-solid-state lithium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Constructing symmetric all-organic proton battery via scalable flux synthesis of vinylene-linked covalent organic frameworks. JACS, 147(40), 36547--36556. (www)

  @article{ , abstract = {The design and assembly of symmetric all-organic batteries, eliminating the need for distinct cathode/anode materials while maintaining comparable energy storage performance, has been a highly sought-after objective but has barely been achieved with both high capacity and long-term stability. Herein, we design and synthesize two pyrazino[2,3- g ]quinoxaline core-based vinylene-linked covalent organic frameworks (COFs) via the flux synthesis method, featuring two-step redox reactions due to the distinct chemical environments of adjacent C═N groups, to fabricate a symmetric all-organic proton battery, which was confirmed by the mechanism study. The assembled COF-based all-organic battery exhibits excellent performance, with good specific capacity (147 mAh g –1 at 0.1 A g –1 ) and maximum energy density (87 Wh/kg) with over 5000 cycles at high current density, among the best of the reported all-organic proton batteries. The flux synthesis method facilitates the gram-scale production of COFs, enabling their successful assembly into functional pouch cells. As a result, the assembled pouch cell delivers a reversible maximum capacity of 92 mAh g –1 at 0.1 A g –1 , corresponding to a total capacity of 0.92 Ah, approaching the theoretical design capacity. This work inspires the design of all-organic proton batteries and promotes practical application of COFs in the future.}, archive = {J_JACS}, author = {Fengdong Wang and Qingxue Ma and Shaochun Wu and Yi Yang and Xiyuan Wang and Yao Chen and Peng Cheng and Zhenjie Zhang}, doi = {10.1021/jacs.5c11360}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36547--36556}, shortjournal = {J. Am. Chem. Soc.}, title = {Constructing symmetric all-organic proton battery via scalable flux synthesis of vinylene-linked covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Asymmetric coordination designed heterocrown ether Host–Guest ferroelectrics with ultrahigh tc. JACS, 147(40), 36539--36546. (www)

  @article{ , abstract = {Crown ether compounds have garnered significant research interest for decades due to their unique host–guest supramolecular structure and various properties, such as ferroelectricity. However, although many crown ether derivatives have been developed, only the classical crown ether represented by 18-crown-6 was used as the host for crown ether host–guest-type ferroelectrics, and the heterocrown ether-based ferroelectrics have never been reported. Here, for the first time, we propose the strategy of asymmetric coordination through heterocrown ether as a host molecule to unlock ferroelectricity in metal-crown host–guest assemblies. Compared to the symmetrical coordination of the parent M(NO 3 ) 2 (18-crown-6) (M = Pb 2+ or Cd 2+ ), an asymmetric coordination environment for the M 2+ ion was created in M(NO 3 ) 2 (1-aza-18-crown-6), enabling precise symmetry breaking and inducing ferroelectricity. Remarkably, Pb(NO 3 ) 2 (1-aza-18-crown-6) exhibits an ultrahigh T c of 470 K, which represents the maximum value reported to date for crown ether-based ferroelectrics. Such high T c originates from the synergistic effect of disordered rotation commonly observed in the host–guest compounds and the unique out-of-plane flipping motion of the −NH– group in aza-crown ether. To the best of our knowledge, M(NO 3 ) 2 (1-aza-18-crown-6) represents the birth of the first heterocrown ether ferroelectric family. Our findings provide a new way to design crown ether host–guest ferroelectrics with high performance and greatly stimulate the further exploration of heterocrown ether ferroelectrics.}, archive = {J_JACS}, author = {Xiao-Gang Chen and Yan-Ran Weng and Yao Zhang and Xian-Jiang Song and Hui-Peng Lv and Yan Qin and Wei-Qiang Liao and Ren-Gen Xiong and Yong Ai}, doi = {10.1021/jacs.5c11537}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36539--36546}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric coordination designed heterocrown ether Host–Guest ferroelectrics with ultrahigh tc}, volume = {147}, year = {2025}, }
• (2025). Access to hybrid sandwich complexes of early transition metals with Cp/Cp* and cyclo-e5 ligands (E = p, as). JACS, 147(40), 36530--36538. (www)

  @article{ , abstract = {Since the groundbreaking discovery of [Cp*Fe(η 5 -P 5 )] (Cp* = η 5 -C 5 Me 5 ), the exploration of hybrid inorganic sandwich complexes combining cyclopentadienyl-type ligands and cyclo -E 5 rings (E = P, As) has been an active research area of inorganic chemistry, for extensive reactivity studies involving the production of numerous derivatives and supramolecular aggregates. However, synthetic limitations have hitherto restricted their accessibility to group 8 transition metals. Herein, we present a facile and versatile approach to access such 16e–18e complexes of early transition metals, [CpV(η 5 -E 5 )] 1–/2– , [CpCr(η 5 -E 5 )] − , and [Cp*Mn(η 5 -P 5 )] − (E = P, As; Cp = η 5 -C 5 H 5 ). By utilizing the Zintl phase precursor K 3 E 7 as a reductant, these new complexes can be rapidly synthesized via one-pot reactions at ambient temperature within 1 h. This method enables the preparation of diverse derivatives from [CpV(η 5 -E 5 )] 2– , including the oxidative coupling product [(CpV) 2 (μ,η 4:4:1:1 -P 10 )] 2– as well as its niobium congener [(CpNb) 2 (μ,η 4:4:1:1 -P 10 )] 2– , and the addition rearrangement products [(CpV) 6 P 10 ] 2– and [(CpV)(μ,η 4:5 -As 5 )Mn(η 3 -As 3 )] 2– . The Zintl-driven reduction strategy provides a viable approach to expand hybrid sandwich complexes beyond group 8 metals and enables the exploration of novel inorganic architectures.}, archive = {J_JACS}, author = {Zi-Chuan Wang and Shuang Wang and Wen-Juan Tian and Zi-Yan Guo and Manfred Scheer and Zhong-Ming Sun}, doi = {10.1021/jacs.5c11444}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36530--36538}, shortjournal = {J. Am. Chem. Soc.}, title = {Access to hybrid sandwich complexes of early transition metals with Cp/Cp* and cyclo-e5 ligands (E = p, as)}, volume = {147}, year = {2025}, }
• (2025). Vertical growth of amorphous carbon ribbons by a salt-lattice trifunctionalized vapor-surface-solid mechanism. JACS, 147(40), 36516--36529. (www)

  @article{ , abstract = {One-dimensional (1D) carbon nanomaterials have attracted significant attention due to their unique directional confinement effect and electronic structure. Conventional synthesis strategies have struggled to achieve vertically aligned architectures with large aspect ratios, scalable yields, and tunable electronic structures. Herein, we propose a sodium chloride (NaCl) salt-assisted template approach to enable the vertical growth of amorphous carbon ribbons (CRs), which have long-range disordered and short-range ordered skeleton structures, with the attributes of a new type of carbon allotrope. The significance of lattice stability, lattice matching, and molecular structure of precursors is investigated to elucidate the trifunctional roles of NaCl microcrystals as induction, catalysis, and growth templates. Furthermore, an advanced vapor-surface-solid (VSS) growth mechanism, stemming from π–π stacking and polymerization of perylene-based skeletons, is validated to afford the vertical growth of CRs. Strikingly, tunable sp 2 /sp 3 carbon ratios allow for modulating the electronic structure. Correspondingly, the representative CRs are p-type semiconductors with a wide band gap of 3.32 eV, exhibiting rapid responsiveness to ultraviolet (UV) radiation. The free-standing CR films deliver an out-of-plane conductive network, a large permittivity in the X-wave frequency range, and outstanding stability. Our contribution opens a novel roadmap in terms of innovative synthesis and fascinating applications of the 1D carbon family.}, archive = {J_JACS}, author = {Changxiao Fu and Qian Yang and Yan Jin and Ya Ma and Qian Zhang and Daliang Zhang and Baoshan Hu}, doi = {10.1021/jacs.5c11387}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36516--36529}, shortjournal = {J. Am. Chem. Soc.}, title = {Vertical growth of amorphous carbon ribbons by a salt-lattice trifunctionalized vapor-surface-solid mechanism}, volume = {147}, year = {2025}, }
• (2025). Efficient photoinduced living polymerization driven by shortwave infrared CuInSe2/CuInS2 quantum dots. JACS, 147(40), 36508--36515. (www)

  @article{ , abstract = {Shortwave infrared (SWIR) light-driven photoinduced electron/energy transfer reversible addition–fragmentation chain transfer (PET-RAFT) polymerization holds great promise for applications such as 3D printing and transdermal photopolymerization. However, efficient SWIR-active photocatalysts remain lacking. Herein, we report the use of lead-free CuInSe 2 /CuInS 2 core/shell quantum dots (QDs), with their absorption onset extending to 1100 nm, to drive efficient SWIR PET-RAFT polymerization. Time-resolved spectroscopy reveals that both band-edge and trap-state electrons can transfer to the RAFT agent. The relatively sluggish hole transfer, due to hole localization to copper states, can be accelerated by introducing amines as hole scavengers. The reaction exhibits well-defined characteristics of living polymerization and proceeds efficiently in the presence of a 3 mm biological tissue barrier under 1050 nm irradiation.}, archive = {J_JACS}, author = {Yongshun Lyu and Qun Zhang and Cyrille Boyer and Kaifeng Wu and Jun Du}, doi = {10.1021/jacs.5c11312}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36508--36515}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient photoinduced living polymerization driven by shortwave infrared CuInSe2/CuInS2 quantum dots}, volume = {147}, year = {2025}, }
• (2025). Engineering Cu/Ru heterointerface-shelled nanocavities by the kirkendall effect for highly efficient nitrate electroreduction to ammonia. JACS, 147(40), 36494--36507. (www)

  @article{ , abstract = {Electrochemical nitrate (NO 3 – ) reduction to ammonia (NH 3 ) offers a sustainable approach for NH 3 synthesis while concurrently addressing NO 3 – pollution. However, achieving efficient NO 3 – -to-NH 3 conversion remains challenging due to sluggish multistep proton-coupled electron transfer processes and poor intermediate converison. Here, we present a nanocatalyst featuring a hollow nanocavity encased within a shell rich in Cu/Ru heterointerfaces, which synergistically leverages both interfacial and structural advantages to effectively lower energy barriers and accelerate intermediate conversion kinetics, thereby enhancing the overall catalytic performance for NH 3 production. Density functional theory (DFT) computations, supported by operando and control experiments, reveal that CuRu heterointerfaces with their optimized electronic structure act as the primary active sites, establishing a favorable NO 3 – -to-NH 3 reaction pathway. Simultaneously, the catalytic synergy between Cu and CuRu sites enables tandem catalysis, which is further amplified by nanocavity-induced spatial confinement of the key intermediate NO 2 – . This nanocatalyst is realized via a Kirkendall effect–driven strategy, with its structural features systematically optimized. The resulting catalyst demonstrates outstanding NH 3 production performance in a 0.1 M KNO 3 + 0.1 M KOH electrolyte, delivering a Faradaic efficiency of 97.4%, a yield of 152.6 mg h –1 mg metal –1 , and an energy efficiency of 40% at a low potential of −0.1 V RHE ─positioning it as a top contender among state-of-the-art NO 3 – -to-NH 3 electrocatalysts. By elucidating mechanistic insights into interfacial effects, tandem catalysis, and nanoconfinement, this work highlights the synergistic impact of compositional and structural engineering and offers a generalizable design strategy for advancing NO 3 – -to-NH 3 electroconversion and broader sustainable catalytic transformations.}, archive = {J_JACS}, author = {Shuangqun Chen and Zhouhao Zhu and Kepeng Song and Hengrui Zhang and Dan Luo and Tong Cao and Yongtu Zou and Changxu Liu and Liyong Gan and Daliang Zhang and Yu Han and Jianfeng Huang}, doi = {10.1021/jacs.5c11097}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36494--36507}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering Cu/Ru heterointerface-shelled nanocavities by the kirkendall effect for highly efficient nitrate electroreduction to ammonia}, volume = {147}, year = {2025}, }
• (2025). Anomalous metallic cubic CsCuBr3 perovskites: Pressure- and temperature-driven suppression of Jahn–Teller distortion. JACS, 147(40), 36486--36493. (www)

  @article{ , abstract = {Distinct from traditional halide perovskites, which are based on main-group elements (e.g., Pb 2+ , Sn 2+ , Ge 2+ ) and are typically semiconducting, transition metals like Cu 2+ ─characterized by partially filled d-orbitals─offer unique advantages in modulating the electronic behavior of perovskite materials. However, the strong Jahn–Teller effect of Cu 2+ makes it a significant challenge for stabilizing a robust three-dimensional perovskite framework. Herein, we report the first synthesis of a metallic cubic perovskite phase of CsCuBr 3 via a tailored structural design under high-temperature and high-pressure conditions. In situ synchrotron X-ray diffraction reveals that the orthorhombic nonperovskite CsCuBr 3 precursor (space group C 222 1 ) transforms into a cubic perovskite structure (space group Pm -3 m ) featuring an undistorted corner-sharing octahedral framework at ∼22 GPa and ∼603 K. The perovskite structure remains stable at pressure down to 4.3 GPa at room temperature, while at low temperatures below 50 K, it may be recovered to ambient pressure. Notably, the structure lacks both the expected luminescence and a distinct absorption edge, instead exhibiting a metallic behavior, as confirmed by temperature-dependent resistance measurements. Electronic structure calculations at 22.4 GPa and 0 K further reveal pronounced hybridization between the Cu-3d and Br-4p orbitals near the Fermi level, leading to an enhanced orbital degeneracy and electron delocalization. These findings demonstrate that the lattice contraction effectively suppresses the strong Jahn–Teller distortion intrinsic to Cu 2+ , offering a promising strategy for the design of high-performance novel materials.}, archive = {J_JACS}, author = {Mei Li and Pengfei Shan and Bohao Zhao and Yiming Wang and Kejun Bu and Junlong Li and Hao Wang and Tingting Zhao and Shang Peng and Dongliang Yang and Sheng Jiang and Jiao An and Jinguang Cheng and Wenge Yang and Xujie Lü and Chuanlong Lin}, doi = {10.1021/jacs.5c11030}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36486--36493}, shortjournal = {J. Am. Chem. Soc.}, title = {Anomalous metallic cubic CsCuBr3 perovskites: Pressure- and temperature-driven suppression of Jahn–Teller distortion}, volume = {147}, year = {2025}, }
• (2025). Site-, stereo-, and chemoselective enzymatic halogenation of terpenoids by a substrate masquerade. JACS, 147(40), 36478--36485. (www)

  @article{ , abstract = {Enzymatic halogenation of C–H bonds is a promising approach to synthesize chlorine-containing compounds. However, few halogenases chlorinate C(sp 3 )–H bonds of molecules lacking a carrier protein, and only a small subset readily accommodate non-native substrates. Competitive oxygenation of non-native substrates makes their halogenation a challenge to achieve. Herein, we report a strategy for the halogenation of unnatural substrates by which an anchoring group leads them to masquerade as the native substrate. By this approach, a series of terpenoids connected to an indole moiety, undergo enzymatic halogenation catalyzed by WelO5*, a non-heme, α-ketoglutarate-dependent halogenase. By in silico substrate evaluation and mutagenesis, we generated WelO5* variants that catalyze the chlorination of C(sp 3 )–H bonds in a series of non-native substrates with high selectivity for chlorination over oxygenation and with excellent stereoselectivity, as well as variants that catalyze bromination and azidation. Studies that vary the anchoring group showed that a series of heteroaromatic and aromatic groups can enhance reactivity and can influence the degree of chlorination of the anchored menthol substrate. Cleavage of the ester tethering the indole anchoring group to the terpenoid gives the free halogenated compound.}, archive = {J_JACS}, author = {Colby S. Kayrouz and Jenna L. Manske and Martí Garçon and Isaac A. Joyner and Yuehan Wang and Yifei Ge and Alexandra E. Paton and Alison R. H. Narayan and John F. Hartwig}, doi = {10.1021/jacs.5c11068}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36478--36485}, shortjournal = {J. Am. Chem. Soc.}, title = {Site-, stereo-, and chemoselective enzymatic halogenation of terpenoids by a substrate masquerade}, volume = {147}, year = {2025}, }
• (2025). Zn2+ binding shifts the conformational ensemble of α-synuclein monomers toward accelerated amyloid formation. JACS, 147(40), 36464--36477. (www)

  @article{ , abstract = {Alpha-synuclein (αS) is an intrinsically disordered protein (IDP) that can self-assemble into amyloid fibrils, undergoing a transition from disordered monomers to ordered β-sheet-rich fibrils. The amyloid state of αS is implicated in various synucleinopathies, most notably Parkinson’s disease (PD), in which αS fibrils accumulate as insoluble Lewy body deposits. Colocalized with αS in Lewy bodies are elevated levels of metal ions including Zn 2+ . We find in vitro that Zn 2+ accelerates aggregation of N-terminally acetylated αS, decreasing the t 50 ca. 5-fold, as measured by thioflavin T (ThT) fluorescence. Strikingly, the extent of Zn 2+ binding (native mass spectrometry; MS) and shifts of the monomeric αS conformational ensemble toward compaction, measured using ion mobility MS (IM-MS) at different αS:Zn 2+ ratios, mirror precisely the accelerated aggregation kinetics. Chemical shift perturbations in Nuclear Magnetic Resonance (NMR) spectroscopy were investigated together with molecular dynamics (MD) to map the Zn 2+ binding sites and subsequent effects on conformation under identical solution conditions to those used in IM-MS. Zn 2+ is found to predominantly interact with negative residues in the C-terminal region of αS but also His50 in the N-terminal region. This promiscuity in interactions potentially guides compaction of the protein chain by bridging residues between the N- and C-terminal regions through Zn 2+ ion co-ordination. This study provides insights into the early stages of amyloid assembly, correlating aggregation kinetics with structural compaction in monomeric αS and highlighting the capability of native IM-MS to resolve complex structural ensembles of a disordered protein.}, archive = {J_JACS}, author = {Emily J. Byrd and Benjamin Rowlinson and Joel A. Crossley and David J. Brockwell and James F. Ross and Sheena E. Radford and Frank Sobott}, doi = {10.1021/jacs.5c11056}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36464--36477}, shortjournal = {J. Am. Chem. Soc.}, title = {Zn2+ binding shifts the conformational ensemble of α-synuclein monomers toward accelerated amyloid formation}, volume = {147}, year = {2025}, }
• (2025). Dipole-induced inversion of spin-dependent charge transport through α-helical peptide-based single-molecule junctions. JACS, 147(40), 36453--36463. (www)

  @article{ , abstract = {We report on a remarkable phenomenon of interfacial electric dipole inversion coupled to changes in atomic spin densities that translates into the enantiomeric inversion of electron spin-dependent conductance in a 2-terminal single-molecule junction, consisting of a 22 amino acid chiral α-helical peptide sequence connecting two metal electrodes. This phenomenon is conventionally associated with the Chirality-Induced Spin Selectivity (CISS) effect and how it induces spin polarization and spin filtering of the electron transport along the main peptide axis. Here, the inversion of the spin-dependent charge transport behavior is achieved by keeping constant the chiral symmetry of the junction while inverting the direction of the internal electrical dipole moment running along the main helical peptide axis. Using a spinterface model, in which the electrode-molecule injection barriers are dependent both on the electric dipole and magnetic spin moment, we have been able to rationalize the current pattern as arising from a surface dipole inversion and changes in the atomic spin densities in atoms located within the peptide backbone. Both experimental and computational results show that the observed electric dipole-induced spin-dependent transport inversion in the chiral peptide junction links to an inversion in the spin-dependent resistance due to the combined effect of the helical-based CISS effect and the electrode/molecule spinterface.}, archive = {J_JACS}, author = {Albert C. Aragonès and Monica Varese and Kavita Garg and Wenzhu Kuang and Qiankun Wang and Ernest Giralt and Vladimiro Mujica and Rafael Gutierrez and Gianaurelio Cuniberti and Luis Puerta and Ismael Díez-Pérez}, doi = {10.1021/jacs.5c10892}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36453--36463}, shortjournal = {J. Am. Chem. Soc.}, title = {Dipole-induced inversion of spin-dependent charge transport through α-helical peptide-based single-molecule junctions}, volume = {147}, year = {2025}, }
• (2025). Nitric oxide oxygenation reaction in water at room temperature inside a cage. JACS, 147(40), 36442--36452. (www)

  @article{ , abstract = {Nitric oxide (NO) is a vital biological signaling molecule, but its overproduction can be toxic, necessitating its rapid conversion to nitrate (NO 3 – ) via NO dioxygenase (NOD) enzymes. These Fe-containing enzymes bind NO to form {FeNO} 6 or {FeNO} 7 intermediates, a key step in NO 3 – formation upon reaction with O 2 . However, synthetic NOD models that function in water remain rare. Here, we report the stabilization of a mononuclear nonheme {FeNO} 6 ⊂ Cage ( 2 ) nitrosyl complex within a water-soluble cationic Pd 6 L 4 12+ nanocage using host–guest chemistry. In an aqueous solution at room temperature, the encapsulated {FeNO} 6 complex is stable for days yet reacts readily with O 2 to exclusively yield NO 3 – . We further show that a previously reported Fe IV –O 2 •– ⊂ Cage complex ( 3 ) also reacts with NO to produce NO 3 – exclusively in water. Mechanistic investigations suggest the formation of a peroxynitrite intermediate. This study presents the first integrated model of NOD activity of both {FeNO} 6 ⊂ Cage and Fe IV –O 2 •– ⊂ Cage within the same supramolecular framework in water at ambient temperature, demonstrating both indirect and direct NOD pathways.}, archive = {J_JACS}, author = {Puja De and Prabhakar Bhardwaj and Lucia Velasco and Asterios Charisiadis and J.F. Marco and Aisworika Mohanty and Rahul Gera and Derya Demirbas and Dooshaye Moonshiram and Jyotishman Dasgupta and Pankaj Kumar and Sayam Sen Gupta}, doi = {10.1021/jacs.5c10883}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36442--36452}, shortjournal = {J. Am. Chem. Soc.}, title = {Nitric oxide oxygenation reaction in water at room temperature inside a cage}, volume = {147}, year = {2025}, }
• (2025). Shear force cropping organic molecular crystals based on adaptive hydrogen bonding network reconstructions. JACS, 147(40), 36428--36441. (www)

  @article{ , abstract = {Organic molecular crystals are stereotypically considered brittle, fragile, and prone to disintegration, especially when under anisotropic shear forces. However, robust intermolecular interactions and subtle molecular packing motifs may enable a crystal lattice with extraordinary mechanical properties. Here, we present an organic molecular crystal composed of a chiral dithiolane derivative ( R - TAE ) that can be cropped and cut into arbitrary shapes by external shear forces. Macroscopic R - TAE crystals prepared through a three-solvent diffusion method can be mechanically torn apart by tweezers or precisely cut into desirable shapes, such as semicircles, triangles, triangular waves, pentagons, and stars, by using ordinary scissors, while retaining high crystallinity and structural integrity. Compared with the racemic crystals ( RS - TAE ), an R - TAE crystal possesses a more flexible and adaptive lattice, enabling the crystal to bend and curl under mechanical stress reversibly. The unconventional yet simple crystal shape programming peculiarity emanates from a specific molecular design and organization that inherently incorporate chiral symmetry-breaking effects in the R - TAE crystal lattice. Moreover, it is revealed that the high asymmetry facilitates effective energy dissipation during the shear force-driven reconstruction of the adaptable hydrogen-bonding network and crystal lattice slippage when the crystal is subjected to shear forces. Instead of cracking or shattering, R - TAE crystals retain their overall morphology intact and exhibit a significant elastic modulus enhancement after ultraviolet-induced disulfide bond reorganization, suggesting robust resistance to photoinduced internal stress. Our research highlights the strategic integration of top-down and bottom-up approaches, resulting in dynamic crystals with desirable anisotropic properties and enabling their precise and straightforward processability.}, archive = {J_JACS}, author = {Hui-Yao Lin and Le Li and Chengxi Zhao and Fei Tong and Qi Zhang and Chengyuan Yu and He Tian and Ben L. Feringa and Da-Hui Qu}, doi = {10.1021/jacs.5c10822}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36428--36441}, shortjournal = {J. Am. Chem. Soc.}, title = {Shear force cropping organic molecular crystals based on adaptive hydrogen bonding network reconstructions}, volume = {147}, year = {2025}, }
• (2025). Amplification of chirality in self-assembled chiral perovskite superstructure films. JACS, 147(40), 36420--36427. (www)

  @article{ , abstract = {Chiral hybrid organic–inorganic perovskites (CHOIPs) represent a distinctive class of chiral materials, exhibiting remarkable potential for facilitating chiral information transfer across multiple length scales. However, the currently reported CHOIPs predominantly rely on the molecular chirality arising from the interaction between chiral organic cations and inorganic backbones, leading to suboptimal chiral expression. Herein, we report the synthesis of a CHOIP superstructure film ( R -MBA) x ( S -MBA) (1– x ) BiI 4 , which exhibited significantly enhanced chirality through a subtle enantiomeric excess ( ee ) approach. The implementation of a 20% ee in a mixture of two CHOIP enantiomers resulted in a substantial enhancement of the genuine circular dichroism (CD) asymmetry factor ( g CD > 0.03), exhibiting an increase of more than 50-fold compared to that of the enantiopure film. X-ray diffraction (XRD) analysis revealed that the superstructure adopted an identical crystalline phase to that of the pure enantiomeric ones, suggesting that the observed enhancement does not originate from intracrystalline chirality. Integrating theoretical simulations, we posit that the observed chiral enhancement is predominantly attributed to crystal transfer from the nanoscale, defined as the superstructure chirality formed by mixed enantiomers. These findings establish a novel framework for exploring superstructure chirality in CHOIPs, offering new perspectives for future research in this field.}, archive = {J_JACS}, author = {Li Yao and Qihang Zhang and Mingsheng Li and Chao Chen and Honggang Gu and Shiyuan Liu and Guankui Long and Feng Liu and Wenlong Yang and Jiang Tang}, doi = {10.1021/jacs.5c10609}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36420--36427}, shortjournal = {J. Am. Chem. Soc.}, title = {Amplification of chirality in self-assembled chiral perovskite superstructure films}, volume = {147}, year = {2025}, }
• (2025). Cu(II)-catalyzed hydrofunctionalization of unactivated alkynes via π-lewis acid activation. JACS, 147(40), 36407--36419. (www)

  @article{ , abstract = {A copper(II)-catalyzed stereodivergent hydrooxygenation of electronically unactivated alkynes with carboxylic acids is reported. Regioselectivity and kinetic reactivity are facilitated by a bidentate auxiliary, and syn - or anti -stereoselectivity is controlled through the judicious tuning of reaction conditions. The method affords trisubstituted E - or Z -alkenes with an enol ester functionality in a highly selective manner. Beyond carboxylic acids, a variety of other OH- and NH-nucleophiles react smoothly to furnish enol ether, enamine, and alkylidene β-lactam building blocks. Mechanistic experiments and density functional theory (DFT) calculations shed light on the nature of π-Lewis acid activation with Cu(II) and support a catalytic cycle that features an inner-sphere nucleocupration mechanism via a six-membered transition state for syn -addition and a base-assisted outer-sphere nucleocupration mechanism for anti -addition.}, archive = {J_JACS}, author = {Juntao Sun and Thomas H. Tugwell and Mithun C. Madhusudhanan and Letian Xu and Shenghua Yang and Peng Liu and Keary M. Engle}, doi = {10.1021/jacs.5c10387}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36407--36419}, shortjournal = {J. Am. Chem. Soc.}, title = {Cu(II)-catalyzed hydrofunctionalization of unactivated alkynes via π-lewis acid activation}, volume = {147}, year = {2025}, }
• (2025). Quadrupolar ligand-to-metal charge transfer excited states in octahedral Zr(IV) complexes. JACS, 147(40), 36393--36406. (www)

  @article{ , abstract = {Earth-abundant, visible light absorbing zirconium photosensitizers are of great interest for their long-lived excited states. These photosensitizers consist of two electron rich tridentate ligands ligated to an electron deficient d 0 Zr(IV) metal center, coordination chemistry that gives rise to ligand-to-metal charge transfer (LMCT) excited states. The vectoral nature of an LMCT transition was expected to give rise to an excited state dipole moment that electroabsorption data reported herein show is in fact absent for these photosensitizers. Electroabsorption spectra of three Zr(IV) photosensitizers bearing two tridentate pyridinedipyrrolide ligands, abbreviated Zr(PDP) 2 , were measured in a 2-MeTHF glass. Analysis of both traditional and higher-order electroabsorption spectra revealed significant changes in the polarizability between the ground and excited state without a dipole moment change. The spectral data indicates that upon the absorption of a single photon a quadrupolar excited state is formed via a simultaneous and equal charge transfer from both tridentate ligands to the Zr metal center. The data presented herein provides the first direct experimental evidence for such behavior in transition metal complexes with charge transfer excited states. The implications for the design of LMCT photosensitizers and our fundamental understanding of symmetry breaking in transition metal complexes are discussed.}, archive = {J_JACS}, author = {Matthew J. Goodwin and Quentin R. Loague and Marisa N. Tordella and Dylan C. Leary and Pierpaolo Vecchi and Gage N. Jackson and Carsten Milsmann and Gerald J. Meyer}, doi = {10.1021/jacs.5c10403}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36393--36406}, shortjournal = {J. Am. Chem. Soc.}, title = {Quadrupolar ligand-to-metal charge transfer excited states in octahedral Zr(IV) complexes}, volume = {147}, year = {2025}, }
• (2025). Optically detected magnetic resonance on carbene molecular qubits. JACS, 147(40), 36383--36392. (www)

  @article{ , abstract = {Solid-state quantum systems with optical and spin degrees of freedom have found widespread application in emerging quantum technologies. Recently, molecular qubits came forward as precisely tunable entities that present a compelling alternative to well-established yet hard-to-tune point defects in solid-state systems. In this work, we disclose ground-state triplet carbenes as purely organic qubits comprising two unpaired electrons in close proximity that can be generated in a crystalline matrix with high spatial accuracy via in situ photoactivation. We further demonstrate how state-of-the-art multireference quantum chemical calculations provide insight into their fundamental spin characteristics. As a result, several key assets were realized in a single solid-state qubit material under cryogenic conditions: The exclusive use of light elements (C, H, N, O), photolithographic patterning, optical spin-selective transitions, and a large zero-field splitting in the GHz regime, which, taken together, lays the ground for optically detected magnetic resonance with remarkable fluorescence contrast of >40% and record-high spin coherence times of T 2 = 157(4) μs at 5 K.}, archive = {J_JACS}, author = {Simon Roggors and Nico Striegler and Thomas Unden and Oleksiy Khavryuchenko and Alon Salhov and Jochen Scharpf and Martin B. Plenio and Alex Retzker and Fedor Jelezko and Matthias Pfender and Philipp Neumann and Tim R. Eichhorn and Tobias A. Schaub and Ilai Schwartz}, doi = {10.1021/jacs.5c10272}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36383--36392}, shortjournal = {J. Am. Chem. Soc.}, title = {Optically detected magnetic resonance on carbene molecular qubits}, volume = {147}, year = {2025}, }
• (2025). Snowballing impact of spontaneously degrading microplastics on atmospheric ice nucleation. JACS, 147(40), 36376--36382. (www)

  @article{ , abstract = {Microplastics (MPs), originating from human activities, represent an escalating threat to the global environment and ecosystems. Here, we demonstrate that persistent MPs in the environment profoundly enhance ice nucleation and alter precipitation patterns, which may disrupt air quality, atmospheric chemistry, and climate. Degradation of MPs leads to micronization, nanoporosification, and surface functionalization, significantly boosting their ice-nucleating activity. By integrating global airborne MP data with ice-nucleation assessments, we find that micronization alone can increase cloud-ice-crystal concentrations by up to an order of magnitude. This effect is further amplified when coupled with nanoporosification or surface functionalization with the potential to trigger extreme precipitation events and contribute to climate anomalies. Our research highlights the far more severe consequences of MPs for the future climate than previously imagined, with profound implications for atmospheric science, environmental chemistry, and climate dynamics.}, archive = {J_JACS}, author = {Xuewei Wang and Rui Luo and Wei Guo and Jianzhong Liu and Hui He and Ping Tian and Hongqiang Zhang and Yurui Gao and Guoying Bai and Zhiyuan He}, doi = {10.1021/jacs.5c10269}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36376--36382}, shortjournal = {J. Am. Chem. Soc.}, title = {Snowballing impact of spontaneously degrading microplastics on atmospheric ice nucleation}, volume = {147}, year = {2025}, }
• (2025). DNA-templated assembly of metalloprotein mimics with hydrolytic activity. JACS, 147(40), 36365--36375. (www)

  @article{ , abstract = {Metalloproteins perform a wide range of biological and chemical functions, but elucidating their sequence–function relationships is difficult due to their complex folding pathways and various interactions involved. In this study, we use a covalently branched DNA trimer to scaffold the assembly of diverse peptide secondary structures into higher-order metalloprotein mimics. These structures exhibit zinc ion binding and hydrolytic activity, resembling the natural enzyme carbonic anhydrase (CA). By independently addressing each peptide fragment, we constructed a diverse library of protein mimics, enabling a systematic, high-throughput exploration of peptide structure–function relationships. This strategy expands the design potential beyond conventional coiled-coil motifs, offering a powerful methodology for constructing functional protein-based architectures.}, archive = {J_JACS}, author = {Fangzhou Zhao and Ziyi Sun and Hanadi F. Sleiman}, doi = {10.1021/jacs.5c10056}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36365--36375}, shortjournal = {J. Am. Chem. Soc.}, title = {DNA-templated assembly of metalloprotein mimics with hydrolytic activity}, volume = {147}, year = {2025}, }
• (2025). Indolequinone-based hypoxia-activated proteolysis targeting chimeras selectively degrade BRD4 in hypoxic cancer cells. JACS, 147(40), 36352--36364. (www)

  @article{ , abstract = {Proteolysis targeting chimeras (PROTACs) have helped to establish proximity induction as an exciting strategy in drug discovery, and there are multiple clinical trials focused on this modality. However, degradation of a full protein in a physiological setting might lead to dose-limiting toxicities, giving rise to the need for PROTACs that are activated in a context-dependent nature. Here, we report the development of hypoxia-activated PROTACs (HAP-TACs) which are selectively activated in conditions of low oxygen (hypoxia) such as those found in solid tumors. To develop HAP-TACs, we have attached an indolequinone bioreductive group to an essential functional group of either the VHL- or cereblon-recruiting component of the PROTAC, reducing affinity for its cognate E3 ligase and preventing degradation of the protein of interest. Using BRD4, we have conducted proof-of-concept studies which demonstrate that the indolequinone group is bioreduced under hypoxic conditions, releasing the active PROTAC, resulting in selective degradation of BRD4 in hypoxia. As the bioreductive group is attached to the VHL or cereblon ligand, this approach is potentially applicable to all PROTACs that recruit these commonly employed E3 ligases.}, archive = {J_JACS}, author = {Marta Serafini and Sophie A. Twigger and George Delfas and Maxim Mallerman and Elliot P. Bailey and Ewen D. D. Calder and Ester M. Hammond and Stuart J. Conway}, doi = {10.1021/jacs.5c10240}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36352--36364}, shortjournal = {J. Am. Chem. Soc.}, title = {Indolequinone-based hypoxia-activated proteolysis targeting chimeras selectively degrade BRD4 in hypoxic cancer cells}, volume = {147}, year = {2025}, }
• (2025). A bioinspired lipopeptide surmounts therapeutic dilemmas of gram-positive and gram-negative polymicrobial infection. JACS, 147(40), 36339--36351. (www)

  @article{ , abstract = {Polymicrobial infections present considerable therapeutic challenges due to the absence of effective antimicrobial agents, particularly those involving both Gram-positive and Gram-negative bacteria. We hypothesize that antimicrobials rationally designed to target both the outer and inner membranes─distinct structural differences between these bacteria─could offer solutions to the therapeutic dilemmas of polymicrobial infections. Through lipid screening, we identified a promising lipid scaffold capable of disrupting the membrane system of both Gram-positive and Gram-negative bacteria. We developed a chemical optimization strategy to design an inverted-conical lipopeptide of LP 3K , which exhibits broad-spectrum antimicrobial activity against polymicrobial infections without the emergence of resistance. We further elucidated the structure–activity relationship and antimicrobial mechanisms of LP 3K . In a mouse model of polymicrobial infection, LP 3K demonstrated substantial antimicrobial and therapeutic effects, with confirmed in vivo biosafety. Our findings highlight the potential of lipopeptides as clinically translatable antimicrobials for the effective treatment of polymicrobial infections.}, archive = {J_JACS}, author = {Dongzhe Zou and Kefurong Deng and Zenan Zeng and Wensheng Gong and Beiling Guo and Yiming Liu and Yuxin Xie and Yachao Li and Xianghui Xu}, doi = {10.1021/jacs.5c10219}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36339--36351}, shortjournal = {J. Am. Chem. Soc.}, title = {A bioinspired lipopeptide surmounts therapeutic dilemmas of gram-positive and gram-negative polymicrobial infection}, volume = {147}, year = {2025}, }
• (2025). Biomimetic dual asymmetric MXene-based nanofluidics for advancing osmotic power generation. JACS, 147(40), 36329--36338. (www)

  @article{ , abstract = {Nanofluidics-based reverse electrodialysis offers a promising approach for harnessing the osmotic energy that exists between saline and fresh water, thereby providing a sustainable source of power. Nevertheless, the key obstacle to realizing a commercially viable power output stems from inadequate ion permselectivity in nanofluidics. Here, we engineer dual asymmetric MXene-based composite nanofluidics (DA-MXCNs) composed of a negatively charged, porous MXene layer and a positively charged, confined MXene layer, which strategically incorporates asymmetric channel dimensions and opposing charge distributions. This design simultaneously reduces ion diffusion paths and amplifies ion potential differences, thereby optimizing the ion permeability and selectivity. The DA-MXCNs exhibit a 3.4-fold increase in ion flux (7.71 mmol m –2 h –1 ) over the unmodified nanofluidics, and thus a high Na + selectivity coefficient of 0.985 and a Na + /Cl – selectivity ratio of approximately 65.7, indicative of superior preferential cation transport. Experimental and theoretical evidence supports that the dual asymmetric manipulations not only enable unidirectional and rapid cation transport but also create a high energy barrier for anions and a low one for cations, thereby achieving ultrahigh ion selectivity. Utilizing the DA-MXCNs, the osmotic energy conversion system achieves an impressive power density of up to 126.0 W m –2 , which surpasses the performance of existing MXene-based nanofluidics and shows the capacity for powering a variety of electrical devices. This strategy, grounded in optimized permselective nanofluidics, lays the foundation for advancements in ion batteries and ion separation technologies.}, archive = {J_JACS}, author = {Jingyi Guo and Tianhao Liu and Weiwen Xin and Nan Wang and Shixuan Xia and Di Shen and Yuying Fan and Zexu Fang and Chungui Tian and Liping Wen and Lei Jiang and Honggang Fu}, doi = {10.1021/jacs.5c10164}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36329--36338}, shortjournal = {J. Am. Chem. Soc.}, title = {Biomimetic dual asymmetric MXene-based nanofluidics for advancing osmotic power generation}, volume = {147}, year = {2025}, }
• (2025). Structural control of band gap and polaron delocalization in 2D azatriangulene covalent organic frameworks. JACS, 147(40), 36320--36328. (www)

  @article{ , abstract = {New two-dimensional (2D) covalent organic frameworks (COFs) with a tri(oxa)azatriangulene (TANG) node and different polarity of the imine linkers (C═N vs N═C) and internode distance have been synthesized using a transimination polymerization. The orientation of the imine linker controls the donor–acceptor interactions in these π-conjugated COFs, resulting in a large modulation of the valence band maximum (−4.2 to −5.4 eV) and the band gap ( E g ≈ 1.2–1.6 eV). p -Doping of COFs in iodine vapor results in the formation of highly delocalized polarons with an absorption band extending into the far-infrared (THz band) region. Reducing the TANG–TANG internodal distance increases the 2D bandwidth dispersion and leads to the highest (in the series) electrical conductivity (10 –1 S/cm), the lowest conductance activation energy (50 meV near room temperature), and the most red-shifted polaron absorption (λ edge ∼ 160 μm, 8 meV) in the series.}, archive = {J_JACS}, author = {Chang Wan Kang and Ehsan Hamzehpoor and Pegah Ghamari and Yuze Tao and Mohammad Hossein Gohari and Cheng-Hao Liu and Zhenzhe Zhang and Rustam Z. Khaliullin and Dmytro F. Perepichka}, doi = {10.1021/jacs.5c10041}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36320--36328}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural control of band gap and polaron delocalization in 2D azatriangulene covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Unexpected oversolubility of CO2 measured at Electrode–Electrolyte interfaces. JACS, 147(40), 36310--36319. (www)

  @article{ , abstract = {Enhancements in gas solubility in pore-confined liquids─termed oversolubility─can drastically influence gas separation and catalytic efficiency in confined environments; however, they remain poorly understood in electrochemical CO 2 capture and reduction systems. While previous investigations of oversolubility have emphasized the importance of mesoporosity and incomplete pore saturation by the solvent, in this work, we report an unprecedented 30-fold oversolubility effect for CO 2 in solely microporous activated carbons saturated with 1 M Na 2 SO 4(aq) . The oversolubility effect occurs regardless of the activated carbon’s functional groups and level of disorder and is enhanced for smaller pore sizes. Oversolubility is quantified using solid-state 13 C nuclear magnetic resonance spectroscopy (NMR), enabling differentiation between in-pore and ex-pore CO 2 and HCO 3 – . Atomistic modeling of the system, based on a machine-learning model delivering first-principles accuracy, suggests that the effect is driven by an adsorption-like mechanism underpinned by favorable interactions between CO 2 and the pore walls. Our findings demonstrate the unexpected importance of oversolubility for gas uptake in microporous, solvent-saturated carbon electrodes, an effect with direct relevance for improving electrochemical CO 2 capture and conversion technologies.}, archive = {J_JACS}, author = {Zeke Coady and Samuel G. H. Brookes and Zhaohan Shen and Benjamin J. Rhodes and Grace Mapstone and Zhen Xu and Wei Yu and Hirotomo Nishihara and Christoph Schran and Angelos Michaelides and Alexander C. Forse}, doi = {10.1021/jacs.5c09712}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36310--36319}, shortjournal = {J. Am. Chem. Soc.}, title = {Unexpected oversolubility of CO2 measured at Electrode–Electrolyte interfaces}, volume = {147}, year = {2025}, }
• (2025). Cell-selective targeting chimeras (SelecTACB) for membrane protein degradation on b cells. JACS, 147(40), 36301--36309. (www)

  @article{ , abstract = {Membrane protein degradation chimeras (MPDs) have expanded the application space of current targeted protein degradation technologies (TPDs), yet cell-selective MPDs are still lacking, particularly for surface proteins on immune cells. Precise degradation of a target protein on a specific cell type is challenging when it is expressed across multiple immune cell types. Here, we introduce SelecTAC B as a targeted membrane protein degradation chimera that is selective on B cells. By leveraging CD22 as the B cell specific lysosome-targeting receptor to induce endocytosis and lysosome degradation, SelecTAC B allowed membrane protein degradation in a targeted and cell-selective manner. We show that SelecTAC B can effectively degrade indicated proteins such as CD40 and ICOSL on B cells from human peripheral blood mononuclear cells (PBMCs) without affecting protein expression in other immune cell types. The degradation of key proteins involved in T cell stimulation pathways led to sustained inhibition of B cell functions. Together, our work established a cell-type selective degradation platform that offers a general strategy for targeted membrane protein degradation on immune cells.}, archive = {J_JACS}, author = {Zhenlin Yang and Jianfei Jiang and Yuhui Cao and Haoming Fang and Xianrui Zhang and Yuxuan Zhang and Heng Zhang and Peng R. Chen}, doi = {10.1021/jacs.5c09630}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36301--36309}, shortjournal = {J. Am. Chem. Soc.}, title = {Cell-selective targeting chimeras (SelecTACB) for membrane protein degradation on b cells}, volume = {147}, year = {2025}, }
• (2025). Reversible interfacial hydride transfer as a complementary tool to measure molecular hydricity. JACS, 147(40), 36291--36300. (www)

  @article{ , abstract = {Hydride transfer is an essential elementary reaction across the chemical value chain, but there are limited methods available for quantifying thermodynamic hydricity (Δ G H– ), particularly among main group reagents. Herein, we exploit facile H 2 activation and reversible hydride transfer from a metal surface to a molecular reagent, the net hydrogen reduction reaction (HRR), to develop a potentiometric method for quantifying Δ G H– of main group reagents recalcitrant to conventional methods. HRR potentiometry is first validated with a benzimidazole-based hydride donor and then applied to uncover the impact of the reaction environment on hydricity. For a benzimidazole-based hydride donor, HRR equilibrium potentials are roughly invariant across solvents, indicating that the solvent dependence of its hydricity largely reflects the differential solvation of H – across media. For formate, HRR potentials and corresponding hydricities depend strongly on water content. For borohydrides, HRR potentiometry reveals that effective hydricity values are strongly influenced by Lewis acid–base adduct formation with the hydride acceptor but are minimally influenced by the countercation. Together with these studies, the advantages, limitations, and practical considerations of the HRR potentiometry method are discussed, highlighting the power of this methodology as a complementary tool to measure molecular hydricity.}, archive = {J_JACS}, author = {Hye Won Chung and Hai-Xu Wang and Sai Puneet Desai and Andressa V. Müller and Sebastian Sena and Ksenija D. Glusac and Javier J. Concepcion and Yogesh Surendranath}, doi = {10.1021/jacs.5c09582}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36291--36300}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible interfacial hydride transfer as a complementary tool to measure molecular hydricity}, volume = {147}, year = {2025}, }
• (2025). Elucidating surface adsorption of lithium ions on electrode materials using 7Li dark-state exchange saturation transfer NMR spectroscopy. JACS, 147(40), 36277--36290. (www)

  @article{ , abstract = {Interfacial chemistry plays a central role in the development of next-generation high-energy Li-ion electrode materials. Yet, the rational design of new surface treatments that serve as beneficial solid electrolyte interphases is hindered by the challenges involved in probing their interfacial ion transfer properties. Here, we demonstrate how 7 Li Dark-State Exchange Saturation Transfer (DEST) NMR can be used to directly measure the Li-ion surface adsorption process at the solid–liquid interface. The development of an optimized model system composed of monodisperse submicron particles allowed for comparison between different surface functionalities, enabling the characterization of state-of-the-art electrode coating layers in terms of their Li-ion affinity. Numerical simulations based on Bloch–McConnell equations enable a quantitative analysis of the surface exchange rates and binding properties, cementing DEST as a valuable tool for elucidating the structure–function relationship in electrode materials.}, archive = {J_JACS}, author = {Shakked Schwartz and Ayan Maity and Vaishali Arunachalam and Yuval Bernard and Ortal Lidor-Shalev and Tehila Meshita and Liat Avram and Malachi Noked and Michal Leskes}, doi = {10.1021/jacs.5c09603}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36277--36290}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating surface adsorption of lithium ions on electrode materials using 7Li dark-state exchange saturation transfer NMR spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Identifying representative structural model in atomically dispersed catalysts. JACS, 147(40), 36266--36276. (www)

  @article{ , abstract = {Atomically dispersed catalysts (ADCs) embedded within carbon substrates are gaining considerable attention for their high metal atom utilization and exceptional catalytic activity. The coordination structure of the active catalytic center is crucial to catalytic performance; however, accurately characterizing these structures remains challenging due to the inherent structural diversity in real-world ADCs and the difficulty of identifying the light elements (e.g., C and N) surrounding central metal atoms. Herein, we propose a protocol to interpret the X-ray absorption spectroscopy, thereby identifying the most probable representative structures of ADCs. Our method integrates average coordination numbers, oxidation states of central metal atoms, and the specific light elements bonded to these metal atoms. This protocol is applicable to single-, dual-, and trimetal atom catalysts, offering a more rational method for structural assignment. By addressing key methodological limitations in current structural assignments for ADCs, our approach improves the reliability of active site identification and provides a foundation for more accurate structure–activity relationship studies in catalytic systems.}, archive = {J_JACS}, author = {Guolei Cai and Haifeng Lv and Yifan Li and Guikai Zhang and Jing Zhang and Xianghua Kong and Xiaojun Wu and Song Jin and Hengxing Ji}, doi = {10.1021/jacs.5c09614}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36266--36276}, shortjournal = {J. Am. Chem. Soc.}, title = {Identifying representative structural model in atomically dispersed catalysts}, volume = {147}, year = {2025}, }
• (2025). On-demand nonalternating copolymerization enables upcycling of mixed polyethylene and nylon plastics. JACS, 147(40), 36254--36265. (www)

  @article{ , abstract = {The increasing accumulation of plastic waste in the environment brings about a potential danger for ecosystems and human society; mechanical recycling remains one of the most economical strategies to deal with the growing crisis of plastic pollution; however, it suffers from substantial performance deterioration when processing immiscible blends of polyethylene and nylon plastics. Here, we report on-demand nonalternating copolymerization of ethylene with carbon monoxide (CO) via a facile tandem gas compensation strategy, which achieves a precision control over carbonyl incorporation with uniform distribution across a broad range (0–50%). Such a synthetic advance offers a unique multiblock structure having short polar segments ((CH 2 –CH 2 ) n –CO−) ( n < 4) and extended nonpolar methylene sequences ( n > 4). Remarkably, the resulting quasi-multiblock copolymer (q-MBCP) delivers a robust compatibilization for polyethylene and nylon blends, thus transforming brittle materials into mechanically tough composites. This work elucidates the mechanistic evolution between nonpolar polyethylene and polar alternating polyketone phases, while offering a practical and sustainable solution to advance closed-loop recycling of mixed plastic waste.}, archive = {J_JACS}, author = {Wen-Li Zhang and Shi-Yu Chen and Xiao-Bing Lu and Ye Liu}, doi = {10.1021/jacs.5c09549}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36254--36265}, shortjournal = {J. Am. Chem. Soc.}, title = {On-demand nonalternating copolymerization enables upcycling of mixed polyethylene and nylon plastics}, volume = {147}, year = {2025}, }
• (2025). Mechanically adaptive Cathode–Electrolyte interphase via dynamic covalent chemistry for long-life ni-rich lithium batteries. JACS, 147(40), 36244--36253. (www)

  @article{ , abstract = {High-nickel LiNi 0.83 Co 0.12 Mn 0.05 O 2 (NCM83) cathodes suffer from interfacial instability resulting from cathode–electrolyte reactions and anisotropic mechanical strain within secondary particles. Herein, we present a mechanically adaptive cathode–electrolyte interphase (CEI) engineered via a dynamic covalent network that features a supramolecular ion-conducting polyurethane ureido-pyrimidinone (SPU-UPy) elastomer. The dynamic network integrates cooperative hydrogen bonds and disulfide bonds and imparts exceptional mechanical resilience and autonomous self-healing capabilities that allow it to accommodate volume fluctuations without compromising structural integrity. The SPU-UPy layer is also designed with strong transition metal ion–O/N coordination bonds that greatly enhance adhesion to the NCM83 surface and mitigate transition metal dissolution in the electrolyte. The polyether backbone facilitates efficient Li-ion transport across the interface and ensures a homogeneous interfacial Li concentration during intercalation/deintercalation. Consequently, the dynamic CEI-coated NCM83 cathodes achieve exceptional long-term cycling stability with a high-capacity retention of 82.2% after 400 cycles at 1 C. This work elucidates the critical role of dynamic covalent chemistry in stabilizing Ni-rich cathode interfaces and establishes a new paradigm for the design of high-energy-density batteries through mechano-adaptive interfacial engineering.}, archive = {J_JACS}, author = {Yi-Shun Li and Yao-Lu Ye and Zi-Xin Xie and Xu-Dong Zhang and Xu-Sheng Zhang and Chang-Hui Ke and Zi-Han Zhang and Rui Wen and Hui Yang and Huan Ye and Fei-Fei Cao}, doi = {10.1021/jacs.5c09355}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36244--36253}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanically adaptive Cathode–Electrolyte interphase via dynamic covalent chemistry for long-life ni-rich lithium batteries}, volume = {147}, year = {2025}, }
• (2025). Fusion deep learning for predicting conductivity in electron-doped organic polymers. JACS, 147(40), 36233--36243. (www)

  @article{ , abstract = {The development of efficient and air-stable n-type organic semiconductors suitable for molecular n-doping is critical for advancing high-performance, durable organic electronic devices, including transistors, thermoelectrics, and photovoltaics. Machine learning offers a powerful approach to uncovering hidden relationships between molecular structures and their electronic properties, thereby accelerating the discovery and design of promising materials. To support this effort, we constructed a curated database comprising 84 n-type conductive polymers, each characterized by experimental measurements under n-doping conditions with 4-(1,3-dimethyl-2,3-dihydro-1 H -benzoimidazol-2-yl)phenyl dimethylamine (N-DMBI-H), and augmented with density functional theory calculations to provide complementary molecular descriptors. After constructing the database, we developed a fusion deep learning model that integrates convolutional neural networks with fully connected artificial neural networks to capture both structural and property-based features of the polymers. The model was trained on the data set and evaluated using leave-one-out cross-validation. The model was further applied to a test set of n-type polymers bearing oligoethylene glycol (OEG) side chains, enabling the identification of key physical factors that influence their conductivity when doped with N-DMBI-H. Finally, a double-blind experiment was conducted to validate the model’s practical utility by predicting the conductivity of four BDPPV-type polymers and one N2200-type polymer doped with N-DMBI-H. For the N2200-type polymer and two of the BDPPV-type polymers, the predicted conductivities agreed with experimental values within the same order of magnitude. These results demonstrate the fusion model’s reliability and establish a strong foundation for data-driven property prediction and the design of high-conductivity n-type polymers.}, archive = {J_JACS}, author = {Ziyu Zhang and Xinzheng Yang and Liang Yan and Sungwoo Jung and Wei You and Ting Cao and Xiaosong Li}, doi = {10.1021/jacs.5c09172}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36233--36243}, shortjournal = {J. Am. Chem. Soc.}, title = {Fusion deep learning for predicting conductivity in electron-doped organic polymers}, volume = {147}, year = {2025}, }
• (2025). Sensitive and accurate detection of low-frequency mutations via pyrophosphorolysis-activated selective amplification and MALDI-TOF-MS single-nucleotide resolution identification. JACS, 147(40), 36223--36232. (www)

  @article{ , abstract = {Nucleic acid mutation profiling is crucial for early screening, diagnosis, and prognosis of cancer patients. However, detecting rare mutations at low variant allele frequencies (VAFs) in clinical samples is often hindered by interference of abundant wild-type (WT) backgrounds as well as incorrect signal readout. To tackle this challenge, we propose a Hybrid Ultrasensitive Nucleic acid Targeted Enrichment and Readout (HUNTER) platform for highly sensitive, accurate and multiplexed detection of low-frequence single nucleotide variants (SNVs). HUNTER leverages pyrophosphorolysis-activated polymerization (PAP) based selective variant amplification to enhance the abundance of rare mutations for improved detection sensitivity. The matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) readout with single-nucleotide resolution further enables precise genotyping across multiple loci. Consequently, HUNTER can accurately detect SNVs as low as 3 copies, with a detection limit of 0.01% in a high-WT background. Additionally, HUNTER enables simultaneous detection of up to 10 target SNVs in a single pot. In clinical lung cancer samples, the HUNTER assay demonstrates 1.6- to 5-fold higher sensitivity compared to the conventional amplification refractory mutation system quantitative PCR (ARMS-qPCR), and maintains 100% specificity across diverse SNV types. With its high sensitivity, accuracy and multiplex capability, HUNTER is well-positioned to emerge as a groundbreaking tool for the detection of rare mutations in precision medicine.}, archive = {J_JACS}, author = {Shanshan Liang and Yu Ning and Xiaoting Wu and Guihua Zhang and Yinuo Hou and Rui Wang and Xing Xu and Chaoyong Yang}, doi = {10.1021/jacs.5c08741}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36223--36232}, shortjournal = {J. Am. Chem. Soc.}, title = {Sensitive and accurate detection of low-frequency mutations via pyrophosphorolysis-activated selective amplification and MALDI-TOF-MS single-nucleotide resolution identification}, volume = {147}, year = {2025}, }
• (2025). Ligand-induced self-complementing tag (LiSC-tag) as an epitope tag for live-cell super-resolution imaging and functional manipulation of cellular proteins. JACS, 147(40), 36210--36222. (www)

  @article{ , abstract = {Epitope tags, or peptide tags, are ideal genetically encodable labels for super-resolution imaging due to their compact size. However, their application in live-cell super-resolution imaging of intracellular proteins has been limited by low labeling specificity and efficiency. To address this limitation, we developed the ligand-induced self-complementing tag (LiSC-tag) as a novel epitope tag for live-cell super-resolution imaging and the functional manipulation of cellular proteins. The LiSC-tag utilizes a split FKBP mutant that self-complements upon the addition of small-molecule fluorescent probes. It integrates the compact size of epitope tags with the high brightness and photostability of small-molecule dyes, enabling multicolor nanoscopy imaging using STED, STORM, and SIM. The LiSC-tag exhibits improved brightness and photostability relative to split fluorescent proteins. It is compatible with endogenous protein imaging and can be engineered in tandem arrays to enhance fluorescence signals. Beyond imaging, the LiSC-tag also enables the manipulation of protein localization and targeted protein degradation.}, archive = {J_JACS}, author = {Liuxin Tu and Hong Qin and Siyuan Luo and Xiaofei Liu and Ruikang Zhao and Xiangyan Ding and Shuyi Zhang and Ling Chu}, doi = {10.1021/jacs.5c07733}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36210--36222}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand-induced self-complementing tag (LiSC-tag) as an epitope tag for live-cell super-resolution imaging and functional manipulation of cellular proteins}, volume = {147}, year = {2025}, }
• (2025). Anomeric selectivity of glycosylations through a machine learning lens. JACS, 147(40), 36197--36209. (www)

  @article{ , abstract = {Predicting the stereoselectivity of glycosylations is a major challenge in carbohydrate chemistry. Herein we show that it is possible to build machine learning models that can predict the major anomer of a glycosylation, whether the other anomer is observed as the minor product, and the anomeric ratio of the two anomers. The three models are integrated into a publicly available tool, GlycoPredictor. From a statistical analysis of literature data, we analyze glycosylation trends and compare them to known trends in the field of carbohydrate chemistry, making it possible to elucidate a hierarchy of rules governing the stereoselectivity of glycosylations and discover promising new trends that complement expert intuition, which are tested in novel glycosylation methods.}, archive = {J_JACS}, author = {Natasha Videcrantz Faurschou and Victor Friis and Priyanka Raghavan and Christian Marcus Pedersen and Connor W. Coley}, doi = {10.1021/jacs.5c07561}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36197--36209}, shortjournal = {J. Am. Chem. Soc.}, title = {Anomeric selectivity of glycosylations through a machine learning lens}, volume = {147}, year = {2025}, }
• (2025). Are hemilabile Metal–Organic frameworks overlooked as promising water-stable adsorbents? elucidating their physical and hydrolytic properties using machine-learned potentials. JACS, 147(40), 36180--36196. (www)

  @article{ , abstract = {Poor water stability of many metal–organic frameworks (MOFs) is a persistent bottleneck toward their practical applications. Hemilabile STAMs (St. Andrews Materials) demonstrate greater water stability, as well as improved adsorption performance under humid conditions, compared to compositionally similar HKUST-1. Yet, the fundamental properties of STAMs remain largely unexplored. Herein, we leverage machine-learned potentials (MLPs) to simulate physical and hydrolytic properties, water stability and adsorption in STAMs functionalized with various hydrophobic/hydrophilic groups. Encouragingly, STAMs are predicted to exhibit high mechanical strength and low heat capacity, which are desirable attributes in adsorption processes. Moreover, defective STAMs are shown to possess greater mechanical robustness than defective HKUST-1. From MLP-based molecular dynamics simulations, we demonstrate that Cu-paddlewheels of STAMs are relatively stable even at high water loadings. The hydrolysis mechanism of Cu-paddlewheels is examined meticulously, and for the first time, we quantitatively reveal a higher energy barrier is required to hydrolyze Cu–O bonds in STAMs than in HKUST-1, unambiguously elucidating the crucial role of Cu···OH 2 interactions in water stability of hemilabile STAMs. From MLP-based Monte Carlo simulations, water adsorption isotherms predicted in STAMs match well with experimental data. Importantly, it is concretely demonstrated that water adsorption in the hexagonal pore can be tailored by modifying the hydrophobicity of functional groups, while adsorption in the triangular pore is affected marginally. Beyond showing that STAMs are promising adsorbents, we provide new microscopic insights into physical and hydrolytic properties in Cu paddlewheel-based MOFs. More generally, our findings suggest that incorporating hemilability is a promising but underexplored strategy for the development of new water-stable MOFs.}, archive = {J_JACS}, author = {Yifei Yue and Athulya S. Palakkal and N. Duane Loh and Jianwen Jiang}, doi = {10.1021/jacs.5c07377}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36180--36196}, shortjournal = {J. Am. Chem. Soc.}, title = {Are hemilabile Metal–Organic frameworks overlooked as promising water-stable adsorbents? elucidating their physical and hydrolytic properties using machine-learned potentials}, volume = {147}, year = {2025}, }
• (2025). A glutathione S-transferase pi molecular glue tethers splicing factors and remodels cell metabolism. JACS, 147(40), 36170--36179. (www)

  @article{ , abstract = {Here, we discovered a tyrosine-reactive GSTP1 inhibitor can function as a molecular glue via a ligand induced protein tethering (LIPT) mechanism. Electrophilic modification of GSTP1 results in disulfide tethering of protein complexes in live cells, and these protein–protein interactions (PPIs) can be reversed using reducing agents. A substantial fraction of GSTP1 tethered interactions represent neo-PPIs that were enriched for splicing factors and nuclear proteins as determined by immunopurification mass spectrometry. LIPT colocalized GSTP1 with serine/arginine repetitive matrix protein 1 (SRRM1), resulting in its redistribution from nuclear speckles to cytoplasmic foci. Cancer cells with enhanced sensitivity to LIPT showed downregulation of metabolic proteins that led to altered lipid metabolism and reduced cell proliferation from GSTP1 molecular glue treatment. Collectively, we show covalent molecular glues of GSTP1 can alter localization of disulfide tethered binding partners and disrupt metabolism in cancer cells.}, archive = {J_JACS}, author = {David M. Leace and Madeleine L. Ware and Olivia Murtagh and Hsiao-Kuei Tsai and Chin-Yuan Chang and Ku-Lung Hsu}, doi = {10.1021/jacs.5c06951}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36170--36179}, shortjournal = {J. Am. Chem. Soc.}, title = {A glutathione S-transferase pi molecular glue tethers splicing factors and remodels cell metabolism}, volume = {147}, year = {2025}, }
• (2025). Chiral water strongly couples to N−H groups of chiral biomolecular assembly but decouples from the nearby achiral interfacial water and bulk water. JACS, 147(40), 36162--36169. (www)

  @article{ , abstract = {Insights into the imprint of biomolecular chirality on the hydration water of biomolecules are crucial for comprehending biomolecular function and the molecular origin of biological homochirality in life, yet they remain poorly understood. In this study, we successfully constructed chiral water superstructures templated by a chiral biomolecular assembly under ambient conditions and performed the first investigation of its ultrafast vibrational dynamics by utilizing femtosecond time-resolved chiral sum frequency generation vibrational spectroscopy (SFG-VS). Chiral biomolecular templates were prepared by assembling achiral amphiphilic molecules into chiral superstructures with C 1 point group symmetry at the lipid membrane surface. The formation of chiral water superstructure is dictated by the amide moieties of the chiral biomolecular assembly, particularly by the N−H group with the C 1 point group. The vibrational relaxation time of chiral water (0.8 ± 0.1 ps) is identical to that of the N−H group but significantly longer than that of both bulk water and typical interfacial achiral water (≤ 0.3 ps). This indicates that chiral water strongly couples with the N−H vibrational mode but decouples from nearby achiral interfacial water and bulk water. Chiral water exhibits distinctly different behavior from achiral water. Our findings highlight the significant role of chiral water in vibrational energy redistribution and propagation within biomolecules and contribute to understanding the mechanism of chirality generation and transfer.}, archive = {J_JACS}, author = {Ruoqi Pei and Mengmeng Wang and Feixiang Chen and Jing Lai and Junjun Tan and Yi Luo and Shuji Ye}, doi = {10.1021/jacs.5c06423}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36162--36169}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral water strongly couples to N−H groups of chiral biomolecular assembly but decouples from the nearby achiral interfacial water and bulk water}, volume = {147}, year = {2025}, }
• (2025). Nucleotide-specific RNA conformations and dynamics as precursors to ribonucleoprotein condensates. JACS, 147(40), 36146--36161. (www)

  @article{ , abstract = {Ribonucleoprotein (RNP) condensates have distinct physiological and pathological significance, but the structure of RNA within them is not well understood. Using contrast-variation solution X-ray scattering, which discerns only the RNA structures within protein-RNA complexes, alongside ensemble-based structural modeling, conformational changes of poly-U and poly-A RNA are characterized as they interact with polybasic peptides. Coarse-grained molecular dynamics simulations are used to elucidate RNA dynamics within RNP condensates. At high salt, where peptide-RNA association is weak, RNA structural changes are discerned at subsaturated conditions. At lower salt concentrations, where association is enhanced, positional order of only poly-A RNA is detected within phase separated RNP mixtures. This method is also applied to study trinucleotide CAG and CUG repeats, alone and in complex with peptides. RNA association is enhanced by the addition of peptides and, as in the poly-A system, these motifs exhibit positional ordering.}, archive = {J_JACS}, author = {Tong Wang and Qingyue Hu and Scout Fronhofer and Lois Pollack}, doi = {10.1021/jacs.5c05892}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36146--36161}, shortjournal = {J. Am. Chem. Soc.}, title = {Nucleotide-specific RNA conformations and dynamics as precursors to ribonucleoprotein condensates}, volume = {147}, year = {2025}, }
• (2025). Strong electric fields on water microdroplets enable near-unity selectivity in H2O2 photosynthesis. JACS, 147(40), 36136--36145. (www)

  @article{ , abstract = {Selective conversion of solar energy to chemical bonds remains a grand challenge in artificial photosynthesis. Though H 2 O 2 production via photocatalytic two-electron oxygen reduction (2e – -ORR) offers a sustainable alternative to the energy-intensive anthraquinone process, competing hydrogen evolution reaction (HER) severely limits both efficiency and selectivity. Here, we reveal that the strong electric fields on water microdroplet surfaces serve as powerful selectivity switches, directing photogenerated electrons exclusively toward H 2 O 2 synthesis while completely suppressing hydrogen evolution. This interfacial electric field control mechanism transforms ZnIn 2 S 4 -based photocatalysts─commonly dominated by HER─into H 2 O 2 producers with near-unity selectivity and production rates 2 orders of magnitude higher than bulk reactions. Through spatially resolved spectroscopy characterizations and theoretical calculations, we elucidate that the high electric fields on water microdroplets simultaneously enhance charge carrier separation, lower energy barriers for 2e – -ORR, and erect kinetic barriers against HER. Beyond providing an energy-efficient route to selective H 2 O 2 photosynthesis, this study offers valuable insights into selectivity control in other solar-to-chemical transformations without the need for catalyst modification or system engineering.}, archive = {J_JACS}, author = {Kejian Li and Wenbo You and Yucheng Zhu and Wei Wang and Longqian Wang and Yangyang Liu and Qiuyue Ge and Tao Wang and Runbo Wang and Xuejun Ruan and Hanyun Cheng and Liwu Zhang}, doi = {10.1021/jacs.5c06077}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36136--36145}, shortjournal = {J. Am. Chem. Soc.}, title = {Strong electric fields on water microdroplets enable near-unity selectivity in H2O2 photosynthesis}, volume = {147}, year = {2025}, }
• (2025). Selective toluene electrooxidation to benzyl alcohol. JACS, 147(40), 36117--36135. (www)

  @article{ , abstract = {We report a novel electrocatalytic approach that couples water oxidation with toluene oxidation in wet DMF or DMSO electrolyte. Electrocatalytic oxidation of water, a sustainable oxygen atom source, favored hydroxyl ( ·̇ OH) radical formation over hydrogen peroxide and oxygen evolution because the organic solvent molecules suppressed O–O bond formation via hydrogen bonding. Water oxidation was catalyzed by laser-synthesized [NiFe]-(OH) 2 nanosheets supported on hydrophilic carbon fiber paper anodes, enhancing water oxidation activity and toluene oxygenation efficiency. Under optimized conditions in wet DMF electrolyte, toluene oxidation achieved 100% selectivity for benzyl alcohol at an unprecedented conversion yield of 87%. In wet DMSO electrolyte, 100% selectivity for benzyl alcohol was obtained, albeit with significantly lower conversion yield. Combined experimental and computational results reveal a new mechanistic pathway, based on electrocatalytic water oxidation to · OH radicals and protons. Protonation of DMF enabled the formation of H + -DMF– · OH radical complexes stabilized by hydrogen bonding among the radical, protonated and unprotonated DMF molecules, and water. This radical stabilization played a crucial role in promoting benzyl alcohol production. In contrast, DMSO consumed · OH radicals to form methanesulfinic acid, limiting benzyl alcohol generation. The wet organic solvent environment additionally prevented overoxidation beyond the alcohol by stabilizing radical intermediates through hydrogen bonding networks, effectively arresting the reaction after the first oxygenation. Likewise, benzyl alcohol oxidation yielded benzaldehyde, with no overoxidation to benzoic acid. Our findings establish fundamental design principles for selective hydrocarbon oxidations by leveraging solvent-mediated interactions, with broad implications for sustainable chemical synthesis.}, archive = {J_JACS}, author = {Madeleine K. Wilsey and Nathalia Cajiao and Aleksa Radovic and Michael L. Neidig and Yasemin Basdogan and Astrid M. Müller}, doi = {10.1021/jacs.5c05986}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36117--36135}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective toluene electrooxidation to benzyl alcohol}, volume = {147}, year = {2025}, }
• (2025). Retention and rearrangement of membrane protein complexes’ higher order structure by collisionally activated dissociation- and electron capture dissociation-mass spectrometry. JACS, 147(40), 36105--36116. (www)

  @article{ , abstract = {Membrane proteins (MPs) challenge biophysical and structural biology methods. Native mass spectrometry (MS) has emerged as a powerful tool to study MP structures and their modulation by lipids. We examine the pathways by which three MPs, tetrameric Aquaporin Z (AqpZ), trimeric ammonium transporter (AmtB), and pentameric mechanosensitive channel of large conductance (MscL) decompose following collisionally activated dissociation (CAD) or electron capture dissociation (ECD) in native top-down MS. MPs subjected to CAD typically decompose along well-characterized pathways releasing highly charged monomers and low-charge state complementary subunits, but a lesser pathway accessed by low pressure collisions cleaves the backbone into fragments covering much of the sequence. Collisions also rearrange structures, e.g., AmtB subunits rearrange to form novel interactions and/or salt bridges that surprisingly retain a formerly surface-exposed segment despite ejecting the binding interface. MscL dissociation pathways depend on precursor charge-state, a behavior observed in a few soluble complexes, yet unaddressed mechanistically. Salt bridges in low charge state complexes stabilize subunits from ejection while facilitating only smaller, local rearrangements that release covalently cleaved products from transmembrane regions. With fewer opposite charges, on average, higher charge state molecules can rearrange intersubunit salt bridges on the experimental time scale to partition charge asymmetrically and free a subunit. ECD with supplemental activation can retain higher order structures of proteins and inform about the strongly interacting regions that preclude product ion release. With extensive regions lacking ionizable residues, MPs enable key interactions that guide the structure and dynamics of gas phase protein assemblies to be probed.}, archive = {J_JACS}, author = {Jessie Le and Wonhyeuk Jung and Mark A. Arbing and Pascal F. Egea and Rachel R. Ogorzalek Loo and Joseph A. Loo}, doi = {10.1021/jacs.5c05797}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36105--36116}, shortjournal = {J. Am. Chem. Soc.}, title = {Retention and rearrangement of membrane protein complexes’ higher order structure by collisionally activated dissociation- and electron capture dissociation-mass spectrometry}, volume = {147}, year = {2025}, }
• (2025). Mechano-ID: Proximity labeling of mechanically active receptors reveals the mechanome and tags mechanically active cells. JACS, 147(40), 36097--36104. (www)

  @article{ , abstract = {A major challenge in the field of mechanobiology relates to the lack of methods that enable the identification of mechanically active receptors, associated proteins, and the individual cells that display enhanced force generation. For example, potent T cell activation requires the transmission of biophysical forces between the T cell receptor (TCR) and its peptide-loaded major histocompatibility (pMHC) complex antigens. Interestingly, TCR-antigen interactions are highly dynamic, displaying a broad range of force magnitudes between different cells and even within the same cell. Therefore, methods that can chemically tag mechanically active T cells, TCRs, and their associated proteomes, or mechanomes are highly desirable. Such techniques may enable a deeper understanding of the mechanisms governing immune responses and may also have broad applications in immunotherapy. Herein, we report a technique dubbed mechano-ID, which allows for mechanically selective proximity tagging by leveraging DNA-based molecular force probes that recruit proximity tagging enzymes. We demonstrate mechano-ID tagging of T cells using microscopy and flow cytometry, with further confirmation by proteomics and Western blotting of mechanically active T cell receptors.}, archive = {J_JACS}, author = {Rong Ma and Mohamed Husaini Bin Abdul Rahman and Christian M. Beusch and Brendan R. Deal and David E. Gordon and Khalid Salaita}, doi = {10.1021/jacs.5c05203}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36097--36104}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechano-ID: Proximity labeling of mechanically active receptors reveals the mechanome and tags mechanically active cells}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of (±)-crokonoid a. JACS, 147(40), 36090--36096. (www)

  @article{ , abstract = {We report herein a total synthesis of crokonoid A, featuring a dually bridged 6/7/6/5-fused tetracyclic carbon framework incorporating an unprecedented tricyclo[4.4.1.1 1,4 ]dodecane-2,11-dione core. The synthesis is highlighted by the following key transformations: (a) a regioselective decarboxylative allylation of a 1,3-dienyl carbonate to furnish an α-allyl-β,γ-unsaturated ketone; (b) a domino sequence involving ozonolysis, intramolecular aldol reaction, and acetalization to construct the bicyclo[4.3.1]decanedione core from a fused ring system, in which the acetalization step effectively stabilized the otherwise unstable aldol intermediate; (c) a palladium-catalyzed intramolecular cycloalkenylation of a ketone to assemble the bicyclo[3.2.1]octanedione system, in which the hybridization state of the neighboring carbon proved crucial for the success of this cyclization; and (d) SmI 2 –HMPA-mediated regio- and stereoselective reduction of the C14 ketone.}, archive = {J_JACS}, author = {Dan Forster and Qian Wang and Jieping Zhu}, doi = {10.1021/jacs.5c14479}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36090--36096}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of (±)-crokonoid a}, volume = {147}, year = {2025}, }
• (2025). A convergent approach to phragmalin-type limonoids: Total synthesis of thaigranatin p. JACS, 147(40), 36085--36089. (www)

  @article{ , abstract = {Herein, we report the total synthesis of erythrocarpines M and L and thaigranatin P, topologically complex phragmalin-type limonoids, the latter exhibiting potent agonism on the human pregnane X receptor (hPXR). A key transformation is a SmI 2 -mediated reductive coupling of an aldehyde and an alkene, which constructs the signature tricyclo[3.3.1 2,10 .1 1,4 ]decane framework characteristic of phragmalin natural products. The synthesis features a strategically convergent construction of the phragmalin core structure via a cuprate addition, triflation, and intramolecular Heck reaction sequence. This route offers a versatile platform for the synthesis of structurally diverse phragmalin analogs for future biological investigation.}, archive = {J_JACS}, author = {Jaehoo Lee and Spencer C. Davis and Amber Sheu and Jacqueline W. Gu and Timothy R. Newhouse}, doi = {10.1021/jacs.5c13081}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36085--36089}, shortjournal = {J. Am. Chem. Soc.}, title = {A convergent approach to phragmalin-type limonoids: Total synthesis of thaigranatin p}, volume = {147}, year = {2025}, }
• (2025). Supramolecular length-dependent encapsulation of c90, c100, c120, and c130: A shape-selective approach to fullertube purification. JACS, 147(40), 36079--36084. (www)

  @article{ , abstract = {There are no studies on the supramolecular encapsulation of the newly discovered [5,5]C 90 , -C 100 , -C 120 , and -C 130 fullertubes, a family of fixed diameter allotropic carbons differing by symmetry and nanotubular length. This permits an opportunity to probe their supramolecular encapsulation and evaluate how fullertube length is influencing the former. We report a nanocapsule with an inner cavity height (14.1 Å) capable of selectively encapsulating fullertubes with a diameter of 7 Å. Results show an increased affinity for encapsulation in proportion to increasing tubular length following a trend of [5,5]C 90 < [5,5]C 100 < [5,5]C 120 < [5,5]C 130 , as deduced from K a values, inferred from competition experiments and corroborated by molecular dynamics simulations. This tubular shape selectivity could be leveraged for “tuning” the isolation of giant fullertubes of C 150 –C 200 .}, archive = {J_JACS}, author = {Valentina Iannace and Clara Sabrià and Riley D. Schmitt and Ferran Feixas and Steven Stevenson and Xavi Ribas}, doi = {10.1021/jacs.5c12991}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36079--36084}, shortjournal = {J. Am. Chem. Soc.}, title = {Supramolecular length-dependent encapsulation of c90, c100, c120, and c130: A shape-selective approach to fullertube purification}, volume = {147}, year = {2025}, }
• (2025). Hyperporphyrinization-enhanced electron transfer in covalent organic frameworks for metal-free photocatalytic C–H functionalization. JACS, 147(40), 36071--36078. (www)

  @article{ , abstract = {The development of efficient covalent organic framework (COF)-based photocatalysts has been hindered by topological constraints on photosensitizer incorporation and inefficient charge transfer resulting from electron localization across the linkages. To overcome these limitations, we report a hyperporphyrinization strategy in a novel COF (HP-COF), constructed by linking porphyrinic photosensitizers to bipyridine N-oxide moieties via imine bonds. The unprecedented hyperporphyrin effect in HP-COF originates from linker-to-linker charge transfer (LLCT) across the imine linkage, as demonstrated by comparison with an amide-linked analogue (NP-COF), where the nonconjugated linkage disrupts this delocalization pathway. Upon photoexcitation, the porphyrinic unit oxidizes the bipyridine N-oxide to generate a pyridine N-oxyl radical, which acts as a hydrogen atom transfer catalyst for C–H bond activation. In HP-COF, the LLCT process enhances photooxidative potential, electron delocalization, and charge transport, resulting in superior photocatalytic performance in metal-free C–H functionalization compared to both NP-COF and homogeneous analogues. HP-COF is readily recyclable and retains its photocatalytic activity over five consecutive cycles.}, archive = {J_JACS}, author = {Zhibei Zhou and David Wang and Yubin Fu and Chenghua Deng and Daqian Bian and Zitong Wang and Wenbin Lin}, doi = {10.1021/jacs.5c12771}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36071--36078}, shortjournal = {J. Am. Chem. Soc.}, title = {Hyperporphyrinization-enhanced electron transfer in covalent organic frameworks for metal-free photocatalytic C–H functionalization}, volume = {147}, year = {2025}, }
• (2025). Histidine nτ-imidazole ligation to copper in proteins: Innate or entatic?. JACS, 147(40), 36066--36070. (www)

  @article{ , abstract = {Histidine is among the most versatile amino acids by virtue of its imidazole ring, which is capable of shuttling protons and binding metals at each of its two nitrogen atoms, N π (N δ ) and N τ (N ε ). Despite having a tautomeric relationship and similar basicities, the nitrogen atoms used in copper enzymes are differentiated functionally, with near exclusive N τ -ligation associated with substrate activation sites and exclusive N π -ligation with electron-transfer sites. The results herein show that the innate thermodynamic preference is N τ -ligation to Cu(II) centers, a conclusion drawn from ligand competition experiments at −145 °C between histidine imidazoles within synthetic μ-η 2 :η 2 -peroxodicopper(II) cores. The findings from these faithful models of oxygenated binuclear copper sites in tyrosinase enzymes are informed by spectroscopic data from a series of related complexes with monodentate methylated imidazoles. This preference of histidine N τ -ligation is ascribed enthalpically to greater basicity and entropically to the greater molecular volume of the resulting metal complex compared to its N π -ligated isomer. These results support that the N τ -ligation observed in copper enzymatic sites is the innate thermodynamic form, independent of the protein matrix, while the N π -ligation observed in electron transfer sites is presumably entatic in origin─requiring evolved protein structural influences. This structural distinction provides a powerful indicator of function among the biological copper sites.}, archive = {J_JACS}, author = {Tao A. G. Large and Richard Hage and Jasper Ainsworth and Viet H. Tran and T. Daniel P. Stack}, doi = {10.1021/jacs.5c11347}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36066--36070}, shortjournal = {J. Am. Chem. Soc.}, title = {Histidine nτ-imidazole ligation to copper in proteins: Innate or entatic?}, volume = {147}, year = {2025}, }
• (2025). Reliable pKa prediction through efficient incorporation of anharmonicity within the Nuclear–Electronic orbital framework. JACS, 147(40), 36059--36065. (www)

  @article{ , abstract = {Accurate p K a prediction is critical for understanding chemical reactivity and molecular properties across a wide range of applications. Computational approaches usually invoke a harmonic treatment of the vibrational modes for zero-point energies, as well as thermal and entropic contributions. Herein, we present a general protocol for relative p K a prediction that incorporates the significant anharmonic effects using nuclear–electronic orbital (NEO) theory. This protocol is validated against experimental data for a range of molecules in acetonitrile, including protonated nitrogen bases, nitrophenols, anilines, and diamines, as well as cobalt electrocatalysts. For simple acids, the NEO approach offers only a slight improvement over conventional density functional theory with the standard harmonic vibrational treatment, whereas for hydrogen-bonded acids, the NEO approach offers more significantly improved performance at a comparable computational cost. This accessible methodology provides a practical route for accurate p K a prediction in challenging systems and is extendable to related thermodynamic properties such as hydricities and proton-coupled redox potentials.}, archive = {J_JACS}, author = {Jang Mok Yoo and Mathew Chow and Eno Paenurk and Sharon Hammes-Schiffer}, doi = {10.1021/jacs.5c11332}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36059--36065}, shortjournal = {J. Am. Chem. Soc.}, title = {Reliable pKa prediction through efficient incorporation of anharmonicity within the Nuclear–Electronic orbital framework}, volume = {147}, year = {2025}, }
• (2025). Use of electron-transfer mediators to access higher electrochemical current densities in ni-catalyzed cross-electrophile coupling. JACS, 147(40), 36053--36058. (www)

  @article{ , abstract = {Ni-catalyzed cross-electrophile coupling (XEC) reactions are versatile methods for carbon–carbon bond formation, and they often use electrochemistry to supply the requisite electrons. These reactions, however, typically exhibit slow rates and operate at low current densities (e.g., 1–4 mA/cm 2 ) to avoid formation of undesirable side products. Here, we show that much higher current densities and reaction selectivity can be accessed by using a homogeneous electron-transfer (ET) mediator. Bis(ethylcyclopentadienyl)cobalt(II), which has a redox potential similar to that of the bipyridyl-ligated Ni catalyst (−1.45 and –1.50 V vs Fc/Fc + , respectively), exhibits the best performance. This ET-mediator strategy is applied to numerous C(sp 2 )–C(sp 3 ) coupling reactions and extended to a flow-based reaction on 10 mmol-scale that proceeds in 96% yield with 91% Faradaic efficiency at a current density of 18 mA/cm 2 .}, archive = {J_JACS}, author = {Jieru Zhu and Shannon S. Stahl}, doi = {10.1021/jacs.5c10599}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36053--36058}, shortjournal = {J. Am. Chem. Soc.}, title = {Use of electron-transfer mediators to access higher electrochemical current densities in ni-catalyzed cross-electrophile coupling}, volume = {147}, year = {2025}, }
• (2025). The allosteric regulator inositol phosphate dramatically affects the efficacy and selectivity of inhibitors for different HDAC complexes. JACS, 147(40), 36044--36052. (www)

  @article{ , abstract = {Class I histone deacetylases regulate gene transcription and are established therapeutic targets. HDAC1–3 form the catalytic subunit in several distinct multiprotein complexes; however, HDAC inhibitors are rarely studied in the context of these complexes. We evaluated multiple inhibitors, using seven HDAC complexes, and found that the inhibition profiles were highly complex-dependent, despite targeting the same enzyme. We also investigated the effect of the allosteric regulator inositol phosphate on these inhibitors. We observed very large, complex-selective reductions in the potency of benzamides bearing a “foot-pocket group”, proposed to be selective for HDAC1/2. The potencies of these compounds are likely to be profoundly different in vivo compared with in vitro potencies in the absence of inositol phosphates. Our findings are supported by cell-based assays evaluating histone acetylation and HDAC degradation, highlighting the importance of evaluating HDACi in the context of HDAC complexes and inositol phosphates.}, archive = {J_JACS}, author = {Wiktoria A. Pytel and Urvashi Patel and Joshua P. Smalley and Christopher J. Millard and Edward A. Brown and Aline R. Pavan and Siyu Wang and Jay H. Kalin and Jean Leandro dos Santos and Philip A. Cole and James T. Hodgkinson and John W. R. Schwabe}, doi = {10.1021/jacs.5c08929}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36044--36052}, shortjournal = {J. Am. Chem. Soc.}, title = {The allosteric regulator inositol phosphate dramatically affects the efficacy and selectivity of inhibitors for different HDAC complexes}, volume = {147}, year = {2025}, }
• (2025). Silica-supported vanadium-oxo-alkylidene for self-metathesis of propene. JACS, 147(40), 36039--36043. (www)

  @article{ , abstract = {Olefin metathesis is a widely used catalytic process for the construction of C═C bonds. This study describes the grafting of [V(═CHSi(CH 3 ) 3 )(═O)(OC(CF 3 ) 2 Mes)(IMes)] ( 1 ) onto the surface of partially dehydroxylated silica using surface organometallic chemistry, yielding [(≡SiO)V(═CHSi(CH 3 ) 3 )(═O)(IMes)] ( V/SiO 2 ). The surface species is fully characterized by infrared spectroscopy, elemental analysis, and solid-state NMR spectroscopy. In contrast to its molecular analogue, which shows minimal activity in ring-closing metathesis, V/SiO 2 is a productive catalyst in this transformation with a maximum TON of 94 for the ring-closing of (H 5 C 3 ) 2 N-Ts (Ts = p -tolylsulfonyl). We also demonstrate that V/SiO 2 is an active catalyst for the self-metathesis of propene under flow conditions, achieving a TON of 930. This is the first report of a V-alkylidene being active for the self-metathesis of propene with activity being an order of magnitude greater than other V-based catalysts reported for the self-metathesis of olefins.}, archive = {J_JACS}, author = {Rahul Koottanil Haridasan and Shirley Hernandez and Selena Kuenzig and Gabriela Tejeda and James H. P. Collins and Konstantin V. Bukhryakov and Keith Searles}, doi = {10.1021/jacs.5c07854}, journal = {Journal of the American Chemical Society}, month = {10}, number = {40}, pages = {36039--36043}, shortjournal = {J. Am. Chem. Soc.}, title = {Silica-supported vanadium-oxo-alkylidene for self-metathesis of propene}, volume = {147}, year = {2025}, }
• (2025). Correction to “Antitumor activity of a unique polymer that incorporates a fluorescent self-assembled metallacycle”. JACS, 147(39), 36037--36038. (www)

  @article{ , archive = {J_JACS}, author = {Guocan Yu and Mingming Zhang and Manik Lal Saha and Zhengwei Mao and Jin Chen and Yong Yao and Zijian Zhou and Yijing Liu and Changyou Gao and Feihe Huang and Xiaoyuan Chen and Peter J. Stang}, doi = {10.1021/jacs.5c14232}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {36037--36038}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Antitumor activity of a unique polymer that incorporates a fluorescent self-assembled metallacycle”}, volume = {147}, year = {2025}, }
• (2025). Catalytic alternating copolymerization to access mechanoresponsive cyclic olefin copolymers with on-demand recyclability. JACS, 147(39), 36027--36036. (www)

  @article{ , abstract = {Precise sequence control remains a fundamentally important yet synthetically challenging strategy for tailoring the properties of polymeric materials. Although it offers great potential for accessing functional polyolefins with novel properties, progress toward this goal has been limited. Here we report a catalytic alternating copolymerization protocol between ethylene and bicyclic cyclobutenes, affording cyclic olefin copolymers densely functionalized with bicyclic cyclobutane mechanophores. The spatial distribution of these bicyclic mechanophores along the polymer backbone plays a critical role in determining the copolymer’s properties, including strength, toughness, and crystallinity. Notably, transitioning from a random to an alternating copolymer structure leads to marked changes in both stress and strain responses. Meanwhile, near-alternating ethylene/bicyclic cyclobutene copolymers exhibit both high optical performance and desirable toughness. Furthermore, the alternating copolymer can be transformed into an unsaturated polymer via force-induced mechanophore cycloreversion upon bulk ball-milling, enabling upcycling into chemically recyclable polymers.}, archive = {J_JACS}, author = {Minghang Ji and Shan Tang}, doi = {10.1021/jacs.5c14243}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {36027--36036}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic alternating copolymerization to access mechanoresponsive cyclic olefin copolymers with on-demand recyclability}, volume = {147}, year = {2025}, }
• (2025). Methyl radical dominated highly selective methane oxidation to liquid oxygenates. JACS, 147(39), 36016--36026. (www)

  @article{ , abstract = {Selective oxygenation of methane to value-added chemicals remains a great challenge due to the higher oxidation tendency of products than inert methane that leads to uncontrollable overoxidation. Herein, a strategy of photoinduced direct generation of methyl radicals ( • CH 3 ) from methane is proposed. Unlike traditional mechanisms that rely on highly oxidative activators (such as • OH radicals), this approach enables controllable methane oxygenation and properly avoids the overoxidation of formed products to CO 2 . To this end, Pt single-atom-decorated ZnO (Pt 1 /ZnO) is assembled as the proof-of-concept photocatalyst, in which Pt single atoms serve as both hole trapping and methane activation sites; the yielded • CH 3 with an enriched surface coverage then drives the radical chain process by first incorporating the environmentally benign molecular oxygen (or its derivative O 2 •– ), achieving a remarkable liquid product selectivity and formaldehyde yield of 95% and 2.98 mmol g –1 h –1 , respectively, with a record quantum efficiency of 14.14% at 350 nm.}, archive = {J_JACS}, author = {Jingwen Jiang and Zhonghua Li and Wangxi Liu and Changhao Liu and Huiting Huang and Zhexing Lin and Zhetong Yang and Shiyu Zhang and Xiaoming Xu and Bin Gao and Chen Li and Jianyong Feng and Zhigang Zou and Zhaosheng Li}, doi = {10.1021/jacs.5c13767}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {36016--36026}, shortjournal = {J. Am. Chem. Soc.}, title = {Methyl radical dominated highly selective methane oxidation to liquid oxygenates}, volume = {147}, year = {2025}, }
• (2025). Coordination chemistry of an emerging group of diazeniumdiolate siderophores: Crystal structures of M(III)-gramibactin (M= fe and ga). JACS, 147(39), 36007--36015. (www)

  @article{ , abstract = {To overcome iron starvation, microorganisms often produce siderophores─chelators with high affinity and selectivity for Fe(III). The recent discovery of the siderophore gramibactin garnered significant interest, as it added the C -diazeniumdiolate as a new Fe(III)-binding group in siderophores. Gramibactin is a mixed ligand siderophore, comprised of two graminine residues harboring the diazeniumdiolate donors and a β-hydroxy-aspartate donor. Diazeniumdiolate siderophores have so far evaded crystallographic characterization and few structures of synthetic diazeniumdiolate complexes are reported. To address the gap in structural information, the complexes K[M(III)-gramibactin] (M = Fe and Ga) were prepared, crystallized and their structures solved by X-ray diffraction (XRD). The four Fe–O bond lengths in the two diazeniumdiolates are quite similar, ranging from 1.978 Å to 2.059 Å, indicating an equal contribution in bonding. In contrast, the differing Fe–O bond lengths in β-hydroxy-aspartate reflect the relative donor strengths of the carboxylate (1.997 Å) and alkoxide (1.902 Å) groups. Gramibactin coordinates Fe(III) in a Δ-configured distorted octahedral geometry. The diamagnetic nature of Ga(III) is often leveraged in NMR studies to infer the solution structure of the corresponding Fe(III)-siderophores, which are assumed to be identical. The structural similarity of Ga(III)- and Fe(III)-gramibactin is striking and represents the first crystallographic verification of the assumed isostructural relationship between a Ga(III)- and an Fe(III)-siderophore. By providing concrete evidence, this study promotes Ga(III) as a reliable proxy for Fe(III) in siderophore complexes, with implications for solution structure determination of siderophores and design of Ga(III)-siderophore-based theranostics.}, archive = {J_JACS}, author = {Emil Thomsen and Guang Wu and Alison Butler}, doi = {10.1021/jacs.5c13791}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {36007--36015}, shortjournal = {J. Am. Chem. Soc.}, title = {Coordination chemistry of an emerging group of diazeniumdiolate siderophores: Crystal structures of M(III)-gramibactin (M= fe and ga)}, volume = {147}, year = {2025}, }
• (2025). A general metallaphotoredox platform for N-alkylated sulfoximines as bioisosteric building blocks. JACS, 147(39), 35995--36006. (www)

  @article{ , abstract = {The precise modulation of physicochemical and ADME properties is critical in drug discovery. We report a unified, mild, and broadly applicable metallaphotoredox-enabled protocol for the N -alkylation of sulfoximines, a versatile S(VI) motif gaining prominence as a bioisostere. This method overcomes limitations of previous N -substitution approaches by accommodating diverse alkyl sources, including alcohols, alkyl bromides, and carboxylic acids, under visible-light irradiation. The strategy features high functional group tolerance and offers efficient access to both primary and secondary N -alkyl sulfoximines. Its utility is showcased through the late-stage functionalization of pharmacologically active compounds, natural product derivatives, and short peptides, enabling rapid access to novel analogues with enhanced structural diversity. Furthermore, we demonstrate the strategic coupling of bicyclo[1.1.1]pentyl moieties with sulfoximines to achieve a synergistic bioisosteric design. A preliminary drug optimization campaign, exemplified by an atuveciclib analogue, highlights the platform’s potential for improving key ADME properties such as lipophilicity and cellular permeability, underscoring its value for lead diversification and refinement in medicinal chemistry.}, archive = {J_JACS}, author = {Johannes J. Großkopf and Danielle C. Morgan and Aimee K. Clarke and David W. C. MacMillan}, doi = {10.1021/jacs.5c13726}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35995--36006}, shortjournal = {J. Am. Chem. Soc.}, title = {A general metallaphotoredox platform for N-alkylated sulfoximines as bioisosteric building blocks}, volume = {147}, year = {2025}, }
• (2025). Manipulating the coordination environment of cu single atoms via regulating ZrO2 support crystal phases for enhanced CO2 electroreduction. JACS, 147(39), 35985--35994. (www)

  @article{ , abstract = {For electrochemical CO 2 reduction (ECR), high-precision manipulation of the single-atomic catalytic centers is significant and remains an issue. Here, we report a support crystal phase engineering (SCPE) strategy by regulating the crystal phase of the ZrO 2 support to modulate its interaction with Cu atomic centers, synergizing the coordination environment of Cu atoms and the local microenvironment for ECR. Specifically, tetragonal ZrO 2 (tZrO 2 ) supports a Cu 1 O 3 structure, and the rich bridging O atoms at the tZrO 2 surface could serve as basic sites. In contrast, the monoclinic ZrO 2 (mZrO 2 ) forming a Cu 1 O 4 structure has weak basicity. The Cu 1 O 3 –tZrO 2 site displays a high activity for ECR to methane, with 3.16 (FE CH 4 ) and 2.54 ( j CH 4 ) times higher than those of the Cu 1 O 4 –mZrO 2 counterpart. Density functional theory (DFT) and attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR–SEIRAS) reveal that the dynamic *OH on Cu 1 O 3 –tZrO 2 helps to significantly lower the Gibbs free-energy change (Δ G ) for the rate-determining step (RDS). The rich basic sites on tZrO 2 could also facilitate the adsorption and activation of CO 2 and create an H 2 O-expelling local microenvironment to suppress the competing hydrogen evolution reaction. Our work demonstrates a facile strategy to simultaneously manipulate the coordination environment of the active centers and the local microenvironment for the catalytic reaction.}, archive = {J_JACS}, author = {Zhuojun Yang and Jiaqi Zhang and Xin Tan and Haojie Zhu and Lekai Xu and Xueyan Wu and Zhiyuan Xu and Jixi Guo and Dianzeng Jia and Chen Chen}, doi = {10.1021/jacs.5c13661}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35985--35994}, shortjournal = {J. Am. Chem. Soc.}, title = {Manipulating the coordination environment of cu single atoms via regulating ZrO2 support crystal phases for enhanced CO2 electroreduction}, volume = {147}, year = {2025}, }
• (2025). Zeolites as photoactive scaffolds for efficient photooxidation. JACS, 147(39), 35975--35984. (www)

  @article{ , abstract = {Zeolites are widely applied in thermal catalysis as highly efficient catalysts but show limited photocatalytic activities. In this work, we demonstrated zeolites as photoactive scaffolds for perovskite nanocrystals that triggered a hydroxyl radical ( • OH)-mediated reaction pathway for selective C(sp 3 )-H bond activation. The as-prepared Cs 2 AgBiBr 6 @ZSM-5 (CABB@ZSM-5) photocatalyst afforded efficient toluene oxidation to benzaldehyde at ambient conditions under visible light irradiation, with >98% selectivity and an exceptional reaction rate of 40.9 mmol g –1 h –1 , surpassing those of previously reported photocatalytic systems under comparable conditions. The host–guest design of CABB@ZSM-5 favored the adsorption of toluene and oxygen molecules and preactivated the adsorbed toluene molecules by Lewis acidic sites within ZSM-5 to reinforce the oxidation process. Significantly, we discovered that the adsorbed water in zeolite channels promoted the • OH-mediated oxidation reaction pathway, offering thermodynamic advantages over the conventional superoxide radical ( • O 2 – )-dominated reaction pathway. The incorporation of Zn 2+ into CABB@ZSM-5 further boosted benzaldehyde production by 2-fold. This work redefines the role of zeolites, transforming them from passive supports into multifunctional scaffolds with significant potential in advanced photochemical applications.}, archive = {J_JACS}, author = {Shiqin Gao and Guangyuan He and Bolun Wang and Qingyi Li and Xiao Chen and Donghai Mei and Jihong Yu}, doi = {10.1021/jacs.5c13535}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35975--35984}, shortjournal = {J. Am. Chem. Soc.}, title = {Zeolites as photoactive scaffolds for efficient photooxidation}, volume = {147}, year = {2025}, }
• (2025). Insights into reactive carbon capture through heterogeneously catalyzed electrochemical reduction of an imidazolium carboxylate. JACS, 147(39), 35962--35974. (www)

  @article{ , abstract = {In reactive carbon capture (RCC) approaches, sorbents capture CO 2 from a dilute source as opposed to pure CO 2 and electrochemical conversion proceeds through the bound-CO 2 form, bypassing the energy losses and expense of sequential CO 2 capture, purification, and compression. N-heterocyclic carbenes (NHCs) have shown promise as capture agents, with reports of RCC conversion of CO 2 to CO or CH 4 via homogeneous electrocatalysis. However, RCC using NHCs is underexplored with heterogeneous electrocatalysts. Herein, the electroreduction of 1,3-bis(2,6-diisopropylphenyl)imidazolium-2-carboxylate (IPrCO 2 ) was investigated as the CO 2 -adduct form of the corresponding imidazole carbene on Ag and other cathodes. In acetonitrile with dilute water, IPrCO 2 reduction led to formate product at up to 88% faradaic efficiency (FE). Carboxylation of the NHC with 13 CO 2 and subsequent electroreduction led to 13 C-labeled formate, supporting the interpretation of RCC conversion of the carboxylate. Compared to reduction of IPrCO 2 , reduction of the smaller -R group 1,3-dimethylimidazolium-2-carboxylate (IMeCO 2 ) led to much lower formate selectivity (∼8% FE), in part due to rapid degradation of the IMeCO 2 molecule. Ab initio calculations further supported favorable energetics of IPrCO 2 conversion compared to IMeCO 2 , while indicating that a mechanism through carboxylate adsorption is unfavorable and more likely to proceed through a surface hydride. In situ surface-enhanced Raman spectroscopy (SERS) supported a weak surface adsorption of IPrCO 2 during the reaction. Despite relatively high selectivity conversion of IPrCO 2 to formate, CO 2 sorption and reduction cycling studies showed limited durability of the system due to decomposition of the IPrCO 2 , indicating a need for more reductively stable NHCs.}, archive = {J_JACS}, author = {Manu Gautam and Jared S. Stanley and Saudagar Dongare and Francois Nkurunziza and Matthew C. Mulvehill and Bhavi Shah and Burcu Gurkan and Robert J. Nielsen and Jenny Y. Yang and Joshua M. Spurgeon}, doi = {10.1021/jacs.5c13415}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35962--35974}, shortjournal = {J. Am. Chem. Soc.}, title = {Insights into reactive carbon capture through heterogeneously catalyzed electrochemical reduction of an imidazolium carboxylate}, volume = {147}, year = {2025}, }
• (2025). Extended stability window in water-in-salt electrolytes: Understanding the origins. JACS, 147(39), 35953--35961. (www)

  @article{ , abstract = {Water-in-salt electrolytes extend the voltage stability range beyond that of dilute systems, enabling the use of high-voltage materials in aqueous energy storage. This stability is often attributed to the formation of a solid electrolyte interphase (SEI) or reduced water activity. However, by studying the hydrogen evolution reaction (HER) on platinum in NaClO 4 electrolytes (1–17 molal) using electrochemical measurements, MD simulations, and DFT calculations, we show that alternative mechanisms strongly influence the stability window. Specifically, we disentangle the effects from water activity, the local pH increase, and kinetic and transport limitations arising from disrupted hydrogen bonding and sluggish water transport. We observe a nearly linear relationship between the decrease in the surface water coverage and HER exchange current density. As a result, the HER kinetics is slower: with a 7 times decrease in the exchange current density and a 1.5 times increase in the Tafel slope in 17 m solution compared to 1 m. Our MD simulations further reveal that sluggish water transport within the double layer significantly limits the HER, extending the experimental stability window. Ultimately, in this non-SEI-forming electrolyte, reduced bulk water activity plays only a relatively minor role in enhancing the stability of water-in-salt systems.}, archive = {J_JACS}, author = {Dario Gomez Vazquez and Johannes Ingenmey and Katharina Trapp and Dennis Ciliak and Mathieu Salanne and Maria R. Lukatskaya}, doi = {10.1021/jacs.5c12989}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35953--35961}, shortjournal = {J. Am. Chem. Soc.}, title = {Extended stability window in water-in-salt electrolytes: Understanding the origins}, volume = {147}, year = {2025}, }
• (2025). Design of tau aggregation inhibitors using iterative machine learning and a polymorph-specific brain-seeded fibril amplification assay. JACS, 147(39), 35942--35952. (www)

  @article{ , abstract = {The aggregation of tau into amyloid fibrils is associated with Alzheimer’s disease (AD) and related tauopathies. Since different tauopathies are characterized by the formation of distinct tau fibril morphologies, it is important to combine the search of tau aggregation inhibitors with the development of in vitro tau aggregation assays that recapitulate aggregation as it may occur in the brain. Here we address this problem by reporting an in vitro tau aggregation assay in which AD brain homogenates are used to seed the generation of first-generation tau fibrils in a polymorph-specific manner under quiescent conditions. These fibrils are then used to create amyloid seed libraries from which second-generation kinetic assays can be readily performed. Using this strategy, we illustrate an iterative machine learning method for the identification of small molecules for the polymorph-specific inhibition of the in vitro formation of tau fibrils. We further show that the small molecules selected by this procedure are potent inhibitors in a Drosophila tauopathy model.}, archive = {J_JACS}, author = {Alessia Santambrogio and Robert I. Horne and Michael A. Metrick, II and Nicholas C. T. Gallagher and Z. Faidon Brotzakis and Dillon Rinauro and Ergina Vourkou and Katerina Papanikolopoulou and Efthimios M. C. Skoulakis and Sara Linse and Byron Caughey and Michele Vendruscolo}, doi = {10.1021/jacs.5c12812}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35942--35952}, shortjournal = {J. Am. Chem. Soc.}, title = {Design of tau aggregation inhibitors using iterative machine learning and a polymorph-specific brain-seeded fibril amplification assay}, volume = {147}, year = {2025}, }
• (2025). D0 cation-based spinel-type sulfide semiconductors with color-tunable direct-gap and ambipolar dopability. JACS, 147(39), 35935--35941. (www)

  @article{ , abstract = {This work proposes a materials design concept based on chemical bonding and atomic orbital symmetry to realize a direct bandgap and both n- and p-type dopability in spinel-type AB 2 X 4 , which have been overlooked as optoelectronic semiconductors. By combining a heavy s 0 cation, a d 0 cation, and sulfur at the A, B, and X sites, the conduction band minimum is formed mainly by the deep s 0 orbital, whereas the valence band maximum is formed by the shallow nonbonding sulfur p orbitals. These are appropriately aligned for n- and p-type doping. Furthermore, the anisotropic d 0 orbitals of B suppress dispersion of competing bands, resulting in a direct bandgap. In the candidate ZnSc 2 S 4 , the band gap and photoluminescence are widely tuned via isovalent substitution. Additionally, the n- and p-type conductivities can be controlled through chemical doping by over 9 orders of magnitude from the insulating state, validating the effectiveness of our concept in exploring next-generation semiconductors suitable for photoabsorbers of solar cells and green light-emitting diode sources.}, archive = {J_JACS}, author = {Kota Hanzawa and Takayuki Nagai and Ryoga Nagasawa and Takayoshi Katase and Hideo Hosono and Hidenori Hiramatsu}, doi = {10.1021/jacs.5c12816}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35935--35941}, shortjournal = {J. Am. Chem. Soc.}, title = {D0 cation-based spinel-type sulfide semiconductors with color-tunable direct-gap and ambipolar dopability}, volume = {147}, year = {2025}, }
• (2025). Dual-vacancy-induced selective oxidative cleavage of Cα–Cβ bonds for the electrocatalytic depolymerization of lignin. JACS, 147(39), 35924--35934. (www)

  @article{ , abstract = {The electrocatalytic depolymerization of lignin into phenolic and carboxylic acid compounds presents a promising strategy for biomass valorization via selective C–C/C–O bond cleavage under mild conditions. However, two major challenges hinder its practical implementation: inefficient C–C bond cleavage and excessive overoxidation of the desired phenolic products. Herein, we demonstrate an engineered vacancy-rich nickel hydroxide catalyst (Ni(OH) 2 –V) that achieves exceptional performance in both C α –C β bond cleavage of β- O -4 lignin linkages and suppression of phenol overoxidation. Through integrated experimental and computational analyses, this study elucidates how the synergistic introduction of cations and oxygen dual-vacancy in Ni(OH) 2 –V contributes to its enhanced catalytic activity. Specifically, these dual-vacancies (1) significantly enhance the interfacial adsorption of hydroxide ions on the 2-phenoxy-1-phenylethanol (2-PPE) substrate, (2) effectively lower the energy barrier of the rate-determining step (C α –OH → C α ═O), and (3) promote the timely desorption of phenol, thereby preventing overoxidation. The optimized catalyst achieved complete conversion of 2-PPE, yielding exceptional yields of 85.7% for phenol and 96.5% for benzoic acid at 1.40 V vs the reversible hydrogen electrode (V RHE ). These results represent 2.4-fold and 2.3-fold improvements over pristine Ni(OH) 2 . Furthermore, the practical utility of Ni(OH) 2 –V was validated through the depolymerization of poplar lignin and corn stover lignin, successfully yielding 14.24 and 19.54 wt % aromatic monomers. This research establishes a dual-vacancy engineering framework for precise lignin bond cleavage and offers crucial insights into the structure–activity relationship of vacancy-rich electrocatalysts for biomass valorization.}, archive = {J_JACS}, author = {Yulu Yang and Lingyi Kong and Zhongcheng Xia and Yuanqing He and Yafei Li and Shuangyin Wang and Yuqin Zou}, doi = {10.1021/jacs.5c12841}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35924--35934}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual-vacancy-induced selective oxidative cleavage of Cα–Cβ bonds for the electrocatalytic depolymerization of lignin}, volume = {147}, year = {2025}, }
• (2025). Impact of hot carrier dynamics on photoelectrocatalytic activity on Au@Pd antenna-reactor nanoparticles. JACS, 147(39), 35913--35923. (www)

  @article{ , abstract = {Photoinduced hot carriers generated from the decay of surface plasmons in noble metals play a decisive role in producing green hydrogen gas through the photoelectrochemical (PEC) water splitting reaction, a process driven by visible light absorption. To optimize the utilization of these hot carriers, we employed a plasmonic antenna-reactor model based on core–shell structured Au@Pd nanoparticles (NPs) with an ultrathin Pd shell. In this study, we demonstrate that TiO 2 nanotube arrays (TNAs) decorated with Au@Pd NPs exhibit superior performance with the Pd shell serving as a catalytic reactor that efficiently extracts hot carriers from the plasmonic Au antenna. The photocatalytic performance in PEC measurements increased with higher Pd coverage, and Au 70 @Pd 30 /TNAs exhibited a 2.2-fold higher photocurrent compared with bare Au/TNAs. The enhanced oxygen evolution reaction (OER) activity observed for Au 70 @Pd 30 /TNAs is attributed to the higher population of hot holes on the surface of Au@Pd NPs, which enhances the oxidation capability for interactions with electrolytes. Femtosecond transient absorption (fs-TA) spectra of Au@Pd NPs revealed a shorter lifetime of hot electrons through electron–phonon (e–p) scattering in Au 70 @Pd 30 NPs compared to Au NPs, indicating suppressed charge recombination and increased hot hole population on the surface. Therefore, this study suggests that the plasmonic antenna-reactor model, critically influenced by hot carrier dynamics, provides a promising framework for efficient photoelectrocatalytic systems.}, archive = {J_JACS}, author = {Hyewon Park and Seunghyun Chun and Jeong Hoon Lee and Jihan Son and Sookyung Kim and Jungkweon Choi and Hyotcherl Ihee and Hyosun Lee and Jeong Young Park}, doi = {10.1021/jacs.5c12825}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35913--35923}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of hot carrier dynamics on photoelectrocatalytic activity on Au@Pd antenna-reactor nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Mechanism inversion in visible light-induced photoclick reactions. JACS, 147(39), 35903--35912. (www)

  @article{ , abstract = {Photoclick chemistry has emerged as a powerful methodology for achieving precise spatial and temporal control in photochemical transformations, enabling various applications ranging from surface functionalization, polymer conjugation, and photo-cross-linking to bioimaging and protein labeling. Despite significant advances, the absence of an unambiguous structure–property–mechanism relationship limits the design and application of photoclick systems in biological and material contexts. Herein, we report a novel strategy for tuning the reactivity and reaction mechanism of photoclick reactions of 9,10-phenanthrenequinone ( PQ ) with electron-rich alkenes ( ERA s) through the design of 2,2’-substituted PQ derivatives incorporating electron-withdrawing groups (EWGs) and electron-donating groups (EDGs). Our experimental studies reveal that the reaction rate via a direct pathway involving the direct coupling between PQ and ERA gradually declines, while that of the triplet–triplet energy transfer-mediated pathway increases with the stepwise change of substitutions from EWGs to EDGs. Theoretical calculations and transient absorption spectroscopy measurements show that these observations can be traced back to the excited-state energy-level inversion between 1 n π* and 1 ππ* states, which directly affects intersystem crossing yields. Furthermore, the reaction pathways can be modulated by changing the polarity of the solvent. These remarkable findings provide valuable mechanistic insights and establish a robust platform for the rational tuning of the reactivity and selectivity of PQ–ERA photoclick reactions using visible light while offering a unique strategy for the control of photochemical applications in complex environments.}, archive = {J_JACS}, author = {Youxin Fu and Jingwen Zhou and Xinyi Zou and Liuhui Shi and Xing Zhang and Anna M. Doze and Michiel F. Hilbers and Wybren Jan Buma and Jianyu Zhang and Ben L. Feringa}, doi = {10.1021/jacs.5c12759}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35903--35912}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanism inversion in visible light-induced photoclick reactions}, volume = {147}, year = {2025}, }
• (2025). Encapsulation of an electron in a diborencine macrocycle: Synthesis, structure, and reactivity. JACS, 147(39), 35895--35902. (www)

  @article{ , abstract = {Encapsulation of a single electron within the internal cavity of a host system poses significant challenges, as the electron tends to delocalize over the surface. In this study, we successfully trap a single electron through a B–B one-electron σ-bond in a diborencine macrocycle (compound 4 ). The structure of this one-electron σ-bond has been characterized using X-ray single-crystal analysis and EPR studies, indicating that this bond exhibits considerable s -character, with the boron atoms adopting sp 3 hybridization, as supported by DFT computations. Additionally, compound 4 demonstrates rich reactivity: it can facilitate O 2 cleavage, generating a B–O–B cyclic product; its reaction with PhSSPh produces a B–S–B linked ring-expansion product, while reactions with PhSeSePh and quinone yield ring-contraction products. The resulting products have been fully characterized through X-ray single-crystal analysis, NMR, and HRMS spectroscopy. Finally, DFT computational studies have been performed to elucidate the reaction mechanism of this one-electron B–B bond.}, archive = {J_JACS}, author = {Yuhao Wu and Yi Pan and Jiachen Yao and Gan Xu and Kai-Chung Lau and Zhenpin Lu}, doi = {10.1021/jacs.5c12718}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35895--35902}, shortjournal = {J. Am. Chem. Soc.}, title = {Encapsulation of an electron in a diborencine macrocycle: Synthesis, structure, and reactivity}, volume = {147}, year = {2025}, }
• (2025). Photochemical metallonitrene formation for n atom transfers. metal- versus azide-centered excited states and the role of their energetic order. JACS, 147(39), 35881--35894. (www)

  @article{ , abstract = {Square-planar d 8 -configured transition metal complexes, [M II (dppe)(N 3 ) 2 ] ([ 1 M ]) with M = Ni, Pd, Pt and dppe = 1,2-bis(diphenylphosphino)ethane, are used as photolabile precursors for metallonitrenes, an important class of subvalent species that serve as reactive intermediates in the direct amination of CH bonds. We monitored the relaxation dynamics of [ 1 M ], following their ultrafast excitation at 266 nm, with femtosecond-to-microsecond mid-infrared (MIR) spectroscopy in the antisymmetric N 3 -stretching region. Regardless of M, the metallonitrene, [M II (dppe)(N 3 )(N)] ([ 2 M ]), could be identified as the predominant photoproduct through the N 3 -stretching absorption of its remaining intact azido ligand. Accompanying quantum-chemical calculations demonstrate that the N α –N β bond cleavage required for metallonitrene formation is facilitated by an intriguing triplet azide-ππ* state, which is electronically preconfigured for the adiabatic release of a neutral N 2 fragment. This state extrapolates smoothly via a small barrier to the electronic ground state of [ 2 M ], which is the N-centered triplet diradical. No evidence was found for a closed-shell singlet nitrene intermediate, which was previously invoked in the photoinduced formation of organic nitrenes. The photochemical conversion yield was found to increase systematically in the order Ni > Pd > Pt, which was found to reflect an energetic reversal of the lowest metal-centered triplet d-d states and the productive, purely ligand-centered, azide-ππ* state. Our findings thus advocate a simple design guideline for efficient CH-amination catalysts: use strong-field ancillary ligands in combination with 4d- and 5d-transition metals to shift the lowest metal-centered state above the azide-ππ* state, thus eliminating detrimental deactivation pathways.}, archive = {J_JACS}, author = {Markus Bauer and Tobias Unruh and Luis I. Domenianni and Peter Vöhringer}, doi = {10.1021/jacs.5c12680}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35881--35894}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemical metallonitrene formation for n atom transfers. metal- versus azide-centered excited states and the role of their energetic order}, volume = {147}, year = {2025}, }
• (2025). Precision synthesis of polyrotaxanes using cascade metathesis polymerization. JACS, 147(39), 35871--35880. (www)

  @article{ , abstract = {Mechanically interlocked polymers (MIPs), such as polyrotaxanes (PRs) and polycatenanes, represent intriguing synthetic macromolecules distinguished by their unique architectures and topology. These MIPs, characterized by their mechanical bonds and movable component parts, have been extensively utilized across various contemporary fields of chemistry, presenting opportunities for the design of functional materials with enhanced mechanical properties. However, the precision synthesis of MIPs, specifically PRs, with controlled molecular weights and narrow dispersity remains a significant challenge, hindering the progression of well-defined mechanically interlocked materials that exhibit a clear structure–property relationship. Herein, we disclose the controlled chain-growth synthesis of main-chain PRs through cascade metathesis polymerization by employing a catenane-based monomer. A series of PRs with targeted molecular weights, narrow dispersities, and tunable mechanical properties was successfully prepared by adjusting the monomer-to-catalyst feed ratio. The “livingness” of this polymerization was validated through kinetic studies, and the detailed structural characteristics of the synthesized PRs were supported by 1 H NMR spectroscopy and mass spectrometry. Both block and statistical copolymers were produced in a controlled manner through the copolymerization of the catenane-based monomer with other monomers that can undergo ring-opening metathesis polymerization (ROMP), allowing for easy access to PRs featuring different architectures and, most importantly, tunable ring densities. This work significantly advances beyond the majority of previously reported studies concerning the controlled synthesis of PRs, paving the way for the rational design and synthesis of mechanically interlocked materials with desired functionalities.}, archive = {J_JACS}, author = {Jiaqi Han and Seung Eun Choi and Xin Jiang and Hua Zhong and Xiaoyang Wang and Chengyu Zeng and Yunyan Qiu}, doi = {10.1021/jacs.5c09098}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35871--35880}, shortjournal = {J. Am. Chem. Soc.}, title = {Precision synthesis of polyrotaxanes using cascade metathesis polymerization}, volume = {147}, year = {2025}, }
• (2025). Electrochemically mediated atom transfer radical polymerization employing rapid alternating polarity. JACS, 147(39), 35858--35870. (www)

  @article{ , abstract = {Mass transfer limitations pose considerable challenges in electrochemical synthesis, particularly in high-viscosity environments that are inherent to electrochemically mediated polymerizations. In such scenarios, inadequate transport of redox-active species to and from the electrode surface results in electrode fouling and premature termination of the polymerization. Herein, we have thoroughly investigated electrochemically mediated atom transfer radical polymerization ( e ATRP) as a model platform to address the challenges arising from mass transfer limitations associated with electrochemical polymerizations by employing rapid alternating polarity (rAP). In detail, we propose a straightforward strategy for e ATRP employing readily available graphite electrodes within an undivided cell, and we implement a single constant alternating current on a millisecond time scale throughout the entire polymerization process. This method effectively prevents over-reduction of copper catalysts and electrode fouling, thereby facilitating the polymerizations of methyl acrylate with near-quantitative monomer conversions and exceptionally narrow dispersities ( Đ < 1.1). Polymerization kinetics can be further regulated by tuning the applied current ( I app ) and pulse duration. Most importantly, our approach allows e ATRP to be performed with significantly reduced copper catalyst loading (2.5 ppm), while maintaining excellent control over polymerization, resulting in an ultrahigh molecular weight PMA ( M n = 1,598,000, Đ = 1.26). The monomer scope is extended to include methyl methacrylate and styrene. The high “livingness” and chain-end fidelity, as confirmed by the mass spectrometric analysis, enable the one-pot synthesis of a block copolymer PMMA- b -PMA and star-shaped polymer 4- star -PMA. This work could underpin future research on rAP in various controlled electrochemical polymerizations.}, archive = {J_JACS}, author = {Jiajia Ping and Yunyan Qiu}, doi = {10.1021/jacs.5c12675}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35858--35870}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemically mediated atom transfer radical polymerization employing rapid alternating polarity}, volume = {147}, year = {2025}, }
• (2025). Controlled electron transfer: Implementing a reservoir-pump-integrated strategy to develop a type i photosensitizer for evoking long-term tumor immunological memory. JACS, 147(39), 35843--35857. (www)

  @article{ , abstract = {Type I photosensitizers (PSs), due to reduced dependence on O 2 , have outstanding prospects for cancer treatment. However, it is difficult to manipulate electron transfer of molecules during excited state transitions (T 1 –S 0 ), which makes it a challenging task to systematically create type I PSs, especially with a deficiency of an instructive molecular construction strategy. Herein, for the first time, we proposed the “electron reservoir-pump-integrated” molecular design strategy, that is, “electron reservoir” and “electron pump” were dexterously fused in one appropriate dye, which greatly facilitated the creation of type I PS molecules through the manipulation of spatial electron flow (verified by the density functional theory and spectral experiments). On this basis, we constructed a series of organic small-molecule type I PSs; especially, the prominent type I PS Cy5-NF could specifically produce a large amount of O 2 •– under 660 nm laser irradiation. Notably, without the sulfonic acid groups (electron reservoir) or the electron-withdrawing group (electron pump), both derivatives of Cy5-NF are unable to generate O 2 •– , which fully validated the above strategy. More encouragingly, Cy5-NF could effectively destroy cytomembranes under irradiation and further lead to pyroptosis of tumor cells, which not only ablated the primary/distant tumors but also halted tumor metastasis to the different organs via enhancing CD4 + and CD8 + T cell infiltration-mediated long-term immunological memory. Notably, the “electron reservoir-pump-integrated” strategy represents a kind of modular approach for constructing organic small-molecule type I PSs, potentially offering valuable guidance for future type I PS development.}, archive = {J_JACS}, author = {Li Xu and Haifeng Ge and Fang Zhu and Mingri Zhao and Hongwen Liu and Xiao-Bing Zhang and Zhe Li}, doi = {10.1021/jacs.5c12631}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35843--35857}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlled electron transfer: Implementing a reservoir-pump-integrated strategy to develop a type i photosensitizer for evoking long-term tumor immunological memory}, volume = {147}, year = {2025}, }
• (2025). Fused octapyrrolyl cyclooctatetraene with large NIR-II faraday rotation. JACS, 147(39), 35836--35842. (www)

  @article{ , abstract = {The increased mechanical flexibility, solution processability, ease of fabrication, and high Verdet constants have made organic Faraday rotators a promising alternative to conventional inorganic magneto-optical (MO) materials. Despite this, organic Faraday rotators have not been developed to address near-infrared (NIR) MO applications, limiting their device applications. Here, we describe a three-step synthesis and MO characterization of a fused octapyrrolyl cyclooctatetraene ( FOPCOT ) which exhibits a record high Verdet constant of a small molecule in the NIR-II region. Notably, the cyclooctatetraene core is constructed in a three-step one-pot reaction whereby a N , N ′-dipyrrolyl acetylene is generated and immediately reacted with Rosenthal’s complex to produce the corresponding zirconacycle intermediate in situ. The cascade is completed with a copper-mediated transmetalation that reductively eliminates to yield the octapyrrolyl cyclooctatetraene. This transformation offers a distinct alternative to conventional methods for pyrrole incorporation into polycyclic aromatic hydrocarbons. Stoichiometric oxidation with AgPF 6 affords the oxidized analogues FOPCOT • + and FOPCOT 2+ , which display strong optical absorptions at 1743 and 1198 nm, respectively. Magnetic circular dichroism study on spin-coated thin films of FOPCOT 2+ yielded a maximum Verdet constant of −2.5 × 10 5 deg T –1 m –1 at 1224 nm.}, archive = {J_JACS}, author = {Daniel J. Martinez and Molly C. Warndorf and Avisek Dutta and Harrison M. Bergman and Jojo P. Joseph and Peter Müller and Paras N. Prasad and Timothy M. Swager}, doi = {10.1021/jacs.5c12451}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35836--35842}, shortjournal = {J. Am. Chem. Soc.}, title = {Fused octapyrrolyl cyclooctatetraene with large NIR-II faraday rotation}, volume = {147}, year = {2025}, }
• (2025). Air- and water-stable sulfide radical cations supported by cyclic (Alkyl)(amino)carbenes. JACS, 147(39), 35829--35835. (www)

  @article{ , abstract = {Stable organic radicals have attracted significant attention owing to their key role in understanding reactive intermediates and their diverse applications as functional materials. Sulfide radical cations, in particular, serve as crucial intermediates in various fields such as organic chemistry, biochemistry, and polymer/materials science. However, the development of air- and water-stable sulfide radical cations has remained a significant challenge. In this study, highly stable sulfide radical cations supported by two cyclic (alkyl)(amino)carbene (CAAC) moieties have been synthesized. In addition to demonstrating high air- and water stability, these radical cations can withstand harsh conditions, including exposure to reactive chemicals such as sulfuric acid and hydrogen peroxide, as well as elevated temperatures. Combined experimental and computational studies reveal that the sulfur-centered unpaired electron is stabilized through electronic delocalization and steric protection provided by the CAAC substituents. These findings establish a new class of exceptionally stable sulfur-based radicals and pave the way for their potential applications as functional materials.}, archive = {J_JACS}, author = {Dongmin Kang and Minseok Kim and Heenang Choi and Jeong-Yoon Hwang and Gayeong Lim and Jaelim Kim and Youngsuk Kim}, doi = {10.1021/jacs.5c12377}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35829--35835}, shortjournal = {J. Am. Chem. Soc.}, title = {Air- and water-stable sulfide radical cations supported by cyclic (Alkyl)(amino)carbenes}, volume = {147}, year = {2025}, }
• (2025). The 2,240-atom unit cell of PrMg1.6Zn5.4: An intergrowth of the laves and heusler structures illustrating a mechanism for the stabilization of complex intermetallics. JACS, 147(39), 35818--35828. (www)

  @article{ , abstract = {The crystal structures of intermetallic phases encompass a fundamental mystery about the chemistry of metals: what drives atoms that prefer simple sphere packings as pure elements to adopt complex structures, sometimes with unit cells containing thousands of atoms? We recently developed the interface nucleus concept to interpret their most complicated arrangements in terms of chemical pressure (CP)-driven assemblies of modules of simple parent structures. The predictions of this approach earlier led us to the Pr–Mg–Zn system and the discovery of the modular structure of PrMg 4 Zn 10 built from MgZn 2 - and EuMg 5 -type units. Herein, we present the structure of a second intergrowth compound in this system that exhibits far greater complexity: PrMg 1.6 Zn 5.4 , whose 34.50 Å cubic unit cell contains 2,240 atoms. Its structure can be simply decoded in terms of a 5 × 5 × 5 supercell of the Heusler structure (or alternatively a 10 × 10 × 10 supercell of the body-centered cubic (BCC), structure) embedded with Laves phase fragments. The nearly seamless transition between the Heusler and Laves domains observed here reflects a simple relationship between these structures, in which they can be interconverted by the exchange of a tetrahedron of atoms for a single larger atom (MgCu 2 type to BCC), or vice versa (BCC to MgCu 2 type). Driving forces underlying PrMg 1.6 Zn 5.4 ’s structure are inferred from the CP analysis of the parent structures, which highlight the overcompression of the Pr atoms in a model Heusler phase and the opportunities for relief by expanded environments available at the boundaries between the Laves and Heusler domains in PrMg 1.6 Zn 5.4 .}, archive = {J_JACS}, author = {Danica G. Gressel and Leah C. Garman and Daniel C. Fredrickson}, doi = {10.1021/jacs.5c12386}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35818--35828}, shortjournal = {J. Am. Chem. Soc.}, title = {The 2,240-atom unit cell of PrMg1.6Zn5.4: An intergrowth of the laves and heusler structures illustrating a mechanism for the stabilization of complex intermetallics}, volume = {147}, year = {2025}, }
• (2025). Chemical facets of superconductivity in UTe2. JACS, 147(39), 35809--35817. (www)

  @article{ , abstract = {Understanding superconductivity requires a deep comprehension of the chemical structure. The discovery of a new unconventional superconductor UTe 2 a few years ago prompted many detailed investigations of its physical properties. Despite its unconventional ground state being rather well-studied, a strong sample-to-sample variation of superconducting behavior as a result of different preparation conditions has remained largely unexplained until now. In this work, an in-depth analysis of the UTe 2 crystal structure and resultant physical properties by implementing several types of synthetic routes was carried out. The difference between superconducting and non-superconducting UTe 2 lies in the presence of uranium vacancies, on the order of 4%. As a result, the b and c lattice parameters vary, yielding a volume difference of about 0.51%. A subtler difference between samples exhibiting one and two superconducting transitions is driven by local deviations from the translational symmetry in the main atomic arrangement. Several well-pronounced maxima have been observed in the difference density map, predominantly located in the bc plane due to a local appearance of the similar atomic arrangements in different orientations. The extreme sensitivity of UTe 2 to such a small number of defects re-emphasizes the unconventional nature of superconductivity in this compound. Furthermore, this work underscores the importance of a thorough, combined chemical and physical analysis of intriguing strongly correlated materials─in particular for compounds that are known to exhibit nontrivial ground states and exotic accompanying phenomena.}, archive = {J_JACS}, author = {Eteri Svanidze and Andreas Leithe-Jasper and Marcus Schmidt and Nazar Zaremba and Mitja Krnel and Yurii Prots and Ulrich Burkhardt and Markus König and Reiner Ramlau and Berit H. Goodge and Yuri Grin}, doi = {10.1021/jacs.5c12203}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35809--35817}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemical facets of superconductivity in UTe2}, volume = {147}, year = {2025}, }
• (2025). Chemical control of symmetry and bandgap in tungsten oxyhalide van der waals semiconductors. JACS, 147(39), 35801--35808. (www)

  @article{ , abstract = {Tunability in solid-state materials is essential for testing theory, discovering quantum phases, and enabling functionality. Layered van der Waals (vdW) semiconductors offer a unique platform, providing new degrees of freedom at the two-dimensional (2D) limit through exfoliation and external controls. Here, we demonstrate tunability of symmetry and electronic structure via halogen substitution in a family of layered vdW tungsten oxyhalides. Substituting the halogens in WO 2 X 2 (X = I, Br, Cl) tunes the bandgap across a broad energy range and modifies the structural symmetry from centrosymmetric to noncentrosymmetric. By alloying WO 2 I 2– y Br y , we continuously tune the polar distortion and optical gap across the visible range. These insights into halogen substitution effects on symmetry and electronic structure lay the foundation for new tunable vdW semiconductors for optoelectronics and nonlinear optics.}, archive = {J_JACS}, author = {Jordan Cox and Willa Mihalyi-Koch and Sophie Beck and Eric Seewald and Asish K. Kundu and Zhi-Hao Cui and Till Schertenleib and Chun-Ying Huang and Yinming Shao and Siyuan Qiu and Chiara Trovatello and Daniel G. Chica and Xiong Huang and Xiaoyu Song and André Koch Liston and Michael E. Ziebel and Elio Vescovo and Milan Delor and P. James Schuck and David R. Reichman and Xiaoyang Zhu and S. J. L. Billinge and Dmitri N. Basov and Abhay N. Pasupathy and Xavier Roy}, doi = {10.1021/jacs.5c12238}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35801--35808}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemical control of symmetry and bandgap in tungsten oxyhalide van der waals semiconductors}, volume = {147}, year = {2025}, }
• (2025). Unimolecular and bimolecular pathways in bidirectional redox molecular catalysis. JACS, 147(39), 35788--35800. (www)

  @article{ , abstract = {The expression “catalytic reversibility” describes the situation where a bidirectional molecular redox catalyst can function in either direction of the reaction under near equilibrium conditions, as observed with various redox enzymes and with an increasing number of synthetic inorganic complexes. Understanding how this property emerges is crucial to the design of efficient catalysts. Here, for a two-electron reaction, we compare the voltammetric responses of the catalysts for two distinct general mechanisms: the unimolecular pathway includes two successive electron transfers with the electrode and pseudo-first-order chemical steps and was described before (Fourmond et al., J. Am. Chem. Soc. 141, 11269 (2019)); the bimolecular mechanism includes a single interfacial electron transfer and one intermolecular electron transfer in solution. The general theory of the latter is derived here. The predictions of the kinetic models are compared to data available in the literature, and diagnosis criteria are discussed with emphasis on the shapes of the sigmoidal steady-state catalytic voltammograms. We describe the kinetic and thermodynamic requirements for redox molecular catalysts to work reversibly.}, archive = {J_JACS}, author = {Vincent Fourmond and Antoine Jacob-Villedieu and A. Jalila Simaan and Bruno Faure and Christophe Léger}, doi = {10.1021/jacs.5c12075}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35788--35800}, shortjournal = {J. Am. Chem. Soc.}, title = {Unimolecular and bimolecular pathways in bidirectional redox molecular catalysis}, volume = {147}, year = {2025}, }
• (2025). Structure over states: Planarity, not energy, dictates photoactivation in Ru(II) PACT agents. JACS, 147(39), 35767--35787. (www)

  @article{ , abstract = {Photoactivated chemotherapy (PACT) employs light to precisely control the activity of prodrugs, enabling spatial and temporal regulation of therapeutic effects while minimizing systemic toxicity. Transition-metal complexes, particularly Ru(II) polypyridyl compounds, have emerged as promising PACT agents due to their ability to undergo photodissociation via triplet excited states. However, rationalizing and predicting photosubstitution quantum yields remain challenging due to complex excited-state dynamics, solvent effects, and limitations of traditional modeling approaches. In this study, we synthesized nine Ru(II) complexes incorporating a monodentate thioether ligand, a terpyridine ligand, and various bidentate polypyridyl ligands. Upon red-light irradiation in aqueous solution, these complexes showed selective photosubstitution of the thioether by an aqua ligand. Despite similar absorption properties, these compounds exhibited markedly different photosubstitution quantum yields that static DFT calculations failed to explain. These modeling difficulties prompted us to develop a novel triplet-state molecular dynamics protocol using the GFN-xTB method, explicit solvation, and enhanced sampling techniques. Our approach enabled full simulations of the ligand exchange process on the triplet hypersurface and comparison to experimental data. It revealed that both cis and trans substitution of the thioether by a water molecule is possible; it was also able to distinguish between photoactive and photoinactive compounds. Unexpectedly, we found that the deviation from planarity of the bidentate ligand, rather than the energy levels of the different triplet excited states ( 3 MLCT, 3 MC) involved in the photosubstitution reaction, was the primary determinant of photosubstitution efficiency, as it promoted access to the trans photosubstitution pathway. Furthermore, our simulations uniquely identified whether dissociative, interchange, or associative mechanisms governed the reactivity of each complex. These results provide for the first time mechanistic insights into Ru(II)-based photosubstitution reactions in a solvent and offer a practical, scalable computational tool for designing next-generation PACT agents with optimized light-responsive properties.}, archive = {J_JACS}, author = {Matthijs L. A. Hakkennes and Irene Regeni and Yurii Husiev and Valeriia D. Andreeva and Maxime A. Siegler and Francesco Buda and Sylvestre Bonnet}, doi = {10.1021/jacs.5c12226}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35767--35787}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure over states: Planarity, not energy, dictates photoactivation in Ru(II) PACT agents}, volume = {147}, year = {2025}, }
• (2025). Asymmetric dearomative [2 + 2] photocycloaddition of quinoline and indole derivatives with bicyclo[1.1.0]butanes. JACS, 147(39), 35755--35766. (www)

  @article{ , abstract = {The dearomative photocycloaddition reactions of (hetero)arene feedstocks have emerged as an efficient platform for the construction of three-dimensional complexity, which is of increasing interest in medicinal chemistry. Nevertheless, the catalytic asymmetric version of such transformations with quinolines remains a challenging task because of regio-, diastereo-, and enantioselective control. Especially the presence of substituents with divergent electronic effects on the aromatic ring presents a regioselectivity control dilemma. Herein, we report highly regio-, diastereo-, and enantioselective dearomative [2 + 2] photocycloadditions of quinolines with bicyclo[1.1.0]butanes (BCBs) by utilizing a chiral Lewis acid-mediated strain-release approach. The regioselectivity and stereocontrol challenges were addressed by strategically designing catalysts with tailored steric bulk that modulated the chiral pocket in response to the electronic and steric characteristics of diverse substrate substituents. This strategy was compatible with isoquinoline, indole derivatives, naphthalene, and benzo[ b ]thiophene, providing highly decorated chiral heterocycle-fused bicyclo[2.1.1]hexanes (BCHs) in moderate to good yields with high regio-, diastereo-, and enantioselectivities (52 examples, up to 99% yield, >19:1 rr, >19:1 dr, 99% ee). Based on experimental studies and theoretical calculations, a catalytic cycle along with possible transition states was provided to understand the reaction mechanism.}, archive = {J_JACS}, author = {Jia Yang and Longqing Yang and Yuexing Zhao and Liuzhen Hou and Yong Qiu and Guihua Pan and Xiaohua Liu and Xiaoming Feng and Shunxi Dong}, doi = {10.1021/jacs.5c12057}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35755--35766}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric dearomative [2 + 2] photocycloaddition of quinoline and indole derivatives with bicyclo[1.1.0]butanes}, volume = {147}, year = {2025}, }
• (2025). Cooperative magnetic phase evolution via oxygen spin coupling in a layered Metal–Organic framework. JACS, 147(39), 35742--35754. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) constructed from appropriate building units can exhibit both porosity and long-range magnetic order, enabling the modulation of magnetic states via mass transport. In most guest-responsive MOF magnets, the guest inclusions perturb the framework electronically or structurally and trigger abrupt phase transitions. In contrast, spin-active guests can directly mediate exchange pathways, enabling the continuous and controllable evolution of the magnetic order; however, the kinetic pathways of guest adsorption and spin mediation remain poorly understood. In this study, we demonstrated that the entrapment of O 2 dimers in bottlenecked isolated pores between ferrimagnetic layers triggered a gradual evolution from ferromagnetism to antiferromagnetism in an isostructurally layered MOF. Systematic O 2 sorption studies revealed a time-resolved shift in the Néel temperature ( T N ) from 17 to 28 K, correlating with the extent of O 2 loading and indicating a cooperative growth of antiferromagnetic (AFM) domains. In contrast, the insertion of diamagnetic CO 2 dimers preserved the original ferromagnetic (FM) ground state. Density functional theory calculations showed that the antiferromagnetically coupled O 2 dimer acted as an efficient superexchange bridge between adjacent ferrimagnetic layers, stabilizing the AFM ground state. These findings provide direct evidence of the guest-induced, spin-mediated evolution of the magnetic phase in porous magnets and establish the entrapment of molecular oxygen as a versatile strategy for finely tuning the magnetic order in MOF magnets.}, archive = {J_JACS}, author = {Jun Zhang and Yang Cao and Wataru Kosaka and Masaki Mimura and Yasutaka Kitagawa and Hitoshi Miyasaka}, doi = {10.1021/jacs.5c12038}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35742--35754}, shortjournal = {J. Am. Chem. Soc.}, title = {Cooperative magnetic phase evolution via oxygen spin coupling in a layered Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Degradation of FeNC electrocatalysts for acidic and alkaline oxygen reduction. JACS, 147(39), 35730--35741. (www)

  @article{ , abstract = {Iron–nitrogen-carbon (FeNC) catalysts represent promising alternatives to platinum-group metals for the oxygen reduction reaction (ORR) in energy conversion technologies. However, their operational stability remains a critical challenge. In this study, we unravel the distinct degradation mechanisms and active-site behaviors of FeNC catalysts under acidic and alkaline ORR conditions. Intriguingly, catalysts subjected to electrochemical cycling in acidic media but tested in alkaline conditions exhibit nearly preserved ORR activity, revealing that degradation pathways differ fundamentally between the two environments. With the help of density functional theory calculations, we identify Fe-centered sites as the primary active centers in acidic media, whereas under alkaline conditions─where hydroxyl adsorption passivates Fe sites─neighboring carbon atoms adjacent to nitrogen become the dominant active sites. The Mössbauer spectroscopy results show that under acidic cycling, pyrrolic nitrogen-coordinated Fe (S1) sites suffer a significant loss while the pyridinic nitrogen-coordinated Fe (S2) sites retain high stability. In contrast, during alkaline cycling, Fe site losses are minimal, while the carbon support undergoes more severe corrosion. By selectively engineering the Fe sites and carbon support, we experimentally validated the conclusions on the active sites. This work provides critical insights into the site-dependent durability of FeNC catalysts and underscores the necessity of tailored catalyst design for stable and efficient ORR across diverse operating conditions.}, archive = {J_JACS}, author = {Weiwei Chen and Yanyang Qin and Changqi Heng and Shifu Wang and Mengshu Ge and Yangfan Li and Xin Wan and Xuning Li and Jianglan Shui and Yaqiong Su and Dong Su}, doi = {10.1021/jacs.5c11985}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35730--35741}, shortjournal = {J. Am. Chem. Soc.}, title = {Degradation of FeNC electrocatalysts for acidic and alkaline oxygen reduction}, volume = {147}, year = {2025}, }
• (2025). Conformational plasticity of LptC regulates lipopolysaccharide transport by the LptB2FGC complex. JACS, 147(39), 35718--35729. (www)

  @article{ , abstract = {The outer membrane of Gram-negative bacteria is coated with lipopolysaccharide (LPS). The Lpt system generates membrane asymmetry by transporting LPS from the inner to the outer membrane. Transport begins with the LptB 2 FGC complex, where the ABC transporter LptB 2 FG associates with LptC to extract LPS. LPS is then passed via LptA to the LptDE translocon. While LptB 2 FGC structures suggest an extrusion mechanism, the role of LptC remains unclear. Here, we reconstituted the complex in vitro from purified LptB 2 FG and LptC, and demonstrate that LptC stabilizes the complex and modulates ATPase activity. Using differential isotope labeling and solid-state NMR including dynamic nuclear polarization, we observed that the LptC transmembrane helix LptC TMH is tightly associated with the transporter in the apo state. Upon LPS or ATP binding, LptC TMH becomes more flexible and samples a distinct conformational space which favors cavity collapse and substrate-coupled ATPase activity. Our data support a model in which LptC acts as a mechanical transducer linking transport and energy consumption.}, archive = {J_JACS}, author = {Aaron Klausnitzer and Jagdeep Kaur and Tobias Rath and Samuel Seidl and Johanna Becker-Baldus and Nina Morgner and Clemens Glaubitz}, doi = {10.1021/jacs.5c11923}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35718--35729}, shortjournal = {J. Am. Chem. Soc.}, title = {Conformational plasticity of LptC regulates lipopolysaccharide transport by the LptB2FGC complex}, volume = {147}, year = {2025}, }
• (2025). Development of a heteroleptic palladium catalyst for the fluorination of arylboronic acids using data science tools. JACS, 147(39), 35705--35717. (www)

  @article{ , abstract = {We report the development of a rare example of metal-catalyzed arylboronic acid fluorination that utilizes heteroleptic palladium complexes─catalysts that utilize two distinct ligands to achieve effective catalysis. Reaction optimization was achieved using high-throughput experimentation (HTE) for data collection, accelerated using multiobjective Bayesian optimization (EDBO+) for selection of experiments. Substrate scope was selected employing data science tools, and evaluation of these substrates revealed excellent functional group tolerance. Extensive mechanistic studies suggest that the two ligand types play unique roles in promoting the reaction wherein the Pd-terpyridine complex promotes facile transmetalation with the aryl boronic acid, while the addition of a second bidentate ligand is required for effective oxidation of this intermediate to form a high-valent Pd–F species that undergoes reductive elimination. This data science-driven workflow presents an illustrative example of exploiting heteroleptic catalysts to advance new fluorination reactions.}, archive = {J_JACS}, author = {Shubham Deolka and David Dalmau and Aleria Garcia Roca and Serhii Vasylevskyi and Mohammad H. Samha and Matthew S. Sigman}, doi = {10.1021/jacs.5c11929}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35705--35717}, shortjournal = {J. Am. Chem. Soc.}, title = {Development of a heteroleptic palladium catalyst for the fluorination of arylboronic acids using data science tools}, volume = {147}, year = {2025}, }
• (2025). Immobilized azole layer tunes interfacial hydrogen source for CO2 electroreduction in strong acid. JACS, 147(39), 35698--35704. (www)

  @article{ , abstract = {Achieving selective electrochemical CO 2 reduction reaction (CO 2 RR) in strong acid holds potential to resolve the “carbonate formation” problem yet is hindered by the competing hydrogen evolution reaction (HER). The interplay between different hydrogen sources (i.e., H + vs H 2 O) and its impact on CO 2 RR selectivity in acidic electrolytes remains poorly understood. Herein, we introduce an immobilized N-containing azole layer (phTA) onto Bi catalysts to dynamically regulate the interfacial hydrogen source in strong acid (pH 0.4). Combining experimental and modeling approaches, we reveal a dual mechanism dependent on local interfacial conditions. At lower potentials with high local [H + ], the protonated phTA layer (NH + sites) serves as a proton relay while electrostatically shielding bulk H + diffusion. Conversely, at higher potentials with low local [H + ], less protonated phTA disrupts the interfacial hydrogen-bond network, impeding Grotthuss-type proton transport, thus suppressing HER through hydrogen source shifts toward H 2 O. As a result, the faradaic efficiency for formic acid (FE HCOOH ) on Bi-phTA significantly increases to 36% at −300 mA cm –2 (pH 0.4) compared to <10% for bare Bi. This work demonstrates the controlled manipulation of the hydrogen source via a dynamically responsive organic layer, highlighting the importance of managing interfacial hydrogen species for enhancing the CO 2 RR in acid.}, archive = {J_JACS}, author = {Yaohui Shi and Yu Yang and Aoni Xu and Kwun Nam Hui and Fengwang Li and Jie Zeng}, doi = {10.1021/jacs.5c11829}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35698--35704}, shortjournal = {J. Am. Chem. Soc.}, title = {Immobilized azole layer tunes interfacial hydrogen source for CO2 electroreduction in strong acid}, volume = {147}, year = {2025}, }
• (2025). Ligand desorption and surface oxidation drive nanoparticle coalescence in diffusion-limited aggregation. JACS, 147(39), 35684--35697. (www)

  @article{ , abstract = {We previously reported that peptides can drive diffusion-limited aggregation (DLA) of silver nanoparticles (AgNPs) into complex, fractal assemblies, but the mechanism behind this behavior remained unclear. In this study, we dissect how surface ligand chemistry governs this process: not merely by mediating interparticle interactions but by enabling structural transformation of the nanoparticle cores themselves. Using a panel of nine ligands spanning phosphine, thiolate, and polyphenol classes, we systematically examine how ligand identity dictates aggregation dynamics, redox behavior, and structural outcomes. Our findings reveal that aromatic phosphine ligands, especially bis( p -sulfonatophenyl)phenylphosphine (BSPP), uniquely promote DLA by facilitating partial ligand desorption and silver surface oxidation, which together enable nanoparticle coalescence and recrystallization into micron-scale fractal architectures. In contrast, thiol- and polyphenol-based ligands either bind too strongly to permit coalescence or lack the electronic features necessary to support oxidation-driven restructuring. We support this mechanism with multiple lines of evidence: zeta potential data demonstrate charge neutralization, X-ray photoelectron spectroscopy confirms the presence of oxidized silver species in BSPP-AgNP fractals, and enhanced light scattering suggests increased surface heterogeneity. Electron microscopy and elemental analyses validate the resulting architecture and ligand distribution. These findings establish a mechanistic framework for chemically directed DLA and introduce a tunable strategy for building structurally fused, hierarchical nanomaterials for biosensing, catalysis, and soft matter engineering.}, archive = {J_JACS}, author = {Lubna Amer and Maurice Retout and Mengchen Liu and Rand Kingsford and Zhicheng Jin and Sumathi Kakanar and Moumita Halder and Ping Liu and Jesse V. Jokerst}, doi = {10.1021/jacs.5c11783}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35684--35697}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand desorption and surface oxidation drive nanoparticle coalescence in diffusion-limited aggregation}, volume = {147}, year = {2025}, }
• (2025). Nickel-catalyzed enantioselective direct addition of styrenes to imines enabled by chiral spiro phosphine ligands. JACS, 147(39), 35675--35683. (www)

  @article{ , abstract = {Enantioenriched allylic amines are key structural motifs found in a wide array of bioactive molecules and serve as versatile intermediates in organic synthesis. Despite significant advances in their preparation, the enantioselective direct addition of simple alkenes to imines has remained a formidable challenge. Herein, we report a nickel(0)-catalyzed enantioselective direct addition of styrenes and their derivatives to aldimines, enabled by a newly developed family of electron-rich, C 2 -symmetric chiral spiro monophosphine ligands based on the tetramethyl-1,1′-spirobiindane scaffold. This method features highly efficient, atom-economical construction of chiral allylic amines with excellent regio- and enantioselectivities under mild conditions, and exhibits broad functional group tolerance.}, archive = {J_JACS}, author = {Ye-Wei Huang and Tianze Zhang and Shi-Hui Cheng and Qi-Lin Zhou and Li-Jun Xiao}, doi = {10.1021/jacs.5c11639}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35675--35683}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-catalyzed enantioselective direct addition of styrenes to imines enabled by chiral spiro phosphine ligands}, volume = {147}, year = {2025}, }
• (2025). Cyclic BODIPY arrays: A class of macrocycle-based molecular solids for hydrogen isotope separation and iodine capture. JACS, 147(39), 35664--35674. (www)

  @article{ , abstract = {Macrocyclic hosts are pivotal in supramolecular chemistry, yet the discovery of synthetically scalable platforms that combine rich host–guest behavior, facile crystallizability, and solid-state functionality remains a challenge. Here, we present the synthesis of a new cyclic BODIPY array, trimer 1 , composed of three BODIPY units linked by m -phenylene spacers. Two dynamic conformers of 1 , namely, cone-shaped c - 1 and partial-cone-shaped pc - 1 , exist in solution and have been characterized by their X-ray crystal structures. These two conformers undergo interconversion in response to changes in external environments, including solvents and guests. Conformer c - 1 is capable of hosting neutral guests bearing electron-deficient methyl groups in solution, driven by collective C–H···F interactions, while cationic guests with ammonium groups are preferentially hosted by conformer pc - 1 . Crystallization conditions were optimized, enabling the preparation of gram-scale crystals of c - 1 with different packing arrangements, designated as c - 1a and c - 1b . Activation of these two samples led to transformations from single-crystal to single-crystal or to amorphous, yielding crystalline c - 1a′ and amorphous c - 1b′ , respectively. Importantly, crystalline c - 1a′ exhibits excellent adsorption capacity and separation selectivity for hydrogen isotopes, benefiting from its permanent ultramicroporosity. In contrast, amorphous c - 1b′ is an effective adsorbent for molecular iodine, with binding interactions fully elucidated through X-ray crystallographic analysis. This work establishes cyclic BODIPY arrays as a highly tunable platform for creating adaptive molecular solids with applications in separation science, moving beyond their inherent optical properties.}, archive = {J_JACS}, author = {Weinan Zhou and Yang Li and Lin Xiong and Wenjing Wang and Ruiyu Guan and Zhonghang Chen and Daqiang Yuan and En-Qing Gao and Dawei Zhang}, doi = {10.1021/jacs.5c11567}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35664--35674}, shortjournal = {J. Am. Chem. Soc.}, title = {Cyclic BODIPY arrays: A class of macrocycle-based molecular solids for hydrogen isotope separation and iodine capture}, volume = {147}, year = {2025}, }
• (2025). Reprocessing thermoset polyurethane foams using their residual polymerization catalysts. JACS, 147(39), 35655--35663. (www)

  @article{ , abstract = {Reprocessing thermoset polyurethane (PU) using carbamate exchange reactions is a novel approach to recycling PU foam waste. Previous works on PU reprocessing have required carbamate exchange catalysts to be added during the recycling process. However, adding new exchange catalysts increases processing costs, raises concerns about health or environmental damage from catalyst leaching, and would require the reformulation of established commercial products. However, PU foams contain residual synthesis catalysts that might also catalyze carbamate exchange such that existing commercial products might be reprocessable without further modification. We selected 1,4-diazabicyclo[2.2.2]octane (DABCO), the most widely used PU gelling catalyst, as a representative tertiary amine catalyst and evaluated its catalytic activity using model compound studies. Crossover experiments showed that the dominant mechanism of carbamate exchange varies, depending on the concentration of the free alcohols in the system: DABCO catalyzes both dissociative and associative carbamate exchange, but excess alcohol groups inhibit catalysis of DABCO. The catalytic activity of DABCO in the reprocessing environment was examined through crossover between linear polymers in a twin-screw extruder. Microcompounding accelerated bond exchange compared to the small molecule study due to the high shear force. Model thermoset PU films synthesized with DABCO displayed faster stress relaxation compared to a catalyst-free film. Three commercial thermosetting PU foams were successfully reprocessed into PU films at elevated temperatures using the remaining DABCO or other tertiary amine catalysts incorporated in the PU foams during synthesis. The resulting films maintained the glass transition temperature of the original foam, and the tensile properties of PU films resemble those of the feedstock PU foams (rigid or soft). Appliance PU foams were reprocessed while adding glass fibers to produce composites with a tunable elastic modulus. This study shows the promise of recycling thermosetting PU waste using residual catalysts in PU products without altering their commercial formulations.}, archive = {J_JACS}, author = {Subeen Kim and Lillian M. Felsenthal and Oliver Sala and Oliver Welz and Maike Bergeler and Alaaeddin Alsbaiee and William R. Dichtel}, doi = {10.1021/jacs.5c11319}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35655--35663}, shortjournal = {J. Am. Chem. Soc.}, title = {Reprocessing thermoset polyurethane foams using their residual polymerization catalysts}, volume = {147}, year = {2025}, }
• (2025). Multicyclic peptides targeting PD-l1 for radiotheranostics: From discovery to clinical proof-of-concept. JACS, 147(39), 35638--35654. (www)

  @article{ , abstract = {Radiotheranostics holds transformative potential for precision oncology by integrating diagnostic imaging with targeted radionuclide therapy. However, advancements in this field are significantly hindered by the limited availability of high-affinity ligands that are capable of engaging challenging cell-surface antigens, particularly flat, low-druggability targets such as programmed death-ligand 1 (PD-L1). Here, we overcome this barrier through de novo discovery and rational engineering of a disulfide-directed multicyclic peptide (DDMP), dmp10, which achieves a picomolar affinity for PD-L1 by leveraging conformationally constrained structural scaffolds. By combining disulfide-directed library design with iterative directed evolution, we successfully generated dmp10, a ∼3 kDa multicyclic peptide that establishes unprecedented shape complementarity to the expansive binding interface of PD-L1. Preclinical evaluations demonstrated that 68 Ga-labeled dmp10 enables high-contrast PET imaging of PD-L1 + tumors in murine models, achieving a tumor uptake of 13.27 %ID/g at 4 h post-injection. The therapeutic counterpart, 177 Lu-labeled dmp10, effectively eradicated 92.47% of established tumors in tumor models while sparing healthy tissues, thereby validating its dual radiotheranostic utility. The translational relevance of our findings was further confirmed in a first-in-human pilot study, where 68 Ga-labeled dmp10 was well tolerated and allowed visualization of PD-L1 + lesions in patients with solid tumors. This work not only establishes DDMPs as a versatile platform for targeting geometrically complex antigens but also delivers a promising radiotheranostic agent that bridges molecular imaging and precision radionuclide therapy for PD-L1-driven malignancies. Our findings advance current strategies for designing ultrahigh-affinity peptide binders and underscore the untapped potential of multicyclic architectures in overcoming longstanding challenges in cancer theranostics.}, archive = {J_JACS}, author = {Xueting Cheng and Shuo Jiang and Xingtong Peng and Pan Yang and Siqi Zhang and Chaoying Xu and Xin Gao and Shihui Fan and Hongtan Liu and Jie Zhuang and Xueyao Chen and Naixin Liang and Bingni Lin and Qingshuang Lu and Meirong Chen and Yibei Xiao and Zhaohui Zhu and Rui Wang and Kuan Hu and Chuanliu Wu}, doi = {10.1021/jacs.5c11292}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35638--35654}, shortjournal = {J. Am. Chem. Soc.}, title = {Multicyclic peptides targeting PD-l1 for radiotheranostics: From discovery to clinical proof-of-concept}, volume = {147}, year = {2025}, }
• (2025). One-dimensional hybrid metal halide with polymer-like flexible inorganic chains and glass-forming ability. JACS, 147(39), 35627--35637. (www)

  @article{ , abstract = {Hybrid glasses made from hybrid metal halides (HMHs) have shown intriguing properties such as environmental durability, optical transparency, and excellent processability, which have fueled an ever-expanding set of applications. However, due to the melt instability, HMH glasses, particularly with one-dimensional or two-dimensional structures, are still rare. Herein, we report the uncommon one-dimensional chain structure comprising corner-sharing lead-bromide trimers in (4-EAMP) 2 Pb 3 Br 10 (4-EAMP = 4-(ethylaminomethyl)pyridine), whose polymer-like flexible chains enable soft, elastic, and meltable characteristics. By systematically scrutinizing HMHs constructed from face-, edge-, and corner-sharing chains, we find that the chain configurations substantially define the mechanical and thermal properties when organic ligands possess relatively analogous structures. The corner-sharing structure of (4-EAMP) 2 Pb 3 Br 10 crystals offers conformational freedom for melting, which allows stable melt over a wide temperature range of 70 K. The amorphization of (4-EAMP) 2 Pb 3 Br 10 does not significantly reduce the coordination degree of the inorganic framework and has realized high-performance X-ray detection and imaging functions with an elevated sensitivity of 8581.7 μC Gy air –1 cm –2 . Our results present a material platform toward understanding the origin and structural manifestation of melting and vitrification in hybrid organic–inorganic solids.}, archive = {J_JACS}, author = {Yuchen Zhu and Da Liu and Xinyuan Sui and Qing Li and Mengyao Song and Yan Zhu and Dongdong Li and Kuan Xue and Yu Peng and Haiyang Yuan and Shuang Yang and Hua Gui Yang and Yu Hou}, doi = {10.1021/jacs.5c11135}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35627--35637}, shortjournal = {J. Am. Chem. Soc.}, title = {One-dimensional hybrid metal halide with polymer-like flexible inorganic chains and glass-forming ability}, volume = {147}, year = {2025}, }
• (2025). Hydration (H2O and D2O) dictates the stabilities and conformational entropy of transthyretin tetramers. JACS, 147(39), 35616--35626. (www)

  @article{ , abstract = {Transthyretin (TTR) is a 56 kDa tetrameric protein complex that plays a key role in transporting thyroxine and retinol. Despite its important biological role, TTR exhibits adverse effects, including disassembly into monomers, dimers, and trimers that then aggregate into disease-causing oligomers and fibrils. Hydration (referring to H 2 O or D 2 O) has been shown to have strong effects on TTR tetramer stabilities; however, probing how perturbation of hydration alters tetramer dynamics and stabilities is challenging. Here, we use variable-temperature (5–50 °C) electrospray ionization and ion mobility-mass spectrometry to better understand the influence of D 2 O and H 2 O hydration on the structures, stabilities, and dynamics of both wild-type TTR and several mutants (TTR L55P , TTR V30M , TTR T119M , and TTR V122I ). Our findings include the following: (i) TTR tetramers in D 2 O have lower average charge states compared to those in H 2 O at temperatures between 5 and 50 °C; (ii) there are fewer disassembly products (monomers and dimers) in D 2 O compared to H 2 O at different temperatures; and (iii) the relative abundances of compact versus extended tetrameric forms are shifted in D 2 O compared to H 2 O. Results from hydrogen–deuterium exchange (HDX) combined with bottom-up proteomics of different TTR mutants are consistent with hydration in β-sheet and interface-forming regions providing tetramer stability. Additionally, HDX combined with bottom-up proteomics indicates that shifts in hydration at the interface are responsible for the observed differences between mutants. Overall, our results show that D 2 O significantly alters the TTR stabilities and conformational entropy, highlighting the important role that hydration plays in protein dynamics.}, archive = {J_JACS}, author = {Carter Lantz and Robert L. Rider and Syuan-Ting Kuo and Zhenyu Xi and Emily Burningham and Sangho D. Yun and Arthur Laganowsky and David H. Russell}, doi = {10.1021/jacs.5c11055}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35616--35626}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydration (H2O and D2O) dictates the stabilities and conformational entropy of transthyretin tetramers}, volume = {147}, year = {2025}, }
• (2025). Bio-photo dual action of intracellular radical polymerization. JACS, 147(39), 35604--35615. (www)

  @article{ , abstract = {Achieving spatiotemporal control over intracellular polymerization presents a fundamental challenge in merging synthetic chemistry with living systems. Here, we introduce a stimuli-responsive photocatalyst strategy that enables biomarker- and light-gated radical polymerization within cells. Engineered 3,4,5,6-tetrabromofluorescein (TBF) photocatalysts incorporate protecting groups─responsive to endogenous reactive oxygen/sulfur species (ROS/RSS) or enzymes─that suppress photoinduced electron/energy transfer-reversible addition–fragmentation chain transfer (PET-RAFT) activity until simultaneous biomarker activation and irradiation occur. This AND-gated mechanism confines polymerization exclusively to target cells. Leveraging monomer design and this dual-control paradigm, in situ polymer growth selectively disrupts endoplasmic reticulum (ER) integrity, triggering ER stress, calcium release, and paraptosis─a caspase-independent cell death pathway characterized by cytoplasmic vacuolization and ER dilation. This platform establishes a versatile chemical approach for precision organelle intervention, advancing therapeutic discovery and synthetic biology applications.}, archive = {J_JACS}, author = {Chunxiao Wu and Ze Wei and Changfeng Li and Sheng Yang and Guhuan Liu and Ronghua Yang}, doi = {10.1021/jacs.5c10871}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35604--35615}, shortjournal = {J. Am. Chem. Soc.}, title = {Bio-photo dual action of intracellular radical polymerization}, volume = {147}, year = {2025}, }
• (2025). Inverse hydrocarbon recognition via nitro Group–Programmed soft porous crystal for one-step C3H6 purification. JACS, 147(39), 35595--35603. (www)

  @article{ , abstract = {The energy-intensive separation of propylene (C 3 H 6 ) from propane (C 3 H 8 ) is a major industrial challenge. To address this, we introduce a concept of molecular recognition based on hydrogen atom content (H δ + ) using cooperative host–guest interactions in soft porous crystals. Guided by this principle, we designed a flexible porous crystal, NTU-99-NO 2 , incorporating electronegative nitro group receptors into a dynamic framework. This material exhibits unprecedented inverse selectivity: a 2-fold higher uptake of C 3 H 8 over C 3 H 6 at 298 K, 1 bar. Crystallographic, theoretical, and in situ studies reveal that only C 3 H 8 triggers pore expansion and secondary adsorption, enabled by nitro group-mediated recognition. Comparative studies with hydroxyl- and methyl-functionalized analogs confirm the crucial role of receptor electronegativity. NTU-99-NO 2 enables the direct, one-step production of polymer-grade C 3 H 6 , combining breakthrough selectivity, structural adaptability, and scalable synthesis. This work establishes a generalizable design strategy for adaptive, receptor-guided separations in porous materials.}, archive = {J_JACS}, author = {Jingmeng Wan and Jia-jia Zheng and Ling Huang and Junfeng Bai and Susumu Kitagawa and Jingui Duan}, doi = {10.1021/jacs.5c10706}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35595--35603}, shortjournal = {J. Am. Chem. Soc.}, title = {Inverse hydrocarbon recognition via nitro Group–Programmed soft porous crystal for one-step C3H6 purification}, volume = {147}, year = {2025}, }
• (2025). In cellulo cysteine umpolung for protein structure probing. JACS, 147(39), 35587--35594. (www)

  @article{ , abstract = {Proteome-wide intramolecular cross-linking of amino acids allows for protein structure probing and is often achieved by reactive intermediates generated in situ . For example, carbene insertion chemistry forms versatile products but relies on two-step protocols that first introduce a photoreactive group and then generate a reactive intermediate via UV light irradiation. Alternatively, direct cross-linking with bifunctional electrophilic reagents enables modification of natural amino acids in a single transformation but proceeds via intermediates with a sufficiently long half-life in solution to capture unfavorable protein conformations. Herein, we report the use of commercially available vinyl thianthrenium tetrafluoroborate ( VTT ) for a single-step cross-linking strategy based on the umpolung of native cysteinyl thiols to electrophilic episulfonium ions in cells. We demonstrate that the umpolung reaction proceeds within minutes in various cell types. Even when competing with cysteine-reactive maleimide or iodoacetamide reagents, the fast cellular uptake of VTT enables efficient intracellular labeling and ensures the formation of products with a short and stable ethylene linker between cysteine and nucleophilic natural amino acids. We anticipate that the fast generation of episulfonium ions, which enable cross-linking without exogenous activation, will assist researchers in predicting protein structures based on quantitative proteome-wide information generated in cellulo .}, archive = {J_JACS}, author = {Philipp Hartmann and Kostiantyn Bohdan and Lara Vogelsang and Dario Marchionni and Christian Preisinger and Alessandro Vetere and Karl-Josef Dietz and Tobias Ritter}, doi = {10.1021/jacs.5c10259}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35587--35594}, shortjournal = {J. Am. Chem. Soc.}, title = {In cellulo cysteine umpolung for protein structure probing}, volume = {147}, year = {2025}, }
• (2025). Local electric fields originate unusual kinetic isotope effects in the hydrogen abstraction reactions of the functionally analogous p450 and TauD enzymes. JACS, 147(39), 35576--35586. (www)

  @article{ , abstract = {Cytochrome P450 enzymes (P450s) and their functionally analogous TauD enzyme (taurine D α-KG-dependent dioxygenase) oxidize alkanes by an initial hydrogen atom abstraction. We use molecular dynamics (MD) simulations and hybrid quantum mechanics/molecular-mechanics (QM/MM) calculations to comprehend the origins of the counterintuitive kinetic isotope effects (KIEs), which are exhibited by these two enzyme families. Thus, P450s exhibit low KIE values, which indicate the absence of quantum mechanical tunneling (QMT) contributions, whereas TauD exhibits high KIEs, which apparently include QMT. Furthermore, the calculations show that the P450 protein-folds compensate for the lack of QMT, by reactivity enhancement due to the favorable interactions of the substrate(s) with the corresponding local electric field (LEF) of these enzymes. By contrast, TauD exhibits higher hydrogen abstraction barriers as well as a significant QMT. Thus, the relative reactivities of the two enzyme-types, toward a given substrate, are determined by the larger LEF in P450s vis-à-vis the higher QMT in TauD. The present manuscript provides a comprehensive understanding of the root-causes of the LEF effects of the protein-folds vs the QMT factors, in modulating hydrogen-atom abstraction reactivity, in two distinct mechanistic strategies, for the functionally analogous P450 and TauD enzymes.}, archive = {J_JACS}, author = {Surajit Kalita and David Danovich and Sason Shaik}, doi = {10.1021/jacs.5c10488}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35576--35586}, shortjournal = {J. Am. Chem. Soc.}, title = {Local electric fields originate unusual kinetic isotope effects in the hydrogen abstraction reactions of the functionally analogous p450 and TauD enzymes}, volume = {147}, year = {2025}, }
• (2025). Iodonitrene-mediated nitrogen transfer to alkenes for the direct synthesis of NH-aziridines. JACS, 147(39), 35567--35575. (www)

  @article{ , abstract = {This work presents a novel and efficient method for the direct synthesis of NH-aziridines from a broad range of alkenes under mild conditions. The developed method uses aqueous ammonia and (diacetoxyiodo)benzene (PIDA) at 0 °C, offering a straightforward and atom-economical approach. Notably, this approach addresses the common challenge of chemoselectivity, effectively preventing the overoxidation of aziridines to nitriles. Mechanistic studies support the involvement of an in situ-generated iodonitrene as the key nitrogen-transfer intermediate. Overall, this method represents a significant advancement in aziridine synthesis, combining simplicity and selectivity, and complements the existing procedures for the direct NH insertion into alkenes.}, archive = {J_JACS}, author = {Yuri Gelato and Laura Marraffa and Francesco Pasca and Philipp Natho and Giuseppe Romanazzi and Arianna Tota and Marco Colella and Renzo Luisi}, doi = {10.1021/jacs.5c10372}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35567--35575}, shortjournal = {J. Am. Chem. Soc.}, title = {Iodonitrene-mediated nitrogen transfer to alkenes for the direct synthesis of NH-aziridines}, volume = {147}, year = {2025}, }
• (2025). Magnetic hysteresis up to 73 k in a dysprosium cyclopentadienyl-amide single-molecule magnet. JACS, 147(39), 35555--35566. (www)

  @article{ , abstract = {Single-molecule magnets (SMMs) based on dysprosocenium cations, [Dy(Cp R ) 2 ] + (Cp R = substituted cyclopentadienyl), have set record effective energy barriers to magnetic reversal ( U eff ) and temperatures at which open magnetic hysteresis is observed ( T H ), due to their highly axial crystal fields (CFs) and rigid ligand frameworks. Dysprosium bis(amide) cations, [Dy(NR 2 )] + (R = bulky silyl, aryl), can potentially show superior SMM properties as more charge-dense N-donor atoms can enforce stronger axial CFs to increase U eff , but these more flexible ligands can also promote under-barrier magnetic relaxation processes that diminish T H . Here, we combine the favorable SMM properties of each ligand in a single complex, [Dy{N(Si i Pr 3 ) 2 }(Cp*)][Al{OC(CF 3 ) 3 } 4 ] ( 1-Dy ; Cp* = C 5 Me 5 ). We find that 1-Dy has large magnetic anisotropy, with U eff = 2191(33) K; this is comparable with the best-performing dysprosium Cp R -based SMMs, but lower than the dysprosium bis(amide)-alkene complex [Dy{N(Si i Pr 3 )[Si( i Pr) 2 C(CH 3 )=CHCH 3 ]}{N(Si i Pr 3 )(Si i Pr 2 Et)}][Al{OC(CF 3 ) 3 } 4 ] ( U eff = 2652(16) K). A combination of the bent N–Dy–Cp* cent angle ( ca . 152.5(2)°) and flexible amide substituents of 1-Dy limits T H to 73 K, which is below the record T H value of 100 K for the bis(amide)-alkene. Together, this work shows that dysprosium SMMs containing one π-aromatic and one monodentate ligand can have comparable U eff values to bis-π-aromatic complexes, but in common with dysprosium bis(amide) complexes, they show a greater sensitivity of interligand angle toward under-barrier relaxation processes. This new class of dysprosium complexes are promising candidates for high-temperature SMMs, and it is likely that large improvements on this first example can be made with exquisite control of molecular geometry.}, archive = {J_JACS}, author = {Jack Emerson-King and Jack Baldwin and Sophie C. Corner and William J. A. Blackmore and Nicholas F. Chilton and David P. Mills}, doi = {10.1021/jacs.5c10400}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35555--35566}, shortjournal = {J. Am. Chem. Soc.}, title = {Magnetic hysteresis up to 73 k in a dysprosium cyclopentadienyl-amide single-molecule magnet}, volume = {147}, year = {2025}, }
• (2025). High-entropy electrolytes downsizing solvated clusters and enabling parallel ion transport for low-temperature aqueous zinc batteries. JACS, 147(39), 35544--35554. (www)

  @article{ , abstract = {Rechargeable zinc-based batteries are promising candidates for electrochemical energy storage, but their deliverable capacity, rate capability, and cycle performance are limited by conventional aqueous electrolytes at low temperatures. Here, we report an aqueous electrolyte formulation by increasing the chloride salt diversity to maximize both mixing and excess entropies. In a ternary-chloride-salt electrolyte, we reveal that the increased mixing entropy can tune the coordination environments, which disrupts the hydrogen-bonding network and reduces the aggregation of [ ZnCl m ] n 2 n ‐ m n clusters to increase tetrahedral entropies and total pair-correlation excess entropies. The high-entropy electrolyte exhibits a lower freezing temperature, higher ionic conductivity, and diverse and small solvated clusters at low temperatures. Furthermore, the entropy-mediated solvation structures desolvate and access the Zn anode in a parallel process with a high Zn 2+ flux for uniform plating and stripping, which breaks through the traditional sequential isolated desolvation/deposition pathway of large aggregated clusters that induce dendritic anode morphology. The formulated electrolyte endows Zn||Zn cells with stable cycling over 13320 h at 1 mA cm –2 with 99.97% average Coulombic efficiency for Zn plating/stripping and matches cathodes of tetrachlorobenzoquinone, VOPO 4 · x H 2 O or Na 3 V 2 (PO 4 ) 3 to enable full cells working at −60 °C.}, archive = {J_JACS}, author = {Yang Dong and Xiulin Chai and Jinhan Li and Linlin Xue and Fanqi Kong and Zhaodong Wang and Fangming Liu and Meng Yu and Fangyi Cheng}, doi = {10.1021/jacs.5c10307}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35544--35554}, shortjournal = {J. Am. Chem. Soc.}, title = {High-entropy electrolytes downsizing solvated clusters and enabling parallel ion transport for low-temperature aqueous zinc batteries}, volume = {147}, year = {2025}, }
• (2025). Photocatalyzed decarboxylative B–C couplings for the synthesis of carboranyl amino acids and peptides. JACS, 147(39), 35531--35543. (www)

  @article{ , abstract = {Boron neutron capture therapy (BNCT) is a promising and selective strategy for treating aggressive and refractory tumors, but its clinical success depends on the development of effective boron delivery agents. These agents must offer high tumor selectivity, structural stability, and sufficient boron content─criteria that current clinical options fail to fully satisfy. Herein, we report a visible-light-driven decarboxylative B–C cross-coupling between boron-functionalized carborane carboxylic acids and dehydroalanine (Dha)-containing peptides, enabling the first synthesis of boron-vertex-substituted carboranyl peptides under mild conditions. This photocatalyzed site-selective Giese involves the reaction of photogenerated boron vertex-centered carboranyl radicals to Dha residues, affording carborane-peptide conjugates in good to high yields and with excellent functional group tolerance. Enantiopure boron-vertex-substituted carboranylalanines were successfully synthesized using chiral Karady–Beckwith Dha derivatives, enabling their incorporation into well-defined complex peptides (comprising 5 and 15 residues) via solid-phase peptide synthesis. The synthetic utility of this platform was further demonstrated through a DNA-compatible click reaction, which enabled the attachment of carborane-bearing motifs to DNA tags. Moreover, B–C coupled carboranylalanines were conjugated to biologically relevant molecules such as nucleic acid aptamers to enhance tumor-targeting properties. Preliminary cellular studies confirmed that aptamer–carborane–amino acid conjugates exhibit efficient tumor cell recognition and uptake. Collectively, this work establishes a versatile and late-stage strategy for the site-selective installation of carborane units onto biomolecules via B–C bond formation, significantly expanding the chemical space of boron-rich peptide architectures and advancing the development of next-generation BNCT agents.}, archive = {J_JACS}, author = {Zhenghong Zhou and Han Ma and Jie Zhou and Yang Sun and Rongfeng Wu and Sen Gao and Shiyin Zhao and Bing Liu and Yong Nian and Bo Yang and Lijuan Zhu and Feng Zhu}, doi = {10.1021/jacs.5c10308}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35531--35543}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalyzed decarboxylative B–C couplings for the synthesis of carboranyl amino acids and peptides}, volume = {147}, year = {2025}, }
• (2025). A general copper-catalyzed radical cross-coupling of unactivated alkyl halides. JACS, 147(39), 35520--35530. (www)

  @article{ , abstract = {The first-row transition metal-catalyzed C(sp 3 )–carbon/heteroatom cross-coupling of unactivated alkyl halides is a powerful strategy for constructing diverse molecular frameworks. Copper-based systems dominate C(sp 3 )–N cross-coupling, likely owing to their strong propensity for reductive elimination, whereas other first-row transition metal catalysts have been reported only in rare cases. However, the intrinsically lower reducing capability of copper catalysts greatly limits their application to unactivated alkyl halides─particularly alkyl chlorides─in C(sp 3 )–N cross-coupling reactions. Here, we demonstrate a general copper-catalyzed C(sp 3 )–C/N cross-coupling of unactivated alkyl halides with diverse nucleophiles under mild thermal conditions. The success of this reaction relies on the use of anionic N,N,N -ligands to enhance the reducing capability of Cu(I) catalysts for the reduction of alkyl halides. This protocol accommodates a wide range of coupling partners, including primary to tertiary alkyl bromides and bench-stable chlorides, as well as primary and secondary alkyl iodides, and an array of nucleophiles (such as (hetero)aromatic amines, indoles, carbazoles, amides, azoles, and alkynes) with good functional-group compatibility. Furthermore, the present system provides a highly versatile platform for the late-stage functionalization of complex molecules.}, archive = {J_JACS}, author = {Fu-Li Wang and Qian Xie and Xiao-Yu Chen and Xue-Man Ye and Ning-Yuan Yang and Jia-Le Deng and Shou-Hao Zhong and Yu-Xuan Zhang and Ji-Jun Chen and Xin-Yuan Liu}, doi = {10.1021/jacs.5c10285}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35520--35530}, shortjournal = {J. Am. Chem. Soc.}, title = {A general copper-catalyzed radical cross-coupling of unactivated alkyl halides}, volume = {147}, year = {2025}, }
• (2025). Determining the state of a pd/γ-Al2O3 catalyst using pulsed flow and transient spectroscopy. JACS, 147(39), 35510--35519. (www)

  @article{ , abstract = {A precise understanding of heterogeneous catalyst structure and activity is required to design more efficient, greener, industrial chemical processes. While it is possible to resolve both the structure and activity of a catalyst, their innate complexity means it is nontrivial to unambiguously assign one to the other. Herein, we demonstrate how transient measurements, coupled with kinetic modeling, can be used to resolve kinetics with sufficient precision such that it is possible to resolve the identity of an “active site” over technical catalysts. We find that under CO rich conditions the transient activity and coverage dependencies measured over a Pd/γ-Al 2 O 3 catalyst during pulsed flow and transient spectroscopy CO oxidation experiments can be quantitatively predicted using a kinetic model derived from ultrahigh vacuum surface science experiments over Pd(111) single crystals. Thus, we conclude that the state (i.e., structure and composition of the active site) of the Pd/γ-Al 2 O 3 catalyst under reaction conditions is equivalent to that of a Pd(111) surface. Instead of determining a catalyst’s structure and assigning it to activity, we instead propose a new approach: using precise kinetic measurements to infer the catalyst’s state. This approach enables the identification of active sites that have been challenging to resolve using traditional spectroscopic or microscopic methods, offering a powerful and complementary tool for designing new catalysts.}, archive = {J_JACS}, author = {Christopher R. O’Connor and Eric A. High and Taek-Seung Kim and Audrey Dannar and Christian Reece}, doi = {10.1021/jacs.5c10235}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35510--35519}, shortjournal = {J. Am. Chem. Soc.}, title = {Determining the state of a pd/γ-Al2O3 catalyst using pulsed flow and transient spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Stimuli-responsive luminophore drives mechanism switch for highly efficient electrochemiluminescence immunosensing. JACS, 147(39), 35501--35509. (www)

  @article{ , abstract = {Although widely used in clinical diagnostics, the sensitivity of electrochemiluminescence (ECL) bead-based immunoassays is intrinsically limited by the reaction mechanism driving the emission of [Ru(bpy) 3 ] 2+ on the bead surface. Depending mostly on the coreactant oxidation, the ‘remote’ pathway is hindered by the slow coreactant oxidation rate and the short half-lives of electrogenerated radicals. In this work, we synthesized a [Ru(bpy) 3 ] 2+ derivative featuring a stimuli-responsive disulfide bond in its linker to the bead. Electrogenerated tri- n -propylamine (TPrA) neutral radicals reduce disulfide moieties, electrochemically inducing the release of Ru(II) labels in solution and thereby leading to an unprecedented mechanism shift toward the more efficient “homogeneous” ECL pathway. Leveraging ICP-MS, ECL microscopy, and finite element simulations, we demonstrate rapid bond cleavage and an impressive signal enhancement of up to 613%. Using an experimental configuration designed to emulate commercial clinical analysis, we developed an ECL-based immunoassay for the rapid detection of the SARS-CoV-2 Spike (S) protein in whole virus samples from swab formulations. The immunosensor incorporating the cleavable luminophore demonstrated a 40% lower detection limit and a 2-fold increase in sensitivity, while reducing TPrA consumption by 72%. These findings establish stimuli-responsive luminophores as a groundbreaking class of ECL labels, promising substantial improvements in the sensitivity of commercial biosensors.}, archive = {J_JACS}, author = {Alessandro Fracassa and Giulia Ferrari and Maria Vittoria Balli and Isabella Rimoldi and Giorgio Facchetti and Lorenzo Arnal and Alessia Marconi and Matteo Calvaresi and Luca Prodi and Luisa De Cola and Giovanni Valenti}, doi = {10.1021/jacs.5c10211}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35501--35509}, shortjournal = {J. Am. Chem. Soc.}, title = {Stimuli-responsive luminophore drives mechanism switch for highly efficient electrochemiluminescence immunosensing}, volume = {147}, year = {2025}, }
• (2025). Triplet spin delocalization and temperature dependence for adiabatic and non-adiabatic Z–E isomerization pathways in azoarenes. JACS, 147(39), 35493--35500. (www)

  @article{ , abstract = {Photoswitching molecules like the azoarenes have myriad potential applications, ranging from energy storage to targeted drug delivery. Upon irradiation, azoarenes convert from an E -form to a Z -form. The Z -form can thermally revert to the E -form through a classical-adiabatic or a triplet-assisted rotational mechanism. We show that strategic placements of heteroatoms and substituents can modulate spin delocalization in the triplet state, thereby tuning the S 0 –T 1 –S 0 crossing points. Increased spin delocalization lowers the crossing point and shortens the thermal half-life of the Z -form. Computed spin densities at the diazo N atoms, along with computed S 0 –T 1 –S 0 crossing points, activation entropies, and rate constants for 15 azoarenes are compared with available experimental data. There is evidence that some of the studied Z – E isomerizations proceed simultaneously via a classical-adiabatic and a triplet-assisted mechanism. The ratio of the two reaction pathways is temperature-dependent. Triplet spin density at the diazo N atoms is recognized as a useful indicator for predicting the thermal half-lives of these species.}, archive = {J_JACS}, author = {Francisco A. Martins and Renan V. Viesser and João Vitor Schober and Rainer Herges and Judy I. Wu}, doi = {10.1021/jacs.5c09852}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35493--35500}, shortjournal = {J. Am. Chem. Soc.}, title = {Triplet spin delocalization and temperature dependence for adiabatic and non-adiabatic Z–E isomerization pathways in azoarenes}, volume = {147}, year = {2025}, }
• (2025). Discovery of BRD9 molecular glue degraders that spare cardiomyocytes. JACS, 147(39), 35481--35492. (www)

  @article{ , abstract = {Molecular glue degraders (MGDs) represent a class of drug-like small molecules that induce targeted protein degradation (TPD) by promoting selective protein–protein interactions. MGDs offer a promising therapeutic approach by selectively eliminating disease-associated proteins; however, their rational design and discovery have historically remained a significant challenge. The field remains constrained by a lack of strategies to effectively utilize ubiquitin ligases (E3s) for TPD, thus missing the therapeutic potential offered by tissue-specific E3 expression. In this study, we developed ZZ7, a molecular glue degrader that selectively degrades BRD9, a critical component of the SWI/SNF chromatin remodeling complex, specifically in synovial sarcoma cells, while sparing cardiomyocytes. The discovery of ZZ7 was driven by a “chemocentric” approach, incorporating a cysteine-reactive, reversible covalent warhead into a BRD9 inhibitor to transform its function from inhibition to degradation. ZZ7 covalently engages DCAF16 at Cys178, an E3 ligase that is highly expressed in synovial sarcoma cells but relatively underexpressed in human iPSC-derived cardiomyocytes, leveraging a cysteine residue that has not been previously exploited. These findings pave the way for new strategies in tissue- and disease-specific precision therapies, particularly for malignancies characterized by an elevated level of DCAF16 expression.}, archive = {J_JACS}, author = {Woong Sub Byun and Zhe Zhuang and Anna P. Hnatiuk and Cyrus Jin and Zixuan Jiang and Kheewoong Baek and Evelyn Chao and Katherine A. Donovan and Eric S. Fischer and Mark Mercola and Nathanael S. Gray}, doi = {10.1021/jacs.5c09857}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35481--35492}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of BRD9 molecular glue degraders that spare cardiomyocytes}, volume = {147}, year = {2025}, }
• (2025). ZnSnAuBiCuO-derived electrocatalysts rich in grain boundaries for CO reduction to n-propanol. JACS, 147(39), 35471--35480. (www)

  @article{ , abstract = {Electrocatalytic carbon monoxide reduction (CORR) to n -propanol, powered by renewable energy, offers a promising approach for energy storage and carbon recycling, while avoiding the high CO 2 emissions associated with current industrial n -propanol production methods. However, electrocatalysts capable of achieving both high Faradaic efficiency for CO reduction to n -propanol and long-term durability remain scarce. While monometallic and bimetallic dilute Cu-based alloys have been studied extensively for electrochemical CO 2 reduction (CO 2 RR) and CORR, multimetallic (≥5 elements) electrocatalysts are less explored. Here we screen and investigate the electrocatalytic CORR performance of multimetallic electrocatalysts. Notably, the ZnSnAuBiCuO catalyst achieves Faradaic efficiencies (FE) of 47 ± 1% for n -propanol production, while demonstrating stable performance for 60 h at 100 mA cm –2 . The enhanced CORR performance is attributed to the higher grain boundary density and the higher Cu valence state compared to CuO. Calculation is consistent with the possibility that grain boundaries are, in the context of n -propanol production, energetically favorable, compared to within-grain sites. The stable electrosynthesis of n -propanol with high FE by ZnSnAuBiCuO may motivate the exploration of other multimetallic systems, which have vast compositional space.}, archive = {J_JACS}, author = {Yong Wang and Ke Xie and Mercouri G. Kanatzidis and Edward H. Sargent}, doi = {10.1021/jacs.5c09652}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35471--35480}, shortjournal = {J. Am. Chem. Soc.}, title = {ZnSnAuBiCuO-derived electrocatalysts rich in grain boundaries for CO reduction to n-propanol}, volume = {147}, year = {2025}, }
• (2025). Kondo resonance of a carbon-centered radical in a single-molecule junction. JACS, 147(39), 35464--35470. (www)

  @article{ , abstract = {The low spin–orbit coupling and weak hyperfine interactions make organic radicals promising components used in molecular spintronics. Triphenylmethyl (TPM) is the first stable carbon-centered organic radical discovered more than a century ago. Here, we use scanning tunneling spectroscopy to study quantum transport through single TPM radicals that are attached to a Au(111) electrode via atomic contacts of Ni atoms. The transport exhibits a Kondo resonance, evidencing that the unpaired electron of the radical forms a spin singlet with the itinerant electrons of the electrode. Density functional theory calculations reveal an indirect Kondo screening mechanism: the itinerant electrons couple with the radical π electron via the d orbitals of the Ni atoms. These results envision a new way to regulate the spin transport of organic radicals using atomic contacts in solid-state spintronic devices.}, archive = {J_JACS}, author = {Chengyi Chen and Hua Zhu and En Li and Henan Chen and Huilin Xie and Jacky W. Y. Lam and Ben Zhong Tang and Wei Ji and Nian Lin}, doi = {10.1021/jacs.5c09680}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35464--35470}, shortjournal = {J. Am. Chem. Soc.}, title = {Kondo resonance of a carbon-centered radical in a single-molecule junction}, volume = {147}, year = {2025}, }
• (2025). Atmospheric corrosion-driven redox coordination enables spontaneous carbonate conversion of lithium-ion battery cathodes. JACS, 147(39), 35456--35463. (www)

  @article{ , abstract = {The growing demand for lithium-ion batteries (LIBs) has intensified the need for sustainable methods to recover critical metals. Current recycling strategies, including pyrometallurgy and hydrometallurgy, often involve high energy consumption, harsh reagents, and poor selectivity, limiting their environmental and economic viability. Here, we report a chemically autonomous and energy-neutral cathode recycling process driven by atmospheric corrosion. Under humid air and dissolved CO 2 , aluminum current collectors undergo sustained oxidative dissolution, releasing electrons that selectively reduce transition metals (TM) in the layered oxide to TM(II). This redox reaction triggers H + insertion, Li + /H + exchange, and lattice destabilization, forming Li x H y TMO 2 intermediates that spontaneously coordinate with CO 3 2– to yield TMCO 3 or Ni 2 (OH) 2 CO 3 , while Li + precipitates as Li 2 CO 3 . CO 2 acts both as a proton carrier and as a coordinating ligand, sustaining the redox–coordination loop. This chemistry-driven approach redefines corrosion as a tool for selective redox transformations and offers a reagent-free, scalable pathway for LIB recycling under ambient conditions.}, archive = {J_JACS}, author = {Wendi Tang and Tianran Yan and Wenbin Dai and Kaidan Shen and Tingting Zhang and Jialong Yu and Liang Zhang and Wei Zhang}, doi = {10.1021/jacs.5c09473}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35456--35463}, shortjournal = {J. Am. Chem. Soc.}, title = {Atmospheric corrosion-driven redox coordination enables spontaneous carbonate conversion of lithium-ion battery cathodes}, volume = {147}, year = {2025}, }
• (2025). Tightly yet dynamically bound aliphatic guanidinium ligands for lead halide perovskite nanocrystals. JACS, 147(39), 35446--35455. (www)

  @article{ , abstract = {Lead halide perovskites (LHPs) have disrupted the field of visible-range emitting colloidal semiconductor nanocrystals (NCs) owing to their exceptional emissivity as classical and quantum light sources. Their appeal is countered by the stability challenges arising from inherent lattice softness and labile surface ligand bonding. Recent ligand design efforts have drastically improved the structural integrity of LHP NCs by pursuing strongly and statically bound ligands, as found with zwitterionic headgroups. Here, we venture into a new class of cationic ligands featuring guanidinium headgroups, which combine the compactness of primary ammoniums with the deprotonation resistance of quaternary ammoniums. We reasoned that strong yet dynamic ligand binding offers distinct benefits. A library of aliphatic guanidinium molecules was synthesized and surveyed as capping ligands for CsPbBr 3 , FAPbBr 3 , and CsPbI 3 NCs, enabling up to 95% photoluminescence quantum yields for bromide compositions. We then compare binding behavior of guanidinium ligands with those of other widely used ligands. Zwitterionic ligands phosphocholines and phosphoethanolamines bind more strongly than sulfobetaines and quaternary ammonium ligands, yet all these headgroups impart relatively static binding with exchange rates below 5 s –1 . Primary ammonium ligands are champions in dynamicity but lag behind in ligand-coverage retention and, hence, long-term stability. Guanidinium ligands strike a favorable balance: they match the binding dynamics of primary ammonium ligands while significantly enhancing binding strength, enabling rigorous purification and compatibility with relatively polar solvents such as tetrahydrofuran. We then showcase the benefits of dynamically bound ligands in photocatalytic C–C coupling reactions.}, archive = {J_JACS}, author = {Yuliia Berezovska and Sebastian Sabisch and Caterina Bernasconi and Yesim Sahin and Federica Bertolotti and Antonietta Guagliardi and Maryna I. Bodnarchuk and Dmitry N. Dirin and Maksym V. Kovalenko}, doi = {10.1021/jacs.5c09354}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35446--35455}, shortjournal = {J. Am. Chem. Soc.}, title = {Tightly yet dynamically bound aliphatic guanidinium ligands for lead halide perovskite nanocrystals}, volume = {147}, year = {2025}, }
• (2025). Well-defined cu precatalysts indicate design rules for reactivity in nitrate electroreduction. JACS, 147(39), 35438--35445. (www)

  @article{ , abstract = {The electrochemical nitrate reduction reaction (NO 3 RR) to ammonia (NH 3 ) is a promising route for sustainable NH 3 synthesis. Cu-based materials are the most used and promising catalysts for this reaction. However, Cu undergoes uncontrollable compositional and structural changes under NO 3 RR conditions, necessitating a deeper understanding of the relationship between precatalyst features, structural evolution, and catalytic performance for the advancement of current catalyst design rules. Here, we exploit well-defined Cu and Cu oxide nanocrystals (NCs) as precatalysts to elucidate these correlations. We find that the size, shape, and oxide content of the Cu precatalysts all play a role in driving structural evolution and, thus, the catalytic behavior during NO 3 RR. In particular, a higher oxide content, an optimized {111}/{100} facet ratio, and the spatial proximity of these facets forming grain boundaries within the active catalysts emerge as key factors to enhance NH 3 selectivity. Among the studied Cu precatalysts, 10 nm Cu spheres integrate these key features, achieving a competitive NH 3 production rate compared to the state of the art. This work links pre- and in situ-formed catalyst features to catalytic performance, offering insights into the morphological dynamics of Cu catalysts under NO 3 RR conditions.}, archive = {J_JACS}, author = {Jia Du and Anna Loiudice and Krishna Kumar and Ludovic Zaza and Raffaella Buonsanti}, doi = {10.1021/jacs.5c09246}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35438--35445}, shortjournal = {J. Am. Chem. Soc.}, title = {Well-defined cu precatalysts indicate design rules for reactivity in nitrate electroreduction}, volume = {147}, year = {2025}, }
• (2025). High-pressure synthesis of two Pb3(C3N6) polymorphs featuring fully deprotonated [C3N6]6– melaminate anions. JACS, 147(39), 35431--35437. (www)

  @article{ , abstract = {Graphitic carbon nitride (g-C 3 N 4 ), melamine, and their derivatives are of significant interest due to their diverse structural properties and potential applications in catalysis, energy storage, and materials science. In this study, two new compounds, both with the Pb 3 (C 3 N 6 ) chemical formula, were synthesized at pressures of 40(2) to 48(2) GPa through a direct reaction between Pb, C and N 2 , or Pb and C 6 N 4 , in laser-heated diamond anvil cells. Their crystal structures were solved and refined using synchrotron single-crystal X-ray diffraction. The two Pb 3 (C 3 N 6 ) polymorphs, namely tP 48-Pb 3 (C 3 N 6 ) and hP 72-Pb 3 (C 3 N 6 ), crystallize in the noncentrosymmetric space groups P 4̅2 1 m and P 6 1 22, respectively. Both solids contain the previously unknown hydrogen-free [C 3 N 6 ] 6– melaminate anion and were experimentally found recoverable to ambient conditions. Density functional theory calculations provide further insights into the structural and electronic properties, and reveal that both compounds are direct narrow band gap semiconductors.}, archive = {J_JACS}, author = {Umbertoluca Ranieri and Akun Liang and Charles Lamb and James Spender and Sarah Bolton and Andrey Aslandukov and Bernhard Massani and Ferenc Tasnádi and Pierre-Olivier Autran and James A. D. Ball and Angelika D. Rosa and Bihan Wang and Florian Trybel and Dominique Laniel}, doi = {10.1021/jacs.5c09198}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35431--35437}, shortjournal = {J. Am. Chem. Soc.}, title = {High-pressure synthesis of two Pb3(C3N6) polymorphs featuring fully deprotonated [C3N6]6– melaminate anions}, volume = {147}, year = {2025}, }
• (2025). Sono-uncaging for spatiotemporal control of chemical reactivity. JACS, 147(39), 35422--35430. (www)

  @article{ , abstract = {Photo-uncaging─the use of light to reveal the active part of a chemical compound by photolysis of a protecting group─has long been used to study and actuate biochemical processes. However, light scattering limits the applications of photo-uncaging in opaque specimens or tissues. Here, we introduce sono-uncaging , a process in which a chemical functional group becomes exposed upon the application of ultrasound, which can be applied and focused in optically opaque materials. We engineered gas vesicles (GVs), air-filled protein nanostructures sensitive to ultrasound, to contain cysteines on their concealed inner surface, hypothesizing that the application of ultrasound would collapse the GV shell and reveal the cysteines. The resulting SonoCage construct reacted with monobromobimane (mBBr), a fluorogenic, thiol-reactive molecule, only after treatment with ultrasound, establishing the sono-uncaging proof of concept. We then demonstrated the spatial patterning capability of sono-uncaging by embedding the SonoCages in an mBBr-containing hydrogel and creating fluorescent patterns with phased array ultrasound. This patterning could be accomplished using a diagnostic imaging transducer with mild ultrasound conditions. This work establishes sono-uncaging as a method for spatiotemporal control over chemical reactivity using widely available ultrasound technology.}, archive = {J_JACS}, author = {Erik Schrunk and Sunho Lee and Przemysław Dutka and Di Wu and Mikhail G. Shapiro}, doi = {10.1021/jacs.5c09181}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35422--35430}, shortjournal = {J. Am. Chem. Soc.}, title = {Sono-uncaging for spatiotemporal control of chemical reactivity}, volume = {147}, year = {2025}, }
• (2025). Harnessing Chromium(V) hydrazido intermediates for n2 functionalization to multisubstituted hydrazines through ligand migration. JACS, 147(39), 35413--35421. (www)

  @article{ , abstract = {The direct conversion of N 2 into N-containing organic compounds remains a fundamental challenge in synthetic chemistry. Here, we report a high-valent chromium(V)-mediated strategy for synthesizing multisubstituted hydrazine derivatives via ligand migration, representing ligand migration to N α in a Cr-hydrazido complex. Our approach begins with the oxidation of chromium(IV) hydrazido precursor 1 by benzyl bromide, which replaces the 1,2-bis(diethylphosphino)ethane (depe) ligand with two bromide ions to generate the high-valent chromium(V) dibromide hydrazido complex 2 . Sequential ligand metathesis of 2 with aryl Grignard reagents (ArMgBr, Ar = biphenyl, p -methylphenyl, o -methoxyphenyl), alkenyl or alkyl Grignard reagents (1-phenylvinylmagnesium bromide and isopropylmagnesium bromide), followed by ligand migration from the Cr center to the N α atom and electrophilic trapping (MeOH, PhCH 2 Br), affords structurally diverse hydrazines ( 4a–c , 5a–c , and 6 ). Single-crystal X-ray crystallography, in situ UV–vis spectroscopy, and DFT calculations collectively reveal a ligand migration mechanism in chromium chemistry, directly forging N–C bonds from N 2 without ammonia intermediates. This migration not only constructs new N–C bonds but also enables the direct construction of complex hydrazine structures directly from N 2 .}, archive = {J_JACS}, author = {Xueli Wang and Yue Wu and Yixi Wang and Rong Sun and Junnian Wei and Zhenfeng Xi}, doi = {10.1021/jacs.5c09083}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35413--35421}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing Chromium(V) hydrazido intermediates for n2 functionalization to multisubstituted hydrazines through ligand migration}, volume = {147}, year = {2025}, }
• (2025). The role of halides in the bonding and electronic structure of Actinyl(VI) Halides─Energy match driven stability. JACS, 147(39), 35401--35412. (www)

  @article{ , abstract = {The role of the equatorial ligands and their influence on the electronic structures and bonding properties of uranyl and other actinyls are not well understood and are thus at the forefront of actinide research. In the study presented here, we found that the good energy match of uranyl(VI) with F – valence orbitals leads to substantial changes in the uranyl electronic structure, compared to uranyl–Cl – and uranyl–Br – . The good energy match between uranyl(VI) and F – likely enhances the stability of the uranyl–F – bond, contributing to the higher U–F – affinity in aqueous solution compared to uranyl–Cl – /Br – , which is also demonstrated for plutonyl(VI). These findings are based on studies of equatorial and axial ligand covalency in three uranyl halides: NaRb 8 (UO 2 ) 5 F 19 ·2H 2 O, Rb 2 UO 2 Cl 4 ·2H 2 O, and Rb 2 UO 2 Br 4 ·2H 2 O. We describe covalent uranium–halide interactions, following the trend Br – ≈ Cl – > F – . Ligand K-edge XANES and DFT (including TDDFT and LFDFT) reveal significant electronic structure differences, with the F-based compound having a uranyl-based HOMO, while Cl- and Br-based compounds show predominant ligand p character in the HOMO. A newly introduced theoretical index evaluates bond covalency. U M 4 edge HR-XANES and RIXS exhibit unexpected σ* peak trends not directly correlated with U═O bond lengths but well explained by LFDFT RIXS calculations.}, archive = {J_JACS}, author = {Thomas S. Neill and Harry Ramanantoanina and Natalia Palina and Tim Prüßmann and Jörg Rothe and Xavier Gaona and David Fellhauer and Dieter Schild and Constantin Wansorra and Dirk Hauschild and Ralph Steininger and Bianca Schacherl and Clemens Heske and Lothar Weinhardt and Olaf Walter and Florian Weigend and Tonya Vitova}, doi = {10.1021/jacs.5c08999}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35401--35412}, shortjournal = {J. Am. Chem. Soc.}, title = {The role of halides in the bonding and electronic structure of Actinyl(VI) Halides─Energy match driven stability}, volume = {147}, year = {2025}, }
• (2025). Disentangling the roles of dissolved oxygen, common salts, and pH on spontaneous hydrogen peroxide production in water: No o2, no H2O2. JACS, 147(39), 35392--35400. (www)

  @article{ , abstract = {Despite mounting evidence that the air–water interface or microdroplet geometry has no bearing on the spontaneous formation of hydrogen peroxide (H 2 O 2 ) down to a 50 nM limit of detection, the debate persists. Recent studies have demonstrated connections between the spontaneous formation of hydroxyl (HO • ) radicals and H 2 O 2 in sprayed microdroplets and the solution pH, dissolved salts, nebulizing gas, and gaseous environment. Among the halides, chloride (Cl – ), bromide (Br – ), and iodide (I – ), the studies found that Br – dominated H 2 O 2 formation because of its enhanced fractionation at the air–water interface and ability to donate electrons. The studies also suggested that H 2 O 2 production at the air–water interface scales with the alkalinity of water. In response, this report employs a comprehensive set of techniques, encompassing nuclear magnetic resonance, potentiodynamic polarization, electron microscopy, and H 2 O 2 assay kit fluorometry, to examine these claims. The experiments reveal that the air–water interface or microdroplet geometry does not drive H 2 O 2 formation, regardless of the presence of halide in water. The reduction of oxygen gas (O 2 ) at the solid–water interface produces H 2 O 2 (i.e., in the absence of O 2 , no H 2 O 2 is formed regardless of the halide). This work explains the relative dependence of H 2 O 2 concentrations on halides based on their propensity to drive pitting corrosion (Cl – > Br – > I – ). As pits appear in the passivating layer, exposing the metal, H 2 O 2 is consumed during further oxidation. This work also disproves the claim that alkalinity drives H 2 O 2 formation, as it demonstrates that aluminum and titanium surfaces generate higher H 2 O 2 concentrations in acidic and alkaline conditions, respectively. Taken together, this report provides alternate explanations for the observations that should help draw the debate toward its closure.}, archive = {J_JACS}, author = {Muzzamil Ahmad Eatoo and Himanshu Mishra}, doi = {10.1021/jacs.5c09028}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35392--35400}, shortjournal = {J. Am. Chem. Soc.}, title = {Disentangling the roles of dissolved oxygen, common salts, and pH on spontaneous hydrogen peroxide production in water: No o2, no H2O2}, volume = {147}, year = {2025}, }
• (2025). Trotline-inspired mesoporous carriers for prolonged gastrointestinal retention. JACS, 147(39), 35379--35391. (www)

  @article{ , abstract = {Overcoming the challenges of precise localization, prolonged retention, and targeted release remains a fundamental barrier in the development of effective oral drug delivery systems. These limitations are particularly critical in diseases requiring site-specific action within the gastrointestinal (GI) tract such as inflammatory bowel disease (IBD). Inspired by the trotline fishing technique, where multiple hooks are suspended along a main line to increase capture efficiency, we present a smart oral drug delivery platform featuring trotline-inspired mesoporous carriers with dynamic anchoring capability. This delivery system integrates three key components: (1) a trotline-inspired bioadhesive carrier, consisting of carbon nanotube (CNT) decorated with multiple submicrometer-scale periodic mesoporous organosilica (PMO) “hooks” (denoted as CNT@PMOs or CNTP); (2) therapeutic drugs loaded within the PMO mesopores (such as 5-aminosalicylic acid (5-ASA) for IBD); (3) a reactive oxygen species (ROS)-responsive camouflage polymer coating, designed to modulate site-specific adhesion and on-demand drug release. Following oral administration, the outer polymer coating effectively shields the PMO hooks, facilitating safe passage through the stomach and healthy intestinal regions. Upon reaching inflamed sites in the intestine, the elevated ROS levels trigger the degradation of the polymer coating, exposing the PMO hooks. This controlled unmasking enables selective adhesion to inflamed tissues and prolongs local drug retention. Simultaneously, degradation of the polymer also triggers controlled release of 5-ASA at the lesion site. The one-dimensional, multihooked design further enhances mechanical interlocking with the intestinal mucosa, anchoring the carrier at the desired site. Importantly, the system shows minimal systemic exposure, with nearly 100% fecal excretion of unabsorbed carriers within 72 h. By integrating stimuli-responsive activation, dynamic anchoring, and spatiotemporal drug release, this platform addresses long-standing barriers in oral drug delivery. It offers a broadly applicable strategy for enhancing therapeutic precision and efficacy in GI-targeted treatments and beyond.}, archive = {J_JACS}, author = {Enyun Xing and Yan Yu and Kui Yan and Tianbao Zhu and Yixiang Wang and Yating Zhan and Hao Xing and Xiaomin Li and Dongyuan Zhao}, doi = {10.1021/jacs.5c08856}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35379--35391}, shortjournal = {J. Am. Chem. Soc.}, title = {Trotline-inspired mesoporous carriers for prolonged gastrointestinal retention}, volume = {147}, year = {2025}, }
• (2025). Weakly solvating hydrated eutectic electrolyte for high-performance aluminum-ion batteries with wide temperature range. JACS, 147(39), 35367--35378. (www)

  @article{ , abstract = {Aqueous aluminum-ion batteries have emerged as a promising alternative to lithium-ion batteries due to their high theoretical capacity, enhanced safety, and low cost. However, their practical application is still hindered by inhomogeneous aluminum deposition, hydrogen evolution reaction, and corrosion during cycling, especially under extreme temperatures and high load conditions. In this study, a hydrated eutectic electrolyte composed of Al(ClO 4 ) 3 ·9H 2 O and methyl carbamate in a 1:4 molar ratio was designed to improve the stability of aqueous aluminum ion batteries across a wide temperature range. The optimized electrolyte forms a water-deficient, weakly solvated structure, [Al 3+ (MC) 2 (H 2 O) 2 (ClO 4 – ) 2 ] + , which kinetically promotes a homogeneous aluminum deposition/stripping behavior. In addition, this electrolyte facilitates the formation of a dense, anion-rich solid electrolyte interface layer on the aluminum anode surface, maintaining long-term anode stability. The Al//Al symmetric cell demonstrated stable cycling for 600 h at a current density of 0.2 mA cm –2 , while the Al//polyaniline (PANI) full battery maintained a specific capacity of 117.7 mAh g –1 (based on the mass of PANI) after 1100 cycles at 1 A g –1 . Remarkably, this electrolyte also demonstrated excellent cycling stability over a wide temperature range from −15 to 50 °C, offering valuable design principles for aluminum-ion battery applications in large-scale energy storage systems.}, archive = {J_JACS}, author = {Yuzhao Xu and Yixin Li and Qi Zhang and Jianmin Wang and Qing Zhao and Haiyan Wang and Yougen Tang and Jun Chen}, doi = {10.1021/jacs.5c08778}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35367--35378}, shortjournal = {J. Am. Chem. Soc.}, title = {Weakly solvating hydrated eutectic electrolyte for high-performance aluminum-ion batteries with wide temperature range}, volume = {147}, year = {2025}, }
• (2025). Tandem topotactic reactions for low-temperature synthesis of ni-rich layered oxide cathodes without anti-site defect. JACS, 147(39), 35355--35366. (www)

  @article{ , abstract = {Ni-rich layered oxides (LiNi x Co y Mn z O 2 , x > 0.6) have garnered significant attention in electric transportation due to the high energy density (>700 Wh/kg). Traditional synthesis of Ni-rich cathodes typically involves high-temperature (>700 °C) long-duration (∼10 h) sintering procedures, which not only increase energy consumption but also present challenges in precisely controlling the synthesis conditions. Here we designed a two-step tandem topotactic phase-transition route that allows low-temperature synthesis of Ni-rich cathodes. Temperature-resolved X-ray scattering techniques combined with ex situ spectroscopy experiments substantiated that the layered hydroxide precursor first transformed to a layered oxyhydroxide intermediate through a topotactic deprotonation reaction, which was then converted to Ni-rich layered oxide cathode by a rapid topotactic lithiation. Radically distinguished from the destruction-reconstruction process of layered structures in the conventional synthesis route, the layered framework was maintained throughout the whole topotactic route, lowering the energy barrier of synthetic kinetics and thus enabling the successful preparation of Ni-rich cathodes at low temperature (150 °C), which brings an unprecedented reduction of energy consumption (by 57%) and considerable cost-savings. Furthermore, Ni-rich cathodes synthesized through the topotactic route exhibited comparable electrochemical activity and even better cycling stability (∼80% after 500 cycles) than those synthesized through conventional routes. This work presents an enlightening methodology of Ni-rich layered cathode synthesis, laying a substantial foundation for cost-effective and eco-friendly production of high-performance cathode materials on an industrial scale.}, archive = {J_JACS}, author = {Honghao Wang and Chenxi Li and Zuoguo Xiao and Haoyu Xue and Zhao-Hui Dong and Ke Yang and Nian Zhang and Yuansheng Lin and Yingbo Deng and Zhaowei Lin and Enze Li and Yixuan Liu and Zhe Pu and Yuncong Bai and Zian Liu and Hao Wang and Cihang Zhang and Zengzhu Li and Yanzhao Niu and Bingkai Zhang and Bowen Nan and Hai Lin and Xiang Liu and Mingjian Zhang}, doi = {10.1021/jacs.5c08560}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35355--35366}, shortjournal = {J. Am. Chem. Soc.}, title = {Tandem topotactic reactions for low-temperature synthesis of ni-rich layered oxide cathodes without anti-site defect}, volume = {147}, year = {2025}, }
• (2025). Understanding and controlling the colloidal stability of CdSe nanoplatelets by solvation force engineering. JACS, 147(39), 35347--35354. (www)

  @article{ , abstract = {The interaction and steric stability of colloidal nanocrystals are determined by the interplay of various contributions, including van der Waals, dipole–dipole, and solvation forces. Recent simulations have unveiled that the solvation force dictates the colloidal stability of two-dimensional nanomaterials with no experimental validation. Here, we introduce optical-pump THz-probe spectroscopy (OPTP) as a novel approach to track the colloidal aggregation of two-dimensional nanoplatelets. We show that far below the saturation concentration previously determined by scattering methods, OPTP can already report nanoscale aggregations by sensitively probing the short-range free carrier photoconductivity arising from internanoplatelet electronic coupling. Combining the OPTP and molecular dynamics simulations allows us to (1) confirm that increasing the nanoplatelet base facet area results in enhanced solvation force and thus aggregation tendency, and (2) demonstrate that the attraction between the nanoplatelets increases with their chain length for n -alkane solvents. Finally, we extend our simulations to study the shape of the interaction that can be tuned via the isomer of the solvent molecules. Our results provide not only a new sensitive tool to probe the aggregation effects of semiconducting colloidal particles but also fundamental insights into the critical parameters to engineer colloidal stability.}, archive = {J_JACS}, author = {Shuai Chen and Nanning Petersen and Omar Valsson and Martin Girard and Hai I. Wang}, doi = {10.1021/jacs.5c08392}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35347--35354}, shortjournal = {J. Am. Chem. Soc.}, title = {Understanding and controlling the colloidal stability of CdSe nanoplatelets by solvation force engineering}, volume = {147}, year = {2025}, }
• (2025). Emergent ferromagnetism and spin gapless conductivity in atomically thin Co3Sn2S2 nanosheets. JACS, 147(39), 35339--35346. (www)

  @article{ , abstract = {Spin-gapless semiconductors (SGSs) represent an intriguing class of quantum materials that bridge the gap between half-metallic ferromagnets and conventional semiconductors, offering promising avenues for spintronic applications. The discovery of intrinsic ferromagnetism in ultrathin two-dimensional van der Waals crystals has further fueled interest in exploring magnetism at the ultimate two-dimensional limit. Here, we demonstrate the growth of environmentally stable, atomically thin Co 3 Sn 2 S 2 nanosheets via a simple hydrothermal method. These nanosheets exhibit robust ferromagnetism with a Curie temperature of ∼100 K and remarkably, host a spin-gapless semiconducting (SGS) state, distinct from the well-known half-metallic Weyl ferromagnetism observed in the bulk counterpart. Structural analysis reveals that enhanced lattice distortion and strain effects in the nanosheets, induced by reduced dimensionality and surface defects, play a critical role in stabilizing this phase. Williamson-Hall analysis confirms the presence of strain, while DFT calculations reveal that strain-induced lattice distortions annihilate the Weyl points and the emergence of SGS semiconductivity. Charge transport measurements indicate a Mott variable-range hopping mechanism, while temperature-dependent conductivity suggests a coexistence of semiconducting and weakly gapless features. These findings not only establish atomically thin Co 3 Sn 2 S 2 nanosheets as a novel platform for SGS physics but also open up exciting possibilities for strain-engineered topological phases and next-generation spintronic and quantum technologies.}, archive = {J_JACS}, author = {Abhinav Pancholi and Pranav Negi and Kartik Samanta and Abhishek Das and Premakumar Yanda and Shishir Kumar Pandey and Subhajit Roychowdhury}, doi = {10.1021/jacs.5c08223}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35339--35346}, shortjournal = {J. Am. Chem. Soc.}, title = {Emergent ferromagnetism and spin gapless conductivity in atomically thin Co3Sn2S2 nanosheets}, volume = {147}, year = {2025}, }
• (2025). Seq2Saccharide: Discovering oligosaccharides and aminoglycosides natural products by integrating computational mass spectrometry and genome mining. JACS, 147(39), 35323--35338. (www)

  @article{ , abstract = {Natural oligosaccharides and aminoglycosides are important sources of new drug candidates, especially in the development of antibiotics. In the past, discovering novel saccharides has been time-consuming and costly. However, the rapid expansion of high-throughput data, including genomic and mass spectrometry data sets, has greatly increased opportunities for natural saccharide discovery. Yet, due to the complex biosynthesis pathways of saccharides, no existing method can predict their structures with high precision. To address this, we introduce Seq2Saccharide, a tool designed to automate saccharide natural product discovery by integrating both genomic and mass spectrometry data. To enhance accuracy, Seq2Saccharide predicts hundreds or thousands of putative structures for each gene cluster. The correct structure is then identified from these predictions using a mass spectral search. Benchmarks against saccharides in the MiBIG database show that Seq2Saccharide outperforms existing methods in predicting the structure of saccharides. Furthermore, mass spectrometry analysis indicates that the variable search module can correct mispredictions from genome mining. By searching genomic and mass spectrometry data of microbial strains, Seq2Saccharide correctly identified the biosynthetic gene cluster for the polysaccharide oligosaccharide trestatin B.}, archive = {J_JACS}, author = {Donghui Yan and Bahar Behsaz and Yanjing Li and Xiaofeng Wang and Leigh Skala and Sitong Liu and Hyun Woo Lew and Mustafa Guler and Hunsica Jayaprakash and Muqing Zhou and Liu Cao and Ashootosh Tripathi and Jason A. Clement and Taifo Mahmud and Roland D. Kersten and Hosein Mohimani}, doi = {10.1021/jacs.5c08251}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35323--35338}, shortjournal = {J. Am. Chem. Soc.}, title = {Seq2Saccharide: Discovering oligosaccharides and aminoglycosides natural products by integrating computational mass spectrometry and genome mining}, volume = {147}, year = {2025}, }
• (2025). Coherent control over nuclear hyperpolarization using an optically initializable chromophore-radical system. JACS, 147(39), 35313--35322. (www)

  @article{ , abstract = {Chromophore radicals (CR) are emerging as important components for molecular quantum information science (QIS), especially in the context of quantum sensing. Here, we demonstrate that the optically hyperpolarized electrons in a 1,6,7,12-tetrakis(4- tert -butylphenoxy)-perylene-3,4,9,10-bis(dicarboximide) (tpPDI) covalently linked to a partially deuterated 1,3-bis(diphenylene)- d 16 -2-phenylallyl radical (BDPA- d 16 ) can be coherently manipulated via pulsed dynamic nuclear polarization (DNP) methods to transfer polarization to nuclear spins and back. Under light illumination at 85 K, electron hyperpolarization in BDPA is enhanced 2.1- to 2.4-fold over thermal polarization and lasts for more than 100 ms. By applying nuclear orientation via electron spin-locking (NOVEL) DNP, this optically amplified electron hyperpolarization was successfully transferred to a 1 H nuclear spin within the CR system and efficiently returned to the electron spin for readout via reverse-NOVEL. The NOVEL transfer efficiency of 65% amounts to a 688-fold nuclear spin hyperpolarization of the target nuclear spin, considering the 2.1-fold electron spin hyperpolarization. This reversible coherent manipulation of hyperpolarization transfer highlights the utility of CR systems to initialize and read out nuclear spin states in a disordered matrix at moderate cryogenic temperatures. Coupled with CRs’ environmental compatibility, tunability, and precise state initialization, these results highlight the promising role of nuclear spins in CRs for QIS applications, including quantum sensing and memory.}, archive = {J_JACS}, author = {Hoang M. Le and Joshua S. Straub and Quentin Stern and Asif Equbal and Yunfan Qiu and Matthew D. Krzyaniak and Michael R. Wasielewski and Songi Han}, doi = {10.1021/jacs.5c07862}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35313--35322}, shortjournal = {J. Am. Chem. Soc.}, title = {Coherent control over nuclear hyperpolarization using an optically initializable chromophore-radical system}, volume = {147}, year = {2025}, }
• (2025). Spinel/Rock salt Core/Shell high-entropy oxides for selective CO2 hydrogenation. JACS, 147(39), 35304--35312. (www)

  @article{ , abstract = {High-entropy oxides (HEOs) exhibit exceptional structural stability through configurational entropy maximization, yet their catalytic activity can be inadvertently constrained by the inherent activity–stability trade-off arising from dynamic site regeneration limitations. Here, we present an entropy recombination strategy that designs a spinel/rock salt core/shell mixed-phase HEO catalyst. This catalyst, featuring a spinel-core entropy modulator, achieves thermodynamic equilibrium via compositional entropy exchange, resulting in an ultra-active thin rock salt shell HEO. The catalyst demonstrates superior mass activity (318 μmol CO g cat –1 s –1 at 380 °C) and stability in the reverse water gas shift reaction, surpassing Cu-based and even noble metal-based catalysts. The core/shell architecture facilitates a multicomponent surface, oxygen vacancy generation, and Cu exsolution, accelerating the redox pathway’s rate-determining step via enhanced hydrogen transport. This work represents a breakthrough in HEO structural engineering, with promising advancements in diverse catalytic applications.}, archive = {J_JACS}, author = {Ke Wang and Wooseok Lee and Rui Zhang and Zijian Wang and Yu Zhang and Junseok Moon and Dongho Shin and Megalamane S. Bootharaju and Juan Du and Aibing Chen and Seoin Back and Taeghwan Hyeon and Shuyan Song and Hongjie Zhang and Xiao Wang}, doi = {10.1021/jacs.5c07731}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35304--35312}, shortjournal = {J. Am. Chem. Soc.}, title = {Spinel/Rock salt Core/Shell high-entropy oxides for selective CO2 hydrogenation}, volume = {147}, year = {2025}, }
• (2025). Phase-regulatable synthesis of single-atom alloy nanocages for efficient alkaline hydrogen evolution. JACS, 147(39), 35293--35303. (www)

  @article{ , abstract = {Crystal phase engineering of metal nanocatalysts presents a promising strategy to modulate the catalyst–adsorbate interaction for enhanced catalysis. However, conventional synthetic methods have faced substantial challenges in achieving regulatable crystal phases and lack precise control over catalyst composition at the atomic level, which is detrimental, especially for reactions involving multiple intermediates. Here, we report a facile strategy for simultaneously regulating the crystal phase and composition (Pt single-atom alloying) of ultrathin Ru nanocages (<2 nm in thickness), enabling efficient hydrogen evolution reaction (HER) in alkaline electrolytes. In situ characterizations and theoretical calculations reveal that both the metastable face-centered cubic (fcc) Ru phase and isolated Pt atoms contribute to stabilizing metallic Ru, facilitating Pt–Ru synergy for optimized adsorption of H* and *OH intermediates and accelerated HER kinetics. Consequently, the Pt–Ru fcc single-atom alloy nanocages exhibit impressive alkaline HER performance, with an overpotential as low as 8.5 mV at 10 mA cm –2 , an 18.0-fold enhancement in mass activity relative to commercial Pt/C and commendable stability over 400 h of operation at ampere-level current densities. This work provides insights into the atomic-level design and preparation of metal nanocrystals with unconventional phases for advanced catalysts.}, archive = {J_JACS}, author = {Wenbin Jiang and Song Lin Zhang and Jing Yang and Shengnan Hu and Delong Duan and Jerry Zhi Xiong Heng and Ziyu Wang and Weiwei Yang and Xinyang Liu and Qingdian Yan and Mingsheng Zhang and Wen-Ya Wu and Jingcong Hu and Jiakai Li and Ning Ding and Siew Lang Teo and Chui Yu Chan and Ming Lin and Hong Liu and Xian Jun Loh and Yong-Wei Zhang and Zhaolin Liu and Enyi Ye and Yujie Xiong and Ming Zhao}, doi = {10.1021/jacs.5c06662}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35293--35303}, shortjournal = {J. Am. Chem. Soc.}, title = {Phase-regulatable synthesis of single-atom alloy nanocages for efficient alkaline hydrogen evolution}, volume = {147}, year = {2025}, }
• (2025). Deformable, crack-free, and low-cost NaFeCl4 cathode with highly structural reversibility for stable all-solid-state sodium batteries. JACS, 147(39), 35283--35292. (www)

  @article{ , abstract = {All-solid-state sodium batteries (ASSSBs) with a working voltage of approximately 3.5 V hold great potential for safe, sustainable, and high-energy-density electrochemical energy storage. However, 3.5 V oxide-type cathodes (e.g., NaNi 1/3 Fe 1/3 Mn 1/3 O 2 ) may suffer from interfacial contact loss with solid electrolytes due to their intrinsic rigidity, resulting in irreversible capacity degradation during cycling. Herein, we report a highly deformable chloride cathode, NaFeCl 4 , displaying Young’s modulus of only 1.33 GPa and excellent structural reversibility. Benefiting from the soft lattice, the NaFeCl 4 cathode maintains a crack-free morphology despite significant changes in structural units between tetrahedra [Fe 3+ Cl 4 ] and octahedra [Fe 2+ Cl 6 ] upon repeated Na + insertion/extraction, achieving a high capacity retention of 84.4% over 500 cycles. Moreover, with only 5.2% of the cost of the NaNi 1/3 Fe 1/3 Mn 1/3 O 2 and 3.7% of the cost of Na 3 V 2 (PO 4 ) 3 cathode, NaFeCl 4 can deliver a working voltage of ∼3.45 V vs Na + /Na and energy density of ∼405 Wh kg –1 . This chloride cathode offers new insight into solving the mechanical issues in solid-state systems, guiding future developments of low-cost, stable, and high-voltage cathodes for ASSSBs.}, archive = {J_JACS}, author = {Zi-Wei Wang and Jin-Da Luo and Zhong-Yuan Huang and Wanxia Li and Hao-Yuan Tan and Xiaobin Cheng and Mei-Yu Zhou and Xu-Dong Hao and Chen-Peng Luo and Chuan Wan and Linjun Wang and Yi-Chen Yin and Shuhong Jiao and Hong-Bin Yao}, doi = {10.1021/jacs.5c06106}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35283--35292}, shortjournal = {J. Am. Chem. Soc.}, title = {Deformable, crack-free, and low-cost NaFeCl4 cathode with highly structural reversibility for stable all-solid-state sodium batteries}, volume = {147}, year = {2025}, }
• (2025). Hydrogen activation by a σσ*-carbene through quantum tunneling. JACS, 147(39), 35275--35282. (www)

  @article{ , abstract = {The electronic structure of carbenes arises from the occupation of a σ and a π frontier orbital. While parent methylene possesses a triplet ground state (σ 1 π 1 ), substituents are capable of stabilizing the singlet as the ground state (σ 2 π 0 or σ 0 π 2 ) by altering the frontier orbital energies. Here, we reveal that the 1,2[I]-shift isomer of 2-iodopyridine, the N -iodo Hammick intermediate, features a resonance between its carbene σ and N–I bond σ* orbitals, rendering them frontier orbitals. This singlet carbene is efficiently generated via UV photolysis of 2-iodopyridine in solid neon at 4.4 K and reacts with molecular hydrogen – but not deuterium – via N–I bond cleavage enabled by quantum tunneling. Instanton theory computations demonstrate the preference for a concerted hydrogen addition mechanism at elevated temperatures, while hydrogen atom abstraction dominates below 100 K despite a higher kinetic barrier for this process. Our findings introduce an unprecedented carbene class, unlocking new opportunities for reactivity and electronic structure explorations.}, archive = {J_JACS}, author = {Virinder Bhagat and Jan Meisner and J. Philipp Wagner}, doi = {10.1021/jacs.5c06016}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35275--35282}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen activation by a σσ*-carbene through quantum tunneling}, volume = {147}, year = {2025}, }
• (2025). Dynamic regulation of proton and water transport through an acylhydrazone-based photoresponsive channel. JACS, 147(39), 35264--35274. (www)

  @article{ , abstract = {Proton transport is crucial for cellular energy, and synthetic systems having the ability to control this process offer promising applications in drug development and cancer treatment. Herein we report a unique light-responsive proton/water transport system using self-assembled acylhydrazone-imidazole channels with tunable activity via E – Z isomerization. Three channel-forming molecules with varying alkyl chains were synthesized, namely, 1a (C4), 1b (C8), and 1c (C12). The photoswitching behavior of the molecule was confirmed by UV–vis spectroscopy within the liposome. The crystallographic analysis revealed that the E -isomer forms an H-bonded proton transport pathway mediated by water molecules. Patch clamp assays confirmed proton channel formation for 1a with a transport rate of 2.18 × 10 7 H + /s/channel and high proton selectivity over other ions. Ion transport assays with EYPC-LUVs entrapped with HPTS and NaCl revealed the complete rejection of external cations and anions. The compounds demonstrated significant proton transport when combined with valinomycin, indicating transmembrane proton transport for 1a – c . Upon irradiation at 310 nm, all derivatives showed increased proton transport rates, which subsequently decreased after exposure to 365 nm, confirming the photoresponsive behavior of the system. A similar trend was observed in water transport, where the single-channel permeability of 1a increased from 6.5 × 10 6 to 3.5 × 10 7 water molecules/s/channel upon switching from the E to Z isomers, then decreased to 1.8 × 10 7 after reverting to the E conformer. Molecular simulation confirmed that stable supramolecular porous water crystal patches may form, featuring multivalent water H-bonding to acylhydrazone and imidazole units that serve as water-cluster relays within the channel.}, archive = {J_JACS}, author = {Paras Wanjari and Ioan Stroia and Arie van der Lee and Marc Baaden and Mihail Barboiu}, doi = {10.1021/jacs.5c05942}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35264--35274}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic regulation of proton and water transport through an acylhydrazone-based photoresponsive channel}, volume = {147}, year = {2025}, }
• (2025). Powering molecular motors with light across the rainbow using quantum dots. JACS, 147(39), 35255--35263. (www)

  @article{ , abstract = {Overcrowded alkene-based molecular motors have high potential in building artificial molecular machines, precise drug delivery, and smart responsive materials due to their unidirectional rotation at the molecular scale under UV light. Powering molecular motors with visible light, especially in the low-energy green, yellow, and red regions, has been a significant challenge, limiting their further application. Herein, we report a general and versatile strategy to overcome this challenge and drive molecular motors using low-energy, low-intensity, noncoherent light across the visible spectrum. Our approach is achieved by simply mixing molecular motors with semiconductor colloidal quantum dots (QDs) and a triplet mediator (9-anthracenecarboxylic acid). The size-tunable absorption of QDs can precisely match the desired color for activating the motor. The mechanism of our design relies on the unique property of QDs, which can efficiently sensitize molecular triplets. Through two-step triplet energy transfers, the rotation of the motor can be efficiently activated using low-energy photons. For the first time, we accomplished driving molecular motors at wavelengths beyond 530 nm under low-intensity and noncoherent light. This breakthrough not only expands the capabilities of visible-light-activated molecular systems to operate in a broad wavelength range but also opens numerous opportunities toward controlling dynamic functions while circumventing competing photochemical processes (i.e., photodegradation).}, archive = {J_JACS}, author = {Jiayi Liu and Shuai Zhang and Lin Xi and Jiawei Liu and Yuxin He and Rui Wang and Da-Hui Qu and Ben L. Feringa and Tiegen Liu and Lili Hou}, doi = {10.1021/jacs.5c05548}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35255--35263}, shortjournal = {J. Am. Chem. Soc.}, title = {Powering molecular motors with light across the rainbow using quantum dots}, volume = {147}, year = {2025}, }
• (2025). Locking cascade reaction path of bulk degradation achieves stable unmodified solid electrolyte. JACS, 147(39), 35244--35254. (www)

  @article{ , abstract = {The severe structural degradation of solid electrolytes induced by the complex parasitic reactions associated with cathode materials has hampered the practical application of solid-state batteries. However, the degradation process of solid electrolytes influenced by the cathode is not well understood. Herein, we discover that electrolyte degradation is strongly associated with bulk decomposition, unlike conventional insight into only the interface-catalyzed decomposition. The highly acidic HTFSI produced by the triggering event can induce subsequent Ni dissolution and bulk decomposition of solid electrolytes through cascade reaction of bulk decomposition behavior, leading to a continuous decline in the electrochemical performance of solid-state batteries. By introducing a dissolution-retardant active structure onto the Ni-rich electrode, it mitigates the bulk cascade reaction and maintains the energy density. The designed electrode demonstrated an impressive 84% retention of maximum reversible capacity after 2000 cycles at 2C under 4.3 V. This study opens a new avenue in the design of next-generation long-life batteries.}, archive = {J_JACS}, author = {Qingsong Liu and Yajie Song and Ruoyang Gao and Chuankai Fu and Hanwen An and Jiaxuan Liu and Xue Sun and Shuaifeng Lou and Geping Yin and Biao Deng and Haibo Xue and Lujun Huang and Jiajun Wang}, doi = {10.1021/jacs.5c04945}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35244--35254}, shortjournal = {J. Am. Chem. Soc.}, title = {Locking cascade reaction path of bulk degradation achieves stable unmodified solid electrolyte}, volume = {147}, year = {2025}, }
• (2025). Two-stage machine learning framework for accurate discrimination of isomers and very-similar molecules on surfaces. JACS, 147(39), 35232--35243. (www)

  @article{ , abstract = {The accurate detection and discrimination of on-surface organic isomers and very similar molecules are crucial for monitoring chemical reaction processes and analyzing various reaction mechanisms and molecular properties. Despite its importance, nano- and surface science communities still lack an efficient, robust, precise, and automated detection approach for on-surface isomers and highly similar molecules. Here, we present ReSTOLO, a convolution neural network (CNN)-based framework for precise detection and identification of multiple types of sparsely distributed molecules on surfaces, particularly designed for scanning tunneling microscopy (STM) images containing numerous molecules with analogous features. To address challenges arising from molecular shape and size similarities, we implemented a two-stage framework comprising two CNN models: YOLO v5.m was used for molecular localization, and ResNet-101 for classification. The framework optimally harnesses the advantages of both models by applying a box normalization connection. We demonstrated the framework’s effectiveness by applying it to analyze a surface reaction process involving six molecules with nearly identical STM signatures. The training process employed an STM image database of single molecules augmented with physical and experimental tools constructed using standardized image boxes. This two-stage approach achieved approximately ∼20% improvements in performance metrics, including precision, recall, and accuracy, compared to conventional frameworks. The framework exhibits robust capabilities in automatically and efficiently pinpointing and discriminating between molecular species with similar configurations in complex surface reactions. This automated molecular discriminator represents a significant advance in facilitating STM tip-manipulated chemical reactions on surfaces.}, archive = {J_JACS}, author = {Zixuan Wei and Qigang Zhong and Jinbo Pan and Fang Han Lim and Lifeng Chi and Shixuan Du}, doi = {10.1021/jacs.5c03730}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35232--35243}, shortjournal = {J. Am. Chem. Soc.}, title = {Two-stage machine learning framework for accurate discrimination of isomers and very-similar molecules on surfaces}, volume = {147}, year = {2025}, }
• (2025). One-electron Boron–Carbon triel bonding. JACS, 147(39), 35227--35231. (www)

  @article{ , abstract = {Aiming to interrogate the possibility of heteronuclear B–C one-electron σ-bonding, we have prepared a naphthalene-based platform ([ 5 ] + ) decorated at its peri-positions by a carbenium and a boryl unit separated by a B–C distance of 2.994(4) Å. Reduction of this cationic platform by one electron affords a radical ( 5 • ) with a shortened B–C distance of 2.874(3) Å, suggesting the onset of B–C one-electron bonding. This radical, which was also characterized by EPR spectroscopy, undergoes a second reduction, affording a borate ([ 5 ] − ) with a long, polar covalent B–C bond of 1.793(8) Å. These compounds have been structurally, spectroscopically, and computationally investigated, shedding light on the polarization and weakness of the B–C bond of 5 • , which is best described as a noncovalent one-electron B···C triel bond rather than a covalent one-electron σ-bond.}, archive = {J_JACS}, author = {Paula Castro Castro and Wei-Chun Liu and François P. Gabbaï}, doi = {10.1021/jacs.5c13589}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35227--35231}, shortjournal = {J. Am. Chem. Soc.}, title = {One-electron Boron–Carbon triel bonding}, volume = {147}, year = {2025}, }
• (2025). Room-temperature electrocatalytic dehydrogenation and partial fragmentation of n-alkanes. JACS, 147(39), 35219--35226. (www)

  @article{ , abstract = {Light alkenes are central building blocks in the chemical industry, yet their production from alkanes requires energy-intensive processes that generate substantial CO 2 emissions and suffer from catalyst deactivation and overoxidation. In this work, we demonstrate that alkane dehydrogenation can be accomplished at ambient temperature and pressure by modulating the voltage applied to an electrocatalyst surface. Voltage manipulation provides real-time control over the adsorption and dehydrogenation of alkanes, as well as the potential-driven desorption of dehydrogenated adsorbates. By using a newly developed sensitive gas chromatographic (GC) analysis method, we were able to quantify the formation of 1-butene from n -butane, as well as the formation of a distribution of shorter chain alkanes and alkenes. We show that the product distribution depends on the potential applied during adsorption and is sensitive to both catalyst identity and electrolyte composition. Palladium suppresses C–C bond cleavage relative to platinum, and replacing protons with sodium cations increases 1-butene selectivity by promoting desorption over hydrogenation. To rationalize the observed product distribution, we propose a reaction mechanism supported by grand canonical density functional theory calculations. Together, these results reveal a new pathway for alkane dehydrogenation under ambient conditions and establish time-programmed electrochemical control as a promising tool for manipulating surface-catalyzed transformations of n -alkanes.}, archive = {J_JACS}, author = {Gong Zhang and Lee Fuller and Christine Lucky and Alexander J. Zielinski and Dongfang Cheng and Enner Mendoza and Philippe Sautet and Marcel Schreier}, doi = {10.1021/jacs.5c12806}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35219--35226}, shortjournal = {J. Am. Chem. Soc.}, title = {Room-temperature electrocatalytic dehydrogenation and partial fragmentation of n-alkanes}, volume = {147}, year = {2025}, }
• (2025). Late-stage tryptophan modification of native peptides through photochemical indole-to-quinazoline editing. JACS, 147(39), 35211--35218. (www)

  @article{ , abstract = {Site-specific late-stage modification of native peptides is an appealing strategy for generating analogues of bioactive peptides in an effort- and cost-effective manner. The concept of skeletal editing emerging recently is attractive for developing a new generation of late-stage peptide modification methods. In this work, we developed a facile tryptophan-specific late-stage peptide modification based on photocatalytic indole-to-quinazoline editing. The method showed a broad scope regarding both linear and cyclic peptide substrates and was applied to the modification of commercially available peptide drugs. A mechanism based on singlet oxygen oxidation of tryptophan and the interruption of oxidative indole cleavage by ammonia addition was proposed.}, archive = {J_JACS}, author = {Heng-Hui Li and Yisa Xiao and Han Liu and Xuechen Li}, doi = {10.1021/jacs.5c12511}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35211--35218}, shortjournal = {J. Am. Chem. Soc.}, title = {Late-stage tryptophan modification of native peptides through photochemical indole-to-quinazoline editing}, volume = {147}, year = {2025}, }
• (2025). Palladium-catalyzed asymmetric carbonylation of alkynes to axially chiral carbothioate esters. JACS, 147(39), 35203--35210. (www)

  @article{ , abstract = {Herein, we report a novel palladium-catalyzed asymmetric hydrothioesterification of alkynes under mild conditions, enabling the precise construction of axially chiral carboxylic thioester derivatives with excellent yields, regioselectivity, E / Z selectivity, and enantioselectivity. Disulfides and thiosulfonates were applicable, as well.}, archive = {J_JACS}, author = {Wang Yao and Yang Yuan and Ting Yang and Yong-Gui Zhou and Xiao-Feng Wu}, doi = {10.1021/jacs.5c11864}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35203--35210}, shortjournal = {J. Am. Chem. Soc.}, title = {Palladium-catalyzed asymmetric carbonylation of alkynes to axially chiral carbothioate esters}, volume = {147}, year = {2025}, }
• (2025). Cytochrome p450 induction through the efficient photoinduced release of a pyridine-substituted agent from Ru(II). JACS, 147(39), 35198--35202. (www)

  @article{ , abstract = {We report the first example of using photoinduced ligand release from a Ru(II) complex for light-triggered cytochrome P450 (CYP) induction. CYPs are pivotal enzymes in biosynthesis and drug metabolism, and their induction can be leveraged for therapeutics and biochemical research. We show the activation of a CYP1A1 with visible light through the efficient photorelease of an aryl hydrocarbon receptor (AHR; 1 ) agonist with a quantum yield, Φ 500 , of 0.16(1) with λ irr = 500 nm in [Ru(tpy)(Me 2 bpy)( 1 )] 2+ (tpy = 2,2′:6′,2″-terpyridine, Me 2 bpy = 6,6′-dimethyl-2,2′-bipyridine). This value is consistent with that previously reported for pyridine (py) exchange in the analogous [Ru(tpy)(Me 2 bpy)(py)] 2+ complex, Φ 500 = 0.16(1), which is driven by steric effects. In contrast to [Ru(tpy)(bpy)(py)] 2+ (bpy = 2,2′-bipyridine), with Φ 500 < 10 –4 , the ligand photodissociation in [Ru(tpy)(bpy)( 1 )] 2+ proceeds with Φ 500 = 0.015(1), at least 2 orders of magnitude more efficiently. Similarly, [Ru(tpy)(biq)( 1 )] 2+ ( 4 ; biq = 2,2′-biquinoline) undergoes photoinduced exchange of 1 with CH 3 CN solvent with Φ 500 = 0.064(3), more efficiently than [Ru(tpy)(biq)(py)] 2+ with Φ 500 = 0.03. Through experiments and calculations, we show the involvement of intraligand charge transfer (ILCT) within the leaving ligand in an unprecedented mechanism for ligand photodissociation from Ru(II). Chemical tools based on these findings hold the promise of advancing research on tissue-specific CYP activity by enabling precise spatiotemporal control. Moreover, these compounds may pave the way for the development of highly specific and light-activated pharmaceuticals that enhance the synergy with existing drugs.}, archive = {J_JACS}, author = {Kelli Hummel and Sayak Gupta and Alexia Marques Silva and Santana P. Garcia and Donna H. Odhiambo and Dylan Sygit and Juan Cai and Cassandra Ward and Thomas Kocarek and Alexander Yu. Sokolov and Claudia Turro and Jeremy J. Kodanko}, doi = {10.1021/jacs.5c11695}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35198--35202}, shortjournal = {J. Am. Chem. Soc.}, title = {Cytochrome p450 induction through the efficient photoinduced release of a pyridine-substituted agent from Ru(II)}, volume = {147}, year = {2025}, }
• (2025). Stable isotope labeling of pyrimidines using a Deconstruction–Reconstruction strategy. JACS, 147(39), 35192--35197. (www)

  @article{ , abstract = {Incorporating stable isotopes into bioactive molecules is crucial in pharmaceutical development, particularly for metabolic studies where higher mass isotopologs of candidate compounds are required. Here we present an isotope exchange method for synthesizing isotopically enriched pyrimidines. By deconstructing pyrimidines into vinamidinium salts and reconstructing them with deuterium, 13 C, and 15 N-enriched amidines, we achieve high isotopic enrichment across various substitution patterns, including complex drug-like pyrimidine derivatives. The process involves a Tf 2 O-mediated ring-opening and ring-closing sequence to form a pyrimidinium ion, followed by cleavage to the vinamidinium salt with pyrrolidine. Cyclization with labeled amidines under basic conditions then forms the labeled pyrimidine. Additionally, we deuterated the 5-position of pyrimidines using this approach to offer further versatility in generating higher mass isotopologs.}, archive = {J_JACS}, author = {Benjamin J. H. Uhlenbruck and Andrew McNally}, doi = {10.1021/jacs.5c09719}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35192--35197}, shortjournal = {J. Am. Chem. Soc.}, title = {Stable isotope labeling of pyrimidines using a Deconstruction–Reconstruction strategy}, volume = {147}, year = {2025}, }
• (2025). Mo-catalyzed asymmetric allylic alkylation enabling the construction of highly enantioenriched 1,4-dicarbonyl scaffolds. JACS, 147(39), 35185--35191. (www)

  @article{ , abstract = {Herein, we report a Mo-catalyzed allylic alkylation that couples malonate nucleophiles with linear, trisubstituted allylic electrophiles, followed by a rapid ozonolysis. The process delivers 1,4-dicarbonyl compounds containing an α-quaternary aldehyde motif with excellent enantioselectivity. This constitutes the first example of a Mo-catalyzed asymmetric allylic alkylation to form an electrophile-derived all-carbon quaternary stereocenter. The reactivity and stereoselectivity of the process was enabled by the invention of ShabyDACH , a novel C 1 -symmetric diaminocyclohexane (DACH) pyridyl ligand. The utility of this method was demonstrated through a series of diverse synthetic transformations.}, archive = {J_JACS}, author = {Chloe S. Cerione and Farbod A. Moghadam and Brian M. Stoltz}, doi = {10.1021/jacs.5c09250}, journal = {Journal of the American Chemical Society}, month = {10}, number = {39}, pages = {35185--35191}, shortjournal = {J. Am. Chem. Soc.}, title = {Mo-catalyzed asymmetric allylic alkylation enabling the construction of highly enantioenriched 1,4-dicarbonyl scaffolds}, volume = {147}, year = {2025}, }
• (2025). Correction to “NIR-II photoacoustic-active DNA origami nanoantenna for early diagnosis and smart therapy of acute kidney injury”. JACS, 147(38), 35183--35184. (www)

  @article{ , archive = {J_JACS}, author = {Yanan Xu and Qian Zhang and Runzhi Chen and Haiting Cao and Jie Tang and Yuqi Wu and Xing Lu and Binbin Chu and Bin Song and Houyu Wang and Yao He}, doi = {10.1021/jacs.5c14095}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35183--35184}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “NIR-II photoacoustic-active DNA origami nanoantenna for early diagnosis and smart therapy of acute kidney injury”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Exogenous metal cations in the synthesis of CsPbBr3 nanocrystals and their interplay with tertiary amines”. JACS, 147(38), 35182. (www)

  @article{ , archive = {J_JACS}, author = {Zhanzhao Li and Luca Goldoni and Ye Wu and Muhammad Imran and Yurii P. Ivanov and Giorgio Divitini and Juliette Zito and Iyyappa Rajan Panneerselvam and Dmitry Baranov and Ivan Infante and Luca De Trizio and Liberato Manna}, doi = {10.1021/jacs.4c15032}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35182}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Exogenous metal cations in the synthesis of CsPbBr3 nanocrystals and their interplay with tertiary amines”}, volume = {147}, year = {2025}, }
• (2025). Type-I supramolecular photosensitizer enables GSH depletion by hydrogen atom transfer. JACS, 147(38), 35172--35181. (www)

  @article{ , abstract = {Photodynamic therapy (PDT) induces oxidative stress that triggers a compensatory upregulation of intracellular glutathione (GSH), thereby diminishing PDT efficacy. The simultaneous generation of reactive oxygen species and depletion of GSH holds promise for amplifying oxidative damage and enhancing therapeutic outcomes yet remains a challenge. In this work, we present a Type-I supramolecular photosensitizer designed to deplete GSH through a hydrogen atom transfer mechanism while concurrently generating superoxide radicals. This photosensitizer is constructed through the supramolecular host–guest assembly of cyclodextrin-conjugated N -hydroxyphthalimide ( CD-NHPI ) and a BODIPY-based photosensitizer ( BDP ). Upon light irradiation, electron transfer from CD-NHPI to BDP forms a radical ion pair: CD-NHPI +• and BDP –• . CD-NHPI +• undergoes deprotonation to yield an oxygen-centered radical that oxidizes GSH by directly abstracts hydrogen atoms from GSH, while BDP –• concurrently reduces molecular oxygen to superoxide radicals. As a result, this photosensitizer exhibits remarkable photocytotoxicity and significant antitumor efficacy in mouse models. This work offers a strategy for synergistically photocatalytic oxidation of antioxidants and generation of reactive oxygen species for PDT.}, archive = {J_JACS}, author = {Yi Lin and Li-Ya Niu and Kun-Xu Teng and Qing-Zheng Yang}, doi = {10.1021/jacs.5c14257}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35172--35181}, shortjournal = {J. Am. Chem. Soc.}, title = {Type-I supramolecular photosensitizer enables GSH depletion by hydrogen atom transfer}, volume = {147}, year = {2025}, }
• (2025). A dinitrogen complex without donor ligands: Isolation and characterization of a [Mn(CO)5(η1-n2)]+ salt. JACS, 147(38), 35164--35171. (www)

  @article{ , abstract = {Dinitrogen complexes are intermediates in nitrogen fixation. Until now, all isolated molecular dinitrogen complexes have relied on ancillary ligands that are net electron donors, yielding N 2 ligands carrying a clear negative partial charge. Here, we present the synthesis, isolation, and characterization of the complex salt [Mn(CO) 5 (η 1 -N 2 )] + [F(Al(OR F ) 3 ) 2 ] − (R F = C(CF 3 ) 3 ) that resulted from the oxidation of Mn 2 (CO) 10 under a dinitrogen atmosphere in pentafluorobenzene solvent. The IR/Raman spectra reveal a high N 2 frequency of 2301/2303 cm –1 close to free N 2 gas (2330 cm –1 ) that indicates little π-back-donation. QTAIM and CD-NOCV analyses show that the carbonyl ligands act as net acceptor ligands that induce the formation of an inversely polarized dinitrogen ligand with a +0.2 charge on the terminal atom that holds the potential to be susceptible to nucleophilic attack.}, archive = {J_JACS}, author = {Malte Sellin and James D. Watson and Julia Fischer and Manuel Schmitt and Graham E. Ball and Leslie D. Field and Ingo Krossing}, doi = {10.1021/jacs.5c13214}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35164--35171}, shortjournal = {J. Am. Chem. Soc.}, title = {A dinitrogen complex without donor ligands: Isolation and characterization of a [Mn(CO)5(η1-n2)]+ salt}, volume = {147}, year = {2025}, }
• (2025). Macromolecular diamidobenzimidazole conjugates can activate stimulator of interferon genes. JACS, 147(38), 35149--35163. (www)

  @article{ , abstract = {A promising class of stimulator of interferon genes (STING) agonists is the non-nucleotide, small molecule, dimeric amidobenzimidazoles (diABZI), which have recently been incorporated into polymer- and antibody-drug conjugates to improve pharmacokinetics and modulate biodistribution for disease-specific applications. These approaches have leveraged diABZI variants functionalized at the 7-position of the benzimidazole for conjugation and tunable drug release from carriers. However, since this position does not interact with STING and is exposed from the binding pocket when bound in an “open lid” configuration, we sought to evaluate the activity of macromolecular diABZI conjugates that lack stimuli-responsive release and are instead conjugated to polymers via a stable amide linker. By synthesizing stable mPEG-diABZI conjugates and N , N -dimethylacrylamide (DMA) homopolymers from a diABZI-functionalized reversible addition–fragmentation chain-transfer (RAFT) agent, we found that these conjugates could activate STING in vitro with similar kinetics to highly potent diABZI analogues. Our data indicate that although diABZI-DMA conjugates enter cells via endocytosis, they can still colocalize with the ER, suggesting that intracellular trafficking processes can promote the delivery of endocytosed macromolecular diABZI compounds to STING. Furthermore, we demonstrated the in vivo activity of these macromolecular diABZI platforms, which inhibited tumor growth to a similar extent as small molecule variants. In conclusion, we have described new chemical strategies for the synthesis of stable macromolecular diABZI conjugates with unexpected immunostimulatory activity─findings that have potential implications for the design of polymer-diABZI conjugates and further motivate investigation of endosomal and intracellular trafficking as an alternative route for STING activation.}, archive = {J_JACS}, author = {Karan Arora and Taylor L. Sheehy and Jacob A. Schulman and Jack R. Loken and Zachary Lehmann and Blaise R. Kimmel and Caitlin McAtee and Vijaya Bharti and Payton T. Stone and Alissa M. Weaver and Matthew Tyska and Rakesh Kumar Pathak and John T. Wilson}, doi = {10.1021/jacs.5c13195}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35149--35163}, shortjournal = {J. Am. Chem. Soc.}, title = {Macromolecular diamidobenzimidazole conjugates can activate stimulator of interferon genes}, volume = {147}, year = {2025}, }
• (2025). Deciphering the synchronization of alternating current frequency with the nickel catalytic cycle in selective C–N cross-coupling. JACS, 147(38), 35139--35148. (www)

  @article{ , abstract = {Alternating current (AC) electrolysis offers a promising strategy for modulating redox states in metal-catalyzed reactions, yet its mechanistic basis remains poorly understood. Here, we uncover how AC frequency synchronizes with key steps in a Ni-catalyzed cross-coupling cycle to control product selectivity between C–N and C–C coupling. We show that optimal C–N selectivity arises from minimizing the exposure of a key intermediate, Ni II (Ar)Br, to reducing conditions that otherwise promote off-cycle Ni I species and undesired C–C homocoupling. By developing a simple cyclic voltammetry-based method, we accurately predict the optimal AC frequency across diverse aryl bromides and amines, eliminating the need for time-consuming trial-and-error reaction optimization. The predicted values align well with experimentally determined frequencies, validating the approach. This work establishes a mechanistic foundation for integrating AC waveform control into metal catalysis and highlights its potential for advancing selective electrochemical transformations in synthetic and medicinal chemistry.}, archive = {J_JACS}, author = {Atanu Hazra and Marisa Organiscak and Long Luo}, doi = {10.1021/jacs.5c13155}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35139--35148}, shortjournal = {J. Am. Chem. Soc.}, title = {Deciphering the synchronization of alternating current frequency with the nickel catalytic cycle in selective C–N cross-coupling}, volume = {147}, year = {2025}, }
• (2025). Ultrastable copper cluster enables highly site-selective and chemoselective carbocation C(sp3)–H and C(sp2)–H bonds functionalization. JACS, 147(38), 35128--35138. (www)

  @article{ , abstract = {The C–H functionalization represents a universal and important method for constructing new C–C bonds by carrying out reactions directly on inert C–H bonds. The major challenges are to control the site-selectivity and chemoselectivity because most complex organic compounds have many similar C–H bonds or different functional groups, such as a C═C bond or O–H bond. Here, we develop a versatile copper cluster (Cu 3 NC (NHC) ) with high stability and dynamic catalytic sites. Unlike traditional copper catalysts (which activate diazoesters to form intermediate Cu-carbenes, catalyzing cyclopropanation and O–H insertion), the Cu 3 NC (NHC) , as a versatile catalyst, has resolved the site-selective and chemoselective challenges of the C(sp 3 )–H bond and C(sp 2 )–H bond functionalization by forming Cu 3 NC (NHC) stabilized carbocations. Moreover, turnover number (TON) values of the C–H functionalization are elevated to a whole new level (up to 123,200). Mechanistic studies and density functional theory (DFT) demonstrate that site-selectivity and chemoselectivity derive from the energy differences among these key intermediates. The diverse applicability of Cu 3 NC (NHC) provides a generic platform for optimizing chemical reactions and fostering their innovative development, thereby promoting the rapid development of the intersection between cluster chemistry and organic chemistry.}, archive = {J_JACS}, author = {Teng Jia and Cai-Fang Sun and Miao-Miao Zhang and Jie Ai and Yi-Xin Li and Zheng Wang and Yu Lan and Xin-Qi Hao and Shuang-Quan Zang}, doi = {10.1021/jacs.5c13006}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35128--35138}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrastable copper cluster enables highly site-selective and chemoselective carbocation C(sp3)–H and C(sp2)–H bonds functionalization}, volume = {147}, year = {2025}, }
• (2025). Alkali metal cations induce pseudo-outer-sphere oxygen reduction reaction mechanism in electrolyte-catalyst synergy. JACS, 147(38), 35118--35127. (www)

  @article{ , abstract = {Alkali metal cations (AMCs) are known to play pivotal roles in modulating electrocatalytic systems, significantly affecting the oxygen reduction reaction (ORR). While their macroscopic effects are well recognized, the molecular-level interactions of AMCs at the electrochemical interface remain poorly understood. Here, using constant-potential ab initio molecular dynamics simulations, we uncover that AMCs (Li + , Na + , and K + ) act as molecular switches that trigger a pseudo-outer-sphere ORR mechanism. In this mechanism, surface-adsorbed water molecules serve as dynamic bridges that simultaneously mediate interfacial electron transfer and proton transport. As a result, the reactive zone extends beyond the catalyst surface, overcoming the spatial constraints of traditional inner-sphere pathways. Crucially, H 2 O 2 is generated directly within the outer Helmholtz plane via reduction of AMC-O 2 complexes, effectively bypassing the catalyst surface and avoiding over-reduction. This results in significantly enhanced selectivity and production efficiency. Our results demonstrate that AMCs activate interfacial coupling to unlock alternative reaction pathways, while concurrently elucidating the critical yet often overlooked role of solute molecules in governing electrocatalytic behavior. This work establishes a framework for the understanding of electrolyte-catalyst coupling and provides principles for designing next-generation electrochemical systems.}, archive = {J_JACS}, author = {Yumiao Tian and Pengfei Hou and Yuanyuan Zhou and Quan Li}, doi = {10.1021/jacs.5c12947}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35118--35127}, shortjournal = {J. Am. Chem. Soc.}, title = {Alkali metal cations induce pseudo-outer-sphere oxygen reduction reaction mechanism in electrolyte-catalyst synergy}, volume = {147}, year = {2025}, }
• (2025). Mo atom rearrangement drives layer-dependent reactivity in two-dimensional MoS2. JACS, 147(38), 35109--35117. (www)

  @article{ , abstract = {Two-dimensional (2D) materials offer a valuable platform for manipulating and studying chemical reactions at the atomic level, owing to the ease of controlling their microscopic structure at the nanometer scale. While extensive research has been conducted on the structure-dependent chemical activity of 2D materials, the influence of structural transformation during the reaction has remained largely unexplored. In this work, we report the layer-dependent chemical reactivity of MoS 2 during a nitridation atomic substitution reaction and attribute it to the rearrangement of Mo atoms. Our results show that the chemical reactivity of MoS 2 decreases as the number of layers is reduced in the few-layer regime. In particular, monolayer MoS 2 exhibits significantly lower reactivity compared with its few-layer and multilayer counterparts. Atomic-resolution transmission electron microscopy (TEM) reveals that MoN nanonetworks form as reaction products from monolayer and bilayer MoS 2 , with the continuity of the MoN crystals increasing with layer number, consistent with the local conductivity mapping data. The layer-dependent reactivity is attributed to the relative stability of the hypothetically formed MoN phase, which retains the number of Mo atomic layers present in the precursor. Specifically, the low chemical reactivity of monolayer MoS 2 is attributed to the high energy cost associated with Mo atom diffusion and migration necessary to form multilayer Mo lattices in the thermodynamically stable MoN phase. This study underscores the critical role of lattice rearrangement in governing chemical reactivity and highlights the potential of 2D materials as versatile platforms for advancing the understanding of materials chemistry at the atomic scale.}, archive = {J_JACS}, author = {Zifan Wang and Jiaxuan Wen and Tina Mihm and Shaopeng Feng and Kelvin Huang and Jing Tang and Tianshu Li and Liangbo Liang and Sahar Sharifzadeh and Keji Lai and Xi Ling}, doi = {10.1021/jacs.5c12760}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35109--35117}, shortjournal = {J. Am. Chem. Soc.}, title = {Mo atom rearrangement drives layer-dependent reactivity in two-dimensional MoS2}, volume = {147}, year = {2025}, }
• (2025). Photofunctionalization of light alkanes by FeOx/BCN at 12 °C. JACS, 147(38), 35098--35108. (www)

  @article{ , abstract = {The activation of methane and other gaseous hydrocarbons at low temperature remains a substantial challenge for the chemistry community. Here, we report an anaerobic photosystem based on crystalline borocarbonitride (BCN) supported Fe–O nanoclusters, which can selectively functionalize C–H bonds of methane, ethane, and higher alkanes to value-added organic chemicals at 12 °C. Scanning transmission electron microscopy and X-ray absorption spectroscopy corroborated the ultrafine FeOOH and Fe 3 O 4 species in Fe–O clusters, which enhanced the interfacial charge transfer/separation of BCN as well as the chemisorption of methane. Mechanism studies with in situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory calculations unveiled methane bonding and polarization on the Lewis acid–base sites of terminal iron hydroxyl, essentially lowering the energy barriers of C–H activation. Catalyzed in tandem with chlorine radical initiated by BCN, C–H bond homolysis of methane, ethane, and higher alkanes proceeded smoothly, affording amination, alkylation, and arylation products in a manner of broad substrate scope (36 examples). This study offers a promising pathway of heterogeneous photocatalysis for the sustainable transformation of natural gases with minimized energy consumption and high efficiency.}, archive = {J_JACS}, author = {Tao Yuan and Xuanzhe Mei and Kunlong Liu and Yuanxing Fang and Jiajia Cheng and Meifang Zheng and Xinchen Wang}, doi = {10.1021/jacs.5c12625}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35098--35108}, shortjournal = {J. Am. Chem. Soc.}, title = {Photofunctionalization of light alkanes by FeOx/BCN at 12 °C}, volume = {147}, year = {2025}, }
• (2025). Exploring phage peptide scaffolds: Tyrosinase-mediated cyclization for selective generation of bioactive cyclic peptides. JACS, 147(38), 35090--35097. (www)

  @article{ , abstract = {Phage display is an ideal platform for selecting peptide hits and offers a diverse array of cyclic binders with high affinity. While many recently developed phage display platforms incorporate chemical strategies, the vast majority of these are detrimental to the phage life cycle due to cross-reactivity with the capsid protein. In contrast, enzyme catalysis, which combines high efficiency and biocompatibility, offers a promising approach for phage-based cyclic peptide display. However, enzyme-mediated cyclization approaches remain underexplored. Here, we present a tyrosinase-mediated phage display platform that enables one-step cyclization via o -quinone-cysteine coupling, which is a simple and efficient strategy that does not compromise phage infectivity. Importantly, the catalytic property of tyrosinase is highly selective and spatially constrained, allowing it to bypass native tyrosine residues in the phage and selectively recognize only the engineered tyrosine residues. Using this platform, we constructed a macrocyclic peptide library that facilitated the discovery of macrocyclic peptide inhibitors targeting therapeutically relevant proteins. Notably, the cyclic peptide ACI1 demonstrated potent inhibition of PIP4K2A kinase activity with an IC 50 value of 0.93 ± 0.05 μM, while ACP1 effectively inhibited the dephosphorylation activity of PTP1B with an IC 50 of 1.06 ± 0.25 μM. The generality and efficiency of this strategy highlight its potential as a valuable tool for the development of bioactive cyclic peptides.}, archive = {J_JACS}, author = {Li-Wen Bai and Peng Cheng and Ting Dan and Hua Xiang and Xiao-Qin Yang and Yi-Fei Chen and Shu-Sen Li and Zheng-Hui Li and Jin-Ming Gao and Xinxiang Lei}, doi = {10.1021/jacs.5c12291}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35090--35097}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploring phage peptide scaffolds: Tyrosinase-mediated cyclization for selective generation of bioactive cyclic peptides}, volume = {147}, year = {2025}, }
• (2025). Five-membered [C5O5]2– rings as birefringence-active genes for ultrabirefringent crystals. JACS, 147(38), 35081--35089. (www)

  @article{ , abstract = {Birefringent crystals are a vital class of optoelectronic materials capable of modulating and detecting the polarization state of light. The pursuit of high-performance birefringent materials has largely focused on incorporating functional units with strong polarization anisotropy and favorable alignment. In this work, we introduce a novel birefringence-active group (BAG), the five-membered ring [C 5 O 5 ] 2– , and demonstrate its potential by synthesizing four alkali metal croconate crystals: Na 2 C 5 O 5 ·2H 2 O ( NNCO·2H 2 O ), Na 2 C 5 O 5 ·3H 2 O ( NNCO·3H 2 O ), NaCsC 5 O 5 ( NCCO ), and NaRbC 5 O 5 ( NRCO ). Remarkably, NNCO·2H 2 O and NNCO·3H 2 O exhibit ultrahigh experimental birefringence values of Δ n exp(010) = 1.062 and Δ n exp(01̅1) = 0.893 at 546 nm, respectively. These exceptional values arise from the highly anisotropic nature and well-aligned arrangement of the [C 5 O 5 ] 2– units, combined with their moderate spatial density. In addition, the hydrated compounds feature wider bandgaps (2.67 and 2.55 eV) than their anhydrous analogues NCCO (2.24 eV) and NRCO (2.14 eV), thereby achieving a desirable balance between large birefringence and moderate bandgap─key criteria for optical applications. First-principles calculations and quantum chemical analysis confirm that the [C 5 O 5 ] 2– unit is the primary contributor to the observed optical anisotropy. Notably, NNCO·2H 2 O , NNCO·3H 2 O , and NCCO readily form high-quality, centimeter-scale single crystals via a simple aqueous evaporation method, with NCCO reaching up to 10 × 9 × 2.5 mm 3 . This work establishes [C 5 O 5 ] 2– as a new and effective structural motif for designing advanced birefringent materials, offering both outstanding optical performance and practical crystal growth capabilities.}, archive = {J_JACS}, author = {Jiachen Lu and Yang Li and Kang Min Ok}, doi = {10.1021/jacs.5c12128}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35081--35089}, shortjournal = {J. Am. Chem. Soc.}, title = {Five-membered [C5O5]2– rings as birefringence-active genes for ultrabirefringent crystals}, volume = {147}, year = {2025}, }
• (2025). Efficient mn2+ doping in non-stoichiometric cesium lead bromide perovskite quantum dots. JACS, 147(38), 35069--35080. (www)

  @article{ , abstract = {Doping magnetic transition metal ions (e.g., Mn 2+ ) into colloidal quantum dots endows novel optical and magnetic properties to the host materials. CsPbBr 3 quantum dots (QDs) are emerging light-emitting materials with high structural and chemical flexibility in the visible spectral regime. However, efficiently doping Mn 2+ ions in CsPbBr 3 QDs remains challenging, especially when size confinement and ensemble uniformity are needed for understanding the underexplored exciton-dopant exchange interaction. Here, we introduce a doping mechanism based on electrostatic surface Mn 2+ adsorption that enables efficient Mn 2+ incorporation in strongly confined CsPbBr 3 QDs. The resultant QDs are found to have a Cs-deficient stoichiometry compared to their undoped counterparts. A redox reaction-based purification method was developed to remove Mn 2+ cations that are tightly adsorbed on the surface to determine the concentration of lattice-incorporated Mn 2+ . Our synthesis enables a Mn 2+ doping/alloying concentration of up to ∼44% with a Mn 2+ photoluminescence efficiency exceeding 90%. This allows for the determination of the intrinsic exciton-to-dopant energy transfer rate.}, archive = {J_JACS}, author = {Lamia Hidayatova and Chenjia Mi and Novruz G. Akhmedov and Yuan Liu and Arjumand K. Shafiq and Hadi Afshari and Nishya Mohamed-Raseek and Dilruba A. Popy and Sisi Xiang and Yi-Chen Chen and Bayram Saparov and John W. Peters and Dmitri V. Talapin and Bin Chen and Madalina Furis and Evan R. Glaser and Yitong Dong}, doi = {10.1021/jacs.5c12086}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35069--35080}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient mn2+ doping in non-stoichiometric cesium lead bromide perovskite quantum dots}, volume = {147}, year = {2025}, }
• (2025). Optimizing the synthesis of deuterated isotopomers and isotopologues of cyclohexene using molecular rotational resonance spectroscopy. JACS, 147(38), 35055--35068. (www)

  @article{ , abstract = {Despite advances in reactions such as hydrogen isotope exchange (HIE) and reductive deuteration, achieving controlled and selective deuteration remains challenging. Moreover, the difficulty of developing successful deuteration platforms is compounded by a lack of means to assess the stereoisotopic purity of deuterated products. We previously reported a highly regio- and stereoselective approach for generating semideuterated cyclohexenes via tandem protonation (H + /D + ) and reduction (H – /D – ) sequences of a dihapto-coordinate tungsten-benzene complex. While NMR and HRMS analyses suggested successful deuterium incorporation, molecular rotational resonance (MRR) spectroscopy identified numerous over-, under-, and mis-deuteration impurities. At the time of publication, these impurities were attributed to H/D scrambling that could occur during thermolysis of the tungsten-bound cyclohexene ligand prior to MRR analysis. In this work, we describe the analysis of semideuterated cyclohexenes using MRR spectroscopy with an improved thermolysis apparatus that eliminates deuterium scrambling during analysis. Quantitative analysis of both racemic and enantiopure samples enables the optimization of deuteration conditions by providing multiple mechanistic insights into the formation of impurities.}, archive = {J_JACS}, author = {Justin T. Weatherford-Pratt and Jacob A. Smith and Martin S. Holdren and Haley N. Scolati and Reilly E. Sonstrom and Megan N. Ericson and Sarah E. Brewster and Alvin Q. Meng and Diane A. Dickie and Brooks H. Pate and W. Dean Harman}, doi = {10.1021/jacs.5c12001}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35055--35068}, shortjournal = {J. Am. Chem. Soc.}, title = {Optimizing the synthesis of deuterated isotopomers and isotopologues of cyclohexene using molecular rotational resonance spectroscopy}, volume = {147}, year = {2025}, }
• (2025). De novo chemoenzymatic assembly of complex sulfated N-glycans to comprehensively profile the ligand binding of human siglecs. JACS, 147(38), 35042--35054. (www)

  @article{ , abstract = {The Siglec family represents one of the major classes of human glycan-binding proteins (GBPs) that regulates a broad range of biological processes through engagement with their glycan ligands. Human Siglecs have attracted a great deal of attention in recent years, as they are regarded as new immune checkpoints. The disruption of Siglec–sialoglycan interactions represents a promising next-generation strategy for cancer immunotherapy. In addition to the sialic acid moiety, it has been well established that glycan sulfation plays an essential role in the ligand binding of human Siglecs. Therefore, there is an urgent need to thoroughly understand the subtle differences in the glycan scaffolds and sulfation patterns that govern Siglec binding. N -Glycans are the most abundant class of glycans occurring in living cells, while sulfation is the most widespread postglycosylation modification of N -glycans, indicating that sulfated N -glycans serve as key ligands for human Siglecs. However, the synthetic generation of large libraries of complex sulfated N -glycans is impractical as sulfation introduces additional challenges to the already demanding process of N -glycan synthesis. Herein, we describe a de novo chemoenzymatic approach for the efficient preparation of complex sulfated N -glycans. Using this approach, a comprehensive 72-member library of sulfated N -glycans encompassing the most typical complex structures was successfully prepared. With the well-defined library (comprising 72 sulfated N -glycans and 26 nonsulfated controls), we systematically investigated the binding activities of all human Siglecs. Beyond the synthetic breakthroughs, this work provides the most comprehensive profile to date for understanding how sulfation patterns and N -glycan scaffolds affect Siglec ligand binding, which will have an immediate impact on the development of Siglec-targeted immunotherapy strategies.}, archive = {J_JACS}, author = {Shengzhou Ma and Jiabin Zhang and Fangyu Wei and Xiao Tian and Yinping Tian and Liuqing Wen}, doi = {10.1021/jacs.5c11949}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35042--35054}, shortjournal = {J. Am. Chem. Soc.}, title = {De novo chemoenzymatic assembly of complex sulfated N-glycans to comprehensively profile the ligand binding of human siglecs}, volume = {147}, year = {2025}, }
• (2025). Electrophilic cyanation with carbon isotopes: A versatile access to 13C, 14C, and 11C aryl nitriles from labeled NCTS. JACS, 147(38), 35031--35041. (www)

  @article{ , abstract = {In this work, we provide mild and direct access to carbon-labeled electrophilic cyanating agents suitable for both radioactive 14 C and 11 C. Carbon isotopes are at the foundation of applications in life science such as nuclear medicine and are essential for the determination of pharmacokinetic and dynamic profiles of new pharmaceuticals. While cyanations are key synthetic transformations in the arsenal of radiochemists, access to such precious building blocks still poses a severe challenge. Here, we report a two-step procedure that utilized [ 14 C]CO 2 and [ 11 C]CO 2 as primary isotope sources and takes place under exceptionally mild conditions compared to those of the state of the art. The utility of this procedure was demonstrated with the labeling of a panel of nitriles using traditional reactions as well as with unprecedented examples of carbon-isotope exchange.}, archive = {J_JACS}, author = {Maxime Molins and Alexandre Hauwelle and Louise Fogel and Quentin Lemesre and Olivier Loreau and Frédéric Taran and Fabien Caillé and Davide Audisio}, doi = {10.1021/jacs.5c11876}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35031--35041}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrophilic cyanation with carbon isotopes: A versatile access to 13C, 14C, and 11C aryl nitriles from labeled NCTS}, volume = {147}, year = {2025}, }
• (2025). Molecularly tuned carbon dots for visible-light-driven boryl radical generation via enhanced hole transfer. JACS, 147(38), 35019--35030. (www)

  @article{ , abstract = {Carbon-based, metal-free photocatalysts are emerging as sustainable alternatives to transition-metal-based systems due to their tunability, abundance, and environmental friendliness. Among them, carbon dots (CDs) offer unique opportunities in visible-light-driven transformations owing to their excellent photostability, electronic tunability, and surface functionalization capacity. However, the development of structurally defined CD-based catalysts that enable efficient hole transfer, a broad substrate scope, and scalability remains a key challenge. Herein, we report the first bifunctional, quasi-homogeneous CD-based photocatalytic platform that combines visible-light absorption with cooperative hydrogen atom transfer (HAT) catalysis. Using a covalent molecular design, thiol groups were precisely anchored onto the CD surface, enabling fast and efficient hole transfer and promoting the reductive quenching of the excited CD to produce thiyl radicals. This molecular tuning facilitates efficient boryl radical generation via HAT of N-heterocyclic carbene–borane (NHC-BH 3 ), and enables broad substrate applicability on boration of naphthalenes, indoles, alkenes, and polyfluoroarenes. The method is readily scalable, performing smoothly under both gram-scale batch and continuous flow conditions. Detailed mechanistic studies reveal that the thiol groups accelerate excited-state charge separation and act as hole acceptors, highlighting a hole-transfer-driven catalytic mechanism. This work demonstrates how molecularly tailored CDs can serve as multifunctional, metal-free photocatalysts and provides a new blueprint for advancing dual catalytic organic transformations under visible light.}, archive = {J_JACS}, author = {Wengang Xu and Qihang Xu and Mingrui Liu and Haibo Shan and Xinze Bi and Qiao Zhang and Jingshan Ai and Qiong Liu and Mingbo Wu}, doi = {10.1021/jacs.5c11870}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35019--35030}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecularly tuned carbon dots for visible-light-driven boryl radical generation via enhanced hole transfer}, volume = {147}, year = {2025}, }
• (2025). Ruthenium-mediated N-arylation for DNA-encoded libraries. JACS, 147(38), 35011--35018. (www)

  @article{ , abstract = {C–N cross coupling reactions are widely employed for the construction of carbon–nitrogen bonds. However, control of chemoselectivity in the presence of the amino functionality in oligonucleotides remains a challenge. Here, we report the development of a new ruthenium reagent that enables the chemoselective N -arylation of amine–DNA conjugates with distinct chemoselectivity when compared to conventional palladium-based C–N bond-forming catalysts. The ruthenium reagent activates commercially available haloarenes in situ via η 6 π-arene coordination for subsequent S N Ar with the amine. The method is compatible with various commercially available haloarenes and aliphatic amines, and the reaction proceeds under mild conditions.}, archive = {J_JACS}, author = {Suraj Kanoo and Eduardo de Pedro Beato and Tim Schulte and Lara Vogelsang and Luca Torkowski and Felix Waldbach and Philipp Hartmann and Riya Kayal and Karl-Josef Dietz and Tobias Ritter}, doi = {10.1021/jacs.5c11842}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35011--35018}, shortjournal = {J. Am. Chem. Soc.}, title = {Ruthenium-mediated N-arylation for DNA-encoded libraries}, volume = {147}, year = {2025}, }
• (2025). Enabling solar water oxidation by BiVO4 in strongly acidic solutions. JACS, 147(38), 35002--35010. (www)

  @article{ , abstract = {The oxygen evolution reaction (OER) is paired with various electrochemical and photoelectrochemical reduction reactions used for fuel and chemical production. As there is a strong interest in performing many of these reduction reactions in strongly acidic solutions to increase the reaction rate, efficiency, or selectivity, there is also a great interest in enabling efficient and stable OER in strongly acidic solutions. In this study, we report stable photoelectrochemical OER (POER) of a BiVO 4 photoanode in 0.1 M HNO 3 (pH 1). This was achieved by using Nb 2 O 5 as a protection layer. While Nb 2 O 5 was rarely used as a protection layer for photoelectrodes in the past, we show its excellent capability to suppress both the chemical and photoelectrochemical dissolution of BiVO 4 at pH 1. After stabilizing BiVO 4 with a Nb 2 O 5 protection layer, we added Co 2+ ions to the electrolyte as an OER catalyst to enhance the POER. We found that Co (aq) 2+ can serve as a homogeneous OER catalyst without being deposited as a CoO x solid catalyst on Nb 2 O 5 . When we performed the POER using unprotected BiVO 4 with Co (aq) 2+ under the same condition, although POER was enhanced, the enhancement could not be sustained due to the chemical dissolution of BiVO 4 . After the POER, we found that a Co 3+ -containing OER catalyst was deposited on the bare BiVO 4 surface. This result suggested that the use of Co 2+ ions as a homogeneous catalyst was possible due to the inertness of the Nb 2 O 5 surface toward the adsorption or deposition of Co ions. This study enabling stable POER of BiVO 4 in 0.1 M HNO 3 using the combination of a Nb 2 O 5 protection layer and Co (aq) 2+ as a homogeneous OER catalyst provides promising possibilities for acidic POER and OER.}, archive = {J_JACS}, author = {Daye Seo and Dae Han Wi and Kyoung-Shin Choi}, doi = {10.1021/jacs.5c11785}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {35002--35010}, shortjournal = {J. Am. Chem. Soc.}, title = {Enabling solar water oxidation by BiVO4 in strongly acidic solutions}, volume = {147}, year = {2025}, }
• (2025). Synergy between inter- and intramolecular interactions on relaxation pathways of oligomeric pentacene assemblies. JACS, 147(38), 34989--35001. (www)

  @article{ , abstract = {Precise control over the couplings between molecules that govern excited-state relaxation processes remains a challenge in organic materials. A primary example of this is in singlet fission, which has the potential to boost photovoltaic efficiencies through exciton multiplication. While detailed solution-phase mechanistic studies of this phenomenon now exist, bridging the gap to practical devices has yet to be realized. We address this issue by showcasing several different ways to steer the excited-state relaxation of new fission-active pentacene and fission-inactive anthracene oligomers, highlighting how the balance of inter- and intramolecular coupling plays a crucial role. We achieve this by engineering specific interactions via supramolecular self-assembly. These interactions promote the uncommon occurrence of strong J-aggregation in acenes. Within the aggregates, intermolecular couplings result in the formation of a strongly bound 1 TT state, which outcompetes the parasitic charge transfer process that dominates in isolated molecules. These findings highlight that balancing intra- and intermolecular interactions offers an effective strategy for regulating the singlet fission process, a critical requirement for advancing future solid-state devices and applications.}, archive = {J_JACS}, author = {David C. Bain and Manoj K. Sharma and Juno Kim and Satish Patil and Andrew J. Musser}, doi = {10.1021/jacs.5c11799}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34989--35001}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergy between inter- and intramolecular interactions on relaxation pathways of oligomeric pentacene assemblies}, volume = {147}, year = {2025}, }
• (2025). Coordination-driven assembly modulates the piezoelectric response of bio-inspired amino acid-based supramolecular materials. JACS, 147(38), 34972--34988. (www)

  @article{ , abstract = {Metal ion coordination confers unique supramolecular structures and electronic properties to biomolecular assemblies in living organisms, inspiring the design of metallo-supramolecular piezoelectric biomaterials. However, the piezoelectric response of biomolecule-based metallo-supramolecular materials and structure-piezoelectricity relationships are still largely unexplored. Herein, we present a bio-inspired metal coordination strategy to modulate the piezoelectricity of copper(II) amino acid assemblies toward energy harvesting. Interestingly, crystal structures indicated dimensionally diversified coordination networks in copper(II) amino acid assemblies, including zero-dimensional (0D) discrete blocks, one-dimensional (1D) infinite chains, and two-dimensional (2D) infinite sheets. Notably, density functional theory (DFT) calculations revealed that the dimensionality of coordination networks fundamentally modulates the maximum piezoelectric strain coefficient of assemblies with the order: 1D > 2D > 0D, in which the copper(II) l -glutamate (Glu+Cu) coordination assemblies exhibited the highest value of 57.7 pC/N. The Glu+Cu crystal-based piezoelectric device produced stable open-circuit voltages exceeding 3.0 V under 55 N mechanical force, which could be fabricated into real-time monitoring systems for cervical and lumbar spine health. This work presents a novel metal biocoordination strategy to manipulate the piezoelectric response of amino acid-based assemblies, providing essential design clues for developing innovative piezoelectric biomaterials.}, archive = {J_JACS}, author = {Shuaijie Liu and Bingbing Yang and Yehong Huo and Jingwen Zhao and Jian Hu and Liqin Chen and Lingling Li and Mei-Ling Tan and Peng Liu and Kaiyong Cai and Wei Ji}, doi = {10.1021/jacs.5c11727}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34972--34988}, shortjournal = {J. Am. Chem. Soc.}, title = {Coordination-driven assembly modulates the piezoelectric response of bio-inspired amino acid-based supramolecular materials}, volume = {147}, year = {2025}, }
• (2025). Highly selective photo-oxidation of methane to methanol by Fe–Au site-supported SrTiO3 hollow nanotubes with oxygen vacancies. JACS, 147(38), 34959--34971. (www)

  @article{ , abstract = {Solar-driven methane (CH 4 ) conversion to value-added chemicals with high selectivity remains a long-standing challenge. Here, we present closely attached atomically dispersed Fe species and ultrafine Au-supported SrTiO 3 hollow nanotubes with oxygen vacancies (STO v ) for highly selective CH 4 conversion to CH 3 OH. An impressive CH 3 OH production rate of 7.53 mmol g –1 h –1 with a selectivity up to 95.4% has been achieved, corresponding to an apparent quantum efficiency of 15.8% at 365 nm, representing a record among all of the representative photocatalysts under comparable conditions. Experimental results and theoretical simulations elucidate that the created oxygen vacancies on SrTiO 3 without Ti 3+ facilitate CH 4 adsorption to effectively capture photogenerated holes for producing methyl radicals. In parallel, the photogenerated electrons could be rapidly extracted by the anchored Au and then transferred to the adjacent single-atom Fe sites for activating O 2 to generate the key intermediate Fe–*OOH toward highly selective CH 3 OH production. Significantly, a commendable electron transfer efficiency of 67.5% for O 2 activation is achieved on Fe–Au/STO v based on the quantitative in situ microsecond transient absorption spectra. This work provides a deep understanding of the regulation of both activity and selectivity by the engineering of adjacent sites and the investigation of electron kinetics for O 2 activation during CH 4 photo-oxidation.}, archive = {J_JACS}, author = {Yangyang Zhu and Zhuo Li and Ji Bian and Ziqing Zhang and Cailing Chen and Lunqiao Xiong and Junwang Tang and Liqiang Jing}, doi = {10.1021/jacs.5c11683}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34959--34971}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly selective photo-oxidation of methane to methanol by Fe–Au site-supported SrTiO3 hollow nanotubes with oxygen vacancies}, volume = {147}, year = {2025}, }
• (2025). Peptide-programmable DNAzyme converter for artificial autocatalytic gene regulation. JACS, 147(38), 34944--34958. (www)

  @article{ , abstract = {The in-depth integration of gene regulation with protein modulation can enhance cellular information processing, yet it is significantly constrained by ineffective and complex protein-to-gene transduction strategies. Herein, we developed a simple protease-guided autocatalytic gene silencing platform named iPAD (intelligent peptide-programmed deoxyribonuclease) that converts the protease recognition events into versatile DNA readout signals by rationally designing a native protease-responsive cationic peptide (PP) to efficiently modulate the DNAzyme (Dz) activity. Without requiring additional chemical modifications, the multifunctional PP regulator consists simply of one cell-specific targeting peptide segment and two cationic peptide segments isolated by one protease-specific peptide substrate. The catalytic activity of Dz can be potently disrupted via the cooperatively stabilized electrostatic interactions between cationic PP and the anionic Dz. Subsequently, the Dz activity is efficiently restored via the protease-specific cleavage of the PP, which disrupts the cooperative stabilization between PP and Dz, thus achieving robust and accurate monitoring of protease activity. Molecular dynamic simulations theoretically validate that the on-demand regulation of Dz activity was indeed acquired from the programmed oligomerization of oligo-peptides. As a universal protease sensing platform, this method was successfully applied to probe Caspase-3 and thrombin, facilitating the early evaluation of tumor therapeutic efficacy. Moreover, the endogenous Caspase-3-activated Dz facilitates the construction of an autocatalytic gene regulation platform that self-adaptively upregulates the expression of apoptotic proteases, accelerating tumor cell apoptosis. This simple yet intelligent iPAD system provides a versatile toolbox for high-performance biosensing and bioengineering applications, paving the way for new strategies in smart theragnostic research.}, archive = {J_JACS}, author = {Qingqing Zhang and Jian Hao and Yuqiu He and Benrui Weng and Shanshan Yu and Chunsen Li and Fuan Wang}, doi = {10.1021/jacs.5c11409}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34944--34958}, shortjournal = {J. Am. Chem. Soc.}, title = {Peptide-programmable DNAzyme converter for artificial autocatalytic gene regulation}, volume = {147}, year = {2025}, }
• (2025). Atomic exploration of the fluorination-driven structural rearrangement of carbon electrocatalysts toward efficient oxygen reduction reactions. JACS, 147(38), 34933--34943. (www)

  @article{ , abstract = {The atom arrangement in carbon electrocatalysts is crucial for enhancing the intrinsic activity toward oxygen reduction reactions (ORRs), a key process in multiple renewable energy systems. However, the challenge of designing electrocatalysts with improved performance by manipulating atomic arrangement has been limited by synthetic constraints and a lack of understanding of the catalytic phase formation. Herein, we gain atomic-level insight into the origin of a highly active site by creating a model catalyst with a heteroatom-decorated carbon matrix of a specific configuration. The introduction of fluorine (F) during the synthesis of the nitrogen (N)-decorated carbon matrix induces structural rearrangement, converting most pyrrolic-N (P r -N) into highly stable graphitic-N (G-N), thereby achieving a N configuration predominantly composed of pyridinic nitrogen (P y -N) and G-N. The multidopant synergistic effect of F, P y -N, and G-N causes a destabilized π-conjugated electron network of the carbon matrix, resulting in a more localized electronic structure. As a result, multiple dopant configurations with high ORR activity have been explored, among which the asymmetric P y -N and G-N configurations feature the lowest theoretical ORR overpotential, ultimately enabling the optimized F@NC catalyst to exhibit excellent oxygen reduction activity. This work establishes a foundation for the rational design of metal-free carbon-based electrocatalysts toward ORR.}, archive = {J_JACS}, author = {Yang Li and Zhen Cao and Cailing Chen and Guoxiang Zhao and Edy Abou-Hamad and Zhi-Peng Wu and Zirui Wang and Qiaohong Li and Magnus Rueping and Yu Han and Luigi Cavallo and Huabin Zhang}, doi = {10.1021/jacs.5c11417}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34933--34943}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic exploration of the fluorination-driven structural rearrangement of carbon electrocatalysts toward efficient oxygen reduction reactions}, volume = {147}, year = {2025}, }
• (2025). Pit morphology, dissolution kinetics, and gas generation monitored in real time during localized anodic aluminum corrosion. JACS, 147(38), 34920--34932. (www)

  @article{ , abstract = {Localized corrosion in metallic materials is a stochastic phenomenon that causes irreversible structural failure. Its initiation, which occurs at the solid–liquid interface on the nanometer scale, remains difficult to predict and challenging to characterize. Herein, we describe an experimental platform that exploits advances in electrochemical liquid-phase scanning and transmission electron microscopy (LPSEM and LPTEM) to study pitting corrosion of thin-film pure aluminum in a saline environment in real time. Galvanostatic measurements at increasing current levels showed that localized corrosion of Al begins with the appearance of blisters in parallel with nanosized pits. It progresses with the coexistence of round and fractal-like pit morphologies before transitioning to the complete fractal-like dissolution of Al at high currents. Although gas bubble formation appeared to be more pronounced at higher currents, we were able to locally probe that the gas is produced at the corrosion front, which we experimentally confirmed to be molecular hydrogen. Our findings reveal the kinetic mechanism of the early stages of localized anodic corrosion in Al, which may have more general implications for proposing corrosion resistance descriptors.}, archive = {J_JACS}, author = {Morgan Barbey-Binggeli and Vasiliki Tileli}, doi = {10.1021/jacs.5c11352}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34920--34932}, shortjournal = {J. Am. Chem. Soc.}, title = {Pit morphology, dissolution kinetics, and gas generation monitored in real time during localized anodic aluminum corrosion}, volume = {147}, year = {2025}, }
• (2025). Molecular tailoring of iron chelates for long-cycling and high-efficiency all-iron redox flow batteries. JACS, 147(38), 34910--34919. (www)

  @article{ , abstract = {All-soluble all-iron redox flow batteries (AS-AIRFBs) represent a highly promising next-generation technology for long-duration energy storage, leveraging their low cost, decoupled energy/power characteristics, and controllable side reactions. Achieving long-term cycling stability necessitates a stable Fe 2+/3+ -ligand chelate to mitigate the electrolyte crossover, which is the main bottleneck for the flow batteries, in particular for AIRFBs. Herein, we designed a novel ligand─2-hydroxy-1,3-propanediamine tetra-sulfonate sodium salt (HPDTS)─through tailoring both ligand structure and chelate configuration. Benefiting from the macromolecular and flexible ligand framework, HPDTS dramatically accelerates the electron transfer kinetics of Fe 2+/ Fe 3+ , leading to the highest energy efficiency (EE: 71.79% at 200 mA cm –2 ) and power density (446.9 mW cm –2 at 623.39 mA cm –2 ) reported so far. In particular, unlike the traditional penta-coordinate chelate, HPDTS forms a tightly bonded symmetric hexa-coordinate Fe chelate with thermodynamic stability, which not only inhibits the side reaction (e.g., decomposition and HER) but also suppresses the electrolyte crossover when paired with a nonfluorinated proton exchange membrane. Electrochemical testing reveals the record-long lifespan of 15,000 cycles with an ultralow fading rate of 0.000741% per cycle and an ultrahigh Coulombic efficiency of 99.25%. Furthermore, practical AIRFB was also demonstrated to stably cycle for over 6500 cycles without any decay. The new molecular configuration tailoring strategies presented here provide a new paradigm for the development of high-efficiency and long-life AIRFBs.}, archive = {J_JACS}, author = {Mingda Luo and Chang Liu and Dongfang Dong and Lingbo Yao and Yichao Wang and Gege Wang and Xiaowei Chi and Yu Liu}, doi = {10.1021/jacs.5c11383}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34910--34919}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular tailoring of iron chelates for long-cycling and high-efficiency all-iron redox flow batteries}, volume = {147}, year = {2025}, }
• (2025). Structure-guided engineering of a bacterial sesterterpene synthase for sesterviridene diversification. JACS, 147(38), 34901--34909. (www)

  @article{ , abstract = {Terpene synthases produce a remarkable structural diversity from acyclic precursors through complex carbocation cascades. Here, we report the crystal structure of the bacterial sesterterpene synthase StvirS bound to geranylfarnesyl thiopyrophosphate (GFSPP), revealing a preorganized active site that enforces a defined folding of the C25 backbone. Guided by this structure, active-site engineering at 11 positions yielded 23 enzyme variants and 13 new sesterterpenes. Specific substitutions altered reaction trajectories, stereochemistry, or induced premature termination, emphasizing the sensitivity of StvirS to subtle structural changes. Isotopic labeling established the absolute configurations of 11 products and experimentally confirmed a conserved cyclization pathway. These results illustrate how precise noncovalent interactions govern terpene biosynthesis and highlight the promise of structure-based design to reprogram terpene cyclase reactivity.}, archive = {J_JACS}, author = {Heng Li and Philip Troycke and Zhiyong Yin and Michael Groll and Jeroen S. Dickschat}, doi = {10.1021/jacs.5c11309}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34901--34909}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure-guided engineering of a bacterial sesterterpene synthase for sesterviridene diversification}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic conversion of p-xylene into p-tolualdehyde with near 100% selectivity via a novel hydroxyl radical-mediated oxygenation route. JACS, 147(38), 34891--34900. (www)

  @article{ , abstract = {p -Tolualdehyde ( p -TALD) is an important chemical intermediate that is widely used in the fragrance and pharmaceutical industries. Photocatalytic upgrading of p -xylene into p -TALD is a promising route but suffers from undesired overoxidation via conventional molecular oxygen-mediated oxygenation due to difficulties associated with desorbing the products from catalyst active sites. In this work, a novel photocatalytic hydroxyl radical (·OH)-mediated oxygenation route is reported for p -xylene to p -TALD conversion, in which the ·OH serves as oxygen donors to generate intermediates containing hydroxyl functional groups that readily form hydrogen bonds with surface hydroxyl groups of the P25 photocatalyst. This hydrogen bonding interaction effectively regulates the adsorption–desorption behavior of intermediates and products, thereby significantly enhancing the selectivity toward p -TALD from 45.25% to nearly 100%, delivering an impressive p -TALD production rate of 3568.8 μmol g –1 h –1 . This work provides a promising strategy for overcoming the common issue of severe overoxidation encountered during photocatalytic upgrading of organic substrates.}, archive = {J_JACS}, author = {Yuan Lu and Seungho Yu and Jie Jin and Zhonghao Wang and Tae-Kyung Liu and Ki Chul Kim and Kan Zhang and Jong Hyeok Park}, doi = {10.1021/jacs.5c10960}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34891--34900}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic conversion of p-xylene into p-tolualdehyde with near 100% selectivity via a novel hydroxyl radical-mediated oxygenation route}, volume = {147}, year = {2025}, }
• (2025). Plasmon-induced ultrafast interfacial charge transfer for enhanced photocatalytic hydrogen evolution. JACS, 147(38), 34881--34890. (www)

  @article{ , abstract = {The localized surface plasmon resonance (LSPR) effect of precious metals plays a pivotal role in photocatalytic H 2 evolution, where plasmon-generated hot electrons are efficiently injected into the photocatalytic system, profoundly modulating interfacial electron transfer dynamics. Regrettably, the specific impact of the LSPR effect of precious metals on the ultrafast interfacial charge transfer and its kinetic characteristics remains inadequately explored in photocatalystic systems. To address these knowledge gaps, Au nanoparticles are incorporated into the CdS/ReS x photocatalyst to comprehensively investigate the LSPR-induced ultrafast interfacial charge transfer, ultimately boosting photocatalytic H 2 production activity. The experimental results reveal that the developed CdS/Au 0.5 @ReS x photocatalyst achieves a notable H 2 -production activity with a rate of 8.6 mmol g –1 h –1 (AQE = 35.9%), which is evidently higher than that of CdS/Au (1.8 mmol g –1 h –1 ) and CdS/ReS x (4.0 mmol g –1 h –1 ). In situ XAFS and fs-TAS characterizations confirm that the Au LSPR effect generates electron-deficient Au δ+ species and contracts Au–S bond lengths, dramatically accelerating electron transfer in the Au@ReS x cocatalyst. This plasmon-induced ultrafast charge transfer mechanism enables efficient photogenerated electron migration in the CdS/Au@ReS x system, promoting interfacial charge dynamics for exceptional photocatalytic H 2 evolution performance. The findings offer a new understanding of charge transfer mechanisms enabled by LSPR effects and create a blueprint for engineering next-generation plasmonic photocatalysts.}, archive = {J_JACS}, author = {Xinyu Yin and Duoduo Gao and Jianjun Zhang and Hermenegildo García and Jiaguo Yu and Huogen Yu}, doi = {10.1021/jacs.5c11154}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34881--34890}, shortjournal = {J. Am. Chem. Soc.}, title = {Plasmon-induced ultrafast interfacial charge transfer for enhanced photocatalytic hydrogen evolution}, volume = {147}, year = {2025}, }
• (2025). Stereodivergent synthesis of allylic all-carbon quaternary centers by bimetallic Iridium/Magnesium-catalyzed allylic alkylation. JACS, 147(38), 34869--34880. (www)

  @article{ , abstract = {Stereodivergent synthesis of the structural motif bearing vicinal stereocenters is highly important for complete evaluation of their physiological activities. Branched- and enantioselective allylic alkylation using synergistic dual catalysis has emerged as a powerful strategy to access multiple molecular stereoisomers with precise control of the absolute and relative configuration. Despite impressive progress in this field, the stereodivergent allylic alkylation by employing trisubstituted allylic electrophiles to construct allylic quaternary stereocenters remains an unsolved challenge. Herein, we report a combination of iridium and magnesium catalysis for stereodivergent allylic alkylation of α-benzothiazyl acetamide by using challenging trisubstituted allylic carbonates. Such a stereodivergent process gives a range of all four stereoisomers of α-allylated acetamide products containing congested allylic quaternary and vicinal tertiary stereocenters in good yields with excellent diastereo- and enantioselectivities. The synthetic utility of this methodology is demonstrated through the preparation of key intermediates for a number of natural products. Particularly, stereodivergent synthesis of an analgesic drug derivative Me -tapentadol has been achieved, exhibiting significantly enhanced μ-opioid receptor agonistic activity compared to its parent compound.}, archive = {J_JACS}, author = {Xinlong Yan and Zichun Zhang and Zhenwei Wu and Fule Wu and Xiaoming Feng and Yangbin Liu}, doi = {10.1021/jacs.5c11017}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34869--34880}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereodivergent synthesis of allylic all-carbon quaternary centers by bimetallic Iridium/Magnesium-catalyzed allylic alkylation}, volume = {147}, year = {2025}, }
• (2025). Giant low-field magnetocaloric effect at sub-kelvin temperatures in ferromagnetic NH4GdF4. JACS, 147(38), 34862--34868. (www)

  @article{ , abstract = {The development of materials for helium-free sub-Kelvin adiabatic demagnetization refrigeration (ADR) is crucial for advancing research in condensed matter physics, quantum computing, astrophysical measurements in space, and other related fields. Among such materials, Gd 3 Ga 5 O 12 (GGG) has been widely regarded as a benchmark cryogenic refrigerant for ADR systems. In this article, we report on a rare-earth fluoride, NH 4 GdF 4, whose low-field magnetocaloric effect is significantly stronger than that of GGG. NH 4 GdF 4 orders at T c = 0.85 K and exhibits a ferromagnetic ground state at low temperatures as proved by the nearest neighbor exchange interaction model and the specific heat analysis. It has excellent low-field magnetization properties, as evidenced by approaching its saturation magnetization of 160 emu/g below a magnetic field of 10 kOe. Furthermore, the magnetic entropy change of up to 38.2 J·kg –1 ·K –1 and its measured temperature change of 1.1 K at an initial temperature of 1.8 K under the magnetic field change of 0–10 kOe are greater than all reported results and much greater than the entropy change and temperature change of GGG under the same conditions. Thus, NH 4 GdF 4 is a competitive refrigerant candidate for low-field-driven ADR applications at sub-Kelvin temperatures.}, archive = {J_JACS}, author = {Qing Guo and Weijun Ren and Peng Liu and Jiwei Yao and Junsen Xiang and Kun Zhang and Yanxu Wang and Loku Singgappulige Rosantha Kumara and Xiaolei Wang and Wei Li and Bing Li}, doi = {10.1021/jacs.5c10979}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34862--34868}, shortjournal = {J. Am. Chem. Soc.}, title = {Giant low-field magnetocaloric effect at sub-kelvin temperatures in ferromagnetic NH4GdF4}, volume = {147}, year = {2025}, }
• (2025). Reactions of Np(VI) and Pu(VI) with phenanthroline result in bending the [NpVIO2]2+ unit and a reduced Pu(V) species. JACS, 147(38), 34849--34861. (www)

  @article{ , abstract = {Despite decades of actinyl chemistry, genuinely bent actinyl structures remain rare beyond uranium. We report the first crystallographic characterization of a bent neptunyl(VI) complex, NpO 2 Cl 2 (phen) 2 , along with a linear plutonyl species that, unexpectedly, adopts the +V oxidation state. Coordination of two 1,10-phenanthroline ligands to NpO 2 2+ enforces pronounced bending of the O yl –Np–O yl unit to 162° through steric clashes with the axial phenathroline ligand, representing the sharpest angle reported for any neptunyl(VI) complex. In contrast, synthesis with PuO 2 2+ produces a reduced linear Pu(V) species, PuO 2 Cl(phen) 2 , underscoring the redox lability and the reluctance of plutonium to distort. Raman and IR spectra yield the first experimental stretching and interaction force constants for plutonyl(V). Comparison with values for plutonyl(VI) and bent and linear uranyl(VI) and neptunyl(VI) compounds shows that reduction perturbs the actinyl bond more than bending within one oxidation state. Electrochemical and spectroscopic studies clarify phenanthroline binding to Pu(VI) and the system’s reactivity. Quantum chemical calculations indicate that bending is energetically favored in the U–Np–Pu series, but the stabilization energy decreases as the actinide atomic number increases. NBO and QTAIM analyses reveal systematic trends: increasing 5f occupancy and decreasing An–O yl bond covalency from U to Pu. These results demonstrate that ligand-induced bending in neptunyl(VI) species is not only electronically feasible but also synthetically achievable, though plutonyl(VI) is constrained by redox reactivity. This work expands the frontier of nonlinear actinyl chemistry and illuminates how structure, oxidation state, and electronic configuration interrelate across the actinyl series.}, archive = {J_JACS}, author = {Emily R. Mikeska and David D. Schnaars and Richard E. Wilson and Gomes André Severo Pereira and Valérie Vallet}, doi = {10.1021/jacs.5c10795}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34849--34861}, shortjournal = {J. Am. Chem. Soc.}, title = {Reactions of Np(VI) and Pu(VI) with phenanthroline result in bending the [NpVIO2]2+ unit and a reduced Pu(V) species}, volume = {147}, year = {2025}, }
• (2025). Direct conversion of ethanol to ethyl acetate by dynamic Polyoxometalate/Carbon nanohorn electrocatalytic interfaces. JACS, 147(38), 34840--34848. (www)

  @article{ , abstract = {The electrosynthesis of ethyl acetate (EtOAc) by oxidative esterification of aqueous (up to 20% water) ethanol (EtOH) is performed by employing the tetraruthenate polyoxometalate [Ru 4 (μ-O) 4 (μ–OH) 2 (H 2 O) 4 (γ-SiW 10 O 36 ) 2 ] 10– (Ru 4 POM) electrocatalyst with carbon nanohorns (CNHs) as a heterogeneous support. This strategy involves a voltage-gated electro-adsorption of Ru 4 POM on CNH-modified glassy carbon anodes with favorable interfacial dynamics, maintained under electrocatalytic conditions. These conditions are reached through the continuous reconstruction of the organic/inorganic interface (catch-and-release), as probed by converging thermal, microscopic, and electrochemical analyses. In fact, control experiments reveal that both pristine and N-doped CNHs display a Ru 4 POM loading in the range 13–18 nmol mg –1 with a remarkable ∼100 mV onset potential anticipation and current enhancement in the range 400–700% compared to the homogeneous conditions. By adopting the “catch-and-release” protocol, electro-esterification of aqueous EtOH features long-term stability of the productive current in the mA range ( J chrono ≈ 2 mA cm –2 at +1.2 V vs Ag/AgCl probed up to 18 h), with Faradaic efficiencies, FE EtOAc , of >90%. This effect is attributed to the crucial role of CNHs hydrophobicity to control hydrolysis equilibria, thus outperforming the solution-phase behavior, which levels off at FE EtOAc < 60%.}, archive = {J_JACS}, author = {Simone Guazzi and Robin N. Dürr and Andrea Bogo and Elena Bassan and Goretti Arias-Ferreiro and Michele Cacioppo and Maurizio Prato and Marcella Bonchio}, doi = {10.1021/jacs.5c10817}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34840--34848}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct conversion of ethanol to ethyl acetate by dynamic Polyoxometalate/Carbon nanohorn electrocatalytic interfaces}, volume = {147}, year = {2025}, }
• (2025). Salt-induced polymorphs observed in colloidal single crystals. JACS, 147(38), 34831--34839. (www)

  @article{ , abstract = {Polymorphs are solid materials with the same chemical composition but different crystallographic structures. A unique aspect of polymorphs is that they exhibit different physical properties, such as solubility, melting point, density, color, hardness, and bioavailability. Here, we synthesized polymorphs of colloidal crystals engineered with DNA by slow-cooling gold nanoparticle-core programmable atom equivalents (PAEs, particles with DNA sequences that control their bonding characteristics) under salt concentrations ranging from 0.5 to 4 M NaCl. This approach yielded a diverse set of single-crystalline phases with cubic, tetragonal, and hexagonal lattice symmetries. The structural transitions observed here arise solely from the modulation of interparticle repulsion via ionic strength and thermal processing. Notably, in certain cases, we observed diffusionless phase transformations, wherein the superlattices evolve from cubic to lower-symmetry tetragonal lattices. By tuning the thermal stability and salt concentration, we captured intermediate, metastable body-centered tetragonal structures during the slow-cool process, indicating that subtle changes in free energy can direct crystallization to low-symmetry phases. This study demonstrates that thermal and ionic parameters can be tuned to access and stabilize colloidal crystal polymorphs with emergent structures and interesting functional properties.}, archive = {J_JACS}, author = {Soyoung E. Seo and Byeongdu Lee and Taegon Oh and Martin Girard and Chad A. Mirkin}, doi = {10.1021/jacs.5c10844}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34831--34839}, shortjournal = {J. Am. Chem. Soc.}, title = {Salt-induced polymorphs observed in colloidal single crystals}, volume = {147}, year = {2025}, }
• (2025). PH-responsive self-assembly of renal-clearable nanoparticles in the kidneys: One assembly per endosome. JACS, 147(38), 34823--34830. (www)

  @article{ , abstract = {Renal clearance is traditionally viewed as a passive filtration process governed by fenestrated glomerular capillaries. However, proximal tubular epithelial cells (PTECs) can still actively internalize, transform, and re-eliminate nanoparticles following glomerular filtration. Herein, we report that pH-responsive renal-clearable gold nanoparticles (AuNPs) of ∼2 nm in size can rapidly self-assemble into a single ∼180 nm nanosphere within individual PTEC endosomes in vivo once their isoelectric points (IEPs) overlapping the endocytic pH range (4.5–6.5), which has never been observed at the animal level. This pH-triggered one assembly per endosome delays subsequent reactive oxygen species (ROS)-mediated intracellular biotransformation into larger nanostructures while preserving membrane extrusion-based re-elimination. These findings reveal that endosomal acidity, alongside ROS, is a critical determinant of nanoparticle biotransformation and suggest that tailoring isoelectric points offers a route to control the subcellular assembly and clearance of renal-clearable nanomedicines at the animal level.}, archive = {J_JACS}, author = {Yingyu Huang and Jie Zheng and Mengxiao Yu}, doi = {10.1021/jacs.5c10759}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34823--34830}, shortjournal = {J. Am. Chem. Soc.}, title = {PH-responsive self-assembly of renal-clearable nanoparticles in the kidneys: One assembly per endosome}, volume = {147}, year = {2025}, }
• (2025). Synthesis of diverse glycosyl bicyclo[1.1.1]pentanes enabled by electrochemical functionalization of [1.1.1]Propellane. JACS, 147(38), 34813--34822. (www)

  @article{ , abstract = {Over the past decade, bicyclo[1.1.1]pentanes (BCPs) have emerged as valuable bioisosteres of aromatic rings, offering unique three-dimensional architectures for medicinal chemistry. Meanwhile, glycosyl derivatives play a pivotal role in chemical biology and drug discovery due to their widespread presence in biologically active molecules; however, the potential of bicyclo[1.1.1]pentanes (BCPs) as versatile scaffolds in glycoscience remains largely unexplored. Herein, we report an electrochemistry strategy for the synthesis of BCP–glycosides via the functionalization of [1.1.1]propellane. By leveraging an electrochemical halogen-atom transfer ( e -XAT) process, we achieved a one-step, three-component reaction of glycosyl bromides, [1.1.1]propellane, and radical acceptors under mild conditions, enabling the construction of glycosyl BCP–iodides, glycosyl BCP–H, and glycosyl BCP–pinacolboronic esters (Bpins) with exceptional functional group tolerance and scalability. Mechanistic studies suggested that the electrochemical process facilitated the generation of radical intermediates, which underwent selective addition to [1.1.1]propellane, followed by trapping with radical acceptors. This study establishes a versatile platform for late-stage functionalization and streamlined access to privileged scaffolds in drug discovery and chemical biology.}, archive = {J_JACS}, author = {Jiandong Liu and Rajeshwaran Purushothaman and Fabian Hinrichs and Max Surke and Svenja Warratz and Lutz Ackermann}, doi = {10.1021/jacs.5c10732}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34813--34822}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of diverse glycosyl bicyclo[1.1.1]pentanes enabled by electrochemical functionalization of [1.1.1]Propellane}, volume = {147}, year = {2025}, }
• (2025). Chemical bond engineering in charge-balanced layered TiSe2 derivatives: 3D charge transport and lattice anharmonicity for exceptional thermoelectric performance. JACS, 147(38), 34804--34812. (www)

  @article{ , abstract = {Layered transition metal dichalcogenides (TMDs) have emerged as a paradigm for investigating emergent quantum phenomena, particularly through their unique charge density wave (CDW) transitions and electron correlation effects. However, the inherent semimetallic characteristics of prototypical compounds such as TiSe 2 fundamentally constrain their thermoelectric performance. Herein, we unveil a breakthrough in thermoelectric TMDs through dual chemical control of both intralayer bonding and interlayer charge dynamics under valence compensation. Through partial substitution of 1/3 Ti 4+ ions with Cr 3+ in the intralayer TiSe 6 octahedral framework, we effectively suppress antibonding orbital interactions, thereby widening the bandgap from −0.46 to 0.53 eV. Simultaneously, controlled Cu + intercalation into interlayer selenium-coordinated void octahedra (i.e., van der Waals gaps) establishes three-dimensional charge transport pathways, resulting in a remarkable 50% enhancement in carrier mobility. Meanwhile, the vibrationally anharmonic Cu–Se bonding configuration dramatically reduces the lattice thermal conductivity to one-fourth that of pristine TiSe 2 . This concerted optimization culminates in a record-breaking dimensionless figure of merit ( ZT = 0.82) at 673 K in Cu-deficient composition of Cu 0.8 CrTi 2 Se 6 , representing a 40-fold enhancement over undoped TiSe 2 and setting a new benchmark for single-phase bulk TMD thermoelectrics. Our work demonstrates how atomic-scale coordination engineering can unlock superior thermoelectric performance in traditionally “non-ideal” material systems.}, archive = {J_JACS}, author = {Weibin Xu and Weiping Guo and Lin Liao and Chenghao Xie and Jingjing Cui and Qicai Mei and Songlin Li and Jinsong Wu and Zhongzhen Luo and Qingjie Zhang and Xinfeng Tang and Gangjian Tan}, doi = {10.1021/jacs.5c10634}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34804--34812}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemical bond engineering in charge-balanced layered TiSe2 derivatives: 3D charge transport and lattice anharmonicity for exceptional thermoelectric performance}, volume = {147}, year = {2025}, }
• (2025). Water adsorption in Metal–Organic frameworks: Characteristics, mechanisms, and Structure–Property relationships. JACS, 147(38), 34791--34803. (www)

  @article{ , abstract = {To address the increasingly limited water availability, using metal–organic frameworks (MOFs) to capture atmospheric water vapor as usable resources has emerged as a promising strategy. The adsorption characteristics of MOFs as well as their step pressure (i.e., the pressure when the steep rise in water uptake, if any, occurs) directly influence the amount of collectable water and thus their harvesting effectiveness. To date, a comprehensive understanding of water adsorption behaviors and how they are influenced by MOF properties remains lacking. This study addresses this gap by systematically investigating water adsorption in >200 strategically selected MOFs with diverse features. The results demonstrate that water adsorption in MOFs is highly complex, revealing various subtypes of both non-S-shaped and S-shaped isotherms. Moreover, among S-shaped isotherms, distinct phase behaviors that, in turn, govern different adsorption mechanisms and hydrogen-bonding environments are identified, as evidenced by analyses of their macrostate probability distributions (MPDs), thermodynamic stability limits, and grand potential free energy landscapes. Further structure–property analyses also uncover key design principles: A moderate heat of adsorption is critical for enabling S-shaped isotherms, while the size of pores critically modulates the steepness of the adsorption step by controlling the phase transition nature of confined water. The density and, more importantly, the uniformity of adsorption sites are found as well to dictate the step pressure. Overall, this study provides a comprehensive overview of diverse adsorption behaviors in MOFs as well as informs general design principles for the development of advanced adsorbents for atmospheric water harvesting.}, archive = {J_JACS}, author = {Shiue-Min Shih and Li-Chiang Lin}, doi = {10.1021/jacs.5c10686}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34791--34803}, shortjournal = {J. Am. Chem. Soc.}, title = {Water adsorption in Metal–Organic frameworks: Characteristics, mechanisms, and Structure–Property relationships}, volume = {147}, year = {2025}, }
• (2025). Proton, electron, and hydrogen-atom transfer thermodynamics of the Metal–Organic framework, ti-MIL-125, are intrinsically correlated to the structural disorder. JACS, 147(38), 34777--34790. (www)

  @article{ , abstract = {Interfacial charge transfer reactions involving protons and/or electrons are fundamental to heterogeneous catalysis and many other reactions relevant to energy, chemical, and biological sectors. Metal–organic frameworks (MOFs) with redox-active metal-oxo nodes have emerged as candidate materials to examine these reactions with near-atomic-level precision, given their crystalline nature. Here, we employed a colloidally stable, Ti-based MOF, Ti-MIL-125, with different crystal sizes to examine catalytically relevant charge transfer thermodynamics. The Ti 8 (μ 2 -O) 8 (μ 2 -OH) 4 nodes structurally mimic TiO 2 , which has shown some PCET reactivity toward reactions of H 2 , O 2 , and others. In this report, we have demonstrated that a change in crystal size induces different amounts of structural disorder to the Ti-oxo node, further changing the thermodynamics of proton/electron/hydrogen-atom transfer reactions. Using electrochemical open-circuit potential ( E OCP ) measurements, we have determined that all crystallites undergo a 1H + /1e – redox reaction, which, given the stoichiometry, can be considered as a net H atom transfer (HAT) reaction. The thermodynamics of this HAT reaction, the Ti 3+ O–H bond dissociation free energy (BDFE), was dependent on the crystal size of the MOF, as the decrease in crystal size induced more structural disorder. Our computational calculations have indicated that this difference in BDFE is due to a local change in the geometry of Ti cations, rather than the commonly invoked defects, such as the “missing-linker” defect sites. Individual proton/electron transfer (PT/ET) thermodynamics were also highly dependent on the crystal sizes. These were probed using p K a or band gaps ( E g ), respectively. These findings suggest that, particularly when MOFs are nanosized with a large amount of structural disorder, they should no longer be considered “true” single-site catalysts; this is an implicit, but widespread assumption within the MOF-based catalysis field. Implications of these findings will be contrasted with structurally similar metal oxides like TiO 2 and other redox-active MOFs.}, archive = {J_JACS}, author = {Nazmiye Gökçe Altınçekiç and Chance W. Lander and Jiaqi Yu and Ayman Roslend and Yihan Shao and Hyunho Noh}, doi = {10.1021/jacs.5c10498}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34777--34790}, shortjournal = {J. Am. Chem. Soc.}, title = {Proton, electron, and hydrogen-atom transfer thermodynamics of the Metal–Organic framework, ti-MIL-125, are intrinsically correlated to the structural disorder}, volume = {147}, year = {2025}, }
• (2025). Convergent paired electrolysis enables electrochemical halogen-atom transfer-mediated alkyl radical cross-coupling. JACS, 147(38), 34767--34776. (www)

  @article{ , abstract = {The direct cross-coupling of unactivated alkyl halides with aryl or heteroaryl partners remains a fundamental challenge in synthetic chemistry due to their inertness and propensity for side reactions. Herein, we report a transition-metal-free electrochemical halogen-atom transfer strategy that enables efficient alkyl radical cross-coupling via convergent paired electrolysis. In this system, anodically generated α-aminoalkyl radicals mediate the activation of alkyl iodides, while aryl/heteroaryl aldehydes or nitriles undergo cathodic reduction to afford persistent ketyl radical anions or aryl radical anions. The matched redox processes facilitate selective radical–radical anion cross-coupling to furnish diverse alcohols and C(sp 3 )–C(sp 2 ) coupling products under mild conditions. This operationally simple, scalable protocol exhibits broad functional group tolerance and is applicable to a wide range of primary, secondary, and tertiary alkyl iodides and structurally diverse aryl and heteroaryl coupling partners. The utility of this strategy is further demonstrated in the late-stage modification of natural products, biomolecules, and pharmaceuticals.}, archive = {J_JACS}, author = {Xiang Sun and Ke Zheng}, doi = {10.1021/jacs.5c10472}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34767--34776}, shortjournal = {J. Am. Chem. Soc.}, title = {Convergent paired electrolysis enables electrochemical halogen-atom transfer-mediated alkyl radical cross-coupling}, volume = {147}, year = {2025}, }
• (2025). Magnetically induced iron-catalyzed hydrodeoxygenation of benzylic esters and polyesters. JACS, 147(38), 34758--34766. (www)

  @article{ , abstract = {The selective hydrodeoxygenation of benzylic esters with molecular hydrogen (H 2 ) provides a synthetic approach to methyl-substituted aromatic compounds used widely as intermediates and products in the chemical and pharmaceutical industries in accordance with green chemistry principles. In particular, it can open novel pathways for the use of biomass-derived substrates or waste plastics as chemical feedstocks. We present here an efficient catalytic approach focusing on the use of earth abundant iron in the form of iron carbide nanoparticles (ICNPs) activated by magnetic induction, allowing the reaction to proceed at pressures of only 3 bar of H 2 . The activity of the ICNPs responds in real time to on/off switches of the alternating current magnetic field (ACMF, 350 kHz, 70 mT), mimicking the use of intermittent renewable electricity, and the magnetic properties of the ICNPs allow for their easy separation and reuse. The reaction proceeds with higher yield and selectivities at global temperatures more than 130 °C below thermal activation, leading to at least four times higher energy efficiency. The method was successfully applied to a range of synthetic targets and to the selective depolymerization of real polyester (PET) products.}, archive = {J_JACS}, author = {Sihana Ahmedi and Lise-Marie Lacroix and Derya Demirbas and Daniel J. SantaLucia and Claudia Weidenthaler and Walid Hetaba and Walter Leitner and Alexis Bordet}, doi = {10.1021/jacs.5c10464}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34758--34766}, shortjournal = {J. Am. Chem. Soc.}, title = {Magnetically induced iron-catalyzed hydrodeoxygenation of benzylic esters and polyesters}, volume = {147}, year = {2025}, }
• (2025). Zwitterionic sulfadiazine-based micelle achieves effective drug delivery to glioblastoma by overcoming multiple biological barriers. JACS, 147(38), 34742--34757. (www)

  @article{ , abstract = {Multiple biological barriers in vivo severely restrict the delivery efficiency of nanoparticles (NPs) to tumors. To overcome biological barriers, traditional NPs usually require a complex design, which increases the difficulty of clinical translation. Therefore, there appears to be a dilemma between the complex biological barriers in vivo and clinical requirement for a simple molecular structure of NPs. Herein, an unprecedented zwitterionic polycaprolactone-poly(4-( N , N -dimethylamino- N -acetyl sulfadiazine) benzoyl oligo(ethylene glycol) methacrylate) (PCL–PSDMA) micelle is synthesized via atom transfer radical polymerization (ATRP), capable of overcoming multiple biological barriers with minimalistic structure. First, the PCL–PSDMA micelle shows a zwitterionic state in a physiological environment, exhibiting long blood circulation without triggering accelerated blood clearance. Second, the PCL–PSDMA micelle traverses the blood–brain barrier effectively owing to the pathway mediated by the l -type amino acid transporter on cerebrovascular endothelial cells. Third, the PCL–PSDMA micelle converts from zwitterionic state to positively charged state in tumor extracellular environment, facilitating deep tumor penetration and enhanced tumor cellular uptake. Lastly, the zeta potential of the PCL–PSDMA micelle transforms to a stronger positive value in the lysosomal microenvironment, resulting in effective lysosomal escape. The outstanding performance of overcoming five sequential biological barriers endows the PCL–PSDMA micelle with high drug delivery efficiency to glioblastoma, leading to pronounced antitumor effect in two types of glioblastoma-bearing mice model. Overall, this work not only adds a new member to the zwitterionic family but also broadens the horizon of developing powerful NPs for antiglioblastoma drug delivery.}, archive = {J_JACS}, author = {Ke Zheng and Xumei Ouyang and Jing Li and Yongbin Cao and Shaojun Peng}, doi = {10.1021/jacs.5c10422}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34742--34757}, shortjournal = {J. Am. Chem. Soc.}, title = {Zwitterionic sulfadiazine-based micelle achieves effective drug delivery to glioblastoma by overcoming multiple biological barriers}, volume = {147}, year = {2025}, }
• (2025). Stochastic interface formation in nanoscale heterostructures visualized by atomic-resolution microscopy. JACS, 147(38), 34731--34741. (www)

  @article{ , abstract = {Well-defined heterostructures exhibit emergent properties distinct from their single-phase constituents, enabling advances across diverse technologies. Typically classified as self-assembly and epitaxy, heterointerface formation is generally assumed to proceed unidirectionally and irreversibly at bulk scales. Here we use in situ electron microscopy at 298 K to visualize the heterostructure formation from nanoscale mixtures of intrinsically immiscible salts at ambient conditions, NaCl and NaI. We find that both self-assembly and heteroepitaxy occur reversibly, governed by stochastic equilibria. During self-assembly, the system fluctuates between order and semiordered states, with kinetically favored iodide–graphene interactions and eventual formation of thermodynamically favored charge-neutral planes. The ions in the liquid state move rapidly. In the epitaxial regime, NaI layers repeatedly grow and exfoliate from a buffer layer. The observed motion of atoms driven by high interfacial energy occurs with an energy barrier of 18 kcal mol –1 or less as estimated from the Nyquist frequency of the frame rate of the movie. These observations reveal that heterointerface formation is governed by dynamic and stochastic processes, providing a framework for the understanding of the initiation stage of the heterointerface formation in high interface energy regimes such as surface and structural defects of bulk solids.}, archive = {J_JACS}, author = {Miyuki Hanazawa and Masaya Sakakibara and Ryo Ishikawa and Naoya Shibata and Takayuki Nakamuro and Eiichi Nakamura}, doi = {10.1021/jacs.5c10326}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34731--34741}, shortjournal = {J. Am. Chem. Soc.}, title = {Stochastic interface formation in nanoscale heterostructures visualized by atomic-resolution microscopy}, volume = {147}, year = {2025}, }
• (2025). Modulating molecular microheterogeneity within electrolytes controls macroscopic battery performance. JACS, 147(38), 34721--34730. (www)

  @article{ , abstract = {Narrow electrochemical windows and high reactivity of aqueous solutions remain critical bottlenecks for the practical application of aqueous batteries. However, the mechanisms for tuning microscopic reactivity of H 2 O molecules in aqueous electrolytes remain elusive. This study employs six ether molecules with distinct structures and solvation powers to regulate the microstructure of aqueous solutions. We reveal underlying correlations between the reactivity of H 2 O and microstructural parameters in organic-aqueous electrolytes. A more positive solvation power difference value between ether and H 2 O is appealing to drive enhanced microheterogeneity, which accordingly lowers the average Li + coordination number and reduces H 2 O cluster size. A small and isolated H 2 O cluster, which bridges the microstructural parameters and macroscopic electrolyte performance, is critical to suppress long-range H 2 O diffusion, thereby enhancing the electrochemical stability of the electrolyte. Diethyl ether with an optimal positive solvation energy difference with H 2 O forms minimal [Li(H 2 O) 4 ] + clusters and moderate anion aggregation, simultaneously enabling fast Li + ion diffusion and an expanded electrochemical window. LiMn 2 O 4 ||Li 4 Ti 5 O 12 full cells achieved 200 cycles with 97.5% capacity retention at 1 C. Additionally, a 1 Ah aqueous pouch cell delivered a high energy density of 80.93 Wh kg –1 . This work provides valuable insights into electrolyte stabilization and the design of high-performance electrolytes for energy storage and conversion applications.}, archive = {J_JACS}, author = {Canfu Zhang and Zhineng Ren and Yuan Tu and Binbin Chen and Changhe Tian and Huilin Pan}, doi = {10.1021/jacs.5c10202}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34721--34730}, shortjournal = {J. Am. Chem. Soc.}, title = {Modulating molecular microheterogeneity within electrolytes controls macroscopic battery performance}, volume = {147}, year = {2025}, }
• (2025). Cage balancing enhances optoelectronic and lasing performance in stable quasi-2D tin iodide perovskites. JACS, 147(38), 34706--34720. (www)

  @article{ , abstract = {Two-dimensional (2D) tin halide perovskites are highly tunable and low-toxicity semiconductors, promising for next-generation optoelectronics. However, achieving air stability and excellent photophysical properties simultaneously necessitates deliberate structure tuning using organic spacer cations and A-site cations. Here, we report a series of new quasi-2D Ruddlesden–Popper tin halide perovskites using a fluorinated aromatic spacer cation, 4-fluorophenethylammonium (4FPEA), and systematically investigate the impacts of layer thickness, spacer cation, and A-site cation on the crystal structures and optical properties of (4FPEA) 2 (A) n −1 Sn n I 3 n +1 . These 4FPEA-based 2D tin perovskites, further tuned by the A-cations, exhibit uniquely undistorted 180° out-of-plane Sn–I–Sn bond angles and low octahedral distortions compared to other quasi-2D perovskites and demonstrate prolonged air stability, excellent photophysics, and amplified spontaneous emission and lasing in exfoliated microflakes. A comprehensive survey of reported n = 2 lead and tin iodide perovskites reveals that all structures can be classified into three types (tilted, balanced, and buckled) based on the structural distortion parameters of their perovskite cages. Notably, (4FPEA) 2 (A)Sn 2 I 7 are among the handful of “balanced” n = 2 perovskites with minimal distortion and excellent optoelectronic performance. The structural insights and cage-balancing approach revealed herein motivate the deliberate design of quasi-2D perovskites through the synergy of the spacer and cage cations, further paving the way for high-performance optoelectronic applications of stable tin halide perovskites.}, archive = {J_JACS}, author = {Christopher T. Triggs and Chun-Sheng Jack Wu and Yarong He and Eliana Bernat and Willa Mihalyi-Koch and Kristel M. Forlano and Ilia A. Guzei and Daniele Cortecchia and Annamaria Petrozza and Song Jin}, doi = {10.1021/jacs.5c09938}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34706--34720}, shortjournal = {J. Am. Chem. Soc.}, title = {Cage balancing enhances optoelectronic and lasing performance in stable quasi-2D tin iodide perovskites}, volume = {147}, year = {2025}, }
• (2025). Isotropic zero thermal expansion in Yb(Al,Mn)2: Achieving continuous shiftability over a wide temperature range. JACS, 147(38), 34697--34705. (www)

  @article{ , abstract = {Zero thermal expansion (ZTE) substances, whose volume remains invariant under temperature variations, have attracted significant attention owing to their extensive potential applications in advanced technology fields. However, practical challenges persist, including thermal expansion anisotropy, ferromagnetism, high density, and restricted ZTE temperature windows. In this study, we have achieved a lightweight, nonferromagnetic, isotropic ZTE in Yb(Al,Mn) 2 alloys, which exhibits continuous shiftability of the ZTE temperature window across a wide range (140–650 K). By employing multiple advanced experimental techniques and combining first-principles calculations, we have elucidated that the ZTE behavior originates from valence fluctuations accompanied by local structural distortions. The latter manifests as the first two observed effects: the splitting of local bond lengths and the attenuation of atomic displacements. More importantly, the induced enhancement of hybridization between Mn-3 d and Yb-4 f orbitals is identified as the primary mechanism responsible for the emergence of shiftability over a wide temperature range. This work presents an unprecedented phenomenon of continuously shiftable ZTE temperature windows observed in the mixed-valence system Yb(Al,Mn) 2 , which holds significant potential for diverse thermal expansion control applications in advanced technological fields, paving the way for next-generation devices requiring exceptional dimensional stability. Furthermore, the modulation of valence fluctuations provides new strategies for the development of new ZTE materials in the future.}, archive = {J_JACS}, author = {Hao Wang and Yuanji Xu and Yuzhu Song and Andrea Sanson and Yuanpeng Zhang and Yonghao Yao and Hui Liu and Takeshi Watanabe and Jianrong Zeng and Naike Shi and Jun Chen}, doi = {10.1021/jacs.5c10024}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34697--34705}, shortjournal = {J. Am. Chem. Soc.}, title = {Isotropic zero thermal expansion in Yb(Al,Mn)2: Achieving continuous shiftability over a wide temperature range}, volume = {147}, year = {2025}, }
• (2025). Tuning the lifetimes of photoinduced deligation in a Metal–Organic framework via linker functionalization. JACS, 147(38), 34690--34696. (www)

  @article{ , abstract = {Recently photoinduced dynamic ligation in a metal–organic frameworks (MOFs) was reported, where a long-lived charge-transfer excited state (ca. 30 μs) featuring partial dissociation between the carboxylate linker and metal-based node was probed by time-resolved infrared (TRIR) spectroscopy. The study offers a new mechanistic perspective to evaluate the potential contribution from the excited state molecular configuration to the performance of MOF photocatalysts. In this work, by employing MIL-101(Fe) as the study platform, we have further explored the influence of intramolecular interactions on the stability of relevant excited states and demonstrated the effective tuning of their lifetimes through the incorporation of different functional groups into the system. The correlations between the varied excited state lifetimes and coordination configurations with specific functional groups (−NH 2 or −NO 2 ) was inferred from the analyses of infrared spectroscopic data and theoretical calculations, revealing the essential role of the intramolecular interactions (i.e., between the added functional groups and the carboxylate group) in the modulation of system energetics. Overall, the work presents a pathway to tune the excited state dynamics and expands the knowledge regarding the photoinduced dynamic ligation in carboxylate-based MOFs.}, archive = {J_JACS}, author = {Qingyu Ye and Isabelle A. Herlinger and Lisa A. Fredin and Daniel R. Cairnie and Xiaozhou Yang and Minliang Yan and Amanda J. Morris}, doi = {10.1021/jacs.5c09921}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34690--34696}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the lifetimes of photoinduced deligation in a Metal–Organic framework via linker functionalization}, volume = {147}, year = {2025}, }
• (2025). Enzyme-click postsynthetic modification of covalent organic frameworks for photocatalytic H2O2 production. JACS, 147(38), 34681--34689. (www)

  @article{ , abstract = {Postsynthetic modification (PSM) is a powerful strategy for tailoring the structure and functionality of covalent organic frameworks (COFs). In this work, we present a novel enzymatic PSM strategy for functional group engineering within COFs. By taking advantage of enzymatic catalysis, 2-hydroxyethylthio (-S-EtOH) and ethylthio (-S-Et) groups were covalently implanted within the COF pore channels with high grafting efficiency under ambient aqueous conditions, highlighting the mild, efficient, and ecofriendly nature of this approach. Theoretical calculations and in situ experiments revealed that the incorporation of -S-EtOH not only promotes exciton dissociation with a superior charge separation efficiency but also strengthens the proton supply for the formation of hydrogenation intermediates and lowers the Gibbs free energy difference (Δ G ), thereby facilitating the photocatalytic H 2 O 2 production. Our work bridges the gap between enzymatic catalysis and reticular materials engineering, offering a conceptual breakthrough in COF postsynthetic modification and functionalization.}, archive = {J_JACS}, author = {Quan Zuo and Bingxian Chu and Xinhe Ye and Fayan Li and Lei Li and Qiang Xu}, doi = {10.1021/jacs.5c09922}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34681--34689}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzyme-click postsynthetic modification of covalent organic frameworks for photocatalytic H2O2 production}, volume = {147}, year = {2025}, }
• (2025). Enzyme-activated sugar-coated bifunctional degraders. JACS, 147(38), 34672--34680. (www)

  @article{ , abstract = {Targeted protein degradation with compounds like proteolysis targeting chimeras (PROTACs) directs disease-associated proteins to the E3 ligase ubiquitin-proteasome system for removal. However, commonly employed E3 ligases such as cereblon (CRBN) are broadly expressed. To metabolically gate PROTAC activity, we developed an enzymatic activation strategy by integrating an O-GlcNAc modification to the cyclimids, ligands derived from the natural motifs recognized by CRBN. These sugar-coated PROTACs (SCPs) were designed using structural analyses of representative cyclimid degraders complexed with CRBN and target protein BRD4. We found that glycosylation of the cyclimid reduced CRBN binding and complex formation with BRD4 until enzymatic removal of the O-GlcNAc moiety by O-GlcNAcase (OGA). The requirement for enzymatic activation is demonstrated by in vitro biochemical binding, cellular degradation, and cell viability assays in engineered and native cell lines. O-GlcNAc is thus an effective mechanism to gate targeted protein degradation modalities that motivates the development of similar strategies to enhance selectivity with other protein modifications.}, archive = {J_JACS}, author = {Qian Zhu and Gerhard Fischer and Steven S. Cheng and N. Connor Payne and Daniel Peter and Alison C. Mody and Silvia Arce-Solano and Dacheng Shen and Zhi Lin and Ralph Mazitschek and Dirk Kessler and Christina M. Woo}, doi = {10.1021/jacs.5c09843}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34672--34680}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzyme-activated sugar-coated bifunctional degraders}, volume = {147}, year = {2025}, }
• (2025). An activatable and covalent tumor-associated antigen capturer enabling systemic injection in vivo for promoted antitumor immunity. JACS, 147(38), 34659--34671. (www)

  @article{ , abstract = {Antigen-capturing nanomaterials hold great promise for cancer immunotherapy; however, the need for tumor localized administration and limited antigen-binding affinity remains the “Achilles heel” of this strategy. Herein, we present a tumor microenvironment (TME)-activatable nanoplatform, TDR848@FPB, designed for systemic administration and enhanced covalent capture of tumor-associated antigens (TAAs), enabling effective immunotherapy with minimal off-target effects and independent of localized tumor administration. This platform encapsulates a photosensitizer-conjugated, light-activated toll-like receptor (TLR) agonist, which induces immunogenic cell death and triggers a pro-inflammatory TME conducive to antigen capture upon light irradiation. TDR848@FPB covalently binds TAA-generated postphotodynamic therapy and promotes their efficient delivery to enhance dendritic cell maturation, T cell activation, and immunogenetic reprogramming of the TME. Following intravenous injection and light irradiation, TDR848@FPB demonstrates superior 1 O 2 generation capability and TAA capture efficiency, leading to significant tumor growth inhibition. Moreover, the captured TAAs and TLR agonists synergistically activate adaptive antitumor immunity, as evidenced by their potentiated T cell responses. These findings highlight the critical role of TME-activatable covalent antigen capture in enabling systemic delivery of antigen-capturing nanomaterials and validate TDR848@FPB as a versatile platform for precise cancer immunotherapy with a high therapeutic outcome and low off-target effects, independent of tumor localized administration.}, archive = {J_JACS}, author = {Zhiyuan Gao and Zhizhao Miao and Shaorui Jia and Dongping Zhang and Hongkai Zhang and Jianwu Tian and Jiliang Zhao and Jingrui Xin and Dan Ding}, doi = {10.1021/jacs.5c09791}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34659--34671}, shortjournal = {J. Am. Chem. Soc.}, title = {An activatable and covalent tumor-associated antigen capturer enabling systemic injection in vivo for promoted antitumor immunity}, volume = {147}, year = {2025}, }
• (2025). Confined assembly of well-defined single-unit chain with charge delocalization for boosting catalysis. JACS, 147(38), 34647--34658. (www)

  @article{ , abstract = {The ultimate miniaturization of catalysts to single-atomic dimensions offers a promising route to maximize the catalytic performance through fully exposed active sites and precisely tailored electronic structures. However, the synthesis of atomically precise one-dimensional single-cluster or single-atom catalysts with the simplest periodicity remains challenging due to their thermodynamic instability. Here, we report a general strategy for fabricating single-unit-chain catalysts confined within single-walled carbon nanotubes (SWCNTs), where charge delocalization dramatically enhances the catalytic performance. Through a liquid-phase assembly approach, diverse clusters and atoms can be uniformly packed into ordered single-unit chains inside SWCNTs, irrespective of their electronic properties or solubility. These identical, well-defined single-unit chains maintain intimate contact with the conductive graphene walls of SWCNTs, enabling tunable positive or negative charge delocalization across the nanotube surfaces. The resulting catalysts demonstrate remarkable activity enhancements in both redox and coupling reactions, exhibiting rate constants 7.5∼28 times greater than their isolated cluster counterparts. Mechanistic studies reveal that charge delocalization simultaneously increases the density of active sites and reduces the activation barriers. This synthetic approach and catalytic mechanism show universal applicability to various single-chain catalysts. These systems maintain nearly undiminished activity in 230 h continuous-flow reactions, highlighting their exceptional stability for practical applications.}, archive = {J_JACS}, author = {Boyuan Yu and Zhen Yao and Zheyi Cheng and Yulong Jiang and Hao Yang and Zhi Wang and Guodong Jia and Kun Wang and Meihui Song and Yingbo Li and Chengkai Zhang and Haibin Chu and Yang-Gang Wang and Di Sun and Yan Li and Feng Yang}, doi = {10.1021/jacs.5c09743}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34647--34658}, shortjournal = {J. Am. Chem. Soc.}, title = {Confined assembly of well-defined single-unit chain with charge delocalization for boosting catalysis}, volume = {147}, year = {2025}, }
• (2025). Coexistence of metallocene cations and anions. JACS, 147(38), 34641--34646. (www)

  @article{ , abstract = {We report the synthesis and structural characterization of the rhodocene anion [Rh(C 5 Me 5 )(C 5 (CF 3 ) 5 )] − [ 1 ] − as the [Co(C 5 Me 5 ) 2 ] + salt, representing an unprecedented coexistence of metallocene cations and anions in different oxidation states. [Co(C 5 Me 5 ) 2 ] + [ 1 ] − was synthesized by the reduction of the rhodocenium cation [Rh(C 5 Me 5 )(C 5 (CF 3 ) 5 )][BF 4 ] ([ 1 ] + [BF 4 ] − ) with two equivalents of decamethylcobaltocene [Co(C 5 Me 5 ) 2 ], since the strongly electron-withdrawing effect of the [C 5 (CF 3 ) 5 ] − ligand shifts the first and second reduction potentials of [ 1 ] + to moderate values of −0.90 and −1.46 V vs FcH 0/+ . [Co(C 5 Me 5 ) 2 ] + [ 1 ] − was characterized by single-crystal X-ray diffraction (XRD), providing the first example of a structurally characterized 4d metallocene anion. Whereas the Rh III cation has two η 5 -bound Cp ligands, the perfluorinated Cp* ligand is only η 3 -bound in the Rh I anion in order to obey the 18-electron rule. The reduction of the rhodocenium center is accompanied by a significant shift of the 103 Rh NMR signal from −9308 ppm of [ 1 ] + to −6895 ppm of [ 1 ] − (referenced to Rh(acetylacetonate) 3 ).}, archive = {J_JACS}, author = {Nico Gino Kub and Robin Sievers and Marc Reimann and Tim-Niclas Streit and Simon Steinhauer and Johanna Schlögl and Martin Kaupp and Moritz Malischewski}, doi = {10.1021/jacs.5c09718}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34641--34646}, shortjournal = {J. Am. Chem. Soc.}, title = {Coexistence of metallocene cations and anions}, volume = {147}, year = {2025}, }
• (2025). Galvanic corrosion of lithium metal anodes in Lithium–Sulfur batteries. JACS, 147(38), 34632--34640. (www)

  @article{ , abstract = {Lithium–sulfur (Li–S) batteries are promising next-generation rechargeable batteries due to their ultrahigh theoretical energy density. However, their cycling lifespan is hindered by the poor stability of Li metal anodes. The main challenge lies in the severe Li polysulfide (LiPS) corrosion on Li metal anodes. Herein, galvanic corrosion induced by LiPSs is identified as the main cause of nonuniform Li deposition and dissolution in working Li–S batteries. Concretely, LiPSs continuously corrode the Li metal anode and thereby increase its electrode potential to different extents according to the corrosion kinetics. The electrical connection of the Li metals with different corrosion kinetics causes galvanic corrosion and consequent selective Li deposition in severely corroded locations. Consequently, spatially heterogeneous LiPS corrosion eventually induces localized Li utilization, uneven Li distribution, and accelerated cell failure. To alleviate the galvanic corrosion, a Li fluoride-rich solid electrolyte interphase is preconstructed to passivate Li metal, suppress LiPS corrosion, and extend the cycling lifespan of Li–S batteries by 57% under harsh working conditions. This work identifies the chemical nature of nonuniform Li deposition following the galvanic corrosion mechanism and highlights the importance of passivating Li metal anodes to realize long-cycling Li–S batteries.}, archive = {J_JACS}, author = {Chen-Xi Bi and Yu-Jie Zhu and Xi-Yao Li and Jin Ma and Xue-Qiang Zhang and Meng Zhao and Bo-Quan Li and Jia-Qi Huang}, doi = {10.1021/jacs.5c09705}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34632--34640}, shortjournal = {J. Am. Chem. Soc.}, title = {Galvanic corrosion of lithium metal anodes in Lithium–Sulfur batteries}, volume = {147}, year = {2025}, }
• (2025). Immunoglobulin-directed phase separation for cell-specific modulation of receptor signaling. JACS, 147(38), 34620--34631. (www)

  @article{ , abstract = {Liquid-liquid phase separation is a fundamental process in cellular biology, influencing various cellular functions. Recent research highlights the critical role of phase separation in membrane-associated signaling complexes, where it spatiotemporally modulates signaling pathways. In this research, we have engineered a phase-separation system utilizing specific antibody-peptide multivalent interaction. In particular, the phase-separation system was constituted by a mutant Fc fragment from the human IgG1 and a peptide specifically bound to the mutant Fc. Further, by tethering the phase separation scaffolds to nanobodies targeting specific cell-surface receptors CXCR4 and DR5, we could specifically activate DR5 signaling in CXCR4 + cells. Moreover, the CXCR4/DR5-targeting phase separation system efficiently induced tumor cell apoptosis and tumor growth inhibition in the xenograft model, offering a novel strategy for tumor-specific apoptosis induction. This work demonstrates the potential of the immunoglobulin-directed phase separation systems as a tool for cell-specific signaling modulation for scientific research and therapeutic applications.}, archive = {J_JACS}, author = {Weishuai Ren and Peiyuan Zheng and Ziting Zhou and Min Zhou and Mengling Wu and Yanchao Ding and Haolin Jiang and Pilong Li and Juanjuan Du}, doi = {10.1021/jacs.5c09699}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34620--34631}, shortjournal = {J. Am. Chem. Soc.}, title = {Immunoglobulin-directed phase separation for cell-specific modulation of receptor signaling}, volume = {147}, year = {2025}, }
• (2025). Intermolecular lithium η2-alkene and κ2-alkane complexes: Synthesis, bonding, and facile interconversion. JACS, 147(38), 34610--34619. (www)

  @article{ , abstract = {In this work, an approach enabling the synthesis of η 2 -alkene lithium complexes (Carb 2,4,6- i Pr )Li(η 2 -L) (L = 1-octene, cyclohexene) is elaborated. For 1,5-hexadiene, the same approach results in a binuclear μ-η 2 :η 2 -diene complex. The QTAIM parameters reveal the electrostatic nature of the Li-alkene interaction. When treated with cyclohexane, alkene ligands in (Carb 2,4,6- i Pr )Li(η 2 -L) are readily replaced to afford the Li-alkane complex (Carb 2,4,6- i Pr )Li(κ 2 -C 6 H 12 ) featuring anagostic Li···H interactions. The reverse reaction readily proceeds in the presence of excess alkene. The QTAIM and LED analyses performed at the DLPNO–CCSD(T) level show a small difference between the complexes in the total dispersion contribution (16.0–18.5 kcal/mol) and interaction energy for Li–alkene (∼3.5 kcal/mol) or Li–C 6 H 12 (∼4 kcal/mol). These values suggest the presence of an equilibrium between these entities, which can be readily shifted by the presence of an excess of alkene or alkane. (Carb 2,4,6- i Pr )Li(η 2 -L) and (Carb 2,4,6- i Pr )Li(κ 2 -C 6 H 12 ) are transformed into η 2 -arene complexes upon treatment with benzene; however, a reverse reaction is not possible at room temperature.}, archive = {J_JACS}, author = {Mikhail A. Bogachev and Alexander N. Selikhov and Anton V. Cherkasov and Rinat R. Aysin and Sergey S. Bukalov and Alexander A. Trifonov}, doi = {10.1021/jacs.5c09648}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34610--34619}, shortjournal = {J. Am. Chem. Soc.}, title = {Intermolecular lithium η2-alkene and κ2-alkane complexes: Synthesis, bonding, and facile interconversion}, volume = {147}, year = {2025}, }
• (2025). Enhanced sensitivity of nonlinear optical signatures of aggregation-induced emission. JACS, 147(38), 34601--34609. (www)

  @article{ , abstract = {Understanding how molecular aggregation influences nonlinear optical properties is essential for advancing organic fluorophores in imaging, sensing, and photonic applications. However, the relationship between the molecular aggregation and the magnitude of nonlinear two-photon absorption cross-section remains underexplored. Here, we systematically investigate the aggregation-dependent two-photon absorption properties of the fluorophore TPAPhCN by tuning the degree of aggregation. We observe a steady increase in the two-photon absorption cross-section as the fluorophore evolves from the single molecular state to the highly aggregated state. It is found that two-photon absorption signal emerges at an early stage of aggregation that is not observable by one-photon excitation. This divergence between the nonlinear and linear optical responses enables the construction of a dual-mode optical signature, allowing TPAPhCN to function as a self-reporting probe for each aggregation state. This work presents a sensitive and structure-responsive platform for precise aggregation-state sensing in complex environments and opens new opportunities for applications in materials diagnostics and intelligent optical sensing systems.}, archive = {J_JACS}, author = {Bo Zhou and Xia Ling and Tarun Senthil and Bin Liu and Theodore Goodson III}, doi = {10.1021/jacs.5c09619}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34601--34609}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced sensitivity of nonlinear optical signatures of aggregation-induced emission}, volume = {147}, year = {2025}, }
• (2025). Tandem catalysis enables the hydrocarboxylation of γ-valerolactone with CO2 and h2 to produce adipic acid. JACS, 147(38), 34589--34600. (www)

  @article{ , abstract = {Adipic acid is an industrially important chemical that is currently produced from fossil resources. In this work, we report the first method for the production of adipic acid from biomass-derived γ-valerolactone (GVL) with CO 2 and H 2 . It was discovered that the Rh catalyst with an I 2 promoter in a binary solvent system of AcOH/H 2 O could catalyze the reaction efficiently at an industrially relevant temperature (140 °C). A systematic and detailed analysis of the reaction pathway was conducted via experimental and DFT studies. The tandem one-pot process permits thermodynamic leveraging by coupling the thermodynamically unfavored GVL ring-opening with highly favored hydrocarboxylation, driving the overall reaction forward to diacid products. The reaction involves three key steps, including the reduction of CO 2 to CO and H 2 O by H 2 , the ring-opening of GVL to reaction intermediates, and the hydrocarboxylation of the intermediates with CO and H 2 O. The stable GVL can maintain a low concentration of the highly reactive intermediates and prevent their hydrogenation side reactions, which favors the high selectivity of diacids. Moreover, this strategy affords access to various diacids in high yields from different lactones, and the yield of the diacids could reach 89%. This protocol opens the way for the sustainable synthesis of adipic acid from two renewable carbon resources and a green reductant (H 2 ).}, archive = {J_JACS}, author = {Ying Wang and Yanru Zhang and Chenglong Yu and Jia Guo and Jun He and Longbo Zhang and Yanyan Wang and Jianling Zhang and Tianbin Wu and Qingli Qian and Buxing Han}, doi = {10.1021/jacs.5c09561}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34589--34600}, shortjournal = {J. Am. Chem. Soc.}, title = {Tandem catalysis enables the hydrocarboxylation of γ-valerolactone with CO2 and h2 to produce adipic acid}, volume = {147}, year = {2025}, }
• (2025). Unraveling the dichotomy exerted by boron reagents in site-selective functionalization of c(sp2)– and C(sp3)–OMe bonds. JACS, 147(38), 34575--34588. (www)

  @article{ , abstract = {Although C(sp 2 )– and C(sp 3 )–OMe bonds are arguably the simplest and most atom-economical derivatives in the alcohol series, these linkages have rarely been utilized as coupling partners in the context of metal-catalyzed carbon-heteroatom bond-formation. Among other scenarios, Ni-catalyzed borylation of aryl and benzyl methyl ethers via C(sp 2 )– and C(sp 3 )–OMe cleavage is a particularly attractive endeavor, given that the resulting organoboranes are privileged synthons of utmost relevance in organic synthesis and materials science. Intriguingly, the nature of the boron reagent dictates whether functionalization occurs at the C(sp 2 )– or C(sp 3 )–OMe fragment. Herein, we report a detailed study aimed at understanding the mechanistic underpinnings of this reaction and the origins of site-selectivity. We conclude that the divergency in site-selectivity arises from a different nickel speciation within the catalytic cycle. Specifically, our investigations reveal that catalytic functionalization at the C(sp 2 )–OMe bond occurs via a Ni(I) manifold in the presence of B 2 nep 2 whereas a canonical Ni(0)/Ni(II) regime is responsible for the corresponding C(sp 3 )–OMe bond-cleavage with B 2 pin 2 as coupling partner. These findings focus attention on the critical role that metal speciation might have for dictating site-selectivity in other related cross-coupling reactions.}, archive = {J_JACS}, author = {Pan-Pan Chen and Tomás G. Santiago and Carlota Odena and Chi Zhang and Ruben Martin and K. N. Houk}, doi = {10.1021/jacs.5c09306}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34575--34588}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the dichotomy exerted by boron reagents in site-selective functionalization of c(sp2)– and C(sp3)–OMe bonds}, volume = {147}, year = {2025}, }
• (2025). An alkyne-directed cleavage approach for activity-based Cu(I) sensing reveals manganese-promoted sensitization of cuproptosis. JACS, 147(38), 34564--34574. (www)

  @article{ , abstract = {Copper is an essential element for sustaining life. However, disruptions in copper homeostasis underpin disease, as illustrated by cuproptosis, an emerging form of cell death resulting from aberrant accumulation of copper pools in loosely bound, labile forms. Along these lines, activity-based sensing (ABS) offers a powerful strategy for tracking labile copper fluxes with metal and oxidation state selectivity by exploiting analyte reactivity for analyte detection. Traditional ABS probes for Cu(I), the major oxidation state of copper in cells, are selective but require O 2 as a coadditive, thus limiting their temporal resolution and sensitivity. Here, we present the design, synthesis, and biological evaluation of a first-generation ABS strategy for direct Cu(I) sensing by leveraging alkyne-directed cleavage reactivity. Copper Alkyne Probe-1 (CAP-1) features a rapid response to changes in intracellular Cu(I) pools with over 400-fold selectivity for Cu(I) over competing biological metals. We apply this probe to identify novel metal–metal crosstalk in cuproptosis, where we observe that Mn(II) exposure sensitizes cells to cuproptosis through upregulating the mitochondrial reductase FDX1 and depleting reduced glutathione, thus synergistically elevating labile Cu(I) levels. By revealing an interplay between copper and manganese in regulating cell death, this work provides a starting point for broader investigations of metal–metal nutrient crosstalk in biology and medicine.}, archive = {J_JACS}, author = {Xiao Xie and Gen Li and Aidan T. Pezacki and Jiaying Gao and Miku Oi and Christopher J. Chang}, doi = {10.1021/jacs.5c09297}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34564--34574}, shortjournal = {J. Am. Chem. Soc.}, title = {An alkyne-directed cleavage approach for activity-based Cu(I) sensing reveals manganese-promoted sensitization of cuproptosis}, volume = {147}, year = {2025}, }
• (2025). Automated reactivity prediction of complex molecules and its application to total synthesis of ageliferin. JACS, 147(38), 34556--34563. (www)

  @article{ , abstract = {Predicting the reactivity of complex molecules and planning reliable synthetic routes have long been challenges in natural product synthesis. We have addressed these challenges by using automated reactivity prediction using ConfoTS, an integrated program based on ACCeL, and have completed the total synthesis of ageliferin. The optimal substrate equipped with a d -tartrate scaffold for the dearomative Diels–Alder reaction of the hymenidin unit was designed through automated evaluation of the energy barriers for various virtual substrates. The highly functionalized six-membered framework was stereoselectively constructed by the cycloaddition of the designed substrate, leading to the synthesis of ageliferin in 15 steps from a known tetrahydropyridazine.}, archive = {J_JACS}, author = {Yudai Fujino and Keisuke Fukaya and Daisuke Urabe}, doi = {10.1021/jacs.5c09045}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34556--34563}, shortjournal = {J. Am. Chem. Soc.}, title = {Automated reactivity prediction of complex molecules and its application to total synthesis of ageliferin}, volume = {147}, year = {2025}, }
• (2025). The hydroxyl migration mechanism through vibrational rocking unveiled from magic-numbered hydrated lanthanum oxide clusters. JACS, 147(38), 34548--34555. (www)

  @article{ , abstract = {A deep understanding of the structural evolution of metal oxide clusters and the migration of surface functional groups is of fundamental importance for understanding their catalytic mechanisms. However, due to the structural complexity and the difficulty in the generation and characterization of these species, such a study at the molecular level is still challenging. Herein, a series of magic-numbered cluster ions of hydrated lanthanum oxide were studied by combining laser ablation mass spectrometry, infrared photon dissociation spectroscopy, and theoretical calculations. Based on the identified most stable isomers of the clusters, a new mechanism for OH migration has been revealed, in which the vibrational rocking of OH groups results in the migration of OH groups on the surfaces of the clusters with an energy barrier less than 12 kcal/mol. This work reveals the rocking-induced OH migration process and corresponding energy barriers, shedding light on the effects of rocking vibration modes on the mobility of OH groups and possible subsequent impacts on surface catalysis.}, archive = {J_JACS}, author = {Shumei Yang and Yameng Hou and Shen Bian and Kairui Yang and Xianglei Kong}, doi = {10.1021/jacs.5c09002}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34548--34555}, shortjournal = {J. Am. Chem. Soc.}, title = {The hydroxyl migration mechanism through vibrational rocking unveiled from magic-numbered hydrated lanthanum oxide clusters}, volume = {147}, year = {2025}, }
• (2025). Engineering colloidal quasi-2D quantum wells for high-performance room-temperature single-photon sources. JACS, 147(38), 34540--34547. (www)

  @article{ , abstract = {Single-photon sources (SPSs) are essential for quantum technologies. Colloidal quasi two-dimensional (2D) quantum wells (QWs) possess high emission uniformity, photoluminescence quantum yields (PLQYs), and narrow linewidths at room temperature, all contributing to ideal SPSs. However, their large lateral dimensions make excitons sensitive to environments and enhance multiexciton emission, casting long-standing doubt on their viability as SPSs. Here, we demonstrate bright room-temperature single-photon emission (SPE) with high purity and minimal blinking from in-plane-engineered (IPE) 2D QWs incorporating a doubly gradient architecture. A compositionally graded CdSe/CdSe x S 1– x core in the in-plane direction tailors electron–hole wavefunctions to control multiexciton Auger dynamics, while a graded Cd y Zn 1– y S shell in the thickness direction suppresses interfacial strain and nonradiative defects. This design unites 0D and 2D structural advantages, achieving near-unity ensemble PLQY and bright SPE (0.6–1.2 × 10 5 counts/s, NA = 0.65). Controlling the CdSe core size via IPE, we attain 92% single-photon purity (2 nm core), and suppressed blinking with a 96.9% ON-time fraction (8 nm core). This work establishes deterministic design rules for colloidal 2D QWs as high-performance SPSs for scalable quantum technologies.}, archive = {J_JACS}, author = {Tingting Yin and Xiao Liang and Yuqing Huang and Yi Tian Thung and Zhenhua Ni and Handong Sun and Hilmi Volkan Demir}, doi = {10.1021/jacs.5c08797}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34540--34547}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering colloidal quasi-2D quantum wells for high-performance room-temperature single-photon sources}, volume = {147}, year = {2025}, }
• (2025). Catalytic consequences of pore structure, nodal identity, and coordination environment on styrene oxidation by hydrogen peroxide over fe MOFs. JACS, 147(38), 34527--34539. (www)

  @article{ , abstract = {Selective hydrocarbon oxidation processes are central in fine and commodity chemical production and are sensitive to the nature of the active metal sites and their surrounding coordination environment. Isometallic Fe-based carboxylate MOFs (MIL-100, MIL-101, and NH 2 -MIL-101) are employed to elucidate how Fe coordination environments and framework topology influence a probe aryl (styrene) oxidation mediated by hydrogen peroxide (H 2 O 2 ). MIL-101 shows the highest oxygenate production turnover rates, as normalized by in situ thiophene titrations, followed by NH 2 -MIL-101 and MIL-100. Post reaction e x situ Mössbauer spectroscopy elucidates Fe(II) formation under reaction conditions that underpin increased oxygenate production turnover rates; this Fe(II) formation was enabled by the reductive elimination of halide capping ligands unique to the MIL-101 family but not present in MIL-100 that only contains hydroxyls. Defect undercoordinated Fe sites promote unproductive H 2 O 2 decomposition and secondary oxygenate formation but do not perturb primary oxygenate selectivities. Conversely, stabilizing hydrogen-bonding interactions between N–H donors and postulated benzaldehyde metallocycle transition state structures confer NH 2 -MIL-101 100% selectivity for the primary oxygenate product benzaldehyde over styrene oxide at differential styrene conversions (<3%) compared to a maximum of 59% for MIL-101. Although a fraction of linker amine moieties oxidize to form nitro groups within NH 2 -MIL-101, Fe leaching, identified as a contributor to catalyst deactivation for all frameworks, is reduced. Overall, this work showcases how seemingly subtle changes and perturbations to the coordination environments local to metal sites influence the observed reactivity, selectivity, and stability for oxidative (and other) transformations within MOF-catalyzed reaction systems throughout their lifetimes.}, archive = {J_JACS}, author = {Rachel A. Yang and James L. Trettin and Joshua L. Miller and Michele L. Sarazen}, doi = {10.1021/jacs.5c08736}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34527--34539}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic consequences of pore structure, nodal identity, and coordination environment on styrene oxidation by hydrogen peroxide over fe MOFs}, volume = {147}, year = {2025}, }
• (2025). Biosynthesis of unnatural cyclodipeptides through genetic code expansion and cyclodipeptide synthase evolution. JACS, 147(38), 34517--34526. (www)

  @article{ , abstract = {Genetic code expansion (GCE) technology has primarily been devoted to the introduction of noncanonical amino acids (ncAAs) into ribosomally synthesized proteins or peptides. Its potential for modifying nonribosomal natural products remains unexplored. In this study, we introduce a novel strategy that integrates GCE with the directed evolution of cyclodipeptide synthase (CDPS) to engineer a new class of CDPSs capable of biosynthesizing cyclodipeptides containing ncAAs. Using this approach, we achieve the efficient incorporation of 4-azido- l -phenylalanine into AlbC-derived cyclodipeptides, generating a diverse array of new-to-nature cyclodipeptides. Molecular dynamics simulations and binding free energy calculations provide insights into the potential catalytic mechanisms responsible for the enhanced recognition of ncAA-tRNAs by engineered CDPS variants. Furthermore, we expand the substrate scope to additional ncAAs and extend this approach to other CDPSs, enabling the creation of an even broader range of novel compounds. Together, these findings reveal the significant potential of GCE technology to precisely engineer biomolecules beyond proteins, unlocking new structural and functional diversity.}, archive = {J_JACS}, author = {Yu Hu and Linqi Cheng and Yijie Liu and Rui Liu and Shiyu Jason Jiang and Teng Yuan and Yixian Wang and Haoxin Ye and Han Xiao}, doi = {10.1021/jacs.5c08627}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34517--34526}, shortjournal = {J. Am. Chem. Soc.}, title = {Biosynthesis of unnatural cyclodipeptides through genetic code expansion and cyclodipeptide synthase evolution}, volume = {147}, year = {2025}, }
• (2025). Radical isomerization upon dissociative electron ionization of anthracene and phenanthrene. JACS, 147(38), 34508--34516. (www)

  @article{ , abstract = {Polycyclic aromatic hydrocarbons (PAHs) are abundantly present in space. The grandPAH hypothesis states that small PAHs are photodissociated, while large symmetric PAHs survive the harsh environments in space. Moreover, it has been hypothesized that large aromatic molecules (C n H m with n ≥ 60) can convert to buckminsterfullerene (C 60 ). In this work, we test these hypotheses by studying the products formed upon dissociative electron ionization of two isomeric C 14 H 10 PAHs, anthracene and phenanthrene. The fragment ions that are formed following H loss and H 2 loss are isolated in a cryogenically-cooled 22-pole ion trap and tagged with neon. Infrared predissociation spectra are recorded of the thus formed van der Waals bound complexes and the PAH dissociation fragments are identified based on a comparison with density functional theory (DFT) calculated spectra. The ionized PAHs undergo radical isomerization prior to the loss of H or H 2 , resulting in a highly symmetric daughter ion that is identical for the two distinctly different parent PAHs. Moreover, the product ions are found to obey the isolated pentagon rule, which also curves fullerenes and contributes to their structural stability. We propose a mechanism for the radical isomerization based on existing molecular dynamics simulations from the literature augmented by DFT calculations. This study lends credit to the grandPAH hypothesis by showing that PAH species isomerize drastically to form a new molecule that is highly symmetric. Moreover, the formation of a daughter species that obeys the isolated-pentagon rule suggests that there is a strong chemical link between interstellar PAHs and fullerenes.}, archive = {J_JACS}, author = {Madison M. Patch and Rory McClish and Sanjana Panchagnula and Daniël B. Rap and Shreyak Banhatti and Helgi R. Hrodmarsson and Sandra Brünken and Harold Linnartz and Alexander G. G. M. Tielens and Jordy Bouwman}, doi = {10.1021/jacs.5c08619}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34508--34516}, shortjournal = {J. Am. Chem. Soc.}, title = {Radical isomerization upon dissociative electron ionization of anthracene and phenanthrene}, volume = {147}, year = {2025}, }
• (2025). Harnessing radical-based dynamic covalent chemistry and supramolecular synthon for directional self-assembly. JACS, 147(38), 34498--34507. (www)

  @article{ , abstract = {The discovery of new weak supramolecular interactions and supramolecular synthons is essential for directing self-assembly processes with enhanced precision, diversity, and functionality in complex molecular architectures. Here, we report the controlled self-assembly of diverse supramolecular architectures by a new directional bonding approach through the integration of radical-based dynamic covalent chemistry and supramolecular synthons. A novel macrocyclic synthon, S1 , with a linear direction is constructed via radical-based dynamic covalent bonds from the phenothiazine building block substituted with two dicyanomethyl radicals. By coupling S1 with phenanthrene- and carbazole-based linkers with different angles, we achieve precise and controllable self-assembly. As anticipated, when S1 is paired with a 60° phenanthrene linker, a triangular superstructure, the macrocycle-bridged macrocycle M1 , is formed. Notably, coupling S1 with a nearly 90° carbazole linker yields two distinct superstructures, M2 and M3 , with triangular and quadrangular geometries, respectively. Interestingly, both the synthon and its assembled superstructures exhibit intriguing thermal association and dissociation behaviors, facilitated by the formation of stable chromogenic radicals. This dynamic process was thoroughly investigated by using VT-UV–vis–NIR, VT-NMR, and VT-EPR spectroscopies. More significantly, the reversible dissociation and association of radical-based dynamic covalent bonds enable the full thermal conversion of M2 and M3 . This study highlights the potential of integrating radical-based dynamic covalent chemistry with supramolecular synthons as an emerging strategy for the precise construction of sophisticated and multifunctional supramolecular architectures, paving the way for the development of novel stimuli-responsive materials.}, archive = {J_JACS}, author = {Shengzhong Li and Xiao-Li Zhao and Xueliang Shi and Hai-Bo Yang}, doi = {10.1021/jacs.5c08506}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34498--34507}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing radical-based dynamic covalent chemistry and supramolecular synthon for directional self-assembly}, volume = {147}, year = {2025}, }
• (2025). Structural basis for HIV-1 maturation inhibition by PF-46396 determined by MAS NMR. JACS, 147(38), 34487--34497. (www)

  @article{ , abstract = {Among the different types of HIV-1 maturation inhibitors, those that stabilize the junction between the capsid protein C-terminal domain (CA CTD ) and the spacer peptide 1 (SP1) within the immature Gag lattice are promising candidates for antiretroviral therapies. Here, we report the atomic-resolution structure of CA CTD -SP1 assemblies with the small-molecule maturation inhibitor PF-46396 and the assembly cofactor inositol hexakisphosphate (IP6), determined by magic angle spinning (MAS) NMR spectroscopy. Our results reveal that although the two PF-46396 enantiomers exhibit distinct binding modes, they both possess similar anti-HIV potency. PF-46396 binding arrests IP6 dynamics in the six-helix bundle pore, and the two enantiomers induce unique IP6 orientations in the pore. Importantly, our data suggest the presence of monoanionic IP6 form in the complex. Our study establishes the structural basis for PF-46396 action and suggests a mechanistic model for drug resistance.}, archive = {J_JACS}, author = {Roman Zadorozhnyi and Caitlin M. Quinn and Kaneil K. Zadrozny and Sherimay D. Ablan and Brandon J. Kennedy and Glenn P. A. Yap and Daniel Sanner and Christina Kraml and Eric O. Freed and Barbie K. Ganser-Pornillos and Owen Pornillos and Angela M. Gronenborn and Tatyana Polenova}, doi = {10.1021/jacs.5c08455}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34487--34497}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural basis for HIV-1 maturation inhibition by PF-46396 determined by MAS NMR}, volume = {147}, year = {2025}, }
• (2025). Photosynthetic biohybrid system for enhanced abiotic n2-to-NH3 conversion under ambient conditions. JACS, 147(38), 34477--34486. (www)

  @article{ , abstract = {Photosynthetic biohybrid systems (PBSs) offer an eco-friendly approach to transforming solar energy into value-added products by integrating biological entities with inorganic semiconductors. However, the chemical conversion capacity of most PBSs has inherent limitations, as whole-cell bacteria and isolated enzymes require fine-tuning of environmental conditions. Here, we report a new PBS developed by introducing free-standing ceria nanoparticles into the purple membrane (PM) of Halobacterium salinarum archaea, which can unidirectionally transfer charge carriers in response to incident photons, even after separation from living archaea at various conditions. Our microscopy, spectroscopy, and synchrotron X-ray scattering analyses confirm that the electrostatic assembly between ceria and PM creates seamless interfacial contact, thereby enhancing the photocatalytic capacity of ceria. Although the conversion of dinitrogen (N 2 ) to ammonia (NH 3 ) is thermodynamically challenging due to the triple bond in N 2 and a series of charge-transfer reactions, our PM–ceria (PMC) hybrid nanoparticle efficiently produces NH 3 by reducing N 2 using solar energy even under atmospheric pressure and room temperature while simultaneously converting glycerol into value-added derivatives. Additionally, our PMC nanoparticle involves neither toxic/precious metals nor bioengineering processes to achieve enhanced photocatalytic N 2 -to-NH 3 conversion. This study sheds light on the new aspect of PBSs by employing PM to potentially resolve the global energy and environmental challenges posed by the conventional Haber–Bosch process.}, archive = {J_JACS}, author = {Jinhyeong Jang and Yuzi Liu and David J. Gosztola and Ivan Kuzmenko and Jens Niklas and Oleg G. Poluektov and Byeongdu Lee and Elena A. Rozhkova}, doi = {10.1021/jacs.5c08453}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34477--34486}, shortjournal = {J. Am. Chem. Soc.}, title = {Photosynthetic biohybrid system for enhanced abiotic n2-to-NH3 conversion under ambient conditions}, volume = {147}, year = {2025}, }
• (2025). Solid-state ionomer-interlayered bulk monolayer MoS2 membranes with thickness-scalable bright luminescence. JACS, 147(38), 34466--34476. (www)

  @article{ , abstract = {Monolayer MoS 2 is attractive for future photonics and optoelectronics for its direct-gap excitons with ultrahigh binding energies. However, the atomically thin structure is prone to nonradiative defects, challenging to scale for large-area production, and inherently limited in optical cross-section, all hindering technological integration. Stacking monolayers to increase the optical cross-section results in multilayers with diminished photoluminescence activity. Electrochemical molecular intercalation of multilayer MoS 2 weakens interlayer coupling, creating a bulk monolayer material that retains monolayer characteristics within a multilayered “bulk” architecture. However, the electrochemical process often severely degrades the optical quality and is difficult to implement for scalable thin film production. Here, we report a luminescent monolayer MoS 2 colloidal ink for scalable solution processing of large-area bulk monolayer MoS 2 membranes with thickness-scalable bright luminescence. Using perfluorinated sulfonic-acid ionomer (Nafion) as a multifunctional ligand, we achieve a stable dispersion of monolayer MoS 2 ink that can be readily processed into large-area stretchable membranes with diverse form factors. The Nafion interlayers decouple interlayer interactions while effectively passivating nonradiative defects, preserving direct-gap monolayer characteristics in thickness-scalable MoS 2 /Nafion membranes. This leads to unprecedented enhancements in both linear and nonlinear excitonic transitions, showing over 100-fold brighter excitonic photoluminescence and nearly 1000 times stronger second harmonic generation. These remarkable properties remain robust against intense laser irradiation, diverse environmental conditions, and mechanical deformations. Our studies overcome the longstanding challenge of poor optical quality in solution-processed monolayer MoS 2 ink materials, establishing a large-area, thickness-scalable platform for excitonic devices across diverse technological domains, including photonics, optoelectronics, solution-processable bioelectronics, and electrochemical sensing.}, archive = {J_JACS}, author = {Boxuan Zhou and Chen Li and Haoyang Li and Zidi Yang and Bangyao Hu and Ran Wang and Yucheng Zhang and Ao Zhang and Martin-Louis Y. Riu and Xingxu Yan and Ting-Jung Hsiao and Xiaoqing Pan and Matthew Nava and Yu Huang and Xiangfeng Duan}, doi = {10.1021/jacs.5c08388}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34466--34476}, shortjournal = {J. Am. Chem. Soc.}, title = {Solid-state ionomer-interlayered bulk monolayer MoS2 membranes with thickness-scalable bright luminescence}, volume = {147}, year = {2025}, }
• (2025). Strain-promoted mRNA transdermal delivery by lipoic lipid nanoparticles for therapeutic skin genome editing. JACS, 147(38), 34449--34465. (www)

  @article{ , abstract = {Lipid nanoparticle (LNP)-mRNA formulations have revolutionized the field of nucleic acid therapeutics, yet their broader clinical application is constrained by inflammatory side effects and oxidative stress, particularly in the context of inflammatory diseases. Herein, we report the rational design and synthesis of a lipoic acid-based ionizable lipid library to address these limitations. By leveraging the antioxidant properties and thiol-mediated uptake potential of lipoic acid, we identified LA-A2B2CD3 as an optimal candidate through a structure–activity relationship study and design of experiment (DOE) optimization. LA-A2B2CD3 LNPs exhibited superior reactive oxygen species scavenging, enhanced mRNA translation, and reduced inflammatory cytokine production in vitro and in vivo . Mechanistic studies revealed that the efficient cellular uptake and the transdermal delivery capacity of LA-A2B2CD3 heavily rely on the reducible disulfide ring of lipoic acid. Application of LA-A2B2CD3 LNPs for the localized transdermal delivery of Cas9 mRNA and CD93 sgRNA in a murine model of psoriasis resulted in effective CD93 genome editing and the inhibition of the CD93–p38 MAPK–AKT–SMAD2/3 pathway, leading to significant therapeutic improvement. This work presents a robust, biocompatible LNP platform with minimized immunogenicity and strong potential for genome-editing therapies in inflammatory conditions, offering a transformative approach for the mRNA-based treatment of skin and other inflammation-related disorders.}, archive = {J_JACS}, author = {Chaorong Wang and Qi Pan and Shuangxiang Chen and Yicheng Zhang and Xiaojie Xu and Xiaojie Yan and Jiajing Guo and Xiaohong Chen and Bowen Li and Ganzorig Chimed and Zhijia Liu and Yuan Ping}, doi = {10.1021/jacs.5c08376}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34449--34465}, shortjournal = {J. Am. Chem. Soc.}, title = {Strain-promoted mRNA transdermal delivery by lipoic lipid nanoparticles for therapeutic skin genome editing}, volume = {147}, year = {2025}, }
• (2025). Long-lived hole accumulation in Al:SrTiO3/Rh–Cr photocatalyst systems under continuous irradiation and its correlation with overall water splitting efficiency. JACS, 147(38), 34438--34448. (www)

  @article{ , abstract = {Photocatalytic water splitting offers a scalable and potentially low-cost route for the production of renewable hydrogen. Recently, a state-of-the-art system based on flux-mediated Al 3+ -doped SrTiO 3 , modified with Rh–Cr-based proton reduction and CoOOH water oxidation cocatalysts, achieved apparent quantum yields for unassisted water splitting of up to 93%. Herein, we focus on the role of Al 3+ doping and Rh–Cr-based cocatalyst deposition on the accumulation and reaction dynamics of the long-lived holes required to drive water oxidation. We employ in situ and operando photoinduced absorption spectroscopy (PIAS) under water splitting conditions complemented by X-ray photoelectron spectroscopy (XPS). XPS data indicate that Al 3+ doping suppresses surface Ti 3+ defect states, coinciding with a 5-fold increase in the accumulation of long-lived SrTiO 3 holes observed by PIAS. Rh–Cr-based cocatalyst addition is observed to further enhance the yield and lifetime (s–10 s time scales) of these photoaccumulated holes, assigned to the efficient electron extraction by this cocatalyst. These photoaccumulated holes exhibit fast (ca. 1 s) and slow (ca. 10 s) decay phases. While the dominant fast phase is assigned to the desired water oxidation reaction, the slow phase is assigned to deeply trapped unreactive holes; the yield of these unreactive holes is suppressed by facet-selective photodeposition of cocatalysts or preillumination. These results provide key insights into how Al:SrTiO 3 functionalized by Rh–Cr-based cocatalysts accumulates oxidizing holes with lifetimes long enough to drive the kinetically challenging water oxidation reaction, thus achieving remarkably high quantum efficiencies for overall water splitting, insights which can be applied in the design of future photocatalytic materials.}, archive = {J_JACS}, author = {Anna A. Wilson and Benjamin Moss and Aysha A. Riaz and Curran Kalha and Pardeep K. Thakur and Tien-Lin Lee and Anna Regoutz and Tsuyoshi Takata and Takashi Hisatomi and Kazunari Domen and James R. Durrant}, doi = {10.1021/jacs.5c07521}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34438--34448}, shortjournal = {J. Am. Chem. Soc.}, title = {Long-lived hole accumulation in Al:SrTiO3/Rh–Cr photocatalyst systems under continuous irradiation and its correlation with overall water splitting efficiency}, volume = {147}, year = {2025}, }
• (2025). Development of cyclooctyne-nitrone based click release chemistry for bioorthogonal prodrug activation both in vitro and in vivo. JACS, 147(38), 34425--34437. (www)

  @article{ , abstract = {The advancement of bioorthogonal cleavage platforms has emerged as a critical frontier in chemical biology, offering precise molecular liberation through physiologically compatible activation mechanisms. Despite its significant potential, ensuring efficacy in vivo typically requires rapid reaction kinetics, high-efficiency payload release, and stable reactants; however, relevant reports remain sparse. Herein, we developed a strain-promoted alkyne-nitrone cycloaddition (SPANC)-based click-release chemistry through installation of a carbamate-linked release moiety at the propargyl position of cyclooctyne, triggering a spontaneous elimination following click cycloaddition to achieve efficient payload liberation. This bioorthogonal click-release system demonstrates rapid reaction kinetics and high-yield payload liberation while maintaining exceptional stability under both in vitro and cellular conditions. Furthermore, we established a facile synthesis of highly click-reactive nitrones, enabling the construction of a systematic substrate library and validating the broad applicability of this strategy. In the context of implementation, our developed bioorthogonal anticancer prodrugs utilize nitrone-mediated activation to unmask anticancer activity. In 4T1 murine breast cancer models, this bioorthogonal prodrug activation strategy demonstrated significant tumor suppression with favorable safety profiles, validating the feasibility of this click-release chemistry for in vivo use.}, archive = {J_JACS}, author = {Xiaowei Xu and Yuanan Wang and Yangfei Shi and Xin Wang and Xidan Tong and Yanzhao Chen and Yan Zhao and Jiaxuan Chen and Weiwei Guo and Yueqin Zheng}, doi = {10.1021/jacs.5c08152}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34425--34437}, shortjournal = {J. Am. Chem. Soc.}, title = {Development of cyclooctyne-nitrone based click release chemistry for bioorthogonal prodrug activation both in vitro and in vivo}, volume = {147}, year = {2025}, }
• (2025). A hybrid ultrastrong coordinating solvent and an ion-conductive diluent for high-voltage ether-based li-metal batteries. JACS, 147(38), 34411--34424. (www)

  @article{ , abstract = {The Li + solvation structure and the electrode–electrolyte interface critically determine the cell performance. Here, we systematically compare the effects of the coordination ability of ether with Li + on cell performance, from ultrastrong coordinating solvents (crown ethers) to a moderate coordinating solvent (dimethoxyethane) and weak coordinating solvents (diol dimethyl ethers). Compared with the moderate coordinating ether, both weak and strong coordinating ethers show improved antioxidation capability, while weak coordinating ethers facilitate faster Li + desolvation and enable better performance with the Li-metal anode. Dimethoxypropane shows a relatively better electrochemical performance owing to the coexistence of strong chelating and weak monodentate coordination with Li + . Furthermore, introducing interfacial passivators of lithium bis(fluorosulfonyl)imide and fluoroethylene carbonate further improves the cell performance and narrows the gap among solvents. Based on their respective benefits of solvents, we propose a hybrid electrolyte combining strongly coordinating 12-crown-4 (12-C-4) for Li + capture and weakly coordinating hexanediol dimethyl ether (HDE) as an ion-conductive diluent. The strong coordination of 12-C-4 with Li + and the dual anions in axial coordination facilitate the construction of an inorganic-rich cathode/electrolyte interphase, while the HDE diluent buffers the energy barrier during Li + desolvation and uniforms Li-plating. This hybrid electrolyte exhibits higher ionic conductivity and better interfacial stability with both the anode and cathode than single ether, significantly improving the cycling stability of Li//LiNi 0.85 Mn 0.075 Co 0.075 O 2 cells and bringing a new electrolyte design paradigm for high-voltage ether electrolytes.}, archive = {J_JACS}, author = {Xiaoxin Xie and Junjun Fu and Ruoxi Wang and Jinhui Han and Shu-Meng Hao and Weidong Zhou}, doi = {10.1021/jacs.5c07899}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34411--34424}, shortjournal = {J. Am. Chem. Soc.}, title = {A hybrid ultrastrong coordinating solvent and an ion-conductive diluent for high-voltage ether-based li-metal batteries}, volume = {147}, year = {2025}, }
• (2025). A 100,000-fold increase in C–H bond acidity gives palladium a key advantage in C(sp3)–H activation compared to nickel. JACS, 147(38), 34395--34410. (www)

  @article{ , abstract = {Carbon–hydrogen bond activation is a pillar of synthetic chemistry. While it is generally accepted that Pd is more facile than Ni in C–H activation catalysis, there are no experimental platforms available to directly compare the magnitude of C–H bond weakening between Ni and Pd prior to bond scission. This work presents the first direct measurements of C(sp 3 )–H bond acidity (p K a ) and bond dissociation free energy (BDFE) for a species containing a ligated alkane–palladium interaction (R 2 CH 2 ···Pd), also known as an agostic interaction. Through standard-state equilibrium measurements and advanced computational modeling, we show that Pd acidifies C(sp 3 )–H bonds 100,000 times more than Ni (5 p K a units), indicating that acidification is a key factor making Pd a privileged metal in C(sp 3 )–H functionalization reactions. Energy decomposition analysis (EDA) calculations show that this is primarily due to a greater electrophilicity of the palladium containing fragment, as forward charge transfer (Δ E CTf ) from the agostic methylene moiety into [Pd] is significantly increased. More broadly, these valuable findings help unravel fundamental performance differences between Earth-abundant and precious metals, potentially guiding future ligand design efforts for catalysis.}, archive = {J_JACS}, author = {Lirong Lin and Tim K. Schramm and Pavel Kucheryavy and Roger A. Lalancette and Andreas Hansen and Demyan E. Prokopchuk}, doi = {10.1021/jacs.5c07649}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34395--34410}, shortjournal = {J. Am. Chem. Soc.}, title = {A 100,000-fold increase in C–H bond acidity gives palladium a key advantage in C(sp3)–H activation compared to nickel}, volume = {147}, year = {2025}, }
• (2025). Construction of zeolite framework-anchored Rh–(O–Zn)x sites for ethylene hydroformylation. JACS, 147(38), 34381--34394. (www)

  @article{ , abstract = {Zeolite-confined Rh-based catalysts have emerged as promising heterogeneous candidates for olefin hydroformylation. However, they face challenges of reactant- and product-induced Rh leaching and aggregation. Herein, zeolite framework-anchored Rh δ+ –(O–Zn) x sites were designed and are shown to have remarkable activity and stability for gas-phase ethylene hydroformylation. The bimetallic catalysts were synthesized by coencapsulating Rh and Zn species into Silicalite-1 zeolite, and the Rh δ+ –(O–Zn) x sites were in situ constructed during the induction period of the hydroformylation process through the interaction between mobile Rh-carbonyl species and framework ≡SiOZn–O(H). The change of the Zn/Rh molar ratio significantly affects the dispersion of Rh and the proportion of highly active Rh δ+ . The optimal 0.2Rh@Zn 3 -S-1 catalyst achieves a propanal turnover frequency as high as 148 h –1 at 363 K and shows no sign of deactivation during the 40 h test. In contrast, zinc-free 0.2Rh@S-1 suffers rapid deactivation due to Rh aggregation. In situ Fourier transform infrared (FTIR) spectroscopy reveals that the transfer desorption of propanal from Rh to Zn–O contributes to the redispersion of Rh during the construction of Rh δ+ –(O–Zn) x structures. Moreover, the observed HRh(CO) 2 species together with the enrichment of Rh δ+ -propionyl intermediates on the catalyst indicates that the hydrogenation of acyl species is the rate-limiting step of ethylene hydroformylation, which is further supported by kinetic analysis. This study presents a new strategy for designing stable and efficient gas-phase ethylene hydroformylation catalysts using zeolite-anchored metal species as inorganic ligands for Rh δ+ centers and provides insights into the hydroformylation mechanism occurring on the bimetallic sites.}, archive = {J_JACS}, author = {Haocheng Hu and Wenhao Cui and Mingbin Gao and Linying Wang and Shiping Liu and Liang Qi and Wenfu Yan and Peng Tian and Zhongmin Liu}, doi = {10.1021/jacs.5c07586}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34381--34394}, shortjournal = {J. Am. Chem. Soc.}, title = {Construction of zeolite framework-anchored Rh–(O–Zn)x sites for ethylene hydroformylation}, volume = {147}, year = {2025}, }
• (2025). A conserved Cia1–Cia2 interface mediates client recruitment in the cytosolic Iron–Sulfur cluster assembly pathway. JACS, 147(38), 34372--34380. (www)

  @article{ , abstract = {The cytosolic iron–sulfur cluster assembly (CIA) targeting complex maturates over 30 cytosolic and nuclear Fe–S proteins, raising the question of how a single complex recognizes such a diverse set of clients. The discovery of a C-terminal targeting complex recognition (TCR) peptide in up to 25% of CIA clients provided a clue to substrate specificity, yet the molecular and energetic basis for this interaction remained unresolved. By integrating computational and biochemical approaches, we show that the TCR peptide binds a conserved interface between the Cia1 and Cia2 subunits of the targeting complex, even in the absence of the Fe–S cluster. Since this same site also mediates binding of predominantly apo-Nar1, the proposed Fe–S cluster carrier, we provide in vitro evidence for Nar1’s role as a cluster trafficking protein in the CIA pathway. We further show that Cia1–Cia2 complex formation is essential for CIA function as substitutions disrupting this interface, including the disease-linked R65W Cia1 variant, impair TCR peptide-dependent client recruitment. Our findings also clarify the role of the poorly characterized human paralog Cia2a, proposed to act solely in iron regulatory protein 1 (IRP1) maturation. We find that a Cia1–Cia2a complex can bind the TCR peptide, suggesting a broader role for Cia2a in Fe–S protein biogenesis, as IRP1 lacks a TCR motif. Together, these findings define a well-conserved molecular mechanism for client recognition in the CIA pathway and uncover how CIA targeting complex assembly and client identification are mechanistically linked to human disease.}, archive = {J_JACS}, author = {Anastasiya Buzuk and Melissa D. Marquez and Jackson V. Ho and Yaxi Liu and Beatrice Wang and Chen Cheng Qi and Deborah L. Perlstein}, doi = {10.1021/jacs.5c07386}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34372--34380}, shortjournal = {J. Am. Chem. Soc.}, title = {A conserved Cia1–Cia2 interface mediates client recruitment in the cytosolic Iron–Sulfur cluster assembly pathway}, volume = {147}, year = {2025}, }
• (2025). Capturing a transition phase during birnessite-to-spinel transition for efficient water oxidation. JACS, 147(38), 34361--34371. (www)

  @article{ , abstract = {The transition phase is a unique intermediate-state material with structural characteristics of two distinct phases, and the coexistence of diverse structural units endows it with intriguing chemical properties. However, preparing stable transition phase materials is a challenge. Here, a highly active transition phase is precisely captured from a birnessite-to-spinel transition via an ion-steric strategy. The intercalation of Ca 2+ affects the thermodynamics of phase transition, hinders the migration of Co 2+ , and broadens the phase transition temperature window from 450–500 °C to 400–600 °C, enabling the capture of favorable transition phase material (Ca-TP-op) with short-range ordered spinel configuration and long-range disordered MO 6 (M = Mn, Co) octahedral framework structure at 500 °C. The novel structures within transition phases promote electron transfer, alter orbital hybridization, and activate lattice oxygen. Consequently, Ca-TP-op demonstrates efficient oxygen evolution reaction activity, surpassing both the composite and mechanical mixture of birnessite and spinel. The universality of the ion-steric strategy can be demonstrated by the intercalation of Na, K, Mg, Sr, and Ba ions. This work successfully pioneers a new transition phase catalytic material system that offers insights on the development of efficient functional catalysts.}, archive = {J_JACS}, author = {Xu Zhao and Zhibin Geng and Xinbo Li and Jingze Shao and Guichen Gao and Zhiyu Shao and Shilong Fu and Taotao Huang and Liping Li and Guangshe Li}, doi = {10.1021/jacs.5c07103}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34361--34371}, shortjournal = {J. Am. Chem. Soc.}, title = {Capturing a transition phase during birnessite-to-spinel transition for efficient water oxidation}, volume = {147}, year = {2025}, }
• (2025). Lighting up arginine metabolism dynamics in neural differentiation through ratiometric fluorescence imaging. JACS, 147(38), 34350--34360. (www)

  @article{ , abstract = {Arginine (Arg) is a critically important amino acid in the central nervous system and plays a pivotal role in the differentiation of neural stem cells (NSCs). However, specifically and quantitatively tracking Arg dynamics in situ presents a significant challenge. Herein, we developed a series of Arg probes (Rap1–9) based on the nucleophilic substitution reaction between a phenyl-activated ester and a primary amine. Among these, the optimized NIR-emission ratiometric fluorescent probe Rap-9 demonstrated the most pronounced electrophilicity at its reactive site, enabling rapid and specific detection of Arg both in vitro and in vivo. Notably, Rap-9 was successfully utilized for real-time imaging of Arg dynamics during O 2 ·– -stimulated NSC differentiation. Further studies revealed that Arg-mediated activation of the mTORC1 pathway could coordinate qNSC reactivation and neuronal differentiation by regulating mitochondrial energy metabolism from glycolysis to mitochondrial oxidative phosphorylation. These findings not only enhanced our understanding of the metabolic pathways governing NSC differentiation but also offered new perspectives for neuroscience research and potential therapeutic interventions.}, archive = {J_JACS}, author = {Jin Yan and Yuxiao Mei and Yudan Zhao and Yang Tian}, doi = {10.1021/jacs.5c05685}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34350--34360}, shortjournal = {J. Am. Chem. Soc.}, title = {Lighting up arginine metabolism dynamics in neural differentiation through ratiometric fluorescence imaging}, volume = {147}, year = {2025}, }
• (2025). Reusable noncomplementary DNA-based neural network. JACS, 147(38), 34339--34349. (www)

  @article{ , abstract = {Neural network computation is a cornerstone of modern artificial intelligence, with electronic software-based approaches achieving widespread success due to their ability to enable continuous, iterative learning on the same platform. DNA-based neural networks, with their potential advantages in versatility, scalability, and energy efficiency, offer a promising alternative to traditional systems. However, despite significant advancements in pattern recognition and algorithm accuracy, current DNA-based neural networks, relying on the complementary pairing of DNA nucleobases, suffer from the nonreusability of their computing materials. This limitation not only raises operational costs but also restricts their capacity for implementing learning mechanisms. Here, we introduce an unprecedented noncomplementary DNA-based perceptron (NCP) computation strategy, marking the first successful demonstration of a reusable DNA-based neural network. We present a “tagging” strategy to facilitate the scaling-up of noncomplementary DNA-based neural network. We show that 4-bit molecular pattern recognition can be simply achieved through strand-displacement reactions between four input strands and four pairs of noncomplementary DNA duplexes in the NCP, with weighting values modulated by duplex concentrations. Furthermore, a noncomplementary “winner-take-all” module enables decision-making, as demonstrated in an “I Spy” game task. Most importantly, by utilizing removable input strands (lipid–oligonucleotide conjugates), our NCP-based neural network enables reliable multicycle computations, overcoming the critical reusability challenge in DNA-based neural network computation. This work pioneers reusability in DNA-based neural networks, offering a practical path to molecular computing systems with learning capabilities.}, archive = {J_JACS}, author = {Chengjie Sun and Xiaoyang Liu and Jiafeng Zhong and Qin Zhou and Jianjun Cheng}, doi = {10.1021/jacs.5c04886}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34339--34349}, shortjournal = {J. Am. Chem. Soc.}, title = {Reusable noncomplementary DNA-based neural network}, volume = {147}, year = {2025}, }
• (2025). Sulfate promotes amine salt ozonation in atmospheric aerosols. JACS, 147(38), 34327--34338. (www)

  @article{ , abstract = {Low molecular weight amines promote sulfate (SO 4 2– and HSO 4 – ) formation through acid–base reactions, contributing to fine particulate matter (PM). Heterogeneous ozonation converts nontoxic amine salts into highly toxic products, yet the ozonation activation mechanism is unclear. This work reveals a sulfate-dominant ozonation mechanism of amine salts in fine PM by combining advanced mass spectrometry and ab initio calculation methods. With the synergy of • OH-initiated oxidation, SO 4 2– activates amine ions through deprotonation, producing imine molecules as ozonation intermediates. Subsequently, HSO 4 – accelerates the formation of the intermediate aminomethanol and ozonation products. Moreover, this novel ozonation mechanism of amine salt is verified to be efficient for sulfate fine PM and is not feasible for chloride or nitrate fine PM. In this study, the key role of sulfate in the ozonation of inert organic compounds is highlighted, which needs to be considered in fine PM chemistry.}, archive = {J_JACS}, author = {Weina Zhang and Dayuan Zheng and Jiale Lao and Ruijing Li and Baihang Chen and Jiangyao Chen and Jie Zhong and Yuemeng Ji and Guiying Li and Joseph S. Francisco and Taicheng An}, doi = {10.1021/jacs.5c04343}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34327--34338}, shortjournal = {J. Am. Chem. Soc.}, title = {Sulfate promotes amine salt ozonation in atmospheric aerosols}, volume = {147}, year = {2025}, }
• (2025). Quantification of membrane protein conformational free energy from mutations and a single atom. JACS, 147(38), 34316--34326. (www)

  @article{ , abstract = {Secondary active transporters are membrane proteins involved in moving substrates across the cellular membrane. Conformational dynamics underlie this process, allowing the transporter to sample at least two conformations, nominally grouped into inward- and outward-facing states. While studies of structure and dynamics have revealed atomistic insight into transport mechanisms and transport rates, the relative free energy differences among conformations remain underexplored. In this work, we quantified free energy differences between inward- and outward-facing conformations of the multidrug E. coli transporter EmrE using 19 F NMR spectroscopy. EmrE consists of an antiparallel and asymmetric homodimer, where its quaternary structure resembles the inverted repeat structures found in larger nonoligomeric transporters. NMR experiments were performed using a minimal heterodimer of EmrE, where a single mutation was introduced into one monomer of the native EmrE homodimer. We discovered that a single conservative mutation perturbed the conformational equilibrium between inward- and outward-facing states by up to 1.5 kcal/mol. Surprisingly, we also found that as little as a single fluorine atom influenced the equilibrium by up to 0.8 kcal/mol. These measurements provide quantitative evidence that subtle changes influence the free energy landscape of a transporter, suggesting a plasticity that may be beneficial in divergent evolution to tune the transport mechanism.}, archive = {J_JACS}, author = {Belen Ramirez-Cordero and Nathaniel J. Traaseth}, doi = {10.1021/jacs.5c04065}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34316--34326}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantification of membrane protein conformational free energy from mutations and a single atom}, volume = {147}, year = {2025}, }
• (2025). Tailoring near fermi-level topological flatbands in clar’s goblet graphene nanoribbons through regioselective cyclization of five-membered rings. JACS, 147(38), 34303--34315. (www)

  @article{ , abstract = {On-surface synthesis via metal-surface-catalyzed C–C bond formation presents unique advantages for the design of graphitic nanomaterials with atomic precision. Following this approach, the coimplantation of nontrivial topology and flatband structures in graphene nanoribbons (GNRs) has emerged as a compelling pursuit, serving as platforms for realizing exotic quantum phases of matter through the interplay of topological states and strong correlations. However, the exploration of these intriguing properties has been largely constrained by the limited known on-surface reactions capable of creating topological flatbands in GNRs. In this work, we promote the intermolecular oxidative coupling of concealed non-Kekuléan nanographenes to construct topological flatband GNRs and GNR heterojunctions on the Au(111) surface. Utilizing Clar’s goblet as a proof of concept, we demonstrate repetitive intermolecular cyclodehydrogenation with high regioselectivity to form pentagon-embedded GNRs. The coupling of the zero modes in Clar’s goblets generates extended electronic states with evident nodes between them, arising from inherent topological frustration, thus resulting in topological flatbands close to the Fermi level and topologically protected end states. Our atomically resolved measurements obtained using scanning tunneling microscopy and noncontact atomic force microscopy, complemented by density functional theory and tight-binding model calculations, illustrate the on-surface reaction cascade and the electronic properties of the designed products. These findings open significant opportunities for the on-surface construction of low-dimensional carbon-based quantum materials.}, archive = {J_JACS}, author = {Ruoting Yin and Xinyong Meng and Xin-Jing Zhao and Jianing Wang and Xiaoqing Wang and Qi Chen and Jie Meng and Zhengya Wang and Yifan Liang and Yuan-Zhi Tan and Bin Li and Wei Hu and Qunxiang Li and Shijing Tan and Chuanxu Ma and Jinlong Yang and Bing Wang}, doi = {10.1021/jacs.5c03736}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34303--34315}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailoring near fermi-level topological flatbands in clar’s goblet graphene nanoribbons through regioselective cyclization of five-membered rings}, volume = {147}, year = {2025}, }
• (2025). Cell-membrane-anchored synthetic dynamic DNA circuits for signaling transient cell migration. JACS, 147(38), 34292--34302. (www)

  @article{ , abstract = {A DNA reaction circuit consisting of components E/Q 1 , E 1 /T 1 , F/Q 1 , and F 1 /T 1 in which each includes the antimesenchymal epithelial transition (Met) receptor aptamer sequence is anchored within MCF-7 cells to emulate the natural signaling network on the live cell membrane. Subjecting the membrane-integrated circuit to an auxiliary fuel strand, in the presence of a nicking enzyme, results in the dynamic reconfiguration of the circuit into a constitutional dynamic network, CDN, in which the pre-engineered duplex interactions between the constituents lead to allosterically stabilized Met-dimer complexes. The concomitant nickase-induced separation of the CDN leads to the parent reaction circuit, and to the transient formation and depletion of the Met-dimer complex. By labeling the components comprising the reaction circuits with fluorophores, the dynamic transient reconfiguration of the CDN and the accompanying Met-dimer formation and separation within the cell membranes are characterized by temporal confocal fluorescence microscopy imaging. Moreover, the transient formation of the Met-dimer in the MCF-7 cell membrane induces intracellular signaling and activation of the Akt/FAK phosphorylation pathway. This is reflected by the network-guided control over the transient migration/motility functions of the MCF-7 cells.}, archive = {J_JACS}, author = {Nina Lin and Yu Ouyang and Yunlong Qin and Songqin Liu and Itamar Willner and Yuanjian Zhang and Zhixin Zhou}, doi = {10.1021/jacs.5c03070}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34292--34302}, shortjournal = {J. Am. Chem. Soc.}, title = {Cell-membrane-anchored synthetic dynamic DNA circuits for signaling transient cell migration}, volume = {147}, year = {2025}, }
• (2025). Harnessing heterogeneous asymmetric oxide interface for efficient photodehydrogenation of isopropanol through α-C–H bond activation. JACS, 147(38), 34283--34291. (www)

  @article{ , abstract = {Photocatalytic α-C–H activation of alcohols to form aldehydes and ketones represents an important synthetic pathway, although the selective formation of C-centered radicals remains challenging due to competing O–H activation processes. While extensive research has explored heterojunction band alignment, charge transfer directionality, and component-specific redox reactions, the atomic structure at interfaces and its catalytic role have received limited attention. Here, we demonstrate a TiO 2 -CuO heterojunction photocatalyst that achieves exceptional selectivity in the oxidation of isopropanol to acetone, with a hydrogen production rate of approximately 4400 μmol/g/h. Through complementary characterization using X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and ab initio molecular dynamics (AIMD), we identify the formation of asymmetric Ti-O(H)-Cu + units at the TiO 2 /CuO heterojunction interface. In situ EPR reveals a ·C(OH)(CH 3 ) 2 radical intermediate, confirming that the reaction proceeds via selective hydrogen atom transfer (HAT) of the α-C–H bond in isopropanol, in contrast to that of TiO 2 or CuO, which proceed via hydrogen extraction of the OH group. These mechanistic insights into interface-mediated catalysis provide new design principles for engineering atomic-scale catalytic interfaces, offering new opportunities for developing next-generation photocatalysts across diverse catalytic applications.}, archive = {J_JACS}, author = {Hang Yin and Zhehao Sun and Kaili Liu and Zhuofeng Li and Yi-Lun Chen and Ruhan Liu and Julien Langley and Ary Anggara Wibowo and Xuechen Jing and Daniel Macdonald and Guohua Jia and Nicholas Cox and Zongyou Yin}, doi = {10.1021/jacs.4c17517}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34283--34291}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing heterogeneous asymmetric oxide interface for efficient photodehydrogenation of isopropanol through α-C–H bond activation}, volume = {147}, year = {2025}, }
• (2025). Discovery of RNA-reactive small molecules guides the design of electrophilic modules for RNA-specific covalent binders. JACS, 147(38), 34271--34282. (www)

  @article{ , abstract = {RNA is a key drug target that can be modulated by small molecules; however, covalent binders of RNA remain largely unexplored. Using a high-throughput mass spectrometry screen of 2,000 electrophilic compounds, we identified ligands that react with RNA in a binding-dependent manner. RNA reactivity was influenced by both the reactive group and the noncovalent RNA-binding scaffold. In addition to known RNA-reactive electrophiles such as N -acylimidazoles and bis(2-chloroethyl)amines, covalent screening enabled the surprising discovery that common thiol-reactive electrophiles (chloroacetamide) and rarely characterized electrophiles (3-chloropivalamide) cross-linked to RNA. These results suggest that electrophiles commonly used for protein targeting can also covalently modify RNA, potentially contributing to both on- and off-target effects. This insight enabled the design of an RNA-specific covalent compound by modifying a bis-benzimidazole scaffold, originally identified to bind DNA, to react selectively with the expanded triplet repeat RNA, r(CUG) exp , that causes myotonic dystrophy type 1 (DM1). Selectivity appears to arise from differences in the RNA and DNA binding modes, revealing that proper positioning of the electrophile toward the nucleophilic guanine residue is important for efficient covalent bond formation. Overall, this study highlights the potential of rationally designing covalent RNA-targeting small molecules.}, archive = {J_JACS}, author = {Noah A. Springer and Patrick R. A. Zanon and Amirhossein Taghavi and Kisu Sung and Matthew D. Disney}, doi = {10.1021/jacs.5c06802}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34271--34282}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of RNA-reactive small molecules guides the design of electrophilic modules for RNA-specific covalent binders}, volume = {147}, year = {2025}, }
• (2025). Discovery of macrocyclic peptide binders, covalent modifiers, and degraders of a structured RNA by mRNA display. JACS, 147(38), 34256--34270. (www)

  @article{ , abstract = {RNA targeting represents a compelling strategy for addressing challenging therapeutic targets that are otherwise intractable through traditional protein targeting. Revolutionary approaches in RNA-focused small molecule libraries have successfully identified RNA-binding ligands but generally remain limited in diversity and impeded by a dearth of structural insight into RNA and RNA complexes. Cyclic peptides are potential structural mimics of evolutionary RNA-protein interacting motifs and can be massively diversified and selected via genetically encoded libraries, offering a complementary approach. This study introduces genetically encoded thioether cyclic peptide libraries constructed through mRNA display using a dibromoxylene linker and its fluorosulfonyl derivative that can covalently engage RNA nucleophiles. Using an optimized mRNA display workflow for RNA binders, we discovered high affinity, covalent and noncovalent binders for SNCA 5′ UTR IRE, the upstream iron-responsive element that post-transcriptionally regulates the expression of α-synuclein, an intrinsically disordered protein implicated in Parkinsonism and related neurodegenerative diseases. Notably, a stringent selection strategy employing “base-paired” target analog counterselection enhanced specificity by deenriching nonspecific electrostatic interactions mediated by polycationic residues. Further engineering hit peptides with an imidazole tag yielded selective RNA degraders in which covalent degraders showed noticeably improved potency from noncovalent counterparts. This work provides a prototype framework for evolution-driven, high-throughput, RNA-targeted drug discovery using cyclic peptides.}, archive = {J_JACS}, author = {Xiyuan Yao and Kanokpol Aphicho and Shubhashree Pani and Anuchit Rupanya and Tong Lan and Bryan C. Dickinson}, doi = {10.1021/jacs.5c05540}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34256--34270}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of macrocyclic peptide binders, covalent modifiers, and degraders of a structured RNA by mRNA display}, volume = {147}, year = {2025}, }
• (2025). The divergent reduction chemistry of Ln(II) bis(terphenylthiolate) complexes, Ln(SAriPr6)2, leads to KLn(μ-SAriPr6)2, C─H bond activation products, and two-electron reduction reactivity. JACS, 147(38), 34249--34255. (www)

  @article{ , abstract = {Potassium graphite (KC 8 ) reduction of the terphenylthiolate La(II) and Nd(II) complexes, Ln(SAr i Pr6 ) 2 , 1-Ln (SAr i Pr6 = C 6 H 3 -2,6-(C 6 H 2 -2,4,6- i Pr 3 ) 2 ; Ln = La, Nd), forms KLn(μ-SAr i Pr6 ) 2 , 2-Ln , which displays characteristic metal–arene interactions involving the flanking ring of the sterically bulky ligand. In contrast, when the Yb(II) complex, Yb(SAr i Pr6 ) 2 , is treated with KC 8 , C–H bond activation of a ligand yielded an Yb(II) complex of a dianionic ligand, Yb{SC 6 H 3 -2-(C 6 H 2 -2,4,6- i Pr 3 )-6-[C 6 H 2 -2,6- i Pr 2 -4-C(CH 3 ) 2 ]}(OEt 2 ) 2 , 3 . 2-La functions as a two-electron reductant in its reaction with iodomethane to form the terminal methyl complex La(SAr i Pr6 ) 2 (CH 3 ), which provides a new synthetic route to Ln–C bonds using electrophilic reagents.}, archive = {J_JACS}, author = {Makayla R. Luevano and Cary R. Stennett and Eric Ma and Joseph W. Ziller and Filipp Furche and William J. Evans}, doi = {10.1021/jacs.5c14054}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34249--34255}, shortjournal = {J. Am. Chem. Soc.}, title = {The divergent reduction chemistry of Ln(II) bis(terphenylthiolate) complexes, Ln(SAriPr6)2, leads to KLn(μ-SAriPr6)2, C─H bond activation products, and two-electron reduction reactivity}, volume = {147}, year = {2025}, }
• (2025). Prolonging all-optical molecular electron spin coherence in the tissue transparency window. JACS, 147(38), 34244--34248. (www)

  @article{ , abstract = {Coherent electron spin states within paramagnetic molecules hold significant potential for microscopic quantum sensing. However, all-optical coherence measurements amenable to high spatial and temporal resolution under ambient conditions remain a significant challenge. Here we conduct room-temperature, picosecond time-resolved Faraday ellipticity/rotation (TRFE/R) measurements of the electron spin decoherence time T 2 * in [IrBr 6 ] 2– . Decoherence is strongly sensitive to solution phase viscosity, pointing to molecular tumbling as an important decoherence mechanism. Accordingly, immobilization of [IrBr 6 ] 2– molecules in thin polymer films results in an order-of-magnitude increase in coherence lifetime and significantly greater magnetic field sensitivity. By tuning energies of ligand-to-metal charge transfer (LMCT) states, TRFE/R enables spin initialization and readout in the tissue transparency window, paving the way toward all-optical, ultrafast molecular electron spin coherence imaging in biological systems.}, archive = {J_JACS}, author = {Erica Sutcliffe and Jacob O. Rothbaum and Jonathan P. Aalto and Juliette C. Whiteside and Ryan G. Hadt}, doi = {10.1021/jacs.5c13180}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34244--34248}, shortjournal = {J. Am. Chem. Soc.}, title = {Prolonging all-optical molecular electron spin coherence in the tissue transparency window}, volume = {147}, year = {2025}, }
• (2025). Cyclic hydroxylamines for native residue-forming peptide ligations: Synthesis of ubiquitin and tirzepatide. JACS, 147(38), 34238--34243. (www)

  @article{ , abstract = {The α-ketoacid-hydroxylamine (KAHA) ligation enables the chemoselective coupling of unprotected peptide segments. The most commonly used hydroxylamine building block, ( S )-5-oxaproline, yields homoserine residues at ligation sites, limiting applications where the native sequence is essential. To overcome this limitation, we developed cyclic dipeptide-derived hydroxylamine building blocks that enable the formation of canonical amino acids directly under modified KAHA ligation conditions. These building blocks are prepared from dipeptides and are applicable at nonobvious peptide ligation junctions, including Leu–Ile and Lys–Ile. We applied this approach to the synthesis of K48/K63 selectively protected ubiquitin monomers for chemoenzymatic ubiquitin chain formation and the total synthesis of tirzepatide, a GLP-1 receptor agonist peptide therapeutic containing amino-isobutyric acid (Aib) residues and a fatty acid side chain modification. This work establishes a practical approach for KAHA ligation at fully native sites and expands its applicability to the practical synthesis of challenging peptide targets.}, archive = {J_JACS}, author = {Jiling Han and Kohtaro Hirao and Toshiki Mikami and Nicolas Y. Nötel and Leonardo L. Seidl and Jeffrey W. Bode}, doi = {10.1021/jacs.5c11881}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34238--34243}, shortjournal = {J. Am. Chem. Soc.}, title = {Cyclic hydroxylamines for native residue-forming peptide ligations: Synthesis of ubiquitin and tirzepatide}, volume = {147}, year = {2025}, }
• (2025). A bifunctional chiral disulfide catalyst for highly enantioselective anti-markovnikov hydrophosphinylation. JACS, 147(38), 34231--34237. (www)

  @article{ , abstract = {By the strategic integration of squaramide with amino acid derivatives, a type of modular H-bonding catalyst for the enantioselective hydrogen atom transfer (HAT) process was developed. With these disulfides, a photoinduced asymmetric anti-Markovnikov hydrophosphinylation was achieved, providing a series of chiral β -hydroxyphosphine oxides with reasonable to high enantioselectivity. Mechanism studies revealed the critical role of the H-bonding interactions between the squaramide scaffold and radical intermediates in governing the enantioselectivity and catalytic reactivity.}, archive = {J_JACS}, author = {Lin Tang and Shaoyu Hao and Chaoren Shen and Kaiwu Dong}, doi = {10.1021/jacs.5c11528}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34231--34237}, shortjournal = {J. Am. Chem. Soc.}, title = {A bifunctional chiral disulfide catalyst for highly enantioselective anti-markovnikov hydrophosphinylation}, volume = {147}, year = {2025}, }
• (2025). Catalytic asymmetric (ene–endo)-Carbonyl–Ene type cyclizations. JACS, 147(38), 34225--34230. (www)

  @article{ , abstract = {The carbonyl–ene reaction between aldehydes and olefins constitutes a perfectly atom economic approach to homoallylic alcohols with concomitant C–C bond formation. However, the scope of catalytic asymmetric intermolecular versions is currently limited to activated substrates, while of the two intramolecular types only catalytic asymmetric ( ene – exo )-carbonyl–ene type cyclizations can be considered mature. The corresponding ( ene – endo )-cyclizations would arguably find equal utility in chemical synthesis but remain underdeveloped. Herein, we report an efficient regio- and enantioselective catalytic asymmetric ( ene – endo )-carbonyl–ene type cyclization of unbiased alkenyl aldehydes using a strong and confined IDPi Brønsted acid catalyst. High enantioselectivities of up to 98:2 e.r. were obtained for a range of homoallylic alcohols.}, archive = {J_JACS}, author = {Lixia Shi and Nobuya Tsuji and Chendan Zhu and Markus Leutzsch and Joyce A. A. Grimm and Benjamin List}, doi = {10.1021/jacs.5c11553}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34225--34230}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic asymmetric (ene–endo)-Carbonyl–Ene type cyclizations}, volume = {147}, year = {2025}, }
• (2025). Modular access to N-SF5 azetidines. JACS, 147(38), 34218--34224. (www)

  @article{ , abstract = {A general and modular strategy has been developed for the synthesis of N –SF 5 azetidines, a new class of scaffolds with potential utility in medicinal chemistry. This transformation leverages bench-stable and scalable SF 5 -transfer reagents to generate the SF 5 radical, which engages azabicyclo[1.1.0]butanes bearing ketone, ester, alkyl, or aryl substituents in strain-release difunctionalization reactions. The method proceeds under mild reaction conditions, features broad functional group tolerance, and offers operational simplicity. The resulting N –SF 5 azetidines demonstrate high aqueous stability and increased lipophilicity, positioning them as a novel class of potential bioisosteres in medicinal chemistry.}, archive = {J_JACS}, author = {Renzhe Li and Chao Hu and Chang Liu and Thomas Lyness and Wenyuan Li and Chen-Yan Cai and Eric Crossley and Yuzuru Kanda and Rohan R. Merchant and Bryan S. Matsuura and Noelle S. Williams and Tian Qin}, doi = {10.1021/jacs.5c10954}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34218--34224}, shortjournal = {J. Am. Chem. Soc.}, title = {Modular access to N-SF5 azetidines}, volume = {147}, year = {2025}, }
• (2025). Nickel-catalyzed cross-dehydrogenative coupling of aldehydes and alkenes toward skipped enones. JACS, 147(38), 34211--34217. (www)

  @article{ , abstract = {The direct transformation of C–H bonds into C–C bonds via cross-dehydrogenative coupling (CDC) represents a powerful strategy in synthetic chemistry, enabling streamlined bond construction without the need for prefunctionalized substrates. While traditional CDC approaches rely on polar mechanisms and preactivation of one of the C–H partners, recent advances have introduced radical-based strategies that employ a hydrogen atom transfer (HAT) approach to access carbon-centered radicals from unactivated substrates. Herein, we report a nickel-catalyzed CDC reaction between aldehydes and alkenes for the synthesis of skipped enones, leveraging aryl radicals as intermolecular HAT agents. The transformation proceeds via the in situ generation of aryl radicals from aryl bromides, which mediates HAT from both the aldehydic and allylic C–H bonds to generate acyl and allylic radicals, respectively. These radicals are then engaged in a nickel-catalyzed radical–radical cross-coupling to deliver the skipped enone products. This method demonstrates a broad substrate scope, high chemoselectivity, and excellent tolerance to diverse functional groups, providing a versatile platform for late-stage functionalization and synthesis of valuable skipped enone scaffolds.}, archive = {J_JACS}, author = {Sidhant Wagulde and Pramod Rai and Vladimir Gevorgyan}, doi = {10.1021/jacs.5c10306}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34211--34217}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-catalyzed cross-dehydrogenative coupling of aldehydes and alkenes toward skipped enones}, volume = {147}, year = {2025}, }
• (2025). Programming Aptamer–Protein complexation kinetics via modulation of G-quadruplex secondary structure. JACS, 147(38), 34204--34210. (www)

  @article{ , abstract = {Aptamers have emerged as key receptors in the pursuit of universal biomolecular monitoring. However, while many aptamers possess excellent association rates, they tend to exhibit slow dissociation kinetics. While these slow off-rates are great for single-use applications, they pose a significant challenge for applications requiring continuous, repeated measurements where hysteresis complicates subsequent binding events. The G-quadruplex represents a common motif in many high-specificity aptamers and is composed of complexed guanine residues. Here, we present a method for modulating G-quadruplex aptamer binding kinetics through use of a polycytosine strand that can destabilize quadruplex structure and accelerate target release in a predictable manner. We demonstrate this phenomenon for several aptamer targets, including thrombin, interferon-gamma, and nucleolin, and highlight the ability of these modified aptamers to capture dynamic changes in analyte concentration on minute time scales.}, archive = {J_JACS}, author = {Connor D. Flynn and Dingran Chang and Yebin Lee and Scott E. Isaacson and Zhenwei Wu and Jonathan Rivnay and Shana O. Kelley}, doi = {10.1021/jacs.5c10067}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34204--34210}, shortjournal = {J. Am. Chem. Soc.}, title = {Programming Aptamer–Protein complexation kinetics via modulation of G-quadruplex secondary structure}, volume = {147}, year = {2025}, }
• (2025). A complete mechanistic framework for molecular glue characterization. JACS, 147(38), 34199--34203. (www)

  @article{ , abstract = {The use of molecular glues to modulate protein–protein interactions has emerged as a promising approach to drug previously intractable targets. Despite strong interest in this modality, a comprehensive theoretical framework is lacking. We have established a complete mechanistic analysis which enables the determination of molecular glues’ binding and cooperativity values from a simple biochemical matrix experiment. We validated the model using numerical integration and experimental data from fluorescence resonance energy transfer and fluorescence polarization assays. As the derived models enable the determination of all thermodynamic parameters of any molecular glue, they have significant applications in drug discovery, particularly for molecular glue optimization and characterization of neo-substrates.}, archive = {J_JACS}, author = {Maxime Couturier and Ryan Guilbert and Paul Clarkson and Argyrides Argyrou}, doi = {10.1021/jacs.5c09166}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34199--34203}, shortjournal = {J. Am. Chem. Soc.}, title = {A complete mechanistic framework for molecular glue characterization}, volume = {147}, year = {2025}, }
• (2025). Electrochemical CO2 conversion toward sustainable methanol production: Experimental considerations and outlook. JACS, 147(38), 34183--34198. (www)

  @article{ , abstract = {To achieve a sustainable future, the electrification of the chemical manufacturing industry is crucial. The electrochemical CO 2 reduction reaction (CO 2 RR) offers a promising pathway to produce value-added chemicals and fuels, including methanol─a key chemical building block and energy carrier. This approach presents a carbon-neutral alternative to conventional, fossil fuel-based methanol production. However, replacing well-established thermochemical processes and achieving cost-competitive production requires the development of highly efficient and selective catalysts for CO 2 -to-methanol conversion, as well as systematic device-level optimization. In this Perspective, we discuss the potential of methanol production via CO 2 RR and provide an overview of recent advances in catalyst development. We also propose experimental protocols for methanol quantification, emphasizing the critical need for rigorous evaluation of catalysts to ensure the validity and reproducibility of results, and demonstrating boron phosphide as an irreproducible case. We review seminal studies on CO 2 RR by cobalt phthalocyanine to make methanol, and current understanding of the reaction mechanistic details. Lastly, we discuss the challenges associated with its translation into practical devices and outline future research opportunities to advance electrochemical CO 2 RR for methanol production at scale.}, archive = {J_JACS}, author = {Sunmoon Yu and Davide Menga and Ankita Morankar and Sokseiha Muy and Michael Busch and Vasiliki Tileli and Yang Shao-Horn}, doi = {10.1021/jacs.5c09438}, journal = {Journal of the American Chemical Society}, month = {9}, number = {38}, pages = {34183--34198}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical CO2 conversion toward sustainable methanol production: Experimental considerations and outlook}, volume = {147}, year = {2025}, }
• (2025). Correction to “Photochemical deracemization of 4,7-diaza-1-isoindolinones by unidirectional hydrogen atom shuttling”. JACS, 147(37), 34181--34182. (www)

  @article{ , archive = {J_JACS}, author = {Philip Freund and Mike Pauls and Daria Babushkina and Thomas Pickl and Christoph Bannwarth and Thorsten Bach}, doi = {10.1021/jacs.5c12600}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34181--34182}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Photochemical deracemization of 4,7-diaza-1-isoindolinones by unidirectional hydrogen atom shuttling”}, volume = {147}, year = {2025}, }
• (2025). Structure engineering enabled O–O radical coupling in spinel oxides for enhanced oxygen evolution reaction. JACS, 147(37), 34169--34180. (www)

  @article{ , abstract = {Developing cost-effective spinel oxide catalysts with both high oxygen evolution reaction (OER) activity and stability is crucial for advancing sustainable clean energy conversion. However, practical applications are often hindered by the activity limitations inherent in the adsorbate evolution mechanism (AEM) and the stability limitations associated with the lattice oxygen mechanism (LOM). Herein, we demonstrate structural changes induced by phase transformation in Co 1.5 Mn 1.5 spinel oxides, which yield more active octahedral sites with shortened intersite distance. This structure optimization favors a direct O–O radical coupling mechanism, which circumvents the involvement of the *OOH intermediate and prevents overoxidation of the active sites, significantly enhancing both the OER activity and stability. Consequently, the optimized CoMn-400 catalyst exhibits an overpotential of 268 mV at 10 mA cm –2 in 0.1 M KOH (310 mV for commercial RuO 2 ), and maintains negligible activity loss over 300 h’ chronopotentiometry test at a current density of 100 mA cm –2 . This simple strategy provides fundamental insights into transition metal oxide catalyst design and opens new possibilities for optimizing electrochemical energy conversion.}, archive = {J_JACS}, author = {Long Shang and Shuo Xu and Youxuan Ni and Yong Lu and Haixia Li and Kai Zhang and Zhenhua Yan and Fangyi Cheng and Jun Chen}, doi = {10.1021/jacs.5c13198}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34169--34180}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure engineering enabled O–O radical coupling in spinel oxides for enhanced oxygen evolution reaction}, volume = {147}, year = {2025}, }
• (2025). Iron(III)-mediated C–H alkylation: One-electron differentiation increases activity and chemoselectivity. JACS, 147(37), 34150--34168. (www)

  @article{ , abstract = {The C–H functionalization of arenes mediated by well-defined bis(phosphine)-supported organometallic iron(III) complexes is described. One-electron oxidation of trans -(depe) 2 Fe(CH 3 ) 2 (depe = 1,2-bis(diethylphosphino)ethane) generated the corresponding isolable iron(III) dimethyl derivative that was unstable toward Fe–CH 3 homolysis. Oxidation of the corresponding iron(II) bis(aryl) complex trans -(depe) 2 Fe(tolyl) 2 resulted in rapid reductive elimination of the biaryl with formation of iron(I). These observations motivated the synthesis of the cationic iron(III) metallacycle derived from C–H activation of a neophyl ligand. This complex mediated the ortho -selective C(sp 2 )–H alkylation of a host of arene derivatives containing ketone, amide, pyridine, ester, and sulfoxide directing groups with greater selectivity and reactivity than the iron(II) counterpart. The effect of bis(phosphine) ligands was examined, where decreasing ligand lability correlated with a higher barrier. The experimental rate law, deuterium labeling studies, deuterium kinetic isotope effect experiments, and computational modeling support a reversible C–H activation step followed by rate-determining C(sp 2 )–C(sp 3 ) reductive elimination. Using design principles to minimize undesired reactivity, the iron(III) cycloneophyl complex mediated more facile and chemoselective C–H functionalization with a broader directing group compatibility than the iron(II) analog, arising from a combination of increased ligand lability, less exergonic substrate coordination, an enhanced orbital hybridization effect in C–H activation, and more facile C–C reductive elimination.}, archive = {J_JACS}, author = {Tianyi Zhang and William G. Whitehurst and Matthew V. Pecoraro and Junho Kim and Stefan G. Koenig and Paul J. Chirik}, doi = {10.1021/jacs.5c12754}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34150--34168}, shortjournal = {J. Am. Chem. Soc.}, title = {Iron(III)-mediated C–H alkylation: One-electron differentiation increases activity and chemoselectivity}, volume = {147}, year = {2025}, }
• (2025). Biosynthesis of the thiofuranose core in albomycin requires a versatile enzyme AbmG that catalyzes net dehydration via cryptic phosphorylation. JACS, 147(37), 34143--34149. (www)

  @article{ , abstract = {Albomycins are unusual sulfur-containing nucleosides from the species of Streptomyces that exhibit potent antibiotic activities against both Gram-negative and Gram-positive bacteria including clinical pathogens. Previous studies demonstrated that the twitch radical SAM enzyme AbmM catalyzes an oxidative sulfur-for-oxygen swapping reaction converting CDP to a 4′-hydroxy-4′-thiocytidine 5′-diphosphate intermediate in the initial step of albomycin biosynthesis. However, the fate of this intermediate in the biosynthetic pathway has remained elusive. Herein, the above intermediate after 5′-dephosphorylation is shown to undergo AbmG-catalyzed transformations via a cryptic double phosphorylation of its 4′-hydroxyl group followed by C–O bond cleavage to yield 5′-oxo-4′-thiocytidine. X-ray crystal structure analysis and site-directed mutagenesis of AbmG revealed Glu188 as the general base to perform C5′ deprotonation. Subsequent mechanistic studies using deuterated substrates demonstrated that the deprotonation at C5′ is pro - R specific and likely occurs concerted with elimination of pyrophosphate from C4′. This study not only highlights a unique nucleoside kinase with lyase activity to complete an overall dehydration reaction but also fills the gaps in the biosynthesis of the atypical thiofuranose core essential to the biological activities of albomycins.}, archive = {J_JACS}, author = {Ziyang Zheng and Richiro Ushimaru and Takahiro Mori and Mark W. Ruszczycky and Ikuro Abe and Hung-wen Liu}, doi = {10.1021/jacs.5c12827}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34143--34149}, shortjournal = {J. Am. Chem. Soc.}, title = {Biosynthesis of the thiofuranose core in albomycin requires a versatile enzyme AbmG that catalyzes net dehydration via cryptic phosphorylation}, volume = {147}, year = {2025}, }
• (2025). Spectro-electrochemical insights into electrocatalytic CO2 reduction in acidic media through model catalyst design. JACS, 147(37), 34132--34142. (www)

  @article{ , abstract = {Electrocatalytic CO 2 reduction (eCO 2 R) under acidic conditions is the game changer of resourceful CO 2 utilization owing to the alleviated carbon loss but faces severe competition from the hydrogen evolution reaction (HER) that greatly curtails the electric current efficiency. Leveraging the eCO 2 R side of the teeterboard calls for a fundamental understanding of the triphasic electrode process involving a complex arrangement of electric double layers (EDLs). Herein, a series of model catalysts with tailored cavernous parameters are fabricated to geometrically and spectroscopically decipher the competing HER and eCO 2 R processes that engage different proton sources. A comprehensive set of in situ/ operando spectro-electrochemical tools, including differential electrochemical mass spectrometry, vibrational spectra (Raman and Infrared), and rotating disk electrode, are combined to interrogate the geometrically modulated HER and eCO 2 R kinetics with exceptional temporal and spectral resolutions. We uncover that an overcrowded EDL zone comprising capacitively stored K + cations in closely packed nanocages disfavors eCO 2 R at high current densities via limited reaction volume, restrained CO 2 supply, and escalated water dissociation. We further show that, by meticulously crafting the mesoporous cavity structure and suitably expanding the hierarchical EDL zone, great acidic eCO 2 R performance of near-unity CO Faradaic efficiency can be achieved across a wide current range over a prolonged operation. This work offers profound insights into the spatial regulation of mass transport, local chemical environment, and EDL arrangement via tailored catalyst geometry toward high-efficiency eCO 2 R.}, archive = {J_JACS}, author = {Jian Cheng and Zhangyi Zheng and Xinyu Zhang and Min Wang and Lingyu Wang and Yang Wang and Xiang Chen and Zhao Deng and Yang Peng}, doi = {10.1021/jacs.5c12659}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34132--34142}, shortjournal = {J. Am. Chem. Soc.}, title = {Spectro-electrochemical insights into electrocatalytic CO2 reduction in acidic media through model catalyst design}, volume = {147}, year = {2025}, }
• (2025). Enantioselective assembly of (Hetero)aryl alkyl sulfilimines via copper-catalyzed S-arylation of S-alkyl sulfenamides with (Hetero)aryl iodides. JACS, 147(37), 34126--34131. (www)

  @article{ , abstract = {Currently, most sulfoximine clinical candidates feature both S -aryl and S -alkyl substituents. The asymmetric synthesis of these compounds typically relies on oxidizing corresponding enantioenriched sulfilimines. Herein, we describe an effective catalytic system comprising CuI and an azabicyclo[2.2.1] carboxylic acid-derived amide ligand. This system enables the highly enantioselective coupling of S -alkyl sulfenamides with (hetero)aryl iodides to afford aryl alkyl sulfilimines. A wide range of functionalized (hetero)aryl iodides and S -alkyl sulfenamides are compatible under the reaction conditions, providing an attractive approach for assembling enantioenriched aryl alkyl sulfilimines. The utility of this method is demonstrated by the gram-scale asymmetric synthesis of clinical candidate TNG 260 and the formal asymmetric synthesis of three additional drug candidates.}, archive = {J_JACS}, author = {Rongxing Zhang and Tongkun Wang and Mingchuang He and Xiao-Song Xue and Dawei Ma}, doi = {10.1021/jacs.5c12689}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34126--34131}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective assembly of (Hetero)aryl alkyl sulfilimines via copper-catalyzed S-arylation of S-alkyl sulfenamides with (Hetero)aryl iodides}, volume = {147}, year = {2025}, }
• (2025). CH–π interactions elucidated at the single-molecule level. JACS, 147(37), 34118--34125. (www)

  @article{ , abstract = {CH−π interactions represent a weak yet significant molecular force that is prevalent in diverse biological and chemical systems. Despite compelling evidence supporting the existence of CH−π interactions, experimentally measuring these weak interactions remains challenging due to the coexistence of numerous stronger noncovalent interactions. Here, we construct a refined system to accurately compare the strength of CH−π interactions between phenylalanine derivatives and aliphatic amino acids through molecular exchange processes inside a protein nanopore. Based on a quantitative comparison of binding strengths, we found that CH−π interactions are primarily governed by dispersive attraction, and a more acidic C–H bond results in stronger CH−π interactions, both of which are consistent with the literature. Most importantly, we resolved the long-standing debate regarding the deuterium isotope effect on CH−π interactions and confirmed that deuterium forms weaker CD−π interactions compared to protic CH−π interactions.}, archive = {J_JACS}, author = {Qianyuan Ren and Wenying Hao and Lixia Wang and Ke Zhou and Lei Liu and Hai-Chen Wu}, doi = {10.1021/jacs.5c12708}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34118--34125}, shortjournal = {J. Am. Chem. Soc.}, title = {CH–π interactions elucidated at the single-molecule level}, volume = {147}, year = {2025}, }
• (2025). Picric acid removal from water using an anion-coordination-based supramolecular organic framework. JACS, 147(37), 34109--34117. (www)

  @article{ , abstract = {In contrast to metal ions that have been routinely used to construct metal–organic frameworks (MOFs), anions have rarely been used as essential coordination centers in supramolecular organic frameworks (SOFs). In this work, we present a SOF, chloride-SOF , based on the coordination of chloride anions and a flexible oligopyrrole. Owing to the multiple interactions between individual oligopyrrole molecules and an A–B–C-style stacking of the 2D honeycomb layers, crystalline chloride-SOF exhibits reasonable thermal stability and retains its structure upon desolvation. Treating contaminated water containing 100 mg L –1 picric acid (PA) with the desolvated form of chloride-SOF reduced the PA concentration to the low ng L –1 (ppt) level. Supporting studies provide evidence for the conclusion that the material captures PA through anion exchange and adaptive structural transformation, rather than pore-selectivity. Chloride-SOF thus showcases the potential of SOFs as structurally transformable materials useful for hazardous waste removal.}, archive = {J_JACS}, author = {Huiqi Wei and Gen Liu and Yicheng Fang and Tianlong Huang and Yingcong Wu and Yajie Xu and Baoyu Yang and Xinyun Zhao and Zhengxi Huang and Hua Zhang and Lamei Wu and Jonathan L. Sessler and Zhan Zhang}, doi = {10.1021/jacs.5c12626}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34109--34117}, shortjournal = {J. Am. Chem. Soc.}, title = {Picric acid removal from water using an anion-coordination-based supramolecular organic framework}, volume = {147}, year = {2025}, }
• (2025). Enhanced *COOH adsorption over edge-rich Ni–N4 sites for efficient acidic CO2 electroreduction. JACS, 147(37), 34101--34108. (www)

  @article{ , abstract = {Single-atom Ni catalysts hold great promise for the acidic CO 2 reduction reaction (CO 2 RR), owing to their high CO selectivity. However, their performance under industrially relevant high current conditions is limited by the weak interaction between isolated Ni–N 4 sites and *COOH intermediates, restricting efficient CO 2 conversion. Here, we introduced edge-rich Ni–N 4 sites via support vacancy engineering to enhance *COOH adsorption, thereby boosting the CO 2 RR activity and selectivity in acidic media. Density functional theory calculations revealed that edge-rich Ni–N 4 sites induced an upward shift in the Ni d -band center, leading to stronger *COOH binding and improved reaction kinetics. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy images confirmed the uniform dispersion of single-atom Ni sites at the edge of the carbon support. X-ray adsorption spectroscopy further validated the successful anchoring of Ni–N 4 sites on the carbon nanotube matrix. Furthermore, in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy directly evidenced the enhanced *COOH binding on the engineered active sites. As a result, the optimized catalyst achieved a high CO faradaic efficiency exceeding 94.5% at 800 mA cm –2 , alongside a cathodic energy efficiency above 44.2% at pH = 1, suppressing previously reported benchmarks. This work establishes a versatile strategy for electronic structure modulation through edge-site engineering, offering a pathway to unlock the full potential of single-atom catalysts for the acidic CO 2 RR at high current densities.}, archive = {J_JACS}, author = {Ziwen Mei and Yingjie He and Kang Liu and Wenjie Luo and Yao Tan and Qin Chen and Haiying Wang and Xiaoxi Guo and Qing Wu and Chao Ma and Junwei Fu and Zhang Lin and Min Liu}, doi = {10.1021/jacs.5c12583}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34101--34108}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced *COOH adsorption over edge-rich Ni–N4 sites for efficient acidic CO2 electroreduction}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic oxidative dimerization of electronically diverse phenols using borate to prevent overoxidation. JACS, 147(37), 34089--34100. (www)

  @article{ , abstract = {Phenol overoxidation has severely hindered the advancement and synthetic utility of oxidative phenol coupling for over two decades, preventing the development of general catalytic methods. Electron-deficient phenols resist selective coupling due to their high oxidation potential, while monosubstituted phenols undergo uncontrolled overoxidation, making their selective transformation highly challenging. We present a strategy that harnesses in situ biphenol-boron complexation to suppress overoxidation, unlocking the selective catalytic oxidative coupling of both electron-deficient and monosubstituted phenols. This method is broadly applicable to both heterogeneous and homogeneous photocatalytic systems, each operating via distinct mechanisms. By overcoming a fundamental barrier in oxidative phenol coupling, this work not only redefines the scope of catalytic oxidative transformations but also paves the way for new advances in oxidative couplings with implications in pharmaceuticals and materials science.}, archive = {J_JACS}, author = {Jingze Wu and Yoshito Koga and Gang Hong and Madeline E. Rotella and Marisa C. Kozlowski}, doi = {10.1021/jacs.5c12438}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34089--34100}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic oxidative dimerization of electronically diverse phenols using borate to prevent overoxidation}, volume = {147}, year = {2025}, }
• (2025). Functionalization of gold-pincer nanocluster for asymmetric catalysis. JACS, 147(37), 34079--34088. (www)

  @article{ , abstract = {Organic ligand-protected metal nanoclusters feature ultrasmall size, well-defined compositions, and diverse chiral structures. They have the potential to combine the advantages of asymmetric organocatalysis and nanometal catalysis. The major challenge is designing and synthesizing appropriate metal nanocluster structures for achieving high catalytic activity and excellent enantioselectivity. In this work, based on our developed metal-pincer nanoclusters and their unique di-coordination mode, we explored a functionalization method that allows flexible regulation of the spatial match/mismatch between the nanometal catalytic sites and the chiral organocatalytic sites of metal nanoclusters. A proline-functionalized Au 11 nanocluster was constructed as the dominant catalyst. It enables asymmetric Michael addition of aldehydes and nitroalkenes with high TON and enantio-/diastereoselectivity, affording γ-nitroaldehydes that can be further transformed into important organic molecules. Mechanism studies revealed the catalytic synergy of the metal kernel and surface ligand, endowing the metal-pincer nanocluster catalyst with significantly higher efficiency than the individual proline and nanometal catalysts.}, archive = {J_JACS}, author = {Ying Zhang and Ruo-Fan Liu and Sheng Zhang and Man-Bo Li}, doi = {10.1021/jacs.5c12393}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34079--34088}, shortjournal = {J. Am. Chem. Soc.}, title = {Functionalization of gold-pincer nanocluster for asymmetric catalysis}, volume = {147}, year = {2025}, }
• (2025). Thermoset architecture fusion enabled by catalyst-free C═C/C═N metathesis chemistry. JACS, 147(37), 34070--34078. (www)

  @article{ , abstract = {Thermosets with permanent cross-linked structures provide excellent durability but pose significant challenges for reprocessing and recycling, raising engineering and environmental concerns as their usage expands. The advent of covalent adaptable networks (CANs) with dynamic covalent linkages has improved thermoset recyclability and enabled the fusion of identical polymer networks (A-A type fusion). However, fusing different thermosets (A-B type fusion) remains challenging due to their distinct dynamic behaviors and variable activation energies for bond exchange. This study introduces catalyst-free solid-state C═C/C═N metathesis chemistry to achieve A-B type fusion between two distinct thermosets. Furthermore, by simply adjusting the mixing ratio of the parent thermosets, the thermal behavior, mechanical properties, activation energy ( E a ), and topology freezing transition temperature ( T v ) of the fused networks can be precisely tailored. This approach offers enhanced control over thermal and mechanical characteristics, rendering them suitable for diverse high-performance applications. Our findings represent a significant step forward in developing recyclable thermosets with improved engineering performance, contributing to the advancement of a more sustainable circular economy.}, archive = {J_JACS}, author = {Jie Zheng and Wendy Rusli and Karen Yuanting Tang and Wei Peng Goh and Ning Ding and Sheau Wei Chien and Nikos Hadjichristidis and Zibiao Li}, doi = {10.1021/jacs.5c12217}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34070--34078}, shortjournal = {J. Am. Chem. Soc.}, title = {Thermoset architecture fusion enabled by catalyst-free C═C/C═N metathesis chemistry}, volume = {147}, year = {2025}, }
• (2025). Synergetic electrolyte chemistry enables flame-retardancy, k+-desolvation, anti-corrosion and wide-temperature-tolerance in potassium-ion batteries. JACS, 147(37), 34059--34069. (www)

  @article{ , abstract = {Potassium-ion batteries (PIBs) have emerged as an appealing, sustainable and cost-effective candidate for grid-scale energy storage due to abundant K resources and reversible K + de/intercalation in graphite anodes (KC 8 , 279 mAh g –1 ). However, their practical operation suffers from sluggish kinetics and severe capacity deterioration in traditional carbonate electrolytes. Herein, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) and methyl (2,2,2-trifluoroethyl) carbonate (FEMC) are introduced as cosolvents to rejuvenate conventionally low-concentration (1 M) 1,2-dimethoxyethane (DME)-based electrolytes. In the resultant 1 M KFSI-DME/PFPN/FEMC (3 vol %) electrolyte, the cyclotriphosphazene group of PFPN is revealed to not only mitigate the flammability of DME but also diminish the K + -DME interaction through steric hindrance. While FEMC preempts the DME-induced corrosion of the potassium anode by facilitating the formation of a KF-enriched interface. Consequently, ether cointercalation into graphite is successfully suppressed in K||graphite cells, exhibiting 96% capacity retention over 1800 cycles (a running time of 402 days). When the temperature drops from 50 to −20 °C, the K-ion full device retains a capacity as high as 89%. The study introduces a novel electrolyte regulation strategy that harmonizes intrinsic safety, rapid kinetics at subzero temperatures, and enduring cycle stability at the same time, thereby advancing the practical implementation of PIBs for the future.}, archive = {J_JACS}, author = {Zhifei Mao and Huanwen Wang and Taoqiu Zhang and Yifeng Wang and Wanhai Zhou and Dongliang Chao}, doi = {10.1021/jacs.5c11948}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34059--34069}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergetic electrolyte chemistry enables flame-retardancy, k+-desolvation, anti-corrosion and wide-temperature-tolerance in potassium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Aspergillus fumigatus metallothionein CmtA binds and receives a [2Fe-2S] cluster from monothiol glutaredoxin GrxD. JACS, 147(37), 34045--34058. (www)

  @article{ , abstract = {Iron homeostasis is essential for the virulence of the opportunistic fungal pathogen Aspergillus fumigatus . The cytosolic monothiol glutaredoxin GrxD was recently shown to play a critical role in A. fumigatus iron metabolism via regulation of iron–sulfur (Fe–S) binding iron-responsive transcription factors and interaction with components of the cytosolic Fe–S cluster assembly pathway. Interestingly, the putative copper-binding metallothionein CmtA was also identified as a binding partner for GrxD; however, the metal-binding properties of both proteins and the nature of their interactions were unclear. Here, we addressed these open questions by recombinant expression and purification of GrxD and CmtA and analysis of their metal–protein and protein–protein interactions. Using elemental analysis and UV–visible absorption, circular dichroism, EXAFS, Mössbauer and EPR spectroscopies, we demonstrate that recombinant CmtA expressed in Escherichia coli can bind a [2Fe-2S] 2+ cluster, mononuclear Fe 2+ , Zn 2+ , and Cu + , while recombinant GrxD ligates a mixture of [2Fe-2S] 2+ and [3Fe-4S] + clusters at its dimer interface. Furthermore, we discovered that the interaction between GrxD and CmtA involves thermodynamically-driven transfer of a [2Fe-2S] 2+ cluster from GrxD to CmtA. Accordingly, coexpression of GrxD with CmtA in E. coli increases in vivo Fe–S cluster loading in CmtA, supporting a role for GrxD in delivery of [2Fe-2S] 2+ clusters to CmtA. Taken together, these results suggest that the sole metallothionein in A. fumigatus represents a unique class of fungal metallothioneins that functionally interacts with Fe–S cluster trafficking and storage proteins.}, archive = {J_JACS}, author = {David Eap and Megan Ugro and Timothy W. Sherrier and Angela N. Albetel and Paul A. Lindahl and Pamela Riggs-Gelasco and Caryn E. Outten}, doi = {10.1021/jacs.5c11899}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34045--34058}, shortjournal = {J. Am. Chem. Soc.}, title = {Aspergillus fumigatus metallothionein CmtA binds and receives a [2Fe-2S] cluster from monothiol glutaredoxin GrxD}, volume = {147}, year = {2025}, }
• (2025). An engineered supramolecular fluorescent chemosensor for multiscale visualization of glutamate dynamics in living systems. JACS, 147(37), 34034--34044. (www)

  @article{ , abstract = {Glutamate (Glu) plays a critical role in the brain, and the ability to directly measure glutamate activity is essential for understanding its physiological functions and pathological processes. Herein, we engineered a family of Glu sensors ( TympG n ) based on host–guest interactions through the indicator displacement method (IDA) strategy. The optimized supramolecular chemosensor TympG 2 exhibited specificity, sensitivity, signal-to-noise ratio, rapid kinetics (∼145 ms), and photostability, enabling it to be suitable for monitoring Glu dynamics in neuronal organelles, brain tissues, and zebrafish. Significantly, we established the first Glu-associated functional network map across 24 deep brain regions using a homemade high-density fiber photometry array. It was discovered that the correlations between adjacent brain regions, especially between cortex, hippocampus and thalamic populations, were significantly reduced in the hypoxic mice compared to normal mice. Overall, TympG 2 enabled spatiotemporally resolved quantification of glutamatergic activity ranging from subcellular compartments to expansive neural networks across various model organisms. This comprehensive approach not only enhances our understanding of Glu dynamics but also aids in identifying potential neurological disruptions associated with altered glutamatergic signals.}, archive = {J_JACS}, author = {Yuxiao Mei and Jing Sun and Zhichao Liu and Yudan Zhao and Qiwei Zhang and Yang Tian}, doi = {10.1021/jacs.5c11915}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34034--34044}, shortjournal = {J. Am. Chem. Soc.}, title = {An engineered supramolecular fluorescent chemosensor for multiscale visualization of glutamate dynamics in living systems}, volume = {147}, year = {2025}, }
• (2025). Localized 2′-OH acylation at Poly(A) extends RNA translation. JACS, 147(37), 34027--34033. (www)

  @article{ , abstract = {The potential of coding RNAs as a general therapeutic modality is limited by their short intracellular lifetime. Here, we investigate the effects of localized post-transcriptional RNA modification on protein expression over time. While 2′-OH acylation of GFP RNA with stable adducts in the protein-coding region strongly suppressed protein expression, acylation at the poly(A) tail extended translation duration, with protein output increased by up to 8-fold at 36 h. Aryl amino acid derivatives proved to be most effective, while alkyl variants showed little effect. Preliminary mechanistic experiments point to disruption of the poly(A) helical structure as a contributing factor. Our study demonstrates the potential of post-transcriptional localized 2′-acylation as a simple molecular solution to enhance protein-expression capabilities of RNAs.}, archive = {J_JACS}, author = {Linglan Fang and Wenrui Zhong and Lu Xiao and Ryuta Shioi and Allan Lee and Charlotte H. Bravo and Eric T. Kool}, doi = {10.1021/jacs.5c11900}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34027--34033}, shortjournal = {J. Am. Chem. Soc.}, title = {Localized 2′-OH acylation at Poly(A) extends RNA translation}, volume = {147}, year = {2025}, }
• (2025). Flexibility-induced robustness in molecular catalysts for electrocatalytic CO2 reduction. JACS, 147(37), 34019--34026. (www)

  @article{ , abstract = {CO 2 electroreduction to produce fuels and chemicals is of great significance. Molecular catalysts offer valuable advantages in light of their well-defined active sites and tunable structural and electronic properties. However, their stability is often compromised by rigid conjugated structures. Herein, we proposed a hydrogen-bond regulation strategy that enables reversible structural deformation of metal phthalocyanines (MPcs) by incorporating methoxy groups into the phthalocyanine framework, thereby improving the flexibility and stability of MPcs. Calculations suggested that intermediate absorption induced structural deformation in MPcs. Moreover, hydrogen-bond interactions and conformational changes enriched with substituted methoxy groups in MPcs enhance structural flexibility. Operando Raman studies revealed that these hydrogen bonds correlated with the reversible structural deformation of NiPc. The optimized catalysts, facilitated by hydrogen bonds, achieved stable operation for over 500 h at 100 mA cm –2 with >98% Faradaic efficiency in CO 2 -to-CO electrocatalytic reduction, significantly outperforming molecular catalysts lacking appropriate hydrogen-bond interactions.}, archive = {J_JACS}, author = {Kejun Chen and Pengfei Ou and Maoqi Cao and Linlin Wu and Kang Liu and Lihong Jing and Adrián Pinilla-Sánchez and Ziwen Mei and Junwei Fu and Hongmei Li and Wenzhang Li and Kaizhi Gu and Xusheng Zheng and Ting-Shan Chan and Cheng-Wei Kao and Changxu Liu and F. Pelayo García de Arquer and Sen Yang and Tianfu Wang and Juan Zhang and Liyuan Chai and Zhang Lin and Min Liu and Buxing Han}, doi = {10.1021/jacs.5c11449}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34019--34026}, shortjournal = {J. Am. Chem. Soc.}, title = {Flexibility-induced robustness in molecular catalysts for electrocatalytic CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic C–X bond cleavage facilitates peptide synthesis. JACS, 147(37), 34011--34018. (www)

  @article{ , abstract = {The ability to selectively cleave C-heteroatom bonds is critically important in chemical science, from peptide and protein synthesis to biomolecule manipulation. For example, C-heteroatom bond cleavage is widely used in fluorenylmethyloxycarbonyl/ tert -butyl (Fmoc/ t Bu)-based solid-phase peptide synthesis (SPPS). Despite its usefulness, it has inextricable limitations, such as issues with hydrophobicity and side reactions, owing to the need for the use of a strong trifluoroacetic acid (TFA, a pervasive forever chemical) as the cleavage reagent. To overcome these drawbacks, alternative strategies to replace Fmoc/ t Bu-based protection and deprotection for SPPS are urgently needed. Here, we introduce a novel SPPS platform based on Fmoc/pyridinemethyl (Pic) chemistry, which enables the orthogonal protection of amino acid side chains and their efficient removal via photocatalytic C-heteroatom bond cleavage under mild conditions. Our approach utilizes the feedstock Pic group to cage amino acid side chains, which eliminates the need for TFA, thereby offering an environmentally friendly alternative to traditional peptide synthesis. Furthermore, this approach seamlessly integrates with automated peptide synthesizers, enabling acid-free, on-resin photorelease of structurally complex peptides, which remains challenging for conventional SPPS methodologies.}, archive = {J_JACS}, author = {Hanxi Bai and Farong Ye and Dalovai Purnachandar and Xinliang Liu and Ping Huang and Ping Wang}, doi = {10.1021/jacs.5c11459}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34011--34018}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic C–X bond cleavage facilitates peptide synthesis}, volume = {147}, year = {2025}, }
• (2025). Cation dehydration by surface-grafted phenyl groups for enhanced c2+ production in cu-catalyzed electrochemical CO2 reduction. JACS, 147(37), 34001--34010. (www)

  @article{ , abstract = {The challenge to produce multicarbon (C 2+ ) products in high current densities in the electrochemical reduction of carbon dioxide (CO 2 RR) has motivated intense research. However, the ability of solvated cations to tune and activate water for C 2+ production in the CO 2 RR has been overlooked. In this study, we report the incorporation of a covalently grown layer of functionalized phenyl groups on the Cu surface that leads to a 7-fold increase in ethylene production (to −530 mA cm –2 ) and a 6-fold increase in C 2+ products (to −760 mA cm –2 ). Our mechanistic study, notably by in situ infrared, isotope effect, and electrochemical impedance spectroscopy, reveals that the surface grafting provokes the reduction of the hydration shell around alkali cations at the electrode–electrolyte interface. This reduction weakens the hydrogen bond network and thus enhances water dissociation to provide a proton for the CO 2 RR. Moreover, it increases cation density at the outer Helmholtz plane, resulting in a larger local electric field that further stabilizes intermediates en route to C 2+ production. Our study brings to light the crucial role of cations in modulating the interfacial water structure, which has to be optimal for efficient C 2+ production in CO 2 RR.}, archive = {J_JACS}, author = {Miyeon Chang and Suhwan Yoo and Wenchao Ma and Hubert Girault and Yun Jeong Hwang and Xile Hu}, doi = {10.1021/jacs.5c11313}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {34001--34010}, shortjournal = {J. Am. Chem. Soc.}, title = {Cation dehydration by surface-grafted phenyl groups for enhanced c2+ production in cu-catalyzed electrochemical CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). Reactivity studies of bipyridine-ligated Nickel(I) and nickel(0) complexes inform the mechanism in modern cross-coupling reactions. JACS, 147(37), 33991--34000. (www)

  @article{ , abstract = {Bipyridine-ligated nickel(I) and nickel(0) intermediates are widely proposed in Ni-catalyzed cross-coupling reactions. However, few isolable Ni I and Ni 0 complexes with catalytically relevant bipyridine ligands are known, limiting our understanding of these complexes’ speciation and reactivity. In this work, we identify and investigate well-defined, isolable ( t -Bu bpy)Ni I and ( t -Bu bpy)Ni 0 complexes to characterize their behavior in catalytic systems. Employing spectroscopic and stoichiometric studies, we identified a solvent dependence on rates of the irreversible dimerization of ( t -Bu bpy)NiBr, measured rates for the activation of aryl halides and alkyl halides by ( t -Bu bpy)Ni I and ( t -Bu bpy)Ni 0 , and found that the reduction of ( t -Bu bpy)NiBr to Ni 0 is inefficient with common heterogeneous metal reductants. Taken together, these studies enable us to propose a general mechanism for cross-electrophile coupling reactions.}, archive = {J_JACS}, author = {T. Judah Raab and Abigail G. Doyle}, doi = {10.1021/jacs.5c11247}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33991--34000}, shortjournal = {J. Am. Chem. Soc.}, title = {Reactivity studies of bipyridine-ligated Nickel(I) and nickel(0) complexes inform the mechanism in modern cross-coupling reactions}, volume = {147}, year = {2025}, }
• (2025). Molecular engineering of self-folded lithium salts toward high-energy and high-power lithium metal pouch cells. JACS, 147(37), 33976--33990. (www)

  @article{ , abstract = {Molecular engineering of electrolytes for practical high-power and high-energy lithium metal batteries (LMBs) is a significant challenge due to the difficulty of simultaneously achieving high Li + transport efficiency, minimal gas evolution, and stable cathode-electrolyte and anode-electrolyte interphases (CEI and SEI, respectively), with low charge-transfer resistance. Here, we introduce a fluorinated asymmetric lithium salt, lithium (2-(2-(2,2-difluoroethoxy)ethoxy)ethyl) ((trifluoromethyl)sulfonyl)amide (LiFOA), designed to optimize electrolyte physicochemical/electrochemical properties for stable LMB pouch cells under fast cycling conditions. LiFOA features a Li + -affinitive side chain, which folds up and suppresses anion migration, resulting in a significantly heightened Li + transference number ( t Li + ). Moreover, the folding enables a self-cleaning mechanism for both the SEI and CEI. Thus, robust and ultrathin CEI and SEI with low charge-transfer resistance are self-evolved simultaneously. Importantly, a semifluorinated methyl terminal of the side chain further optimizes molecular folding strength with a tuned donor number, which not only elevates the electrochemical stability of the functional salt but also significantly mitigates the gas-evolution issue of the electrolyte during harsh cycling of the battery. Through this molecular design, industrial pouch cells with LiFOA achieve an outstanding combination of practical demanding performances in terms of high energy density (523 W h kg –1 at 0.1 C), high power density (1782 W kg –1 at 5 C), excellent cycling stability, suppressed gas evolution, modest cell volume expansion, and a significantly lowered defect under rigorous operating conditions, highlighting LiFOA’s potential for next-generation high-energy-density and high-power-density practical LMB applications.}, archive = {J_JACS}, author = {Yu Ou and Yingchun Xia and Da Zhu and Changjian Li and Pan Zhou and Wenhui Hou and Yang Lu and Shuaishuai Yan and Xuan Song and Hangyu Zhou and Zhi Liu and Xiao Ma and Yuhao Wu and Xuwen Peng and Kezhuo Li and Lai Wei and Hao Liu and Hong Xu and Kai Liu}, doi = {10.1021/jacs.5c11172}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33976--33990}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular engineering of self-folded lithium salts toward high-energy and high-power lithium metal pouch cells}, volume = {147}, year = {2025}, }
• (2025). Pillar-like macrocycle reversibly self-assembled from a molecular thermally activated delayed fluorescence emitter based on b ← n dative bonds with intriguing fluorescence. JACS, 147(37), 33963--33975. (www)

  @article{ , abstract = {Incorporating boron atoms into organic macrocycles imparts unique chemical, electronic, and optical properties. The concept of making use of dative boron–nitrogen (B ← N) bonds for the construction of macrocycles has been proposed, but very few examples have been prepared with functional structures, much less pillar-like and other prismatic macrocycles, and their various functionalities have not been fully exploited. Here, we introduce a “functional molecular wall” synthetic protocol based on the self-assembly characteristics of B ← N dative bonds to construct highly symmetrical macrocycles, forming a quasi-pentagonal-shaped macrocycle (named [5]pyBN- p ) with a pillar-like structure. Single-crystal analysis confirmed that its structure exhibited a 5-fold symmetric crown-shaped cavity with a diameter of approximately 9.65 Å, forming four sets of three-dimensional channel stacking structures. In solution, thermal cycling between heating and cooling allows for a fast and fully reversible conversion between monomer pyBN- p and pentameric macrocycle [5]pyBN- p . The resultant macrocycle [5]pyBN- p exhibited delayed fluorescence (DF) property and high photoluminescence quantum yield in the solid state. Notably, the supramolecular aggregates of macrocycle [5]pyBN- p possessed permanent porosity and showed an efficient C 2 H 6 /C 2 H 4 inverse separation capacity. This work highlights a new molecular design strategy for B ← N-containing macrocycles, enriching the family of molecular species and expanding new avenues for their applications.}, archive = {J_JACS}, author = {Yanru Li and Jiawei Chen and Wenyu Jiao and Jianeng Ma and Yongsheng Chen and Jun Xu and Zhiqiang Liang and Shaoqiang Dong and Xing Chen and Martin Heeney and Zhuping Fei}, doi = {10.1021/jacs.5c11129}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33963--33975}, shortjournal = {J. Am. Chem. Soc.}, title = {Pillar-like macrocycle reversibly self-assembled from a molecular thermally activated delayed fluorescence emitter based on b ← n dative bonds with intriguing fluorescence}, volume = {147}, year = {2025}, }
• (2025). X-ray crystallographic visualization of a nucleation and anisotropic growth in thiolate-protected gold clusters: Toward targeted synthesis of gold quantum needles. JACS, 147(37), 33953--33962. (www)

  @article{ , abstract = {Understanding and controlling the nucleation and growth processes of gold clusters are crucial for advancing the nucleation theory and targeted cluster synthesis. While in situ mass spectrometry has revealed the intermediate species formed during the growth process, the overall structural evolution remains unclear due to a lack of crystallographic information. In this study, we examined a new synthetic method for thiolate-protected gold clusters in their embryonic stage. In this method, only partial Au(I) precursors are reduced by a minimal amount of mild reductant in the presence of a substoichiometric amount of thiol. Under optimized conditions, we obtained a series of small gold clusters, including Au 15 (SCTMS) 13 , Au 18 (SCTMS) 14 , Au 22 (SCTMS) 18 , Au 23 (SCTMS) 17 , Au 25 (SCTMS) 18 , Au 33 (SCTMS) 25 , and Au 34 (SCTMS) 26 (TMSCS – : trimethylsilylmethanethiolate), and successfully determined their geometric structures via single-crystal X-ray diffraction analysis. Unexpectedly, the synthetic yield of Au 25 (SCTMS) 18 with an icosahedral Au 13 core was very low despite the stability of this composition. The obtained structural information suggests that under our synthetic conditions the dominant process is the assembly of triangular Au 3 and tetrahedral Au 4 units, each with two electrons, in an anisotropic structure followed by passivation with unreduced Au(I)-SCTMS complexes. Notably, Au 33 (SCTMS) 25 and Au 34 (SCTMS) 26 have a pencil-shaped Au 16 core with an Au 3 width and exhibit strong absorption and emission in the near-infrared region. Due to their extremely thin diameter and quantized electronic structures, we propose naming these anisotropic species “gold quantum needles”. This study deepens our understanding of the cluster formation mechanism at the atomic level and provides a novel synthetic route for highly anisotropic gold clusters.}, archive = {J_JACS}, author = {Shinjiro Takano and Yuya Hamasaki and Tatsuya Tsukuda}, doi = {10.1021/jacs.5c11089}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33953--33962}, shortjournal = {J. Am. Chem. Soc.}, title = {X-ray crystallographic visualization of a nucleation and anisotropic growth in thiolate-protected gold clusters: Toward targeted synthesis of gold quantum needles}, volume = {147}, year = {2025}, }
• (2025). Energy transfer from multiple excitons in a perovskite nanocrystal to organic dyes revealed by single-particle spectroscopy. JACS, 147(37), 33944--33952. (www)

  @article{ , abstract = {Colloidal semiconductor quantum dots (QDs) can generate multiple excitons (MXs) within a single QD. Owing to their large absorption cross-section, efficient utilization of MX is anticipated for the development of light-harvesting systems. However, MXs typically undergo nonradiative decay via Auger recombination (AR). In this study, we investigated the possibility of energy transfer from the MXs in a single QD to multiple cyanine dyes (Cy3) adsorbed on the QD surface. Based on the linear relationship between the AR lifetime and QD volume, formamidinium lead bromide perovskite nanocrystals (PNCs) with three distinct size distributions were synthesized. Simultaneous measurements of emission photon correlations and individual pristine PNC sizes revealed that the probability of multiphoton emission increased in PNCs larger than 12 nm. This was attributed to a slowdown in the AR rate, which was evaluated by transient absorption spectroscopy. Subsequently, multiple Cy3 dyes were adsorbed onto the PNCs as energy acceptors to evaluate the transfer of energy from the MXs to multiple Cy3 dyes. Photon correlation measurements of Cy3 emission via energy transfer─induced by excitation of a single PNC─showed an increased probability of multiphoton emission in PNC-Cy3 systems with PNC sizes exceeding 12 nm. These findings indicate that multiple Cy3 dyes were excited and emitted via the energy transfer from MXs. Thus, we clearly demonstrate that energy transfer from MXs to multiple surface dyes is feasible using large-sized PNCs.}, archive = {J_JACS}, author = {Tetsuo Yamaguchi and Tomoya Fukumasu and Yukihide Ishibashi and Sadahiro Masuo}, doi = {10.1021/jacs.5c11022}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33944--33952}, shortjournal = {J. Am. Chem. Soc.}, title = {Energy transfer from multiple excitons in a perovskite nanocrystal to organic dyes revealed by single-particle spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Bifunctional catalysis of aldol reactions by foldamer dihydrazides: Assessment of conformational preorganization. JACS, 147(37), 33932--33943. (www)

  @article{ , abstract = {We previously reported that molecules containing two cyclic hydrazide units connected by a polymethylene linker could catalyze aldol condensations via a bifunctional mechanism. One hydrazide apparently provides nucleophilic activation, via enamine formation, while the other provides electrophilic activation, via iminium formation. Here, we ask whether catalytic efficacy can be enhanced by using a conformationally preorganized linker to connect the hydrazide units. In the new catalyst series, the linkers are α/β-peptides (oligomers containing α- and β-amino acid residues). The α/β-peptide scaffold features a 1:2 α:β backbone repeat and forms a helix with approximately three residues per turn. When α residues with hydrazide-containing side chains have an i , i +3 sequence relationship, helical folding induces alignment of the hydrazides. Incremental variation of side chain length allowed us to identify an optimal spacing between the hydrazide units, comprising 16 atoms. Catalytic efficacy, as judged by relative initial rates of an aldol condensation, was ∼3.5-fold greater for this α/β-peptide relative to the dihydrazide with a flexible 16-atom spacer from the previous series. Single-crystal X-ray crystallographic analyses of three α/β-peptide catalysts provide insight into modes of conformational flexibility available to these foldamers.}, archive = {J_JACS}, author = {Philip P. Lampkin and Kyana M. Sanders and Leah C. Garman and Ilia A. Guzei and Samuel H. Gellman}, doi = {10.1021/jacs.5c10914}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33932--33943}, shortjournal = {J. Am. Chem. Soc.}, title = {Bifunctional catalysis of aldol reactions by foldamer dihydrazides: Assessment of conformational preorganization}, volume = {147}, year = {2025}, }
• (2025). Synthesis of bicyclo[2.1.0]pentanes and vinylcyclopropanes using palladium carbenes: Ligand-controlled carbene reactivity. JACS, 147(37), 33923--33931. (www)

  @article{ , abstract = {Once physical organic curiosities, bicyclo[2.1.0]pentanes (colloquially termed housanes) are useful strain-release reagents and are unique structural motifs for medicinal chemistry campaigns because of their high Fsp 3 content. Despite this, methods to synthesize housanes are lacking due to their highly strained nature. Herein, we report an intramolecular cyclopropanation strategy to obtain functionalized housanes using palladium carbenes (20 substrates, up to 89% yield). Key to the success of this reaction was the insight that the reactivity of Pd(0) carbenes is controlled by the supporting ligand. Strongly donating N -heterocyclic carbene ligands promote cyclopropanation reactivity, while some π-accepting phosphoramidite ligands (e.g., rac -MonoPhos) afford C–H insertion products (8 examples, up to 20:1 selectivity). Deuterium-labeling studies revealed a KIE of 2.1 at 80 °C, suggesting a palladium carbene is involved in the C–H insertion step, and the independent synthesis of alkyldiazenes confirms that they are not relevant intermediates in this reaction. The housane products were amenable to late-stage cross-coupling reactions and ring-opening reactions to provide cyclopentanes.}, archive = {J_JACS}, author = {Isaiah K. Eckart-Frank and Emily S. Arnold and Liam P. Murphy and Sidney M. Wilkerson-Hill}, doi = {10.1021/jacs.5c10617}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33923--33931}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of bicyclo[2.1.0]pentanes and vinylcyclopropanes using palladium carbenes: Ligand-controlled carbene reactivity}, volume = {147}, year = {2025}, }
• (2025). Harnessing dynamic heteroleptic complexation for self-assembly of robust nested metallo-supramolecular cages. JACS, 147(37), 33914--33922. (www)

  @article{ , abstract = {The exclusive formation of artificial multicomponent assemblies remains a significant challenge, in contrast to the well-established organization observed in natural systems, due to intrinsic entropic constraints. To overcome this limitation, recent efforts have been focused on developing precision self-assembly strategies for the rational construction of such architectures. Here, we construct an ideal complementary pair of 2,2′:6′,2″-terpyridine (tpy)-based ligands by fine-tuning the substituent bulkiness, which enables the quantitative formation of robust nested cages through efficient dynamic heteroleptic complexation with multivalent coordination. The multivalent ligand design proves essential for successful self-assembly, as the smaller incarcerated cage cannot be independently synthesized in an exclusive manner. Notably, the improved solubility and exceptional stability of the nested cage even at low concentrations allow for structural characterization by high-field nuclear magnetic resonance (NMR) spectroscopy, solution-based small-angle X-ray scattering (SAXS), and scanning transmission electron microscopy (STEM). Moreover, its well-defined internal cavity permits the in situ reductive formation of gold nanoparticles, demonstrating its potential as a functional nanoreactor.}, archive = {J_JACS}, author = {Soumyakanta Prusty and Hung-Kai Hsu and Mahesh Madasu and Alisha Rani and Jun-Hao Fu and Lin-Ting Lin and Ming-Hao Lee and Ming-Wen Chu and Chun-Hong Kuo and Yi-Tsu Chan}, doi = {10.1021/jacs.5c10891}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33914--33922}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing dynamic heteroleptic complexation for self-assembly of robust nested metallo-supramolecular cages}, volume = {147}, year = {2025}, }
• (2025). Targeted synthesis and development of neotype antiviral agents with a radical-mediated deoxyphosphoamination strategy. JACS, 147(37), 33903--33913. (www)

  @article{ , abstract = {The persistent threat of emerging and re-emerging viral infections underscores the urgent need for the continuous development of next-generation antiviral agents. The deoxygenative functionalization of oxygen-containing compounds offers a powerful route to address this challenge. Herein, we report a radical-mediated deoxyphosphoamination of ketones to synthesize a new class of antiviral compounds, including N -(2-(diphenylphosphoryl)-1 H -inden-3-yl)- P , P -diphenylphosphinic amide (IDPA) and its homologues. This transformation proceeds under simple, mild, and easily operable reaction conditions, exhibiting a broad substrate scope and excellent functional group tolerance. Mechanistic investigations, including control and radical inhibition experiments, high-resolution mass spectrometry detection of key intermediates, and density functional theory calculations, reveal a concerted pathway involving nitrogen, oxygen, and phosphorus radicals that facilitate N–O bond cleavage and the formation of C═C, C–P, and N–P bonds. Biological evaluations demonstrate that these scaffolds possess potent broad-spectrum antiviral activity with low cytotoxicity. Proteomic analysis, molecular docking, and Western blotting further elucidate the mechanism by which IDPA inhibits porcine reproductive and respiratory syndrome virus (PRRSV) replication through its interactions with receptor protein CD163 and host protein HSP70. These findings establish a versatile strategy for developing radical-based antiviral agents and provide promising candidates for therapeutic intervention.}, archive = {J_JACS}, author = {Jian-Wu Zhang and Xiao Liu and Dian Wei and Shuo Liu and Fang Lv and Bo Peng and Yang Li and Zhiqian Ma and Zhiwei Li and Zifang Zheng and Yingtong Feng and Xuyang Guo and Lele Xu and Haixue Zheng and Shuqi Xiao}, doi = {10.1021/jacs.5c10745}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33903--33913}, shortjournal = {J. Am. Chem. Soc.}, title = {Targeted synthesis and development of neotype antiviral agents with a radical-mediated deoxyphosphoamination strategy}, volume = {147}, year = {2025}, }
• (2025). Surface-driven electron localization and defect heterogeneity in ceria. JACS, 147(37), 33888--33902. (www)

  @article{ , abstract = {The exceptional performance of ceria (CeO 2 ) in catalysis and energy conversion is fundamentally governed by its defect chemistry, particularly oxygen vacancies. The formation of each oxygen vacancy (V O •• ) is assumed to be compensated by two localized electrons on cations (Ce 3+ ). Here, we show by combining theory with experiment that while this 1 V O •• : 2Ce 3+ ratio accounts for the global charge compensation, it does not apply at the local scale, particularly in nanoparticles. Hybrid quantum mechanical/molecular mechanical (QM/MM) defect calculations, together with synchrotron X-ray photoelectron spectroscopy (XPS) measurements, show that electrons have a strong preference to localize and segregate on surfaces, which can overcome the trapping force from the V O •• sites in the bulk. At a given Fermi level, the surface V O •• tends to trap more electrons than those in bulk, resulting in a higher Ce 3+ to V O •• ratio on surfaces than that in the bulk, driven by the preferential localization of electrons and enhanced V O •• –Ce 3+ coupling. Large-scale unbiased Monte Carlo simulations on ceria nanoparticles confirmed this trend and further show that the surface segregation of electrons is more pronounced at low reduction levels and in smaller nanoparticles. In highly reduced ceria nanoparticles, however, the enhanced repulsive interactions lead to a less significant extent of defect heterogeneity or even reverse the location preference of defects in some nanoparticles. Our findings underscore the need to consider both the overall nonstoichiometry and local defect behavior in easily reducible oxides, with direct relevance to their performance in catalytic and energy applications.}, archive = {J_JACS}, author = {Xingfan Zhang and Akira Yoko and Yi Zhou and Woongkyu Jee and Alvaro Mayoral and Taifeng Liu and Jingcheng Guan and You Lu and Thomas W. Keal and John Buckeridge and Kakeru Ninomiya and Maiko Nishibori and Susumu Yamamoto and Iwao Matsuda and Tadafumi Adschiri and Osamu Terasaki and Scott M. Woodley and C. Richard A. Catlow and Alexey A. Sokol}, doi = {10.1021/jacs.5c10679}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33888--33902}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface-driven electron localization and defect heterogeneity in ceria}, volume = {147}, year = {2025}, }
• (2025). Triplet carbene insertion enables modular access to c2-substituted bicyclo[1.1.1]pentanes. JACS, 147(37), 33879--33887. (www)

  @article{ , abstract = {Bicyclo[1.1.1]pentanes (BCPs) play crucial roles as saturated bioisosteric replacements of planar benzene rings. As strategic three-dimensional alternatives to ortho - or meta -substituted arenes, C2-substituted BCPs provide access to an underexplored chemical space. The pursuit of efficient and broadly applicable synthetic routes for these scaffolds remains a significant challenge, primarily due to the unique topological features of BCP cores. Here, we report a robust and modular strategy for the direct synthesis of C2-substituted BCPs from readily available bicyclo[1.1.0]butanes (BCBs) and diazo compounds. Leveraging homolytic cleavage of the central bond in BCBs, a triplet energy transfer-initiated carbene insertion process occurs, to form 1,4-biradical species, which are ultimately converted to the target BCPs via rapid radical recombination. This methodology establishes a modular platform for systematic access to the C2-functionalized BCP architectures, enabling expeditious diversification of the three-dimensional skeletons. Its practicability has been further demonstrated through the collective replacement of the phenyl moiety with bioisosteric BCP in 15 bioactive molecules.}, archive = {J_JACS}, author = {Jin-Teng Che and Hong-Bo Zhang and Wei-Yi Ding and Shao-Hua Xiang and Bin Tan}, doi = {10.1021/jacs.5c10649}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33879--33887}, shortjournal = {J. Am. Chem. Soc.}, title = {Triplet carbene insertion enables modular access to c2-substituted bicyclo[1.1.1]pentanes}, volume = {147}, year = {2025}, }
• (2025). Metal–Organic crystallized glasses: Microstructure formation and their properties. JACS, 147(37), 33870--33878. (www)

  @article{ , abstract = {Partial crystallization within a glass matrix to form microcrystalline domains offers a pathway to glass-ceramic materials with properties distinct from those of both the parent glass and crystalline phases. This concept has been limited to inorganic glasses. Here, we introduce metal–organic crystallized glasses (MOCGs), prepared by controlling the crystallization process within metal–organic framework (MOF) glasses, and explore their properties. By adjusting the annealing temperature and duration above the glass transition temperature ( T g ), we control the crystallinity and crystallite size in 2D Cd(H 2 PO 4 ) 2 (1,2,4-triazole) 2 -based MOCGs, enabling modulation of their micromechanical properties, dielectric constants, and proton conductivities. The MOCG with a 15% relative crystallinity exhibits a dielectric constant of 3.3 × 10 2 at 100 kHz, an order of magnitude higher than that of both the parent glass and crystalline phases across 30–100 °C. We further extend this concept to a mixed-metal MOF glass system, where solid solutions occur through the incorporation of Cd 2+ and Mn 2+ ions from the amorphous matrix into crystallizing lattices upon annealing.}, archive = {J_JACS}, author = {Soracha Kosasang and Nattapol Ma and David L. Christensen and Morten M. Smedskjaer and Hiroki Yamada and Satoshi Horike}, doi = {10.1021/jacs.5c10513}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33870--33878}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal–Organic crystallized glasses: Microstructure formation and their properties}, volume = {147}, year = {2025}, }
• (2025). Proton ordering induces a polar structure in the antiferromagnetic solid proton conductor FeH6(PO4)3. JACS, 147(37), 33859--33869. (www)

  @article{ , abstract = {Materials exhibiting coexisting exploitable properties often result in especially attractive behavior from both fundamental and applied perspectives. In particular, magnetoelectric materials combining ferroelectric and magnetic properties are increasingly becoming paramount nowadays. Here, we show that FeH 6 (PO 4 ) 3 exhibits proton conductivity and the coexistence of magnetic and polar structural features, suggesting that such frameworks may be of broader interest beyond the field of proton conductors. By a combination of neutron diffraction and second harmonic generation experiments, we have demonstrated that FeH 6 (PO 4 ) 3 crystallizes in the polar R 3 c space group. Inversion symmetry breaking is triggered by a polar proton ordering within the structure. In FeH 6 (PO 4 ) 3 , this particular cation ordering in combination with the polar displacement of the adjacent structural units results in a polar crystal structure with a calculated net polarization of approximately 10 μC cm –2 between 10 and 300 K. Together with an antiferromagnetic state below 28 K, determined from a combination of neutron diffraction and magnetic measurements and associated with the particular Fe 3+ octahedral arrangement, the result is the coexistence of both properties. By a detailed study of this system with a full description of the crystal structure as well as the ionic and magnetic properties, we aim to spark further investigations in magnetoelectric materials existing in the solid ionic conductor phase space.}, archive = {J_JACS}, author = {Lara M. Gronych and Marvin A. Kraft and Matthias Hartmann and Vasiliki Faka and Dana Glikman and Iven Koers and Cheng Li and Jon Newnham and Björn Braunschweig and Wolfgang G. Zeier and Xabier Martinez de Irujo-Labalde}, doi = {10.1021/jacs.5c10508}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33859--33869}, shortjournal = {J. Am. Chem. Soc.}, title = {Proton ordering induces a polar structure in the antiferromagnetic solid proton conductor FeH6(PO4)3}, volume = {147}, year = {2025}, }
• (2025). Diversity-oriented C–H activation reactions of the naphthalene scaffold. JACS, 147(37), 33850--33858. (www)

  @article{ , abstract = {Diversity-oriented synthesis (DOS) has emerged as an efficient strategy for constructing diverse compound libraries, facilitating hit or lead identification in the drug discovery process. In parallel, developing diverse transformations at different sites is an appealing strategy to expand the diversity of appendages on scaffolds. Owing to the availability of C–H bonds at multiple sites of pharmacophores, diversity-oriented C–H activation reactions are an ideal approach to realize this goal. Given the pharmacophoric significance of the naphthalene scaffold in clinical drugs, diversity-oriented C–H functionalization reactions on this scaffold would be useful for drug discovery. Direct C–H activation at the challenging C6 and C7 positions has remained unexplored due to electronic similarity, remote distance from the directing group, and interference from geometrically identical positions (C7 vs C3, C6 vs C4). Herein, we report two types of templates designed to differentiate the C6 and C7 positions on the naphthalene scaffold. The success is attributed to manipulation of the distance parameter in the template and the utilization of an oligopeptide ligand. Notably, the utility of this diversity-oriented C–H activation is showcased through the divergent modification of naphthalene-containing complex molecules.}, archive = {J_JACS}, author = {Zhoulong Fan and Md Emdadul Hoque and Kevin Wu and Maximilian D. Palkowitz and Upender Velaparthi and Kevin W. Gillman and Jennifer X. Qiao and Jin-Quan Yu}, doi = {10.1021/jacs.5c10482}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33850--33858}, shortjournal = {J. Am. Chem. Soc.}, title = {Diversity-oriented C–H activation reactions of the naphthalene scaffold}, volume = {147}, year = {2025}, }
• (2025). Lanthanide Core–Satellite nanoprobes with dually activatable magnetic resonance and second near-infrared fluorescence signals for perioperative image-guided cancer surgery. JACS, 147(37), 33838--33849. (www)

  @article{ , abstract = {Image-guided surgery plays a critical role in improving the cancer patient prognosis. However, current clinical probes are often single-modal with “always-on” signals, failing to provide complementary and precise guidance across all perioperative phases. To tackle this hurdle, we develop a biomarker-activatable, multimodal nanoprobe – LanCop – based on redox-mediated manganese valence switching for tumor-specific, perioperative image-guided surgery. LanCop comprises a lanthanide nanoparticle (LnNP) core surrounded by high-valence manganese-rich MnO 1.69 satellites, which initially exhibits negligible T 1 -weighted magnetic resonance imaging (MRI) contrast and second near-infrared (NIR-II) fluorescence. In the glutathione-rich tumor microenvironment, Mn 3+ /Mn 4+ ions are reduced to free Mn 2+ ions, effectively generating strong MRI contrast via increased unpaired electrons and enhanced spin relaxation and simultaneously disrupting energy quenching between the core and satellites to restore NIR-II fluorescence. This dual-signal activation enables precise preoperative MRI tumor localization, real-time intraoperative fluorescence-guided tumor resection, and rapid optical biopsy confirmation (within 5 min) in mouse glioma models. Deep-seated tumors are detected in real-time with a high signal-to-background ratio (12.6 ± 0.7), and microtumors as small as ∼0.5 mm × 0.7 mm are precisely excised under NIR-II fluorescence guidance. Notably, it accurately distinguishes human glioma specimens from adjacent normal tissue, demonstrating its potential for histopathological assessment. To our knowledge, LanCop is the first activatable multimodal probe capable of guiding all perioperative phases, offering a promising strategy to enhance surgical precision and improve clinical outcomes in cancer treatment.}, archive = {J_JACS}, author = {Yufei Liu and Jinzhao Huang and Wenzhen Zhu and Yan Zhang}, doi = {10.1021/jacs.5c10319}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33838--33849}, shortjournal = {J. Am. Chem. Soc.}, title = {Lanthanide Core–Satellite nanoprobes with dually activatable magnetic resonance and second near-infrared fluorescence signals for perioperative image-guided cancer surgery}, volume = {147}, year = {2025}, }
• (2025). Ion-exchange catalyst marries cationic ring-opening polymerization with functional carboxylic acid initiators. JACS, 147(37), 33828--33837. (www)

  @article{ , abstract = {Compared with the conventionally used strong acid/electrophile initiators, carboxylic acids are much more compatible with other functional groups but are incapable of initiating cationic polymerization for the one-step synthesis of end-functionalized polymers. Using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as a catalyst, we realized carboxylic acid-initiated cationic ring-opening polymerization (CROP) of 2-ethyl-2-oxazoline (EtOx). The dynamic exchange between carboxylate and TFSI – anions, driven by Li + –carboxylate interaction, significantly enhances the activity of oxazolinium propagating species and ensures uniform chain growth, as shown by both experiments and calculations. Interestingly, a proper solvent, γ-valerolactone, also plays a vital role, likely by promoting ion-pair separation at elevated temperatures. A wide scope of functional groups is readily introduced by commercialized carboxylic acids, especially benzoic acid derivatives and analogues, with controlled molar mass, low dispersity, and high/quantitative end-group fidelity achieved, and polymerization rate varying with the initiator structure. The end functionalities of polyEtOx are exemplified by surface adsorption–protein resistance and aggregation-induced emission properties. This catalytic paradigm breaks through long-standing limitations in weak-acid-initiated CROP, indispensably upgrading the toolkit for macromolecular engineering.}, archive = {J_JACS}, author = {Tingwei Chen and Chenke Zhao and Junpeng Zhao}, doi = {10.1021/jacs.5c10299}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33828--33837}, shortjournal = {J. Am. Chem. Soc.}, title = {Ion-exchange catalyst marries cationic ring-opening polymerization with functional carboxylic acid initiators}, volume = {147}, year = {2025}, }
• (2025). Controlling magnetic anisotropy of endohedral lanthanide ions by carbene addition: Paramagnetic NMR, lanthanide luminescence, and single-molecule magnetism in adamantylidene adducts of MSc2N@C80 (M = nd, dy). JACS, 147(37), 33812--33827. (www)

  @article{ , abstract = {Metallofullerenes with endohedral lanthanides have emerged as a versatile class of single-molecule magnets owing to strong single-ion magnetic anisotropy, which can be realized in the interior of the fullerene cage. Since exohedral chemical modification of fullerenes is often used to adjust their properties and processability for prospective practical applications, it is necessary to understand how it can affect their magnetic properties. In this work, we studied how a popular [2 + 1] cycloaddition reaction, photochemical addition of adamantylidene (Ad), affects single-ion magnetic anisotropy and single-molecule magnetism of MSc 2 N@C 80 (M = Nd, Dy). For each lanthanide, the reaction yielded [5,6]-open and [6,6]-open isomers of the monoadduct MSc 2 N@C 80 (Ad). Paramagnetic 1 H NMR was demonstrated that the Ad-addition site in [5,6] isomers is predominantly coordinated by Sc, whereas both Sc and lanthanide coordination coexist in [6,6] isomers. Ab initio calculations and Nd-based photoluminescence showed that the [5,6] isomer has enhanced ligand-field splitting, whereas coordination of the lanthanide to the Ad-addition site in the [6,6] isomer reduces magnetic axiality and ligand-field splitting. For DySc 2 N@C 80 (Ad), Dy-Ad coordination leads to a noticeable reduction in the blocking temperature of magnetization, whereas Dy coordination to the unfunctionalized fragments of the fullerene cage improves the SMM performance in comparison to the unfunctionalized DySc 2 N@C 80 . Thus, carbene addition can enhance or deteriorate SMM properties depending on the regioisomerism and the lanthanide-cage coordination geometry in MSc 2 N@C 80 (Ad) adducts. These results demonstrate that chemical derivatization of EMFs can become a useful tool for improving their magnetic properties, but will require careful evaluation of different factors for each reaction type.}, archive = {J_JACS}, author = {Wei Yang and Matheus Felipe de Souza Barbosa and Noel Israel and Marco Rosenkranz and Fupin Liu and Stanislav M. Avdoshenko and Alexey A. Popov}, doi = {10.1021/jacs.5c10147}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33812--33827}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlling magnetic anisotropy of endohedral lanthanide ions by carbene addition: Paramagnetic NMR, lanthanide luminescence, and single-molecule magnetism in adamantylidene adducts of MSc2N@C80 (M = nd, dy)}, volume = {147}, year = {2025}, }
• (2025). Probing photoinduced halide segregation in CH3NH3Pb(BrxI1–x)3 perovskites via in situ nuclear quadrupole resonance spectroscopy. JACS, 147(37), 33799--33811. (www)

  @article{ , abstract = {Mixed-halide perovskites of formula MAPb(Br x I 1– x ) 3 , where MA is methylammonium, are of great interest for optoelectronic applications (particularly high-efficiency solar cells) due to their finely tunable bandgap, which enables precise control over light absorption. However, their stability remains a critical challenge, notably due to reversible photoinduced halide segregation. Under continuous illumination, this process leads to the formation of Br- and I-rich domains, which lower device performance by introducing low-bandgap regions that trap charge carriers. Despite extensive efforts, the mechanism of photosegregation remains debated, partly due to the difficulty in characterizing these compositionally disordered systems, especially under illumination. Here, we report a systematic investigation across a series of MAPb(Br x I 1– x ) 3 compositions using 79/81 Br and 127 I nuclear quadrupole resonance (NQR) spectroscopy. Furthermore, we present the first application of NQR under in situ illumination to directly probe photoinduced halide segregation, focusing on compositions with x = 0.9, 0.8, and 0.6. Our findings highlight the potential of NQR as a powerful, noninvasive technique for studying local environments under illumination. The results reveal composition-dependent light-induced segregation when comparing substantially different stoichiometries. In contrast, the 81 Br NQR spectra of MAPb(Br 0.9 I 0.1 ) 3 and MAPb(Br 0.8 I 0.2 ) 3 show the emergence of comparable local environments, with preferential formation of MAPbBr 3 -like domains.}, archive = {J_JACS}, author = {Andrea Scarperi and Noemi Landi and Marcello Costamagna and Marco Taddei and Elisa Carignani and Marco Geppi and Silvia Borsacchi}, doi = {10.1021/jacs.5c10094}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33799--33811}, shortjournal = {J. Am. Chem. Soc.}, title = {Probing photoinduced halide segregation in CH3NH3Pb(BrxI1–x)3 perovskites via in situ nuclear quadrupole resonance spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Transition-metal-free aluminosilicate small-pore zeolites upgrade methane to light olefins. JACS, 147(37), 33790--33798. (www)

  @article{ , abstract = {Upgrading methane to value-added chemicals is significant but still challenging. Well-designed catalysts are required to activate methane. Extensive efforts have been dedicated to the catalytic conversion of methane over transition-metal-containing catalysts. A simple aluminosilicate FER-type zeolite has been found to activate methane and nitrous oxide to methanol stably. To further diversify the catalytic properties, zeolites with different topologies were screened in the methane oxidation reaction. Here, we show that small-pore zeolites have unique advantages in the direct upgrading of methane to light olefins. Among them, the CHA-type zeolite (SSZ-13) exhibited an outstanding performance, with a total selectivity of 90.5% to light olefins and a CH 4 conversion of 5.3% at 350 °C, accompanied by excellent regeneration. Penta-coordinated Al species as one of the active centers was figured out for methane activation and further identified as a non-framework tetra-coordinated Al species by density functional theory (DFT) calculations. The acidity of the zeolite was confirmed to influence the tandem conversion of methanol to light olefins. Our study revealed a novel possibility that transition-metal-free aluminosilicate small-pore zeolites can serve as bifunctional catalysts directly and continuously upgrade methane to light olefins via methanol as the intermediate. This approach avoided energy consumption and cumbersome operations and achieved high-efficiency and low-energy production of light olefins.}, archive = {J_JACS}, author = {Peipei Xiao and Xiaomin Tang and Jingyi Tan and Kengo Nakamura and Hiroto Toyoda and Masato Sawada and Yong Wang and Hermann Gies and Anmin Zheng and Toshiyuki Yokoi}, doi = {10.1021/jacs.5c09969}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33790--33798}, shortjournal = {J. Am. Chem. Soc.}, title = {Transition-metal-free aluminosilicate small-pore zeolites upgrade methane to light olefins}, volume = {147}, year = {2025}, }
• (2025). Cation-controlled assembly, activity, and organization of biomimetic DNA receptors in synthetic cell membranes. JACS, 147(37), 33780--33789. (www)

  @article{ , abstract = {Biological cells use cations as signaling messengers to regulate a variety of responses. Linking cations to the functionality of synthetic membranes is thus crucial to engineering advanced biomimetic agents such as synthetic cells. Here, we introduce bioinspired DNA-based receptors that exploit noncanonical G-quadruplexes for cation-actuated structural and functional responses in synthetic lipid membranes. Membrane confinement grants cation-dependent control over receptor assembly and, when supplemented with hemin cofactors, their peroxidase DNAzyme activity. Cation-mediated control extends to receptor lateral distribution to localize DNA-based catalysis within phase-separated membrane domains of model synthetic cells, imitating the localization of multimeric membrane complexes to signaling hubs in living cells. Our modular strategy paves the way for engineering from the bottom-up cation-responsive pathways for sensing, signaling, and communication in synthetic cellular systems.}, archive = {J_JACS}, author = {Elita Peters and Diana A. Tanase and Lorenzo Di Michele and Roger Rubio-Sánchez}, doi = {10.1021/jacs.5c09928}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33780--33789}, shortjournal = {J. Am. Chem. Soc.}, title = {Cation-controlled assembly, activity, and organization of biomimetic DNA receptors in synthetic cell membranes}, volume = {147}, year = {2025}, }
• (2025). Oxophilic sites mediated dynamic oxygen replenishment to stabilize lattice oxygen catalysis in acidic water oxidation. JACS, 147(37), 33770--33779. (www)

  @article{ , abstract = {Developing efficient and durable catalysts for the oxygen evolution reaction (OER) in acidic media is essential for advancing proton exchange membrane water electrolysis (PEMWE). However, catalyst instability caused by lattice oxygen (O L ) depletion and metal dissolution remains a critical barrier. Here, we propose an oxophilic-site-mediated dynamic oxygen replenishment mechanism (DORM), in which O L actively participates in O–O bond formation and is continuously refilled by water-derived species. Oxophilic dopants modulate the local electronic structure, lower the energy barrier for oxygen vacancy healing, and reorganize the interfacial hydrogen-bond network to enhance water mobility, orientation, and proton accessibility, collectively promoting water dissociation and stabilizing O L catalysis. The optimized catalyst achieves a low overpotential of 289 mV and exceptional durability, operating continuously for 650 h at 10 mA cm –2 in acidic electrolyte and maintaining stable performance for 280 h at 1 A cm –2 in a PEMWE. This work establishes a mechanistic framework for dynamic O L redox and provides a rational strategy for designing robust, noble-metal-free acidic OER electrocatalysts.}, archive = {J_JACS}, author = {Shaoxiong Li and Sheng Zhao and Sung-Fu Hung and Liming Deng and Luqi Wang and Fuke Shi and Ao Dong and Ying Zhang and Tsung-Yi Chen and Feng Hu and Linlin Li and Seeram Ramakrishna and Yuping Wu and Shengjie Peng}, doi = {10.1021/jacs.5c09939}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33770--33779}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxophilic sites mediated dynamic oxygen replenishment to stabilize lattice oxygen catalysis in acidic water oxidation}, volume = {147}, year = {2025}, }
• (2025). A macroporous cyclodextrin monolith for continuous removal of per- and polyfluoroalkyl substances from water. JACS, 147(37), 33761--33769. (www)

  @article{ , abstract = {Per- and polyfluoroalkyl substances (PFASs) are environmentally persistent, bioaccumulative, and toxic chemicals that contaminate global drinking water resources. Their ubiquity and potential impact on human health motivate large-scale remediation. Conventional materials used to remove PFASs during drinking water production are functionally inefficient or energetically expensive, motivating the discovery of new materials and technologies. Here, we introduce cyclodextrin-based monoliths, featuring a highly permeable, mechanically robust porous architecture that enables rapid and continuous PFAS removal from water. The monolith was directly polymerized into flow-through columns and showed water permeability similar to packed sand due to its interconnected macroporous structure. Compared to leading benchmarks under equivalent sorbent mass or contact time, the monolith demonstrated superior PFAS sorption with later breakthroughs for most PFASs. We show the hierarchical morphology of a monolith is more efficient use of sorbent mass than particle-based sorbents, as its macropores enable facile diffusion of PFAS to meso- and microporous sorption sites. The significance of hierarchical pore design was demonstrated by instant PFAS breakthrough passing through the pulverized monolith, where the water primarily flows through interparticle pathways with limited access to sorption sites. After treating 150 L of water spiked with 25 PFAS for 37 days, 47 mg of monolith was regenerated through alcohol wash, with near-complete mass balance of adsorbed PFASs. The regenerated monolithic sorbent treated another 170 L of water for 39 days with comparable removal. The monolith offers a novel morphology with simple and direct synthesis in columns for water treatment and provides superior PFAS removal, regeneration and reuse.}, archive = {J_JACS}, author = {Zhi-Wei Lin and Subeen Kim and Yaryna Dyakiv and Eden Frances P. Gedangoni and Aaron I. Packman and Damian E. Helbling and Gordon J. Getzinger and William R. Dichtel}, doi = {10.1021/jacs.5c09865}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33761--33769}, shortjournal = {J. Am. Chem. Soc.}, title = {A macroporous cyclodextrin monolith for continuous removal of per- and polyfluoroalkyl substances from water}, volume = {147}, year = {2025}, }
• (2025). Spontaneous perfluorooctanoic acid degradation at Gas–Liquid interfaces. JACS, 147(37), 33754--33760. (www)

  @article{ , abstract = {Perfluorooctanoic acid (PFOA), widely used in various industries and released during cooking as a PTFE precursor, poses significant environmental concerns due to its persistence and toxicity. This study investigated the degradation behavior of PFOA at the gas–liquid interface under diverse conditions. The results demonstrate that the coexistence of salts, particularly NaBr, significantly enhances PFOA degradation by promoting electron transfer reactions. Alkaline conditions (pH 9.8) and the presence of oxygen further facilitate its degradation, whereas acidic conditions hinder this process. Mechanistic analysis further confirmed that hydroxyl radicals (•OH) and hydrated electrons (e aq – ) play critical roles in the observed degradation. This work provides new insights into the transformation of PFAS under diverse conditions and offers a basis for developing strategies to degrade PFOA into environmentally benign species.}, archive = {J_JACS}, author = {Yunqian Chen and Zhongyu Guo and Maria Angelaki and Yoan Carreira Mendes Da Silva and Junwei Song and Wanqi Wu and Jingxin Lin and Adrien Gandolfo and Jianmin Chen and Christian George}, doi = {10.1021/jacs.5c09722}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33754--33760}, shortjournal = {J. Am. Chem. Soc.}, title = {Spontaneous perfluorooctanoic acid degradation at Gas–Liquid interfaces}, volume = {147}, year = {2025}, }
• (2025). Anharmonic phonon scattering triggering multi-ion migration in oxide-based superionic conductors. JACS, 147(37), 33743--33753. (www)

  @article{ , abstract = {The thermodynamic equilibrium assumption often invoked in modeling ion migration in solid-state materials remains insufficient to capture the true migration behavior of Li ions, particularly in less-crystalline superionic conductors that exhibit anomalously high Li ion conductivity. Such materials challenge classical frameworks and necessitate a lattice dynamics-based perspective that explicitly accounts for nonequilibrium phonon interactions and transient structural responses. Here, we uncover a phonon-governed Li ion migration mechanism in garnet-structured superionic conductors by comparing Ta-doped Li 6.6 La 3 Zr 1.6 Ta 0.4 O 12 (LLZTO4) to its undoped analogue, Li 6.24 La 3 Zr 2 Al 0.24 O 11.98 (LLZO). Through a synergistic combination of terahertz time-domain spectroscopy (THz-TDS), 7 Li magic-angle spinning nuclear magnetic resonance (MAS-NMR), and Raman spectroscopy, we show that Ta doping softens the host lattice and enhances anharmonic phonons, enabling collective, thereby multi-ion migration beyond the limit of single-ion hopping models. This lattice softening induces a dynamically disordered energy landscape that lowers activation barriers and yields Li ion conductivities approaching those of liquid electrolytes. Our findings demonstrate that anharmonic lattice vibrations can serve as the driving force for ultrafast Li ion migration in solid electrolytes. This paradigm shift establishes a fundamental link between lattice thermodynamics and superionic conduction, providing a conceptual and experimental framework for the design of highly conductive solid-state electrolytes.}, archive = {J_JACS}, author = {Jae-Bum Kim and Chihun Kim and Wootack Chung and Da Hye Yoon and Lulu Lyu and Jeongmin Jang and Hee Jun Shin and Kyung-Wan Nam and Byungju Lee and Yong-Mook Kang}, doi = {10.1021/jacs.5c09777}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33743--33753}, shortjournal = {J. Am. Chem. Soc.}, title = {Anharmonic phonon scattering triggering multi-ion migration in oxide-based superionic conductors}, volume = {147}, year = {2025}, }
• (2025). Vertically stacked boron Nitride/Graphene heterostructure for tunable antiresonant hollow-core fiber. JACS, 147(37), 33735--33742. (www)

  @article{ , abstract = {Incorporating atomically thin two-dimensional (2D) materials with optical fibers expands their potential for optoelectronic applications. Recent advancements in chemical vapor deposition have enabled the batch production of these hybrid fibers, paving the way for practical implementation. However, their functionality remains constrained by the integration of a single 2D material, restricting their versatile performance. Here, we introduce a boron nitride/graphene (BN/Gr) heterostructure in the antiresonant hollow-core fiber (ARF) to modulate its optical resonance and thus enhance graphene nonlinearity by controlling the BN thickness. Hydroxyl-rich methanol is employed to improve the flatness and crystallinity of graphene, promoting the vertical epitaxy of BN with a controllable thickness ranging from 5 to 50 nm. The engineered optical resonance notably tunes the light–graphene interaction within the BN/Gr-ARF, increasing the depth of nonlinear optical modulation from 4% to 10% and enhancing all-optical modulation performance by 75%. Our methodology opens possibilities for tunable optical waveguides via the direct growth of functional 2D material-based heterostructures, offering a robust platform for the development of highly integrated photonic devices.}, archive = {J_JACS}, author = {Yi Cheng and Xu Cheng and Jin Xie and Guang Cui and Shuting Cheng and Xiao Li and Jiajie Gan and Han Dong and Yuyao Yang and Wentao Yu and Ke Chen and Hao Hong and Xu Zhou and Meng Pang and Xin Jiang and Zhipei Sun and Kaihui Liu and Zhongfan Liu}, doi = {10.1021/jacs.5c09658}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33735--33742}, shortjournal = {J. Am. Chem. Soc.}, title = {Vertically stacked boron Nitride/Graphene heterostructure for tunable antiresonant hollow-core fiber}, volume = {147}, year = {2025}, }
• (2025). Molecular simulations with a pretrained neural network and universal pairwise force fields. JACS, 147(37), 33723--33734. (www)

  @article{ , abstract = {Machine Learning Force Fields (MLFFs) promise to enable general molecular simulations that can simultaneously achieve efficiency, accuracy, transferability, and scalability for diverse molecules, materials, and hybrid interfaces. A key step toward this goal has been made with the GEMS approach to biomolecular dynamics [Unke et al., Sci. Adv. 2024 , 10 , eadn4397]. This work introduces the SO3LR method that integrates the fast and stable SO3krates neural network for semilocal interactions with universal pairwise force fields designed for short-range repulsion, long-range electrostatics, and dispersion interactions. SO3LR is trained on a diverse set of 4 million neutral and charged molecular complexes computed at the PBE0+MBD level of quantum mechanics, ensuring broad coverage of covalent and noncovalent interactions. Our approach is characterized by computational and data efficiency, scalability to 200 thousand atoms on a single GPU, and reasonable to high accuracy across the chemical space of organic (bio)molecules. SO3LR is applied to study units of four major biomolecule types, polypeptide folding, and nanosecond dynamics of larger systems such as a protein, a glycoprotein, and a lipid bilayer, all in explicit solvent. Finally, we discuss future challenges toward truly general molecular simulations by combining MLFFs with traditional atomistic models.}, archive = {J_JACS}, author = {Adil Kabylda and J. Thorben Frank and Sergio Suárez-Dou and Almaz Khabibrakhmanov and Leonardo Medrano Sandonas and Oliver T. Unke and Stefan Chmiela and Klaus-Robert Müller and Alexandre Tkatchenko}, doi = {10.1021/jacs.5c09558}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33723--33734}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular simulations with a pretrained neural network and universal pairwise force fields}, volume = {147}, year = {2025}, }
• (2025). Autocatalytic reaction between HCN and cysteamine produces hydrophobic, catalytic, liquid compartments. JACS, 147(37), 33711--33722. (www)

  @article{ , abstract = {Although HCN has been explored extensively as a precursor in the prebiotic synthesis of biological molecules, macroscopic system-level phenomena, originating from reactions of HCN, such as autocatalysis, oscillations, pattern formation, and phase separation have attracted less attention. Autocatalysis and phase separation are particularly interesting in the context of the origin of life because they are sources of self-replication and compartmentalization. In this work, we investigate the reaction between HCN and cysteamine in water, which exhibits both sigmoidal reaction kinetics and the formation of a distinct liquid phase. We studied the origin of the sigmoidal kinetics using NMR spectroscopy and other techniques, investigated the chemical composition of the products using single-crystal X-ray diffraction and mass spectrometry, and probed the absorption of inert additives into the second liquid phase. Our studies show that the sigmoidal kinetics arise from an autocatalytic feedback loop driven by both an increase in pH and the catalytic nature of the newly formed phase itself. Product analysis revealed co-oligomers with a backbone derived from HCN and branches from cysteamine. This composition suggests that co-oligomerization with thiols provides a route to tractable oligomers, mitigating the formation of insoluble HCN polymers. Furthermore, this second liquid phase effectively sequesters hydrophobic molecules like benzene, demonstrating its capacity to act as a primitive compartment. The phenomena that we observed may provide some insight into prebiotic chemical networks and early-stage chemical evolution.}, archive = {J_JACS}, author = {Alexander I. Novichkov and Yael Diskin-Posner and Linda J. W. Shimon and Gregory Leitus and Christoph Flamm and Sergey N. Semenov}, doi = {10.1021/jacs.5c09581}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33711--33722}, shortjournal = {J. Am. Chem. Soc.}, title = {Autocatalytic reaction between HCN and cysteamine produces hydrophobic, catalytic, liquid compartments}, volume = {147}, year = {2025}, }
• (2025). Divergent synthesis of 1-azabicyclo[n.1.1]alkane bioisosteres via photoinduced palladium catalysis. JACS, 147(37), 33700--33710. (www)

  @article{ , abstract = {Nitrogen heterocycles are indispensable structural motifs in pharmaceuticals, agrochemicals, and materials science. However, the development of new synthetic methods to access these frameworks remains a significant challenge. Here, we describe a switchable radical approach for the synthesis of 1-azabicyclo[2.1.1]hexanes and 1-azabicyclo[4.1.1]octenes through the coupling of azabicyclo[1.1.0]butanes with 1,3-dienes, mediated by a visible-light-driven palladium photocatalytic system. This method exhibits a broad substrate scope, excellent functional group compatibility, and the capacity to assemble complex architectures, underscoring its utility in accessing valuable aza-bioisosteres. The strategy has also been employed successfully in DNA-encoded library (DEL) synthesis. Mechanistic studies, synthetic applications, and computational analyses corroborate the proposed open-shell pathway, revealing that allylic palladium intermediate formation and regiodivergent nucleophilic addition are key to achieving divergent synthesis.}, archive = {J_JACS}, author = {Ying Zhang and Kai-Dian Li and Song Yu and Kangyin Pan and Hongtao Xu and Huan-Ming Huang}, doi = {10.1021/jacs.5c09500}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33700--33710}, shortjournal = {J. Am. Chem. Soc.}, title = {Divergent synthesis of 1-azabicyclo[n.1.1]alkane bioisosteres via photoinduced palladium catalysis}, volume = {147}, year = {2025}, }
• (2025). Stereodivergent synthesis of enantioenriched organoboron compounds with Carbon/Boron dual stereocenters via Rh(I)/Cu(I)-catalyzed enantioselective desymmetrization of B–H insertions. JACS, 147(37), 33691--33699. (www)

  @article{ , abstract = {Despite notable progress in the study of chiral boron compounds, research on tetracoordinate chiral boron species remains limited. Achieving a configurationally stable boron stereocenter typically requires stabilizing the tetrahedral structure of the boron atom with suitable Lewis bases. Moreover, due to the high reactivity of borane complexes and the limited methods for their modification, designing and synthesizing tetracoordinate chiral boron compounds with stable stereocenters presents considerable challenges. Herein, we report the use of prochiral NHC carbene-substituted boranes in rhodium(I)/chiral diene and copper(I)/chiral bisoxazoline-catalyzed systems, achieving the stereodivergent synthesis of organoboron compounds featuring contiguous carbon and boron stereocenters via enantioselective desymmetrization of carbene B–H insertion. Both catalytic systems delivered good yields and high stereoselectivity (up to 99% ee and 93:7 dr), allowing access to the full complement of stereoisomers at will. Structural analysis of the typical product revealed a tetrahedral character of 91.1% for the boron stereocenters, demonstrating their high configurational stability. This work provides a robust approach to accessing structurally diverse and configurationally stable tetracoordinate chiral boron compounds.}, archive = {J_JACS}, author = {Jian-Guo Liu and Wen-Ping Zhang and Ming-Hua Xu}, doi = {10.1021/jacs.5c09400}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33691--33699}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereodivergent synthesis of enantioenriched organoboron compounds with Carbon/Boron dual stereocenters via Rh(I)/Cu(I)-catalyzed enantioselective desymmetrization of B–H insertions}, volume = {147}, year = {2025}, }
• (2025). Oxidatively induced reductive n2 binding: A dinickel-bridging bent n2 radical anion and its redox-triggered n2 release. JACS, 147(37), 33679--33690. (www)

  @article{ , abstract = {Nitrogenase accumulates reducing equivalents in hydrides and couples H 2 elimination to the reductive binding of N 2 at a di-iron edge of its FeMo cofactor (FeMoco). Here, we describe that oxidation of a pyrazolato-based dinickel(II) dihydride complex K[L(Ni–H) 2 ] ( 1 K ), either electrochemically or chemically using H + or ferrocenium, triggers H 2 elimination and binding of N 2 in a constrained and extremely bent bridging mode in [LNi 2 (μ 1,2 -N 2 )] ( 3 N2 ). Spectroscopic and computational evidence indicate that the electronic structure of 3 N2 is best described as Ni II –(N 2 •– )–Ni II , with a rare 1e – reduced and significantly activated N 2 substrate ( ṽ ̃NN = 1894 cm –1 ). 3 N2 is also formed upon 1e – oxidation of K[LNi 2 I ] ( 2 K ) under N 2 . This is an unusual and counterintuitive scenario where the oxidation of a dinickel(II) dihydride, or of a dinickel(I) complex, induces the reductive activation of N 2 . Detailed (spectro)electrochemical studies and DFT calculations confirm that N 2 binding by the {LNi 2 } platform occurs only in the regime of the mixed-valent Ni II Ni I species, while both oxidation and reduction induce the release of N 2 from 3 N2 ; the latter represents a redox-induced electron transfer (RIET) process where metal reduction leads to N 2 •– oxidation due to intramolecular back electron transfer. These findings offer new perspectives for understanding the multi-e –/ H + scenarios of N 2 fixation via hydride intermediates inspired by the FeMoco function, and for the development of synthetic platforms that avoid strongly reducing conditions for N 2 activation.}, archive = {J_JACS}, author = {Sara I. Mozzi and Dennis-Helmut Manz and Nils Ostermann and Roland A. Schulz and Peng-Cheng Duan and Thomas Kothe and Martin Diefenbach and Sebastian Dechert and Serhiy Demeshko and Vera Krewald and Inke Siewert and Franc Meyer}, doi = {10.1021/jacs.5c09334}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33679--33690}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxidatively induced reductive n2 binding: A dinickel-bridging bent n2 radical anion and its redox-triggered n2 release}, volume = {147}, year = {2025}, }
• (2025). CO adsorbates induced framework-associated low-valence coδ+ sites in co-ZSM-5 for ethane dehydrogenation. JACS, 147(37), 33666--33678. (www)

  @article{ , abstract = {The dynamic structural evolution of heterogeneous catalysts is a ubiquitous phenomenon that has attracted a lot of interest. Catalyst reconstruction can occur after appropriate pretreatment, resulting in more efficient active catalysts, which is an attractive but challenging issue. Here, we reveal a CO activation strategy that controls the microenvironment of the Co sites in the high-silica Co-ZSM-5 catalyst (denoted as 0.50Co-Z5(340)), resulting in three times higher initial conversion and superior regeneration durability in the ethane dehydrogenation reaction compared to the same catalyst without CO pretreatment. In situ spectroscopy and metadynamics simulations reveal that the Co 2+ sites in 0.50Co-Z5(340) dislodge from the framework and move toward the nearby Brønsted acid sites, forming framework-associated low-valence Co δ+ species. Mechanistic studies indicate that the Co δ+ species catalyze ethane C–H bond cleavage via an oxidative addition mechanism, and ethylene is produced simultaneously with H* coupling (direct pathway). The promoted C–H bond activation and facile ethylene desorption explain the superior ethane dehydrogenation performance of the herein CO preactivated 0.50Co-Z5(340) catalyst.}, archive = {J_JACS}, author = {Shaojia Song and Minjie Zhao and Irene Barba-Nieto and Marcos Fernández-García and Xinyu Chen and Yumeng Fo and Riguang Zhang and Zhen Zhao and Patricia Concepción and Jian Liu and Weiyu Song and Chunming Xu}, doi = {10.1021/jacs.5c09290}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33666--33678}, shortjournal = {J. Am. Chem. Soc.}, title = {CO adsorbates induced framework-associated low-valence coδ+ sites in co-ZSM-5 for ethane dehydrogenation}, volume = {147}, year = {2025}, }
• (2025). Rapid redox hopping charge transfer and electrochromism in a multivariate Metal–Organic framework. JACS, 147(37), 33655--33665. (www)

  @article{ , abstract = {Electrochromic materials exploit a change in molecular absorbance after an electrochemical redox event for applications, such as smart glass and segmented displays. Current applications use metal oxides; however, these materials are plagued by slow response times to potential changes. Herein, we investigate a metal–organic framework (MOF) film loaded with a molecular ruthenium redox carrier for its electrochromic capabilities. Upon the application of a potential jump, the native MOF was found to transport charge with an apparent diffusion coefficient, D app of 8(±3) × 10 –9 cm 2 /s. That said, only 55% of the redox centers, primarily those at the MOF surface, were converted. Using a multivariate (MTV) approach to incorporate sulfonate groups into the backbone of the MOF in addition to the redox carrier allowed for charge transport throughout the MOF with a D app of around 1(±1) × 10 –7 cm 2 /s and 100% conversion, the fastest reported diffusion coefficient in the redox hopping MOF literature to our knowledge. The sulfonated MOF exhibited a rapid electrochromic response, with coloration and bleaching times of approximately 1.29 and 1.33 s, respectively, at 400 mV overpotential. The sulfonate group is hypothesized to break ion pairs, allowing for higher ionic conductivity, which facilitates fast and complete charge transfer.}, archive = {J_JACS}, author = {Benjamin Thomas and Sumanta Basak and Quinn Smith and Minliang Yan and Amanda J. Morris}, doi = {10.1021/jacs.5c09275}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33655--33665}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid redox hopping charge transfer and electrochromism in a multivariate Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). DNA flipping as facile mechanism for transmembrane signaling in synthetic cells. JACS, 147(37), 33643--33654. (www)

  @article{ , abstract = {Transmembrane signaling is essential for cellular communication, yet reconstituting such mechanisms in synthetic systems remains challenging. Here, we report a simple and robust DNA-based mechanism for transmembrane signaling in synthetic cells using cholesterol-modified single-stranded DNA (Chol-ssDNA). We discovered that anchored Chol-ssDNA spontaneously flips across the membrane of giant unilamellar lipid vesicles (GUVs) in a nucleation-driven, defect-mediated process. This flipping enables internal signal processing through hybridization with encapsulated complementary DNA and activation of downstream processes such as RNA transcription. The phenomenon shows a high transduction efficiency, is generic across DNA sequences and lipid compositions, and can be enhanced by glycerol, which modulates membrane dynamics. Mechanistic insights using fluorescence microscopy, nuclease degradation assays, and membrane permeability assays reveal that flipping is dominated by transient membrane pores. Leveraging this facile translocation process, we demonstrate selective transcriptional activation inside synthetic cells, underscoring the potential of Chol-ssDNA flipping as a programmable tool for synthetic biology and bottom-up synthetic cell design.}, archive = {J_JACS}, author = {Lorena Baranda Pellejero and Maria Vonk-de Roy and Doruk Baykal and Livia Lehmann and Andreas Walther}, doi = {10.1021/jacs.5c09188}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33643--33654}, shortjournal = {J. Am. Chem. Soc.}, title = {DNA flipping as facile mechanism for transmembrane signaling in synthetic cells}, volume = {147}, year = {2025}, }
• (2025). A highly versatile enantiodifferentiating polyglutamate alignment medium to measure residual dipolar couplings in non-polar and polar solvents. JACS, 147(37), 33634--33642. (www)

  @article{ , abstract = {Helical structures are ubiquitous in nature and exhibit fascinating properties. They are inherently chiral, and many rely on hydrogen bonds to stabilize their conformation. Homopolypeptides of the glutamate type form α-helical secondary structures and are considered rigid-rod polymers. They form lyotropic liquid crystalline phases in helicogenic solvents. Over the past decade, this property has been exploited in the NMR-based structure elucidation of organic compounds, making anisotropic NMR observables, such as residual dipolar couplings (RDCs), accessible. However, many alignment media are limited in their compatibility, especially with polar (nonhelicogenic) solvents like DMSO, and thus also in their analyte compatibility. Herein, we present poly-γ-(4-propargyloxybenzyl)- l -glutamate (PPOBLG) as an exceptionally versatile alignment medium compatible with several organic solvents, including DMSO and acetone. The polymer not only allows extraction of RDCs in all these solvents but also provides linearly independent orientations of a model compound by simple variation of the solvent. Moreover, a remarkably high enantiodifferentiation is observed. We furthermore show that these improved properties make it compatible with various natural products containing a wide variety of functional groups.}, archive = {J_JACS}, author = {Lukas Laux and Marcel Alcaraz Janßen and Christina M. Thiele}, doi = {10.1021/jacs.5c09152}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33634--33642}, shortjournal = {J. Am. Chem. Soc.}, title = {A highly versatile enantiodifferentiating polyglutamate alignment medium to measure residual dipolar couplings in non-polar and polar solvents}, volume = {147}, year = {2025}, }
• (2025). Oxide interface-stabilized superoxo species for high-temperature catalysis. JACS, 147(37), 33625--33633. (www)

  @article{ , abstract = {High-temperature oxidation reactions catalyzed by earth–abundant transition metal oxides are vital for numerous industrial and environmental processes. However, their performance is often limited by the rapid desorption of active oxygen species at high temperatures. Here, we describe a straightforward approach to constructing a CuMn spinel/Mn 2 O 3 composite oxide catalyst that addresses this limitation and demonstrate that lattice oxygen can spontaneously migrate to form interface-stabilized superoxo species under high-temperature reaction conditions. This catalyst exhibits a 14-fold enhancement in the CH 4 oxidation reaction compared to Mn 2 O 3 , with activity and stability even better than those of many reported noble-metal supported catalysts. In situ characterizations and theoretical calculations reveal that the superoxo species accept electrons from the neighboring Cu and Mn atoms, exhibiting enhanced ability for C–H activation. This work illustrates the critical role of interface-stabilized superoxo species in CH 4 oxidation and establishes a promising route for promoting high-temperature catalytic processes through interface engineering.}, archive = {J_JACS}, author = {Zhongsen Wang and Fanyu Wang and Jiamin Zheng and Yi Liu and Jintong Lan and Zewei Wu and Jun Wang and Fangfang Pan and Xiao Liu and Rentao Mu}, doi = {10.1021/jacs.5c08963}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33625--33633}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxide interface-stabilized superoxo species for high-temperature catalysis}, volume = {147}, year = {2025}, }
• (2025). Regioselective hydroamidation of α,β-unsaturated esters enabled by lewis Acid/Iron relay catalysis. JACS, 147(37), 33615--33624. (www)

  @article{ , abstract = {Achieving precise regioselectivity in the hydroamination of alkenes is in high demand yet remains a longstanding challenge, particularly when electronically competing β-substituents are present. Here, we report a dual boron/iron catalytic system that enables the unprecedented hydroamidation of α,β-unsaturated esters to exclusively access α-amidated esters under mild conditions. The strategy harnesses the Lewis acidity of B(C 6 F 5 ) 3 to rapidly generate reactive silyl ketene acetal intermediates, which are subsequently intercepted by in situ generated iron nitrenoids. Central to this cooperative activation mode is the dual role of the chloride anion in modulating both boron and iron catalytic reactivity. This protocol is operationally simple, requiring no tailored ligands, light, or electrochemical setup, and proceeds efficiently with only 1 mol % of boron and iron catalysts. The system exhibits a broad scope of unsaturated esters, tolerating β-aryl, -alkyl, -silyl, -perfluoroalkyl, and -boryl groups. This work lays the foundation for universal α-selective hydrofunctionalization strategies across electronically complex substrates.}, archive = {J_JACS}, author = {Hoonchul Choi and Dongwook Kim and Sukbok Chang}, doi = {10.1021/jacs.5c08838}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33615--33624}, shortjournal = {J. Am. Chem. Soc.}, title = {Regioselective hydroamidation of α,β-unsaturated esters enabled by lewis Acid/Iron relay catalysis}, volume = {147}, year = {2025}, }
• (2025). Bayesian optimization for multicomponent supramolecular systems. JACS, 147(37), 33607--33614. (www)

  @article{ , abstract = {The diversity of noncovalent interactions makes the design space of multicomponent molecular systems highly complex. To efficiently explore supramolecular design space, data-driven strategies are needed. Here, we demonstrate a methodological framework for the targeted design of multicomponent molecular systems with noncovalent interactions using Bayesian optimization. Its effective applicability to supramolecular polymers is illustrated by three representative cases that reveal accelerated exploration of diverse multicomponent systems with a universal Bayesian optimization framework. The number of experiments required to arrive at optimal compositions is significantly reduced compared to random or uninformed sampling strategies, enabling the experimental study of high-dimensional design spaces. In this way, we can tune the formulation of intricate mixtures and achieve tailored macroscopic properties with minimal experimental effort. Our results show that Bayesian optimization is a general tool for developing multicomponent supramolecular systems with designed functionality.}, archive = {J_JACS}, author = {Stef A. H. Jansen and Albert J. Markvoort and Freek V. de Graaf and Martin G.T.A. Rutten and Patricia Y. W. Dankers and Ghislaine Vantomme and Tom F. A. de Greef and E. W. Meijer}, doi = {10.1021/jacs.5c08539}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33607--33614}, shortjournal = {J. Am. Chem. Soc.}, title = {Bayesian optimization for multicomponent supramolecular systems}, volume = {147}, year = {2025}, }
• (2025). Constructing high-entropy molecular networks on metal surfaces. JACS, 147(37), 33597--33606. (www)

  @article{ , abstract = {High-entropy materials (HEMs) have garnered intense attention due to their unique properties derived from compositional complexity, demonstrating promise in a wide range of applications, from catalysis to energy storage and beyond. Traditionally, HEMs have been primarily concerned with metal alloys. However, expanding the principle to organic systems, specifically high-entropy molecular nanostructures, remains underexplored. In this study, we investigated the construction of high-entropy molecular networks on a metal surface using an on-surface chemistry approach. By employing distinct pyridyl-functionalized ligands with differently shaped aromatic backbones, we constructed 2D molecular networks stabilized through coordination with metal atoms. A high-throughput preparation approach leveraging a mask inspired by a Venn diagram was utilized to create multicomponent sample libraries. Scanning tunneling microscopy provided real-space characterization, revealing both ordered and disordered assemblies and highlighting the critical role of the molecular shape and the number of functional centers in promoting or limiting mixed entropy of these networks. Monte Carlo and Molecular Dynamics simulations were further employed to model the formation mechanisms and examine factors influencing their mixed entropies. Our study provides insights into how molecular species influence disorder and stability in high-entropy molecular networks, paving the way for advancing low-dimensional high-entropy molecular systems.}, archive = {J_JACS}, author = {Jiayi Lu and Xinyi Zhang and Damian Nieckarz and Shaoxuan Yuan and Chanyu Li and Wojciech Rżysko and Yizhang Li and Paweł Szabelski and Qiang Sun}, doi = {10.1021/jacs.5c08377}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33597--33606}, shortjournal = {J. Am. Chem. Soc.}, title = {Constructing high-entropy molecular networks on metal surfaces}, volume = {147}, year = {2025}, }
• (2025). Structural basis for 3-amino-3-carboxypropyl transfer in nocardicin biosynthesis. JACS, 147(37), 33589--33596. (www)

  @article{ , abstract = {S -Adenosyl- l -methionine (SAM) is well-known as a methyl donor for methyltransferases but also functions as a 3-amino-3-carboxypropyl (3-ACP) donor for 3-ACP transferases. NAT is a 3-ACP transferase which accepts β-lactam antibiotic nocardicin G ( 1 ) and SAM to produce isonocardicin C. Due to the lack of structural information about this enzyme, its reaction mechanism has not been fully identified. In this study, we report two X-ray crystal structures of NAT, including its apo and complex structure with 1 and SAH. Examination of them identified the structural basis for substrate recognition. Comprehensive approach integrating site-directed mutagenesis, thermal shift assay, MD simulation, and QM/MM calculation revealed that the Cα-amino group of SAM functions as a Brønsted base to enhance the nucleophilicity of the C6′-OH of 1 , with the assistance of E143, thereby facilitating S N 2 attack on the Cγ of SAM. This study presents structural and computational analysis leading to more precise understanding of 3-ACP transfer.}, archive = {J_JACS}, author = {Yaojie Gao and Masayuki Karasawa and Zhiyang Quan and Takahiro Mori and Masahiro Kanaida and Craig A. Townsend and Tohru Terada and Ikuro Abe and Takayoshi Awakawa}, doi = {10.1021/jacs.5c08367}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33589--33596}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural basis for 3-amino-3-carboxypropyl transfer in nocardicin biosynthesis}, volume = {147}, year = {2025}, }
• (2025). Manganese-catalyzed asymmetric transfer hydrogenation of heteroatom-containing imines and diarylimines. JACS, 147(37), 33581--33588. (www)

  @article{ , abstract = {The efficient synthesis of chiral amines has garnered ongoing interest due to their prevalence in pharmaceuticals and biologically active compounds. However, most existing strategies for their synthesis primarily rely on asymmetric (transfer) hydrogenation (AH/ATH) using noble metal catalysts. Additionally, the AH/ATH of heteroatom-containing imines and diarylimines has posed a longstanding challenge. In this study, we have developed a general method for the ATH of heteroatom-containing imines and diarylimines, catalyzed by a chiral aminobenzimidazole manganese(I) complex, yielding the corresponding amines in up to 99% yield and 99% ee. Furthermore, the reaction proceeds smoothly on a gram scale without any loss of enantioselectivity, indicating its potential applicability in the synthesis of important pharmaceuticals. Based on deuterium labeling and control experiments, we also propose a possible mechanism for this manganese(I)-catalyzed ATH of imines with NH 3 ·BH 3 .}, archive = {J_JACS}, author = {Lixian Wang and Bingyang Wang and Jin Lin and Xiangyun Meng and Qiangsheng Sun and Wei Sun}, doi = {10.1021/jacs.5c08335}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33581--33588}, shortjournal = {J. Am. Chem. Soc.}, title = {Manganese-catalyzed asymmetric transfer hydrogenation of heteroatom-containing imines and diarylimines}, volume = {147}, year = {2025}, }
• (2025). Real-space quantitative molecular analysis at single-molecule resolution. JACS, 147(37), 33571--33580. (www)

  @article{ , abstract = {Advances in molecular analysis and characterization techniques should revolutionize the methods for scientific exploration across physics, chemistry, and biology, fundamentally overturning our understanding of interactions and processes that govern molecular behavior at the microscopic level. Currently, the absence of a molecular analysis method that can both quantify molecules and achieve single-molecule spatial resolution hinders our study of complex molecular systems in sorption and catalysis. Here, we propose a quantitative analysis strategy for small molecules confined in ZSM-5, a zeolite material extensively used in catalysis and gas separation, based on low-dose transmission electron microscopy. This approach enables the visualization of molecular structures with angstrom spatial resolution and facilitates their identification through detailed molecular imaging. By integrating experimental and simulated images with adsorption data, the quantity of small molecules within each zeolite channel is precisely calibrated, thereby advancing the study of the molecular sorption, transport, and reaction dynamics in ZSM-5 channels. The quantitative insights into these processes enhance our understanding of microscale mechanisms, elucidating the roles of host–guest interactions, molecular geometry, and external stimulus. This work expands the application of low-dose electron microscopy in molecular imaging and analysis, establishing it as a spatially resolved and quantitative tool for studying molecular behaviors in real space that is previously inaccessible.}, archive = {J_JACS}, author = {Jiale Feng and Wenbo Li and Mengmeng Ma and Jiayi Zhang and Tongyu He and Tao Cheng and Sheng Dai and Bin Song and Boyuan Shen}, doi = {10.1021/jacs.5c08253}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33571--33580}, shortjournal = {J. Am. Chem. Soc.}, title = {Real-space quantitative molecular analysis at single-molecule resolution}, volume = {147}, year = {2025}, }
• (2025). Tuning magnetism through stoichiometric potassium intercalation into VOCl. JACS, 147(37), 33559--33570. (www)

  @article{ , abstract = {Layered van der Waals (vdW) materials, characterized by their interlayer vdW gaps, offer exceptional tunability of magnetic properties via intercalation chemistry. A wide range of magnetic behaviors have been observed in nonmagnetic transition-metal dichalcogenides intercalated with magnetic atoms. Beyond the incorporation of magnetic ions, we propose the controlled alkali-ion intercalation of intrinsic vdW magnets as a strategy to probe and manipulate spin populations and exchange interactions within individual magnetic layers. Unlike conventional solid-state methods typically used for atomic intercalation, this approach depends on postsynthetic, solution-based reactions, which remain relatively underdeveloped and present unique synthetic challenges. Hence, in this work, we demonstrate precise potassium intercalation of VOCl, a layered antiferromagnet with square-like motifs, using stoichiometric organic reductants, potassium naphthalene and potassium pyrene. Our synthetic approach addresses thermodynamic and kinetic challenges via redox-matching reductants and electrolyte-assisted homogenization. Magnetic measurements reveal a continuous evolution from antiferromagnetism (x = 0) to a spin-glass state (0 < x < 1) with magnetic memory and ultimately to ferrimagnetism (x = 1) in K x VOCl (0 ≤ x ≤ 1). Ab initio calculations support the existence of a spin-glass state, stabilized by mixed valence and competing magnetic interactions. Taken all together, this work establishes a programmable intercalation methodology to access metastable phases and tailor magnetic properties, offering new insights into magnetism in layered compounds with complex spin interactions.}, archive = {J_JACS}, author = {Jiaze Xie and Brahim Marfoua and Brianna L. Hoff and Jaime M. Moya and Scott B. Lee and Mohammad Amirabbasi and Marcus Ekholm and Leslie M. Schoop}, doi = {10.1021/jacs.5c08177}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33559--33570}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning magnetism through stoichiometric potassium intercalation into VOCl}, volume = {147}, year = {2025}, }
• (2025). Modeling-making-modulating high-entropy alloy with activated water-dissociation centers for superior electrocatalysis. JACS, 147(37), 33545--33558. (www)

  @article{ , abstract = {High-entropy alloys (HEAs) have recently emerged as promising electrocatalysts for complex reactions owing to their tunable electronic structures and diverse, unique binding sites. However, their vast compositional space, in terms of both elemental variety and atomic ratios, presents a major challenge to the rational design of high-performance catalysts, as experimental efforts are often hindered by ambiguous element selection and inefficient trial-and-error methods. In this work, a bottom-up research strategy using machine learning-assisted first-principles calculations was applied to accelerate the design of quinary HEAs toward efficient multielectron transfer reactions. Here, we report the design of PtPdRhRuMo, which exhibits key physicochemical properties favoring the methanol oxidation reaction. Notably, the incorporation of Mo as the fifth element significantly activates specific binding sites on HEA surfaces, enhancing methanol adsorption and, in particular, the water dissociation ability. This facilitates hydroxyl species formation, which effectively mitigates CO intermediate adherence while promoting the complete oxidation of CH 3 OH to CO 2 via alternative reaction pathways. Guided by theoretical predictions, experimental samples with different morphologies of mesoporous PtPdRhRuMo catalyst (m-HEANP(Mo) nanoparticles and m-HEAF(Mo) thin film) were then synthesized, demonstrating superior electrocatalysis with a large current density of up to 18.20 mA cm –2 and a mass activity of 9.89 A mg Pt –1 , alongside the long-term durability for efficient methanol electrooxidation applications.}, archive = {J_JACS}, author = {Ho Ngoc Nam and Ravi Nandan and Lei Fu and Yingji Zhao and Yunqing Kang and Tetsuya Fukushima and Kazunori Sato and Yusuke Asakura and Ovidiu Cretu and Jun Kikkawa and Joel Henzie and Jonathan P. Hill and Takeshi Yanai and Quan Manh Phung and Yusuke Yamauchi}, doi = {10.1021/jacs.5c08012}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33545--33558}, shortjournal = {J. Am. Chem. Soc.}, title = {Modeling-making-modulating high-entropy alloy with activated water-dissociation centers for superior electrocatalysis}, volume = {147}, year = {2025}, }
• (2025). Ubiquitous chiral symmetry breaking of conjugated polymers via Liquid–Liquid phase separation. JACS, 147(37), 33530--33544. (www)

  @article{ , abstract = {Spontaneous chiral symmetry breaking remains a fascination in chemistry, biology, materials science, and even astronomy. Chiral symmetry breaking usually requires intrinsic molecular chirality or extrinsic chiral sources but remains rare in nonchiral systems. Here, we reveal a ubiquitous, entropy-driven chiral symmetry breaking mechanism observed in 22 out of 35 conjugated polymers in the absence of any chiral source─a phenomenon overlooked for decades. Chiral assemblies spontaneously occur through liquid–liquid phase separation (LLPS) of lyotropic mesophases from isotropic solutions upon a concentration increase. Machine learning identifies the underpinning molecular features validated by further molecular design. The universality of this phenomenon hints at a possible link between LLPS and chiral symmetry breaking in the origin of life, while paving the way for an emerging frontier of chiral electronics.}, archive = {J_JACS}, author = {Zhuang Xu and Ziming Wang and Rui Zhang and Archana Verma and Justin S. Neu and Priyotosh Bairagya and Sanghyun Jeon and Alec M. Damron and Joshua M. Rinehart and Justine S. Wagner and Sina Sabury and Xuyi Luo and Anna M. Österholm and Jianguo Mei and Jeffrey S. Moore and Wei You and John R. Reynolds and Nicholas E. Jackson and Ying Diao}, doi = {10.1021/jacs.5c07995}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33530--33544}, shortjournal = {J. Am. Chem. Soc.}, title = {Ubiquitous chiral symmetry breaking of conjugated polymers via Liquid–Liquid phase separation}, volume = {147}, year = {2025}, }
• (2025). Solid–Liquid metal single-atom clusters for ultrafast kinetics in fast-charging na-ion batteries. JACS, 147(37), 33518--33529. (www)

  @article{ , abstract = {Na + desolvation and diffusion rates are determining steps that restrict fast charging in sodium-ion batteries (SIBs). Although desolvation and diffusion rates can be improved by the optimization of the solid electrolyte interphase (SEI), no existing architecture has achieved simultaneous rapid ion transport across the bulk phase, interphase, and solvent phase while maintaining 100% initial Coulombic efficiency (ICE). Specifically, we report an atomic-level strategy derived from recyclable materials that uniformly coordinates diverse single-atom alloying reactions to enable the assembly of solid–liquid single-atom channels for rapid ion transport across multiphase systems. Single-atom channels interconnect components through intelligent self-regulation, achieving ∼100% ICE in liquid-derived SEI while minimizing the Na + desolvation and diffusion barrier. Ah-level engineering application cells show 200.62 Wh kg –1 at 5 C, as well as 92.9% capacity retention for over 500 cycles at 7 C. The cells show 8 min charging time for 100% capacity at 10 C. Solid–liquid metal single-atom clusters open the door for fast-charging SIBs at the atomic level.}, archive = {J_JACS}, author = {Xin Jin and Mengfan Pei and Runyue Mao and Chang Su and Shuo Zhuo and Naiwen Hu and Dongming Liu and Wanyuan Jiang and Borui Li and Lin Wang and Hongbo Liang and Shengming Li and Xigao Jian and Fangyuan Hu}, doi = {10.1021/jacs.5c07886}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33518--33529}, shortjournal = {J. Am. Chem. Soc.}, title = {Solid–Liquid metal single-atom clusters for ultrafast kinetics in fast-charging na-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Beyond the amyloid core: Modulation of aggregate conformational diversity by mutations in the noncore regions. JACS, 147(37), 33507--33517. (www)

  @article{ , abstract = {Emerging evidence underscores the regulatory roles of nonamyloidogenic regions in controlling the aggregation dynamics and cytotoxicity of amyloidal proteins, but the mechanism remains unclear. Herein we investigated how flanking sequences modulate the conformational heterogeneity in the p53 238–262 amyloid segment using scanning tunneling microscopy (STM). By comparing the wild-type (wt) and three pathogenic mutations (R248W, R248Q, R249S) in the noncore regions, we reveal that flanking alterations remodel β-sheet aggregates and induce conformational plasticity in β-strand ensembles through the generation of novel conformational substates and selective elimination of existing conformational substates. This conformational diversity establishes a highly heterogeneous intermolecular interaction network that connects different conformational substates. Quantitative mapping shows that flanking mutations drastically diversify the coexisting inter-β-strand interactions while altering the most abundant intermolecular interaction patterns. Our analysis reveals that flanking mutations induce a deterministic conformational remodeling process in the β-sheet aggregates, where specific intermolecular interactions counteract entropy through nonstochastic structural rearrangements. These findings contribute to the mechanistic understanding of the noncore sequence control in protein aggregation and suggest potential therapeutic targets for modulating β-sheet assembly in amyloidopathies.}, archive = {J_JACS}, author = {Mingrui Chen and Zhongyi Jian and Mingzhan Wang and Zhenlin Liu and Yanlian Yang and Chen Wang and Lanlan Yu and Wenbo Zhang and Chenxuan Wang}, doi = {10.1021/jacs.5c07880}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33507--33517}, shortjournal = {J. Am. Chem. Soc.}, title = {Beyond the amyloid core: Modulation of aggregate conformational diversity by mutations in the noncore regions}, volume = {147}, year = {2025}, }
• (2025). Ambient-pressure C–C coupling of CO2 hydrogenation by NiFe/TiO2 bimetallic catalyst. JACS, 147(37), 33495--33506. (www)

  @article{ , abstract = {Catalytic upgrading of CO 2 to value-added C 2+ products offers promising solutions to trim carbon emissions with additional economic benefits. Herein, we report a NiFe bimetallic catalyst showing efficient ambient-pressure C–C coupling performance subject to H 2 pretreatment temperature. An optimal performance was achieved after reducing NiFe/TiO 2 at 350 °C (NiFe-350/TiO 2 ), yielding 27.8% CO 2 conversion and 33.9% selectivity to C 2 –C 3 hydrocarbon (primarily ethane) at 350 °C under atmospheric pressure. Combinatorial studies employing in situ characterizations, kinetic, intermediate control experiments and first-principles calculations indicate the formation of partially oxidized Ni δ+ –O–Fe δ+ in NiFe-350/TiO 2 , the dual-site synergy of which enhances CO 2 activation and facilitates H 2 heterolytic activation into H δ− species that selectively hydrogenate *CO 2 into HCOO* and *CH 3 O intermediates, thus suppressing CO byproduct formation and resulting in effective ambient-pressure C–C coupling likely via an asymmetric *CH 2 –CH 3 coupling mechanism. In stark contrast, the fully reduced NiFe bimetallic catalyst favors a direct CO 2 dissociation pathway instead to form *CO that easily desorbs from the surface, as well as homolytic H 2 activation such that the C–C coupling process is unfavored. In brief, this work reports the ambient-pressure synthesis of C 2 –C 3 paraffins from direct CO 2 hydrogenation and provides design rationales for efficient carbon chain propagation.}, archive = {J_JACS}, author = {Mingxin Jiang and Zhi-Qiang Wang and Zhuo Li and Zhisong Liu and Yiwei Yin and Feixiang Tian and Anyu Li and Haomiao Xu and Xue-Qing Gong and Yulian He}, doi = {10.1021/jacs.5c07878}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33495--33506}, shortjournal = {J. Am. Chem. Soc.}, title = {Ambient-pressure C–C coupling of CO2 hydrogenation by NiFe/TiO2 bimetallic catalyst}, volume = {147}, year = {2025}, }
• (2025). Unveiling the origin of morphological instability in topologically complex electrocatalytic nanostructures. JACS, 147(37), 33482--33494. (www)

  @article{ , abstract = {Coarsening and degradation phenomena in metals have largely focused on thermally driven processes, such as bulk and surface diffusion. However, dramatic coarsening has been reported in high-surface-area, nanometer-sized Pt-based catalysts during potential cycling in an electrolyte at room temperature─a temperature too low for the process to be explained purely by surface mobility values measured in both vacuum and electrolytes (∼10 –22 and ∼10 –18 cm 2 /s, respectively). This morphological evolution must be due to a different mechanism for mass transport that is sensitive to electrochemical conditions (e.g., electrolyte composition, potential limits, and scan rate). However, there have been no notable studies of electrochemically induced coarsening in nanometer-sized electrocatalysts. Here, we unveil the origins of coarsening in an electrolyte through coupled in situ experiments and atomistic kinetic Monte Carlo (kMC) simulations. Our work demonstrates electrochemical coarsening is driven by two concurrent mechanisms that can be explained at the atomistic level: (i) dissolution/redeposition during the reduction of an oxidized species and (ii) rapid surface diffusion of undercoordinated atoms.}, archive = {J_JACS}, author = {Yawei Li and James L. Hart and Ramchandra Gawas and Zhiyong Xia and Pietro P. Lopes and Jieyu Zhang and Siming Li and Yucheng Wang and Mitra Taheri and Ian McCue and Joshua Snyder}, doi = {10.1021/jacs.5c07842}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33482--33494}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling the origin of morphological instability in topologically complex electrocatalytic nanostructures}, volume = {147}, year = {2025}, }
• (2025). Mixed-length multivariate covalent organic framework for combined near-infrared photodynamic therapy and drug delivery. JACS, 147(37), 33472--33481. (www)

  @article{ , abstract = {Covalent organic frameworks (COFs) have been emerging as versatile reticular materials due to their tunable structures and functionalities, enabled by precise molecular engineering at the atomic level. While the integration of multiple components into COFs has substantially expanded their structural complexity, the strategic engineering of diverse functionalities within a single framework via the random distribution of linkers with varying lengths remains largely unexplored. Here, we report a series of highly crystalline mixed-length multivariate COFs synthesized using azobenzene and bipyridine as linkers, where tuning the ratio of linkers and incorporating palladium effectively modulates the balance between near-infrared (NIR) light absorption and catalytic sites for NIR-generation of hydrogen peroxide (H 2 O 2 ). Capitalizing on the deep tissue penetration of NIR light and the generated H 2 O 2 as reactive oxygen species, as a proof of concept, the optimal mixed-length multivariate COF reduces breast cancer cell viability by almost 90% after 1 h of irradiation in a combined in vitro photodynamic therapy and drug delivery.}, archive = {J_JACS}, author = {Andrés Rodríguez-Camargo and Erdost Yildiz and Diego Juela and Felix Richard Fischer and Daniel Graf and Bibhuti Bhusan Rath and Christian Ochsenfeld and Matthias Bauer and Metin Sitti and Liang Yao and Bettina V. Lotsch}, doi = {10.1021/jacs.5c07787}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33472--33481}, shortjournal = {J. Am. Chem. Soc.}, title = {Mixed-length multivariate covalent organic framework for combined near-infrared photodynamic therapy and drug delivery}, volume = {147}, year = {2025}, }
• (2025). Epoxidation selectivity of cyclohexene catalyzed by electric field at the interface of microdroplets without catalyst. JACS, 147(37), 33460--33471. (www)

  @article{ , abstract = {The interface of aqueous microdroplets has been proven to have a large number of unique properties, which can initiate reactions that cannot occur in bulk solution. In this work, we found that cyclohexene spontaneously oxidized at the gas–liquid interface of the microdroplets under mild conditions. Notably, tetrabutylammonium bromide as an electrolyte added to the reaction system can promote the directional epoxidation of cyclohexene. The control variable experiment proved that oxygen was the main oxygen source of the epoxidation reaction, and the product of cyclohexene oxide was detected by gas chromatography–mass spectrometry and nuclear magnetic resonance hydrogen spectrum. Additionally, density functional theory calculation results show that the energy barrier of the cyclohexene oxidation reaction at the interface in the presence of an electric field is reduced by 89.37 kJ/mol. The observed 89 kJ/mol reduction in activation energy represents the maximum achievable effect under optimal field-reaction axis alignment. The possible reasons for the increase in interfacial selectivity were analyzed from the electrochemistry. So far, there are a few reports on the effect of microdroplet interface on reaction selectivity; the impact of interfacial electric field may have broader applications in the electrochemistry field.}, archive = {J_JACS}, author = {Yanan Li and Fangqin Wu and Zhongxuan Geng and Yi Wang and Jia Liu and Yi Chen and Xinyao Li and Zheng Zhou and Zhibing Zhang}, doi = {10.1021/jacs.5c07686}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33460--33471}, shortjournal = {J. Am. Chem. Soc.}, title = {Epoxidation selectivity of cyclohexene catalyzed by electric field at the interface of microdroplets without catalyst}, volume = {147}, year = {2025}, }
• (2025). Chemical bonding between helium and fluorine under pressure. JACS, 147(37), 33453--33459. (www)

  @article{ , abstract = {High-pressure phases of helium-bearing compounds have attracted much interest owing to their diverse structures and unique properties. However, the formation of helium bonds has never been achieved due to helium’s closed-shell electronic configuration and unfavorable energetics. Strikingly, by mixing inert helium with reactive fluorine at the multi-TPa regime, we report a finding of a stable He 3 F 2 compound, characterized by the presence of F-shared HeF 2 herringbone chains, from an ab initio evolutionary structure search. Electronic localization function, crystal orbital Hamilton population, electron density topological analysis, and Bader charge analysis demonstrate that helium’s typically inert 1s electrons participate in chemical bonding in He 3 F 2 , thus forming unexpected polar covalent He–F bonds within the HeF 2 chains. Furthermore, molecular orbital calculations reveal that this type of bond stems from the strong interaction between the He-1s orbital and the F-2p orbital under high pressure, challenging conventional notions of helium’s chemical inertness.}, archive = {J_JACS}, author = {Jingyu Hou and Xiaojun Wang and Qiang Zhu and Xi Shao and Shengchao Qiu and Xiao-Ji Weng and Guochun Yang and Xiao Dong and Xiang-Feng Zhou and Yongjun Tian}, doi = {10.1021/jacs.5c06707}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33453--33459}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemical bonding between helium and fluorine under pressure}, volume = {147}, year = {2025}, }
• (2025). Promotion of CO2 reactivity by organic acid on aerosol surfaces. JACS, 147(37), 33442--33452. (www)

  @article{ , abstract = {Recently, the atmospheric aerosol surface, which is reported to be quite acidic, is recognized as an important microreactive medium for atmospheric chemistry, profoundly impacting air quality and global climate. Nevertheless, the molecular-level understanding of the effect of surface-bound acids on atmospheric chemical reactions remains limited. Herein, the reactions between CO 2 and NH 3 /amines at the air–water interface with organic acids are investigated using combined molecular dynamic simulations and quantum chemical calculations. The results show that the reactions of CO 2 -NH 3 /amines predominantly occur at the interface of water droplets since CO 2 /NH 3 /amines show a surface tendency. At the surface with formic acid (HCOOH), the barrier of C–N compound formation from the CO 2 -NH 3 reaction catalyzed by HCOOH is calculated to be 6.8 kcal/mol, which can be easily overcome at ambient temperature and is significantly decreased in comparison to both gas phase and surface without organic acid. Furthermore, the HCOOH-mediated mechanism can also promote CO 2 reactions with alkylamines (methylamine (MA) and dimethylamine (DMA)), as the nucleophilicity of the N-site in these amines is significantly stronger than that in NH 3 . Overall, the results highlight the significance of organic acid on the aerosol surface in efficient capture of gaseous CO 2 and uncover the catalytic role of interfacial organic acid for assessing the potential contribution of gas-particle partitioning of pollutants to aerosol formation.}, archive = {J_JACS}, author = {Hao Li and Qi Yin and Qing Cao and Jie Zhong and Qingxin Ma and Peng Zhang and Yonghong Wang and Tianzeng Chen and Biwu Chu and Xiuhui Zhang and Joseph S. Francisco and Hong He}, doi = {10.1021/jacs.5c06583}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33442--33452}, shortjournal = {J. Am. Chem. Soc.}, title = {Promotion of CO2 reactivity by organic acid on aerosol surfaces}, volume = {147}, year = {2025}, }
• (2025). Metallicity, atomic disorder, and li-ion storage in fast-charging anodes. JACS, 147(37), 33432--33441. (www)

  @article{ , abstract = {Oxides of Nb with Wadsley-Roth shear structures comprise a family of stable, high-rate anode materials for Li-ion batteries. A particular pair of them offers the unusual opportunity to test how important metallic conduction of the starting electrode is for electrode performance. The selected pair of compounds with similar 4 × 3 Wadsley-Roth block structures are insulating Ti 2 Nb 10 O 29 and metallic Nb 12 O 29 . A combination of diffraction, electrochemistry, magnetic measurements, and entropic potential measurements is employed to establish key findings for these two anode materials. We find that starting with a metallic oxide is not especially advantageous over a comparable material that readily transitions into a metallic state upon lithiation. Second, the rate performance appears to be dictated by ion mobility, and atomic Ti/Nb disorder in Ti 2 Nb 10 O 29 contributes to improved capacity retention at high rates by suppressing Li-ion ordering. However, subtle details in the nature of redox processes make Nb 12 O 29 a slightly better electrode material for long-term cycling at slower rates.}, archive = {J_JACS}, author = {Kira E. Wyckoff and Arava Zohar and Tianyu Li and Yucheng Zhou and Linus Kautzsch and Welton Wang and Ananya Kepper and Ashlea R. Patterson and H. Cein Mandujano and Krishna Prasad Koirala and Anna Kallistova and Wenqian Xu and Jue Liu and Laurent Pilon and Anthony K. Cheetham and Ram Seshadri}, doi = {10.1021/jacs.5c06578}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33432--33441}, shortjournal = {J. Am. Chem. Soc.}, title = {Metallicity, atomic disorder, and li-ion storage in fast-charging anodes}, volume = {147}, year = {2025}, }
• (2025). Derivation of a nonstoichiometric 1/1 quasicrystal approximant from a stoichiometric 2/1 quasicrystal approximant and maximization of the magnetocaloric effect. JACS, 147(37), 33424--33431. (www)

  @article{ , abstract = {The present research introduces a novel strategy for tuning magnetic properties by overcoming the compositional limitation of stoichiometric intermetallic compounds via extension of their compositional domain into the valence electron-per-atom ( e/a ) parameter space. Focusing on approximant crystals (ACs), a “double heterovalent elemental substitution” is employed in a stoichiometric Ga–Pt–Gd 2/1 AC whereby e/a is lowered from approximately 1.98 to 1.60. Through this approach, a new family of Ga-based Tsai-type 1/1 ACs with an exceptionally wide compositional domain within e/a space is derived. Remarkably, the magnetic ground state is altered from initially spin-glass to ferromagnetic (FM) with second-order phase transition and mean-field-like critical behavior. More importantly, through this strategy, the isothermal magnetic entropy change ( ΔS M ) enhanced significantly and reached a maximum value of −8.7 J/K mol-Gd under a 5 T magnetic field change, even comparable to leading rare-earth magnetocaloric materials including RCo 2 phases. These findings demonstrate the high potential of a double heterovalent elemental substitution for tailoring magnetic properties and magnetocaloric response in stoichiometric compounds, offering a new pathway for designing high-performance magnetic refrigeration materials even beyond the quasicrystals and ACs.}, archive = {J_JACS}, author = {Farid Labib and Hiroyuki Takakura and Asuka Ishikawa and Takenori Fujii and Ryuji Tamura}, doi = {10.1021/jacs.5c05947}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33424--33431}, shortjournal = {J. Am. Chem. Soc.}, title = {Derivation of a nonstoichiometric 1/1 quasicrystal approximant from a stoichiometric 2/1 quasicrystal approximant and maximization of the magnetocaloric effect}, volume = {147}, year = {2025}, }
• (2025). Interfacial self-assembly of sugars at nanoscale membranes leads to micron-scale, spectroscopically ice-like chiral suprastructures of water. JACS, 147(37), 33413--33423. (www)

  @article{ , abstract = {Life requires chemical chiral specificity. The emergence of enantioselectivity is unknown but has been linked to diverse scenarios for the origin of life, ranging from an extraterrestrial origin to polarization-induced effects, and magnetic field-induced mineral templating. These scenarios require an originating mechanism and a subsequent enhancement step, leading to widespread chiral specificity. The common denominator in all scenarios is water, which provides an environment for the enantioselective process. Because water is a nonchiral molecule, it has not been considered as an active ingredient in either of these processes. Here, we show that water can form extended chiral ordered structures that are induced by interactions with simple chiral prebiotic molecules, such as lipids and sugars. Using a combination of molecular dynamics simulations, chiral-sensitive and interface-specific vibrational sum frequency scattering, second harmonic scattering, and atomic force microscopy, the interfacial structure of water on nanoscale lipid membranes was investigated. Out-of-plane H-bonding interactions between achiral liposomes and simple chiral cyclic sugars lead to ordered, spectroscopically ice-like, chiral water suprastructures that extend along the self-assembled lipid-sugar complex over distances >10 μm. Such highly ordered self-assemblies could potentially have provided microenvironments that enable the enhancement of chirality.}, archive = {J_JACS}, author = {Li Zhang and Jinchan Liu and Kislon Voïtchovsky and Chaudhary E. Rani and Saranya Pullanchery and Jan Dedic and Victor S. Batista and Georg E. Fantner and Sylvie Roke}, doi = {10.1021/jacs.5c05215}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33413--33423}, shortjournal = {J. Am. Chem. Soc.}, title = {Interfacial self-assembly of sugars at nanoscale membranes leads to micron-scale, spectroscopically ice-like chiral suprastructures of water}, volume = {147}, year = {2025}, }
• (2025). Rare-earth silicates as high-temperature surfactants for the controlled synthesis of ε-Fe2O3 nanoparticles. JACS, 147(37), 33403--33412. (www)

  @article{ , abstract = {The functional properties of nanocrystals can be finely tuned through controlled morphology and size. However, this can be challenging for metastable nanostructures that require harsh synthesis conditions, such as high temperatures. Here, we present a method for preparing large ε-Fe 2 O 3 nanorods that are not affected by magnetic relaxation. This study presents a novel growth mechanism in which high-aspect-ratio rods evolve from spherical ε-Fe 2 O 3 particles in a silica matrix containing Y 3+ . With the presence of Y 3+ , the glassy matrix undergoes a metastable binodal decomposition yielding the formation of nanodroplets of a Y-rich silicate of composition ∼Y 2 Si 2 O 7 . This Y silicate selectively coats the ε-Fe 2 O 3 planes perpendicular to the rod axis along the [100] direction but is not observed in the rod apexes. Structural optimizations and energy calculations of different crystal faces of ε-Fe 2 O 3 in contact with Y 2 Si 2 O 7 obtained using machine-learning force fields provide an atomistic interpretation of these observations: the affinity of Y with the oxygen atoms exposed at ε-Fe 2 O 3 surfaces explains the preferential capping of ε-Fe 2 O 3 surfaces that present a large density of oxygen atoms and its absence in surfaces such as (100), where this density is significantly lower. The presence or absence of the silicate capping layer results in different surface energies and/or mass transfer coefficients across the interface, originating two independent Ostwald ripening processes, which drive the high aspect ratio growth. By using La 3+ instead of Y 3+ , ε-Fe 2 O 3 rods with even larger aspect ratios are obtained. Notably, this synthetic approach counteracts the progressive diminution of the average nanoparticle size observed in ε-(Fe 1– x Cr x ) 2 O 3 upon Cr 3+ addition, enabling to elucidate the effect of this substitution on the intrinsic magnetic anisotropy and the anisotropy fields that determine the high-frequency ferromagnetic resonances of this phase.}, archive = {J_JACS}, author = {Naureen Khanam and Zheng Ma and Sergi Ortiz Ropero and Nico Dix and Ana Vila Costa and Judit Oró-Solé and José Luis García-Muñoz and Jordi Faraudo and Martí Gich}, doi = {10.1021/jacs.5c05058}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33403--33412}, shortjournal = {J. Am. Chem. Soc.}, title = {Rare-earth silicates as high-temperature surfactants for the controlled synthesis of ε-Fe2O3 nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Efficient hydrogen production from ethylene glycol steam reforming catalyzed by na-promoted pt/γ-Mo2N. JACS, 147(37), 33395--33402. (www)

  @article{ , abstract = {Ethylene glycol (EG) derived from biomass and plastic wastes can serve as a sustainable H 2 resource through steam reforming (HOCH 2 CH 2 OH + 2H 2 O ⇄ 5H 2 + 2CO 2 ). However, achieving high activity in H 2 production with good selectivity toward CO 2 under mild conditions poses a challenge. A thoughtful understanding of the active sites that accelerate the cleavage of the C–C bond rather than the C–O bond and the activation of the water molecule is still lacking. In this study, we developed a PtNa/γ-Mo 2 N catalyst that efficiently enables hydrogen production from ethylene glycol steam reforming (EGSR) reactions. This catalyst achieved outstanding H 2 productivity, reaching 6000 mol H2 ·mol Pt –1 ·h –1 at 250 °C under 10 bar with high CO 2 selectivity (89%) and low CO selectivity (1%) in carbon-containing products. Comprehensive characterizations revealed the crucial role of the interface between highly dispersed Pt species and Mo 2 N in activating ethylene glycol and water. Additionally, sodium (Na) was found to block acidic sites, preventing the formation of side products from C–O bond cleavage, and to modulate Pt sites, enhancing the reforming process by accelerating the water gas shift reaction.}, archive = {J_JACS}, author = {Xuan Liang and Zirui Gao and Xingjie Peng and Maolin Wang and Yao Xu and Jie Zhang and Shuheng Tian and Chengyu Li and Xuetao Qin and Rongli Mi and Zhaohua Wang and Wu Zhou and Meng Wang and Ding Ma}, doi = {10.1021/jacs.5c04401}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33395--33402}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient hydrogen production from ethylene glycol steam reforming catalyzed by na-promoted pt/γ-Mo2N}, volume = {147}, year = {2025}, }
• (2025). Photoaffinity labeling reveals a role for the unusual triply acylated phospholipid N-acylphosphatidylethanolamine in lactate homeostasis. JACS, 147(37), 33386--33394. (www)

  @article{ , abstract = {Most eukaryotic membranes comprise phospholipids bearing two hydrophobic tails, but N -acylphosphatidylethanolamine (NAPE) stands out as a long-known but poorly understood phospholipid with three hydrophobic groups. What little attention NAPE has received has been devoted to understanding its metabolic functions as a precursor to N -acylethanolamine (NAE), a bioactive lipid that acts as an endocannabinoid. Yet, levels of NAPE increase during myocardial infarction and ischemia, suggesting potential signaling roles for this lipid. Here, we exploit photoaffinity labeling (PAL) to identify NAPE-interacting proteins and elucidate signaling functions of NAPE. By positioning diazirine and alkyne groups in metabolically distinct regions of the NAPE molecule, we ensured that our PAL probe reported on interactions of NAPE and not NAE. Our studies identified several NAPE interactors, including two single-pass transmembrane proteins, CD147/Basigin and CD44, both of which serve as chaperones for monocarboxylate transporters (MCTs) from the SLC16A family that mediate lactate flux across the plasma membrane. Functional studies revealed that NAPE stimulates lactate efflux by MCTs dependent upon CD147 and CD44, establishing NAPE as a bona fide signaling lipid and pointing to potential physiological roles in metabolic and energy homeostasis that may be pathologically relevant in ischemia.}, archive = {J_JACS}, author = {Din-Chi Chiu and Yuan-Ting Cho and Hening Lin and Jeremy M. Baskin}, doi = {10.1021/jacs.5c03851}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33386--33394}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoaffinity labeling reveals a role for the unusual triply acylated phospholipid N-acylphosphatidylethanolamine in lactate homeostasis}, volume = {147}, year = {2025}, }
• (2025). “Cut-and-sew” reactions of β-lactams via C–C bond activation. JACS, 147(37), 33379--33385. (www)

  @article{ , abstract = {Transition metal-catalyzed “cut-and-sew” reactions offer an efficient approach to construct bridged and fused scaffolds; however, the substrates have been primarily restricted to cyclic ketones and activated cyclopropanes. Here we report the first cut-and-sew transformation between β-lactams and alkenes/alkynes via C–C bond activation. Diverse bridged and fused nitrogen-heterocycles are prepared using this method with good functional group tolerance. The synthetic utility is demonstrated in the unified and streamlined preparation of norbenzomorphan-containing bioactive compounds.}, archive = {J_JACS}, author = {Liyan Kan and Rui Zhang and Shou-Lin Lu and Yash Hari and Guangbin Dong}, doi = {10.1021/jacs.5c12770}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33379--33385}, shortjournal = {J. Am. Chem. Soc.}, title = {“Cut-and-sew” reactions of β-lactams via C–C bond activation}, volume = {147}, year = {2025}, }
• (2025). Water as an electron donor for cross-electrophile coupling reactions. JACS, 147(37), 33372--33378. (www)

  @article{ , abstract = {Cross-electrophile coupling (XEC) reactions are considered to be among the most fundamental construction of carbon–carbon bonds in organic chemistry. Traditionally, stoichiometric reductants, including metallic and organic reagents, are required to promote these conversions, resulting in significant waste that contributes to environmental pollution and increased disposal costs. In this study, we report a divided electrochemical synthesis-based cross-coupling platform in which H 2 O is oxidized at the anode surface to generate electrons that produce a lower oxidation state nickel catalyst on the cathode surface, enabling XEC reactions without the need for metallic or organic reagents. To demonstrate the effectiveness of this strategy, a wide array of primary and secondary bromides, as well as pharmaceutically relevant (hetero)aryl halides, were identified as viable coupling partners.}, archive = {J_JACS}, author = {Jun-Li Li and Can-Ming Zhu and Huai-Gui Li and Pan-Feng Yuan and Qing-Yuan Meng}, doi = {10.1021/jacs.5c12176}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33372--33378}, shortjournal = {J. Am. Chem. Soc.}, title = {Water as an electron donor for cross-electrophile coupling reactions}, volume = {147}, year = {2025}, }
• (2025). Direct probing the electrical double layer at Graphite/Nafion interface via depth profiling APXPS. JACS, 147(37), 33366--33371. (www)

  @article{ , abstract = {Understanding the electrical double layer (EDL) is fundamental for enhancing the efficiency, capacity, and stability of electrochemical systems. The EDL at the electrode/polyelectrolyte interface exhibits significantly different properties with a more complex structure compared to liquid electrolyte systems. Characterizing this intricate interface experimentally remains a major challenge. In this study, we directly observed the potential distribution at the electrode–polyelectrolyte interface using a delicate in situ electrochemical cell coupled with ambient pressure X-ray photoelectron spectroscopy (APXPS) at various probing depths. The electrode/polyelectrolyte (graphite/Nafion) interface was successfully constructed, and the APXPS measurements were performed under nonpolarizing conditions. The binding energy shift of the F 1s photoelectron with applied bias provided the information on potential distribution. Experimental results, simulated by the typical exponential and linear potential distribution models, indicate the formation of a 1–3 nm EDL at the electrode/polyelectrolyte interface. This work provides methodological guidance for in situ X-ray photoelectron spectroscopic studies and offers valuable fundamental data for electrochemical research.}, archive = {J_JACS}, author = {Yijing Zang and Shucheng Shi and Jian Liu and Jun Cai and Yong Han and Ning Sun and Yunhong Luo and Shandong Zhu and Bo Yang and Hui Zhang and Yimin Li and Zhi Liu}, doi = {10.1021/jacs.5c11569}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33366--33371}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct probing the electrical double layer at Graphite/Nafion interface via depth profiling APXPS}, volume = {147}, year = {2025}, }
• (2025). A persistent boron tetraradical with tetraphenylethene-linked boraphenanthrene-type units. JACS, 147(37), 33359--33365. (www)

  @article{ , abstract = {We report the first paramagnetic boron tetraradical, comprising four boraphenanthrene-type units with boryl radical centers bridged by a central tetraphenylethene (TPE) linker. With strongly π-accepting and sterically demanding cyclic(alkyl)(amino) carbene ligands ( 3 ), spin densities localize on the boron–carbene fragments (92%), consistent with a true boron-centered tetraradical. Magnetic measurements of 3 reveal minimal spin–spin coupling, consistent with four noninteracting S = 1/2 centers. In contrast, weaker π-accepting diamino N-heterocyclic carbene ligands delocalize spin density over the TPE core (88%), yielding a boron-containing hydrocarbon biradical ( 4 ). Compound 4 exhibits antiferromagnetic interactions (2 J = −118 J·mol –1 ), supporting an open-shell singlet ground state with a thermally accessible triplet excited state.}, archive = {J_JACS}, author = {Heechan Kim and Rebecca K. Walde and Peter Müller and Noah D. McMillion and Andrew Molino and David Ullery and John F. Berry and David J. D. Wilson and Robert J. Gilliard, Jr.}, doi = {10.1021/jacs.5c11428}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33359--33365}, shortjournal = {J. Am. Chem. Soc.}, title = {A persistent boron tetraradical with tetraphenylethene-linked boraphenanthrene-type units}, volume = {147}, year = {2025}, }
• (2025). Ruthenium-catalyzed intermolecular [2 + 2] cycloaddition of unactivated allenes and alkynes with unusual regioselectivity. JACS, 147(37), 33350--33358. (www)

  @article{ , abstract = {Described here is an efficient protocol for intermolecular [2 + 2] cycloaddition of unactivated and unsymmetrical allenes and alkynes with unusual regioselectivity, counterintuitively favoring the most hindered isomer. CpRu(MeCN) 3 PF 6 served as a uniquely effective catalyst, providing diverse 3-alkylidenecyclobutenes with a broad scope and good functional group compatibility. Both experiments and DFT studies provided important insights into the mechanism, particularly the unusual regioselectivity.}, archive = {J_JACS}, author = {Chaoshen Zhang and Herman H. Y. Sung and Ian D. Williams and Yun-Dong Wu and Jianwei Sun}, doi = {10.1021/jacs.5c11285}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33350--33358}, shortjournal = {J. Am. Chem. Soc.}, title = {Ruthenium-catalyzed intermolecular [2 + 2] cycloaddition of unactivated allenes and alkynes with unusual regioselectivity}, volume = {147}, year = {2025}, }
• (2025). MOFClassifier: A machine learning approach for validating computation-ready Metal–Organic frameworks. JACS, 147(37), 33343--33349. (www)

  @article{ , abstract = {The computational discovery and design of new crystalline materials, particularly metal–organic frameworks (MOFs), heavily rely on high-quality, “computation-ready” structural data. However, recent studies have revealed significant error rates within existing MOF databases, posing a critical data problem that hinders efficient high-throughput computational screening. While rule-based algorithms like MOSAEC, MOFChecker, and the Chen and Manz method (Chen–Manz) have been developed to address this, they often suffer from inherent limitations and misclassification of structures. To overcome this challenge, we developed MOFClassifier, a novel machine learning approach built upon a positive-unlabeled crystal graph convolutional neural network (PU-CGCNN) model. MOFClassifier learns intricate patterns from perfect crystal structures to predict a “crystal-likeness score” (CLscore), effectively classifying MOFs as computation-ready. Our model achieves an ROC value of 0.979 (previous best value 0.912) and, importantly, can identify subtle structural and chemical errors that are undetectable by current rule-based methods. By accurately recovering previously misclassified false-negative structures, the MOFClassifier reduces the risk of overlooking promising material candidates in large-scale computational screening campaigns. This user-friendly tool is freely available and has been integrated into the preparation workflow for the updated CoRE MOF DB 2025 v1.0, contributing to the accelerated computational discovery of MOF materials.}, archive = {J_JACS}, author = {Guobin Zhao and Pengyu Zhao and Yongchul G. Chung}, doi = {10.1021/jacs.5c10126}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33343--33349}, shortjournal = {J. Am. Chem. Soc.}, title = {MOFClassifier: A machine learning approach for validating computation-ready Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Kinetic locking of pH-sensitive complexes for mechanically responsive polymer networks. JACS, 147(37), 33337--33342. (www)

  @article{ , abstract = {Achieving sensitive and reversible responsivity over physiologically relevant pH ranges (4.5–7.5) remains of great interest for the design of next-generation autonomous drug delivery devices. Developing molecular interactions that are responsive within this pH range would enable targeted drug delivery at tumor sites or within inflamed or arthritic joints, where these changes in pH occur. Here, we demonstrate pH-responsive molecular interactions by the kinetic locking of host–guest complexes. Employing these complexes as dynamic crosslinks within polymer networks gives rise to materials with highly pH-responsive mechanical and viscoelastic properties. These systems further exhibit pH-dependent release of cargo, offering a self-responsive approach toward targeted drug delivery.}, archive = {J_JACS}, author = {Stephen J.K. O’Neill and Yuen Cheong Tse and Zehuan Huang and Xiaoyi Chen and Jade A. McCune and Oren A. Scherman}, doi = {10.1021/jacs.5c09897}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33337--33342}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetic locking of pH-sensitive complexes for mechanically responsive polymer networks}, volume = {147}, year = {2025}, }
• (2025). Electron-rich macrocycle-based Metal–Organic frameworks for efficient photocatalytic CO2 reduction. JACS, 147(37), 33330--33336. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) are distinguished by their structural diversity, tunable electronic properties, and exceptional performance in various applications. Notably, the electron-donating ability of ligands significantly enhances the ligand-to-metal charge transfer (LMCT) processes within these frameworks, thereby promoting efficient charge migration. Herein, we developed two electron-rich macrocyclic ligands derived from phenothiazine- and phenoxazine-functionalized calix[3]arenes, alongside their corresponding cobalt-coordinated MOFs. Remarkably, the MOF designated as Co-C[3]PTZ-MOF─constructed using the more electron-donating calix[3]phenothiazine ligand (C[3]PTZ-COOH)─exhibited superior photoresponse and enhanced charge-transport characteristics. This optimized material achieved an exceptional CO 2 photoreduction initial efficiency of 17,800 μmol g –1 h –1 with 81% CO selectivity. The outstanding photocatalytic performance originates from the strong electron-donating nature of the calix[3]arene-based ligands, which facilitated efficient LMCT processes. This study provides valuable insights for designing high-performance photocatalysts through rational engineering of macrocyclic ligands.}, archive = {J_JACS}, author = {Zhaohui Zhang and Qiang Xu and Weiran Li and Yunhai Zhu and Jun-Sheng Qin and Yingkui Yang and Heng Rao and Long Chen}, doi = {10.1021/jacs.5c09419}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33330--33336}, shortjournal = {J. Am. Chem. Soc.}, title = {Electron-rich macrocycle-based Metal–Organic frameworks for efficient photocatalytic CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). No microdroplets? no problem. soap films amplify the interface and produce hydrogen peroxide. JACS, 147(37), 33325--33329. (www)

  @article{ , abstract = {Recently, several groups have reported remarkable observations concerning the acceleration or promotion of nonequilibrium reactions in aqueous microdroplets. Such observations often implicate the reactivity of the microdroplet interface or the energy used for the formation (i.e., by nebulization, sonication, or electrospray) of these systems with high surface-area-to-volume ratios.. While the input of energy is important for reactions, such as hydrogen peroxide formation, the spatial distribution of that energy, particularly at interfaces, may strongly influence reaction pathways and yields. Moreover, nebulized microdroplets are inherently dynamic and are, therefore, challenging to study systematically. Thus, investigating less dynamic and energetic means of increasing SA:V ratios could provide the community with a platform to explore the intricate mechanisms at play in these systems. Here, we investigated two-dimensional soap thin films, formed by using a commercial soap bubble wand, as a low-cost, low-energy model system to enhance the SA:V ratio. In this study, we evaluate the thin film’s ability to promote hydrogen peroxide formation. We demonstrate that the formation of soap films promotes the generation of H 2 O 2 . Quantitative ultraviolet–visible spectroscopy assays show the concentration of hydrogen peroxide in a soap film on a commercial bubble wand reaches 1.67 ± 0.16 mM. We confirmed hydrogen peroxide formation by commercial test-strips and 1 H NMR. This soap film experiment arguably represents the least-energy-intensive method to enhance SA:V ratio and produce hydrogen peroxide at complex phase boundaries to-date. Our findings establish soap film reactivity as an open avenue of inquiry for phase boundary curious chemistry.}, archive = {J_JACS}, author = {Alzahraa M. Eldeeb and Andy Berbille and Jeffrey E. Dick}, doi = {10.1021/jacs.5c05887}, journal = {Journal of the American Chemical Society}, month = {9}, number = {37}, pages = {33325--33329}, shortjournal = {J. Am. Chem. Soc.}, title = {No microdroplets? no problem. soap films amplify the interface and produce hydrogen peroxide}, volume = {147}, year = {2025}, }
• (2025). Correction to “Elucidating electric field-induced rate promotion of brønsted acid-catalyzed alcohol dehydration”. JACS, 147(36), 33324. (www)

  @article{ , archive = {J_JACS}, author = {Bhavish Dinakar and Karl S. Westendorff and Juan F. Torres and Mostapha Dakhchoune and Katelyn Groenhout and Nathan Ewell and Yogesh Surendranath and Mircea Dincă and Yuriy Román-Leshkov}, doi = {10.1021/jacs.5c13083}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33324}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Elucidating electric field-induced rate promotion of brønsted acid-catalyzed alcohol dehydration”}, volume = {147}, year = {2025}, }
• (2025). Functional Al/Cd Heterometallics─From controlled Al(I) transfer to nucleophilic transfer of cadmium ions. JACS, 147(36), 33315--33323. (www)

  @article{ , abstract = {Low-valent cadmium compounds have remained largely unexplored as electron reservoirs, with no precedent for their use in reduction or bond activation chemistry. Here, we address this gap by integrating low-valent aluminum into the cadmium coordination sphere. Aluminylene insertion into Cd{N(TMS) 2 } 2 affords bi- and trimetallic cadmium aluminyls 1 and 2 , featuring covalent yet tunable Al–Cd bonding. While 1 is irreversibly formed, 2 exhibits dynamic reactivity, enabling reversible [AlCp*] 0 transfer─a rare and previously undocumented feature in heterobimetallic aluminum chemistry. Acting as a thermodynamically stable yet chemically reactive surrogate for free Al(I), 2 enables selective Al(I) shuttling to B, Cd, Zn, and Ag substrates (compounds 1 Zn , 3 – 5 ). The cooperative Al–Cd framework in 1 and 2 further promotes bond activation of heterocumulenes such as carbodiimides and CO 2 , with 1 serving as a source of nucleophilic cadmium─an unprecedented reactivity mode for this element (compounds 6 – 8 ). Detailed quantum chemical calculations elucidate the electronic structures of 1 and 2 as well as the mechanism for both Al(I) transfer and heterocumulene insertion. These findings establish a platform for bimetallic cooperativity in small-molecule activation and lay the groundwork for Al(I)-based multimetallic systems relevant to future catalysis and main group/transition-metal synergy.}, archive = {J_JACS}, author = {Dominic Herle and Sara Sommer and Fabian Dankert}, doi = {10.1021/jacs.5c12746}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33315--33323}, shortjournal = {J. Am. Chem. Soc.}, title = {Functional Al/Cd Heterometallics─From controlled Al(I) transfer to nucleophilic transfer of cadmium ions}, volume = {147}, year = {2025}, }
• (2025). Multiple template site nitrogen atom deletions from rotaxanes, catenanes, and a molecular knot. JACS, 147(36), 33304--33314. (www)

  @article{ , abstract = {We report the deletion of nitrogen atoms from multiple template sites in rotaxanes, catenanes, and a molecular knot. Nitrogen extrusion from secondary amines in the backbone of the interlocked structures is achieved using O -diphenylphosphinylhydroxylamine (DPPH), forming carbon–carbon bonds while largely maintaining the integrity of the original mechanical bonding. We find that DPPH gives improved yields (up to 51%) for nitrogen atom deletions from template sites in rotaxanes compared to an anomeric amide nitrogen-deletion reagent and overcomes a major substrate limitation in that, using DPPH, only one of the substituents of the secondary amine in the rotaxane axle needs to be radical-stabilizing. Multiple template site nitrogen atom deletions were accomplished from a range of mechanically interlocked architectures, despite the potential for dethreading, unlinking, and/or strand uncrossing during each successive deletion event. Highlights include the deletion of two template sites from a doubly threaded [3]rotaxane (37% yield) and [3]catenane (45%), quadruple N -deletion of amines from both rings of a [2]catenane (33%), and six N -deletions from the six amine groups in a molecular trefoil knot (7%). The combination of skeletal editing with template synthesis provides a general strategy for synthesis that significantly increases the structural diversity of interlocked molecules that are potentially accessible.}, archive = {J_JACS}, author = {Daniel P. Couto and Qi Lin and Jessica B. M. Whittingham and Daniel J. Tetlow and Jiankang Zhong and Prodip Howlader and David A. Leigh}, doi = {10.1021/jacs.5c12617}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33304--33314}, shortjournal = {J. Am. Chem. Soc.}, title = {Multiple template site nitrogen atom deletions from rotaxanes, catenanes, and a molecular knot}, volume = {147}, year = {2025}, }
• (2025). Cu/Ru relay catalysis enables functionalization of allenic alcohols with stereodivergence and skeleton diversity. JACS, 147(36), 33288--33303. (www)

  @article{ , abstract = {The stereodivergent synthesis of structurally complex molecules bearing multiple stereochemical elements represents a pivotal challenge in modern synthetic chemistry, particularly for bioactive compounds, where stereochemical nuances dictate pharmacological profiles. While stereodivergent dual catalysis has advanced full access to stereoisomers with stereogenic centers, the integration of stereodefined alkenes into chiral molecules with both stereochemical and skeletal diversification remains elusive. In this study, we report stereo- and skeleton-divergent access to chiral fluorinated N -heterocycles with comprehensive stereocontrol of [( R , R ), ( S , S ), ( S , R ), ( R , S )] and [( Z , R ), ( Z , S ), ( E , R ), ( E , S )] enabled by a bimetallic Cu/Ru relay catalytic system, featuring redox-neutral efficiency and atom/step economy. The success is achieved through orthogonally merging an asymmetric borrowing-hydrogen reaction with the asymmetric Michael addition between allenic alcohols and α-fluoro azaaryl acetamides/acetates by simply tuning the chiral ligands in the copper and ruthenium catalysts associated with temporal and basicity regulation. Control experiments and kinetic studies provide insights into the underlying mechanisms, revealing that the kinetic resolution of racemic allenic alcohol is involved in this relay-catalyzed cascade dehydrogenation/Michael addition/hydrogenation sequence and Michael addition is the rate-limiting step.}, archive = {J_JACS}, author = {Kui Tian and Xiu-Qin Dong and Chun-Jiang Wang}, doi = {10.1021/jacs.5c12469}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33288--33303}, shortjournal = {J. Am. Chem. Soc.}, title = {Cu/Ru relay catalysis enables functionalization of allenic alcohols with stereodivergence and skeleton diversity}, volume = {147}, year = {2025}, }
• (2025). Adjusting the criteria for hydrogen evolution by single-atom catalysts. JACS, 147(36), 33281--33287. (www)

  @article{ , abstract = {Downsizing noble metal catalysts is essential for improving atomic efficiency in sustainable energy applications. Typically, strategies focus on anchoring atomically scaled catalysts onto heteroatom-rich substrates, but these interactions can unintentionally alter the electronic structure of the catalyst, complicating the hydrogen evolution reaction (HER) mechanism. This study focuses on elucidating the interfacial mechanism of HER using structurally well-defined platinum single-atom (Pt SA) electrocatalysts. Unlike chemically reduced SAs, electrochemically deposited Pt SA catalysts do not rely on strong support interactions. As a result, these isolated Pt atoms can potentially achieve the theoretical maximum hydrogen production efficiency. This work introduces electrocatalysts composed solely of true SA sites, clarifying previous ambiguities surrounding the concept of SA electrocatalysis.}, archive = {J_JACS}, author = {Mansu Kim and Sohui Kim and Xijun Wang and Randall Q. Snurr and Joseph T. Hupp and Dongmok Whang}, doi = {10.1021/jacs.5c12309}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33281--33287}, shortjournal = {J. Am. Chem. Soc.}, title = {Adjusting the criteria for hydrogen evolution by single-atom catalysts}, volume = {147}, year = {2025}, }
• (2025). Dehydration of Oxide:Water interfaces by brines quantified with nonlinear spectroscopy. JACS, 147(36), 33273--33280. (www)

  @article{ , abstract = {Counting the number density of ions and water molecules at aqueous:solid interfaces remains a fundamental challenge, especially under conditions of high ionic strength. Here, we employ an all-optical noncontact approach based on phase- and amplitude-resolved second harmonic generation spectroscopy to estimate the cation and anion coverages and the number density of net-aligned water molecules at fused silica surfaces in contact with aqueous solutions held at pH 5.8 and a wide range of ionic strengths of NaCl, NaClO 4 , Na 2 SO 4 , and Na 2 HPO 4 up to 8 M. At 8 M ionic strength of NaClO 4 , the data are consistent with an interface that is comprised of half of a monolayer of ions (θ Na + + θ ClO 4 - ≈ 5 × 10 14 cm 2 ) and half of a monolayer of water molecules (θ H 2 O ≈ 4 × 10 14 cm –2 ), the latter having flipped their dipolar orientation from “protons to the surface” to “oxygens to the surface”. The interfacial water:total ion ratio is close to ten times smaller than in the bulk solution at these high ionic strengths. The Helmholtz free energy associated with water disordering increases abruptly from near 0 kJ mol –1 below 2 M ionic strength to 10 kJ mol –1 at 8 M ionic strength, indicating perhaps a Kirkwood-like transition from a hydrated to a dehydrated interface.}, archive = {J_JACS}, author = {Nicole M. Gonzalez and Amani O. Alghamdi and Franz M. Geiger}, doi = {10.1021/jacs.5c11999}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33273--33280}, shortjournal = {J. Am. Chem. Soc.}, title = {Dehydration of Oxide:Water interfaces by brines quantified with nonlinear spectroscopy}, volume = {147}, year = {2025}, }
• (2025). On-demand ammonia capture and separation with open aluminophosphate frameworks. JACS, 147(36), 33264--33272. (www)

  @article{ , abstract = {The development of adsorbents for ammonia capture and separation is a challenging task, with significant industrial relevance. We report herein, for the first time, open aluminophosphate frameworks for on-demand ammonia adsorption. Under ambient conditions, the AlPO-18 molecular sieve exhibits exceptional dynamic ammonia uptake of 3.36 mmol/g at an extremely low ammonia concentration of 200 ppm, showing great potential as a disposable adsorbent for trace ammonia capture. AlPO-11 molecular sieve manifests a desirable ammonia dynamic uptake of 5.73 mmol/g at high ammonia concentration of 50,000 ppm, with excellent recyclability upon regeneration under mild conditions. Aspen simulations demonstrate the advantage of the adsorptive separation process employing AlPO-11 adsorbent for ammonia recovery, with huge energy savings of 51% in comparison with the compression-based process currently employed in the ammonia synthesis industry. The underlying mechanism of ammonia adsorption and the nature of ammonia binding in aluminophosphate frameworks are fully elucidated by employing a combination of X-ray photoelectron spectroscopy, in situ Fourier transform infrared spectroscopy, quasi in situ magic angle spinning nuclear magnetic resonance, and density functional theory calculations. The coordination of ammonia on the framework aluminum sites in aluminophosphates is clearly disclosed. The development of low-cost and commercially available aluminophosphate molecular sieves may unlock their potential for on-demand ammonia capture and separation in various scenarios.}, archive = {J_JACS}, author = {Bin Yue and Jian Wang and Qiang Bian and Bin Qin and Shanshan Liu and Yuchao Chai and Guangjun Wu and Landong Li}, doi = {10.1021/jacs.5c11955}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33264--33272}, shortjournal = {J. Am. Chem. Soc.}, title = {On-demand ammonia capture and separation with open aluminophosphate frameworks}, volume = {147}, year = {2025}, }
• (2025). Carbonyl–Olefin/Alkyne metathesis reactions catalyzed by bifunctional H-USY zeolites. JACS, 147(36), 33256--33263. (www)

  @article{ , abstract = {Metal-, organo-, and proton-catalyzed carbonyl–olefin/alkyne metathesis reactions have gained relevance in organic synthesis during the past decade, but their potential implementation in high-volume processes (i.e., in flow) is severely hampered by the lack of a general, robust, easily separable, and nontoxic solid catalyst. Both Brønsted and Lewis acid sites inside molecular-sized soluble cages seem to be involved during the catalytic process in solution; thus, a similar bifunctional acid solid catalyst, in a confined space, could play the desired catalytic role. We show here that commercially available, ultrastabilized aluminosilicate acid faujasites (H-USY zeolites), containing Brønsted and Lewis acid sites in microporous channels and cavities, catalyze a variety of intra- and intermolecular metathesis reactions between aldehydes/ketones and alkenes/alkynes, with diverse structural patterns, in reasonable yields and under mild reaction conditions. The zeolite can be easily recovered after the reaction in batch and reused or implemented in in-flow processes for continuous synthesis of the metathesis products. These results open the way to designing carbonyl–olefin/alkyne metathesis reactions with simple solid catalysts.}, archive = {J_JACS}, author = {Paloma Mingueza-Verdejo and David Velázquez-Ojeda and Cristina Bilanin and Francisco Garnes-Portolés and Silvia Rodríguez-Nuévalos and Raúl Pérez-Ruiz and Judit Oliver-Meseguer and Antonio Leyva-Pérez}, doi = {10.1021/jacs.5c11880}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33256--33263}, shortjournal = {J. Am. Chem. Soc.}, title = {Carbonyl–Olefin/Alkyne metathesis reactions catalyzed by bifunctional H-USY zeolites}, volume = {147}, year = {2025}, }
• (2025). Role of human mitochondrial ketosynthase in long-chain fatty acid biosynthesis. JACS, 147(36), 33248--33255. (www)

  @article{ , abstract = {Although ketosynthases in bacterial type II fatty acid biosynthesis have been extensively studied, the human mitochondrial ketosynthase, OXSM, remains incompletely characterized. Contrary to the assumption that the role of mitochondrial fatty acid biosynthesis is limited to the production of the lipoic acid precursor octanoate, recent studies suggest an ability to produce longer chain fatty acids. Here, we employ covalent, dual site-selective cross-linkers to trap the interactions between OXSM and its mitochondrial acyl carrier protein partner, mACP. Two high-resolution crystal structures that capture OXSM bound to mACP provide molecular details of the conformational changes that guide the chain elongation process. We identify key protein • protein and protein • substrate interactions that regulate the transacylation and condensation steps associated with this process. We also observe a conserved gating mechanism previously identified in bacterial type II ketosynthases. Complemented by site-directed mutagenesis and activity analyses, these findings provide detailed insight into the selectivity of the OXSM substrate. This study explores how the OXSM can elongate fatty acids larger than eight carbons, mirroring that of its bacterial type II progenitor.}, archive = {J_JACS}, author = {Yixing Suo and Ziran Jiang and Graham W. Heberlig and Elsabella Y. Wang and Banumathi Sankaran and James J. La Clair and Michael D. Burkart}, doi = {10.1021/jacs.5c10318}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33248--33255}, shortjournal = {J. Am. Chem. Soc.}, title = {Role of human mitochondrial ketosynthase in long-chain fatty acid biosynthesis}, volume = {147}, year = {2025}, }
• (2025). Interfacial curvature, not simply size, controls spontaneous hydrogen peroxide formation in water microdroplets. JACS, 147(36), 33240--33247. (www)

  @article{ , abstract = {Micron-sized water droplets promote redox reactions that are absent in bulk water, yet the kinetics of these interfacial processes remain poorly understood. Here we use real-time fluorescence imaging to monitor spontaneous hydrogen peroxide (H 2 O 2 ) generation in individual microdroplets. Both the apparent production rate and equilibrium concentration of H 2 O 2 increase with decreasing droplet size, even after normalizing for surface area, revealing an intrinsic curvature-dependent enhancement. This effect arises from the geometry-driven amplification of interfacial electric fields, and this enhancement of electric field strength accelerates redox processes. Modulating interfacial electrostatics further alters reactivity: organic surfactants suppress H 2 O 2 formation to varying degrees, whereas simple salts like NaCl and KCl have minimal impact, even at relatively high concentrations. These results highlight curvature and interfacial charge as key determinants of microdroplet reactivity, governed by mesoscale electrostatic fields that drive chemical transformations at and near the surface of the microdroplet.}, archive = {J_JACS}, author = {Kyoungmun Lee and Masoud A. Mehrgardi and Richard N. Zare}, doi = {10.1021/jacs.5c11575}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33240--33247}, shortjournal = {J. Am. Chem. Soc.}, title = {Interfacial curvature, not simply size, controls spontaneous hydrogen peroxide formation in water microdroplets}, volume = {147}, year = {2025}, }
• (2025). Empowering reactivity predictions through noise-based data augmentation. JACS, 147(36), 33232--33239. (www)

  @article{ , abstract = {Data scarcity is a key obstacle in the pursuit to capitalize on the predictive powers of the A.I. in problems related to bond-making and -breaking at the molecular level. While the generation of artificial data from real data points (known as “data augmentation”) is a widely pursued strategy employed in, for example, image or speech recognition or health data evaluations, among others, to artificially expand existing data sets, it is currently unknown whether this strategy is applicable to reactivity problems at the molecular level, where predictive models are exquisitely sensitive to steric, electronic, and structural nuances. Here, we systematically evaluated the power of data augmentation for a diverse set of reactivity questions ranging from the prediction of activation barriers to stereoselectivities of catalytic transformations. We demonstrate that introducing Gaussian noise to existing data points, which is completed in under a second for a full data set, can dramatically enhance the predictive performance. It can enable model training in low-data regimes where otherwise no meaningful model could be built and achieves accuracy comparable to models built on full data sets, while needing only a fraction of the data. The approach substantially lowers the number of necessary experiments (by 20–50%), conserving time, energy, and resources, while advancing the integration of machine learning in molecular reactivity challenges.}, archive = {J_JACS}, author = {Julian A. Hueffel and Quentin P. Bindschaedler and Francesco Sala and Franziska Schoenebeck}, doi = {10.1021/jacs.5c11632}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33232--33239}, shortjournal = {J. Am. Chem. Soc.}, title = {Empowering reactivity predictions through noise-based data augmentation}, volume = {147}, year = {2025}, }
• (2025). Dimension-tunable supramolecular organic frameworks with chiral pore channels for selective guest encapsulation and enhanced circularly polarized luminescence. JACS, 147(36), 33223--33231. (www)

  @article{ , abstract = {Here, we report a dimension-tunable supramolecular organic framework (SOF) with chiral pore channels, which shows selective guest encapsulation and enhanced circularly polarized luminescence (CPL). SOFs from a chiral para-substituted bis-naphthalene bis-urea (PNU) are fabricated by both vapor diffusion crystallization and an antisolvent self-assembly approach, leading to the formation of one-dimensional (1D) micrometer-sized single crystal and two-dimensional (2D) plate-like and three-dimensional (3D) octahedral self-assembled microstructures, respectively. The similar permanent porosity of these dimension-tunable chiral SOFs is collectively proved by N 2 adsorption–desorption experiments, single-crystal structure, high-resolution transmission electron microscopy (HR-TEM), and density functional theory (DFT) calculations. By soaking octahedral SOFs in aqueous dye solutions, the chiral porous channels effectively absorb size-matched guest dyes and impart their chirality, leading to enhanced CPL with a dissymmetry factor of 1.6 × 10 –2 . This work provides insights for the efficient synthesis of chiral SOFs with pore channels from a single component, which also deepens our understanding of size-selective adsorption and chirality transfer in confined space, as well as the enhancement of circularly polarized luminescence.}, archive = {J_JACS}, author = {Tiejun Li and Dian Niu and Jingdan Zhang and Guanghui Ouyang and Minghua Liu}, doi = {10.1021/jacs.5c11407}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33223--33231}, shortjournal = {J. Am. Chem. Soc.}, title = {Dimension-tunable supramolecular organic frameworks with chiral pore channels for selective guest encapsulation and enhanced circularly polarized luminescence}, volume = {147}, year = {2025}, }
• (2025). Chemically boosting intercalation voltage and cycling stability of layered Na–Fe–Mn–O cathode for na-ion batteries through Li/Cu cosubstitution. JACS, 147(36), 33209--33222. (www)

  @article{ , abstract = {Iron–manganese-based layered Na-ion cathodes are appealing for building low-cost Na-ion batteries. However, their practical realization is hindered by the lower intercalation voltage (<3 V Na + /Na 0 ) and limited cycle life. To tackle these issues, we utilize Li/Cu-cosubstitution into the O3–Na 0.80 (Fe 0.50 Mn 0.50 )O 2 cathode to tune the ionocovalency of Fe/Mn–O bonds, which in turn can modulate the electrochemical properties. With the cosubstitution, the intercalation voltage of Na 0.80 (Li 0.10 Cu 0.10 Fe 0.30 Mn 0.50 )O 2 is raised to >3.2 V, thanks to the introduction of Cu 3+ /Cu 2+ redox and enhanced Fe–O bond ionicity. Na 0.80 (Li 0.10 Cu 0.10 Fe 0.30 Mn 0.50 )O 2 displays extraordinary cycling stability (98 and 60% at 1C after 500 cycles in the window of 4.0–2.0 and 4.0–1.5 V, respectively) compared to the unsubstituted cathode (58 and 24% at 1C after 500 cycles in the window of 4.0–2.0 and 4.0–1.5 V, respectively). The enhanced stability is attributed to the retention of the O3-type structure and suppressed Jahn–Teller MnO 6 distortion during deep sodiation, as revealed by X-ray diffraction and X-ray absorption spectroscopy measurements and DFT calculations. This study highlights the importance of chemical substitution strategies in the development of advanced layered oxide cathodes with higher energy densities and cycling stabilities.}, archive = {J_JACS}, author = {Arindam Ghosh and Rashmi Hegde and Mayank Sharma and Keshav Kumar and Elisa Grépin and Swapan K. Pati and Premkumar Senguttuvan}, doi = {10.1021/jacs.5c11283}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33209--33222}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemically boosting intercalation voltage and cycling stability of layered Na–Fe–Mn–O cathode for na-ion batteries through Li/Cu cosubstitution}, volume = {147}, year = {2025}, }
• (2025). To substitute rather than intercalate: Chimie douce approach to induce ferromagnetism in metastable Pt0.8M0.2Se2 (M = cr, co, ni). JACS, 147(36), 33193--33208. (www)

  @article{ , abstract = {Two-dimensional (2D) magnetic materials with exotic magnetic properties have garnered significant interest due to their potential applications in spintronics and data storage technologies. However, the limited availability of intrinsic 2D magnetic materials has driven efforts to induce and manipulate magnetism in otherwise nonmagnetic 2D systems through approaches such as chemical intercalation, defect engineering, and substitutional doping. Herein, we present a facile, chimie douce method for incorporating 3 d transition metals (Cr, Co, and Ni) into the nonmagnetic PtSe 2 sublattice. This synthetic approach enables control over layer thickness of Pt 1– x M x Se 2 ( M = Cr, Co, Ni) nanosheets by varying the M identity and annealing conditions. Comprehensive scattering and spectroscopic characterizations confirm the successful and homogeneous substitution of M atoms at the Pt site, rather than intercalation, and reveal a strong correlation between nanosheet thickness and the identity of the substituting metal. High-temperature annealing of the nanosheets promotes an irreversible transformation toward the bulk phase, allowing for detailed characterization of structural and magnetic properties. A case study of Pt 0.8 Cr 0.2 Se 2 reveals that nanosheet thickness plays a critical role in modulating local magnetic interactions. While Cr atoms in the as-synthesized few-layers-thick nanosheets exhibit predominantly short-range antiferromagnetic interactions, the emergence of short-range ferromagnetic exchange is revealed in the bulk material. Detailed ac susceptibility and remanent magnetization measurements further demonstrate that bulk Pt 0.8 Cr 0.2 Se 2 adopts a frustrated magnetic ground state with clear signatures of ferromagnetic cluster-glass behavior. The systematic investigation presented herein establishes a clear and robust protocol for the synthesis and in-depth characterization of 2D transition-metal-substituted PtSe 2 materials with varying layer thickness and paves a path toward their realization in spintronic and magnetic device applications.}, archive = {J_JACS}, author = {Yao Abusa and Gayatri Viswanathan and John Obeng and Jemima Opare-Addo and Emma Ross and Richeal Oppong and Iyanu Ojo and Ajay Kumar and Emily Smith and Joel Rosenthal and Yaroslav Mudryk and Oleg I. Lebedev and Kirill Kovnir}, doi = {10.1021/jacs.5c11147}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33193--33208}, shortjournal = {J. Am. Chem. Soc.}, title = {To substitute rather than intercalate: Chimie douce approach to induce ferromagnetism in metastable Pt0.8M0.2Se2 (M = cr, co, ni)}, volume = {147}, year = {2025}, }
• (2025). Semi-targeted nuclear magnetic resonance metabolomics via parahydrogen-induced hyperpolarization for enhanced sensitivity to metabolic composition. JACS, 147(36), 33185--33192. (www)

  @article{ , abstract = {Non-hydrogenative para-hydrogen-induced polarization (nhPHIP) has proven a powerful tool for the enhanced NMR detection of several classes of metabolites in complex mixtures. Particularly, compounds carrying an α-amino acid motif have been previously detected and quantified in biological samples and natural extracts at submicromolar concentrations using 2D nhPHIP NMR spectroscopy. This technique is here applied for the first time in a semi-targeted metabolomics NMR study on urine from patients suffering from Pyridoxine-Dependent Epilepsy (PDE), currently diagnosed by the presence of dilute unique biomarkers. The signal enhancement, combined with the resolving power of 2D nhPHIP, results in a superior sensitivity to the metabolic composition compared to conventional 1 H NMR, demonstrating its potential in NMR-based metabolomics.}, archive = {J_JACS}, author = {Thom B. Posthumus and Udo F. H. Engelke and Ruud L. E. G. Aspers and Jona Merx and Thomas J. Boltje and Jonathan Martens and Ron A. Wevers and Martin C. Feiters and Floris P. J. T. Rutjes and Marco Tessari}, doi = {10.1021/jacs.5c11226}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33185--33192}, shortjournal = {J. Am. Chem. Soc.}, title = {Semi-targeted nuclear magnetic resonance metabolomics via parahydrogen-induced hyperpolarization for enhanced sensitivity to metabolic composition}, volume = {147}, year = {2025}, }
• (2025). Synthesis of highly substituted alkenes from terminal alkynes. JACS, 147(36), 33177--33184. (www)

  @article{ , abstract = {Alkenes make up an important class of compounds prevalent in biologically active molecules and synthetic intermediates. Their significance has driven the development of robust synthetic methods that allow the efficient and selective production of mono- and disubstituted alkenes. However, the selective synthesis of more highly substituted alkenes from readily accessible starting materials remains a significant synthetic challenge. Here, we present a novel approach for synthesizing tri- and tetrasubstituted alkenes through the catalytic coupling of terminal alkynes with alkylboranes and organohalides. The unique reaction mechanism ties the relative positioning of substituents in the alkene products to specific coupling partners that deliver them, enabling the efficient and precise generation of multiple isomers of tri- and tetrasubstituted alkenes from readily available precursors. We also demonstrate the coupling of alkylboranes with terminal alkynes in the presence of a proton source, which unexpectedly provides complementary stereoselectivity in the synthesis of trisubstituted alkenes to further broaden access to various isomers of highly substituted alkenes.}, archive = {J_JACS}, author = {Bradley W. Gardner and Crystal P. Chung and Michael R. Pu and Gojko Lalic}, doi = {10.1021/jacs.5c11173}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33177--33184}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of highly substituted alkenes from terminal alkynes}, volume = {147}, year = {2025}, }
• (2025). Cyclization decoded: Engineering amylomaltase for efficient α-glucan transformations. JACS, 147(36), 33162--33176. (www)

  @article{ , abstract = {α-Glucan, broadly distributed in nature or produced artificially by biotransformation, is fundamental to life. Amylomaltases (AMs) can modulate the biochemical properties of α-glucan through a distinctive cyclization feature to form α-1,4-glucoside-linked large-ring polysaccharides (cycloamyloses; CAs), endowing α-glucan with significant health benefits and medical value. While the industrial application of CAs continues to progress, the mechanistic intricacies of the cyclization process─and its nuanced interplay with hydrolysis─remain only partially understood. Here, we harness large-scale computations in synergy with biochemical experiments to unravel, at atomic resolution, the full covalent and noncovalent catalytic mechanism of AMs, revealing that cyclization (12.8 kcal/mol) outcompetes hydrolysis (17.5 kcal/mol) as the dominant pathway. Furthermore, we identify that postglycosylation noncovalent polysaccharide chain transfer emerges as the decisive factor in cyclization, particularly for AM–degree of polymerization (DP) greater than 30 substrate complexes, where this noncovalent step (≥13.6 kcal/mol) dictates the rate of CA production. 57 variants with enhanced activity (up to a 2.3-fold increase) were engineered in our biochemical experiments by strategically modulating the chain transfer step. Enzyme kinetics results suggest that the improvement in enzyme performance largely stems from the decrease in enzyme–substrate affinity along the substrate transfer pathway. Additionally, through mass spectrometry, CAs with DP ranging from 22 to 61 were detected, confirming our theoretical results. We also quantify the kinetic competitive balance between cyclization and hydrolysis, providing clear engineering blueprints for the AM family. This work delivers a systematic, molecular-level understanding of CA biosynthesis from an industrial-performance perspective, paving the way for next-generation CA innovations.}, archive = {J_JACS}, author = {Han Liu and Tianwen Shang and Scott Mazurkewich and Zhidan Zhang and Junpeng Hu and Tao Cai and Xuegang Luo and Dongyuan Zhang and Leli Wang and Yulong Yin and Yuanxia Sun and Johan Larsbrink and Christophe Chipot and Zhiyou Zong}, doi = {10.1021/jacs.5c11260}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33162--33176}, shortjournal = {J. Am. Chem. Soc.}, title = {Cyclization decoded: Engineering amylomaltase for efficient α-glucan transformations}, volume = {147}, year = {2025}, }
• (2025). Near-infrared photoenzymatic catalysis at ppb levels enables ultrahigh-molecular-weight polymers. JACS, 147(36), 33153--33161. (www)

  @article{ , abstract = {In principle, photocontrolled radical polymerization via near-infrared (NIR) irradiation offers spatiotemporal precision, deep tissue penetration, and biocompatibility. However, its utility is hindered by low efficiency and restricted access to high-molecular-weight polymers. To address these challenges, we report a new supramolecular NIR photoenzyme (SNIRPE) system comprising glucose oxidase (GOx) and tetrasulfonated zinc phthalocyanine (ZnPcS 4 – ) that combines enzymatic deoxygenation with photoredox catalysis. SNIRPE involves a spatially confined cascade mechanism: GOx-generated H 2 O 2 is photodecomposed in situ by ZnPcS 4 – under NIR irradiation to produce hydroxyl radicals (•OH). This enables oxygen-tolerant, high-throughput, reversible addition–fragmentation chain transfer (RAFT) polymerization across microliter-to-100 mL volumes, achieving ultrahigh molecular weights (UHMWs, M n > 1000 kg mol –1 , Đ < 1.20) with ultralow catalyst loadings (50 ppb ZnPcS 4 – , which is 3–4 orders of magnitude lower than conventional NIR photoredox systems). Scalability is demonstrated through 100 mL batch synthesis, while polymerization through porcine tissue underscores its biomedical utility. By combining enzymatic efficiency with photoredox versatility, longstanding problems in NIR-driven polymer synthesis have been eliminated.}, archive = {J_JACS}, author = {Ruoyu Li and Shudi Zhang and Xiuhui Tang and Greg G. Qiao and Steven P. Armes and Zesheng An}, doi = {10.1021/jacs.5c11130}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33153--33161}, shortjournal = {J. Am. Chem. Soc.}, title = {Near-infrared photoenzymatic catalysis at ppb levels enables ultrahigh-molecular-weight polymers}, volume = {147}, year = {2025}, }
• (2025). Divergent total syntheses of elisapterane and relevant diterpenoids assisted by in silico structure reassignment. JACS, 147(36), 33136--33152. (www)

  @article{ , abstract = {Herein, we describe our synthetic endeavors toward elisapterane and relevant diterpenoids through a bioinspired divergent strategy based on an unprecedented late-stage D-ring formation logic. The key tricyclic intermediate bearing a norneoelisabane skeleton could be efficiently prepared via an ODI-(5 + 2) cycloaddition/1,2-acyl migration cascade and a SmI 2 -mediated pinacol coupling/Grob fragmentation/deoxygenation orchestration. The synthesis of the misassigned structure of elisapterosin F led us to revisit the structure elucidation of these natural products. Application of NMR calculation-based in silico structure reassignment disclosed several unheeded structural mutations for elisapterane diterpenoids and accurately revised the structures of elisapterosins A, D, and F. With a computation-rerouted synthetic blueprint, we eventually accomplished collective total syntheses of elisapterosins A–F, alongside biogenetically related aberrarone, elisabanolide, and 3- epi -elisabanolide. By integrating our inference aided by computational tools with validation through total synthesis, this work exemplifies a modern case of total synthesis detective stories, demonstrating the power of computer-assisted structure elucidation (CASE) and the risks of analogical approaches for the structure assignment of natural products.}, archive = {J_JACS}, author = {Chun-Hui Liu and Han Gong and Yidian Sheng and Wentao Wang and Qidong Xia and Hanfeng Ding}, doi = {10.1021/jacs.5c11010}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33136--33152}, shortjournal = {J. Am. Chem. Soc.}, title = {Divergent total syntheses of elisapterane and relevant diterpenoids assisted by in silico structure reassignment}, volume = {147}, year = {2025}, }
• (2025). Late-stage serine modification enables noncanonical peptide synthesis. JACS, 147(36), 33127--33135. (www)

  @article{ , abstract = {Noncanonical amino acids play a critical role in enhancing drug efficacy, specificity, pharmacokinetics, and other key therapeutic properties. However, their incorporation into peptides or small molecules often presents significant synthetic challenges. Late-stage modification of natural residues, after the primary structural framework of a molecule is established, offers an efficient strategy for generating analogue libraries. Serine, one of the most abundant natural amino acids, remains underutilized due to the incompatibility of existing deoxygenative methods with complex peptides. Currently, no method is available for the late-stage modification of serine residues in peptides through carbon–carbon bond formation. Here, we address this gap by developing a site-selective, late-stage deoxygenative functionalization of serine residues. Inspired by automated DNA synthesis, we employ a phosphoramidite reagent in combination with a photocatalytic system to achieve efficient serine deoxygenative activation and radical addition to diverse acceptors, enabling the transformation of serine into various noncanonical residues such as homoglutamine, homoglutamic acid, 5-hydroxynorvaline, phosphonates, and alanine-3- d 1 . The method proved compatible with complex peptides such as enkephalin, bradykinin, and α-MSH both on solid support and in solution. The broad substrate scope, operational robustness, and high chemoselectivity of this approach position it as a versatile platform for peptide diversification and the advancement of medicinal chemistry.}, archive = {J_JACS}, author = {Zhenyan Guo and Tianning Diao}, doi = {10.1021/jacs.5c11065}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33127--33135}, shortjournal = {J. Am. Chem. Soc.}, title = {Late-stage serine modification enables noncanonical peptide synthesis}, volume = {147}, year = {2025}, }
• (2025). A crystalline boravinylidene from an arrested hydroboration reaction. JACS, 147(36), 33120--33126. (www)

  @article{ , abstract = {Boravinylidenes are intermediates in 1,1-hydroboration reactions of alkynes en route to vinyl boranes. Unlike transition metal-vinylidene complexes, boravinylidenes have hitherto, not been crystallographically characterized. Pairing bis(trimethylsilyl)ethyne with an extremely potent hydroboration reagent, bis(1-methyl- ortho -carboranyl)borane, enables crystallization and characterization of a boravinylidene. Solution multinuclear NMR experiments validate the boravinylidene and reveal it is in equilibrium with the starting materials. Density functional theory calculations indicate hyperconjugative interactions from the β-silyl groups and B–H bond stabilize this unusual species. Reaction of the feature compound with nitriles triggered an insertion and rearrangement to furnish an iminium-tethered borataallene.}, archive = {J_JACS}, author = {Manjur O. Akram and Kirk A. French and Kevin L. Shuford and Caleb D. Martin}, doi = {10.1021/jacs.5c11053}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33120--33126}, shortjournal = {J. Am. Chem. Soc.}, title = {A crystalline boravinylidene from an arrested hydroboration reaction}, volume = {147}, year = {2025}, }
• (2025). Sub-2 nm cu and co codoping SnO2 ultrathin nanosheet with mesoporous structure for efficient electrocatalytic urea synthesis. JACS, 147(36), 33108--33119. (www)

  @article{ , abstract = {The production of urea through C–N coupling via the electrochemical coreduction of CO 2 and NO 3 – represents an environmentally friendly and promising approach. However, the C–N coupling reaction encompasses multiple reactants and complex pathways, necessitating a catalyst that exhibits a high efficiency in both CO 2 and NO 3 – reduction. Herein, the sub-2 nm Cu and Co codoped SnO 2 ultrathin nanosheet (SnO 2 CuCo) with mesoporous structure is synthesized for the electrochemical coreduction of CO 2 and NO 3 – for urea synthesis, and the thickness of SnO 2 CuCo is only 1.8 nm, and the mesoporous size in the ultrathin nanosheet is 2 nm. The as-synthesized SnO 2 CuCo achieved a remarkable urea Faraday efficiency (FE) of 50 ± 1% with a production rate as high as 2701.2 ± 99.1 μmol h –1 g cat –1 . Additionally, the SnO 2 CuCo catalyst demonstrated exceptional stability after 10 catalytic cycles. Through in situ spectroscopic analysis combined with density functional theory computations, it has been revealed that Cu doping facilitates the reduction of CO 2 to CO and enhances CO adsorption, favoring the creation of the essential *CO intermediate species. Meanwhile, Co doping effectively reduces the activation energy required for the C–N coupling reaction, thereby promoting the catalytic performance, specifically the activity and selectivity, of the SnO 2 CuCo catalyst in the process of urea synthesis. This finding provides a whole new catalytic strategy for the electrochemical production of urea.}, archive = {J_JACS}, author = {Tianbao Zhang and Ping Wang and Cheng Yang and Ying Gao and Jiasai Yao and Senyao Meng and Huawei Li and Rui Tan and Jinlin Liu and Zhenxing Li}, doi = {10.1021/jacs.5c10986}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33108--33119}, shortjournal = {J. Am. Chem. Soc.}, title = {Sub-2 nm cu and co codoping SnO2 ultrathin nanosheet with mesoporous structure for efficient electrocatalytic urea synthesis}, volume = {147}, year = {2025}, }
• (2025). Enantioselective Radical–Radical cross-couplings of β-hydroxy amides and N-hydroxyphthalimide esters via Ni/Photoredox catalysis. JACS, 147(36), 33097--33107. (www)

  @article{ , abstract = {Enantioselective alkyl–alkyl cross-coupling is a powerful yet challenging strategy for constructing three-dimensional molecular architectures, which are essential in fields such as organic chemistry and pharmaceutical chemistry. While radical–radical cross-coupling offers a promising approach, achieving control over both cross- and enantioselectivity between two distinct alkyl radicals remains a formidable challenge due to their transient nature. In this article, we introduce a practical platform that combines photoredox and chiral nickel catalysis to tame transient primary and secondary alkyl radicals under mild conditions. We also present a one-pot variant wherein the N -hydroxyphthalimide (NHP) ester is generated in situ, enabling the streamlined synthesis of enantioenriched products in a single step from commercially available carboxylic acids and easily accessible alcohols. The utility of this method is demonstrated by diverse transformations to valuable scaffolds and bioactive molecules. A comprehensive mechanistic study has clarified the involvement of a Ni(I)/Ni(II) cycle.}, archive = {J_JACS}, author = {Li-Li Zhang and Lian-Jie Li and Ning Wang and Hui Yu and Ze-Peng Yang}, doi = {10.1021/jacs.5c10963}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33097--33107}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective Radical–Radical cross-couplings of β-hydroxy amides and N-hydroxyphthalimide esters via Ni/Photoredox catalysis}, volume = {147}, year = {2025}, }
• (2025). Spin-state tuning in PrFeO3-δ perovskite for high-temperature oxygen evolution reaction. JACS, 147(36), 33086--33096. (www)

  @article{ , abstract = {The electrocatalytic activity of perovskite oxides is fundamentally governed by their electronic structure. However, a deeper understanding of the relationship between the e g electron occupancy and high-temperature oxygen evolution reaction (OER) performance in solid oxide electrolysis cells (SOECs) remains underexplored. Here, A-site doped Pr 0.5 Ae 0.5 FeO 3−δ (Ae = Ca, Sr, Ba) are constructed with exceptional high-temperature OER performance, and Pr 0.5 Ba 0.5 FeO 3−δ achieves a current density of 3.33 A cm –2 at 2.0 V and 800 °C. X-ray absorption spectroscopy, 57 Fe Mössbauer spectroscopy, and magnetic susceptibility measurements reveal that alkaline earth metal doping induces a spin-state transition from high-spin Fe 3+ (t 2g 3 e g 2 ) to low-spin Fe 4+ (t 2g 4 e g 0 ), with reduced e g occupancy, thus accelerating the charge transfer and oxygen transport in the OER process. This work sheds light on the critical role of the B-site Fe electronic structure in high-temperature OER performance and provides guidance for the rational design of Fe-based perovskites as SOEC anode materials.}, archive = {J_JACS}, author = {Jingcheng Yu and Qingxue Liu and Shuo Wang and Shiming Zhou and Rongtan Li and Weicheng Feng and Yige Guo and Xiaomin Zhang and Rile Ge and Junhu Wang and Limin Liu and Shaowei Zhang and Geng Zou and Yuefeng Song and Guoxiong Wang and Xinhe Bao}, doi = {10.1021/jacs.5c10937}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33086--33096}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin-state tuning in PrFeO3-δ perovskite for high-temperature oxygen evolution reaction}, volume = {147}, year = {2025}, }
• (2025). Atomic resolution interactions regulating partitioning of a FUS folded RRM domain into model CAPRIN1 condensates. JACS, 147(36), 33071--33085. (www)

  @article{ , abstract = {Biomolecular condensates enrich specific client molecules while excluding others, often modulating conformational landscapes, and hence functions, of molecules dissolved within them. NMR-based atomic resolution studies have focused on interactions between scaffold proteins and the unfolded states of client proteins to understand the factors that influence client partitioning into condensed phases. However, characterization of interactions involving the folded client conformer is required to obtain a complete picture of how dissolution within the condensed phase affects the client energy landscape. Here, we use solution NMR spectroscopy to investigate, at atomic resolution, the interactions mediating the selective partitioning of a folded client, the FUS RNA Recognition Motif (RRM), into condensates formed by the scaffold protein CAPRIN1. At 40 °C, approximately 40% of FUS RRM remains folded in the CAPRIN1 condensed phase and high-resolution [ 1 H– 15 N]-HSQC spectra can be recorded, enabling site-specific interactions between the folded client and scaffold to be mapped across the entire FUS RRM sequence. Using intermolecular NOE and PRE (mixed solutions), and chemical shift perturbation (demixed solution) analyses, we identify a set of interaction surfaces on the folded FUS RRM that enable multiple contacts with aromatic- and arginine-rich regions of CAPRIN1. These heterotypic interactions lead to a 30-fold enrichment of FUS RRM within the condensate and overlap with sites responsible for CAPRIN1 homotypic phase separation, suggesting a shared molecular basis for scaffold-scaffold and scaffold-client recognition. Notably, tyrosine phosphorylation of CAPRIN1 disrupts these interactions and reduces client partitioning by over 2 orders of magnitude, highlighting how post-translational modifications can profoundly regulate condensate composition.}, archive = {J_JACS}, author = {Rashik Ahmed and Jeffrey P. Bonin and Julie D. Forman-Kay and Lewis E. Kay}, doi = {10.1021/jacs.5c10918}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33071--33085}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic resolution interactions regulating partitioning of a FUS folded RRM domain into model CAPRIN1 condensates}, volume = {147}, year = {2025}, }
• (2025). Topology-optimized 3D metalloporphyrin covalent organic framework for photocatalytic CO2 fixation. JACS, 147(36), 33060--33070. (www)

  @article{ , abstract = {Three-dimensional (3D) covalent organic frameworks (COFs) represent promising photocatalytic platforms with accessible active sites, yet their development faces challenges in terms of structural diversity and synthetic complexity. Herein, a robust 3D metalloporphyrin COF with scu topology and 2-fold interpenetration is achieved by using high-connectivity metalloporphyrin, and different metal centers within the porphyrin units of 3D COFs lead to intriguing structural variations. Particularly, the 3D cobalt-porphyrin-based COF achieves efficient photocatalytic CO 2 -to-CO conversion with a rate of 21 251.0 μmol g –1 h –1 , 94.2% selectivity, and a cycle stability up to 6 cycles for 30 h. The accessible active sites of 3D COF deliver an exceptional turnover frequency (TOF) and conversion rate compared with reported pristine COFs for photocatalytic CO 2 fixation. Density functional theory (DFT) calculations demonstrate the efficient donor–acceptor (D-A) system constructed in the framework, and the temperature-programmed desorption (TPD) measurement confirms the superiority of the 3D network for CO 2 chemisorption. In contrast, the two-dimensional (2D) counterpart with similar composition and D–A system is restricted by the buried metal centers. Taking the high efficiency and selectivity of CO 2 -to-CO conversion, the robust metalloporphyrin-based 3D COF has been further incorporated into tandem reaction toward higher value-added chemical products.}, archive = {J_JACS}, author = {Wei-Kang Qin and Yan-Ning Jin and Li-Jun Zhang and Cheng Wang and Jian-Peng Sun and Chen-Ho Tung and Li-Zhu Wu}, doi = {10.1021/jacs.5c10862}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33060--33070}, shortjournal = {J. Am. Chem. Soc.}, title = {Topology-optimized 3D metalloporphyrin covalent organic framework for photocatalytic CO2 fixation}, volume = {147}, year = {2025}, }
• (2025). Signal propagation in surface-confined DNA circuits with rigidified DNA origami. JACS, 147(36), 33052--33059. (www)

  @article{ , abstract = {Surface-confined DNA computing has emerged as a powerful information processing paradigm, offering enhanced specificity and accelerated reaction kinetics. Artificially designed DNA origami serves as a key enabler for such systems by providing a highly programmable platform for positioning computational components with nanometer resolution. However, conventional monolayer DNA origami circuits often exhibit non-negligible signal leakage, attributed to structural fluctuation-induced crosstalk between surface-confined molecules. Here, we utilize a rigidified double-layered uniaxial DNA origami platform to suppress the intrinsic structural fluctuation, thereby achieving high-fidelity signal propagation via minimizing fluctuation-mediated leakage. The rigidified DNA origami serves as a reliable computing platform to provide site arrangements that are narrowly distributed and closer to theoretical design. Basic propagation modules of varying orientations and spacings are implemented with reduced leakage and increased on–off ratios. We further demonstrate high-performance parallel transmission lines and logic gates on rigidified DNA origami. This approach establishes a generalizable strategy for engineering reliable platforms for surface-confined DNA computing.}, archive = {J_JACS}, author = {Chenyun Sun and Zhikun Zhao and Haozhi Wang and Mingqiang Li and Qian Zhang and Kai Xia and Haitao Song and Xiaoguo Liu and Fei Wang and Hui Lv and Chunhai Fan}, doi = {10.1021/jacs.5c10818}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33052--33059}, shortjournal = {J. Am. Chem. Soc.}, title = {Signal propagation in surface-confined DNA circuits with rigidified DNA origami}, volume = {147}, year = {2025}, }
• (2025). Spin-electric effect on a chiral dysprosium complex. JACS, 147(36), 33040--33051. (www)

  @article{ , abstract = {The Spin-Electric Effect (SEE) on molecules─the influence of external electric fields on molecular spin states─offers a compelling route toward low-power molecule-based spintronic applications. However, SEE remains elusive in molecular systems due to typically weak spin–electric field coupling. In this study, we observe a relevant SEE in a mononuclear lanthanide complex using Electric Field Modulated Electron Paramagnetic Resonance spectroscopy. We reveal a marked anisotropy of the SEE, evidencing that the most perturbed g tensor component is the one perpendicular to the electric field, providing hints for the most convenient experimental configuration to tune ad hoc spin transitions. Ab initio calculations in synergy with the experimental results revealed that molecular symmetry breaking plays a fundamental role. We also point out the crystal field parameters that are most strongly modulated by the presence of an electric field. These parameters are all off-diagonal, indicating effective electric-field-mediated state mixing.}, archive = {J_JACS}, author = {Leonardo Tacconi and Alberto Cini and Arsen Raza and Lorenzo Tesi and Paolo Bartolini and Andrea Taschin and Joris van Slageren and Matteo Briganti and Lorenzo Sorace and Maria Fittipaldi and Mauro Perfetti}, doi = {10.1021/jacs.5c10840}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33040--33051}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin-electric effect on a chiral dysprosium complex}, volume = {147}, year = {2025}, }
• (2025). Anode–Electrolyte interfacial Fluorine–Hydrogen bonding engineering for boosted electrocatalytic oxidation of small organic molecules. JACS, 147(36), 33031--33039. (www)

  @article{ , abstract = {Ions are essential components in the anode–electrolyte interfacial microenvironment that significantly influence both the activity and the pathway of electrocatalytic molecular oxidation reactions. Nevertheless, most anions are generally considered inhibitory on electrocatalytic molecular (such as alcohols and amines) oxidation reactions due to their specific adsorption at the inner Helmholtz layer, negatively impacting the electrocatalytic performance. In contrast, we have found herein that fluorine ion (F – ) at the outer Helmholtz layer is capable of largely elevating the electrocatalytic activity and promoting the transformation of glyceric acid to lactic acid as the main product by fluorine–hydrogen bonding with water molecules, glycerol reactants, and glyceraldehyde intermediate during the glycerol oxidation reaction. It has been revealed that these interfacial H-bondings facilitate glycerol desolvation and modulate molecular charge distribution, lower the energy barrier of proton-coupled electron transfer, improve the interfacial H-bond network connectivity, and destabilize the configuration of the glyceraldehyde intermediate. Importantly, this strategy is applicable to commonly used model catalysts, including Pt, Au, Pd, and Ni(OH) 2 , and offers enhanced electrolytic oxidation performances for various alcohol and amine molecules. This work provides a new perspective for the efficient electrocatalytic upgrading of alcohol and amine chemicals by establishing interfacial H-bonding.}, archive = {J_JACS}, author = {Bingji Huang and Zining Zhang and Rongyang Yin and Jiabiao Yan and Jing Tang and Lisong Chen and Jianlin Shi}, doi = {10.1021/jacs.5c10554}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33031--33039}, shortjournal = {J. Am. Chem. Soc.}, title = {Anode–Electrolyte interfacial Fluorine–Hydrogen bonding engineering for boosted electrocatalytic oxidation of small organic molecules}, volume = {147}, year = {2025}, }
• (2025). Rational design of a deep-ultraviolet nonlinear optical crystal. JACS, 147(36), 33023--33030. (www)

  @article{ , abstract = {Rational structural design of inorganic materials remains a significant challenge in materials science, particularly for deep-ultraviolet (DUV) nonlinear optical (NLO) crystals. Herein, a new DUV-transparent NLO borate, CsSrB 3 O 6 (CSBO), has been successfully predicted and synthesized by the cation regulation from Cs 2 KY(B 3 O 6 ) 2 (CKYBO). The structural stability of CSBO was confirmed by first-principles phonon vibration calculations, and it was eventually synthesized via a high-temperature solid-state reaction. The substitution of K + /Y 3+ cations with Sr 2+ cations eliminates the disorder and significantly reduces the thermal expansion anisotropy (CKYBO: 9.32, CSBO: 1.95), which effectively protects the crystals from cracking during crystal growth. Furthermore, CSBO successfully achieved the ordered design of B 3 O 6 functional groups, and this structural feature enables it to display well-balanced functional performance, including a strong second-harmonic generation response (5.0 × KH 2 PO 4 ), a short UV absorption edge (<190 nm), and moderate birefringence (0.075@1064 nm). All of these results demonstrate that CSBO is a promising DUV NLO material, and this study establishes an effective strategy for developing high-performance NLO crystals through synergistic computational-experimental approaches.}, archive = {J_JACS}, author = {Haonan Liu and Hongping Wu and Zhanggui Hu and Jiyang Wang and Yicheng Wu and Hongwei Yu}, doi = {10.1021/jacs.5c10583}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33023--33030}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design of a deep-ultraviolet nonlinear optical crystal}, volume = {147}, year = {2025}, }
• (2025). Importance of selective quenching of the triplet excited state of thermally activated delayed fluorescence (TADF) photosensitizers in redox-photosensitized reactions: Case studies on photocatalytic CO2 reduction. JACS, 147(36), 33010--33022. (www)

  @article{ , abstract = {Redox photosensitizers exhibiting thermally activated delayed fluorescence (TADF) are widely used in the various research fields. We investigated the roles of the singlet and triplet excited states of such molecules in photocatalytic CO 2 reduction. Two TADF compounds ( 4DPAIPN and 3DPAFIPN ) were used in combination with a manganese(I) complex as a catalyst and 1,3-dimethyl-2-phenyl-2,3-dihydro-1 H -benzo[ d ]imidazole (BIH) and triethanolamine (TEOA) as sacrificial electron donors. In the case of 4DPAIPN , the quantum yield of CO 2 reduction (Φ CO+HCOO– ) was negatively correlated with the concentration of BIH, equaling 43.2% and 20.3% at [BIH] = 5 and 200 mM, respectively. The reduction of the singlet excited state by BIH afforded a singlet geminate ion pair, 1 ( 4DPAIPN • – ···BIH• + ), which experienced a markedly faster backward electron transfer affording the ground state than the corresponding triplet, 3 ( 4DPAIPN • – ···BIH• + ). The escape yield of the singlet state was approximately 10 times lower than that of the triplet state. High BIH concentrations favored the quenching of the singlet excited state and disfavored the formation of the triplet excited state, resulting in low photocatalytic efficiencies. Although the system with 3DPAFIPN exhibited a similar tendency, the maximum Φ CO+HCOO– was lower (11.9% at [BIH] = 10 mM) because of its greater oxidizing power resulting in the efficient quenching of its singlet excited state by TEOA. Based on these results, we extracted the reaction conditions and molecular designs of TADF photosensitizers suitable for constructing efficient photocatalysts, namely those minimizing the quenching of the singlet excited state and maximizing the quenching of the triplet excited state.}, archive = {J_JACS}, author = {Yusuke Tamaki and Kei Kamogawa and Rei Inoue and Paola Ceroni and Osamu Ishitani}, doi = {10.1021/jacs.5c10614}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33010--33022}, shortjournal = {J. Am. Chem. Soc.}, title = {Importance of selective quenching of the triplet excited state of thermally activated delayed fluorescence (TADF) photosensitizers in redox-photosensitized reactions: Case studies on photocatalytic CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). Plasmon-enhanced C2H4 generation in the CO2 electroreduction reaction on a CuPd tandem catalyst. JACS, 147(36), 33003--33009. (www)

  @article{ , abstract = {Electrocatalysis enables the conversion of CO 2 into value-added fuels and chemicals, offering a sustainable solution for greenhouse gas mitigation. However, achieving high selectivity for C2 products like ethylene (C 2 H 4 ) remains challenging due to competing C1 pathways and complex multielectron processes. Here, we demonstrate that plasmon resonances can selectively enhance the electroreduction of CO 2 to C 2 H 4 by 27.0% on a CuPd catalyst under LED illumination (625 nm) at −1.3 V RHE . Photocurrent response, in situ FTIR spectroscopy, and COMSOL simulations reveal that plasmon-derived hot electrons and heating greatly facilitate *CO formation at the CuPd interface, which diffuses to the Cu surface for subsequent C–C coupling. DFT calculations show that the increased *CO coverage on the Cu sites reduces the energy barrier for C–C coupling, ultimately enhancing C 2 H 4 generation. This work offers valuable mechanistic insights into plasmon-mediated electrocatalysis, guiding the development of more efficient plasmonic tandem electrocatalysts for future carbon recycling technologies.}, archive = {J_JACS}, author = {Li Zhu and Kang Liu and Huang Jingwei Li and Ziwen Mei and Yicui Kang and Qin Chen and Xiaojian Wang and Hang Zhang and Xin Zi and Qiyou Wang and Junwei Fu and Evangelina Pensa and Andrei Stefancu and Min Liu and Emiliano Cortés}, doi = {10.1021/jacs.5c10517}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {33003--33009}, shortjournal = {J. Am. Chem. Soc.}, title = {Plasmon-enhanced C2H4 generation in the CO2 electroreduction reaction on a CuPd tandem catalyst}, volume = {147}, year = {2025}, }
• (2025). Signatures of a conical intersection in two-dimensional spectra of a red-absorbing squaraine dye. JACS, 147(36), 32994--33002. (www)

  @article{ , abstract = {Squaraine dyes are promising for dye-sensitized solar cells (DSSCs) due to their strong absorption in the red and near-infrared regions. However, their ultrafast photophysical behavior remains poorly understood. Using two-dimensional electronic spectroscopy (2DES) and ab initio computations, we reveal signatures of a conical intersection (CI) governing excited-state dynamics in a prototypical squaraine dye. This sub-200 fs decay pathway may hinder squaraine performance as dye-sensitizers. Our results provide experimental evidence of a sloped CI landscape and elucidate the role of at least two vibrational modes strongly coupled to electronic degrees of freedom. The passage through a CI emerges as a key relaxation mechanism, shedding light on the complex photophysics of these dyes.}, archive = {J_JACS}, author = {Vittoria Burigana and Edoardo Buttarazzi and Federico Toffoletti and Elisa Fresch and Francesco Tumbarello and Alessio Petrone and Elisabetta Collini}, doi = {10.1021/jacs.5c10393}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32994--33002}, shortjournal = {J. Am. Chem. Soc.}, title = {Signatures of a conical intersection in two-dimensional spectra of a red-absorbing squaraine dye}, volume = {147}, year = {2025}, }
• (2025). Developing a highly reducing heterogeneous nickel photocatalyst with photoexcited hantzsch esters. JACS, 147(36), 32982--32993. (www)

  @article{ , abstract = {While intricate designs have been implemented to transform noble-metal complexes and sophisticated organic molecules into reactive photocatalysts for the single-electron reduction of unactivated alkyl halides, the development of highly reducing photocatalytic systems based on earth-abundant metals is still in its early stages. Herein, we show that a simple terpyridine-ligated nickel(II) complex, integrated into an imine-linked covalent organic framework, can be readily reduced by photoexcited Hantzsch esters to produce a heterogeneous nickel(I) photocatalyst with a fairly low excited-state oxidation potential of approximately −3.5 V (referenced to the saturated calomel electrode). The efficient electron transfer processes within the framework support and the confinement effects that stabilize the nickel(I) species contribute to the improved performance of this innovative heterogeneous nickel photocatalysis in comparison to its homogeneous counterparts. Notably, the current system allows for substantial reductions in catalyst loadings and exhibits high recyclability in promoting reductive couplings between challenging organohalide electrophiles and allyl sulfones. Our research indicates that employing framework-based heterogenization strategies can facilitate the development of new classes of robust photoredox catalysts with earth-abundant metals for sustainable and practical organic synthesis.}, archive = {J_JACS}, author = {Ming Cui and Deyang Wang and Jun Guo and Minhui Dai and Meng-Ying Sun and Zekun Li and Ching Kit Tommy Wun and Stephanie Bachmann and Wing Ying Chow and Tsz Woon Benedict Lo and Meng Zhou and Wen Wu Xu and Jian He}, doi = {10.1021/jacs.5c10198}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32982--32993}, shortjournal = {J. Am. Chem. Soc.}, title = {Developing a highly reducing heterogeneous nickel photocatalyst with photoexcited hantzsch esters}, volume = {147}, year = {2025}, }
• (2025). Uniform rectangular conjugated polymer platelet micelles via one-step crystallization-driven Nucleation–Growth. JACS, 147(36), 32971--32981. (www)

  @article{ , abstract = {Semiconducting organic nanocrystals derived from the self-assembly of conjugated polymers hold great promise for optoelectronic applications. However, fabrication of these semiconductors with high uniformity and extended dimensions remains a major challenge due to tedious multistep procedures for size control and the formidable task of attaining crystal growth oriented perpendicularly to the π–π stacking direction. Here, we present a straightforward strategy for the preparation of uniform rectangular platelet micelles with tunable size through a single-step heating–cooling–aging protocol from conjugated poly(di- n -hexylfluorene) (PDHF) block copolymers (BCPs). The nucleation and growth stages are dramatically separated during the cooling process, wherein BCPs with longer PDHF blocks spontaneously serve as in situ nuclei and induce controllable epitaxial growth, yielding uniform two-dimensional (2D) morphologies. The crystalline core structure is long-range ordered, synchronously constructed by pitched π – π stacking in the length-growth direction and solvophobic alkyl stacking in the width-growth direction. The platelet dimensions spanning ∼30,000–800,000 nm 2 can be controlled by adjusting the mixed solvent ratio. Furthermore, the universality of this one-step strategy for size-controllable platelets is affirmed by BCPs with varying corona–core block ratios (0.20–0.86) and different corona-forming chains (e.g., quaternized polythiophene (QPT) and polyfluorene (QPF)). Interestingly, complex concentric segmented structures are accessible through the one-pot self-assembly of two PDHF BCPs, whose growth rate and sequence are manipulated by differences in PDHF block lengths (17 versus 14) and block ratios (0.12 versus 0.71). This enables the customization of a facile energy funneling pathway within the integrated structures from the peripheral, crystalline PDHF core to the central, lower-energy QPT corona.}, archive = {J_JACS}, author = {Jiandong Cai and Harvey K. MacKenzie and Chen Li and Huibin Qiu and Ian Manners}, doi = {10.1021/jacs.5c10080}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32971--32981}, shortjournal = {J. Am. Chem. Soc.}, title = {Uniform rectangular conjugated polymer platelet micelles via one-step crystallization-driven Nucleation–Growth}, volume = {147}, year = {2025}, }
• (2025). Photoinduced, copper-catalyzed enantioconvergent azidation of alkyl halides. JACS, 147(36), 32963--32970. (www)

  @article{ , abstract = {Although the nucleophilic substitution of alkyl halides by azide is perhaps the most widely used method for the synthesis of organic azides, we are aware of only two reports of enantioselective variants of this classic transformation. In this study, we establish that a photoinduced chiral copper catalyst (generated in situ from commercially available components) can achieve enantioconvergent azidations of racemic secondary and tertiary alkyl halides (α-halocarbonyl compounds). The resulting enantioenriched alkyl azides are useful end points and building blocks in synthesis. Mechanistic studies furnish support for key intermediates in the proposed catalytic cycle, including copper–azide complexes and an organic radical.}, archive = {J_JACS}, author = {Feng Zhong and Robert L. Anderson and Paul H. Oyala and Gregory C. Fu}, doi = {10.1021/jacs.5c10003}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32963--32970}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoinduced, copper-catalyzed enantioconvergent azidation of alkyl halides}, volume = {147}, year = {2025}, }
• (2025). Streamlined synthesis and immunomodulatory effects of ulvan oligosaccharides from marine green algae. JACS, 147(36), 32951--32962. (www)

  @article{ , abstract = {Green algae, commonly used as a source of food nutrients, contain ulvan, which is a water-soluble sulfated heteropolysaccharide isolated from Ulva . Ulvan exhibits a range of biological properties, including antitumor, antiviral, anticoagulant, and immunomodulatory activities. Its sugar backbone consists of 1→4-linked disaccharide repeating units, which are categorized as ulvanobiuronic acids (types A 3′S and B 3′S ) and ulvanobioses (types U 3′S and U 2S3′S ). Despite its promising therapeutic potential, the detailed structure–activity relationship of ulvan remains unclear. In this study, an efficient strategy was developed, utilizing orthogonally protected α1→4-linked l -Rha- d -Glc, l -Rha- l -Ido, and l -Rha- d -Xyl derivatives as disaccharide building blocks to synthesize di-, tetra-, hexa-, and octasaccharides of types A 3′S , B 3′S , and U 3′S . The immunomodulatory effects of these compounds were evaluated through cytokine induction experiments. The results revealed that only the B 3′S and U 3′S octasaccharides had a significant influence on the gene expression of IL-1β, IL-6, IL-10, GM-CSF, and G-CSF. This chemical glycobiology approach offers valuable insights into the biomedical applications of marine ulvan oligosaccharides.}, archive = {J_JACS}, author = {Junpei Shimabukuro and Ci-Hua Shen and Tsung-Kai Hsueh and Ting-Wen Chen and Yin-Chen Tseng and Veeranjaneyulu Gannedi and Jasper S. Dumalaog and Cheng-Hsiu Chang and Ting-Jen Rachel Cheng and Chung-Shan Yu and Shang-Cheng Hung}, doi = {10.1021/jacs.5c09759}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32951--32962}, shortjournal = {J. Am. Chem. Soc.}, title = {Streamlined synthesis and immunomodulatory effects of ulvan oligosaccharides from marine green algae}, volume = {147}, year = {2025}, }
• (2025). Light-promoted C(sp3)–C(sp3) reductive elimination from dialkyl NiII complexes. JACS, 147(36), 32941--32950. (www)

  @article{ , abstract = {Ni-catalyzed cross-coupling is a powerful strategy to forge C(sp 3 )–C(sp 3 ) bonds. Typically, to do so requires overcoming a challenging C–C bond-forming reductive elimination, often enabled by the intermediacy of highly oxidized Ni species or outer-sphere processes. While direct C(sp 3 )–C(sp 3 ) reductive elimination from the Ni II base oxidation state is normally thermally inaccessible, light-activation provides an avenue to affect such transformations. Here, we investigate the mechanism of light-induced C(sp 3 )–C(sp 3 ) bond formation from dialkyl bipyridine Ni II complexes through a variety of organometallic, spectroscopic, and computational studies. Wavelength-dependent quantum yields, ligand electronics–reactivity relationships, excited-state lifetimes, computed barriers, and product distributions from crossover studies support a photolysis/radical rebound mechanism. This reactivity paradigm complements existing strategies in the literature to promote reductive elimination from Ni II , such as the use of destabilizing, sterically hindered ligands and reduction of electron density at Ni through the binding of electron-deficient olefins. Hence, we envision that light-induced reductive elimination may enable the development of challenging C(sp 3 )–C(sp 3 ) couplings.}, archive = {J_JACS}, author = {Alexander Q. Cusumano and Braden C. Chaffin and David A. Cagan and Stephen DiLuzio and Erica Sutcliffe and Ryan G. Hadt and Abigail G. Doyle}, doi = {10.1021/jacs.5c09925}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32941--32950}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-promoted C(sp3)–C(sp3) reductive elimination from dialkyl NiII complexes}, volume = {147}, year = {2025}, }
• (2025). A computationally optimized ribonucleic acid circularization strategy without byproducts. JACS, 147(36), 32932--32940. (www)

  @article{ , abstract = {Circular mRNA (mRNA) exhibits promising potential in mRNA therapy due to its increased stability and extended duration of protein translation, which has sparked an urgent demand for efficient methods to prepare circular RNAs in vitro . Here, we present a versatile self-circularization strategy that employs simple motifs to synthesize circular RNAs, achieving robust efficiencies for sequences ranging from dozens to thousands of nucleotides. By leveraging an automated computational program, we optimized highly specific lock-key structures to maximize circularization efficiency, particularly for long RNA substrates. Furthermore, the shared sequence and functionality between linear precursor RNAs and circular products eliminate the need for additional purification steps to remove excess nucleic acid components, simplifying the production process. This approach also yields circular RNAs with superior stability and translation efficiency, enabling sustained protein expression in vitro and in vivo . Our computationally optimized, purification-free method holds immense promise for scalable circular RNA production and the development of advanced RNA therapeutics, significantly advancing mRNA therapy.}, archive = {J_JACS}, author = {Ruofan Chen and Yuan Zhuang and Li Zhang and Yuanyuan Wu and Liangzhi Luo and Yufan Pan and Yujie Li and Chenyou Zhu and Rui Xu and Yifan Jiang and Ziyang Hao and Baolei Tian and Liang Zhang and Yuanchen Dong and Dongsheng Liu}, doi = {10.1021/jacs.5c09798}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32932--32940}, shortjournal = {J. Am. Chem. Soc.}, title = {A computationally optimized ribonucleic acid circularization strategy without byproducts}, volume = {147}, year = {2025}, }
• (2025). Phosphorus-doped Cu/Fe2O3 electrocatalysts with optimized synergy between the different sites for efficient urea electrosynthesis. JACS, 147(36), 32924--32931. (www)

  @article{ , abstract = {Urea electrosynthesis from the coelectrolysis of CO 2 and NO 3 – (UECN) has emerged as a promising sustainable alternative to traditional energy-intensive methods; however, the rational design of advanced electrocatalysts capable of achieving concurrent optimization of Faradaic efficiency (FE) and urea yield rates continues to pose a fundamental challenge in this field. Herein, we developed a phosphorus-doped Cu/Fe 2 O 3 electrocatalyst (denoted as P–Cu/Fe 2 O 3 ), where phosphorus atoms partially substitute for oxygen atoms within the Cu/Fe 2 O 3 heterostructure. This engineered electrocatalyst achieves exceptional urea electrosynthesis performance, delivering a very high Faradaic efficiency of 73.81% with a corresponding yield rate of 62.74 mmol h –1 g –1 cat. at −0.68 V vs RHE, which are superior to most UECN electrocatalysts reported to date. Notably, the urea yield rate can be further boosted to 97.11 mmol h –1 g –1 cat. at −0.88 V vs RHE. Operando spectroscopic characterization and density functional theory (DFT) simulations indicated that P doping modulates the electronic structure of the electrocatalyst surface, which promotes the formation of *CO and *NO, lowers the energy barrier for the coupling of *CO and *NO, and increases *H coverage to facilitate the hydrogenation process during UECN. This multisite cooperative mechanism establishes a new paradigm for designing high-performance electrocatalysts, demonstrating substantial potential for industrial-scale urea production.}, archive = {J_JACS}, author = {Ting Deng and Shuaiqiang Jia and Cheng Xue and Hailian Cheng and Jiapeng Jiao and Xiao Chen and Zhanghui Xia and Mengke Dong and Chunjun Chen and Haihong Wu and Mingyuan He and Buxing Han}, doi = {10.1021/jacs.5c09805}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32924--32931}, shortjournal = {J. Am. Chem. Soc.}, title = {Phosphorus-doped Cu/Fe2O3 electrocatalysts with optimized synergy between the different sites for efficient urea electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Dynamic interconversion of Ga(III) and GaHx in ga-MFI zeolites for efficient CO2–Cyclohexane coupling conversion to aromatics. JACS, 147(36), 32915--32923. (www)

  @article{ , abstract = {The catalytic coupling conversion of naphtha and CO 2 to aromatics over metal-zeolites offers a fascinating route for aromatics production, yet, the exploitation of efficient metal-zeolite catalysts and CO 2 coupled naphtha to make CO 2 transformed into high-value-added chemicals remain great challenges. Herein, we synthesized a framework-anchored Ga-MFI catalyst synthesized via ligand-assisted hydrothermal crystallization, achieving 80.76% aromatic selectivity at 99.57% cyclohexane conversion (550 °C, 0.1 MPa, WHSV = 1 h –1 ) with over 110 h stability for CO 2 and cyclohexane (as a model naphthenic compound) coupling reaction. Multimodal in situ characterization (XAFS, synchrotron XRD, and FTIR) reveals that isolated Ga(III) species undergo reversible coordination switching to GaH x under reaction conditions, dynamically mediating CO 2 activation through Ga species transfer. Tetrahedrally coordinated Ga–O sites synergize with proximal Brønsted acid sites. Isotopic tracing ( 13 CO 2 ) demonstrates 56.4% of aromatic carbon originates. The catalyst’s self-recovery capability ensures structural integrity and suppresses deactivation. This work establishes a dynamic single-site catalysis framework for a CO 2 coupled alkane, advancing the design of zeolite-confined metal catalysts through precise microenvironment engineering.}, archive = {J_JACS}, author = {Haohao Feng and Zhong-Pan Hu and Enze Chen and Yimo Wu and Min Li and Jingfeng Han and Yingxu Wei and Zhongmin Liu}, doi = {10.1021/jacs.5c09737}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32915--32923}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic interconversion of Ga(III) and GaHx in ga-MFI zeolites for efficient CO2–Cyclohexane coupling conversion to aromatics}, volume = {147}, year = {2025}, }
• (2025). Postassembly modification of a pd6 host and c70 encapsulation to enhance its ROS-mediated terpene oxidation ability under visible light. JACS, 147(36), 32904--32914. (www)

  @article{ , abstract = {The properties of supramolecules can be modulated by post-assembly modification (PAM) of their building blocks or via guest encapsulation. This work demonstrates a largely uncharted approach to property modulation that integrates both PAM and guest encapsulation in a single system to boost photocatalytic activity. Self-assembly of a “phenothiazine”-functionalized ligand ( L ) with a cis -blocked Pd(II) acceptor ( A ) generated an A 6 L 3 trifacial tube ( T ). Postassembly, T could be modified via irradiation with violet light, leading to the sulfoxidation of the “phenothiazine” moieties in T and thereby generating an oxidized tube ( TO ). Both TO and T could stabilize a C 70 molecule within their cavities, forming C 70 @TO and C 70 @T , respectively. Although T showed relatively poor photocatalytic performance mediated by reactive oxygen species (ROS) with respect to oxidation of terpenes ( S1–S4 ) under visible light, the modified TO was much better in that regard. Expectedly, C 70 @T showed better photocatalytic performance than T due to the presence of photosensitizing C 70 . While PAM or guest encapsulation alone led to reasonable improvements in photocatalytic ability, their combination within C 70 @TO led to a significant improvement. Catalytic amounts of C 70 @TO could instantly oxidize terpenes. Thus, we report here a new host that integrates the effects of both PAM and photosensitizer encapsulation for synergistically boosting its photocatalytic activity.}, archive = {J_JACS}, author = {Soumya Dey and Ranit Banerjee and Neal Hickey and Partha Sarathi Mukherjee}, doi = {10.1021/jacs.5c09667}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32904--32914}, shortjournal = {J. Am. Chem. Soc.}, title = {Postassembly modification of a pd6 host and c70 encapsulation to enhance its ROS-mediated terpene oxidation ability under visible light}, volume = {147}, year = {2025}, }
• (2025). Electrosynthesis of nitriles from nitrate and aldehyde via C≡N bond construction. JACS, 147(36), 32896--32903. (www)

  @article{ , abstract = {Electrocatalytic nitrate reduction offers a promising approach to synthesizing valuable organic nitrogen compounds via C–N coupling, serving as a pivotal solution to the pressing nitrate pollution issue. While significant progress has been made in electrosynthesizing C–N and C═N compounds, the electrosynthesis of nitriles with C≡N bond formation via NO x as nitrogen sources remains challenging. Herein, we introduce a novel method for efficient synthesizing nitriles through electrocatalytic coupling of nitrate ions (NO 3 – ) with aldehydes under ambient conditions, employing ZnO/Sn/SnO 2 as the electrocatalyst. In situ spectroscopic characterization and theoretical calculations demonstrated that the adsorption and accumulation of *NH 2 OH and *RCHO on the catalyst plays a central role in the efficient reaction. The key C–N bond-forming step is found to be the formation of hydroxylamine from nitrate reduction and its subsequent condensation with *RCHO. The C–N coupling strategy can be applied to the synthesis of fatty nitrile and (hetero)aromatic nitrile compounds. This study opens the way for nitriles electrosynthesis from nitrogen wastes, which could contribute to utilization of nitrogen resources.}, archive = {J_JACS}, author = {Cheng Xue and Shuaiqiang Jia and Jiapeng Jiao and Xiao Chen and Mengke Dong and Zhanghui Xia and Ting Deng and Hailian Cheng and Chunjun Chen and Haihong Wu and Mingyuan He and Buxing Han}, doi = {10.1021/jacs.5c09570}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32896--32903}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrosynthesis of nitriles from nitrate and aldehyde via C≡N bond construction}, volume = {147}, year = {2025}, }
• (2025). Exploring the structural divergence of HIV and SRLV lentiviral capsids. JACS, 147(36), 32883--32895. (www)

  @article{ , abstract = {Lentiviruses require a mature capsid to package and traffic their viral genome for successful infection and propagation. Although the HIV-1 capsid structure has been extensively studied, structural information is lacking for other lentiviral capsids, limiting our understanding. Using cryo-electron microscopy (cryo-EM) and a liposome-templating system, we assembled capsid-like particles (CLPs) and resolved capsid protein (CA) pentamer and hexamer lattice structures from the two major phylogenetic groups of small ruminant lentiviruses (SRLVs). These structures exhibit an overall lattice organization like HIV-1 but differ in key characteristics, notably the absence of inositol hexakisphosphate (IP6) in the SRLV CA lattice─a critical factor for HIV-1 capsid assembly and function. Additionally, SRLV CA pentamers show a unique N-terminal domain orientation, providing insights into SRLV capsid assembly mechanisms. These observations, together with our molecular dynamics (MD) simulation, results suggest a possible mechanism for importing deoxynucleotide triphosphate (dNTP) molecules into SRLV capsids. Furthermore, key regions of host factor interaction, such as the CypA binding motifs, have diverged in the SRLV CA assemblies. Our results contribute to understanding the SRLV lentiviral capsids which may facilitate structure-based inhibitor design strategies.}, archive = {J_JACS}, author = {Fidel Arizaga, Jr. and Christian Freniere and Juan S. Rey and Matthew Cook and Chunxiang Wu and Juan R. Perilla and Yong Xiong}, doi = {10.1021/jacs.5c09436}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32883--32895}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploring the structural divergence of HIV and SRLV lentiviral capsids}, volume = {147}, year = {2025}, }
• (2025). Highly selective carbonylation of olefins using CO2 and h2. JACS, 147(36), 32873--32882. (www)

  @article{ , abstract = {A unique multimetallic catalyst system that allows for the direct carbonylation of aliphatic and aromatic olefins with carbon dioxide and hydrogen has been developed. The employment of palladium and iridium precursors, in conjunction with 1,2-bis(di- tert -butylphosphinomethyl)benzene (d t bpx) or its derivatives as active ligands and Zn(OTf) 2 (OTf: trifluoromethanesulfonate) as an essential acidic additive, has been shown to result in the selective formation of aliphatic esters in CO 2 -based carbonylations, exhibiting unparalleled regioselectivity. Detailed control experiments and mechanistic investigations suggest an initial Ir-catalyzed formation of alkyl formates from carbon dioxide, followed by Pd-catalyzed alkoxycarbonylation at a low CO concentration. The desired transformation has been observed to occur in several industrially relevant alkene substrates, thereby creating a potential avenue for further research and industrial applications.}, archive = {J_JACS}, author = {Mohamed Niyaz Vellala Syed Ali and Weiheng Huang and Xinxin Tian and Haijun Jiao and Ralf Jackstell and Robert Franke and Matthias Beller}, doi = {10.1021/jacs.5c09325}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32873--32882}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly selective carbonylation of olefins using CO2 and h2}, volume = {147}, year = {2025}, }
• (2025). Fluorinated deep eutectic gel electrolytes for sustainable lithium metal batteries. JACS, 147(36), 32861--32872. (www)

  @article{ , abstract = {As an emerging class of eutectic mixtures, deep eutectic gel electrolytes (DEGEs) exhibit unique advantages in lithium metal batteries (LMBs), particularly due to their high ionic conductivity and tunable molecular interactions. However, it is challenging to realize high interfacial stability between DEGEs and lithium metal. We developed a series of DEGEs utilizing fluorinated amides, which leverage the electron-withdrawing effects of fluorine to precisely modulate the lowest unoccupied molecular orbital (LUMO) energy levels of amides and their binding affinities for Li + . A bidirectional screening criterion is proposed, integrating the LUMO energy levels of amides and the desolvation barriers of solvated Li + ions. Among the tested amides, 2,2,2-trifluoro- N -methylacetamide (C═Oα3F) demonstrates the lowest LUMO energy level and desolvation energy barrier. The declined LUMO energy level facilitates the formation of a uniform and robust SEI layer enriched with LiF and Li 3 N. Meanwhile, the reduced Li + desolvation energy barrier renders more anions to participate in the solvation process, and this synergistic solvent–anion-derived SEI mechanism further reinforces SEI stability. Additionally, the C═Oα3F-DEGE exhibits superior nonflammability and a high ionic conductivity of 1.24 mS cm –1 . The enhanced properties enable the corresponding Li||Li symmetric battery to achieve stable cycling for over 9000 h and the Li||LiFePO 4 battery counterpart to deliver an impressive lifespan of 2500 cycles with 81.7% capacity retention. These results underscore the advantages of C═Oα3F-DEGE over other fluorinated amide-based systems, providing new insights into the development of high-performance deep eutectic gel electrolytes.}, archive = {J_JACS}, author = {Tongrui Zhang and Jiangtao Yu and Tianxing Lin and Yuqiu Song and Menglin Li and Yang Feng and Libo Song and Ying Jiang and Weiwei Xie and Yong Lu and Tianfei Liu and Kai Zhang and Jun Chen}, doi = {10.1021/jacs.5c08642}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32861--32872}, shortjournal = {J. Am. Chem. Soc.}, title = {Fluorinated deep eutectic gel electrolytes for sustainable lithium metal batteries}, volume = {147}, year = {2025}, }
• (2025). Shake-down spectroscopy as state- and site-specific probe of ultrafast chemical dynamics. JACS, 147(36), 32851--32860. (www)

  @article{ , abstract = {Tracking the multifarious ultrafast electronic and structural changes occurring in a molecule during a photochemical transformation is a challenging endeavor that benefits from recent experimental and computational progress in time-resolved techniques. Measurements of valence electronic states, which provide a global picture of the bonding structure of the molecule, and core electronic states, which provide insight into the local environment, traditionally require different approaches and are often studied separately. Here, we demonstrate that X-ray pulses from a seeded free-electron laser (FEL) enable the measurement of high-resolution, time-resolved X-ray photoelectron spectra (XPS) that capture weak satellite states resulting from shake-down processes in a valence-excited molecule. This approach effectively combines the advantages of both valence- and core-state investigations. We applied this method to investigate photoexcited CS 2 molecules, where the role of internal conversion (IC) and intersystem crossing (ISC) in determining the predissociation dynamics is controversial. We present XPS spectra from photoexcited CS 2 , obtained at the FERMI FEL. High-resolution measurements, compared to the corresponding spectra obtained from accurate multireference quantum chemical calculations, reveal that shake-down satellite channels are highly sensitive to both valence electronic and geometric changes. Previous studies of the predissociation dynamics have led to uncertain assignments of the branching between singlet and triplet excited states. We derive a propensity rule that demonstrates the spin-selectivity of the shake-downs. This selectivity allows us to unequivocally assign contributions from the bright and dark singlet excited states, with populations tracked along the predissociation dynamic pathway.}, archive = {J_JACS}, author = {Henry J. Thompson and Matteo Bonanomi and Jacob Pedersen and Oksana Plekan and Nitish Pal and Cesare Grazioli and Kevin C. Prince and Bruno N. C. Tenorio and Michele Devetta and Davide Faccialà and Caterina Vozzi and Paolo Piseri and Miltcho B. Danailov and Alexander Demidovich and Alexander D. Brynes and Alberto Simoncig and Marco Zangrando and Marcello Coreno and Raimund Feifel and Richard J. Squibb and David M. P. Holland and Felix Allum and Daniel Rolles and Piero Decleva and Michael S. Schuurman and Ruaridh Forbes and Sonia Coriani and Carlo Callegari and Russell S. Minns and Michele Di Fraia}, doi = {10.1021/jacs.5c09162}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32851--32860}, shortjournal = {J. Am. Chem. Soc.}, title = {Shake-down spectroscopy as state- and site-specific probe of ultrafast chemical dynamics}, volume = {147}, year = {2025}, }
• (2025). An 18-porphyrin nanoring at the size limit for global aromaticity. JACS, 147(36), 32840--32850. (www)

  @article{ , abstract = {What is the size limit for global aromaticity? How large can a macrocyclic π-system be and still exhibit an aromatic ring current around its circumference? We address this question by investigating a π-conjugated butadiyne-linked 18-porphyrin nanoring (diameter 8 nm). This nanoring was synthesized by two different strategies: classical template-directed synthesis, using a radial template with 18 pyridyl binding sites, and Vernier templating, using a small hexapyridyl template. Both strategies are effective when the porphyrins have octyloxy side chains, but classical templating is more effective than Vernier templating when the porphyrins have bulky trihexylsilyl substituents. The size and shape of the nanoring were confirmed by scanning tunneling microscopy. 19 F NMR oxidation titrations on the nanoring bound to a fluorinated template revealed shoulder signals indicating weak global aromatic and antiaromatic ring currents in the 10+ and 12+ oxidation states, which have Hückel circuits of 242 and 240 π-electrons, respectively. These shoulder signals do not appear in control experiments with a split-ring complex consisting of the linear porphyrin 18-mer bound to the same fluorinated template, confirming that they arise from global ring currents. Nucleus-independent chemical shift calculations using the BLYP35 functional qualitatively predicted that the 18 porphyrin nanoring would exhibit global aromaticity in the 10+ and 14+ oxidation states and antiaromaticity in the 12+ and 16+ oxidation states, in keeping with the experimental results from NMR spectroscopy and with the Hückel rule. The experimental results show that the ring currents in this 18-porphyrin ring are weaker than those in the homologous 12-porphyrin ring by at least a factor of 2.}, archive = {J_JACS}, author = {Jake M. Holmes and Henrik Gotfredsen and Lene Gödde and Janko Hergenhahn and Kavita Rani and Keigo E. Yamada and Jie-Ren Deng and Liv Warwick and Michael Clarke and Matthew Edmondson and James N. O’Shea and Alex Saywell and Harry L. Anderson}, doi = {10.1021/jacs.5c09149}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32840--32850}, shortjournal = {J. Am. Chem. Soc.}, title = {An 18-porphyrin nanoring at the size limit for global aromaticity}, volume = {147}, year = {2025}, }
• (2025). Orthogonal and multiresponsive quinolinone systems for reversible and recyclable polymer networks. JACS, 147(36), 32830--32839. (www)

  @article{ , abstract = {Achieving precise control over covalent bond formation and cleavage is critical for advancing material recycling and enabling repeated reuse. Here, we introduce quinolinones as versatile, multistimuli-responsive motifs enabling orthogonal and controlled covalent bond manipulation via a reversible [2π + 2π] cycloaddition triggered by light and thermal stimuli. While photochemical bond formation is well-established, thermal reversion of such bonds for material deconstruction remains underexplored. Furthermore, we demonstrate, for the first time, the exceptional ability of quinolinones to undergo symmetrical thermal cleavage, in the solid state with unprecedented efficiency, achieving over 99% monomer recovery at 210 °C within 10 min. This circular process is initially demonstrated at the molecular level, showing an effective cyclability of at least three full bond formation and cleavage cycles with quantitative efficiency. Extending to the macromolecular scale, quinolinones are incorporated into linear polymers to enable phototriggered network formation followed by thermally induced bulk deconstruction. This responsive polymer system highlights remarkable versatility and recyclability. Finally, exploiting their multiresponsivity, quinolinones are applied to advanced coatings with reversible debonding and thermal degradation capabilities. This work establishes quinolinones as a robust platform for stimuli-responsive materials, paving the way for next-generation recyclable systems with enhanced functionalities.}, archive = {J_JACS}, author = {Claas-Hendrik Stamp and Annalena Groß and Aitana Beato Irulegui and Bizan N. Balzer and Céline Calvino}, doi = {10.1021/jacs.5c08976}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32830--32839}, shortjournal = {J. Am. Chem. Soc.}, title = {Orthogonal and multiresponsive quinolinone systems for reversible and recyclable polymer networks}, volume = {147}, year = {2025}, }
• (2025). Site-specific chemoselective cyclization and fluorogenic modification of protein cysteine residues: From side-chain to backbone. JACS, 147(36), 32818--32829. (www)

  @article{ , abstract = {The selective modification of natural protein templates has emerged as a powerful tool for investigating the protein structure and function as well as for designing therapeutic bioconjugates. While significant progress has been made in modifying protein side chains and terminal groups, backbone modifications remain underexplored due to the inherent inertness of amide bonds and the challenge of achieving site specificity. Despite the critical role of the backbone in the protein function, its selective chemical modification under physiological conditions has proven to be difficult. With this research, we introduce a site-specific, chemoselective, and two-step strategy for protein backbone modification via thiol/amine coupling and cyclization reactions driven by the release of volatile methyl mercaptans via a small-molecular conjugate acceptor, operating on small-molecule cysteine mimics, peptides, and proteins. This approach leverages the unique reactivity of the conjugate acceptor to first couple a cysteine residue, followed by intramolecular cyclization with an adjacent amide, forming a five-membered heterocyclic unit under aqueous conditions without requiring catalysts or heating. Additionally, molecular dynamics simulations reveal that the resulting rigid structure induces a local backbone torsion, hydrogen bond disruption, and altered side-chain orientation, thereby influencing protein folding. Preliminary investigations further explore the consequent changes in the protein thermal stability and enzymatic activity induced by backbone modification. More importantly, the process is accompanied by a fluorescence turn-on signal, enabling the real-time in situ monitoring of the modification process. Thus, this unique strategy offers a new platform for backbone-specific chemical modifications, paving the way for potential protein and peptide functional studies, fluorogenic labeling, and the development of novel bioconjugates.}, archive = {J_JACS}, author = {Hui Zhang and Ke Wei and Wanyi Yu and Youshen Wu and Xuhong Qian and Eric V. Anslyn and Xiaolong Sun}, doi = {10.1021/jacs.5c08837}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32818--32829}, shortjournal = {J. Am. Chem. Soc.}, title = {Site-specific chemoselective cyclization and fluorogenic modification of protein cysteine residues: From side-chain to backbone}, volume = {147}, year = {2025}, }
• (2025). Interlayer expansion enables electrochemical domino C–N coupling for formaldoxime formation in aqueous media. JACS, 147(36), 32809--32817. (www)

  @article{ , abstract = {Upcycling C- and N-containing pollutants into value-added resources is key to achieving a sustainable society in the near future. In recent years, coelectrolysis powered by renewable energy sources to generate structurally complicated and functionally diverse C–N bonds is highly desirable yet more challenging compared with C-only or N-only reduction reactions. Oximes, which contain C=N bonds, are important precursors in medicine and the fine chemical industry. Previous attempts to coreduce carbon dioxide and nitrate or nitrite yielded formaldoxime (H 2 C=NOH) as a byproduct with low selectivity. Herein, we demonstrate a new tandem electrocatalytic pathway to produce H 2 C=NOH as the target product using NiFe layered double hydroxides (LDHs) as efficient catalysts. Upon expanding the interlayer spacing of NiFe LDH using dodecyl-sulfonate as an intercalating anion, this catalyst displays a record-high Faradaic efficiency for H 2 C=NOH of 31% in aqueous solution at −1.9 V vs reversible hydrogen electrode. Our findings also show that the lengths of alkyl chains can tune the immediate microenvironment surrounding the dual Ni–Fe active sites, thus boosting the C–N coupling yield rate. Kinetic isotopic effect studies and control experiments under H 2 are further carried out to interrogate the electrocatalytic mechanism of this tandem C–N bond formation process. Overall, this study offers a compelling approach to form a C–N bond via a green electrosynthesis scheme in an aqueous medium. Furthermore, this study underscores the importance of precisely regulating the electrochemical microenvironment for enhancing the synergy between dual-metal active sites for efficient domino electrosynthesis.}, archive = {J_JACS}, author = {Ruijie Yi and Xiaoyong Mo and Hei Tung Yau and Tao Zhou and Zhengxiao Guo and Shu-Chih Haw and Edmund C. M. Tse}, doi = {10.1021/jacs.5c08836}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32809--32817}, shortjournal = {J. Am. Chem. Soc.}, title = {Interlayer expansion enables electrochemical domino C–N coupling for formaldoxime formation in aqueous media}, volume = {147}, year = {2025}, }
• (2025). Bottom-up investigation of spatiotemporal glycocalyx dynamics with interferometric scattering microscopy. JACS, 147(36), 32799--32808. (www)

  @article{ , abstract = {Over recent decades, the glycocalyx, an extracellular organelle composed of a multitude of glycolipids, glycoproteins, proteoglycans, and glycoRNA, has gained considerable interest in cellular biology. While research in this field has revealed its tremendous importance in ever more aspects of physiological and pathological cellular processes, many of the principles that govern the role of the glycocalyx in these processes on a molecular level are still unknown. In order to unravel the fundamental laws underlying glycocalyx function, new technologies are required that enable the distinction between individual subprocesses within the intricate environment of the glycocalyx. Here, we establish an experimental platform to investigate the dynamics of the glycocalyx at the nanometer and microsecond length and time scales in a bottom-up fashion. We synthesized defined oligosaccharides and installed them on supported lipid bilayers. This way, synthetic glycolipids were assembled to glycocalyx model systems with tunable properties. By investigating these tunable model systems with interferometric scattering (iSCAT) microscopy, we gain access to the required spatiotemporal resolution. We found a strong correlation between the molecular structure of several investigated model glycans and global dynamics of the system. Our findings are corroborated by atomistic molecular dynamics simulations and coarse-grained Brownian dynamics simulations. Our results provide the first direct experimental evidence on the relationship between glycan structure, organization, and dynamics, offering a robust and versatile basis for a quantitative understanding of glycocalyx biology and physics at the molecular level.}, archive = {J_JACS}, author = {Carla M. Brunner and Lorenz Pietsch and Ingo vom Sondern and Michael Röhrl and Cristian Popov and Marius F.W. Trollmann and Richard W. Taylor and Martin Blessing and Cornelia Holler and Karim Almahayni and Sven Ole Jaeschke and Vahid Sandoghdar and Rainer A. Böckmann and Thisbe K. Lindhorst and Leonhard Möckl}, doi = {10.1021/jacs.5c08659}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32799--32808}, shortjournal = {J. Am. Chem. Soc.}, title = {Bottom-up investigation of spatiotemporal glycocalyx dynamics with interferometric scattering microscopy}, volume = {147}, year = {2025}, }
• (2025). C(sp3)H/N(sp2) cross-coupling reaction for the synthesis of tertiary arylamines via fluxional SOX·Pd(II) catalysis. JACS, 147(36), 32786--32798. (www)

  @article{ , abstract = {N -alkyl arylamines are important structural motifs in pharmaceuticals, yet traditional alkylating methods rely on the nucleophilicity of the amine and make access to such compounds with valuable bioproperties challenging. While metal-mediated reactions may alleviate these limitations, they often encounter amine-metal interactions that can hinder catalysis or lead to deleterious pathways. Herein, we report a palladium(II) [Pd(II)]/sulfoxide-oxazoline(SOX)/phosphoric acid-mediated C(sp 3 )H/N(sp 2 ) cross-coupling of 53 arylamine nucleophiles and 39 terminal olefins to furnish >80 diverse tertiary (3°) arylamines in excellent yields (average 82%) and selectivities (>20:1 E / Z , >20:1 linear/branched). The reaction furnishes electron-deficient and sterically bulky arylamines as well as those housing alkyl/aryl halides, epoxides, carbonyls, epimerizable centers, carboxylic acids, and N -triflyl/tosyl alkylamines, showcasing orthogonal scope to existing aminations. The generality of this reaction enables facile synthesis of six pharmaceuticals and derivatives (e.g., zafirlukast) and five late-stage drug fragment couplings (e.g., flutamide-duloxetine). Whereas spectroscopic studies identify a catalytically inactive bis(arylamine)·Pd(II) complex 4 as the resting state, the reaction proceeds with high efficiencies (short reaction times, low catalyst loadings). Mechanistic studies reveal that the SOX ligand L1 [(±)-MeO-SOX = MaSOX)] establishes a dynamic equilibrium with 4 to generate the active catalyst. Phosphoric acids promote the reaction by affording a significant increase in the functionalization rate, rendering a lower energy allylic C–H cleavage as the rate-determining step. We anticipate that this reaction will find broad use in the discovery of complex and medicinally relevant N -alkyl arylamines and that the mechanistic insights will be leveraged to improve efficiencies of other metal-catalyzed aminations.}, archive = {J_JACS}, author = {Brenna G. Budaitis and Zachary M. Firestein and Andrew C. Yue and M. Christina White}, doi = {10.1021/jacs.5c08883}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32786--32798}, shortjournal = {J. Am. Chem. Soc.}, title = {C(sp3)H/N(sp2) cross-coupling reaction for the synthesis of tertiary arylamines via fluxional SOX·Pd(II) catalysis}, volume = {147}, year = {2025}, }
• (2025). Defluorinative coupling of (NH)-heteroarenes and unactivated vinyl fluorides enabled by Metal–Organic frameworks. JACS, 147(36), 32776--32785. (www)

  @article{ , abstract = {N -vinyl azoles are prevalent moieties in pharmaceuticals, and fluorovinyl groups are widely recognized as carbonyl bioisosteres in drug design. Thus, N -fluorovinylated heteroarenes represent highly desirable functional groups in medicinal chemistry. To streamline the development of novel N -fluorovinylation and N -pentafluoropropenylation reactions, herein we safely handle fluorinated gases, such as vinylidene fluoride (VDF) and hexafluoropropene (HFP), as solid reagents using a metal–organic framework (MOF), Mg 2 (dobdc) (dobdc 4– = 2,5-dioxidobenzene-1,4-dicarboxylate). We report for the first time that free (NH)-heteroarenes─including various complex, biologically active molecules, react directly with VDF via a defluorinative pathway under mild conditions, yielding terminal N -fluorovinylated products in good to excellent yields. The use of the gas-loaded MOF leads to much higher yields than reactions with the gas alone, likely due to its dual role as both a VDF delivery vessel and a Lewis acid catalyst. Mechanistic investigations, including deuterium incorporation experiments and density functional theory calculations, suggest that this transformation represents a rare example of a concerted nucleophilic vinylic substitution (S N V) process. This protocol can be performed on a gram scale, and the resulting N -fluorovinyl moieties can be further diversified to yield valuable motifs, such as N -fluorocyclopropyl groups. Finally, this defluorinative coupling can be generalized to other fluorinated alkenes, such as HFP. Overall, this robust defluorinative coupling offers a straightforward strategy for synthesizing diverse fluorinated heteroarenes from readily available starting materials, providing broad access to these valuable motifs for the first time.}, archive = {J_JACS}, author = {Kaitlyn T. Keasler and Jaehwan Kim and Julia C. Pitolaj and Phillip J. Milner}, doi = {10.1021/jacs.5c08791}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32776--32785}, shortjournal = {J. Am. Chem. Soc.}, title = {Defluorinative coupling of (NH)-heteroarenes and unactivated vinyl fluorides enabled by Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). The modulatory role of positional isomerism in diolein on the structural features of pH-responsive 2-hydroxyoleic acid nanocarriers. JACS, 147(36), 32761--32775. (www)

  @article{ , abstract = {pH-responsive nonlamellar liquid crystalline nano-self-assemblies are gaining substantial interest in drug delivery applications owing to their unique inherent structural architectures. Using two positional isomers of diolein (namely, 1,2-diolein and 1,3-diolein) and their mixture (designated as diolein) in combination with 2-hydroxyoleic acid (2OHOA, a therapeutic agent with anticancer activity), we report on a family of stabilizer-free and pH-responsive nanoparticles with internal architectures spanning from a lamellar (L α ) phase to inverse hexagonal (H 2 ) and discontinuous (micellar) cubic Fd3m phases. In lipid composition- and pH-dependent manners, the triggered colloidal transformations in these aqueous nanodispersions, combined with alterations in the morphological features and size distributions, were investigated by small-angle X-ray scattering, cryo-transmission electron microscopy, and nanoparticle tracking analysis. The experimental findings support the notion that molecular shapes of lipids, deprotonation/protonation of ionizable lipids, and mutual lipid–lipid and lipid–water interactions at the interfacial area play crucial roles in modulating the biophysical properties of lyotropic liquid crystalline nano-self-assemblies. We discuss how the positional isomerism of diolein can dictate the structural features of the nanoparticles by controlling the interaction modes of diolein with 2OHOA in the interfacial area. Further, the potential of these structurally tunable nanoplatforms in the future development of nanomedicines for the delivery of 2OHOA alone or in combination with other therapeutic agents is highlighted.}, archive = {J_JACS}, author = {Chenyang Wu and Gokce Dicle Kalaycioglu and Stefan Salentinig and Balsam Kadri Abboud and Huiling Mu and Anan Yaghmur}, doi = {10.1021/jacs.5c08715}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32761--32775}, shortjournal = {J. Am. Chem. Soc.}, title = {The modulatory role of positional isomerism in diolein on the structural features of pH-responsive 2-hydroxyoleic acid nanocarriers}, volume = {147}, year = {2025}, }
• (2025). Triggering lattice oxygen release for semiconducting carbon nanotube array synthesis. JACS, 147(36), 32752--32760. (www)

  @article{ , abstract = {Lattice oxygen in metal oxides offers potential pathways for advanced catalyst design, including catalysts for the selective growth of semiconducting single-walled carbon nanotubes (s-SWCNTs). In this study, an increase of lattice-oxygen release flux up to 10 5 is achieved via a lattice oxygen triggering (LOT) strategy for oxide catalysts. The LOT strategy is experimentally realized by ion implantation of titanium (Ti) and iron (Fe) elements into the sapphire substrate, followed by an annealing process for Ti migration onto the surface and Fe stable substitution in the sapphire lattice. The LOT process occurs when Fe atoms dope into Ti oxides, forming the catalysts for SWCNT growth. The continuously released lattice oxygen serves as an in situ etchant for precise removal of metallic tubes, resulting in the direct synthesis of horizontally aligned s-SWCNT arrays with >98% purity. Field-effect transistors based on the s-SWCNT arrays exhibit ultralow subthreshold swing of 60 mV dec –1 , and high carrier mobility of 2291 cm 2 ·V –1 ·s –1 . This LOT strategy establishes a paradigm for tuning lattice oxygen kinetics and thermodynamics, opening avenues for an oxygen-centric catalyst design in nanomaterial synthesis.}, archive = {J_JACS}, author = {Zhe Liu and Hao Li and Zhisheng Peng and Mingzhi Zou and Zhenghang Yu and Yue Li and Zanlin Qiu and Xiucai Sun and Liu Qian and Jin Zhang}, doi = {10.1021/jacs.5c08656}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32752--32760}, shortjournal = {J. Am. Chem. Soc.}, title = {Triggering lattice oxygen release for semiconducting carbon nanotube array synthesis}, volume = {147}, year = {2025}, }
• (2025). Activation of semicore electrons in alkali metals and their role in the B1–B2 phase transition under pressure. JACS, 147(36), 32745--32751. (www)

  @article{ , abstract = {Alkali fluorides are often thought of as archetypical ionic compounds whose structures can be understood in terms of the packing of rigid spheres. At ambient pressure, they assume the rocksalt (B1) structure, while under only a few GPa of pressure, the cesium chloride (B2) structure, with higher coordination numbers, is assumed for KF, RbF, and CsF. NaF requires almost 10 times more pressure to undergo this same phase transition, which has not been observed for LiF. Herein, we provide a detailed analysis, based upon quantum chemical calculations, explaining this behavior. We show that for the heavier alkali metals, the semicore p orbitals engage in metal–metal bonding in the B2 phase, facilitating the pressure-induced B1 → B2 structural transition. These findings suggest that the semicore orbitals of heavy alkali metals can be activated without the need of strong oxidants at very mild levels of compression, resulting in the formation of chemical bonds, challenging both traditional and modern core–valence distinctions. In addition, we argue that Cs 5p–5p bonding in CsCl occurs already at ambient pressure, stabilizing the B2 phase, and suggest experiments that may be able to detect signatures of such bonding.}, archive = {J_JACS}, author = {Stefano Racioppi and Eva Zurek}, doi = {10.1021/jacs.5c08582}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32745--32751}, shortjournal = {J. Am. Chem. Soc.}, title = {Activation of semicore electrons in alkali metals and their role in the B1–B2 phase transition under pressure}, volume = {147}, year = {2025}, }
• (2025). The radical S-adenosyl-l-methionine enzyme HydE forms an Fe(I)Fe(I) dimer en route to the [FeFe] hydrogenase H-cluster. JACS, 147(36), 32737--32744. (www)

  @article{ , abstract = {[FeFe] hydrogenases are highly efficient metalloenzymes that catalyze hydrogen conversion via a sophisticated active site cofactor known as the H-cluster. Biosynthesis of its [2Fe] H subcluster, which contains CO, CN – , and azadithiolate ligands, requires the action of several dedicated enzymes, including the radical S -adenosyl- l -methionine (rSAM) enzyme HydE. HydE has been proposed to convert a mononuclear [Fe(II)(cysteinate)(CO) 2 (CN)] − precursor into a dimeric [Fe I 2 (SH) 2 (CO) 4 (CN) 2 ] 2– complex, yet direct characterization of this product species has remained elusive. Here, we report spectroscopic identification of the dimeric product of the HydE reaction in its one-electron oxidized, mixed-valent Fe 1.5+ Fe 1.5+ ( S = 1/2) state. Continuous wave and pulse 13 C ENDOR spectroscopy confirm the presence of two nonequivalent CN – ligands and delocalized spin density across the diiron core. Oxidation of a synthetic [Fe 2 (SH) 2 (CO) 4 (CN) 2 ] 2– complex reproduces similar electron paramagnetic resonance features only when it is preincubated with HydE, supporting in situ formation and stabilization of the dimer by the enzyme. These findings implicate the Fe I Fe I dimer as the terminal product of HydE and strongly suggest its central role in H-cluster assembly, expanding our understanding of rSAM enzyme catalysis in metallocofactor biosynthesis.}, archive = {J_JACS}, author = {Guodong Rao and Lizhi Tao and Xin Yu and Thomas B. Rauchfuss and R. David Britt}, doi = {10.1021/jacs.5c08533}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32737--32744}, shortjournal = {J. Am. Chem. Soc.}, title = {The radical S-adenosyl-l-methionine enzyme HydE forms an Fe(I)Fe(I) dimer en route to the [FeFe] hydrogenase H-cluster}, volume = {147}, year = {2025}, }
• (2025). Defect-engineered LaFeO3 stabilizing oxidized pt single-atom sites for low-temperature CO oxidation. JACS, 147(36), 32729--32736. (www)

  @article{ , abstract = {The inherent trade-off between activity and stability in platinum single-atom catalysts (SACs) poses a significant challenge for catalytic oxidation reactions. High-coordination Pt sites have good stability, but their overoxidation often passivates activity. In contrast, metastable low-coordination Pt structures typically display high activity but are prone to oxidation and aggregation under harsh conditions. Herein, we propose a defect-engineering strategy to address this dilemma by anchoring oxidized Pt single atoms onto vacancy LaFeO 3 (v-LaFeO 3 ) perovskite. The introduced La-vacancy substantially reduces the oxygen vacancy formation energy of LaFeO 3 , enhancing lattice oxygen mobility while preserving structural integrity. Pt single-atom sites with a high oxidation state (Pt 4+ ) are anchored on the support, and their coordination environments are optimized. The catalyst exhibits high and stable activity for CO oxidation without reduction pretreatment. The structural characterization and in situ experiments indicate that vacancies in LaFeO 3 positively regulate the electronic structure between the Pt and v-LaFeO 3 interface. The longer Pt–O bonds activate interface oxygen species, accelerate O 2 activation, and promote the cycling of CO oxidation. The oxidized Pt atoms and high coordination number enable its stability in long-term and high-temperature oxidation reactions. DFT calculations further verify the structure and reaction mechanism. This work demonstrates that precise control of support defects can concurrently optimize the electronic states and stability of SACs, offering a generalized paradigm for designing robust oxidation catalysts.}, archive = {J_JACS}, author = {Tao Gan and Lei Tao and Zedong Zhang and Awu Zhou and Yu Chen and Jiong Li and Shuo Zhang and Shixuan Du and Yadong Li}, doi = {10.1021/jacs.5c08521}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32729--32736}, shortjournal = {J. Am. Chem. Soc.}, title = {Defect-engineered LaFeO3 stabilizing oxidized pt single-atom sites for low-temperature CO oxidation}, volume = {147}, year = {2025}, }
• (2025). Concentrated zwitterion interfaces for selective promotion of electrochemical hydroxide oxidation. JACS, 147(36), 32717--32728. (www)

  @article{ , abstract = {The electrode/electrolyte interfacial structure is a seminal component that governs the activity of electrocatalytic water splitting, providing alternative approaches to electrocatalyst design. Herein, we demonstrate that a dense interface constituting of zwitterionic betaine could selectively accelerate the alkaline oxygen evolution reaction (OER) by 2 orders of magnitude in current. The hygroscopic betaine molecules not only bind water molecules strongly but also endow the underhydrated characteristics of the hydroxide anions that increase their activity coefficient. The underhydrated hydroxide anions can also be enriched within the inner Helmholtz plane, which forms the mixed hydroxide anion-betaine adsorbate layer that significantly increases the effective potential that drives the OER. This interface can further segregate the reactive zones to selectively promote hydroxide oxidation and retard the oxidative polymerization of neutral anilines for improving the durability by at least an order of magnitude, creating new possibilities for impure water electrolysis.}, archive = {J_JACS}, author = {Jianxiang Wu and Yuxin Chen and Wei Du and Yaming Hao and Shaoyan Wang and Ran Wang and Shuangshuang Cha and Xuejing Yang and Chang Yan and Cheng Lian and Honglai Liu and Ming Gong}, doi = {10.1021/jacs.5c08459}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32717--32728}, shortjournal = {J. Am. Chem. Soc.}, title = {Concentrated zwitterion interfaces for selective promotion of electrochemical hydroxide oxidation}, volume = {147}, year = {2025}, }
• (2025). Allenes as stimuli-responsive chromophores for visible to near-infrared optical modulation. JACS, 147(36), 32710--32716. (www)

  @article{ , abstract = {Despite their rigid, orthogonal π-systems and synthetic modularity, allenes remain underexplored in functional material design. Here, we report that tetraaryl-substituted allenes undergo clean and reversible protonation at the central sp-hybridized carbon, triggering substantial π-electron reorganization. To investigate how substitution patterns modulate the halochromic response, we synthesized a series of five tetraarylallenes, enabling a systematic structure–property relationship study of their optoelectronic behavior. Protonation induces large bathochromic shifts in absorption of up to 500 nm, with extinction coefficients exceeding 30,000 M – 1 cm – 1 in the near-infrared region. Frontier molecular orbital (FMO) analysis and time-dependent density functional theory (TD-DFT) calculations reveal pronounced delocalization upon protonation, resulting in polymethine-like electronic structures with tunable donor–acceptor character. Protonation occurs even with weak acids such as acetic acid, and the process remains fully reversible through base-mediated deprotonation. UV–vis-NIR spectroscopy and ultrafast transient absorption spectroscopy confirm the formation of charge-transfer states. These findings establish allenes as a synthetically accessible and tunable platform for reversible, stimuli-responsive optical modulation across the visible to NIR spectrum.}, archive = {J_JACS}, author = {Jiaoyan Zhao and Lin Jiao and Lilia Kinziabulatova and Tyler J. Williams and Rebecca M. Gracia and Anna Gartner and Troy A. Stich and Wendu Ding and Minjung Son and Cedric Schaack}, doi = {10.1021/jacs.5c08383}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32710--32716}, shortjournal = {J. Am. Chem. Soc.}, title = {Allenes as stimuli-responsive chromophores for visible to near-infrared optical modulation}, volume = {147}, year = {2025}, }
• (2025). Highly branched sulfated glycopolymers as mucin mimetics. JACS, 147(36), 32698--32709. (www)

  @article{ , abstract = {Mucins are highly complex glycoproteins that form protective and lubricating barriers around epithelial surfaces, e.g., in the respiratory tract, to protect against pathogens. The isolation and purification of natural mucins without compromising their structure and thus their properties remain challenging. Glycopolymers as mucin mimetics have shown great potential in biomedical research, for example, in mucosal barrier enhancement and respiratory disease treatment, or in improving surface lubrication and adhesion properties. Here, we introduce double-brushed mucin mimetic glycopolymers, replicating for the first time a structural design that more closely imitates key architectural features of natural mucins. By combining solid-phase synthesis of sequence-defined glycooligomers and their attachment onto polyactive ester scaffolds, we enable access to a library of linear, brushed, and double-brushed glycopolymers with controlled variations of structural parameters, such as overall chain length, number, and length of branches, as well as number of carbohydrates and degree of sulfation. By using light and neutron scattering as well as atomic force microscopy-based single-molecule force spectroscopy and imaging, we can demonstrate that the double-brushed architecture is responsible for successfully mimicking critical mucin properties, such as their adhesion to hydrophilic surfaces and an extended conformation, properties that are not achieved with single-brushed or linear analogues. Thus, our findings show that double-brushed sulfated glycopolymers effectively replicate key characteristics of natural mucins, advancing their potential as mucin models, as well as for use in biomedical applications.}, archive = {J_JACS}, author = {Melina I. Feldhof and Rebecca Schlatterer and Friederike Strahl and Jonathan Garthe and Sylvain Prévost and Stephan Schmidt and Matthias Karg and Bizan N. Balzer and Laura Hartmann}, doi = {10.1021/jacs.5c08232}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32698--32709}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly branched sulfated glycopolymers as mucin mimetics}, volume = {147}, year = {2025}, }
• (2025). A versatile one-pot strategy for thiazolylazo extensions: Visible light-driven photoswitches. JACS, 147(36), 32689--32697. (www)

  @article{ , abstract = {Among various azoheteroarenes, thiazolylazo derivatives have recently emerged as bidirectional visible-light switches. However, their widespread application as molecular photoswitches remains limited due to synthetic challenges like robust reaction conditions, lack of commercial availability of starting material, and low reaction yield. This work presents a straightforward one-pot methodology for synthesizing thiazolylazo derivatives by reacting 2-trimethylsilylthiazole with various diazonium salts. This approach offers mild reaction conditions, short reaction times, and moderate to good yields for different derivatives. Using this de novo synthesis strategy, we developed several new phenylazothiazole derivatives and asymmetric bis-heteroaryl azo compounds. The resulting thiazolylazo derivatives exhibit excellent E -to- Z isomerization under visible light, with a tunable thermal back-isomerization half-life ranging from seconds to days in acetonitrile. The prolonged thermal stability of the metastable isomers of these visible-light switches is attributed to specific noncovalent interactions in the transition state. Our method provides a versatile platform for late-stage thiazolylazo functionalization of complex ligands and drug molecules, paving the way for visible light switchable ligands in photopharmacological applications.}, archive = {J_JACS}, author = {Saugata Sahu and Nobuyuki Tamaoki}, doi = {10.1021/jacs.5c08259}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32689--32697}, shortjournal = {J. Am. Chem. Soc.}, title = {A versatile one-pot strategy for thiazolylazo extensions: Visible light-driven photoswitches}, volume = {147}, year = {2025}, }
• (2025). Elucidation of marcus relationships for hydride transfer reactions involving transition metal hydrides. JACS, 147(36), 32671--32688. (www)

  @article{ , abstract = {The rate of hydride transfer from three Ir hydride complexes of the type Cp*Ir( R bpy)H + (Cp* = C 5 Me 5 ; R bpy = 4,4′-R-2,2′-bipyridine, R = OMe, H, CO 2 Me) to six N -methylacridinium ( R Acr + ) acceptors with electronically different substituents in the 2- or 2,7-positions were measured. Using the thermodynamic hydricity of the donors and the hydride affinity of the acceptors the thermodynamic driving forces for hydride transfer were determined. Brønsted plots, which correlate kinetic and thermodynamic hydricity, demonstrate distinct linear free energy relationships for each complex, with different Brønsted α values. Thus, at the same driving force hydride transfer from Cp*Ir( OMe bpy)H + is faster than for Cp*Ir(bpy)H + or Cp*Ir( CO2Me bpy)H + . Experimental and computational analyses are consistent with a concerted hydride transfer mechanism for all Ir complexes. As the thermodynamic driving force increases an earlier transition state is observed and all transition states also include π-stacking interactions between the donor and acceptor, which likely contribute to the different α values. The experimental data fits well to the Marcus model, enabling the determination of reorganization energies (λ) that range from 58 to 69 kcal mol –1 . These are lower than λ values for hydride transfer reactions involving organic donors and acceptors. This work provides a rare example of the correlation of kinetic and thermodynamic hydricity using only experimental data and shows that hydride transfer reactions involving metal hydrides can follow Marcus theory. The findings offer insight into controlling metal-catalyzed hydride transfer reactions, which is valuable for designing improved systems for a range of transformations.}, archive = {J_JACS}, author = {Abhishek Kumar and Mehmed Z. Ertem and Nilay Hazari and Alexander J. M. Miller}, doi = {10.1021/jacs.5c08248}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32671--32688}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidation of marcus relationships for hydride transfer reactions involving transition metal hydrides}, volume = {147}, year = {2025}, }
• (2025). NRPStransformer, an accurate adenylation domain specificity prediction algorithm for genome mining of nonribosomal peptides. JACS, 147(36), 32662--32670. (www)

  @article{ , abstract = {Nonribosomal peptides serve as pivotal sources for drug discovery. Accurate prediction of the substrate specificity of adenylation domains in nonribosomal peptide synthetases is crucial for genome mining of nonribosomal peptides, yet current prediction methods fall short in accuracy. In this work, we analyzed 4,100 adenylation domains from documented nonribosomal peptide synthetases and found that the flavodoxin-like subdomain universally governs substrate specificity in all bacterial adenylation domains and that its phylogenetic analysis can correlate the sequences of adenylation domains and their substrate specificity. Leveraging the sequences within the flavodoxin-like subdomain, we developed a substrate specificity prediction algorithm using a protein language model, achieving 92% overall prediction accuracy for 43 frequently observed amino acids, significantly improving the prediction reliability. The efficacy of our prediction tool was validated through targeted genome mining, which led to the discovery of novel antimicrobial peptides. Our work lays a foundation to understand the sequence-to-function relationship of the bacterial adenylation domain and will facilitate the exploitation of nonribosomal peptides. NRPStransformer is available at http://www.nrpstransformer.cn .}, archive = {J_JACS}, author = {Zhihan Zhang and Yuyang Zhou and Shengling Xie and Run-Zhou Liu and Zilei Huang and Pachaiyappan Saravana Kumar and Guozhong Feng and Fajie Yuan and Lihan Zhang}, doi = {10.1021/jacs.5c08076}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32662--32670}, shortjournal = {J. Am. Chem. Soc.}, title = {NRPStransformer, an accurate adenylation domain specificity prediction algorithm for genome mining of nonribosomal peptides}, volume = {147}, year = {2025}, }
• (2025). Flame-made surface-substituted Copper–Ceria as an excellent reverse Water–Gas shift reaction catalyst via three reaction pathways. JACS, 147(36), 32649--32661. (www)

  @article{ , abstract = {The limited mechanistic understanding and ambiguous structure–performance relationships have hindered the optimization of Cu-based catalysts for the reverse water–gas shift (rWGS) reaction. Here, we report a flame spray pyrolysis (FSP)-derived Cu–CeO 2 catalyst featuring highly dispersed, surface-substituted Cu + species (Cu y Ce 1– y O 2– x ) anchored on a defect-rich ceria matrix. This catalyst demonstrates excellent stability and outstanding rWGS activity at 600 °C, achieving a CO production rate of 8094 mmol/g cat. /h, surpassing the conventional Cu–CeO 2 catalyst and other reported rWGS catalysts. In situ spectroscopic analyses, supported by DFT calculations, reveal three parallel reaction pathways in which carboxylate- and formate-mediated routes proceed at distinct active sites. A clear structure–activity correlation is established across Cu + , Cu 0 , and ceria defect sites in the FSP-derived catalysts. Notably, a previously underexplored carboxylate-mediated pathway, facilitated on the surface-substituted Cu + structure, is identified as the dominant route, featuring a significantly lower apparent activation energy (20–30 kJ/mol) compared to the classical formate pathway.}, archive = {J_JACS}, author = {Bingqiao Xie and Yi Fen Zhu and Mahdi Shakeri and Seongmin Jin and George O’Connell and Sankhadip Saha and Mounir Mensi and Priyank V. Kumar and Jeremy S. Luterbacher and Emma C. Lovell and Rose Amal and Oliver Kröcher}, doi = {10.1021/jacs.5c07701}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32649--32661}, shortjournal = {J. Am. Chem. Soc.}, title = {Flame-made surface-substituted Copper–Ceria as an excellent reverse Water–Gas shift reaction catalyst via three reaction pathways}, volume = {147}, year = {2025}, }
• (2025). Electrosynthesis of six-carbon acetal from CO2 using a tandem electrolysis. JACS, 147(36), 32640--32648. (www)

  @article{ , abstract = {The conversion of CO 2 into high-value chemicals using renewable electricity offers a promising pathway toward carbon neutrality and sustainable chemical production. However, efficiently transforming CO 2 into molecules with more than three carbon atoms remains a major challenge. Herein, we propose, for the first time, a tandem electrocatalytic strategy for converting CO 2 into the highly valuable six-carbon compound 1,1-diethoxyethane (DEE, valued at ∼$7,000 per ton). This approach couples CO 2 electroreduction to ethanol with the subsequent selective electro-oxidation of ethanol to DEE. Key limitations of the latter step, such as low Faradaic efficiency, poor catalyst durability, and dependence on noble metals, are addressed by employing a large-area (100 cm 2 ) electrochemically functionalized graphite flake electrode. This catalyst achieves high FE (>90% across a wide voltage range) and excellent stability (>140 h). Combined theoretical and experimental studies reveal that the COOH functional groups and carbon defects on the graphite synergistically modulate the adsorption of the key CH 3 CH 2 O* intermediate, reducing the energy barrier of the rate-determining step. Techno-economic and carbon footprint analyses further demonstrate the economic viability and carbon reduction potential of this tandem process, with an estimated net removal of ∼370 kg of CO 2 per ton of DEE produced.}, archive = {J_JACS}, author = {Haoyuan Chi and Zhanpeng Liang and Siyu Kuang and Yaxin Jin and Tiantian Xiao and Jianlong Lin and Dun Han and Lei Wang and Sheng Zhang and Xinbin Ma}, doi = {10.1021/jacs.5c07942}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32640--32648}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrosynthesis of six-carbon acetal from CO2 using a tandem electrolysis}, volume = {147}, year = {2025}, }
• (2025). Ultrathin hf-MOF with dinitrogen chelating sites stabilizing and inducing generation of single-rod Cs3Bi2Br9 nanocrystals for efficient photocatalytic CO2 reduction. JACS, 147(36), 32625--32639. (www)

  @article{ , abstract = {The ordered growth of semiconductor quantum dots (QDs) in confined environments remains a critical challenge in photocatalysis. Herein, Cs 3 Bi 2 Br 9 (CBB) QDs were covalently anchored as single-rod nanocrystals (SRNCs) within Hf-based metal–organic framework (MOF) nanosheets (Hf 12 -bpy, H 2 bpy = 2,2′-bipyridine-5,5′-dicarboxylic acid), forming a series of host–guest photocatalysts CBB@Hf 12 -bpy. By modulation of the thickness of MOF nanosheets, the length of CBB SRNCs was effectively shortened to 18 nm, exhibiting strong quantum confinement effects. Mechanistic studies reveal that the bpy-CBB dual-nitrogen chelation effect induces a discrete distribution of CBB within Hf 12 -bpy pores, and the well-matched interlayer spacing of H 2 bpy (7.95 Å ≈ d Bi···Bi ) guides the anisotropic growth of CBB along the [001] direction into SRNCs. Such a long-range-ordered SRNC architecture significantly improves the bulk-to-surface charge separation efficiency, enabling ultrafast electron supply (average charge excitation rate: 5.320 mV). Additionally, the chelated N–Bi–N moieties work as covalent electron-transfer bridges to markedly reduce charge-transfer resistance (7.75 Ω) and interfacial charge-transfer barriers (100.5 meV), accelerating interfacial charge migration kinetics. These synergistic advantages endow CBB@Hf 12 -bpy(18 nm) with an exceptional electron accumulation rate (1.54 g –1 ·min –1 ) and record-breaking CO 2 -to-CO conversion efficiency (15,982.1 μmol·g –1 ·h –1 ) with 100% selectivity. The durability, stability, and potential photocatalytic mechanisms were also systematically investigated.}, archive = {J_JACS}, author = {Ren Ma and Tianyu Wang and Baoyin Qian and Zhengqiang Xia and Sirong Chen and Weiliang Shi and Qi Yang and Gang Xie and Sanping Chen}, doi = {10.1021/jacs.5c08000}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32625--32639}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrathin hf-MOF with dinitrogen chelating sites stabilizing and inducing generation of single-rod Cs3Bi2Br9 nanocrystals for efficient photocatalytic CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). Photochemical generation of peroxynitrite: Concurrent inhibition of glycolysis and glutamine metabolism for enhanced metabolic therapy. JACS, 147(36), 32610--32624. (www)

  @article{ , abstract = {Disrupting homeostasis within tumor cells by interfering with their diverse metabolic pathways is an attractive tumor treatment method. However, current methods generally focus on one pathway within tumor cells, such as glycolysis or the glutamine (Gln) metabolic pathway, overlooking potential strong correlations between different cellular pathways and preventing a comprehensive blockade of the tumor energy supply, thereby compromising therapeutic efficacy. Herein, a photochemistry-activated peroxynitrite (ONOO – ) nanogenerator, capable of simultaneously inhibiting glycolysis and Gln metabolism in tumor cells, is proposed to achieve enhanced metabolic therapy. Specifically, the ONOO – nanogenerator is constructed by loading the thermally sensitive nitric oxide (NO) donor BNN-6 onto dual-function Prussian blue (PB) nanocubes through electrostatic interaction, followed by coating with tumor cell membranes to achieve homologous targeting. Under near-infrared light irradiation, PB decomposes hydrogen peroxide (H 2 O 2 ) to produce oxygen, while the converted heat induces BNN-6 decomposition to generate NO. Subsequently, NO reacts with oxygen to form nitrite, and then with H 2 O 2 to yield ONOO – under acidic conditions. ONOO – achieves simultaneous inhibition of glycolysis and Gln metabolism through the nitration of key proteins. More importantly, the former effectively reduces lactate levels, and the latter increases Gln levels, which both, in turn, remodel the tumor microenvironment and stimulate a strong immune response. The in vitro and in vivo data demonstrated that these changes significantly inhibited the growth and spread of primary and distant metastatic tumors in a mouse model. This approach takes advantage of tumor-specific physicochemical properties to enable localized and highly efficient ONOO – synthesis, offering promise for enhanced metabolic therapy.}, archive = {J_JACS}, author = {Lizhen Yuan and Liang Yang and Wen Song and Haoyang Song and Jing-Jing Hu and Xiaoding Lou and Fan Xia and Juyoung Yoon}, doi = {10.1021/jacs.5c07860}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32610--32624}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemical generation of peroxynitrite: Concurrent inhibition of glycolysis and glutamine metabolism for enhanced metabolic therapy}, volume = {147}, year = {2025}, }
• (2025). Tuning the conformations of an M4L4 cage and their impact on catalysis. JACS, 147(36), 32600--32609. (www)

  @article{ , abstract = {Enzymes catalyze chemical reactions with remarkable rate enhancements and selectivity. Supramolecular catalysis seeks to understand and emulate these outcomes, leveraging noncovalent interactions, electric fields, and controlled active site microenvironments to enhance catalysis in an enzyme-like fashion. The effects of conformational dynamics on supramolecular catalysts and assemblies are, however, relatively unexplored, despite their crucial role in enzyme rate enhancement. Here, we elucidate the conformational landscape of a model M 4 L 4 supramolecular host through a rational approach: stabilizing a high-energy conformer through distal ligand modification and a transient intermediate state through symmetry-matched guest encapsulation, as well as tuning the conformer distribution through same-charge metal exchange at the host vertices. Each of these structural modifications induces a substantial shift in the host’s conformational landscape, offering insights into the rational design of conformationally dynamic cages and enzymes. Although the thermodynamic properties of the dynamic Ga 4 L 4 12– cage can be influenced by temperature, solvent, and guest binding, we find that conformational change occurs on a time scale that renders it rate-limiting in a model catalytic reaction, precluding rate enhancement through conformational selection. This concept is illustrated by locking the catalytically inactive conformer to a high-energy conformer that is catalytically competent. These findings demonstrate that precise modulation of the conformational landscape of supramolecular hosts provides an effective strategy for controlling their catalytic activity and binding.}, archive = {J_JACS}, author = {Cristina V. Craescu and Sebastian Stahl and Thor Lucas F. Correia and Stephen M. Bierschenk and Nicholas S. Settineri and Robert G. Bergman and Kenneth N. Raymond and F. Dean Toste}, doi = {10.1021/jacs.5c07697}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32600--32609}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the conformations of an M4L4 cage and their impact on catalysis}, volume = {147}, year = {2025}, }
• (2025). High-pressure Mg3Cl7 synthesized in a diamond anvil cell as a polar metal with second-harmonic generation. JACS, 147(36), 32591--32599. (www)

  @article{ , abstract = {Polar metals have attracted growing interest due to both their significance in fundamental science and their potential functionalities. Here, we report the discovery of a novel polar metal, magnesium chloride Mg 3 Cl 7 , in which the metallicity of the polar structure is uniquely driven by attractive halogen interactions. Mg 3 Cl 7 was synthesized in laser-heated diamond anvil cells and observed at pressures of 28(2)–93(3) GPa. Synchrotron single-crystal X-ray diffraction revealed that the structure of the new compound has polar hexagonal space group P 6 3 mc , representing an example of a previously unknown anti -Th 7 Fe 3 structure type. Measurements of the physical properties have shown that the material is a metallic conductor capable of emitting second-harmonic generation light. Ab initio calculations support experimental findings and reveal complex halogen–halogen interactions, anionic metallicity, anisotropic electronic structure, and the presence of Dirac and Weyl points at the Fermi level. Our findings broaden the family of polar metals, provide new insight into halogen bonding under extreme conditions, and offer a platform for further exploration of materials’ unconventional electronic behavior.}, archive = {J_JACS}, author = {Yuqing Yin and Leonid Dubrovinsky and Ferenc Tasnádi and Igor A. Abrikosov and Andrey Aslandukov and Alena Aslandukova and Fariia Iasmin Akbar and Wenju Zhou and Florian Knoop and Dominique Laniel and Anna Pakhomova and Timofey Fedotenko and Konstantin Glazyrin and Gaston Garbarino and Haixing Fang and Natalia Dubrovinskaia}, doi = {10.1021/jacs.5c07812}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32591--32599}, shortjournal = {J. Am. Chem. Soc.}, title = {High-pressure Mg3Cl7 synthesized in a diamond anvil cell as a polar metal with second-harmonic generation}, volume = {147}, year = {2025}, }
• (2025). Cooperative steric modulation of flexibility, disorder, and pore size in two-dimensional covalent organic framework membranes for enhanced selective ion sieving. JACS, 147(36), 32580--32590. (www)

  @article{ , abstract = {The inherent flexibility of two-dimensional covalent organic frameworks (2D COFs), stemming from weak interlayer interactions, often leads to structural disorder that significantly impacts their properties and functionality. However, this intrinsic, solvent-dependent flexibility and disorder pose considerable challenges for the fabrication, processing, and application of 2D COF membranes, hindering both the reproducibility of membrane synthesis and their long-term performance stability. In this work, we address these challenges by precisely controlling the number of methyl groups on the amine monomers, skillfully leveraging steric hindrance effects. Furthermore, we exploit the influence of solvent polarity on the solvent-mediated equilibria between stable and metastable states to synergistically tune the flexibility, disorder, and pore size of the 2D COF membranes. This approach simultaneously reduces the pore size and enhances the framework’s solvent resistance, yielding methyl-functionalized 2D COF membranes that demonstrate preserved permeability homogeneity across different solvent treatments while enabling highly efficient U/Th ion separation.}, archive = {J_JACS}, author = {Yingdi Zou and Yingdan Zhang and Jie Zhang and Pan He and Zhiying Fan and Ningning He and Xuezhu Li and Yang Li and Lijian Ma}, doi = {10.1021/jacs.5c07154}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32580--32590}, shortjournal = {J. Am. Chem. Soc.}, title = {Cooperative steric modulation of flexibility, disorder, and pore size in two-dimensional covalent organic framework membranes for enhanced selective ion sieving}, volume = {147}, year = {2025}, }
• (2025). Potent inducers of paraptosis through electronic tuning of hemicyanine electrophiles. JACS, 147(36), 32571--32579. (www)

  @article{ , abstract = {Paraptosis is a distinct form of programmed cell death characterized by cytoplasmic vacuolization, mitochondrial swelling, and endoplasmic reticulum (ER) dilation, offering an alternative to apoptosis for therapeutic applications. In this study, we identified a hemicyanine derivative that is a potent paraptosis inducer in two cancer cell lines. This compound triggers hallmark paraptotic features, including ER swelling, mitochondrial morphological changes, increased superoxide production, and caspase-independent cell death. This activity is dependent on the ability of the probe to modify thiols covalently. Proteomic analysis using a biotinylated, activity-based probe revealed Sec23 homologue A and GDP-dissociation inhibitor alpha as potential targets implicated in paraptosis activation. This lead compound already displayed some degree of selectivity, exemplified by its minimal interaction with well-known nucleophilic protein targets such as protein disulfide isomerases. These findings establish the hemicyanine chemical family as a promising scaffold for paraptosis research and suggest potential as a therapeutic lead for diseases where traditional apoptosis pathways are dysregulated.}, archive = {J_JACS}, author = {Juan F. Tamez-Fernández and Craig F. Steven and Jade Nguyen and Pablo Rivera-Fuentes}, doi = {10.1021/jacs.5c07109}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32571--32579}, shortjournal = {J. Am. Chem. Soc.}, title = {Potent inducers of paraptosis through electronic tuning of hemicyanine electrophiles}, volume = {147}, year = {2025}, }
• (2025). Visualization of total synthesis from au11 to au13 nanoclusters. JACS, 147(36), 32560--32570. (www)

  @article{ , abstract = {The emergence of geometrically related Au 11 and Au 13 nanoclusters (NCs), both possessing a valence electron count of 8e, has substantiated the feasibility of chemically preparing reduced metal nanoclusters. Nevertheless, a significant challenge remains: the dynamic transformation pathways governing their structural evolution have remained elusive, severely impeding precise atomic-level control in NCs synthesis. Herein, we present a large conjugated quinoline thiol ligand with protonatable sites, which enables the systematic construction of seven structurally related Au 11–13 NCs. For the first time, this approach achieves continuous visualization of the total synthesis and core–shell evolution process from Au 11 to Au 13 NCs. Notably, we successfully synthesized and characterized a metastable corner-missing gold icosahedron Au 12 NC (Au@Au 11 ) as a key intermediate through crystallographic methods. These advancements provide unprecedented insights into the nucleation mechanism of classical icosahedral Au NCs, particularly by elucidating how ligand-shell modifications precisely influence geometric rearrangement, electronic structure, and functional performance. The stepwise reaction pathways demonstrated in the Au 11–13 NC series illustrate that metal NC synthesis can achieve organic chemistry-level precision when guided by strategic ligand engineering.}, archive = {J_JACS}, author = {Xue-Jing Zhai and Meng-Yu Luo and Xi-Ming Luo and Di Cheng and Meng Guo and Kai-Xin Sun and Yubing Si and Zhen Han and Jia-Hong Huang and Shuang-Quan Zang and Thomas C. W. Mak}, doi = {10.1021/jacs.5c06543}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32560--32570}, shortjournal = {J. Am. Chem. Soc.}, title = {Visualization of total synthesis from au11 to au13 nanoclusters}, volume = {147}, year = {2025}, }
• (2025). Determination of mn valence states in nanocatalysts during sustainable syngas conversion. JACS, 147(36), 32548--32559. (www)

  @article{ , abstract = {Constructing structure–activity relationships (SAR) between nanocatalysts under reactive atmospheres makes them indispensable for chemical synthesis, energy transformation, and environmental remediation. However, this structure sensitivity remains ambiguous for metals/metal oxides due to dynamic changes in metal valences under a reductive atmosphere. Herein, this study delves into the complexities of Mn-based nanocatalysts, focusing on the impact of the Mn valence state in a test reaction converting sustainable syngas to aromatics-a process highly sensitive to the catalyst’s redox environment and active site characteristics. We conducted a thorough SAR analysis and discovered a direct correlation between the Sabatier effect, CO adsorption, and the space-time yields of aromatics. Notably, Mn in the +2-oxidation state emerged as the optimal valence for achieving the highest catalytic performance, with a maximum yield of 1.6 mmol·h –1 ·g cat –1 . Our findings provide critical insights into the role of the catalyst’s intrinsic properties in dictating the selectivity and efficiency of CO hydrogenation for the rational design of nanocatalysts that can sustainably transform small molecules into valuable chemicals and fuels.}, archive = {J_JACS}, author = {Zhiping Li and Duohua Liao and Guo Tian and Xiaoyu Fan and Xu Chai and Wenxi Chang and Yuan Gao and Bo Yuan and Zonglong Li and Fei Wei and Chenxi Zhang}, doi = {10.1021/jacs.5c06550}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32548--32559}, shortjournal = {J. Am. Chem. Soc.}, title = {Determination of mn valence states in nanocatalysts during sustainable syngas conversion}, volume = {147}, year = {2025}, }
• (2025). Interactions of aqueous microdroplets and mineral particles drive fluorine-first perfluoroalkyl mineralization. JACS, 147(36), 32537--32547. (www)

  @article{ , abstract = {Anthropogenic perfluoroalkyl and polyfluoroalkyl substances (PFAS) are pervasive contaminants subject to increasingly stringent regulatory thresholds in water resources. Current nonthermal defluorination strategies face critical limitations, including incomplete mineralization, yielding persistent short-chain PFAS byproducts, and residual fluoride ions, thereby hindering compliance with water quality standards. Herein, we demonstrate that wollastonite-bearing microdroplets prioritize defluorination over C–C scission in perfluoroalkyl chains through liquid–solid–gas triple-phase contact electrification. This process results in complete perfluorooctanoic acid mineralization with hardly detectable shorter-chain anionic PFAS byproducts, as confirmed by Fourier transform ion cyclotron resonance mass spectrometry. Microdroplet-mediated weathering of wollastonite triggers the formation of CaF 2 –SiO 2 interfacial structures through Si–F–Ca bonding interactions, thereby enabling fluoride immobilization with negligible leaching. This work reveals that atmospheric clouds containing mineral particles intrinsically exhibit a self-cleansing capacity toward PFAS contaminants, advancing cloud-inspired interfacial engineering for next-generation water purification systems.}, archive = {J_JACS}, author = {Yifan Yang and Jianhan Wu and Zhendong Luo and Xiuquan Jia and Guibin Jiang and Feng Wang}, doi = {10.1021/jacs.5c06438}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32537--32547}, shortjournal = {J. Am. Chem. Soc.}, title = {Interactions of aqueous microdroplets and mineral particles drive fluorine-first perfluoroalkyl mineralization}, volume = {147}, year = {2025}, }
• (2025). Overcoming immune checkpoint inhibitor resistance with potent, selective dual αvβ6/8 inhibitors based on engineered lasso peptides. JACS, 147(36), 32522--32536. (www)

  @article{ , abstract = {Integrins αvβ6 and αvβ8 in the tumor microenvironment (TME) have been shown to activate immunosuppressive TGF-β, which serves as an important mechanism for immune checkpoint inhibitor resistance in a range of tumors. In this study, we demonstrate the utility of lasso peptides as versatile scaffolds for the design of new therapeutics. A series of highly potent and selective dual αvβ6/8 inhibitors were engineered through a combination of epitope scanning, computational design, and directed evolution, whereby inhibition was fine-tuned for two out of the eight related RGD-integrin receptors. NMR structures of two lasso peptide dual integrin inhibitors are provided. Facile conjugation chemistry with a small-molecule albumin binder afforded half-life extended lasso peptide analogs, including 19 , which was fully characterized and shown to robustly and durably halt growth and regress anti-mPD-1-resistant ovarian and triple negative breast cancer tumors in mice when dosed in combination with the checkpoint inhibitor. These studies show that dual inhibition of αvβ6/8 integrins expressed in the TME represents an auspicious tumor-specific strategy to overcome TGF-β-driven resistance and enhance the antitumor efficacy of immune checkpoint inhibitors. Our ability to produce lasso peptides with high titers in fermenters has enabled the first detailed demonstration of their drug-like properties, including tunable in vivo pharmacokinetics and efficacy, thus paving the way for future advances using this promising modality derived from nature.}, archive = {J_JACS}, author = {Anna Lechner and Peter A. Jordan and Gabriella Costa Machado da Cruz and Jacob Lamson and Jessica Gordon and Bethany K. Okada and Kelsey Anderson and Rajan Chaudhari and Christopher J. Rosario and Jasmine Mikesell and Scott A. McPhee and Mark J. Burk}, doi = {10.1021/jacs.5c06142}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32522--32536}, shortjournal = {J. Am. Chem. Soc.}, title = {Overcoming immune checkpoint inhibitor resistance with potent, selective dual αvβ6/8 inhibitors based on engineered lasso peptides}, volume = {147}, year = {2025}, }
• (2025). Computational exploration of polymer mechanochemistry: Quantitation of activation force and systematic discovery of reaction sites by the extended artificial force-induced reaction method. JACS, 147(36), 32502--32521. (www)

  @article{ , abstract = {A collection of mechanophores was computationally studied using the extended artificial force induced reaction (EX-AFIR) method, which utilizes two different sets of forces to determine the activation force level ( F act ) practically and efficiently. Identifying a mechanophore’s F act is a focus of mechanochemistry. As have been done in an existing framework, we generated the Δ G τ ‡ – F τ curve, where F τ is the value of external force and Δ G τ ‡ denotes the force-coupled free energy barrier of a specific reaction under F τ . Such a curve is then used to determine the F act of a certain mechanophore when combined with the Eyring equation. Although generating such a Δ G τ ‡ – F τ curve was tough because locating the force-coupled transition states is time-consuming, the extended AFIR method allowed an efficient exploration of all the relevant transition states on the force-modified potential energy surface (FMPES). The EX-AFIR method was later applied to study the problems encountered in current polymer mechanochemistry research, deriving a concept of “node” which could be used for the design of thermostable mechanophores. The first-ever case study of cubane using EX-AFIR is a vivid example of how the fully automated search of possible reaction pathways on the FMPES is facilitated. Furthermore, it also provided insights into the further design and application of unconventional mechanophores.}, archive = {J_JACS}, author = {Julong Jiang and Koji Kubota and Yu Harabuchi and Mingoo Jin and Zhi Jian Wang and Tasuku Nakajima and Hajime Ito and Jian Ping Gong and Satoshi Maeda}, doi = {10.1021/jacs.5c06150}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32502--32521}, shortjournal = {J. Am. Chem. Soc.}, title = {Computational exploration of polymer mechanochemistry: Quantitation of activation force and systematic discovery of reaction sites by the extended artificial force-induced reaction method}, volume = {147}, year = {2025}, }
• (2025). Constructing monolayer fe clusters as model catalysts for CO2 electroreduction. JACS, 147(36), 32494--32501. (www)

  @article{ , abstract = {Constructing model catalysts to clarify the active sites and elucidate structure–activity relationships represents a bottleneck issue in electrocatalytic reactions. For instance, Fe-based materials have been widely investigated for various electrocatalytic reactions, e.g., CO 2 electroreduction (CO 2 RR). However, the precise role of Fe in the catalytic mechanism remains debated and is under extensive investigation due to the complex properties of those catalysts. Herein, we successfully construct a series of monolayer Fe clusters (ML-Fe) on a single-crystal Au(111) substrate via vapor deposition under ultrahigh vacuum (UHV) conditions, which serve as model catalysts for CO 2 RR. Notably, the size of Fe clusters can be tuned at the atomic scale (∼2 nm) as observed by scanning tunneling microscopy (STM). Experimental and theoretical calculations demonstrate that ML-Fe achieves >60% Faradaic efficiency (FE) for CO production during CO 2 RR. When the Fe layer further increases to form nanoparticles, Fe sites exhibit stronger electron interaction and binding strength with *CO intermediates, consequently shifting the dominant reaction pathway from CO 2 RR to hydrogen evolution (HER). This work could provide valuable insights into designing model catalysts with well-defined active sites to investigate the structure–activity relationships in diverse electrocatalytic systems.}, archive = {J_JACS}, author = {Hengpan Yang and Huizhu Cai and Kai Song and Sizhen He and Shangzhao Feng and Zhi Chen and Xue Zhang and Qi Hu and Chuanxin He}, doi = {10.1021/jacs.5c05325}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32494--32501}, shortjournal = {J. Am. Chem. Soc.}, title = {Constructing monolayer fe clusters as model catalysts for CO2 electroreduction}, volume = {147}, year = {2025}, }
• (2025). Trisilylation of a formal Cr(−I) bis-dinitrogen complex. JACS, 147(36), 32480--32493. (www)

  @article{ , abstract = {The long-sought goal of dinitrogen (N 2 ) fixation chemistry is to effect facile synthesis of nitrogen-containing chemicals directly from N 2 . To date, electrophilic attack of coordinated N 2 ligands of transition metal dinitrogen complexes represents the most straightforward route to construct nitrogen-element bonds. Although electrophilic functionalization of monodinitrogen complexes to furnish diazenido and hydrazido species has been well-documented, for those complexes containing multiple N 2 moieties, analogous reactions invariably lead to N 2 extrusion and at most one N 2 can be derivatized. Herein, we describe electrophilic functionalization of a mononuclear formal chromium(−I) bis-dinitrogen complex supported by a PCP-pincer ligand. Specifically, treatment with TMSCl (TMS = SiMe 3 ) results in silylation of its two N 2 ligands and clean formation of a Cr(IV) complex bearing a diazenido and a hydrazido unit en route from a Cr(II) bis-diazenido intermediate, alongside a Cr(IV) monohydrazido species in a 1:1 ratio. This is the first time that functionalization of two N 2 ligands on a single metal center has been realized. In contrast, the reaction using TMSOTf instead of TMSCl as the electrophile generates a Cr(III) hydrazido complex. On the basis of detailed analyses of the electronic structure evolution during the trisilylation reaction using highly correlated wave function-based ab initio approaches, we identify a necessary condition for functionalization of two N 2 ligands, viz., bis-dinitrogen complexes ought to feature noncompetitive eight-electron M-(N 2 ) 2 π-backdonation. To satisfy this requirement, how to design appropriate dinitrogen complexes to effect this challenging transformation is discussed.}, archive = {J_JACS}, author = {Botao Wu and Wang Chen and Haihan Yan and Xinchao Zhang and Junnian Wei and Zhenfeng Xi and Gao-Xiang Wang and Shengfa Ye}, doi = {10.1021/jacs.5c05591}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32480--32493}, shortjournal = {J. Am. Chem. Soc.}, title = {Trisilylation of a formal Cr(−I) bis-dinitrogen complex}, volume = {147}, year = {2025}, }
• (2025). Chemistry of sugar formation in the gas phase: Following the activated aldehyde. JACS, 147(36), 32468--32479. (www)

  @article{ , abstract = {Sugars are produced by living organisms, and are required building blocks for life as we know it, which raises the foundational question of how sugars formed in a prebiotic environment. The abiotic formose reaction produces sugars from formaldehyde, but our understanding of its initiation step remains murky, with chemists invoking the concept of an “activated aldehyde” to seed this reaction. Singlet hydroxycarbenes, high-energy isomers of aldehydes, were recently reported to facilitate sugar formation under cold, nonaqueous conditions relevant to interstellar environments. We generate singlet methylhydroxycarbene ( 1 CH 3 –C̈–OH) from the photodissociation of pyruvic acid and experimentally measure its gas-phase reaction with d 4 -acetaldehyde using multiplexed photoionization mass spectrometry. The C 4 H 4 D 4 O 2 isomer d 4 -acetoin is the sole product, which we kinetically link to the reactant CH 3 –C̈–OH, and attribute to a carbonyl-ene formation mechanism. We see no evidence of 3-hydroxybutanal, the C–H insertion product expected in carbene chemistry. Using automated exploration we calculate stationary points on the potential energy surface and report master equation rate coefficients from T = 20–600 K, providing quantitative kinetics of this fast reaction for use in chemical models. The prereactive complex in this reaction is stabilized by both hydrogen bonding and electrophilic carbene C═O interactions. These effects create a short-range dynamical bottleneck for the reaction besides the long- and midrange barrierless bottlenecks. Combined with recent reports of 1 HC̈OH production from methanol photodissociation and pyruvic acid production in cold irradiated ices, this work provides evidence that singlet hydroxycarbene + aldehyde chemistry is a feasible path to prebiotic sugar formation.}, archive = {J_JACS}, author = {David L. Osborn and Clément Soulié and Bibek R. Samanta and Hanna Reisler and Judit Zádor}, doi = {10.1021/jacs.5c05357}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32468--32479}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemistry of sugar formation in the gas phase: Following the activated aldehyde}, volume = {147}, year = {2025}, }
• (2025). Cosmic blueprint to nanoscale design: Hoag’s object-like polyoxovanadate encapsulated by a hierarchical silver nanocluster. JACS, 147(36), 32458--32467. (www)

  @article{ , abstract = {The pervasive presence of toroidal architectures across scales, from molecular assemblies to cosmic formations, reveals a universal design principle that integrates aesthetic symmetry with functional topology in nature. Yet, constructing such hierarchical toroidal organization at the nanoscale, particularly for metal nanoclusters, remains an unmet challenge. We present an unprecedented wheel-shaped silver nanocluster, [(V 6 O 19 ⊂V 22 O 66 )@Ag 96 ( t BuPhC≡C) 56 (SO 4 ) 2 (DMF) 12 ] 6+ ( Ag96 ), encapsulating an unparalleled hierarchical toroidal [V 6 O 19 ⊂V 22 O 66 ] 30– polyoxovanadate (POV). The hierarchical toroidal [V 6 O 19 ⊂V 22 O 66 ] 30– mirrors the core–shell geometry of Hoag’s Object, a rare ring galaxy, with a Lindqvist-type [V 6 O 19 ] 8– core enclosed by a macrocyclic [V 22 O 66 ] 22– shell. This work constitutes a unique astronomical morphology in coinage metal nanoclusters, uncovering the universal principles of hierarchical self-assembly at the nanoscale. Leveraging the flexibility of POVs, we further isolated a bowl-shaped [(SO 4 @V 15 O 42 )@Ag 46 ( t BuPhC≡C) 31 (DMF) 2 ] 4+ ( Ag46 ), encapsulating an open-cage [SO 4 @V 15 O 42 ] 11– template by regulating the stoichiometric ratio. Due to their distinct structural configurations, these nanoclusters exhibit markedly different photothermal conversion performance when exposed to visible or near-infrared (NIR) lasers. This breakthrough positions POVs as versatile templates for engineering complex metal nanoclusters, opening new frontiers in materials science and nanotechnology.}, archive = {J_JACS}, author = {Wei-Dan Si and Hao Liang and Seung-Hyun Ji and Taeyeon Kim and Chengkai Zhang and Zhi Wang and Hai-Feng Su and Chen-Ho Tung and Di Sun}, doi = {10.1021/jacs.5c04995}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32458--32467}, shortjournal = {J. Am. Chem. Soc.}, title = {Cosmic blueprint to nanoscale design: Hoag’s object-like polyoxovanadate encapsulated by a hierarchical silver nanocluster}, volume = {147}, year = {2025}, }
• (2025). Spatiotemporally resolved imaging of adenosine in the mouse brain links depression and inflammation. JACS, 147(36), 32447--32457. (www)

  @article{ , abstract = {Depression disrupts central nervous system function and may further elevate the risk of systemic diseases by triggering inflammatory responses. However, the precise mechanisms underlying its role in driving inflammation remain elusive. Adenosine (Ado), a critical molecule in depression, exhibits abnormal concentration changes that are closely associated with neuroinflammation. Thus, precise imaging of adenosine in the whole brain is essential for unraveling the mechanisms linking depression and inflammatory responses. However, current biosensors face limitations in whole-brain adenosine imaging. To address this limitation, a fluorescent nanoprobe with high spatiotemporal resolution was developed. The nanoprobe incorporates a targeting unit consisting of ferrocene-containing aptamers and phospholipid vesicles, ensuring excellent blood–brain barrier (BBB) penetration and high specificity for adenosine detection. Additionally, the nanoprobe features a near-infrared (NIR)-activated light-switching unit, enabling precise and real-time imaging of adenosine dynamics. The results revealed that adenosine activates the A 2A receptor (A 2A R) and downstream extracellular signal-regulated kinase 1/2 (ERK1/2) signaling pathway, inducing the secretion of proinflammatory cytokines by microglia and driving neuroinflammation. Elevated levels of inflammatory cytokines in the blood of depressed mice further suggest that depression may exacerbate systemic disease risk via peripheral inflammation. In summary, this nanoprobe not only achieves high spatiotemporal resolution imaging of adenosine in the brain but also serves as a powerful tool for elucidating the inflammatory mechanisms linking depression to systemic diseases.}, archive = {J_JACS}, author = {Mengge Chu and Lei Zhang and Xuemei Yang and Cailing Ji and Weihong Tan and Jie Tan and Quan Yuan}, doi = {10.1021/jacs.5c04376}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32447--32457}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatiotemporally resolved imaging of adenosine in the mouse brain links depression and inflammation}, volume = {147}, year = {2025}, }
• (2025). Solid-state 2H NMR analysis for hierarchical water clusters confined to quasi-one-dimensional molecular nanoporous crystals. JACS, 147(36), 32440--32446. (www)

  @article{ , abstract = {Water confined to the quasi-one-dimensional hydrophilic molecular nanoporous crystal of {[Co II (H 2 bim) 3 ](TMA)·20H 2 O} n ( 1 ) (H 2 bim = 2,2′-biimidazole, TMA 3– = trimesate) forms dynamic water molecule clusters (WMCs) with a hierarchical three-layered hydrogen-bonding (H-bonding) structure and a time-averaged structure in the melting state due to interactions with the walls of the ∼1.6 nm nanopores. This was first revealed by measuring the solid-state 2 H NMR spectra of a single crystal of {[Co III (D 2 bim) 3 ](TMA)·20D 2 O} n ( 1′ ), which revealed distinct hierarchical peaks of H 2 O H-bonding interactions. In addition, the frozen WMCs in 1 exhibit a premelting state, retaining some ice structures, just before melting through a first-order phase transition during the heating process. Measurements of the spin–lattice relaxation time ( T 1 ) in solid-state 2 H NMR revealed rapid rotation motions for water molecules in these premelting WMCs, resulting in a correlation time τ closer to that of bulk liquid water.}, archive = {J_JACS}, author = {Tomoya Namiki and Akira Saito and Fumiya Kobayashi and Takuya Kurihara and Motohiro Mizuno and Makoto Tadokoro}, doi = {10.1021/jacs.5c04573}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32440--32446}, shortjournal = {J. Am. Chem. Soc.}, title = {Solid-state 2H NMR analysis for hierarchical water clusters confined to quasi-one-dimensional molecular nanoporous crystals}, volume = {147}, year = {2025}, }
• (2025). Ultralow content of chromium species in zeolite for efficient catalytic propane dehydrogenation. JACS, 147(36), 32432--32439. (www)

  @article{ , abstract = {Supported chromia catalysts have been commercially used in propane dehydrogenation, which relies on Cr loading at weight fractions of up to 20 wt %. This leads to problems in managing spent catalysts with a high content of toxic chromium species. These catalysts also rapidly deactivate within 10–15 min, requiring frequent regeneration in each cycle. To overcome these problems, we developed a siliceous MFI zeolite with an ultralow Cr content (e.g., 0.09 wt %) that exhibits high activity and durability for propane dehydrogenation. A mechanism study revealed that the chromic hydroxyl species readily dissociated the C–H bonds, accelerating the rapid desorption of propylene products and resulting in a slow deactivation rate. Therefore, the catalyst lifetime can be prolonged to more than 30 days under mild operating conditions (525 °C).}, archive = {J_JACS}, author = {Hang Zhou and Guodong Qi and Yueying Chu and Liang Wang and Yu Hui and Zhangyi Yao and Feng Ryan Wang and Shengqi Chu and Yucai Qin and Lijuan Song and Lu Liu and Xuedi Qin and Jun Xu and Feng Deng and Feng-Shou Xiao}, doi = {10.1021/jacs.5c04531}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32432--32439}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultralow content of chromium species in zeolite for efficient catalytic propane dehydrogenation}, volume = {147}, year = {2025}, }
• (2025). Rolling circle amplification with an expanded genetic alphabet (ExRCA) generates DNA materials incorporating additional building blocks for enhanced programmable functionalization. JACS, 147(36), 32412--32431. (www)

  @article{ , abstract = {The development of unnatural base pairs (UBPs) has expanded the genetic alphabet, resulting in a tremendous increase in the information capacity and function diversity of DNA. Efficient amplification of DNA containing UBPs is crucial for the broad use of the UBPs. As one of the major methods for DNA amplification, rolling circle amplification has been extensively employed in many fields ranging from biotechnology to DNA nanotechnology. Herein, we explored and revealed the good efficiency and fidelity of the phi29 DNA polymerase for replicating a representative UBP, dNaM-dTPT3, and its analogues. Based on this, we established the method of rolling circle amplification with an expanded genetic alphabet (ExRCA), together with several strategies for preparing the circular templates for ExRCA. We next demonstrated the application of ExRCA for the mass production or amplification of single- and double-stranded DNAs containing an unnatural base or UBP, as well as the use of the single-stranded DNA product for constructing a site-specifically labeled DNA tetrahedron. The great application potential of ExRCA in biotechnology and materials science of DNA was further demonstrated by utilizing ExRCA to develop an ultrasensitive method for biomolecule detection, DNA hydrogels site-specifically loaded with various cargos, programmable multivalent aptaprobes, a fine-tuned DNA cascade catalyst, and a functional DNA hydrogel with site-specific cross-links. This work not only offers an efficient method for isothermal amplification of DNA containing unnatural nucleobases but also exhibits the unique value of the UBPs with natural-like replication efficiency in constructing DNA materials with increased number of building blocks and programmable functionalities.}, archive = {J_JACS}, author = {Leli Peng and Fangkai Ye and Ruimin Zhang and Yuhui Du and Qiaoling Liu and Rujie Zhang and Binliang Zhang and Tingjian Chen}, doi = {10.1021/jacs.5c03404}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32412--32431}, shortjournal = {J. Am. Chem. Soc.}, title = {Rolling circle amplification with an expanded genetic alphabet (ExRCA) generates DNA materials incorporating additional building blocks for enhanced programmable functionalization}, volume = {147}, year = {2025}, }
• (2025). On-cell saturation transfer difference NMR spectroscopy on ion channels: Characterizing negative allosteric modulator binding interactions of P2X7. JACS, 147(36), 32400--32411. (www)

  @article{ , abstract = {P2X7 receptors are important drug targets involved in pathologies ranging from psychiatric disorders to cancer. Being membrane embedded receptors, they are more challenging for structural characterization, and at present, we only have a small number of X-ray and cryo-EM structures for P2X7 bound to antagonists. We demonstrate that saturation transfer difference (STD) NMR on live mammalian cells (on-cell STD NMR) overexpressing P2X7 receptors allows further structural insight on the complexes of P2X7 with two potent negative allosteric modulators, namely, AZ10606120 and JNJ-47965567, via the determination of the binding epitope mapping of the interactions, e.g., the main region of contact between the ligand and the binding pocket. This approach, reported for the first time on membrane-embedded ion channels, in combination with molecular docking, allows us to propose the first NMR-validated ligand binding models for two antagonists as bound to human P2X7 receptors and to correlate the structural knowledge acquired with the pharmacology data. We highlight the transformative potential of this application to aid drug design efforts in a less resource-demanding fashion than X-ray crystallography and cryo-EM, and we envisage on-cell STD NMR to fast become an asset for structure–activity relationship studies helping knowledge-based development of efficient drugs targeting P2X7 and other ion channels/membrane-embedded proteins.}, archive = {J_JACS}, author = {Serena Monaco and Jacob Browne and Matthew Wallace and Jesús Angulo and Leanne Stokes}, doi = {10.1021/jacs.5c02985}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32400--32411}, shortjournal = {J. Am. Chem. Soc.}, title = {On-cell saturation transfer difference NMR spectroscopy on ion channels: Characterizing negative allosteric modulator binding interactions of P2X7}, volume = {147}, year = {2025}, }
• (2025). Enhanced single-molecule imaging via intersystem crossing suppression. JACS, 147(36), 32389--32399. (www)

  @article{ , abstract = {The red-emitting cyanine dye Cy5 is widely used in single-molecule imaging, but its utility is limited by triplet-state accumulation. This state facilitates energy transfer to molecular oxygen, producing reactive oxygen species (ROS) that lead to photobleaching. The triplet state also causes the dye’s fluorescence intermittency and introduces temporal noise. Furthermore, Cy5 in this state is susceptible to nucleophilic attacks in cellular environments, resulting in an inactive off-state. To address these challenges, we engineered a series of phenyl-substituted meso-Cy5 derivatives to suppress intersystem crossing (ISC) and effectively reduce the triplet-state population. Theoretical calculations and transient absorption spectroscopy validated the suppression of ISC in these derivatives. Our lead compound, Cy5-N, featuring an electron-withdrawing nitro modification on the phenyl group, demonstrated a 790% increase in photostability and a 2.3-fold improvement in the signal-to-noise ratio (SNR) compared to conventional Cy5 in single-molecule imaging. Notably, Cy5-N maintained continuous emission even in the presence of the nucleophile β-mercaptoethanol (β-ME), indicating robust resistance to nucleophilic attacks. Using Cy5-N, we successfully performed long-term single-molecule tracking of membrane proteins in live U2OS cells, with enhanced SNR. This study introduces a novel molecular design strategy for enhancing cyanine dye performance in single-molecule imaging, offering substantial improvements in photostability and SNR with broad implications for bioimaging and sensing technologies.}, archive = {J_JACS}, author = {Fan Ding and Song Chen and Fei Du and Congfu Shen and Kuangshi Sun and Tianli Zhai and Yao Tang and Fei Zhao and Yunxiang Zhang and Qian Liu}, doi = {10.1021/jacs.5c02236}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32389--32399}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced single-molecule imaging via intersystem crossing suppression}, volume = {147}, year = {2025}, }
• (2025). Generative design of functional metal complexes utilizing the internal knowledge and reasoning capability of large language models. JACS, 147(36), 32377--32388. (www)

  @article{ , abstract = {Large language models (LLMs) have shown promise in science, such as structure–property prediction and acting as AI agents, yet their intrinsic knowledge and reasoning capability for scientific discovery remains underexplored. We introduce LLM-EO, an integration of LLMs into evolutionary optimization, and demonstrate its success in optimizing transition metal complexes (TMCs). LLM-EO demonstrates advantages in few-sample learning due to the intrinsic chemical knowledge embedded within LLMs and their ability to leverage entire historical data collected during optimizations. Through natural language instructions, LLM-EO offers enhanced accessibility for multiobjective optimizations, potentially lowering barriers for experimental chemists without extensive programming expertise. As generative models, LLM-EO possesses the capability to propose novel ligands and TMCs with unique chemical properties by amalgamating both internal knowledge and external chemistry data, thus combining the benefits of efficient optimization and generation. With advancements in LLMs, both in their capacity as pretrained foundational models and new strategies in post-training inference, we anticipate broad applications of LLM-EO in chemistry and materials design.}, archive = {J_JACS}, author = {Jieyu Lu and Zhangde Song and Qiyuan Zhao and Yuanqi Du and Yirui Cao and Haojun Jia and Chenru Duan}, doi = {10.1021/jacs.5c02097}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32377--32388}, shortjournal = {J. Am. Chem. Soc.}, title = {Generative design of functional metal complexes utilizing the internal knowledge and reasoning capability of large language models}, volume = {147}, year = {2025}, }
• (2025). Asymmetric total synthesis of (−)-psychotriadine featuring [3,3]-rearrangement and stereo-controllable ring-contraction. JACS, 147(36), 32370--32376. (www)

  @article{ , abstract = {The first asymmetric total syntheses of (−)-psychotriadine ( 1 ) and its putative congener tetrahydropsychotriadine ( 2 ) were accomplished in 12 and 13 steps, respectively, featuring Meerwein–Eschenmoser–Claisen rearrangement and Fischer indolization/Plancher rearrangement cascade. A stereochemically controllable dearomative ring contraction was utilized to create the vicinal quaternary stereocenters. The absolute configuration was confirmed through X-ray crystallography and >200 mg of 1 (90% enantiomeric excess (ee)) was obtained. Biological studies revealed that natural product precursor S-10 acts as an agonist toward liver X receptors (LXRs, K D = 1.22/0.79 μM), which upregulates protein levels of ABCA1 and APOE, exhibiting potential as a drug lead in developing medicine for Alzheimer’s disease.}, archive = {J_JACS}, author = {Qingxing Yang and Hanyi Ouyang and Haiyong Yu and Fashun Li and Tao Xu}, doi = {10.1021/jacs.5c11779}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32370--32376}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric total synthesis of (−)-psychotriadine featuring [3,3]-rearrangement and stereo-controllable ring-contraction}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of (−)-psathyrin a enabled by radical cyclization. JACS, 147(36), 32365--32369. (www)

  @article{ , abstract = {We report herein an enantioselective total synthesis of (−)-psathyrin A, an antibacterial diterpene natural product possessing a unique 6/4/5/5 tetracyclic carbon skeleton and seven contiguous stereocenters, including three adjacent all-carbon quaternary centers. Our synthesis begins with commercially available 2-methyl-2-cyclopenten-1-one, which was subjected to an enantioselective copper/NHC-catalyzed conjugate addition, followed by trapping the resulting enolate with 1-bromo-2-butyne to set up the first two stereocenters, including one all-carbon quaternary center. A Suzuki–Miyaura cross coupling introduces an aromatic ring as the six-membered ring precursor, and a gold(I)-catalyzed Conia-ene reaction constructs the 5/5-fused bicyclic ring system and the second all-carbon quaternary center. Following Birch reduction of the aromatic ring, hydrolysis, and double bond isomerization, a Baran reductive olefin coupling, namely, MHAT-initiated olefin-enone radical cyclization, was employed to construct the four-membered ring and establish the third all-carbon quaternary center. This enabling radical cyclization completed the tetracyclic carbon framework for subsequent peripheral decorations, achieving the first total synthesis of (−)-psathyrin A in 19 steps.}, archive = {J_JACS}, author = {Weizhao Zhao and Reem Al-Ahmad and Mingji Dai}, doi = {10.1021/jacs.5c11534}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32365--32369}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of (−)-psathyrin a enabled by radical cyclization}, volume = {147}, year = {2025}, }
• (2025). Circularly polarized luminescence from an inverted Singlet–Triplet chiral dye. JACS, 147(36), 32357--32364. (www)

  @article{ , abstract = {Molecules with an inverted singlet–triplet gap (Δ E ST = E S 1 – E T 1 < 0) hold potential for optoelectronic applications as OLEDs and photocatalysis. Despite growing interest, no single-molecule emission from a chiral dye with an inverted gap has been reported, and only one case has shown such emission from supramolecular aggregates. Here, we present the first circularly polarized light emission (CPL) from a chiral molecule exhibiting an inverted singlet–triplet gap. Our design is based on the achiral heptazine core, functionalized with chiral substituents. Computational screening confirmed that the inversion of the singlet–triplet gap is retained upon derivatization. Photophysical characterization, including temperature-dependent optical spectra and photoluminescence decay profiles, supported by computational results, confirms the inverted gap in both achiral and chiral derivatives. Chiroptical properties show dissymmetry factor g lum values (≈ 10 –3 ) comparable to other chromophores functionalized with chiral groups. Combined with promising photoluminescence quantum yields, these findings highlight the potential of such materials for circularly polarized OLED devices.}, archive = {J_JACS}, author = {Alessandro Altinier and Ewa Machalska and Ilaria Fortunati and Melvin Raulin and Cristiano Zonta and Giuseppe Mazzeo and Giovanna Longhi and Marco Fusè and Klaus Wurst and Simone Veglianti and Luca De Vico and Daniele Padula}, doi = {10.1021/jacs.5c11353}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32357--32364}, shortjournal = {J. Am. Chem. Soc.}, title = {Circularly polarized luminescence from an inverted Singlet–Triplet chiral dye}, volume = {147}, year = {2025}, }
• (2025). Precise identification of radioactive iodine within interlayer molecular cages of Metal–Organic frameworks. JACS, 147(36), 32352--32356. (www)

  @article{ , abstract = {Obtaining direct structural evidence to elucidate the intricate interactions between iodine and adsorbents remains a significant challenge in the development of more effective iodine capture platforms. To address this issue, we report a 2D Co-tib MOF with adaptive interlayer cages that enable precise iodine binding via synergistic I···π, I···H-phenyl, and I···N halogen bonds, as directly observed by single-crystal XRD. Importantly, the 1D pores formed by the Co-tib layered structure enhance the diffusion of I 2 , facilitating its adaptive binding. Co-tib achieves record iodine capacities (7.68 g g –1 in vapor, 2.3 g g –1 in solution) while offering molecular-level mechanistic insights. In summary, this study provides critical insights and guidance for the design of materials with enhanced I 2 adsorption properties.}, archive = {J_JACS}, author = {An-Min Song and Fu-Di Zhang and Zhi-Hai Peng and Ru-Ping Liang and Jian-Zhen Liao and Hua Ke and Li Zhang and Jian-Ding Qiu}, doi = {10.1021/jacs.5c10558}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32352--32356}, shortjournal = {J. Am. Chem. Soc.}, title = {Precise identification of radioactive iodine within interlayer molecular cages of Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Ortho-carborane-supported hypervalent Iodine(III) reagents: A scaffold for enhanced oxidative capability. JACS, 147(36), 32347--32351. (www)

  @article{ , abstract = {The first C-bound ortho-carborane (oCb) supported hypervalent iodine(III) -IL 2 type species are reported in RoCb-IL 2 , for L = F and OTf, including two structurally verified -IF 2 examples. Initial synthetic observations and supporting theoretical calculations suggest that the new oCb-IL 2 type compounds will be more reactive than any known Ar-IL 2 compound. This is exemplified by a previously unobserved oxidative demethylation of trimethylsilyl fluoride, suggesting that many substrates unreactive toward Ar-IL 2 could be susceptible to oxidation by oCb-IL 2 .}, archive = {J_JACS}, author = {Marcus Sceney and Keith F. White and Jason L. Dutton}, doi = {10.1021/jacs.5c10358}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32347--32351}, shortjournal = {J. Am. Chem. Soc.}, title = {Ortho-carborane-supported hypervalent Iodine(III) reagents: A scaffold for enhanced oxidative capability}, volume = {147}, year = {2025}, }
• (2025). Electrocatalytic reduction of nitrogen to ammonia using a trinuclear nickel thiolate complex. JACS, 147(36), 32341--32346. (www)

  @article{ , abstract = {Activation and reduction of N 2 to NH 3 are a formidable challenge. While there have been several reports of metal complexes that can bind and activate N 2 , very few catalysts have been reported to catalyze the electrochemical reduction of N 2 to NH 3 selectively, under ambient conditions, and with reasonable yields. A trinuclear Ni complex with a bulky thiolate ligand and a boat-shaped cavity is synthesized and characterized. This complex can electrocatalytically reduce N 2 selectively by 6e – /6H + to NH 3 using phenol as a proton source with a Faradaic yield of >80% at −2.3 V vs Fc +/0 in CH 3 CN solvent. The selective 6e – /6H + reduction of N 2 contrasts with a previous report of an analogous complex with propanethiolate ligands that could reduce N 2 by 4e – /4H + to N 2 H 4 .}, archive = {J_JACS}, author = {Arkaprabha Das and Sudip Barman and Abhishek Dey}, doi = {10.1021/jacs.5c09896}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32341--32346}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrocatalytic reduction of nitrogen to ammonia using a trinuclear nickel thiolate complex}, volume = {147}, year = {2025}, }
• (2025). Diversity-oriented method development: Multifunctional homoallylic amines and azabicyclooctanes bearing a bridgehead enamine. JACS, 147(36), 32335--32340. (www)

  @article{ , abstract = {Two methods, designed primarily for applications in diversity-oriented synthesis (DOS), are introduced. The first is a Cu–H-catalyzed multicomponent process that involves a nitrile and a trisubstituted allenyl boronate. The first set of products are homoallylic α-secondary NH 2 -amines, containing a trisubstituted alkenyl boronate, formed with >98% enantiospecificity, in up to >98:2 dr and as a single alkene isomer (>98% Z ). The second method is efficient and diastereoselective triflic anhydride-mediated conversion of an unsaturated azapane-amide, generated from modification of the products of the foregoing catalytic process to azabicyclooctanes (ABCOs). The ABCOs contain a bridged enamine moiety and a trisubstituted alkene, which can be functionalized chemo- and stereoselectively. Accordingly, natural product-like rigid bicyclic frameworks can be obtained wherein four different fragments can be installed in space in a controllable fashion.}, archive = {J_JACS}, author = {Zoé C. Mueller and Ryan P. Ponzi and Xin Zhi Sui and Peng Liu and Amir H. Hoveyda}, doi = {10.1021/jacs.5c09730}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32335--32340}, shortjournal = {J. Am. Chem. Soc.}, title = {Diversity-oriented method development: Multifunctional homoallylic amines and azabicyclooctanes bearing a bridgehead enamine}, volume = {147}, year = {2025}, }
• (2025). Atroposelective synthesis of azobenzenes by palladium-catalyzed cross-coupling of racemic biaryl triflates and diazenyl pronucleophiles. JACS, 147(36), 32329--32334. (www)

  @article{ , abstract = {A kinetic resolution of racemic biaryl monotriflates by an atroposelective palladium-catalyzed diazenylation enables the synthesis of azobenzene derivatives decorated with an axially chiral substituent. The C(sp 2 )–N(sp 2 ) cross-coupling reaction makes use of silylated diazenes as diazenyl anion equivalents, and chiral ferrocene-based bisphosphine ligands act as effective supporting ligands. The resulting chiral azobenzenes bearing binaphthyl and naphthyl/phenyl backbones undergo reversible trans – cis isomerization under irradiation with LEDs of different wavelengths, highlighting their potential use in photoresponsive chiroptical materials.}, archive = {J_JACS}, author = {Kezhuo Zhang and Martin Oestreich}, doi = {10.1021/jacs.5c09097}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32329--32334}, shortjournal = {J. Am. Chem. Soc.}, title = {Atroposelective synthesis of azobenzenes by palladium-catalyzed cross-coupling of racemic biaryl triflates and diazenyl pronucleophiles}, volume = {147}, year = {2025}, }
• (2025). Modular access to medium-to-large sized lactams through alkyne-bridging C–C bond activation of unstrained carbonyls. JACS, 147(36), 32321--32328. (www)

  @article{ , abstract = {While the conversion of simple cyclic ketones to lactams via carbon–carbon (C–C) bond cleavage can be accomplished through classical Beckmann and Schmidt rearrangements, these methods suffer from inherent limitations. Beyond regioselectivity challenges, they permit the incorporation of only a single nitrogen atom into the parent carbocyclic framework. Herein, an efficient approach to access medium-to-large sized lactams was developed through an alkyne migratory insertion enabled C–C bond activation of unstrained ketones. Easily available ortho -alkynylaniline derivatives were incorporated regioselectively, leading to formation of a range of medium and large sized lactams in a modular manner. This methodology demonstrates exceptional substrate generality, good functional group tolerance, and direct applicability to biorelevant molecule modification with effective transfer of axial chirality.}, archive = {J_JACS}, author = {Shan Yuan and Qifan Guan and Shican Peng and Yinghua Yu and Shenlin Huang and Xueliang Huang}, doi = {10.1021/jacs.5c08553}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32321--32328}, shortjournal = {J. Am. Chem. Soc.}, title = {Modular access to medium-to-large sized lactams through alkyne-bridging C–C bond activation of unstrained carbonyls}, volume = {147}, year = {2025}, }
• (2025). Unconventional superlattice ordering in intercalated transition metal dichalcogenide V1/3NbS2. JACS, 147(36), 32315--32320. (www)

  @article{ , abstract = {The interplay between symmetry and topology in magnetic materials makes it possible to engineer exotic phases and technologically useful properties. A key requirement for these pursuits is achieving control over local crystallographic and magnetic structure, usually through sample morphology (such as synthesis of bulk crystals versus thin films) and application of magnetic or electric fields. Here we show that V 1/3 NbS 2 can be crystallized in two ordered superlattices, distinguished by the periodicity of out-of-plane magnetic intercalants. Whereas one of these structures is metallic and displays the hallmarks of altermagnetism, the other superlattice, which has not been isolated before in this family of intercalation compounds, is a semimetallic noncollinear antiferromagnet that may enable access to topologically nontrivial properties. This observation of an unconventional superlattice structure establishes a powerful route for tailoring the tremendous array of magnetic and electronic behaviors hosted in related materials and may expand their use in low-power spintronic or topological quantum devices.}, archive = {J_JACS}, author = {Shannon S. Fender and Noah Schnitzer and Wuzhang Fang and Lopa Bhatt and Dingbin Huang and Amani Malik and Oscar Gonzalez and Veronika Sunko and Lilia S. Xie and David A. Muller and Joseph Orenstein and Yuan Ping and Berit H. Goodge and D. Kwabena Bediako}, doi = {10.1021/jacs.5c07385}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32315--32320}, shortjournal = {J. Am. Chem. Soc.}, title = {Unconventional superlattice ordering in intercalated transition metal dichalcogenide V1/3NbS2}, volume = {147}, year = {2025}, }
• (2025). Room-temperature phosphorescence vapochromism through conformational control. JACS, 147(36), 32309--32314. (www)

  @article{ , abstract = {Solid-state room-temperature phosphorescence is rarely observed in organic molecules, and the modification of its color upon application of physical or chemical stimuli is hardly achieved. In this work, we demonstrate that a decorated persulfurated benzene shows reversible phosphorescence switching in the solid state, as a consequence of conformational changes induced by inclusion of solvent molecules. Quantum-chemical calculations suggest that the luminescence changes are due to emission from triplet states of different character. These results display the close relationship between structural factors and phosphorescence in solid state emitters, representing a valuable benchmark for the design of all-organic luminescent sensors with the desired photophysical properties.}, archive = {J_JACS}, author = {Andrea Fermi and Sapna Gahlot and Eric Jorand and Simone d’Agostino and Yasi Dai and Fabrizia Negri and Corinne Moustrou and Marc Gingras and Paola Ceroni}, doi = {10.1021/jacs.5c07339}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32309--32314}, shortjournal = {J. Am. Chem. Soc.}, title = {Room-temperature phosphorescence vapochromism through conformational control}, volume = {147}, year = {2025}, }
• (2025). From circularity to spirality: An integrated, systems-level approach to address the plastics problem. JACS, 147(36), 32299--32308. (www)

  @article{ , abstract = {Plastics offer significant benefits but pose growing environmental and health concerns due to low recycling rates and continued reliance on fossil-derived feedstocks. While plastics circularity has emerged as a key strategy to reduce plastic waste and impacts, current mechanical recycling pathways face major limitations in maintaining material quality over repeated cycles. Advanced methods like chemical recycling and dissolution show promise but raise questions about environmental impacts, scalability, and cost. In this perspective, we introduce the concept of spirality as a more realistic model than perfect circularity, acknowledging the inevitable degradation of plastic quality over consecutive recycling cycles and the need for tiered recycling strategies. We emphasize the importance of early stage integration of mechanical property benchmarking, life cycle assessment (LCA), and techno-economic analysis (TEA) to evaluate emerging chemistry-enabled solutions for plastics recycling. In parallel, we underscore the critical role of high-quality data, and the need for multidisciplinary collaboration to align chemistry, materials science, engineering, systems analyses, and policy for sustainable transitions. Spirality, combined with robust assessment frameworks, can guide innovation toward more pragmatic and sustainable solutions in polymer design and end-of-life management.}, archive = {J_JACS}, author = {Patritsia M. Stathatou and Christos E. Athanasiou and Matthew J. Realff}, doi = {10.1021/jacs.5c05454}, journal = {Journal of the American Chemical Society}, month = {9}, number = {36}, pages = {32299--32308}, shortjournal = {J. Am. Chem. Soc.}, title = {From circularity to spirality: An integrated, systems-level approach to address the plastics problem}, volume = {147}, year = {2025}, }
• (2025). Mixed-solvent crystallization expands the chemical space of 2D perovskites and enables phonon-limited exciton transport. JACS, 147(35), 32287--32298. (www)

  @article{ , abstract = {The advancement of two-dimensional (2D) halide perovskite optoelectronics relies on synthetic methods that enable new material discovery and the growth of high-quality crystals with a low defect density. Despite the vast chemical space of potential organic cations, many remain incompatible with conventional aqueous solution synthesis, which leads to thermodynamically stable non-2D-perovskite structures or introduces chemical reactivity issues. Here, we present a room-temperature evaporation-induced crystallization approach using a mixed organic–aqueous solvent system for the exploratory synthesis of 2D perovskites. This method is compatible with an extended range of organic cations, enabling the facile discovery of 25 new 2D perovskites, including 16 that are either kinetically stable or inaccessible with the conventional method. The expanded 2D perovskite library reveals the critical role of intermolecular interactions between the organic cations in stabilizing the kinetically stable 2D perovskite structures. Moreover, the as-grown crystals exhibit near-intrinsic free exciton emission with significantly reduced defect emissions and exciton diffusion coefficients enhanced by up to 5-fold, approaching the intrinsic transport limits governed by exciton–phonon scattering. This work not only broadens the design space of organic cations for 2D perovskites but also establishes a general synthetic strategy for growing high-quality 2D perovskite crystals, which are essential for high-performance optoelectronics.}, archive = {J_JACS}, author = {Xiaofan Jiang and Jiazhen Gu and Shixuan Zheng and Tianhao Zhang and Xinyu Li and Yan Guan and Chen Li and Jue Wang and Wenkai Zhang and Yongping Fu}, doi = {10.1021/jacs.5c13393}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32287--32298}, shortjournal = {J. Am. Chem. Soc.}, title = {Mixed-solvent crystallization expands the chemical space of 2D perovskites and enables phonon-limited exciton transport}, volume = {147}, year = {2025}, }
• (2025). Making sense of heteroatom effects in π–π interactions. JACS, 147(35), 32273--32286. (www)

  @article{ , abstract = {Heteroatoms can profoundly impact the strength and preferred geometry of parallel and T-shaped interactions between aromatic systems. Understanding these heteroatom effects is vital for the rational design of everything from pharmaceuticals to asymmetric catalysts and organic materials. We first examine how the introduction of N:, NH, and C═O groups changes the shape of the relaxed interaction energy curve for the parallel-displaced benzene dimer. These heteroatom effects are shown to be (1) additive; (2) dependent primarily on the orientation of the heteroatom(s) relative to the displacement axis; and (3) driven by electrostatic effects. We then introduce a simple conceptual model to make sense of these results based on the interaction of a local dipole associated with each heteroatom with the electric field of the other aromatic system. Finally, we demonstrate how this model can be applied to complex parallel stacked dimers as well as T-shaped interactions, providing a way to make sense of heteroatom effects in π–π interactions without computations.}, archive = {J_JACS}, author = {Khue U. Do and Audrey V. Conner and Steven E. Wheeler}, doi = {10.1021/jacs.5c12769}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32273--32286}, shortjournal = {J. Am. Chem. Soc.}, title = {Making sense of heteroatom effects in π–π interactions}, volume = {147}, year = {2025}, }
• (2025). Ultrafast tyrosinase-mediated biotinylation of living cell surface analysis reveals novel cell surface proteins responsible for influenza a virus entry. JACS, 147(35), 32263--32272. (www)

  @article{ , abstract = {Cell surface proteins are integral to a myriad of biological processes, including cell–cell interactions, signal transduction, and cell adhesion. Notably, these proteins also serve as key receptors for numerous pathogens. However, a comprehensive analysis of the surfaceome remains a significant challenge, primarily due to the high hydrophobicity and low abundance of these proteins. Here, we developed a novel cell surface profiling approach, tyrosinase-mediated cell surface labeling (TYRCSL). Tyrosinase can mildly oxidize a phenol or catechol to the corresponding o -quinone, which rapidly reacts with available protein nucleophiles. Leveraging the fast-labeling kinetics (within 1 min) and minimal toxicity of this method, we explored surfaceome dynamics during early stages of influenza A virus (IAV) entry. Our findings reveal that cell surface proteins PODXL2, CNTNAP1, and GPR39 play a crucial role in virus binding and internalization, providing valuable insights into the molecular mechanisms of IAV entry. TYRCSL shows the potential to be applied to the system-wide study of the entry process across a spectrum of pathogens and other instantaneous surfaceome changes under various stimuli.}, archive = {J_JACS}, author = {Yuying Liang and Jian Chen and Shiyun Ma and Haoru Song and Daobin Feng and Guo-Quan Yan and Ying Zhang and Haojie Lu}, doi = {10.1021/jacs.5c12360}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32263--32272}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrafast tyrosinase-mediated biotinylation of living cell surface analysis reveals novel cell surface proteins responsible for influenza a virus entry}, volume = {147}, year = {2025}, }
• (2025). High-density w single atoms in two-dimensional spinel oxide break the structural integrity for enhanced oxygen evolution catalysis. JACS, 147(35), 32249--32262. (www)

  @article{ , abstract = {The performance of oxygen evolution reaction (OER) catalysts heavily depends on intrinsically active and robust sites as well as high active site number, which poses challenges in catalyst design concerning composition and structure. This study presents a general oxygen-vacancy anchoring strategy for preparing oxide-based 4d/5d transition metal single-atom 2D materials as efficient and robust OER catalysts. In a typical synthesis, Keggin-structure polyoxometalate [PW 12 O 40 ] 3– clusters decompose into tetrahedral WO 4 2– anions, which in situ adhere to the newly nucleated metal (Co, Fe, Ni) hydroxide (M(OH) x ) due to the latter’s abundant oxygen vacancies, ensuring a uniform distribution of W single atoms. The anchoring of W stabilizes the ultrathin structure, resulting in the annealed W-Co 3 O 4 exhibiting a specific surface area 5–7 times greater than that of pure Co 3 O 4 , even though W has three times the atomic weight of Co. Moreover, the strengthened adsorption of OH induced by W breaks the surface structural integrity of Co 3 O 4 to form a highly active oxyhydroxide, while the increased distortion in Co–O octahedrons further enhances the intrinsic activity. As a result, the catalyst shows a low η 10 of 261 mV in alkaline media, 84 mV lower than that of pure Co 3 O 4 , and an excellent stability of over 290 h. This places it among the best OER catalysts, particularly in comparison to low-activity Ni or -unstable NiFe alternatives.}, archive = {J_JACS}, author = {Yong Wang and Baorui Jia and Wanjun Qin and Yuhang Wang and Sijia Liu and Yunpu Qin and Yongzhi Zhao and Luan Liu and Di Zhang and Heng Liu and Haoyin Zhong and Jianfang Liu and Juping Tu and Yadong Liu and Haoyang Wu and Deyin Zhang and Jun Fan and Xuanhui Qu and Hao Li and Mingli Qin}, doi = {10.1021/jacs.5c12122}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32249--32262}, shortjournal = {J. Am. Chem. Soc.}, title = {High-density w single atoms in two-dimensional spinel oxide break the structural integrity for enhanced oxygen evolution catalysis}, volume = {147}, year = {2025}, }
• (2025). Bench-stable carbamoylzinc pivalates for modular access to amides, ureas, and thiocarbamates. JACS, 147(35), 32238--32248. (www)

  @article{ , abstract = {Amide units and relative carbonyl families such as ureas and their derivatives are central important backbones of numerous compounds with activities of relevance to biology or medicinal chemistry. Driven by their prevalence, a general technology that enables sustainable amide-unit synthesis should afford new opportunities for chemical innovation. Generally, stoichiometric quantities of activating reagents, (tri)phosgene and its derivatives, or CO are commonly used in the literature to construct such scaffolds, which represent the drawbacks of these approaches. As such, we herein report a new series of salt-stabilized carbamoylzinc pivalates prepared from the corresponding formamides through C–H metalation in the presence of TMPLi (TMP = 2,2,6,6-tetramethylpiperidyl) and Zn(OPiv) 2 . These carbamoylzinc pivalates are obtained as powders with high air and moisture stability under ambient conditions. They also show excellent reactivity in palladium-catalyzed C–S-selective Negishi carbamoylation and copper-catalyzed electrophilic amination, thiolation, and selenolation, thus unlocking a new platform to access functionalized amides, unsymmetric ureas, thiocarbamates, and selenocarbamates through C–H zincation and C–C or C–heteroatom coupling reactions in a sustainable manner. Finally, late-stage modification of drug-like molecules and direct synthesis of drugs showcase the potential of this protocol in medicinal chemistry.}, archive = {J_JACS}, author = {Donghao Luo and Liangjie Ruan and Jiayi Xue and Zicong Jiang and Changrui Nie and Ting Zeng and Laiman Luo and Jie Li}, doi = {10.1021/jacs.5c12107}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32238--32248}, shortjournal = {J. Am. Chem. Soc.}, title = {Bench-stable carbamoylzinc pivalates for modular access to amides, ureas, and thiocarbamates}, volume = {147}, year = {2025}, }
• (2025). Distinct electric fields enable common catalytic function in structurally diverse enzymes. JACS, 147(35), 32225--32237. (www)

  @article{ , abstract = {Enzymes that catalyze the same reaction yet bear no structural resemblance challenge the view that fold dictates function. Here, we probe whether intraprotein electrostatics are a unifying factor in such cases of enzyme catalysis. Focusing on chorismate mutase (CM), a textbook case of electrostatic catalysis found in two structurally unrelated families (AroH and AroQ), we ask (i) whether disparate scaffolds can converge on a common catalytic electric field, and (ii) whether a single reaction can be accelerated by distinct electrostatic fields. Molecular dynamics simulations for six CMs, followed by tensor-based clustering of the three-dimensional electric field (EF), revealed that AroH and AroQ enzymes sample conformations whose active site EFs are nearly identical, eliminating a one-to-one link between tertiary structure and catalytic EF. QM/MM calculations showed a strong linear correlation ( R 2 > 0.8) between differential substrate–protein electrostatic interaction energy and reaction barrier, demonstrating that the active site EF controls catalytic activity. Nevertheless, enzyme conformations with highly dissimilar fields often displayed indistinguishable barriers, implying multiple electrostatic “solutions” to catalyzing the Claisen rearrangement in CMs. Through statistical analysis of the features of the electron density, distinct field-bond strategies emerged, each reallocating charge along different “electronic lever arms” to selectively stabilize the transition state through electrostatic interactions. Together, the results reframe electrostatic catalysis as a modular design space: a desired EF can be retrofitted onto diverse scaffolds, and concurrently several field-bond blueprints can deliver high catalytic efficiency. This shift from fold-based to field-based design supplies a fresh and transferable vocabulary for data-driven enzyme engineering to access novel chemistry.}, archive = {J_JACS}, author = {Shobhit S. Chaturvedi and Anubhav Goswami and Jiayi Qian and Ashley Petersen and Pujan Ajmera and Anastassia N. Alexandrova}, doi = {10.1021/jacs.5c11931}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32225--32237}, shortjournal = {J. Am. Chem. Soc.}, title = {Distinct electric fields enable common catalytic function in structurally diverse enzymes}, volume = {147}, year = {2025}, }
• (2025). Artificial protrusion architectures enabling horizontal-diffusion nucleation for stable zinc-based batteries. JACS, 147(35), 32216--32224. (www)

  @article{ , abstract = {Rechargeable batteries with metal anodes promise superior energy storage; however, dendrite formation poses risks to safety and stability. Conventional methods to inhibit dendrite growth in zinc-based batteries (ZBs) are partially effective and may compromise their performance. Herein, a unique artificial protrusion strategy (APS) is proposed involving the mechanical incorporation of Zn powder particles on the surface of zincophilic metals. This method guides Zn 2+ ions to preferentially obtain electrons on the Zn powders and allows nucleation and growth on the more energetically favorable substrate surface, demonstrating a horizontal-diffusion mechanism of Zn nucleation on the anode surface and steering the subsequent nuclei growth to undergo uniform Zn deposition. The resulting dendrite-free Zn anode extends the Zn symmetrical cell lifespan to nearly 5000 h in the coin cell configuration, notably superior to the reported performance. Additionally, the Zn–I 2 and Zn–MnO 2 pouch cells achieve notable capacities of 480 mAh (3000 h) and 1.8 Ah over multiple cycles, respectively. These results mark a significant advance toward resolving dendrite-related issues through anode structural design, paving the way for future sustainable development.}, archive = {J_JACS}, author = {Zhiqiang Xiao and Zhexuan Liu and Xinru Wu and Xiao Xiao and Yinna Liu and Jiachang Liu and Zhiyang Zheng and Wenxuan Yao and Jin-Cheng Li and Guangmin Zhou}, doi = {10.1021/jacs.5c11951}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32216--32224}, shortjournal = {J. Am. Chem. Soc.}, title = {Artificial protrusion architectures enabling horizontal-diffusion nucleation for stable zinc-based batteries}, volume = {147}, year = {2025}, }
• (2025). Photochemistry of sulfur dioxide mediated by charge transfer through intermolecular chalcogen bonds. JACS, 147(35), 32209--32215. (www)

  @article{ , abstract = {The photochemistry of sulfur dioxide (SO 2 ) plays a crucial role in the Earth’s atmosphere. In contrast to the well-established photochemistry of free SO 2 , the electronic properties and reactivity of SO 2 complexes with other atmospherically relevant gas molecules are barely known. Herein, we demonstrate that the photochemistry of SO 2 can be dramatically influenced by the first formation of charge-transfer (CT) prereaction complexes through intermolecular chalcogen bonds. Specifically, the prototype sulfur–sulfur bonded complex between SO 2 and hydrogen sulfide (H 2 S) displays a strong CT absorption at 290 nm, and photoexcitation of the complex at this CT band furnishes the elusive thiosulfurous acid (HSS(O)OH), which is a missing intermediate in the Claus sulfur recovery process. Similar charge-transfer mediated photochemistry is also applicable to the chalcogen-bonded complexes of SO 2 with the atmospherically important volatile organic sulfur compounds dimethylsulfide and methanethiol, from which sulfinic acids form efficiently through photolytic SO 2 -insertion along with concerted hydrogen atom transfer. This work highlights the pivotal role of intermolecular chalcogen bonds influencing the photochemistry of SO 2 due to the formation of photolabile charge-transfer complexes as prereaction intermediates.}, archive = {J_JACS}, author = {Beibei Sun and Junjie Jiang and Xin Shao and Lina Wang and Tarek Trabelsi and Joseph S. Francisco and Guntram Rauhut and Junhong Li and Jun Li and Xiaoqing Zeng}, doi = {10.1021/jacs.5c11910}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32209--32215}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemistry of sulfur dioxide mediated by charge transfer through intermolecular chalcogen bonds}, volume = {147}, year = {2025}, }
• (2025). Liquid–Solid interface reactions drive enhanced thermoelectric performance in Ag2Se. JACS, 147(35), 32199--32208. (www)

  @article{ , abstract = {Ag 2 Se is a promising n-type thermoelectric material, but its performance is limited by excessive carrier concentration, compositional inhomogeneity, and phase instability, challenges rooted in a narrow homogeneity range and uncontrolled Ag + diffusion in the superionic phase. Here, we address these issues by exploiting liquid–solid interface reactions using CdSe complexes that remove surface excess Ag to yield stoichiometric Ag 2 Se and generate CdSe nanodomains that inhibit Ag + diffusion and constrain grain growth. The resulting Ag 2 Se-CdSe nanocomposites exhibit a reproducible, stable figure of merit ( zT ) of 1.04 between 300 and 390 K. Beyond demonstrating high performance, we elucidate the interfacial chemical reactions that give rise to the observed microstructure and transport properties, providing a foundation for rationally engineering interfacial chemistry to tailor transport properties across diverse thermoelectric material systems.}, archive = {J_JACS}, author = {Yu Liu and Tobias Kleinhanns and Sharona Horta and Ewelina P. Dutkiewicz-Kopczynska and Shaoqing Lu and Maria Chiara Spadaro and Aziz Genç and Lei Chen and Khak Ho Lim and Min Hong and Jordi Arbiol and Maria Ibáñez}, doi = {10.1021/jacs.5c11435}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32199--32208}, shortjournal = {J. Am. Chem. Soc.}, title = {Liquid–Solid interface reactions drive enhanced thermoelectric performance in Ag2Se}, volume = {147}, year = {2025}, }
• (2025). Computationally designed nanobinders as affinity ligands in diagnostic and therapeutic applications. JACS, 147(35), 32187--32198. (www)

  @article{ , abstract = {Detecting protein biomarkers is critical in fundamental research and clinical investigations of extracellular vesicles (EVs). Despite the prevalent use of antibodies as recognition elements, their application is often limited by challenges such as cross-reactivity and inconsistent affinity. Here, we report designed nanobinders (DNBs) as a promising alternative for EV protein analysis. Our approach adopted recent advances in de novo protein design driven by machine learning. We specifically developed a computational pipeline for optimizing DNB design, complemented by a robust validation in vitro. As a proof-of-concept, we engineered a PD-L1-targeting DNB. It demonstrated superior performance compared to antibodies, exhibiting up to a 51-fold increase in signal intensity during cellular imaging and enhanced sensitivity and selectivity in EV analysis. Moreover, the PD-L1 DNB was effective in inhibiting immune checkpoints. These findings underline DNB’s potential as a reliable and scalable platform for EV-based diagnostics and therapeutics.}, archive = {J_JACS}, author = {Jueun Jeon and Q. John Liu and Hyunkyung Woo and Isabel Barth and Yoonjeong Choi and L. Jessica Sang and Hakho Lee}, doi = {10.1021/jacs.5c11289}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32187--32198}, shortjournal = {J. Am. Chem. Soc.}, title = {Computationally designed nanobinders as affinity ligands in diagnostic and therapeutic applications}, volume = {147}, year = {2025}, }
• (2025). Quantifying the localization of charges generated upon molecular doping of conjugated polymers. JACS, 147(35), 32178--32186. (www)

  @article{ , abstract = {Quantifying whether the charges created by molecular doping of organic semiconductors reside in localized versus mobile states is important to understanding doping mechanisms of organic semiconductors. Nevertheless, such quantification remains challenging, as it typically requires Hall effect measurements or specialized equipment. Here, we quantify the mobile and localized charge concentrations in molecularly doped conjugated polymers using spectroelectrochemical calibration, which we cross-validate by applying X-ray photoemission spectroscopy and Hall effect measurements and by fitting to established transport models. As a test case, we study doping with 2,3,5,6-tetrafluoro7,7,8,8-tetracyanoquinodimethane (F4TCNQ) in two different polymers: poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2- b ]thiophene] (PBTTT) and (poly(bithiophene-thienothiophene) derivative modified with a triethylene glycol side chain (Pg2T-TT). In PBTTT, we find that at most ∼10% of the carriers become mobile once carrier concentrations reach ∼3 × 10 20 cm –3 (∼0.4 molar ratio of F4TCNQ:thiophene). In contrast, when using Pg2T-TT, we find that the mobile fraction exceeds 50% at carrier concentrations of ∼3 × 10 20 cm –3 (∼0.1 of the F4TCNQ molar ratio). Not only are these results consistent with Hall effect measurements, but they agree with an analysis of the semilocalized transport (SLoT) model. We fit the SLoT model and extract the depth of potential well in combination with Fermi-level measurements via scanning Kelvin probe microscopy. These fits further indicate that Pg2T-TT reaches delocalized transport conditions while transport in PBTTT remains localized. This work provides a straightforward platform for quantifying charge localization in molecularly doped conjugated polymers by providing explicit parameters governing the charge transport, including carrier concentration, mobility, and the fraction of mobile carriers.}, archive = {J_JACS}, author = {Sung-Joo Kwon and Rajiv Giridharagopal and Yusuf Olanrewaju and Justin Neu and Wei You and Franky So and David S. Ginger}, doi = {10.1021/jacs.5c11337}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32178--32186}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantifying the localization of charges generated upon molecular doping of conjugated polymers}, volume = {147}, year = {2025}, }
• (2025). Radical ring expansion catalyzed by an α-ketoglutarate-dependent dioxygenase in the biosynthesis of tropolones. JACS, 147(35), 32167--32177. (www)

  @article{ , abstract = {Tropolones are the core of numerous remarkable bioactive natural products, such as stipitatic acid and eupenifeldin. The key step of the biosynthetic pathways of tropolones is the ring expansion of a six-membered ring. TropC is the first identified enzyme capable of catalyzing the tropolone ring expansion process, which belongs to the α-ketoglutarate-dependent dioxygenase (α-KGD) family. However, the molecular mechanism underlying this enzymatic process remains elusive. Here, we present biochemical evidence indicating that SpoC, an enzyme closely related to TropC, also catalyzes ring expansion to construct the tropolone core with stringent catalytic specificity. Molecular insight into the oxidative rearrangement mechanism of SpoC has been demonstrated through stable isotope labeling, protein mass spectrometry, crystallographic analyses, mutagenesis studies, and quantum mechanical calculations. These findings support an intriguing radical ring expansion mechanism facilitated by imine-assisted monodentate coordination of the substrate to an oxo-iron center, enabling an efficient radical ring expansion reaction. This understanding is essential for the synthesis of various tropolone-containing natural products, pharmaceuticals, and functional materials with unique properties.}, archive = {J_JACS}, author = {Mingjie Liu and Jiawang Liu and Songlin Bai and Ziang Chen and Yaling Wu and Dan Du and Xiangbing Qi and Xiaojing He and Youcai Hu}, doi = {10.1021/jacs.5c11241}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32167--32177}, shortjournal = {J. Am. Chem. Soc.}, title = {Radical ring expansion catalyzed by an α-ketoglutarate-dependent dioxygenase in the biosynthesis of tropolones}, volume = {147}, year = {2025}, }
• (2025). Electronic configurational transformation of network modifiers in aluminate glass above megabar pressures. JACS, 147(35), 32157--32166. (www)

  @article{ , abstract = {Electronic responses of glasses under extreme pressures differ from those of crystalline analogs. Their distinct electronic environments are found in network formers with well-defined, covalent-bonded coordination environments (e.g., [4] Si and [4] Al) and in network modifiers with more disordered, ionic-bonded configurations (e.g., [5,6,7] Ca). Deciphering the evolution of the bonding environment of network modifier cations upon compression provides atomic insights into the pressure-driven hardening and transport properties of glasses. Despite the importance, in contrast to extensive efforts to uncover how network formers behave under pressure, considerable structural disorder around network modifiers makes it challenging to probe their electronic bonding environments under compression. Our understanding of the evolution of network modifiers above megabars is currently absent. Here, we report a discovery of highly densified electronic configurations of network modifier Ca in aluminate glass under extreme compression via the first inelastic X-ray scattering at the Ca L -edge up to 140 GPa. As evidenced by the prominent pressure-driven increases in electronic dispersion and delocalization, densified calcium environments are characterized by a decreased average Ca–O distance, the formation of highly coordinated calcium, a broader distribution of topological variables, and a greater distortion of Ca polyhedra above megabars. The spectral features for the Ca environments reveal significant electronic and bonding modifications, including pressure-driven increases in the ligand field interaction, the covalence characteristic of the Ca–O bond, and the electron–hole Coulomb interaction. These densification paths identify the electronic adaptation of network modifiers above megabars, shedding light on the origins of enhanced electron transport and the electron-storing capacity of glasses under pressure.}, archive = {J_JACS}, author = {Shujia Li and Jae-Hyeon Parq and Yoo Soo Yi and Yuming Xiao and Paul Chow and Guoyin Shen and Sung Keun Lee}, doi = {10.1021/jacs.5c11161}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32157--32166}, shortjournal = {J. Am. Chem. Soc.}, title = {Electronic configurational transformation of network modifiers in aluminate glass above megabar pressures}, volume = {147}, year = {2025}, }
• (2025). Moiré patterns of two-dimensional covalent organic framework single crystals created by superstacking. JACS, 147(35), 32145--32156. (www)

  @article{ , abstract = {Two-dimensional (2D) covalent organic frameworks (COFs) are useful due to their molecular and crystalline features. However, the knowledge of the interlayer stacking of 2D COFs remains limited. Here, we report a 2D COF, COF-400, exhibiting an unprecedented ABCD stacking mode. Such a stacking mode was inherited in its reduction and oxidation derivatives, COF-400-Re and -Ox, respectively. Their structures were solved by single crystal X-ray/electron diffraction with a resolution up to 0.75 Å, as well as real-space imaging using transmission electron microscopy (TEM) with an interpretable resolution up to 0.95 Å. Furthermore, Moiré patterns were observed in the superstacking of exfoliated COF films with the twisted angle varying from 6.4 to 69.7°. Individual sets of 2D COF single crystals in the Moiré superstructures were clearly identified by TEM with a resolution of 1.6 Å. These findings not only enrich the knowledge on the stacking behaviors of 2D COFs but also offer extra means for the manipulation of 2D COFs, potentially useful for device fabrication.}, archive = {J_JACS}, author = {Lezhi Yi and Yijun Gao and Chunxing Yan and Ying Liu and Shuming Luo and Tianyu Wang and Lingmei Liu and Hexiang Deng}, doi = {10.1021/jacs.5c11049}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32145--32156}, shortjournal = {J. Am. Chem. Soc.}, title = {Moiré patterns of two-dimensional covalent organic framework single crystals created by superstacking}, volume = {147}, year = {2025}, }
• (2025). Interplay between through-space and through-bond electronic coupling in singlet fission. JACS, 147(35), 32124--32144. (www)

  @article{ , abstract = {Singlet fission (SF) is a spin-allowed photophysical process that generates two triplet excited states for one absorbed photon. It therefore has the potential to boost solar cell efficiencies beyond the 33% detailed balance limit. A better understanding of through-space and through-bond electronic coupling in SF, and their interplay, is essential for practical applications of SF materials. We have therefore designed three structurally complex pentacene dimers, two of which contain additional subphthalocyanines (SubPcs). These dimers, on the one hand, provide a continuum of electronic coupling and, on the other hand, mimic the complex situation present in the solid state, where a myriad of different packing interactions exist. Quantum chemical calculations and molecular dynamics simulations helped to shed light on the structure-property relationships of these dimers. We employed both steady-state absorption and emission spectroscopy and transient absorption pump-probe experiments to unravel the excited-state dynamics. The SubPcs complement the characteristics of pentacenes and act as light-harvesting antennae that funnel quantitatively the excitation energy via intramolecular Förster resonance energy transfer to the pentacene dimers to realize panchromatic absorption. The latter are subsequently subject to intramolecular SF ( i -SF). The formation of the correlated triplet-pair 1 (T 1 T 1 ) intermediate occurs with rates and yields that are directly proportional to the interpentacene electronic coupling. In contrast, the yield of uncorrelated triplet excited states (T 1 + T 1 ) is indirectly proportional to the interpentacene electronic coupling. Thus, the three dimers demonstrate the decisive role of electronic coupling in i -SF and how to control it. They serve as textbook examples for the opposing dependencies of formation and decoherence of 1 (T 1 T 1 ) on the electronic coupling.}, archive = {J_JACS}, author = {Dominik Thiel and Henrik Gotfredsen and Phillip M. Greißel and Lan Chen and Marcel Krug and Ilias Papadopoulos and Michael J. Ferguson and Tomás Torres and Timothy Clark and Christian Neiss and Andreas Görling and Mogens Brøndsted Nielsen and Rik R. Tykwinski and Dirk M. Guldi}, doi = {10.1021/jacs.5c10672}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32124--32144}, shortjournal = {J. Am. Chem. Soc.}, title = {Interplay between through-space and through-bond electronic coupling in singlet fission}, volume = {147}, year = {2025}, }
• (2025). Radical propagation via σ-cleavage mediates radical SAM catalyzed sulfur-for-oxygen swapping reaction during the biosynthesis of albomycin δ2. JACS, 147(35), 32118--32123. (www)

  @article{ , abstract = {AbmM is a radical S -adenosyl l -methionine (SAM) enzyme that catalyzes a radical initiated sulfur-for-oxygen swapping reaction, transforming the furanose ring of cytidine diphosphate (CDP) to a 4′-hydroxy-4′-thiofuranose product. While the function of AbmM has been demonstrated, the underlying mechanism regarding the formation of the radical intermediates during the reaction pathway remains to be fully established. To gain additional insight into this vital step in the biosynthesis of albomycin δ 2 , 2′-deoxy-2′-methylidene CDP was synthesized as a mechanistic probe. Upon incubation with AbmM and dithionite, a C1′ radical intermediate is generated from this mechanistic probe in the form of an allylic radical that can be trapped via oxidation to a sulfinate or a sulfenate versus reduction. Moreover, incubation of 2′-deoxy-2′-spirocyclopropryl CDP with AbmM also leads to a C1′ radical intermediate that triggers opening of the cyclopropane ring. In this case, however, the resulting C7′ terminal radical is not directly quenched but instead adds to the C5═C6 double bond of the cytosine base to form a new C7′–C6 bond. Taken together, these studies establish the intermediacy of a C1′ radical species and thus suggest radical propagation from the C4′ radical to the C1′ radical through cleavage of the C1′–O bond prior to the sulfur insertion step during the AbmM-catalyzed reaction.}, archive = {J_JACS}, author = {Ziyang Zheng and Richiro Ushimaru and Conor M. Thomas and Hung-wen Liu}, doi = {10.1021/jacs.5c10855}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32118--32123}, shortjournal = {J. Am. Chem. Soc.}, title = {Radical propagation via σ-cleavage mediates radical SAM catalyzed sulfur-for-oxygen swapping reaction during the biosynthesis of albomycin δ2}, volume = {147}, year = {2025}, }
• (2025). Enantioselective synthesis of α-oxygenated ketones via organocatalytic formal O–H bond insertion of sulfonium ylides. JACS, 147(35), 32110--32117. (www)

  @article{ , abstract = {Described here is an example of organocatalytic enantioselective formal O–H bond insertion of α-carbonyl sulfur ylides, providing efficient access to highly enantioenriched ketones bearing a tertiary α-oxygenated stereocenter. This metal-free approach is complementary to the well-established metal-based diazo carbonyl chemistry, which has gained broad success for esters but not for ketones. The proper choice of a chiral thiourea catalyst in combination with N -hydroxyl phthalimides proved to be crucial to success. Mechanistic studies indicate that the reaction is likely initiated by activation of sulfonium ylides by hydrogen bonding, thus distinct from previous related cases using chiral phosphoric acid catalysis that involves initial protonation of the basic sulfonium ylide functionality. DFT studies provided important insights into the key C–O bond-forming intermediates and transition states.}, archive = {J_JACS}, author = {Chenxiao Qian and Ziwei Zhong and Qingzheng Xu and Pengfei Li and Chaoshen Zhang and Jianwei Sun}, doi = {10.1021/jacs.5c10842}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32110--32117}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective synthesis of α-oxygenated ketones via organocatalytic formal O–H bond insertion of sulfonium ylides}, volume = {147}, year = {2025}, }
• (2025). Red light-driven, oxygen-tolerant RAFT polymerization enabled by methylene blue. JACS, 147(35), 32096--32109. (www)

  @article{ , abstract = {Photoinduced reversible-deactivation radical polymerization (photoRDRP) techniques enable the synthesis of well-defined polymers under mild conditions. However, oxygen inhibition remains a key challenge, requiring either complex deoxygenation methods or in situ oxygen-scavenging strategies. Here, we report a red light-driven, fully oxygen-tolerant reversible addition–fragmentation chain transfer (RAFT) polymerization mediated by methylene blue (MB + ) as a photosensitizer and triethanolamine (TEOA) as an electron donor. This operationally simple method enables polymerization in fully open-to-air vials without stirring, even under direct sunlight, underscoring the robustness and accessibility of the system. Using MB + in the presence of a sacrificial electron donor, the polymerization proceeds to high monomer conversions (>90%), with excellent temporal control, predictable molecular weights, and low dispersities ( Đ < 1.3) across a wide range of conditions. The system is compatible with a broad scope of hydrophilic (meth)acrylamide and (meth)acrylate monomers, including those bearing charged and zwitterionic side groups. Notably, this methodology enables access to ultrahigh molecular weight (UHMW, >1,000,000) polymers under ambient conditions, an outcome rarely achieved in oxygen-tolerant RDRP. This metal-free, red light-driven photoRAFT platform offers a scalable, efficient, and biocompatible strategy for controlled polymer synthesis, with potential applications in bioconjugation, functional coatings, and high-throughput screening.}, archive = {J_JACS}, author = {Lucca Trachsel and Ivan O. Levkovsky and Xiaolei Hu and Hironobu Murata and Krzysztof Matyjaszewski}, doi = {10.1021/jacs.5c10541}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32096--32109}, shortjournal = {J. Am. Chem. Soc.}, title = {Red light-driven, oxygen-tolerant RAFT polymerization enabled by methylene blue}, volume = {147}, year = {2025}, }
• (2025). De novo structure determination of covalent organic frameworks by NMR crystallography. JACS, 147(35), 32085--32095. (www)

  @article{ , abstract = {Further advancement in the research area of covalent organic frameworks (COFs) is in urgent need of structural information with high accuracy. The bottleneck in characterization is the lack of effective strategies to resolve the complex features (e.g., the stacking sequence) of hierarchical structures. Herein, we establish an NMR crystallographic protocol to systematically and precisely measure multinuclear distances through advanced dipolar recoupling techniques, such as rotational echo double resonance (REDOR), double quantum–single quantum (DQ–SQ), and rotational echo adiabatic passage double resonance (REAPDOR) experiments. For the first time, we obtained the atomic distances of 1 H– 1 H, 1 H– 19 F, and 13 C– 19 F within the monolayer, two adjacent layers, and three consecutive layers of a two-dimensional (2D) COF, TPPA-F 4 . Based on these key parameters with an accuracy of 0.10 Å, the structural features of TPPA-F 4 COF, including the covalent connection, intralayer conformation, interlayer distance, the direction and distances of the layer offsets, and stacking mode, have been de novo determined in detail. Moreover, the generality of this NMR crystallographic approach was verified by solving the crystal structure of a selective deuterium-labeled TPPA- d 4 COF via 1 H– 2 H distance measurements. We expect that the NMR crystallographic protocol paves new ways not only for the structural determination of complex 3D COFs but also for the investigation of the crystallization process and dynamic behaviors of COFs with high spatiotemporal resolution. In addition, the selective deuteration strategy developed herein enabled the first NMR measurement of 1 H– 2 H distances in materials research, which may find broad applications for the characterization of weak interactions in solids.}, archive = {J_JACS}, author = {Zhi-Peng Wang and Si-Min Yu and Guan-Le Chen and Ya-Jie Zhang and Shoushun Chen and Jing Niu and Lin Liang and Jie Feng and Muzaffar Ali Khan and Bryan E. G. Lucier and San-Yuan Ding and Wei Wang}, doi = {10.1021/jacs.5c10516}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32085--32095}, shortjournal = {J. Am. Chem. Soc.}, title = {De novo structure determination of covalent organic frameworks by NMR crystallography}, volume = {147}, year = {2025}, }
• (2025). Migrating group strategy for remote functionalization of seven-membered rings. JACS, 147(35), 32077--32084. (www)

  @article{ , abstract = {Seven-membered rings are essential structural components in bioactive compounds, yet their precise synthesis remains challenging compared to smaller ring systems. While traditional approaches rely on ring assembly strategies, direct functionalization of simpler cyclic precursors offers an attractive alternative to substituted building blocks. We report a photocatalytic transannular ketone migration strategy that converts 1,1-disubstituted acylcycloheptanes into 1,4-disubstituted products under mild conditions, promoted by sodium decatungstate and thiol cocatalysts under light-emitting diode (LED) irradiation. The process operates via reversible hydrogen atom abstraction and donation at multiple sites within the ring, followed by site-selective migration via radical addition and β-scission at the exocyclic carbonyl group. This dynamic kinetic approach to site-selective C–H functionalization provides regioselective access to densely substituted seven-membered rings, addressing a longstanding gap in synthetic methodology.}, archive = {J_JACS}, author = {Wenlai Han and Taehwan Hwang and Christina Lian and Simon Kolb and Mina Yamane and Vignesh Palani and Alison E. Wendlandt}, doi = {10.1021/jacs.5c10470}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32077--32084}, shortjournal = {J. Am. Chem. Soc.}, title = {Migrating group strategy for remote functionalization of seven-membered rings}, volume = {147}, year = {2025}, }
• (2025). Dynamic equilibrium between the fluorescent state of tryptophan and its cation-electron ion pair governs triplet state population. JACS, 147(35), 32064--32076. (www)

  @article{ , abstract = {Tryptophan is the most efficient fluorophore of the naturally occurring amino acids and is widely used as a fluorescence probe of protein structure and function. As a result of its importance, there have been numerous studies of the ultrafast photochemical dynamics of tryptophan. Nonetheless, these studies have not identified the pathway to the triplet state, which competes with fluorescence emission. Here, we combine femtosecond-to-microsecond time-resolved transient absorption spectroscopy and time-resolved infrared spectroscopy to explore the photochemical pathway from the UV excitation of tryptophan in aqueous solution to the population of the triplet state and its subsequent relaxation. We observe prompt formation of cations and solvated electrons consistent with autoionization to form a cation-electron ion pair. We find that the cation-electron ion pair subsequently decays with time scales that match the fluorescence lifetime of tryptophan in aqueous solution, indicative of a dynamic equilibrium between the fluorescent state and the cation-electron ion pair. We also find that population of the triplet state occurs on the same time scale as the decay of the cation-electron ion pair and fluorescence, indicating that the triplet state is populated either by recombination of a separated cation and electron after a spin flip or by intersystem crossing from the fluorescent state. Regardless of which mechanism dominates, population of the triplet state of tryptophan is governed by the dynamic equilibrium between the fluorescent state and the cation-electron ion pair.}, archive = {J_JACS}, author = {Rhea Kumar and Sufiyan Khan and Deborin Ghosh and Gabriel Karras and Ian P. Clark and Gregory M. Greetham and Thomas A. A. Oliver and Andrew J. Orr-Ewing and Helen H. Fielding}, doi = {10.1021/jacs.5c10445}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32064--32076}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic equilibrium between the fluorescent state of tryptophan and its cation-electron ion pair governs triplet state population}, volume = {147}, year = {2025}, }
• (2025). Photo-triggerable polymerization and depolymerization of stiff-stilbene lactones. JACS, 147(35), 32054--32063. (www)

  @article{ , abstract = {The development of photoswitchable polymers has unlocked new avenues for controlling polymerization and depolymerization through external stimuli. In this work, we introduce a strategy that integrates stiff-stilbene-based cyclic monomers with reversible E / Z photoisomerization to dynamically modulate the ring strain of monomers for ring-opening polymerization (ROP). A series of stiff-stilbene lactones with varying linker lengths were synthesized and systematically evaluated for their polymerization behavior. The resulting polymers exhibit tunable thermal and optical properties, with select derivatives displaying liquid crystalline behavior, and can be depolymerized to recover the original monomers. Density functional theory (DFT) calculations offer insights into the crucial role of Z / E photoisomerization in governing the polymerization and depolymerization process. This photoswitchable ROP system provides a new paradigm for designing sustainable polymers materials with adaptable and responsive properties.}, archive = {J_JACS}, author = {Yong-Liang Su and Wei Xiong and Timothy M. Hunter and Kaitlyn S. Engle and Will R. Gutekunst}, doi = {10.1021/jacs.5c10480}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32054--32063}, shortjournal = {J. Am. Chem. Soc.}, title = {Photo-triggerable polymerization and depolymerization of stiff-stilbene lactones}, volume = {147}, year = {2025}, }
• (2025). Diastereomeric fullerene composite engineering for enhanced perovskite solar cells. JACS, 147(35), 32045--32053. (www)

  @article{ , abstract = {Achieving high performance and long-term stability in perovskite solar cells (PSCs) typically requires the use of surface passivation layers to suppress the interfacial defects. However, these additional passivation agents often introduce chemical and structural instabilities, limiting the device lifetime. Here, we present a molecular engineering strategy utilizing a chiral series of C 60 -Furan-Sugar (CFS) fullerene derivatives blended with [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) to modify the electron transport layer (ETL). The incorporation of CFSs significantly enhances the electron mobility and dielectric constant of the ETL, while their intrinsic passivation functionality effectively passivates perovskite surface defects. As a result, PSCs employing PCBM:CFS- RS blends achieve a power conversion efficiency (PCE) of 25.81% without the use of additional passivation layers and retain 95% of their initial performance after 1000 h of aging. Notably, CFS- RS is a chiral molecule bearing a side chain with R/S configurational isomers, which facilitates interfacial compatibility and contributes to the enhanced device performance. This work demonstrates that tuning the orientation of polar substituents in fullerene side chains can effectively influence the optoelectronic properties of the blended films, thereby simultaneously enhancing both efficiency and stability in PSCs.}, archive = {J_JACS}, author = {Jianchang Wu and Jiyun Zhang and Luyao Wang and Jovana Jakšić and Anastasia Barabash and Dušan Veljković and Andreas J. Bornschlegl and Vladislav Jovanov and Leopold Lahn and Olga Kasian and M. Eugenia Pérez-Ojeda and Klaus Götz and Tobias Unruh and Chaohui Li and Zijian Peng and Yunuo Wang and Jens A. Hauch and Lin-Long Deng and Veselin Maslak and Aleksandra Mitrović and Gang Li and Christoph J. Brabec}, doi = {10.1021/jacs.5c10340}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32045--32053}, shortjournal = {J. Am. Chem. Soc.}, title = {Diastereomeric fullerene composite engineering for enhanced perovskite solar cells}, volume = {147}, year = {2025}, }
• (2025). Separation-free high-purity hydrogen production via the mechanochemical Ammonia–Silicon reaction under mild conditions. JACS, 147(35), 32035--32044. (www)

  @article{ , abstract = {Ammonia (NH 3 ) has emerged as a promising hydrogen (H 2 ) carrier thanks to its high hydrogen content (17.6 wt %) and easy liquification. However, conventional NH 3 cracking requires high temperatures (400–600 °C) and additional gas separation processes, increasing the regeneration cost of high-purity H 2 . Here, we develop a mechanochemical NH 3 –silicon (Si) reaction that enables high-purity H 2 production under mild conditions (50.0 °C) without further separation. Utilizing dynamic mechanical actions, the mechanochemical NH 3 –Si (MAS) reaction realized 100.0% NH 3 conversion, 100.0% H 2 purity, and a fast H 2 production rate of 102.5 mmol h –1 . The process simultaneously produced high-value silicon nitride (Si 3 N 4 ) from end-of-life Si solar panels, demonstrating the strong economic competitiveness of the MAS reaction. Combining experimental and theoretical analyses, the dynamic evolution of Si nanoparticles was determined to be the key to efficiently extracting H 2 from NH 3 during ball milling.}, archive = {J_JACS}, author = {Seung-Hyeon Kim and Runnan Guan and Jiwon Gu and Yanhua Shao and Qiannan Zhao and Li Sheng and Jae Seong Lee and Se Jung Lee and Jae-Hoon Baek and Changqing Li and Jian Li and Qunxiang Li and Hankwon Lim and Jong-Beom Baek}, doi = {10.1021/jacs.5c10245}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32035--32044}, shortjournal = {J. Am. Chem. Soc.}, title = {Separation-free high-purity hydrogen production via the mechanochemical Ammonia–Silicon reaction under mild conditions}, volume = {147}, year = {2025}, }
• (2025). Post-polymerization modification to synthesize atactic and isotactic polyacrylonitrile copolymers and related carbon fibers. JACS, 147(35), 32028--32034. (www)

  @article{ , abstract = {Over 90% of carbon fibers (CFs) are made from polyacrylonitrile (PAN), which is typically prepared as a copolymer through free radical polymerization that yields a broad dispersity ( D̵ ≥ 2) and little to no control over the stereochemistry in the polymer backbone (∼30% meso – meso ( mm ) triads). PAN-based CFs are fabricated through a series of high-temperature curing steps on wet-spun fiber precursors that lead to cyclization of the nitrile groups and oxidation, followed by the formation of graphitic crystallites during the final carbonization step. The extent of graphitization is expected to be highly dependent on the stereochemistry of the precursor polymer. Here, we introduce a new approach to synthesize isotactic PAN (iPAN) using a two-step chemical process that starts with a Lewis acid–based stereocontrolled polymerization to make low dispersity ( D̵ < 1.25) isotactic poly( tert -butylacrylamide) (iPTBAM; M w ∼ 150 kDa; ∼77% mm triads), followed by a post-polymerization modification step to convert the majority of acrylamide groups to nitriles (up to ∼78%). Atactic PTBAM was also prepared without using a Lewis acid. Conversion to iPAN-TB and aPAN-TB was confirmed using IR and 1 H NMR spectroscopy. Each copolymer, along with a control PAN ( M w ∼ 130 kDa; Sigma-Aldrich), was wet spun into precursor fibers and processed in muffle (250 °C) and tube (1500 °C) furnaces. The results from tensile experiments (pre- and post-muffle furnace) showed iPAN-TB had the highest tensile strength and modulus after heating, nearly six- and four-fold higher, respectively, than the fibers derived from Sigma PAN, while not sacrificing extensibility after heating.}, archive = {J_JACS}, author = {Tarryn C. Trick and Sheila L. Tran and Brent W. Harfmann and Jonathan C. Barnes}, doi = {10.1021/jacs.5c10151}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32028--32034}, shortjournal = {J. Am. Chem. Soc.}, title = {Post-polymerization modification to synthesize atactic and isotactic polyacrylonitrile copolymers and related carbon fibers}, volume = {147}, year = {2025}, }
• (2025). Radiation-powered catalytic alchemy: 3e– reduction of perrhenate via confined active sites in covalent organic framework nanoreactors. JACS, 147(35), 32015--32027. (www)

  @article{ , abstract = {The catalytic reduction of high-valent metal oxysalts to their low-valent counterparts represents a pivotal route for environmental remediation and sustainable resource recovery. However, the inherently low redox potentials of certain oxysalts, exemplified by perrhenate (ReO 4 – ), pose a persistent challenge for conventional reduction strategies. Herein, we report a rationally designed π-conjugated olefin-linked covalent organic framework (COF) catalyst, which incorporates isolated transition metal centers (M = Ni or Cu) to facilitate the γ-ray-powered catalytic reduction of ReO 4 – . Through synergistic spatial confinement and electronic modulation, the catalyst enables near-quantitative selectivity toward ReO 2 production via a unique three-electron (3e – ) transfer pathway, overcoming the bottleneck of multielectron reduction. The energy efficiency of the reduction reaches up to 42.1 mmol MJ –1 . Synergistic experimental and theoretical investigations reveal that radiation-generated hydrated electrons (e aq – ) participate in a coordination-electron relay process, involving a critical μ-oxo double-bridged [M–O(O)–Re] intermediate. Remarkably, the conjugated COF demonstrates superior radiation resistance, retaining crystallinity and porosity after prolonged irradiation. This work establishes a new paradigm for harnessing COFs as robust platforms for heterogeneous radiation catalysis, with potential applications in the treatment of redox-recalcitrant pollutants.}, archive = {J_JACS}, author = {Yue Wang and Weiyi Wang and Haoyu Peng and Yiqian Wu and Chengchang Yang and Yicheng Wang and Jing Peng and Jiuqiang Li and Zhifang Chai and Liyong Yuan and Maolin Zhai and Weiqun Shi}, doi = {10.1021/jacs.5c09962}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32015--32027}, shortjournal = {J. Am. Chem. Soc.}, title = {Radiation-powered catalytic alchemy: 3e– reduction of perrhenate via confined active sites in covalent organic framework nanoreactors}, volume = {147}, year = {2025}, }
• (2025). Electron transfer theory elucidates the hidden role played by triethylamine and triethanolamine during photocatalysis. JACS, 147(35), 32005--32014. (www)

  @article{ , abstract = {Triethylamine (TEA) and triethanolamine (TEOA) are renowned, in part, for their ability to reductively quench excited states by outer-sphere electron transfer with vast and still growing applications as sacrificial electron donors for photocatalytic systems. Upon amine oxidation, the resulting TEA •+ and TEOA •+ radical cations undergo proton transfer (or hydrogen atom transfer), resulting in the formation of a chemical reductant that has an α-carbon centered radical adjacent to the nitrogen center (TEA • and TEOA • ). In this contribution, we have electrochemically and spectroscopically characterized a set of electron acceptors which, upon accepting an electron, are a series of photocatalysts, [ReCl(R 1 R 2 -bpy)(CO) 3 ] •– , where R 1 and R 2 are electron-donating and electron-withdrawing groups in the 4,4′- and 5,5′-positions on the bipyridyl ligand. We substantiated the formation of the electron donors, TE(O)A • , by spin trapping electron paramagnetic resonance spectroscopy, where TE(O)A • reacts with 2,4,6-tri- tert -butylnitrosobenzene to generate N-centered and O-centered radical adducts. Having established the chemical behaviors of the electron acceptors and donors individually, the electron transfer rate constants were determined across a 1.43 V range in driving force. The redox potential of TEA • was benchmarked to within ±80 mV on an absolute scale in V vs Fc + /Fc in CH 3 CN by using an empirical rate vs free-energy correlation, electron transfer theory, and density functional theory calculations. The equilibrium potentials for TEA • and TEOA • were determined to be −1.98 V and −1.76 V, respectively. Based on the kinetic and thermochemical analysis presented for TEA • and TEOA • , these transient radicals can be broadly considered strong homogeneous chemical reductants within the wider context of photoredox potentials. Thus, this work clarifies a frequently unnoticed secondary function for these sacrificial electron donors during photocatalysis and rationalizes the possibility of a one-photon/two-electron conversion process that is dependent on the free-energy exchange between TE(O)A • and photocatalysts.}, archive = {J_JACS}, author = {Cody R. Carr and Michael A. Vrionides and Ilya S. Sosulin and Aliaksandra Lisouskaya and Mehmed Z. Ertem and David C. Grills}, doi = {10.1021/jacs.5c09982}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {32005--32014}, shortjournal = {J. Am. Chem. Soc.}, title = {Electron transfer theory elucidates the hidden role played by triethylamine and triethanolamine during photocatalysis}, volume = {147}, year = {2025}, }
• (2025). Probing dopant size effects on defect clustering and vacancy ordering in lanthanide-doped ceria. JACS, 147(35), 31992--32004. (www)

  @article{ , abstract = {Dopant size is known to influence oxygen vacancy-mediated conduction pathways and ionic conductivity in doped ceria, yet the underlying atomic-scale mechanisms remain unclear. Here, we combine neutron total scattering and large-scale atomistic simulations to analyze the local defect structures of two representative doped ceria systems: Ce 0.8 Gd 0.2 O 1.9 (GDC) and Ce 0.8 Nd 0.2 O 1.9 (NDC). The local structure of GDC, a commercially used ion conductor, is investigated for the first time using neutron total scattering on 160 Gd-enriched samples. GDC exhibits fewer defect clusters, with vacancy pairs preferentially aligned along ⟨111⟩ and ⟨110⟩ directions while disfavoring ⟨100⟩ direction within the cubic fluorite structure. The Gd–Gd interactions in GDC help destabilize ⟨100⟩ ordering, promoting a more open defect network that supports efficient oxygen-ion transport. Unlike Gd 3+ (1.053 Å in 8-fold coordination with oxygen), the slightly larger dopant Nd 3+ (1.109 Å) in NDC promotes a more compact defect configuration, characterized by increased defect clustering and stabilized ⟨100⟩ vacancy alignment due to dominant Nd–vacancy interactions, substantially reducing ionic conductivity. Gd 3+ provides an optimal balance of lattice expansion and preserving favorable defect structure for ion transport. These findings provide a mechanistic understanding of dopant-size controlled conduction pathways in lanthanide-doped ceria and fundamentally contribute to the understanding of charge transport by ions, electrons, and protons in next-generation conducting materials.}, archive = {J_JACS}, author = {Jing Ming and Xingfan Zhang and Marzena Leszczyńska-Redek and Marcin Malys and Maciej Wojcik and Wojciech Wrobel and Stephen Hull and Franciszek Krok and Woongkyu Jee and Marcin Krynski and Alexey A. Sokol and Scott M. Woodley and C. Richard A. Catlow and Isaac Abrahams}, doi = {10.1021/jacs.5c09862}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31992--32004}, shortjournal = {J. Am. Chem. Soc.}, title = {Probing dopant size effects on defect clustering and vacancy ordering in lanthanide-doped ceria}, volume = {147}, year = {2025}, }
• (2025). Observation of water complexes of the Sulfur–Nitrogen compounds HNS and HSN. JACS, 147(35), 31984--31991. (www)

  @article{ , abstract = {The simplest sulfur imide (HNS) and isomeric thiazyl hydride (HSN) are prototype sulfur–nitrogen compounds that have been studied by numerous theoretical calculations; however, their existence remains hitherto elusive. Herein, we report the generation of HNS as a hydrogen-bonded water complex through 254 nm photolysis of the novel aminosulfenic acid (NH 2 SOH → HNS···H 2 O) in an Ar-matrix at 10 K, and the latter was synthesized in the gas phase by high-vacuum flash pyrolysis of tert -butyl(amino)sulfoxide at ca. 700 K. Upon photoexcitation at 193 nm, HNS···H 2 O rearranges to yield the less stable HSN···H 2 O with concomitant dehydrogenation to form water complex of nitrogen monosulfide ( • NS···H 2 O). The characterization of these water complexes with matrix-isolation IR spectroscopy is supported by D- and 15 N-isotope labeling experiments and theoretical calculations at the B3LYP-D3/6–311++G(3df,3pd) level of theory.}, archive = {J_JACS}, author = {Xin Shao and Junjie Jiang and Beibei Sun and Yanqi Du and Jiyang Yu and Joseph S. Francisco and Xiaoqing Zeng}, doi = {10.1021/jacs.5c09768}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31984--31991}, shortjournal = {J. Am. Chem. Soc.}, title = {Observation of water complexes of the Sulfur–Nitrogen compounds HNS and HSN}, volume = {147}, year = {2025}, }
• (2025). An insight into the relation of spin-polarization and oxygen evolution enhancement with a monolayer chiral covalent organic framework model catalyst. JACS, 147(35), 31975--31983. (www)

  @article{ , abstract = {Manipulating the electron spin state through the chiral-induced spin selectivity (CISS) effect provides a novel strategy for enhancing the activity and selectivity of the oxygen evolution reaction (OER). However, developing a quantitative relationship between the CISS effect and the chirality-enhanced OER performance is difficult due to complex influencing factors. Herein, using a ligand exchange strategy, we developed a monolayer chiral covalent organic framework (mc-COF) model catalytic system with adjustable spin polarization (P = ∼49–72%), which allows the decoupling of the CISS effect from other influencing factors on the OER performance. A supralinear dependence between the spin polarization and chirality-enhanced OER performance is established. This confirms that the chirality-enhanced electrocatalytic performance is significantly amplified by spin polarization due to the CISS effect. Moreover, in situ measurements reveal that the CISS effect of mc-COFs optimizes the reaction pathway by aligning *OH spins parallel, suppressing H 2 O 2 formation, facilitating spin-oriented intermediates (*OOH and *OO) at lower potentials, and accelerating *OOH-to-*O–O conversion.}, archive = {J_JACS}, author = {Zhiping Liu and Shaofang Zhang and Enbing Zhang and Kuo Wei and Miao Zhang and Xiaojuan Li and Dejuan Fa and Steven De Feyter and Guangyuan Feng and Shengbin Lei and Wenping Hu}, doi = {10.1021/jacs.5c09729}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31975--31983}, shortjournal = {J. Am. Chem. Soc.}, title = {An insight into the relation of spin-polarization and oxygen evolution enhancement with a monolayer chiral covalent organic framework model catalyst}, volume = {147}, year = {2025}, }
• (2025). Molecular engineering of terminus, conjugation, and energetics for thermally stable inverted perovskite solar cells. JACS, 147(35), 31965--31974. (www)

  @article{ , abstract = {Low-dimensional (LD)/three-dimensional (3D) heterostructure perovskite solar cells (PSCs) have achieved a power conversion efficiency (PCE) greater than 26%. However, the use of some ionic interfacial passivation materials in the construction of LD perovskites compromises device stability, as they can induce ion diffusion, particularly under high temperatures and light stress. In this study, we substitute the ammonium terminus (R-NH 3 + ) of conventional passivators with a carbamate terminus (R-NH-(CO)OR) and synthesized carbamate molecules featuring phenyl (PEA-Boc) and naphthalimide (ND-Boc) scaffolds. Through modulating the ionic terminus and enlarging the conjugated backbone of the passivation materials, the interlayer diffusion across PSCs was effectively inhibited. Moreover, the ND-Boc with electron-accepting moieties optimizes the band energy alignment, reduces defect density, and facilitates interfacial electron transfer of PSCs. As a result, the small-area target PSCs (0.04 cm 2 ) and mini-modules (aperture area of 15.45 cm 2 ) achieved a PCE of 26.04% and 21.83%, respectively. Notably, the encapsulated ND-Boc-based PSC maintained 96.7% of its initial PCE after being tracked at a maximum power point for 1500 h at 85 °C under argon (ISOS-L-2I protocol). Our strategy offers a simple and generally applicable passivation method for fabricating efficient and robust PSCs to facilitate their practical applications.}, archive = {J_JACS}, author = {Jiaonan Sun and Jiarong Wang and Ze-Fan Yao and Leyu Bi and Xiaofei Ji and Jia Wang and Xiaofeng Huang and Ming Liu and Kaikai Liu and Francis R. Lin and Bin Kan and Qiang Fu and Alex K.-Y. Jen}, doi = {10.1021/jacs.5c09669}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31965--31974}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular engineering of terminus, conjugation, and energetics for thermally stable inverted perovskite solar cells}, volume = {147}, year = {2025}, }
• (2025). Jahn–Teller distortion in the amino-functionalized metal–organic framework promotes CH4 partial oxidation with enhanced in situ H2O2 utilization efficiency. JACS, 147(35), 31952--31964. (www)

  @article{ , abstract = {The partial CH 4 oxidation by in situ generation of H 2 O 2 from O 2 and H 2 offers a promising strategy to synthesize CH 3 OH from affordable and sustainable substances. However, it remains a grand challenge to efficiently utilize H 2 O 2 for the exclusive production of methanol. Herein, we report a tandem catalyst by encapsulating Pd nanoparticles in an amino-functionalized Fe-based metal–organic framework, delivering a CH 3 OH productivity of 14.8 mmol·g cat –1 ·h –1 with a selectivity of 98.6%. The spectroscopy characterizations suggest that the modification of the ligand by amino groups not only increases the electron density of the triiron motif through ligand-to-metal charge transfer but also induces the Jahn–Teller distortion of Fe 2+ coordination, giving rise to the unpaired electrons at a high occupancy state, evidenced by theoretical calculations as well. Mechanism studies reveal that this unique electron configuration of Fe 2+ facilitates H 2 O 2 decomposition, resulting in an asymmetrical Fe–O octahedron with further enhanced Jahn–Teller distortion and more unpaired electrons in the σ* antibonding orbitals. This structural evolution promotes CH 4 activation with a reduced barrier of 0.35 eV for the amino-functionalized catalyst, compared to 0.47 eV for the nonfunctionalized counterpart, enabling selective formation of CH 3 OH.}, archive = {J_JACS}, author = {Yueyuan Xu and Ning Cao and Yao Shi and Mi Yan and Pengfei Xie}, doi = {10.1021/jacs.5c09665}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31952--31964}, shortjournal = {J. Am. Chem. Soc.}, title = {Jahn–Teller distortion in the amino-functionalized metal–organic framework promotes CH4 partial oxidation with enhanced in situ H2O2 utilization efficiency}, volume = {147}, year = {2025}, }
• (2025). Highly porous, electrically conductive two-dimensional Nickel–Hexaaminodehydrobenzoannulene frameworks. JACS, 147(35), 31940--31951. (www)

  @article{ , abstract = {Electrically conductive two-dimensional metal–organic frameworks (2D c-MOFs) represent a new frontier in porous crystalline materials, where both charge-carrier transport and mass diffusion are critical to function. However, reconciling high porosity with electrical conductivity remains a major challenge in developing this class of compounds. To address this challenge, we investigate two new 2D c-MOFs featuring hexaamino derivatives of dehydrobenzoannulenes (DBAs)─hexaaminodehydrobenzo[12]annulene (HA12) and hexaamino-dehydrobenzo[18]annulene (HA18) with a C 3 -symmetry axis─as organic ligands. These shape-persistent, fully π-conjugated macrocycles can be viewed as core-expanded analogues of hexaaminotriphenylene (HATP), a prototypical ligand for 2D c-MOFs. Their reactions with nickel ions yield highly porous Ni 3 (HI12) 2 and Ni 3 (HI18) 2 . Notably, Ni 3 (HI18) 2 exhibits a Brunauer–Emmett–Teller surface area of 1520 m 2 g –1 , among the highest reported for 2D c-MOFs. Furthermore, both MOFs show electrical conductivities comparable to that of the HATP-based counterpart, Ni 3 (HITP) 2 , as supported by density functional theory calculations. On the other hand, they differ significantly in electronic properties such as band gap and ionization energy, reflecting variations in their ligand structures. The DBA-based MOFs also demonstrate enhanced chemiresistive sensitivity compared to Ni 3 (HITP) 2 . Overall, this work presents a ligand design strategy that achieves high porosity while preserving electrical conductivity and at the same time enables diversification of electronic and sensing characteristics of 2D c-MOFs.}, archive = {J_JACS}, author = {Enzo Ohkubo and Mitsuharu Suzuki and Naoya Aizawa and Osamu Ikeda and Showa Kitajima and Tomoyuki Koganezawa and Kaoru Ohta and Kouki Oka and Norimitsu Tohnai and Keisuke Tominaga and Ken-ichi Nakayama}, doi = {10.1021/jacs.5c09695}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31940--31951}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly porous, electrically conductive two-dimensional Nickel–Hexaaminodehydrobenzoannulene frameworks}, volume = {147}, year = {2025}, }
• (2025). Ultralong room-temperature qubit lifetimes of covalent organic frameworks. JACS, 147(35), 31930--31939. (www)

  @article{ , abstract = {Molecular electron spin qubits offer atomic-level tunability and room-temperature quantum coherence. Their integration into engineered solid-state matrices can enhance performance toward ambient quantum information technologies. Herein, we demonstrate covalent organic frameworks (COFs) as programmable matrices for stable organic radical qubits, allowing strategic optimization of spin-phonon and spin–spin interactions. Using two classic boronate-ester frameworks, COF-5 and COF-108, to host semiquinone-like radical qubits, we achieve an ultralong spin relaxation time ( T 1 > 300 μs) at 298 K, which outperforms most molecular qubits and rivals inorganic spin defects. The suppression of spin relaxation is attributed to rigid and neutral structures as well as carbon-centered spin distributions that effectively weaken spin-phonon coupling. Employing dynamical decoupling methods to both COFs improves their quantum coherence and enables room-temperature detection of nuclear spins, including 1 H, 11 B, and 13 C. Our work establishes COFs as designer quantum materials, opening new avenues for quantum sensing of nuclear spins at room temperature.}, archive = {J_JACS}, author = {Zhecheng Sun and Weibin Ni and Denan Li and Xiya Du and Aimei Zhou and Shi Liu and Lei Sun}, doi = {10.1021/jacs.5c09638}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31930--31939}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultralong room-temperature qubit lifetimes of covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Molecular design of self-doping cathode interlayer for efficient and humidity-resistant organic photovoltaic cells. JACS, 147(35), 31920--31929. (www)

  @article{ , abstract = {The power conversion efficiency (PCE) of organic photovoltaic (OPV) cells has surpassed 20%. However, their stability remains a critical issue that requires further improvement, particularly due to severe performance degradation under humid conditions. To tackle this challenge, a series of cathode interlayer materials─NDIP-M, NDIP3F-M, and NDIP4F-M─were rationally designed and synthesized through side-chain engineering combined with fluorination strategies. These materials exhibit enhanced hydrophobicity and maintain good solubility in alcohol-based solvents. Among them, NDIP3F-M showed optimized energy level alignment and reduced trap activation energy, leading to an improved fill factor and a PCE of 20.1%. Notably, due to the excellent humidity resistance of NDIP3F-M, an unencapsulated OPV cell based on NDIP3F-M retained 50% of its initial PCE after 400 h of exposure to air at 85% relative humidity, which is significantly higher than that of OPV cells employing commonly used cathode interlayer materials.}, archive = {J_JACS}, author = {Yue Yu and Yong Cui and Zhihao Chen and Miaoning Ou and Tao Zhang and Yang Xiao and Di Jia and Zhen Fu and Guanlin Wang and Junzhen Ren and Xiaotao Hao and Jianhui Hou}, doi = {10.1021/jacs.5c09631}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31920--31929}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular design of self-doping cathode interlayer for efficient and humidity-resistant organic photovoltaic cells}, volume = {147}, year = {2025}, }
• (2025). Periodic trends in M–Fe interactions across an isostructural and isoelectronic series of [MFe3S4] clusters (M = v, cr, mo, w). JACS, 147(35), 31911--31919. (www)

  @article{ , abstract = {The Mo nitrogenase is more efficient for N 2 reduction than the alternative nitrogenases for reasons that are not fully understood. A set of related hypotheses center on the Mo ion facilitating electron delocalization, which could aid in substrate activation and/or provide enhanced stability during turnover, among other possibilities. To understand how the incorporation of Mo or other ‘heterometals’ influences the electronic structures of Fe-S clusters, we prepared and characterized an isostructural and isoelectronic series of [MFe 3 S 4 ] clusters (M = V, Cr, Mo, W) that includes the first example of a [CrFe 3 S 4 ] cluster. Comparison of the clusters’ structural, spectroscopic, and computed properties reveals that the Mo- and W-containing clusters have greater M–Fe delocalization than those containing only 3d metals. Although the [CrFe 3 S 4 ] cluster adopts the same ground spin state as the other clusters ( S = 3/2), the smaller Cr atom engages in substantially attenuated─though not fully obliterated─M–Fe delocalization. Moreover, electrochemical and Mössbauer spectroscopic studies reveal that the clusters with more substantial M–Fe delocalization have more electron-rich Fe sites. Such trends, if they apply to the nitrogenase cofactors, could account for the greater efficiency of the Mo nitrogenase in biological nitrogen fixation.}, archive = {J_JACS}, author = {Madeleine A. Ehweiner and Tong Wu and Daniel L. M. Suess}, doi = {10.1021/jacs.5c09551}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31911--31919}, shortjournal = {J. Am. Chem. Soc.}, title = {Periodic trends in M–Fe interactions across an isostructural and isoelectronic series of [MFe3S4] clusters (M = v, cr, mo, w)}, volume = {147}, year = {2025}, }
• (2025). Modular one-pot access to boron-carboxylated dipyrromethene dyes as visible-light and two-photon activatable photocages. JACS, 147(35), 31900--31910. (www)

  @article{ , abstract = {The photocage, an advanced platform for drug delivery and photoactivation imaging, has attracted wide attention in biomedicine. Despite recent advancements in shifting irradiation wavelengths to visible and near-infrared light, improving photolysis quantum yield and the corresponding uncaging cross section, key parameters for efficient photocages, remains highly challenging. Here, we address this challenge by introducing light-controlled COO-B bond cleavage from tetracoordinate boron linked to dipyrrin, aryl, and carboxylic acid groups. We developed a multicomponent diversity-oriented one-pot method to streamline the synthesis of BODIPY-cages, enabling the creation of a diverse library of photocages for systematic investigation of their photorelease structure–activity relationships and mechanisms. Thanks to efficient COO-B bond photolysis and the impressive extinction coefficients of BODIPYs, the developed photocages possess uncaging cross sections up to 1488 M –1 cm –1 , enabling rapid lysosome photoactivation fluorescence imaging at low light and dye doses (0.2 mW, 50 nM) and sequential two-photon (λ ex = 950 nm) photoactivation in zebrafish. When loaded with the drug valproic acid ( VPA ), these photocages optimize drug uptake and achieve precise photoactivation release in the endoplasmic reticulum or lysosomes, boosting drug efficacy ∼18,540-fold. Our one-pot accessed photocages, with impressive uncaging cross sections, two-photon activation capability, and photoactivatable fluorescence imaging and drug release abilities, provide a valuable paradigm for developing multifunctional photoactivation platform. We expect our study to break new ground in the construction of tetracoordinate boron photocages with diverse structures and functions.}, archive = {J_JACS}, author = {Heng Li and Qian Li and Luying Guo and Xing Guo and Qi Zhang and Zhaoyun Wang and Qinghua Wu and Shaozhen Wang and Lijuan Jiao and Erhong Hao}, doi = {10.1021/jacs.5c09606}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31900--31910}, shortjournal = {J. Am. Chem. Soc.}, title = {Modular one-pot access to boron-carboxylated dipyrromethene dyes as visible-light and two-photon activatable photocages}, volume = {147}, year = {2025}, }
• (2025). Carbon-caged-yttria catalysts for stable electrosynthesis of H2O2 in concentrated acid. JACS, 147(35), 31891--31899. (www)

  @article{ , abstract = {The electrosynthesis of hydrogen peroxide (H 2 O 2 ), with renewable electricity, air, and water as inputs, offers a sustainable alternative to the conventional anthraquinone process. Performing H 2 O 2 electrosynthesis in concentrated acid offers advantages in functionality and energy efficiency over alkaline media yet is currently limited by short longevity. Here, we first investigate the origins of performance loss of oxidized carbon, a proven catalyst for H 2 O 2 electrosynthesis, and observe its gradual reduction to pristine carbon during acidic electrolysis. This inspires us to design a catalyst that can stabilize the oxidized carbon sites via strong Y–O–C coordination─a strategy we instantiate via carbon-caged-yttria (C@Y 2 O x ) catalysts. In acids, the C@Y 2 O x catalyst sustains a H 2 O 2 selectivity of 97% after 10,000 cycles. Integrated into a gas diffusion electrode and operated in concentrated acids of pH < 0, the C@Y 2 O x catalyst delivers a partial current density of ∼100 mA cm – 2 at −0.4 V versus RHE over 100 h in a flow cell. Using quasi in situ NAP-XPS, operando FT-IR, and theoretical calculations, we elucidate that coordination with yttrium energetically suppresses the breakage of the O–C bond and accordingly preserves the oxidized carbon sites for selective and long-term electrosynthesis of H 2 O 2 .}, archive = {J_JACS}, author = {Yong-Yan Zhao and Luming Zhang and Huawei Yang and Menggang Li and Yilin Zhao and Xiaoxuan Sun and Zhengyi Qian and Adnan Ozden and Yifan Li and Yu Gu and Jing-Hui He and Shaojun Guo and Mingchuan Luo and Jian-Mei Lu}, doi = {10.1021/jacs.5c09469}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31891--31899}, shortjournal = {J. Am. Chem. Soc.}, title = {Carbon-caged-yttria catalysts for stable electrosynthesis of H2O2 in concentrated acid}, volume = {147}, year = {2025}, }
• (2025). In situ 3D structural determination of soft biomaterials by computationally assisted polarized raman spectroscopy. JACS, 147(35), 31882--31890. (www)

  @article{ , abstract = {Soft biomaterials, characterized by structural disorder and weak interactions, pose significant challenges for structural characterization by conventional methods, which typically rely on long-range crystalline order or strong electron scattering. Here, we report a computationally assisted polarized Raman spectroscopy strategy that enables direct, in situ determination of three-dimensional (3D) molecular structures and their intermolecular interactions, correlating molecular-scale orientations with macroscopic morphologies. We validated our approach using the well-characterized α-glycine crystal, achieving structural precision comparable to that of single-crystal X-ray diffraction (RMSD = 0.367 ± 0.003 Å). Extending our method to structurally complex peptides, we resolve biomaterial diphenylalanine structure (RMSD = 0.743 ± 0.009 Å) and determine Alzheimer’s-associated peptide (r-acAβ) assemblies at angstrom precision. Furthermore, our approach uniquely identified specific vibrational signatures associated with hydrogen bonding and hydrophobic interactions, linking the reversible switching of peptide self-assembly through environmental stimuli. This method provides a transformative structural characterization platform, offering critical insights into molecular assembly mechanisms and enabling the rational design of next-generation functional biomaterials.}, archive = {J_JACS}, author = {Xiao-Han Xi and Hao Ma and Sen Yan and Lin-Yuan Chen and Xin-Di Pei and Yan-Ti Liu and Ping-Shi Wang and Zi-Ang Nan and Xian-Kui Wei and Xiang Wang and Bin Ren}, doi = {10.1021/jacs.5c09396}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31882--31890}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ 3D structural determination of soft biomaterials by computationally assisted polarized raman spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Engineering motile coacervate droplets via nanomotor stabilization. JACS, 147(35), 31871--31881. (www)

  @article{ , abstract = {Coacervate-based artificial cells have gained significant attraction in synthetic biology for their ability to mimic life-like functions such as compartmentalization, selective molecular uptake, and the hosting of biochemical reactions. However, the incorporation of motility, a key feature of natural cells, remains underexplored. This is mainly caused by the dynamic character of coacervates, which hampers their stability and limits control over functional motile components within the structure. In this contribution, we have been able to address this gap by physically anchoring gold nanoparticles (AuNPs)-coated nanomotors at the coacervate interface in combination with a terpolymer membrane. The positively charged coacervates promoted the assembly of negatively charged nanomotors on their surfaces via electrostatic interactions. By costabilizing the coacervates with a terpolymer membrane, patches of nanomotors were firmly immobilized on the coacervates’ surface and the stability of coacervates was preserved during motion performance. The distribution of nanomotors shifted from spotted distribution, patchy distribution, to almost full coverage upon increasing nanomotors concentration. Optimal motile behavior was found when achieving a patchy coverage of nanomotors at the interface, which enabled the system to become a light-driven micromotor platform through the surface plasmon thermal effect of the AuNPs. Remarkably, the motion dynamics of these coacervate droplets could be modulated by tuning nanomotors’ density on the surface, coacervates’ size, and laser light intensity. This study provides a first example of a coacervate system, which is stabilized by a combination of nanoparticles and a terpolymer membrane, of which their motility is effectively transferred to the artificial cell structure.}, archive = {J_JACS}, author = {Siwen Sun and Jianhong Wang and Yudong Li and Alexander B. Cook and Bingbing Sun and Sebastian Novosedlik and Lars J. M. M. Paffen and Sander G. A. M. Huisman and Lou M. V. Raeven and Alexander D. Fusi and Yunqi Guo and Loai K. E. A. Abdelmohsen and Shukun Li and Tania Patiño Padial and Jan C. M. van Hest}, doi = {10.1021/jacs.5c09366}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31871--31881}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering motile coacervate droplets via nanomotor stabilization}, volume = {147}, year = {2025}, }
• (2025). Cobalt(0)-catalyzed isomerization of allylamines promoted by monodentate benzofuran phosphines. JACS, 147(35), 31859--31870. (www)

  @article{ , abstract = {Isomerization of C–C double bonds is an efficient tool for converting bulk olefins into high-value compounds. Herein we describe a newly developed homogeneous cobalt-based system which enables the isomerization of allylamines to enamines with similar activity and selectivity to noble metal catalysts. The catalyst activity was bound to the presence of furan-2-yl substituents of the phosphine ligand, while the selectivity was increased with the number of benzofuran-2-yl groups. The resulting cobalt(0) catalysts allowed the isomerization of various aliphatic and aromatic allylamines, including the synthesis of industry-relevant products with high catalytic activity. Potential industrial application of our system was substantiated by the scale-up experiment, which provided 311 g of citronellal in 96% yield. We proposed a plausible mechanism based on EPR and NMR analysis combined with deuterium labeling, radical trapping experiments, and kinetic studies.}, archive = {J_JACS}, author = {Sebastian Ahrens and Rafał Kusy and Anke Spannenberg and Thanh H. Vuong and Jabor Rabeah and Bernhard M. E. Russbueldt and Johannes Panten and Haijun Jiao and Kathrin Junge and Matthias Beller}, doi = {10.1021/jacs.5c09017}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31859--31870}, shortjournal = {J. Am. Chem. Soc.}, title = {Cobalt(0)-catalyzed isomerization of allylamines promoted by monodentate benzofuran phosphines}, volume = {147}, year = {2025}, }
• (2025). Porous gold nanoumbrellas with adjustable apical angles for selective electrosynthesis of styrene epoxide from styrene. JACS, 147(35), 31849--31858. (www)

  @article{ , abstract = {Electrocatalytic epoxidation of alkenes in H 2 O offers an appealing yet promising approach for selective electrosynthesis of industrially important epoxides; unfortunately, the performance remains less than expected. Here, we report a physical electrocatalyst design strategy that promotes robust styrene epoxide electrosynthesis via the enrichment of key intermediates within a confined porous umbrella-like nanostructure. Gold porous nanoumbrellas (Au PNUs) are prepared by the electrostatic repulsion interactions between positively charged H + ions and the quaternary ammonium group of assembled lamellar micelles, with different apical angles depending heavily on their strengths. Different from flat counterparts, Au PNUs structurally feature active metal sites along surface pores and nanoconfined microenvironments within a half-open umbrella-like cavity. With styrene as the substrate, Au PNUs deliver a nanostructure-driven enhancement in both activity and selectivity for styrene epoxide electrosynthesis to reach a remarkable selectivity of 99.6% and a superior yield rate of 10.6 mmol h –1 g –1 . Detailed mechanism studies reveal that active Br radicals as the key intermediate are formed around metal pores and further enriched within the confined umbrella-like cavity, which thus facilitate subsequent bromination and further cyclization reactions for robust styrene epoxide electrosynthesis. This work provides a physical engineering route to enhance chemical selectivity for efficient electrosynthesis of renewable chemicals and feedstocks.}, archive = {J_JACS}, author = {Hao Lv and Ruonan Guo and Ben Liu}, doi = {10.1021/jacs.5c09330}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31849--31858}, shortjournal = {J. Am. Chem. Soc.}, title = {Porous gold nanoumbrellas with adjustable apical angles for selective electrosynthesis of styrene epoxide from styrene}, volume = {147}, year = {2025}, }
• (2025). Examination of a chimeric bis-electrophile for selective DNA–Protein cross-linking and mechlorethamine reveals an unknown source of nitrogen mustard cytotoxicity. JACS, 147(35), 31839--31848. (www)

  @article{ , abstract = {DNA–protein cross-links (DPCs) are cytotoxic lesions whose study in cells is complicated by the lack of exogenous agents that produce them selectively over DNA–DNA interstrand cross-links (ICLs). The synthesis and reactivity of a chimeric bis-electrophile (MEBAC) that is comprised of a highly reactive alkylating agent and a lysine selective o -ethynyl benzaldehyde is described. DPC formation in nucleosome core particles (NCPs) by MEBAC is >40-times greater than that of ICLs. Cell viability experiments and the single cell Comet assay are consistent with NCP reactivity. Compared to a nitrogen mustard (mechlorethamine, MCE) MEBAC produces higher DPC yields and lower ICL yields in NCPs and in cells at comparable cytotoxicity. Cell viability experiments show that while DPCs from MEBAC are repaired by the metalloprotease SPRTN and the proteasome, only the former repairs such lesions produced by MCE. The inability of the proteasome to repair DPCs in MCE-treated cells likely contributes to the cytotoxicity of the nitrogen mustard. Proteomic analysis identifies several cysteine-rich E3 ligases involved in ubiquitination that are cross-linked to DNA in MCE-treated but not MEBAC-treated cells and suggests a chemical basis for why DPCs produced by the nitrogen mustard are not repaired by the proteasome. This investigation reveals a previously unknown source of nitrogen mustard cytotoxicity and indicates that MEBAC and molecules like it will be useful tools for studying DPCs in cells.}, archive = {J_JACS}, author = {Xuanhe Jiang and Son Vu and Hanrui Yu and Marc M. Greenberg}, doi = {10.1021/jacs.5c09293}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31839--31848}, shortjournal = {J. Am. Chem. Soc.}, title = {Examination of a chimeric bis-electrophile for selective DNA–Protein cross-linking and mechlorethamine reveals an unknown source of nitrogen mustard cytotoxicity}, volume = {147}, year = {2025}, }
• (2025). A ring-deconstructive carbon-deletion approach to the enantioselective total synthesis of [5]-ladderanoic acid. JACS, 147(35), 31829--31838. (www)

  @article{ , abstract = {The unique architecture of naturally occurring ladderane phospholipids has inspired innovation in strategies for their chemical synthesis and biosynthetic hypotheses. Despite the emergence of a few independent synthetic routes to both their known components, i.e., (+)-[3]-ladderanol and (−)-[5]-ladderanoic acid, a unified strategy for their enantioselective syntheses is yet to be documented. In 2022, we reported an enantioselective total synthesis of [3]-ladderanol using an alkylative desymmetrization reaction, developed in our lab. We have now adapted this desymmetrization strategy for the enantioselective total synthesis of [5]-ladderanoic acid by leveraging the symmetry of its pentacyclododecane skeleton. Our synthetic strategy relies on the installation of a five-carbon linear alkyl chain to the hexacyclic meso -cyclohexenedione through organocatalytic alkylative desymmetrization, followed by a ring-deconstructive formal one-carbon deletion, which transformed cyclobutane-fused α-alkyl cyclohexenediones to alkylated cyclobutanes. This is not only the first time an organocatalytic reaction is applied to the enantioselective synthesis of [5]-ladderanoic acid but also the first example of the application of a symmetry-inspired unified enantioinduction strategy for accessing both these targets. The versatility and modularity of this strategy facilitated the synthesis of inverse -[3]-ladderanol, an unnatural structural isomer of [3]-ladderanol, and paved avenues to its other such isomers. In this context, we proposed a hypothesis for the biosynthetic conversion of (−)-[5]-ladderanoic acid to (+)-[3]-ladderanol through reductive ring rupture. Preliminary biophysical studies hinted at a plausible evolutionary exclusion of inverse -[3]-ladderanol by nature.}, archive = {J_JACS}, author = {Sayan Ray and Subrata Das and Deepak Behera and Prava Biswas and Pradip K. Tarafdar and Santanu Mukherjee}, doi = {10.1021/jacs.5c09164}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31829--31838}, shortjournal = {J. Am. Chem. Soc.}, title = {A ring-deconstructive carbon-deletion approach to the enantioselective total synthesis of [5]-ladderanoic acid}, volume = {147}, year = {2025}, }
• (2025). Quantifying interface-dependent active sites induced by topotactic exsolution for CO2 electrolysis. JACS, 147(35), 31821--31828. (www)

  @article{ , abstract = {Supported metal nanoparticles via in situ exsolution hold great promise for many fields including CO 2 electrolysis in solid oxide electrolysis cells. However, identifying and quantifying such in situ formed interfacial sites remain a challenge. Herein, we present a quantitative analysis of the inherent exsolution process and normalize the interfacial sites to the intrinsic activity of CO 2 electrolysis. CoFe/La 0.6 Sr 0.4 Cr 0.9 Co 0.1 O 3−δ (LSCC) interfaces are architecturally tailored by modulating the concentration of guest Fe cations, enabling precise control over the coverage of exsolved CoFe nanoparticles through a topotactic ion exchange strategy. The promotional role of Fe in facilitating Co cation exsolution is quantitatively investigated via X-ray absorption spectroscopy and Mössbauer spectroscopy. A quantitative correlation between the interfacial parameters of CoFe/LSCC and their intrinsic catalytic performance is well disclosed. CO 2 electrolysis performance is linearly positively correlated with the perimeter of the CoFe/LSCC interface, reaching a peak performance of 1.73 A cm –2 at an optimal interfacial perimeter of 29.3 μm μm –2 . This study offers valuable insights into quantitative research on metal/oxide catalysts for CO 2 electrolysis.}, archive = {J_JACS}, author = {Yuxiang Shen and Shuo Wang and Xiaoqin Chen and Houfu Lv and Yige Guo and Haolin Liu and Hongwu Zhao and Na Ta and Mingrun Li and Xiaomin Zhang and Yuefeng Song and Guoxiong Wang and Xinhe Bao}, doi = {10.1021/jacs.5c09067}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31821--31828}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantifying interface-dependent active sites induced by topotactic exsolution for CO2 electrolysis}, volume = {147}, year = {2025}, }
• (2025). Late-stage aromatic C–H bond functionalization for Cysteine/Selenocysteine bioconjugation. JACS, 147(35), 31811--31820. (www)

  @article{ , abstract = {Bioconjugation of peptides and proteins has become an indispensable tool in fundamental biological research and drug development. Herein, we report a copper-mediated efficient cysteine/selenocysteine-specific bioconjugation through direct C–H functionalization of electron-rich arenes under biocompatible reaction conditions. In this method, a series of commercial electron-rich arenes, including natural products and drug molecules, are conjugated to cysteine/selenocysteine-containing peptides and proteins. Furthermore, we show that this new bioconjugation method allows the efficient stapling of peptides, as well as the cross-linking of different peptides to a single arene, all in high yields. The tunable electron density of small molecules enables the selective modification of selenocysteine in the presence of cysteine residues. Finally, mechanistic studies suggest that the conjugation proceeds via a proton-coupled electron transfer (PCET) process and substrate radical binding to the copper for C–Se/S bond formation. This approach provides an efficient strategy for the late-stage functionalization of complex small molecules to generate peptide/protein conjugates.}, archive = {J_JACS}, author = {Zhenguang Zhao and Jian Huang and Yao Cai and Tai-Ping Zhou and Fatina Khatib and Daphna Shimon and Binju Wang and Norman Metanis}, doi = {10.1021/jacs.5c08936}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31811--31820}, shortjournal = {J. Am. Chem. Soc.}, title = {Late-stage aromatic C–H bond functionalization for Cysteine/Selenocysteine bioconjugation}, volume = {147}, year = {2025}, }
• (2025). Cyanobacteria join the kahalalide conversation: Genome and metabolite evidence for structurally related peptides. JACS, 147(35), 31800--31810. (www)

  @article{ , abstract = {Kahalalide F is a cyclic depsipeptide with notable anticancer properties, initially discovered from the green alga Bryopsis sp. and its molluscan predator Elysia rufescens . Recent studies have pinpointed a bacterial endosymbiont of the green alga, Candidatus Endobryopsis kahalalidefaciens, as the true producer of kahalalide F. In the present work, we characterize a closely related kahalalide F analog, kahalalide Z 5 , from the marine cyanobacterium Limnoraphis sp. collected in the Las Perlas Islands, Panama, and propose the structures of several related compounds by detailed MS analysis. To uncover novel metabolites and prioritize them for targeted isolation from this organism, we employed a robust metabolomics strategy combining LC-MS/MS with SMART NMR and DeepSAT, artificial intelligence platforms trained to infer chemical structures from 1 H– 13 C HSQC NMR data. This integrated approach annotated a compound with structural similarities to kahalalide F, which we subsequently characterized using a suite of spectroscopic techniques and chemical degradation studies. Whole-genome sequencing of the producing strain further revealed a NRPS biosynthetic gene cluster that aligns with the structural features of kahalalide Z 5 . This study identifies the marine cyanobacterium Limnoraphis sp. as an independent source of kahalalide F-like molecules. This work broadens the phylogenetic spectrum of organisms capable of producing these bioactive compounds, reveals marine cyanobacteria as producers of an increased repertoire of unique natural products, and illustrates the potential of AI-enhanced metabolomic and genomic analyses to streamline the discovery and characterization of complex biomedically relevant natural products.}, archive = {J_JACS}, author = {Byeol Ryu and Nicole E. Avalon and Marine Cuau and Jehad Almaliti and M. Omar Din and Caitriona Brennan and Evgenia Glukhov and Rob Knight and Lena Gerwick and William H. Gerwick}, doi = {10.1021/jacs.5c08818}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31800--31810}, shortjournal = {J. Am. Chem. Soc.}, title = {Cyanobacteria join the kahalalide conversation: Genome and metabolite evidence for structurally related peptides}, volume = {147}, year = {2025}, }
• (2025). Orbital-resolved stepwise single-electron capture dynamics in a single fullerene. JACS, 147(35), 31791--31799. (www)

  @article{ , abstract = {Fullerenes (C 60 ), characterized by their unique cage-like structure and strong electron-accepting properties, have found extensive applications in organic electronics, photovoltaics, and photocatalysis. At the same time, they are gaining more attention in emerging fields, such as spintronics and quantum technologies. However, precise manipulation of the electron behavior within C 60 , particularly the capture of varying numbers of electrons by an individual C 60 molecule, remains a formidable challenge. In this study, we realize the accurate monitoring of the sequential single-electron capture process of a single C 60 molecule bound between graphene electrodes. Real-time current measurements reveal four distinct charge states with specific Frontier orbitals under cryogenic conditions (2 K), corresponding to the capture of 0, 1, 2, and 3 electrons. Theoretical calculations suggest that the ability of C 60 to accept multiple electrons originates from the coupling between molecular vibrations and transported electrons. Furthermore, the effect of the electric field on the local density of states highlights its crucial role in the precise control of electron capture on a single C 60 . These findings provide useful insights into the dynamic evolution of stepwise electron capture in fullerene and demonstrate the potential of fullerene-based materials in molecular electronics and quantum technologies.}, archive = {J_JACS}, author = {Zezhou Yang and Boyu Wang and Xinmiao Xie and Hanqiu Nie and Jianning Zhang and Panfeng Chuai and Jie Hao and Wenlong Cai and Zhiheng Yang and Chunyan Gao and Fanyang Mo and Zujin Shi and Jinying Wang and Chuancheng Jia and Xuefeng Guo}, doi = {10.1021/jacs.5c08782}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31791--31799}, shortjournal = {J. Am. Chem. Soc.}, title = {Orbital-resolved stepwise single-electron capture dynamics in a single fullerene}, volume = {147}, year = {2025}, }
• (2025). Tuning catalytic reactivity via wetting control through oxygen vacancies: Ru clusters on anatase TiO2 and CeO2 supports. JACS, 147(35), 31779--31790. (www)

  @article{ , abstract = {The shape of supported metal particles regulates their catalytic reactivity and is determined by the degree of wetting between the metal particle and the support surface. Flattened particles that wet support surfaces were reported in various catalytic systems, particularly in the subnanometer size regime. Such consequential metal–support wetting phenomena are poorly understood, and methods to study them on powder catalysts under realistic conditions are lacking. Here, we investigate the size-dependent wetting behaviors of Ru particles on two reducible-oxide supports, anatase TiO 2 (TiO 2 -A) and CeO 2 , under reducing catalytic conditions. X-ray absorption spectroscopy (XAS), low-energy ion scattering (LEIS), and density functional theory (DFT) are combined to determine the shape of Ru particles. Ru particles remain three-dimensional without wetting the TiO 2 -A support within the coverage range studied (0.06–0.98 Ru nm –2 ). In contrast, at low coverages (<0.25 Ru nm –2 ), Ru wets the CeO 2 support to form flat, disordered structures. The higher wettability of CeO 2 than TiO 2 -A is attributed to oxygen vacancies in the near-surface region. The shape difference between small Ru particles or clusters on the two supports leads to drastically contrasting catalytic reactivities in polyolefin hydrogenolysis, despite similar diameters. This work highlights the implications of metal–support wetting, or cluster shape, on catalytic behaviors of small metal clusters, while establishing the foundation for future systematic studies of such a phenomenon in realistic systems, by delivering a multitechnique methodology and revealing governing fundamental principles.}, archive = {J_JACS}, author = {Linxiao Chen and Carrington G. Moore and Charles E. Umhey and Jorge E. Perez-Aguilar and Jiyun Hong and Adam S. Hoffman and Ryan M. Thorpe and Julia B. Moreira and Libor Kovarik and Simon R. Bare and Simone Raugei and Jean-Sabin McEwen and Janos Szanyi}, doi = {10.1021/jacs.5c08781}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31779--31790}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning catalytic reactivity via wetting control through oxygen vacancies: Ru clusters on anatase TiO2 and CeO2 supports}, volume = {147}, year = {2025}, }
• (2025). Near room-temperature atomic layer deposition of magnesium oxide using bis-3-(N,N-dimethylamino)propyl Magnesium(II) and water. JACS, 147(35), 31764--31778. (www)

  @article{ , abstract = {Magnesium(II) oxide (MgO) is a versatile material that is appealing for a wide range of applications including electronics and biocompatible coatings, as pharmaceutics, and gas barrier layers (GBLs). The growth of MgO films at low temperatures is required for these applications which can be enabled by atomic layer deposition (ALD). However, the chemistry of ALD precursors reported to date for MgO is limited and there are no suitable chemistries for low temperature deposition on sensitive substrates. In this work, we describe the ALD of MgO thin films close to room temperature which was triggered by the use of a new nonpyrophoric Mg precursor that possesses all the prerequisites needed for low temperature ALD. The highly volatile bis-3-( N , N -dimethylamino)propyl magnesium(II) [Mg(DMP) 2 ] precursor is reactive toward water. The unique chemistry of the DMP ligand facilitates the ALD process in a broad temperature range (30–260 °C) with high growth per cycle (GPC) values (2.40 Å at 40 °C and 1.91 Å at 120 °C) on Si substrates and is supported by computational studies. The as deposited films were characterized using complementary tools to investigate the composition, structure and surface topology. Furthermore, we demonstrate the growth of MgO on poly(ethylene terephthalate) (PET) foils that can be exploited for implementation in temperature sensitive flexible devices by low temperature ALD. This work highlights the key role of the DMP ligand in developing a new Mg precursor promoting low temperature ALD of MgO thin films, opening the field of flexible electronics and new applications beyond semiconductor devices.}, archive = {J_JACS}, author = {Florian Preischel and Karl Rönnby and Lukas Mai and David Zanders and Detlef Rogalla and Bert Mallick and Michael Nolan and Anjana Devi}, doi = {10.1021/jacs.5c08514}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31764--31778}, shortjournal = {J. Am. Chem. Soc.}, title = {Near room-temperature atomic layer deposition of magnesium oxide using bis-3-(N,N-dimethylamino)propyl Magnesium(II) and water}, volume = {147}, year = {2025}, }
• (2025). Lewis acid-catalyzed condensation for facile synthesis of quinoidal 2-(5-methylenethiazol-2(5H)-ylidene)malononitrile end-capped shortwave infrared organic semiconductors. JACS, 147(35), 31749--31763. (www)

  @article{ , abstract = {The facile synthesis of ultranarrow-bandgap (<1 eV) small-molecule semiconductors remains a persistent challenge for advancing shortwave infrared (SWIR) organic optoelectronic technologies. Donor–acceptor (D-A)-type molecules featuring quinoidal 2-(5-methylenethiazol-2(5 H )-ylidene)malononitrile (TM) end-groups are promising for achieving this goal. However, despite extensive studies of TM-based asymmetric merocyanine dyes, their optoelectronic performances remain far from satisfactory, and the synthetic methodologies for symmetric TM-end-capped molecules remain largely unexplored. Here, we present a Lewis acid (LA)-catalyzed condensation strategy for synthesizing symmetrical TM-based molecules, overcoming the high activation energy and side reactions plaguing the conventional method. This strategy enables room-temperature construction of ADA and ADA′DA structures with high isolated yields up to 82%. Multiple SWIR absorbing materials with tunable energy levels, bandgaps, and fluorescence characteristics are constructed through systematic TM’s substituent engineering. By leveraging noncovalent O–H or N–H conformational locks provided by heteroaryl substituents on TM, ultranarrow-bandgap TM-based materials down to 0.83 eV in the film state are obtained. Bulk-heterojunction (BHJ) photodetectors are fabricated using an ADA′DA-type molecule as an electron acceptor. The devices exhibit broadband response (400–1100 nm), high external quantum efficiency (EQE) (>40%), and noise-limited detectivity ( D *) exceeding 1 × 10 13 Jones at 1020 nm, alongside a large linear dynamic range (LDR) (118 dB) and fast response (26 kHz at −3 dB). This work establishes TM-based materials as competitive candidates for silicon-rivaled photodetection and highlights the untapped potential of quinoidal TM moieties in designing next-generation organic materials for SWIR-based technologies.}, archive = {J_JACS}, author = {Hanwen Zhang and Yadong Jiang and Liu Yuan and Jiaqi Wang and Jingcheng Li and Jing Wei and Yi Han and Yunhong Huang and Yang Wang and Chunyan Chi and Huiling Tai}, doi = {10.1021/jacs.5c08423}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31749--31763}, shortjournal = {J. Am. Chem. Soc.}, title = {Lewis acid-catalyzed condensation for facile synthesis of quinoidal 2-(5-methylenethiazol-2(5H)-ylidene)malononitrile end-capped shortwave infrared organic semiconductors}, volume = {147}, year = {2025}, }
• (2025). Hydrolysis kinetics at the Air–Water interface. JACS, 147(35), 31741--31748. (www)

  @article{ , abstract = {Reactions at aqueous interfaces are significant in many disciplines and have recently been implicated in explaining the unique chemistry occurring in aqueous microdroplets. However, understanding the mechanisms behind these phenomena remains debated, emphasizing the need for establishing benchmark reactions and examining them under controlled conditions. Toward this goal, we report hydrolysis of a triflate group via nucleophilic substitution at the air–water interface. Triflate is an excellent leaving group and dissociates upon nucleophilic attack by either OH– or water. In addition, possible protonation of the triflate group in acidic solutions further enhances the leaving group ability, providing an acid-catalyzed reaction pathway. Using infrared reflection–absorption spectroscopy (IRRAS), we find that the surface-bound triflate hydrolyzes on a relatively long time scale in the order of several minutes. Surprisingly, we find that the rate of hydrolysis does not change significantly at the extremely basic pH = 13 or acidic pH = 1 conditions, suggesting that the reaction is not rate-limited by pH. The measurements over mixtures of water and ethylene glycol, however, distinctly slow the reaction. Such direct measurement of a textbook organic reaction at the air–water interface and its insensitivity to pH can help promote an understanding of the role of interfacial proton activity and solvation within the broader context of surface and microdroplet reactions.}, archive = {J_JACS}, author = {Kenneth D. Judd and Sean W. Parsons and Dmitry B. Eremin and Valery V. Fokin and Jahan M. Dawlaty}, doi = {10.1021/jacs.5c08461}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31741--31748}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrolysis kinetics at the Air–Water interface}, volume = {147}, year = {2025}, }
• (2025). A biomimetic twisting strategy enables efficient electrocatalytic oxidation of energy-dense hydrazine hydrate on FeN2+2C4+4 sites. JACS, 147(35), 31731--31740. (www)

  @article{ , abstract = {Electrocatalytic hydrazine oxidation holds great promise for enabling fuel cell-powered transportation since hydrazine hydrate (N 2 H 4 ·H 2 O) has the highest energy density of all liquid, CO 2 -free fuels (3.45 kWh/L), and the highest fuel cell voltage (1.56 V vs O 2 ). Inspired by the ruffling of catalytic centers in oxidative enzymes, we designed a twisted single-atom nanozyme comprising twisted FeN 2+2 C 4+4 sites, enabling high accessibility of N 2 H 4 and OH – reactants. Experimental evidence shows that this nanozyme catalyst achieves the lowest oxidation overpotential of all Fe–N–C materials, both in the lab and in direct hydrazine fuel cells, with an open-circuit voltage of 0.95 V, unprecedented for an Fe-based anode. The structure of the catalytic site is elucidated through a combination of electrochemistry, 57 Fe Mössbauer spectroscopy, high-resolution transmission electron microscopy, and X-ray absorption spectroscopy with crystal field multiplet simulations and fits of the pre-edge features, as well as density functional theory calculations and theoretical simulations of X-ray absorption near edge structure. The experimental and theoretical methods reveal that twisting the active site also shifts its oxidation potential positively and improves N 2 bubble removal while limiting ammonia production to less than 10 ppm. This work demonstrates the potential of active site twisting to enhance the oxidation of energy-rich and liquid substrates, representing a crucial step toward building a sustainable society.}, archive = {J_JACS}, author = {Inbal Offen-Polak and Nagaprasad Reddy Samala and Tomer Y. Burshtein and Syeda M. Zahan and Shuting Xiang and Yair Shahaf and Chen Studnik and Lingmei Ni and Mario U. Delgado-Jaime and Ulrike Kramm and Dario R. Dekel and Charlotte Vogt and Anatoly I. Frenkel and Ilya Grinberg and David Eisenberg}, doi = {10.1021/jacs.5c08450}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31731--31740}, shortjournal = {J. Am. Chem. Soc.}, title = {A biomimetic twisting strategy enables efficient electrocatalytic oxidation of energy-dense hydrazine hydrate on FeN2+2C4+4 sites}, volume = {147}, year = {2025}, }
• (2025). In situ identification of dynamic active sites in the electrocatalytic nitrate reduction reaction. JACS, 147(35), 31722--31730. (www)

  @article{ , abstract = {Deciphering the spatiotemporal evolution of catalytic active sites under operational conditions is pivotal for establishing precise design principles in electrocatalysis. However, conventional electrochemical characterization techniques, which are limited in correlating physical topographical features with chemical activity, fundamentally obstruct the linkage between nanoscale structural and macroscopic activity descriptors. To address this challenge, an integrated operando electrochemical atomic force microscopy–scanning electrochemical microscopy platform was implemented, enabling simultaneous nanoscale tracking of the topographic reorganization and local activity distribution during the nitrate reduction reaction. Morphological analysis revealed that the amorphous SnO 2 catalyst undergoes dynamic surface restructuring with an increase in roughness of up to 59.0% during catalysis, while operando current mapping confirmed that these roughened regions exhibited ∼100-fold enhancement in NH 3 production activity compared to basal planes. Height profiling demonstrated that amorphous catalysts undergo ∼60% greater thickness reduction than crystalline counterparts during activation, constructing a dual-functional architecture with surface-exposed highly active Sn(II) sites and subsurface Sn(0) enabling rapid electron transport. These findings provided direct experimental evidence of electrochemically driven defect proliferation in amorphous catalysts, which synergistically contributes to NH 3 yield several times higher than those of crystalline benchmarks, pointing to one of the best Sn-based catalysts. The developed correlative operando imaging strategy established a generalized paradigm for resolving transient catalytic dynamics across material systems with direct applicability to NO 3 RR optimization and emergent electrocatalytic processes.}, archive = {J_JACS}, author = {Yong Zhao and Shuang Gao and Xiangyu Chen and Yue Liu and Mengjuan Zhang and Yifei Liu and Jianxin Kang and Tianqi Guo and Li-Min Liu and Lin Guo}, doi = {10.1021/jacs.5c08371}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31722--31730}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ identification of dynamic active sites in the electrocatalytic nitrate reduction reaction}, volume = {147}, year = {2025}, }
• (2025). High-nuclearity copper molecular catalysts for electrocatalytic CO-to-acetate conversion. JACS, 147(35), 31713--31721. (www)

  @article{ , abstract = {Ligand-modified metal nanoclusters (NCs) have emerged as candidate materials for catalysis owing to their well-defined yet tunable structure and their metal centers’ high nuclearity. We posited that NC-based catalytic behavior will depend on ligand properties, the accessibility of active sites, and their atomic configuration. We synthesized a series of Cu NC-based catalysts, tuned local hydrophobicity through ligand adjustment, balanced the ligand coverage and active site exposure, and found that we were, in this way, able to engender efficient electrosynthesis of acetate via CO electroreduction. Computation and operando spectroscopy show that asymmetric Cu–Cu sites, which determine the CO binding strength, impact the bifurcation step after C–C coupling. The best of these catalysts, Cu 13 Nap, achieved an acetate Faradaic efficiency (FE) of 86% and an energy efficiency of 29% in a 5 bar system, exceeding the single C 2+ FE of <50% previously achieved by NC-based catalysts.}, archive = {J_JACS}, author = {Mohammad Bodiuzzaman and Lizhou Fan and Naveen M Halappa and Yiqing Chen and Yu Yan and Simil Thomas and Rui Kai Miao and Yurou Celine Xiao and Jinhong Wu and Roham Dorakhan and Mutalifu Abulikemu and Omar El Tall and David Sinton and Husam N. Alshareef and Omar F. Mohammed and Edward H. Sargent and Osman M. Bakr}, doi = {10.1021/jacs.5c08144}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31713--31721}, shortjournal = {J. Am. Chem. Soc.}, title = {High-nuclearity copper molecular catalysts for electrocatalytic CO-to-acetate conversion}, volume = {147}, year = {2025}, }
• (2025). Systematic bandgap engineering of a 2D Organic–Inorganic chalcogenide semiconductor via ligand modification. JACS, 147(35), 31704--31712. (www)

  @article{ , abstract = {Hybrid organic–inorganic semiconductors present new opportunities for optoelectronic materials design not available in all-organic or all-inorganic materials. One example is silver phenylselenide (AgSePh) – or “mithrene” – a blue-emitting 2D organic–inorganic semiconductor exhibiting strong optical and electronic anisotropy. Here, we show that the bandgap of mithrene can be systematically tuned by introducing electron-donating and electron-withdrawing groups to the phenyl ligands. We synthesized nine mithrene variants, eight of which formed 2D van der Waals crystals analogous to those of AgSePh. Density functional theory calculations reveal that these 2D mithrene variants are direct-gap or nearly direct gap semiconductors. Furthermore, we identify correlations between the optical gap and three experimental observables – the Hammett constant, 77 Se chemical shift, and selenium partial charge – offering predictive power for bandgap tuning. These findings highlight new opportunities for applying the tools of chemical synthesis to semiconductor materials design.}, archive = {J_JACS}, author = {Tomoaki Sakurada and Watcharaphol Paritmongkol and Yeongsu Cho and Woo Seok Lee and Petcharaphorn Chatsiri and Julius J. Oppenheim and Ruomeng Wan and Annlin Su and Nicholas Samulewicz and Khemika Wannakan and Peter Müller and Mircea Dincă and Heather J. Kulik and William A. Tisdale}, doi = {10.1021/jacs.5c07989}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31704--31712}, shortjournal = {J. Am. Chem. Soc.}, title = {Systematic bandgap engineering of a 2D Organic–Inorganic chalcogenide semiconductor via ligand modification}, volume = {147}, year = {2025}, }
• (2025). Entropy-regulated selective synthesis of cyclic polymers and polycatenanes by lewis pair polymerization. JACS, 147(35), 31689--31703. (www)

  @article{ , abstract = {While cyclic polymers offer a suite of unique material properties relative to their linear counterparts, their precision synthesis remains challenging and often relies on highly dilute reaction conditions to promote topological selectivity. Here, we unravel the nature of a Lewis pair polymerization (LPP) system that has demonstrated itself to be an exception to this general rule. To understand the unique, apparently concentration-independent, topological selectivity observed within this LPP system, we have paired specifically designed experimental studies with computational calculations to develop a mechanistic framework centered on an entropically driven dynamic equilibrium between intermolecular and intramolecular forms of electrostatic preorganization of polymer termini. This nuanced perspective provides a conceptual platform for the future design of topologically selective polymer synthesis. Notably, the polycatenane formation within this system under high concentrations provides strong support for the proposed mechanism. Overall, this work not only provides fundamental insights into the role of chemical dynamics in the precision synthesis of cyclic polymers but also establishes the convenient route toward topologically complex polymers.}, archive = {J_JACS}, author = {Liam T. Reilly and Dimagi Kottage and Luigi Cavallo and Laura Falivene and Eugene Y.-X. Chen}, doi = {10.1021/jacs.5c07933}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31689--31703}, shortjournal = {J. Am. Chem. Soc.}, title = {Entropy-regulated selective synthesis of cyclic polymers and polycatenanes by lewis pair polymerization}, volume = {147}, year = {2025}, }
• (2025). Photoelectrocatalytic upgrading of biomass derivatives for efficient C–N coupling with formamide. JACS, 147(35), 31679--31688. (www)

  @article{ , abstract = {The formation of the C–N bond plays a pivotal role in the ecofriendly synthesis of fertilizers, pharmaceuticals, and chemical products. Photoelectrocatalytic (PEC) upgrading of biomass derivatives powered by renewable energy offers a green and sustainable catalytic strategy to generate formamide, which has scarcely been explored. Herein, we developed a promising PEC approach for constructing a C–N bond to synthesize formamide through the coupling of the oxidation of biomass derivatives. Taking glucose as a representative, we achieved a high formamide yield of 976.6 mmol m –2 h –1 at 1.2 V versus a reversible hydrogen electrode (vs RHE) and Faraday efficiency (FE), >81% at 0.8–1.2 V vs RHE by integrated photoanode, representing excellent performance in comparison to previous reports for electrosynthesis (FE < 43.2%). Moreover, a large-area (5 × 5 cm 2 ) photoanode was also applied for formamide synthesis, representing an industrial current of 100 mA with FE > 78.1%. To ascertain the mechanism, in situ photoelectrochemical spectroscopy and density functional theory calculations confirmed that the formaldehyde radical (*CHO) intermediate was formed by the direct oxidation of photogenerated holes instead of the hydroxyl radical (*OH) attack to break the C–C bond, and then the C–N bond was established by coupling with *CHO and the nitrogen radical (*NH 2 ) formed by NH 3 to form formamide. The substrate could be converted from glucose to biomass-derived aldoses (or polyols), demonstrating its superior reaction suitability. This work deepened the understanding of the C–N coupling mechanism and provided an effective PEC approach for the conversion of biomass derivatives into valuable chemicals.}, archive = {J_JACS}, author = {Yuye Jiao and Biao Yang and Tong Li and Yurou Song and Jingwen Jiang and Chen Wang and Dingfeng Jin and Zhiqiang Hu and Siyu Jiao and Guanghao Chen and Shijie Lu and Jianyong Feng and Jungang Hou}, doi = {10.1021/jacs.5c07718}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31679--31688}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoelectrocatalytic upgrading of biomass derivatives for efficient C–N coupling with formamide}, volume = {147}, year = {2025}, }
• (2025). Controlled molecular orders in layered multiple porphyrins. JACS, 147(35), 31671--31678. (www)

  @article{ , abstract = {Nature precisely regulates multicomponent assemblies with the assistance of cooperativity. However, establishing such high precision in multicomponent assemblies of artificial supramolecular structures remains challenging. Here, we successfully position multiple distinct guest molecules within two equivalent binding cavities of a zinc-metalated trisporphyrin host by combining two distinct negative cooperative interactions, including donor–acceptor π-stacking and metal–ligand coordination. Comprehensive characterization using UV–vis absorption spectroscopy and diffusion-ordered NMR spectroscopy confirmed the exclusive formation of a ternary supramolecular complex. X-ray crystallographic analysis further revealed that the introduction of an additional bridging ligand effectively linked the two ternary complexes to produce an unprecedented septenary supramolecular assembly with alternating guest sequences. In contrast to conventional methods, which require structural differentiation or positive cooperativity, our strategy relies exclusively on negative cooperativity to achieve highly precise molecular ordering. This study presents a novel approach toward constructing sophisticated multicomponent molecular assemblies, emphasizing the significant but underutilized role of negative cooperativity in achieving molecular precision in artificial supramolecular chemistry.}, archive = {J_JACS}, author = {Tomoki Kodama and Naoyuki Hisano and Shin-ichi Tate and Takeharu Haino}, doi = {10.1021/jacs.5c07484}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31671--31678}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlled molecular orders in layered multiple porphyrins}, volume = {147}, year = {2025}, }
• (2025). Thiophenol-catalyzed radical hydroformylation of unactivated sterically hindered alkenes. JACS, 147(35), 31662--31670. (www)

  @article{ , abstract = {Sterically congested alkenes─ubiquitous in pharmaceuticals and industrial intermediates─remain inaccessible to classical hydroformylation due to prohibitive steric strain in transition-metal catalysis. Here, we report a thiophenol-catalyzed radical hydroformylation that overcomes dual steric and electronic constraints through a synergistic system: bench-stable α-chloro N -methoxyphthalimides (formyl precursors) and a tailored thiophenol HAT catalyst. This metal-free strategy achieves unprecedented hydroformylation of unactivated, tri-, and tetrasubstituted alkenes─including electron-rich styrenes and aliphatic alkene systems─with high chemo- and regioselectivity. Key advances include: 1) the first hydroformylation of tetrasubstituted styrenes, delivering β-aryl aldehydes with quaternary centers (up to 74% yield); 2) thiophenol lowers the HAT barrier by 8.3 kcal/mol to enable catalytic turnover under steric congestion. Mechanistic studies confirm a formyl radical pathway, while syngas (CO/H 2 ) elimination establishes a safe, sustainable platform for synthesizing medicinally relevant motifs (e.g., oxime ethers) and industrial targets like Lilial derivatives.}, archive = {J_JACS}, author = {Yisicheng Wang and Panpan Bao and Xiaojuan Dong and Yu Lan and Yiyun Chen}, doi = {10.1021/jacs.5c07415}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31662--31670}, shortjournal = {J. Am. Chem. Soc.}, title = {Thiophenol-catalyzed radical hydroformylation of unactivated sterically hindered alkenes}, volume = {147}, year = {2025}, }
• (2025). Photoactivatable RNA tags for subcellular photolabeling of RNA. JACS, 147(35), 31650--31661. (www)

  @article{ , abstract = {Photoactivatable fluorescent proteins enable precise analysis of subcellular protein dynamics, but a comparable approach for photoactivated tagging subcellular RNA remains lacking. Here, we develop PA-Broccoli, a photoactivatable fluorescent RNA tag that mimics photoactivatable green fluorescent proteins (PA-GFP). Similar to PA-GFP, PA-Broccoli is initially nonfluorescent but emits intense green fluorescence after ultraviolet light irradiation. Notably, complete photoactivation of PA-Broccoli results in a 6000-fold fluorescence enhancement with a rapid activation ( t 1/2 = ∼3 s), outperforming PA-GFP in sensitivity and speed by 1–2 orders of magnitude. Using PA-Broccoli, we first uncovered that cytoplasmic RNAs display restricted mobility compared to proteins. In addition, we revealed that circular RNAs undergo Ran-GTP-dependent nuclear export and slower cytoplasmic accumulation than linear mRNAs. Third, real-time imaging of mRNA within stress granules indicates that mRNA exchange throughout these granules is energy-dependent. These findings establish PA-Broccoli as a transformative tool for live-cell RNA tracking, offering unprecedented insights into RNA dynamics and regulatory mechanisms.}, archive = {J_JACS}, author = {Zhenyin Chen and Haodong Jiang and Lin Yuan and Tuoxin Yao and Xiaoxiao Rong and Wankai Gao and Chenhang Zeng and Liuqin He and Yulong Yin and Samie R. Jaffrey and Fangqing Zhao and Jinyang Zhang and Pingyong Xu and Xing Li}, doi = {10.1021/jacs.5c07380}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31650--31661}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoactivatable RNA tags for subcellular photolabeling of RNA}, volume = {147}, year = {2025}, }
• (2025). Enantioselective construction of β-substituted γ-lactone through catalytic asymmetric Oshima–Utimoto reaction: Divergent total syntheses of (−)-podophyllotoxin and its eleven congeners. JACS, 147(35), 31639--31649. (www)

  @article{ , abstract = {We report the first highly enantioselective Oshima–Utimoto reaction, which is combined with subsequent one-pot oxidation to construct synthetically important enantioenriched β-substituted γ-lactones with high enantioselectivity (up to 97% ee) from two chemical feedstocks (allylic alcohols and vinyl ethers). Significantly, the absolute configuration of chiral β-substituted γ-lactones can be precisely controlled by strategically selecting Z - or E -allylic alcohol substrates, thereby providing an alternative access to both enantiomers of chiral γ-lactones. Capitalizing on this catalytic asymmetric transformation as a key step, we have achieved a concise and stereodivergent total synthesis of the natural aryltetralin lignan drug (−)-podophyllotoxin and its 11 structural congeners in only 6–8 steps from commercial materials through the combination of chemical and chemoenzymatic strategies. The present protocol, featuring the development of a catalytic asymmetric Oshima–Utimoto reaction, not only offers a concise route to the synthetically valuable β-substituted γ-lactones, but also establishes a potential platform for preparing structurally diverse natural drug (−)-podophyllotoxin derivatives through minor modifications of synthetic precursors.}, archive = {J_JACS}, author = {Zhi-Juan He and Ma-Haoran Hong and Ling-Hui Zhang and Wen-Hui Xiong and Fu-Min Zhang}, doi = {10.1021/jacs.5c07358}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31639--31649}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective construction of β-substituted γ-lactone through catalytic asymmetric Oshima–Utimoto reaction: Divergent total syntheses of (−)-podophyllotoxin and its eleven congeners}, volume = {147}, year = {2025}, }
• (2025). A functional assay for mining noninhibitory enzyme ligands from one bead one compound libraries: Application to e3 ubiquitin ligases. JACS, 147(35), 31630--31638. (www)

  @article{ , abstract = {Chemical dimerizers are synthetic molecules that bring into proximity two or more proteins that do not normally interact with one another. A major application of this technology is to recruit an enzyme to a target protein, resulting in its post-translational modification (PTM). In particular, chemical dimerizer-mediated polyubiquitylation of proteins has garnered an enormous amount of interest as a new drug modality. A fundamental requirement for the construction of new PTM-driving dimerizers is an enzyme ligand that does not inhibit its activity. Traditional activity-based high-throughput screening platforms are not suited for this purpose. Here we describe a novel platform for screening libraries of bead-displayed compounds that links a requirement for small-molecule binding to the enzyme with enzyme-mediated modification of a nearby substrate. This system ensures that the enzyme-recruiting small molecules do not interfere with the catalytic function of the enzyme. We demonstrate the utility of this system in the context of E3 ubiquitin ligase-recruiting molecules and report the discovery of a novel low-molecular-mass ligand for the von Hippel–Lindau (VHL) protein.}, archive = {J_JACS}, author = {Weijun Gui and Allison Goss and Thomas Kodadek}, doi = {10.1021/jacs.5c07307}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31630--31638}, shortjournal = {J. Am. Chem. Soc.}, title = {A functional assay for mining noninhibitory enzyme ligands from one bead one compound libraries: Application to e3 ubiquitin ligases}, volume = {147}, year = {2025}, }
• (2025). Regulating and deciphering the selective synthesis of metallacages in microdroplets. JACS, 147(35), 31618--31629. (www)

  @article{ , abstract = {Supramolecular synthesis, driven by reversible noncovalent interactions, offers significant potential for creating functional materials with precise architectures. However, traditional batch synthesis often leads to kinetic trapping, producing polydisperse mixtures of intermediates and products. To address this, we utilize microdroplet reactors─femtoliter-scale confined environments with high surface-to-volume ratios and controlled flow dynamics─to enable precise control over self-assembly. By incorporating the principles of Maxwellian billiards, which describe the behavior of particles in confined spaces, we show how spatial constraints and internal flows within microdroplets enhance entropy, guiding molecular interactions toward thermodynamically stable products. Comparative experiments and simulations reveal that microdroplets favor the formation of a well-defined tetrahedral metallacage with near-perfect selectivity, unlike the heterogeneous mixtures observed in batch reactors. The confined environment accelerates reactant mixing and aligns molecular trajectories, effectively suppressing kinetic traps. Additionally, the metallacages selectively encapsulate hexane isomers, reducing the extraction time by a factor of 15 and improving the efficiency of n -hexane extraction compared to traditional methods. This work highlights the connection between hydrodynamic confinement, molecular entropy, and thermodynamic selectivity, demonstrating the potential of microdroplet reactors for precise material synthesis and efficient separation processes.}, archive = {J_JACS}, author = {Lu Rao and Xin Zhang and Peiwen Liu and Wei-Tao Dou and Hong-Yu Lin and Fang Zhao and Weiping Zhu and Xuhong Qian and Hai-Bo Yang and Lin Xu}, doi = {10.1021/jacs.5c06942}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31618--31629}, shortjournal = {J. Am. Chem. Soc.}, title = {Regulating and deciphering the selective synthesis of metallacages in microdroplets}, volume = {147}, year = {2025}, }
• (2025). Unveiling the switchable chemoselectivity mechanism in electrochemical nickel-catalyzed C(sp2)–O coupling of phenols and aliphatic alcohols. JACS, 147(35), 31603--31617. (www)

  @article{ , abstract = {Achieving chemoselective C(sp 2 )–O bond formation in the presence of unprotected hydroxyl groups remains a formidable challenge, owing to the inherent oxidative sensitivity of phenols and the distinct acidity between phenols and aliphatic alcohols. Herein, we unveil a switchable chemoselectivity mechanism in an electrochemical nickel-catalyzed system that couples aryl and alkenyl halides with phenols and aliphatic alcohols under mild conditions. The addition of catalytic sodium acetate (NaOAc) promotes selective arylation of phenols potentially through modulating electron transfer kinetics and stabilizing a six-membered nickel–phenoxide metallacycle, which may facilitate ligand exchange and accelerate reductive elimination. Strikingly, the introduction of 4-dimethylaminopyridine (DMAP) inverts the chemoselectivity, favoring arylation of aliphatic alcohols. This tunable protocol enables access to a broad spectrum of aryl and alkenyl ethers with high functional-group tolerance, offering a powerful platform for the construction of complex ethers and shedding mechanistic light on ligand- and additive-controlled selectivity in nickel-catalyzed C(sp 2 )–O bond formation.}, archive = {J_JACS}, author = {Shuxiang Zhu and Zhipeng Guan and Yanlong Liu and Heng Zhang and Aiwen Lei and Hong Yi}, doi = {10.1021/jacs.5c07188}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31603--31617}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling the switchable chemoselectivity mechanism in electrochemical nickel-catalyzed C(sp2)–O coupling of phenols and aliphatic alcohols}, volume = {147}, year = {2025}, }
• (2025). Design of a P–O–M (M = mn, zn) d-pπ backbonding electrolyte additive for 40 ah electrolytic Zn–MnO2 batteries. JACS, 147(35), 31591--31602. (www)

  @article{ , abstract = {An electrolytic Zn–MnO 2 battery is highly valued due to its cost-effectiveness, environmental friendliness, and abundant resource availability. However, the battery’s performance is hindered by the slow kinetics at the poorly conductive MnO 2 cathode and hydrogen evolution at the Zn anode. Here, a strategy of P–O–M (M = Mn, Zn) d-pπ backbonding design is proposed for phosphorus–oxygen electrolyte additives, which can be realized by tuning the atomic dipole moment-corrected Hirshfeld (ADCH) population charge of the P/O atom. The reversibility of d-pπ backbonding not only leads to the fast kinetics of Mn 2+ /Zn 2+ at electrodes during both charge and discharge processes to suppress the competitive hydrogen evolution reaction but also enhances the electronic conductivity at the electrode–electrolyte interfaces to sustain the high areal capacity of batteries. Hydroxymethyl dimethyl phosphite (HPD) with d-pπ backbonding is a preferred additive with a suitable ADCH charge. The assembled electrolytic Zn–MnO 2 (HPD) battery exhibits a high discharge capacity of 14.05 mAh cm –2 at an areal capacity of 15 mAh cm –2 and superior cycling stability over 1500 cycles. The Zn–MnO 2 (HPD) soft-pack battery exhibits a discharge capacity of over 1.60 Ah at a discharge rate of 0.5 C and maintains a Coulombic efficiency of ∼80% over 100 cycles. Furthermore, the assembled 50 V 40 Ah commercial Zn–MnO 2 (HPD) battery can drive an electric vehicle for 10 km. The ADCH charge regulation provides a feasible and effective method for developing high-performance aqueous batteries by achieving d-pπ backbonding.}, archive = {J_JACS}, author = {Mingyan Chuai and Hao Tong and Zimin Yang and Siting Deng and Mingqiang Wu and Jidan Xing and Guoliang Chai}, doi = {10.1021/jacs.5c06922}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31591--31602}, shortjournal = {J. Am. Chem. Soc.}, title = {Design of a P–O–M (M = mn, zn) d-pπ backbonding electrolyte additive for 40 ah electrolytic Zn–MnO2 batteries}, volume = {147}, year = {2025}, }
• (2025). Crystal growth modulation of Tin–Lead halide perovskites via chaotropic agent. JACS, 147(35), 31578--31590. (www)

  @article{ , abstract = {Mixed tin–lead (Sn–Pb) halide perovskites, with their tunable bandgaps (1.2–1.4 eV), show great promise for the development of highly efficient all-perovskite tandem solar cells. However, achieving commercial viability and stabilized high efficiency for Sn–Pb perovskite solar cells (PSCs) presents numerous challenges. Among various optimization strategies, the incorporation of additives has proven critical in modulating the crystallization of Sn–Pb perovskites. Despite the widespread use of additives to improve performance, detailed photophysical mechanisms remain unclear. In this work, we elucidate the mechanistic role of guanidinium thiocyanate, a chaotropic agent, in the crystallization of Sn–Pb perovskites. We combine hyperspectral imaging with real-time in situ photoluminescence spectroscopy to study the crystallization process of Sn–Pb perovskites. Our findings reveal that the chaotropic agent modulates the crystal growth rate during perovskite crystallization, resulting in more homogeneous films with reduced nonradiative recombination. We challenge the common assumption that crystallization stops once the solvent evaporates by identifying photoluminescence variations during the cooldown process. The resulting films exhibit a photoluminescence quantum yield of 7.28% and a charge carrier lifetime exceeding 11 μs, leading to a device efficiency of 22.34% and a fill factor of over 80%. This work provides a fundamental understanding of additive-mediated crystal growth and transient cooldown dynamics, advancing the design of high-quality Sn–Pb perovskites for efficient and stable optoelectronics.}, archive = {J_JACS}, author = {Yueyao Dong and Wen-Xian Zhu and Dong-Tai Wu and Xuan Li and Robert J. E. Westbrook and Chi-Jing Huang and Zeyin Min and Weiying Hong and Boyuan Wang and Ganghong Min and Sanjayan Sathasivam and Matteo Palma and Stoichko Dimitrov and Chieh-Ting Lin and Thomas J. Macdonald}, doi = {10.1021/jacs.5c05772}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31578--31590}, shortjournal = {J. Am. Chem. Soc.}, title = {Crystal growth modulation of Tin–Lead halide perovskites via chaotropic agent}, volume = {147}, year = {2025}, }
• (2025). Practical ligand-enabled C–H halogenation of (Hetero)Benzoic and (Hetero)Aryl acetic acids. JACS, 147(35), 31570--31577. (www)

  @article{ , abstract = {For over half a century, ortho -halogenated arenes, widely used in cross-coupling reactions, are mainly synthesized and manufactured by stoichiometric-directed ortho -lithiation/halogenation technology. While catalytic C–H halogenation has emerged as a potentially environmentally friendly method, the need for stoichiometric bases, expensive oxidants, and installation of directing groups prevented its adoption in scalable synthesis. In addition, the ligandless Pd(II)-catalyzed C–H halogenation is incompatible with heterocyclic substrates, thus limiting its use in medicinal chemistry substantially. By the discovery and development of three bifunctional bidentate pyridone ligands, we categorically removed these four detrimental drawbacks, rendering C–H halogenation technology substantially more practical: the reaction conditions require only a ligand-supported Pd(II) catalyst, inexpensive industrial halogenating reagents (NXS), and a commonly used acetonitrile solvent. The utility of this halogenation technology is demonstrated by one-step access to a variety of advanced intermediates for drug molecules that previously involved multistep syntheses.}, archive = {J_JACS}, author = {Haiwei Zhao and Zhen Li and Xinyu Zhu and Jin-Quan Yu}, doi = {10.1021/jacs.5c05774}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31570--31577}, shortjournal = {J. Am. Chem. Soc.}, title = {Practical ligand-enabled C–H halogenation of (Hetero)Benzoic and (Hetero)Aryl acetic acids}, volume = {147}, year = {2025}, }
• (2025). Structure and nitrite reductase activity of the di-iron protein ScdA in staphylococcus aureus. JACS, 147(35), 31558--31569. (www)

  @article{ , abstract = {Pathogenic Staphylococcus aureus endures bursts of host-derived reactive nitrogen species, yet the molecular defenses that enable this resilience have remained unclear. We now show that the previously enigmatic di-iron enzyme ScdA functions as a nitrite reductase, converting nitrite to nitric oxide (NO), and we elucidate the structural elements that support this activity. Using an integrative toolkit─X-ray crystallography, solution NMR, AlphaFold modeling, and pulsed EPR/DEER─we solved the full-length homodimeric structure of ScdA and identified a robust di-iron center that forms stable iron-nitrosyl intermediates. Targeted mutagenesis reveals that redox-active cysteines and dimerization state tune catalytic output, whereas steady-state kinetics confirm efficient nitrite-to-NO turnover. In vivo, ScdA overexpression in Escherichia coli suppresses growth under nitrite-rich conditions, highlighting the cytotoxic potency of the NO it generates. By coupling structure to function, our work clarifies S. aureus strategies for managing nitrosylative stress and points to ScdA as a potential vulnerability in antibiotic-resistant pathogens.}, archive = {J_JACS}, author = {Hung-Ying Chen and Ruei-Fong Tsai and Yi-Shan Lu and Yang-Chun Cheng and Hsiang-Yuan Fan-Chiang and Chu-Ya Wu and Feng-Chun Lo and Hsuan-Wei Kuo and Wei-Kai Yang and Wan-Yi Liao and Nien-Jen Hu and Shih-Che Sue and Yun-Wei Chiang}, doi = {10.1021/jacs.5c05573}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31558--31569}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure and nitrite reductase activity of the di-iron protein ScdA in staphylococcus aureus}, volume = {147}, year = {2025}, }
• (2025). Molecular engineering of interlayer exciton delocalization in 2D perovskites. JACS, 147(35), 31541--31557. (www)

  @article{ , abstract = {In recent years, significant progress has been made in improving the stability, photocurrent efficiency and charge transport properties of 2D hybrid perovskites, making them increasingly relevant for optoelectronic devices. Although these layered systems are typically considered quantum wells due to carrier confinement, an emerging strategy is to generate new perovskite functionalities with π-conjugated electroactive cores as spacer molecules, which introduce electronic coupling between the inorganic metal-halide and organic sublattices. Realizing these functionalities requires an understanding of how this coupling is achieved and how it affects exciton behavior. Using first-principles modeling and single-crystal optical spectroscopy, we find that the linker length (C x , where x = 2 or 4) controls the inorganic–organic electronic coupling and, therefore, the exciton properties of pyrene-alkylammonium (Pyr-C x )-based electroactive 2D perovskites. Whereas both (Pyr-C 2 ) 2 PbI 4 and (Pyr-C 4 ) 2 PbI 4 incorporate the π-conjugated core, only the latter has electroactive characteristics, as the longer linker length ( x = 4) allows favorable π–π stacking that, together with energy alignment of organic and inorganic orbitals, results in interlayer organic–inorganic hybridization. This tailored hybrid coupling induces substantial exciton “leakage” through multiple PbI 4 2– layers, enabling efficient interlayer exciton transport. By contrast, due to a type-I band alignment and orthogonal orientation of the π-systems with respect to the PbI 4 2– layers in (Pyr-C 2 ) 2 PbI 4 , the interlayer hybridization is lost, resulting in traditional quantum well properties. This study reveals new molecular engineering design principles to control excitons in 2D perovskites, emphasizing the importance of active π-core orientation and energetic band alignment─marking a critical step toward harnessing active organic cations in perovskite optoelectronics.}, archive = {J_JACS}, author = {Yorrick Boeije and Fabian Lie and Miloš Dubajić and Ediz Garip and Arthur Maufort and Raisa-Iona Biega and Stijn Lenaers and Mylène Sauty and Pratyush Ghosh and Aleksandar Radić and Amélie Loher and Paola La Magna and Hayden Salway and Arjun Ashoka and Xian Wei Chua and Qichun Gu and Kristof Van Hecke and Laurence Lutsen and Dirk Vanderzande and Akshay Rao and Wouter T. M. Van Gompel and Linn Leppert and Samuel D. Stranks}, doi = {10.1021/jacs.5c05621}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31541--31557}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular engineering of interlayer exciton delocalization in 2D perovskites}, volume = {147}, year = {2025}, }
• (2025). Breaking endosomal barriers: Thiol-mediated uptake lipid nanoparticles for efficient mRNA vaccine delivery. JACS, 147(35), 31530--31540. (www)

  @article{ , abstract = {Lipid nanoparticles (LNPs) are the most clinically advanced delivery platforms for mRNA therapeutics; however, their full potential is significantly limited by suboptimal intracellular mRNA delivery. Herein, we report the rational chemical design and synthesis of a dithiolane-incorporated lipidoid (S-DOPE) to construct an innovative LNP formulation, termed SLNP, for enhanced intracellular mRNA delivery. These chemically engineered SLNPs exploit an inherent thiol-mediated uptake mechanism, whereby the unique dithiolane moiety triggers a dynamic covalent disulfide-thiol exchange reaction with cell surface thiols. This chemically driven reaction facilitates direct cytosolic mRNA delivery, effectively bypassing endosomal entrapment, a major bottleneck for conventional LNPs. In vitro studies demonstrate that SLNP formulations achieve an 11-fold increase in mRNA transfection and translation efficiency compared to standard LNPs. Furthermore, in vivo evaluations reveal a 4.5-fold enhancement in mRNA expression and robust immune responses. SLNP-mediated vaccination at low doses elicits high titers of neutralizing antibodies and a Th1-biased T-cell response. Notably, SLNPs induce neutralizing antibody titers against the SARS-CoV-2 spike protein that are comparable to those achieved with significantly higher doses of conventional LNPs, highlighting their substantial dose-sparing potential. These findings establish that SLNP, by leveraging the chemically innovative thiol-mediated uptake mechanism, offers a promising and chemically distinct strategy to enhance both the efficacy and safety of mRNA vaccines, which is particularly valuable in scenarios of limited vaccine supply and for minimizing potential adverse effects associated with high vaccine dosages.}, archive = {J_JACS}, author = {Zhijie Lian and Lingying Zheng and Shuya Liu and Junjie Zhang and Jie Zhou and Junjun Wu and Songying Ouyang and Jingying Li and Huanghao Yang}, doi = {10.1021/jacs.5c05367}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31530--31540}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking endosomal barriers: Thiol-mediated uptake lipid nanoparticles for efficient mRNA vaccine delivery}, volume = {147}, year = {2025}, }
• (2025). N-heterocyclic selone-catalyzed [2σ + 2π] cycloaddition of bicyclo[1.1.0]butanes via photoredox radical buffer. JACS, 147(35), 31521--31529. (www)

  @article{ , abstract = {The development of Fsp 3 -rich bioisosteres for meta -substituted benzenes remains a significant challenge in medicinal chemistry. We herein disclose novel redox-active N -heterocyclic selone (NHS) catalysts that enable a radical-catalyzed [2σ + 2π] cycloaddition platform, providing direct access to 1,3-bicyclohexane, a geometrically congruent bioisostere for meta -substituted benzene. This method enables efficient radical-mediated cycloaddition of vinyl-bicyclobutanes (V-BCBs) with diverse alkenes, achieving high yields (up to 99%) and broad substrate compatibility (47 examples) with a low catalyst loading (1 mol %). Mechanistic studies and DFT calculations confirm the generation of the NHC-stabilized selenium-centered radical ( C6 · + ) via a radical buffer strategy under blue-light irradiation. Downstream manipulation and the expedient synthesis of an Fsp 3 -rich analogue of the anticancer drug Sonidegib substantiate the synthetic versatility of our catalytic platform.}, archive = {J_JACS}, author = {Kejun Lin and Chen-Rui Luo-Wei and Yuan Gao and Jianyong Lan and Tingshun Zhu}, doi = {10.1021/jacs.5c05306}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31521--31529}, shortjournal = {J. Am. Chem. Soc.}, title = {N-heterocyclic selone-catalyzed [2σ + 2π] cycloaddition of bicyclo[1.1.0]butanes via photoredox radical buffer}, volume = {147}, year = {2025}, }
• (2025). Understanding anomalous cage-escape dynamics in photoredox processes driven by a Fe(III) N-heterocyclic carbene complex. JACS, 147(35), 31509--31520. (www)

  @article{ , abstract = {Solvent cage-escape dynamics of bimolecular photoredox products in solution has been investigated computationally through a combination of molecular dynamics simulations and quantum chemical calculations. The present work focuses on the photoinduced oxidation of the organic electron donor dimethylaniline (DMA) by a Fe(III) N-heterocyclic carbene photosensitizer (Fe(III)NHC + ) in two different solvents, serving as an example of current interest due to their relevance for the development of earth-abundant photocatalytic systems. Calculated solvent cage-escape yields of radical-cation and neutral photoproducts (DMA •+ and Fe(II)NHC, respectively) by molecular dynamics simulations reveal more favorable solvation in acetonitrile than in dichloromethane following the initial photoinduced charge-separation. These results agree with basic expectations from solvent polarity considerations but give an opposite trend compared to experimentally reported cage-escape yields. Alternative cage-escape mechanisms were therefore considered computationally to account for the anomalous experimental cage-escape yields. Both quantum chemical calculations and molecular dynamics simulations support the formation of radical-cation dimers ( [ ( D M A ) 2 ] • + ), allowing for more efficient charge migration involving the radical-cations as the polarity of the solvent is decreased. The results further demonstrate the ability of the counterion (PF 6 – ) to stabilize the photoproducts through radical-cation–anion pairing, suggesting that these bimolecular interactions can also play an important role to preferentially promote photoproduct formation in less polar solvents. Both radical-cation dimer formation and radical-cation–counterion interactions are therefore proposed to provide additional pathways that help to explain the experimental observations of anomalous solvation dependence of the cage-escape dynamics in the investigated system. The broader implications of the bimolecular cage-escape processes on photocatalytic reaction dynamics are also considered based on our findings about light-induced intermolecular interactions.}, archive = {J_JACS}, author = {Iria Bolaño Losada and Ulf Ryde and Petter Persson}, doi = {10.1021/jacs.5c04296}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31509--31520}, shortjournal = {J. Am. Chem. Soc.}, title = {Understanding anomalous cage-escape dynamics in photoredox processes driven by a Fe(III) N-heterocyclic carbene complex}, volume = {147}, year = {2025}, }
• (2025). Universal formation, dynamics, and reactivities of *CObridge accompanying spontaneous reconstruction of cu during electrochemical CO2 or CO reduction. JACS, 147(35), 31497--31508. (www)

  @article{ , abstract = {This study demonstrates a unifying understanding of spontaneous Cu reconstruction during electrochemical CO 2 and CO reduction reactions (CO (2) RR) and its influence on the surface-adsorbed CO (*CO), the most important reaction intermediate of CO (2) RR. Specifically, by employing various in situ/operando Raman and infrared spectroscopy techniques, we reveal a universal gradual formation of bridge-type adsorbed CO (*CO bridge ) accompanying the reconstruction in addition to CO adsorbed on the atop site (*CO atop ). This phenomenon is observed across diverse Cu catalysts and electrolyzer configurations. Especially, it also occurs during CV measurements of Cu, causing interference for spectroscopic characterization of *CO for mechanistic studies. The formation of *CO bridge on reconstructed Cu is revealed to involve two steps: first, CO adsorption to form *CO atop followed by its surface conversion to *CO bridge , while kinetic studies show that *CO bridge is inactive and detrimental to catalytic conversion. Finally, to provide reference results valuable for future studies, we benchmark the line shape and potential-dependent population of *CO for widely utilized Cu catalysts, proposing protocols necessary for accurate measurements. Collectively, these results explain why spontaneous Cu reconstruction would result in lower activities of CO (2) RR, the surface dynamics and activities of *CO bridge , as well as how to accurately characterize *CO for future mechanistic studies. These insights not only advance the fundamental understanding of Cu-based electrocatalysts but also provide a framework for studying the dynamic reconstruction of electrocatalysts for other reactions.}, archive = {J_JACS}, author = {Qiliang Liu and Jianyang Zang and Wentao Ye and Ling Li and Chaochen Wang and Jiali Jin and Wenxing Yang}, doi = {10.1021/jacs.5c03886}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31497--31508}, shortjournal = {J. Am. Chem. Soc.}, title = {Universal formation, dynamics, and reactivities of *CObridge accompanying spontaneous reconstruction of cu during electrochemical CO2 or CO reduction}, volume = {147}, year = {2025}, }
• (2025). Molecular basis for the activation of pseudomonas aeruginosa MsbA by divalent metals. JACS, 147(35), 31488--31496. (www)

  @article{ , abstract = {Proteins involved in the biogenesis of lipopolysaccharide (LPS), a lipid exclusive to Gram-negative bacteria, are promising candidates for drug discovery. Specifically, the ABC transporter MsbA plays a crucial role in translocating an LPS precursor from the cytoplasmic to the periplasmic facing leaflet of the inner membrane, and small molecules that inhibit its function exhibit bactericidal activity. Here, we use native mass spectrometry (MS) to determine lipid binding affinities of MsbA from P. aeruginosa (PaMsbA), a Gram-negative bacteria associated with hospital-acquired infections, in different conformations. Unlike the transporter from E. coli , we show that the ATPase activity of PaMsbA is stimulated by Zn 2+ , Ni 2+ , and Mn 2+ and successfully trapping the protein with vanadate requires one of these metal ions. We also present cryogenic-electron microscopy structures of PaMsbA in occluded and open outward-facing conformations determined to resolutions of 2.58 and 2.44 Å, respectively. The structures reveal a triad of histidine residues, and mutation of these residues abolishes Zn 2+ binding and stimulation of PaMsbA activity by metal ions. Together, our studies provide insight into the structure of PaMsbA and its lipid binding preferences and reveal that a subset of divalent metals stimulates its ATPase activity.}, archive = {J_JACS}, author = {Jixing Lyu and Hanieh Bahramimoghaddam and Tianqi Zhang and Elena Scott and Sangho D. Yun and Gaya P. Yadav and Minglei Zhao and David Russell and Arthur Laganowsky}, doi = {10.1021/jacs.4c18759}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31488--31496}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular basis for the activation of pseudomonas aeruginosa MsbA by divalent metals}, volume = {147}, year = {2025}, }
• (2025). Hydrogen atom transfer-mediated N-heterocycles dehydrogenation coupled with the CO2 photoreduction to syngas. JACS, 147(35), 31482--31487. (www)

  @article{ , abstract = {Homogeneous photocatalytic organic oxidation coupled with CO 2 reduction remains challenging due to the susceptibility to a back electron transfer scenario. Herein, a pyridinethiol iron-catalyzed system is developed to achieve N -heterocycles dehydrogenation coupled with CO 2 photoreduction to syngas. The system is comprised of 2,4,5,6-tetrakis(diphenylamino)isophthalonitrile (4DPAIPN) photoredox catalysts, earth-abundant iron catalysts, and pyridinethiol organocatalysts, and the employment of pyridinethiol both as a hydrogen atom transfer (HAT) catalyst to promote N -heterocycles dehydrogenation and as an effective ligand for CO 2 reduction is the key to realizing the coupled redox reaction. Experimental and theoretical calculation results demonstrate the positive correlation between the reactivity and the S–H bond dissociation enthalpy (BDE) as well as the radical polarity (ω) parameter, gaining deep insights into understanding and designing the coupled reaction.}, archive = {J_JACS}, author = {Yong-Kang Zhang and An-Guo Wu and Liang-Nian He}, doi = {10.1021/jacs.5c12488}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31482--31487}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen atom transfer-mediated N-heterocycles dehydrogenation coupled with the CO2 photoreduction to syngas}, volume = {147}, year = {2025}, }
• (2025). Enantioselective total syntheses of sannamycins a and b. JACS, 147(35), 31476--31481. (www)

  @article{ , abstract = {Aminoglycoside antibiotics are one of the oldest and most clinically relevant classes of anti-infective agents, yet their complex molecular architectures have restricted access through bottom-up syntheses for decades. Herein we report enantioselective syntheses of 2-deoxyfortamine-type aminoglycosides sannamycins A and B. The described strategy involves an enantioselective dearomative hydroamination, rapid stereo- and chemoselective introduction of heteroatom functionalities, and a unique skeletal rearrangement to forge the aminocyclitol core. The carbohydrate fragment was elaborated from Cyrene, a readily available enantioenriched starting material, and was used in a stereoselective glycosylation reaction to deliver natural products in 14 and 17 steps, respectively, from benzene.}, archive = {J_JACS}, author = {Jingyang Zhang and Tsukasa Shimakawa and Chad N. Ungarean and Sungjong Lee and Qingyi Zhu and Shangheng Zhong and David Sarlah}, doi = {10.1021/jacs.5c11901}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31476--31481}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective total syntheses of sannamycins a and b}, volume = {147}, year = {2025}, }
• (2025). Rhodium-catalyzed asymmetric allylic dearomatization of β-naphthols via tandem Etherification/Claisen rearrangement. JACS, 147(35), 31470--31475. (www)

  @article{ , abstract = {Transition metal-catalyzed asymmetric allylic dearomatization of β-naphthols provides efficient access to enantioenriched naphthalenones. However, these reactions generally suffer from limited substrate scope, incompatibility with alkyl-substituted allylic electrophiles, and poor understandings of the reaction mechanism. Herein, we report a rhodium-catalyzed asymmetric allylic dearomatization of β-naphthols utilizing a bisdihydrobenzooxaphosphole (BIBOP) chiral ligand. This catalytic system displays high yields and enantioselectivity and broad substrate scope, efficiently accommodating both alkyl- and aryl-substituted allylic carbonates. Detailed mechanistic studies reveal that the reaction proceeds through a tandem asymmetric allylic etherification/Claisen rearrangement sequence. This provides critical insights into the fundamental pathways for the asymmetric allylic dearomatization of naphthols.}, archive = {J_JACS}, author = {Hu-Chong Wang and Ting-Jia Sun and Zi-Qi Yang and Qing Gu and Shu-Li You}, doi = {10.1021/jacs.5c11943}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31470--31475}, shortjournal = {J. Am. Chem. Soc.}, title = {Rhodium-catalyzed asymmetric allylic dearomatization of β-naphthols via tandem Etherification/Claisen rearrangement}, volume = {147}, year = {2025}, }
• (2025). Catalytic asymmetric ionic hydrogenation of α-alkyl styrenes. JACS, 147(35), 31463--31469. (www)

  @article{ , abstract = {Over the past two decades, chemists have made significant advances in the field of catalytic asymmetric transfer hydrogenation of various unsaturated compounds with biomimetic hydrogen donors. The reduction of carbon–carbon double bonds, however, has been limited to activated substrate classes, such as enals, enones, nitroolefins, or α-(2-hydroxyaryl) styrenes. Here we report a highly enantioselective Brønsted acid-catalyzed ionic hydrogenation of α-alkyl styrenes using a hydrosilane in combination with a protic additive. Mechanistic and computational investigations support a pathway proceeding through a carbocation intermediate and a transient silylated catalyst species, with catalyst turnover dependent on the presence of a protic additive. Moreover, the exemplary stereoconvergent reduction of a trisubstituted alkene highlights the potential of organocatalytic approaches over traditional metal-catalyzed hydrogenations.}, archive = {J_JACS}, author = {Wencke Leinung and Nobuya Tsuji and Michael Merher and Markus Leutzsch and Ravindra K. Raut and Benjamin List}, doi = {10.1021/jacs.5c11514}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31463--31469}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic asymmetric ionic hydrogenation of α-alkyl styrenes}, volume = {147}, year = {2025}, }
• (2025). Enantioselective total synthesis of (−)-novofumigatonin. JACS, 147(35), 31456--31462. (www)

  @article{ , abstract = {We disclose the first and enantioselective synthesis of novofumigatonin, an ortholactone meroterpenoid natural product featuring an unprecedented 7/6/5/6/5/5 hexacyclic skeleton. On a strategic level, this was addressed by a highly convergent strategy that hinges on coupling of a complex neopentylic organolithium reagent and a highly hindered ketone. A unique approach to the ortholactone–acetal was required as it is not peripheral but embedded within the complex carbocyclic framework. This key challenge was addressed by orchestration of a condensation cascade triggered by the selective generation of an oxocarbenium ion. Tempering reactivity in the face of the densely functionalized skeleton proved key and culminated in the total synthesis of novofumigatonin. Of note, this represents the first study on the construction of such an embedded ortholactone, potentially useful for preparation of such motifs in the context of complex molecule synthesis.}, archive = {J_JACS}, author = {Vincent A. P. Ruf and Lukas J. Sprenger and Kirill Volynskiy and Vanessa M. Kandler and Nima Nasiri and Erick M. Carreira}, doi = {10.1021/jacs.5c10466}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31456--31462}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective total synthesis of (−)-novofumigatonin}, volume = {147}, year = {2025}, }
• (2025). Magneto-optical effect of dark state in 0D metal halides through HT/FC vibrational coupling. JACS, 147(35), 31450--31455. (www)

  @article{ , abstract = {Dark excitonic states play a pivotal role in controlling the radiative dynamics of low-dimensional luminescent materials. In this work, we investigate dark states of an emerging zero-dimensional (0D) organic–inorganic hybrid metal halide that diverge markedly from traditional inorganic and organic semiconductors. Our studies reveal that when the dark states dominate the emission, the 0D material exhibits an anomalous giant magneto-blueshift of approximately 9 meV at 7 T. Spectroscopic analysis indicates that the magnetic field modulates the dark state decay pathways, thereby inducing a crossover from the first-order Herzberg–Teller (HT) vibrational coupling mode to the zero-order Franck–Condon (FC) emission mechanism. This field-dependent modulation of dark exciton dynamics underscores the strong interplay between electron–phonon coupling and spin–orbit interactions in these 0D hybrid systems. Our findings provide important insights into the fundamental photophysical processes in these unique materials and open avenues for engineering novel optoelectronic devices.}, archive = {J_JACS}, author = {Zhiyuan Kuang and Xiuyong Li and Xing Wang and Yuyang Zhang and Xinrui Wang and Wei Huang and Qiming Peng and Jianpu Wang}, doi = {10.1021/jacs.5c10273}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31450--31455}, shortjournal = {J. Am. Chem. Soc.}, title = {Magneto-optical effect of dark state in 0D metal halides through HT/FC vibrational coupling}, volume = {147}, year = {2025}, }
• (2025). Catalytic oxidative ligand transfer of rh-carbynoids and alkyl iodides. JACS, 147(35), 31444--31449. (www)

  @article{ , abstract = {Herein, we disclose the first catalytic generation of alkyl–I (III) Rh (II) -carbynoids via oxidative ligand transfer between alkyl iodides and aryl–I (III) Rh (II) -carbynoids. When homoallylic iodides were used, alkyl–I (III) Rh (II) -carbynoids evolved through a diastereoselective cyclopropanation that led to highly electrophilic bicyclic alkyl–I (III) species. We observed that the latter species reacted with a plethora of nucleophiles, enabling access to a valuable class of cyclopropanes that were converted to housanes.}, archive = {J_JACS}, author = {Josep Esteve Guasch and Debasis Pal and Marcos G. Suero}, doi = {10.1021/jacs.5c09559}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31444--31449}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic oxidative ligand transfer of rh-carbynoids and alkyl iodides}, volume = {147}, year = {2025}, }
• (2025). When π–π stacking outcompetes hydrogen bonding: Pre-reactive intermediates in the Furan–Acrolein Diels–Alder reaction. JACS, 147(35), 31439--31443. (www)

  @article{ , abstract = {This study presents the experimental characterization of pre-reactive intermediates in the furan–acrolein Diels–Alder reaction using high-resolution rotational spectroscopy. Three distinct isomers were identified, with π–π stacking unexpectedly prevailing over hydrogen-bonded structures, and the exo structure being slightly more stable than endo . The computationally affordable yet accurate XYG3 method, validated against benchmark CCSD(T) calculations, accurately reproduced the energetic ordering of the isomers. Solvent effects were investigated through microsolvation models, revealing that hexafluoro-2-propanol preserves π–π stacking and enhances exo selectivity via strong hydrogen-bond networks. These findings provide molecular-level insights into the stereocontrol of Diels–Alder reactions, outlining a generalizable role of π–π stacking and solvent-induced noncovalent forces in determining stereoselectivity in solution.}, archive = {J_JACS}, author = {Hao Wang and Gang Fu and Wenping Guo and Yuwei Zhou and Xiao Tian and Xingwu Liu and Jiaxu Zhang and Li Yang and Xingchen Liu and Xiaodong Wen and Walther Caminati and Qian Gou}, doi = {10.1021/jacs.5c08596}, journal = {Journal of the American Chemical Society}, month = {9}, number = {35}, pages = {31439--31443}, shortjournal = {J. Am. Chem. Soc.}, title = {When π–π stacking outcompetes hydrogen bonding: Pre-reactive intermediates in the Furan–Acrolein Diels–Alder reaction}, volume = {147}, year = {2025}, }
• (2025). Correction to “Combining crystallization-driven self-assembly with reverse sequence polymerization-induced self-assembly enables the efficient synthesis of hydrolytically degradable anisotropic block copolymer nano-objects directly in concentrated aqueous media”. JACS, 147(34), 31438. (www)

  @article{ , archive = {J_JACS}, author = {Matthew A. H. Farmer and Osama M. Musa and Steven P. Armes}, doi = {10.1021/jacs.5c11548}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31438}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Combining crystallization-driven self-assembly with reverse sequence polymerization-induced self-assembly enables the efficient synthesis of hydrolytically degradable anisotropic block copolymer nano-objects directly in concentrated aqueous media”}, volume = {147}, year = {2025}, }
• (2025). Heterolytic cleavage of LnPd–SiR3+ bonds enable the ring-opening C–C functionalization of nonstrained ethers. JACS, 147(34), 31429--31437. (www)

  @article{ , abstract = {Silyl palladium cations (R 3 P) 2 Pd–SiR 3 + catalyze the ring opening, C–C bond forming, and functionalization of 5- and 6-membered cyclic allyl ethers with O -silyl nucleophiles. Conditions for high regio-control are achieved by adjustments in the phosphine electronics, with the identity of the 2-substituent also influencing the functionalization location in unsymmetrical furans. Allyl alcohols are obtained with a regio-preference for terminal addition with unsubstituted ethers with E -products being obtained with XantPhos and Z - with (4-CF 3 –Ar) 3 ligation. Styrenes dominate with phenyl-substituted dihydrofurans, and for 2-alkyl-substituted, secondary alcohols result from an allyl migration pathway. Mechanistic studies demonstrate the feasibility of Pd–Si + bonds to facilitate C–O activation to yield π-allyl intermediates, and for one substrate class to also sequence π-allyl migration prior to nucleophilic addition. DFT calculations demonstrated the viability of silylium-activated ether as a competent ligand for Pd(0).}, archive = {J_JACS}, author = {Bradley A. Owen and Kevin Basemann and William A. Hearne and Michel R. Gagné}, doi = {10.1021/jacs.5c12528}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31429--31437}, shortjournal = {J. Am. Chem. Soc.}, title = {Heterolytic cleavage of LnPd–SiR3+ bonds enable the ring-opening C–C functionalization of nonstrained ethers}, volume = {147}, year = {2025}, }
• (2025). A semiconductor nanocluster platform with four structural configurations: An ionic pair with tunable chirality. JACS, 147(34), 31417--31428. (www)

  @article{ , abstract = {In chemistry, a cluster refers to an ensemble of a certain number of atoms that exhibit distinct physicochemical properties as a unified entity. Isostructural clusters, with subtle variations in structure or composition, can display opposite charges, behaving like monatomic ions to undergo classical reaction processes like disproportionation. Herein, we report that the semiconductor nanoclusters can be obtained in the form of a co-crystallized ionic pair, [Cu 56 S 12 (SAdm) 20 (PP) 10 ] + [S@Cu 56 S 12 (SAdm) 20 (PP) 10 ] − (abbreviated as [S-Cu 56 ]·[S@S-Cu 56 ] hereafter). This bi-nanocluster system is a derivative of a neutral copper sulfide nanocluster [S-Cu 56 ] with an interesting onion-like structural configuration containing multiple shells. It consists of two nearly isostructural copper sulfide nanoclusters with opposite charges that differ only by the presence of a S 2– ion at the center of the cluster assembly. This represents an interesting ionic bi-nanocluster system within the p-type copper sulfide semiconductor family, offering the potential to exhibit electrical properties not observed in the individual component nanoclusters. Notably, by utilizing different chiral carboxylate ligands, chirality can be concurrently imparted to the inorganic cores of both ionic clusters, thereby enabling distinct chiroptical responses as revealed by circular dichroism spectroscopy. This eventually results in four different structural configurations based on this onion-like semiconductor nanocluster platform.}, archive = {J_JACS}, author = {Hao Fang and Longlong Geng and Zheng Zhou and Haixiang Han}, doi = {10.1021/jacs.5c12110}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31417--31428}, shortjournal = {J. Am. Chem. Soc.}, title = {A semiconductor nanocluster platform with four structural configurations: An ionic pair with tunable chirality}, volume = {147}, year = {2025}, }
• (2025). C-ALD-grown metal oxide shell enables distance-independent triplet energy transfer from quantum dots to molecular dyes. JACS, 147(34), 31409--31416. (www)

  @article{ , abstract = {Hybrid nanocomposites including quantum dots (QDs) and molecular dyes offer tunability of charge and energy transfer processes, which are attractive for applications spanning from light-emitting devices to photocatalysis and photon upconversion. Core@shell QDs have garnered attention for their ability to modulate charge and energy transfer from the core to the dye via the shell. Recent studies suggested that the core@shell QDs are less demanding in terms of the QD–dye electronic coupling requirements and that the distance dependence of transfer efficiencies may vary from what is traditionally observed in molecular systems. However, these studies remain only a few, and the mechanistic role of the shell is often unclear. Here, we synthesize QD–dye nanocomposites including CdSe@AlOx core@shell QDs, and we report the observation of a nearly distance-independent triplet energy transfer (TEnT) to polyaromatic hydrocarbon (PAH) dyes from the CdSe core of up to almost 2 nm. The use of colloidal atomic layer deposition (c-ALD) for the growth of the metal oxide shell enables tunability of the system, which is crucial to elucidate the role of the shell and the thickness dependence of the TEnT. We propose a plausible mechanism where a hole-transfer-mediated TEnT takes place and defects in the metal oxide act as intermediate states, which enable a long-range, distance-independent TEnT. The versatility of the c-ALD methodology, along with the ability of oxides to preserve the optoelectronic properties of QDs, showcases the potential of oxide shells to optimize the QD–dye interaction to achieve long-range TEnT to molecular dyes, opening new avenues for applying QDs as sensitizers in light-harvesting, emission, and conversion applications.}, archive = {J_JACS}, author = {Marco Fabbiano and Ona Segura Lecina and Huygen J. Jöbsis and Tejas Deshpande and Skylar J. Sherman and Gordana Dukovic and Sascha Feldmann and Raffaella Buonsanti}, doi = {10.1021/jacs.5c11645}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31409--31416}, shortjournal = {J. Am. Chem. Soc.}, title = {C-ALD-grown metal oxide shell enables distance-independent triplet energy transfer from quantum dots to molecular dyes}, volume = {147}, year = {2025}, }
• (2025). Enhancing carbon dioxide reduction performance on copper via surface reconstruction induced by spontaneous diazonium salt grafting. JACS, 147(34), 31395--31408. (www)

  @article{ , abstract = {The electrochemical reduction of CO 2 (eCO 2 RR) is a promising strategy for sustainable energy storage and the production of carbon-neutral chemical feedstocks. Among available catalysts, Cu-based materials uniquely enable the formation of valuable multicarbon (C 2+ ) products; however, achieving high selectivity remains a major challenge. In this study, we present a straightforward and effective strategy to enhance C 2+ product formation by spontaneously grafting a benzenediazonium salt onto polycrystalline Cu electrodes. The resulting covalently bound polyphenylene-like film yields a 6-fold increase in Faradaic efficiency for C 2+ products compared to bare Cu, while concurrently suppressing the hydrogen evolution reaction. Surface characterization reveals that the grafting process induces significant Cu surface reconstruction, alters the Cu valence state, and promotes the formation of high-index facets and defect sites, features associated with improved C–C coupling. Additionally, the organic layer increases the surface hydrophobicity, which may further contribute to product selectivity by modifying the local reaction environment. To isolate the role of surface restructuring and oxidation, control experiments using electrografted films and oxide-derived Cu electrodes were performed. These controls exhibited inferior performance, confirming that the improved selectivity primarily arises from the structural and chemical changes induced by spontaneous grafting. This work highlights the critical role of molecular-film-induced surface reconstruction and hydrophobic tuning in steering product distribution during CO 2 electroreduction.}, archive = {J_JACS}, author = {Pegah Nazari and Siqi Zhao and Oliver Christensen and Zhaozong Sun and Marcel Ceccato and Jeppe Vang Lauritsen and Steen Uttrup Pedersen and Jan Rossmeisl and Alonso Rosas-Hernández and Kim Daasbjerg}, doi = {10.1021/jacs.5c11431}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31395--31408}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing carbon dioxide reduction performance on copper via surface reconstruction induced by spontaneous diazonium salt grafting}, volume = {147}, year = {2025}, }
• (2025). Unraveling the full photochromic reaction pathway of binaphthyl-bridged imidazole dimers. JACS, 147(34), 31387--31394. (www)

  @article{ , abstract = {Light-driven reversible molecular switching is a promising strategy for constructing stimuli-responsive dynamic materials. In this study, we present BN-DBOXPImD, a rationally designed negative photochromic molecule featuring dibenzoxepine units integrated into a binaphthyl-bridged imidazole dimer (BN-ImD) framework. This compound exhibits a markedly accelerated thermal reversion from the metastable colorless isomer to the stable colored isomer. Although BN-ImD derivatives are known to undergo multistate photoisomerization via a short-lived biradical intermediate, a quantitative assessment of each individual step has yet to be accomplished. Global analysis of the transient absorption spectra of the colored and colorless isomers enabled the determination of the rate constants and quantum yields for the individual photoisomerization processes. The photoconversion efficiency from the colored to the colorless isomer was determined to be 0.082, corresponding to an approximate 19% enhancement over the previously reported value of 0.069 for BN-ImD. Furthermore, a previously unknown isomer, exhibiting distinct photoresponsive behavior compared to that of the other isomers, was identified and successfully characterized. Carefully designed quantum chemical calculations successfully reproduced all photoisomerization diagrams, encompassing both thermal and photochemical isomerization pathways. These findings highlight the critical role of structural flexibility in governing the photochromic behavior of BN-ImD and offer a guiding framework for the rational design of next-generation molecular photoswitches exhibiting negative photochromism.}, archive = {J_JACS}, author = {Shiori Yagi and Takumi Aizawa and Jiro Abe}, doi = {10.1021/jacs.5c11403}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31387--31394}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the full photochromic reaction pathway of binaphthyl-bridged imidazole dimers}, volume = {147}, year = {2025}, }
• (2025). Photoinduced charge transfer at discrete molecular interfaces in cocrystals. JACS, 147(34), 31374--31386. (www)

  @article{ , abstract = {Precise construction of molecular heterostructures in organic donor–acceptor (D–A) cocrystals is crucial for understanding charge transfer (CT) dynamics and developing high-performance optoelectronic materials. Although cocrystals with densely packed D–A arrays have been widely investigated, discrete heterojunctions at the molecular scale have been scarcely explored. Herein, we demonstrate an approach to create what we have referred to as discrete molecular interfaces in D–A cocrystals employing a tetracationic naphthalenediimide-based macrocycle ( NBox 4+ ) and an electron-rich guest pyrene ( Pyr ). The large cavity of NBox 4+ reduces its host–guest binding affinity with pyrene in solution but facilitates the formation of A–D–A discrete molecular interfaces in the NBox·Pyr cocrystal. The NBox·Pyr cocrystal exhibits a 20 nm red shift in UV–vis absorption and a ∼0.1 eV lower CT state energy compared to the NPy·Pyr cocrystal, formed from Pyr and the monomeric analogue ( NPy 2+ ) of NBox 4+ , which features conventional 1D alternating D–A stacks. Femtosecond transient absorption microscopy reveals a shorter CT state lifetime of 203 ps in NBox·Pyr (versus 1083 ps in NPy·Pyr ), indicating faster charge recombination as a result of stronger electronic coupling at the discrete molecular interfaces in the NBox·Pyr cocrystal. This research highlights the critical role of discrete molecular interfaces in tailoring CT interactions and excited-state dynamics in the solid state, offering a powerful and versatile strategy for designing optoelectronic materials with molecular-level spatial resolution.}, archive = {J_JACS}, author = {Han Han and Xingang Zhao and Malik L. Williams and Ryan M. Young and Bo Song and Yang Jiao and Bai-Tong Liu and Xueze Zhao and Shuai Fang and Chun Tang and Hongliang Chen and Xuesong Li and Guangcheng Wu and Ruihua Zhang and Yi-Kang Xing and Shuliang Yang and Yong Wu and Penghao Li and Aspen X.-Y. Chen and Charlotte L. Stern and Kang Cai and Michael R. Wasielewski and J. Fraser Stoddart}, doi = {10.1021/jacs.5c11418}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31374--31386}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoinduced charge transfer at discrete molecular interfaces in cocrystals}, volume = {147}, year = {2025}, }
• (2025). Recyclable inorganic subnanowire plastics. JACS, 147(34), 31365--31373. (www)

  @article{ , abstract = {The recycling and reuse of plastics have become pressing global issues due to the severe environmental impact of white pollution. Developing plastic materials that can achieve highly selective recycling through environmentally friendly and energy-saving methods is urgent. Herein, a new class of dynamically cross-linked inorganic subnanowire (SNW) plastics is developed, which can be efficiently recycled through simple redispersion and hot-pressing processes, without the need for complex conditions, catalysts, or pollutant-generating acid or alkaline solutions. The typical SNW 1 plastic demonstrates high mechanical properties, with a tensile strength of 30.55 MPa and a Young’s modulus of 1.46 GPa, surpassing most recyclable plastics with dynamic bonds. Through this universal strategy, multiple types of SNW plastics with excellent mechanical performance, recyclability, good processability, multiple functions, quantity production, and cost efficiency can be prepared successfully. This study provides a new design idea for developing recyclable and high-strength SNWs that exhibit both the functionality of inorganic nanomaterials and the processability of polymers.}, archive = {J_JACS}, author = {Renchan Lei and Bo Qin and Wenxiong Shi and Kaiyang Xing and Simin Zhang and Xun Wang}, doi = {10.1021/jacs.5c11335}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31365--31373}, shortjournal = {J. Am. Chem. Soc.}, title = {Recyclable inorganic subnanowire plastics}, volume = {147}, year = {2025}, }
• (2025). Creating a modular activatable CRISPR–Cas12a system by engineering crRNA scaffold with a steric hindrance effector. JACS, 147(34), 31349--31364. (www)

  @article{ , abstract = {CRISPR–Cas systems inherently lack spatiotemporal control over cleavage events, compromising their accuracy and efficiency in biotechnological applications. Although advances have been made in regulating these systems, developing modular activatable platforms adaptable to diverse stimuli remains challenging. To address this limitation, we developed an innovative modular activatable CRISPR–Cas12a system by engineering a crRNA scaffold with a steric hindrance effector (SHE) motif at its 3′-terminus, attached via a stimulus-cleavable linker. Through systematic evaluation of SHEs with varied sizes and structures─including linear, duplex, hairpin, and triplex─we identified their steric hindrance-dependent inhibitory effects on CRISPR–Cas12a functionality. Notably, the effective SHEs capable of completely inhibiting CRISPR–Cas12a functionality were successfully released upon ultraviolet light exposure, restoring system functionality. Furthermore, the crRNA scaffold-engineering strategy proved applicable to other type V-A Cas12a orthologs. Importantly, the system was adapted to respond to enzymatic stimuli (such as human apurinic/apyrimidinic endonuclease 1 [APE1]) and chemical stimuli (such as glutathione [GSH]). Finally, the modular activatable CRISPR–Cas12a system enabled light-activatable, one-pot nucleic acid diagnostics and APE1-activatable, tumor cell-selective microRNA imaging. Our study highlights the innovative use of steric hindrance to manipulate CRISPR–Cas12a functionality and provides valuable insights for the rational design of modular activatable CRISPR–Cas systems.}, archive = {J_JACS}, author = {Pengfei Liu and Sheng Li and Jiayu Zeng and Meixia Wang and Jinlian Du and Hong-Hui Wang and Erhu Xiong and Ronghua Yang}, doi = {10.1021/jacs.5c11227}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31349--31364}, shortjournal = {J. Am. Chem. Soc.}, title = {Creating a modular activatable CRISPR–Cas12a system by engineering crRNA scaffold with a steric hindrance effector}, volume = {147}, year = {2025}, }
• (2025). Control on the stacking mode in a sulfonic covalent organic framework enabling a precise uranyl-identified pocket for ultrahigh-capacity uranium extraction from seawater. JACS, 147(34), 31340--31348. (www)

  @article{ , abstract = {Designing a precise uranyl-identified motif in materials to meet the planar coordination nature of uranyl ion is highly important for uranium extraction from seawater but remains a challenging issue. Herein, we find that the control on the stacking mode in sulfonic -COF (covalent organic framework) can be used to create a precise uranyl-identified motif. The AB stacking in sulfonic COF leads to the formation of a uranyl-identified pocket that can execute an exact recognition toward uranyl through a planar four coordination, thus allowing for not only a high affinity toward uranyl with a K d value of 10 × 10 9 mL/g but also a high U/V selectivity up to 10 3 . More attractively, in natural seawater, sulfonic -COF in the AB stacking mode affords an ultrahigh extraction capacity of 31.5 mg/g in just 1 day and 37.1 mg/g in 7 days, creating a record in this field. At the same time, the uptake of other ions such as Fe, Cu, Zn, and V is extremely low (less than 2 mg/g), suggesting the superior potential of the sulfonic -COF in AB stacking for acquiring uranium from seawater.}, archive = {J_JACS}, author = {Liecheng Guo and Yuxuan Liu and Yuanzhe Jia and Zhe Cheng Huang and Lele Gong and Xianqing Xie and Feng Luo}, doi = {10.1021/jacs.5c10932}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31340--31348}, shortjournal = {J. Am. Chem. Soc.}, title = {Control on the stacking mode in a sulfonic covalent organic framework enabling a precise uranyl-identified pocket for ultrahigh-capacity uranium extraction from seawater}, volume = {147}, year = {2025}, }
• (2025). Chlorocobaltate-enabled selective separation of CoCl2 from mixed chloride and nitrate salts of mn, co, and ni. JACS, 147(34), 31332--31339. (www)

  @article{ , abstract = {Described here is the effect of anionic metalates─chlorocobaltate and nitratocobaltate─on the heat-driven separation of the critical element cobalt from potentially competing transition metal salts. Resins bearing the hexadentate glycolamide receptor L (PS- L ) exhibit sorption capacities, Q = 1.33 mmol/g for CoCl 2 and Q = 0.66 mmol/g for Co(NO 3 ) 2 , as inferred from sorption isotherm studies. This trend runs counter to the typical Hofmeister series for anion selectivity. Ion chromatographic analysis of a mixed CoCl 2 /Co(NO 3 ) 2 solution revealed an increase in chloride content from 55 mol % to 90 mol % after a single thermally driven catch-and-release cycle. This chloride-selective behavior was recapitulated in a mixed-metal cation, mixed-anion system containing the chloride and nitrate salts of Mn(II), Co(II), and Ni(II) at near-equimolar concentrations. PS- L also displayed enhanced selectivity for Co using this mixed stock solution as observed by ICP-OES. In contrast, for a nitrate-only solution containing Mn(II), Co(II), and Ni(II), PS- L showed increased affinity for Mn, with its proportion rising from 36.6 mol % to 58.1% after a single catch-and-release cycle. Density functional theory calculations support the suggestion that the enhanced uptake of Co(II) in chloride-rich media arises from the high thermodynamic stability of [CoCl 4 ] 2– , which facilitates its outer-sphere coordination to cationic resin-bound cobalt species. Single crystal X-ray crystallographic analyzes of L •MCl 2 (M = Mn, Co, Ni) and L •M(NO 3 ) 2 (M = Mn, Co) confirmed metal complexation by L in the solid state and the concomitant formation of metalate counteranions. The present study highlights a relatively simple approach for separating cobalt from its transition metal congeners.}, archive = {J_JACS}, author = {Sheng-Yin Huang and Debmalya Ray and Jian Yang and Serhii Vasylevskyi and Vyacheslav S. Bryantsev and Jonathan L. Sessler}, doi = {10.1021/jacs.5c10888}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31332--31339}, shortjournal = {J. Am. Chem. Soc.}, title = {Chlorocobaltate-enabled selective separation of CoCl2 from mixed chloride and nitrate salts of mn, co, and ni}, volume = {147}, year = {2025}, }
• (2025). Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom Transfer/Halogen atom transfer acylation of alkyl bromides and chlorides. JACS, 147(34), 31324--31331. (www)

  @article{ , abstract = {Acyl azolium salts have been recently described as good HAT mediators in their excited state-similarly to diaryl ketones-and good acylating reagents, with the beneficial property of enabling incorporation of the acyl residue into the final molecule. Nevertheless, despite significant synthetic efforts in the field, knowledge and understanding of the key reactive intermediates─especially through spectroscopic investigations─remain elusive. Herein, we present a photochemical study of the reactivity of acyl azolium salts that comprises the detection and characterization of the triplet excited state and the decisive ketyl radical intermediate. Moreover, this mechanistic insight allowed us the development of an alternative method based on a silane-mediated tandem HAT/XAT activation strategy that enables not only the acylation of alkyl bromides but also the acylation of the more challenging alkyl chlorides. The method has proven to be efficient, regardless of the electronic properties of the acyl azolium or the substituents present in the alkyl halide. Furthermore, its robustness has been proven through the functionalization of natural product derivatives either as acyl azolium or alkyl bromide derivatives.}, archive = {J_JACS}, author = {Ian MacLean and Daniel Jan Grenda and Elena Echávarri and Stephan Muth and Patrick Nuernberger and Leyre Marzo}, doi = {10.1021/jacs.5c10923}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31324--31331}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemical insights on acyl azolium salts enable the design of a tandem hydrogen atom Transfer/Halogen atom transfer acylation of alkyl bromides and chlorides}, volume = {147}, year = {2025}, }
• (2025). A sterically controlled and tumor-activated programmable singlet-oxygen battery. JACS, 147(34), 31310--31323. (www)

  @article{ , abstract = {Limited light penetration and insufficient oxygen supply within the tumor microenvironment have been the “Achilles’ heel” of traditional photodynamic therapy. Programmable singlet-oxygen batteries (PSOBs) have emerged as a promising strategy to overcome these challenges, capable of storing 1 O 2 pretherapy and releasing it during therapy in the tumor microenvironment, independent of light and oxygen supply. However, effective strategies for constructing lifetime tunable PSOBs remain limited, thereby limiting their application in different scenarios. Herein, we introduce a sterically controlled PSOB strategy featuring an “OFF–ON–OFF” controlled release of 1 O 2 at a tumor site. Specifically, linear substitutions at the bridgehead carbon of SOB-A and SOB-B enhance 1 O 2 storage stability with t 1/2 values of 10.5 and 8.7 h, respectively. SOB-A and SOB-B can be further stabilized by a nanoconfinement effect when encapsulated in Cu (II)-based MOF-199 with a significantly increased half-life of approximately 60 h, ensuring low side-effect pretherapy. On the other hand, in the tumor microenvironment, MOF-199 serves as a precursor of Cu(I), catalyzing the in situ synthesis of SOB-AB with larger cyclic steric hindrance, rapidly releasing 1 O 2 with a t 1/2 of 9.5 min during therapy. This approach unveiled the impact of surrounding steric hindrance on the stability of a metastable oxygen bridge in PSOBs. This paves the way for the next generation of PSOB by constructing dynamic steric effects in the bridgehead carbon, maximizing its efficiency for 1 O 2 delivery with minimized side effects.}, archive = {J_JACS}, author = {Jianwu Tian and Bowen Li and Chongzhi Wu and Zhiyao Li and Wentao Song and Bo Song and Yufu Tang and Weidong Pan and Bin Liu}, doi = {10.1021/jacs.5c10714}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31310--31323}, shortjournal = {J. Am. Chem. Soc.}, title = {A sterically controlled and tumor-activated programmable singlet-oxygen battery}, volume = {147}, year = {2025}, }
• (2025). A compositionally biased oligourethane sensor array to differentiate solids by their surface chemistry: An analogy to the sense of touch. JACS, 147(34), 31300--31309. (www)

  @article{ , abstract = {Array-based differential sensing is inspired by a mammal’s sense of taste and smell. The human sense of touch is also array-based; using mechanosensors in the skin that differentiate surfaces by their surface chemistry. Inspired by this, we aimed to develop a rationally biased and randomized oligomer sensor array which differentiates bulk solids by their surface chemistry. Column chromatography mimics this aspect of the sense of touch, as it is traditionally used to physically separate molecules in solution by the strength of their noncovalent interactions with the stationary phase. In this report, we differentiated column chromatography stationary phases (the analyte) by the retention time (the sensor’s analytical response) of a vast library of oligomers with statistically biased but random monomer compositions (the sensor array). The use of unsupervised principal component analysis (PCA) validated our sensor array design by differentiating five surfaces with tight replicate clustering and a high degree of cross-reactivity.}, archive = {J_JACS}, author = {Hazel A. Fargher and Jongdoo Lim and Julia R. Shuluk and Christopher D. Wight and Silke Asche and Preethi Devireddy and Yuhan Zhou and Marissa S. Vera and Samuel D. Dahlhauser and Sanchita Bhadra and Catherine Maggiori and Sarah S. Johnson and Heather V. Graham and Andrew D. Ellington and Eric V. Anslyn}, doi = {10.1021/jacs.5c10754}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31300--31309}, shortjournal = {J. Am. Chem. Soc.}, title = {A compositionally biased oligourethane sensor array to differentiate solids by their surface chemistry: An analogy to the sense of touch}, volume = {147}, year = {2025}, }
• (2025). Water dynamics in the formation of single-component-based multiphasic droplets. JACS, 147(34), 31290--31299. (www)

  @article{ , abstract = {Despite the significant presence of water in the liquid–liquid phase separation (LLPS) of biomolecular condensates, its critical role beyond the solvent effects has been largely overlooked. In this study, we investigate the synergistic effects of water on modulating the substructure and properties of biomolecular condensates. We designed and synthesized a series of peptide-based droplets with varying microstructures. Utilizing in situ Raman and Fourier transform infrared (FTIR) spectroscopy, we elucidate how an increased hydrogen bonding network between the peptide and water, coupled with a decreased hydrogen bonding network among peptides, drives the transition from multiphasic to homogeneous configurations. Furthermore, we demonstrate that this transformation can be dynamically regulated by adjusting peptide-water interactions through the application of Chaotropic and Kosmotropic agents. Our findings underscore the essential role of hydration water in the LLPS of single-component systems, paving the way for innovative strategies in the design and modulation of advanced hydrated materials.}, archive = {J_JACS}, author = {Laicheng Zhou and Liheng Lu and Yang Zhang and Jing Wang and Jianjun Cheng and Huaimin Wang}, doi = {10.1021/jacs.5c10784}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31290--31299}, shortjournal = {J. Am. Chem. Soc.}, title = {Water dynamics in the formation of single-component-based multiphasic droplets}, volume = {147}, year = {2025}, }
• (2025). Biocatalyzed lactate oxidation enables efficient bias-free hydrogen production in a three-chamber reactor. JACS, 147(34), 31280--31289. (www)

  @article{ , abstract = {The catalytic conversion of low-grade organic substrates into hydrogen offers a promising route for low-energy hydrogen production, thereby supporting sustainable resource utilization. However, realizing this potential requires efficient and robust catalysts that can operate at low overpotential. Conventional inorganic catalysts, including those based on costly precious metals, are generally plagued by high overpotentials for organic oxidation. Here, we demonstrate a unique bacteria-catalyzed lactate oxidation process for hydrogen production using a three-chamber reactor. This three-chamber system integrates a neutral bacteria-driven anolyte, a basic electrolyte bridge, and an acidic catholyte to achieve low-overpotential lactate oxidation coupled with efficient hydrogen evolution. The system enables simultaneous bias-free hydrogen generation and power output, reaching a peak current of ∼13 mA cm –2 , with an electricity generation of ∼0.22 kWh per cubic meter of H 2 at 10 mA cm –2 . The system maintains stable operation for over 1000 h at 10 mA cm –2 with a high Coulombic efficiency (∼95%) and near-unity Faradaic efficiency for H 2 production (∼99%). Moreover, we show that this system can effectively leverage acidic and alkaline waste from semiconductor processing to enable bias-free hydrogen production, advancing low-emission electrolysis technologies for a sustainable hydrogen economy}, archive = {J_JACS}, author = {Leyuan Zhang and Yang Liu and Sibo Wang and Fernando Lopez and Xiangfeng Duan and Yu Huang}, doi = {10.1021/jacs.5c10688}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31280--31289}, shortjournal = {J. Am. Chem. Soc.}, title = {Biocatalyzed lactate oxidation enables efficient bias-free hydrogen production in a three-chamber reactor}, volume = {147}, year = {2025}, }
• (2025). Chirality-assisted self-assembly of low-symmetry noncovalent capsules with quantitative diastereoisomeric selection. JACS, 147(34), 31270--31279. (www)

  @article{ , abstract = {One of the main aspects in which artificial capsules and cages still differ from their biological counterparts is symmetry─a fundamental trait that gives natural systems exceptional selectivity in molecular recognition. While the symmetry challenge has been recently addressed within metallosupramolecular or covalent systems, the creation of purely noncovalent capsular assemblies with tunable symmetry remains elusive. One exciting avenue toward reducing symmetry is to avail chirality in chiral-sensitive self-assembly, where symmetry is altered upon component binding. Herein, we report new pathways for the self-assembly of purely noncovalent capsules, wherein both the assembly outcome and symmetry can be finely adjusted through the strategic design of hydrogen bonding motifs and chirality. Specifically, depending on the mixture composition and hydrogen bonding centers embedded on the amino acid-derived benzene-1,3,5-triamide components, the system yields purely noncovalent capsules, ranging from highly symmetrical dimers to reduced symmetry octamers and new heterochiral tetrameric assemblies of low symmetry. The self-assembly processes presented here can be selectively modulated between narcissistic self-sorting pathways and diastereoselective social mixing, as well as toward the creation of social heterocomponent libraries─all yielding distinct capsular products. By showcasing the unique ability for molecular recognition, we believe our approach will pave the way for creating new capsular-type assemblies with unique functionalities and provide a fresh perspective on intricate, nature-inspired molecular dynamics.}, archive = {J_JACS}, author = {Grzegorz Markiewicz and Xujun Qiu and Gokay Avci and Emma H. Wolpert and Kim E. Jelfs and Jeremy K. M. Sanders and Artur R. Stefankiewicz}, doi = {10.1021/jacs.5c10523}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31270--31279}, shortjournal = {J. Am. Chem. Soc.}, title = {Chirality-assisted self-assembly of low-symmetry noncovalent capsules with quantitative diastereoisomeric selection}, volume = {147}, year = {2025}, }
• (2025). In situ single-crystal X-ray diffraction studies of an anomalous nitric oxide adsorption in a partially activated Metal–Organic framework. JACS, 147(34), 31260--31269. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs), with their high porosities and surface areas, show great utility in the field of gas adsorption. To unlock this porosity, MOFs are generally fully activated by removing all adsorbed guests using high temperatures and low pressures. However, this is energy intensive and can be unfeasible if the MOF is part of a composite, where the maximum temperature of the composite is below the activation temperature. To investigate the effect of activation temperature on adsorption, a series of in situ single-crystal X-ray diffraction (scXRD) studies were performed on Ni-MOF-74 loaded with the gas nitric oxide (NO) under different conditions. These experiments uncovered anomalous adsorption results where partially activated samples adsorb ∼14% more NO per framework material than did the fully activated sample. The scXRD experiments revealed a new NO binding site that is only present if the open metal sites are partially occupied by water molecules. To shed more light on the respective binding of the two different NO sites in Ni-MOF-74, these were studied in situ under different treatment conditions, such as the exposure to vacuum at different temperatures. This study yields insights into the nature of binding sites in MOFs, how these are affected by activation, and helps to pave the way for the improved design of processing conditions.}, archive = {J_JACS}, author = {Russell M. Main and Romy Ettlinger and Tia K. Tajnšek and Deborah A. Brako-Amoafo and Maximillian G. Stanzione and Morven J. Duncan and Philip Ettlinger and Gaynor B. Lawrence and Mark R. Warren and Christopher J. Heard and Russell E. Morris}, doi = {10.1021/jacs.5c10395}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31260--31269}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ single-crystal X-ray diffraction studies of an anomalous nitric oxide adsorption in a partially activated Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Anode-protective covalent organic framework layer with synergistic Cation–Anion regulation for dendrite-free lithium metal batteries. JACS, 147(34), 31249--31259. (www)

  @article{ , abstract = {Lithium (Li) dendrite formation in Li metal batteries intrinsically challenges Coulombic efficiency (CE) and safety. While constructing an anode protective layer offers a potential solution for dendrite suppression, existing approaches are limited by insufficient molecular-level control over both Li + and anion dynamics simultaneously. Herein, we construct a binary cooperative magnesium porphyrin-based covalent organic framework (Mg-Por-COF) protective layer designed for synergetic cation–anion regulation at the anode–electrolyte interface. This design spatially separates lithiophilic and anionophilic sites within the pore walls and framework. Specifically, Mg-Por-COF promotes Li + desolvation through strong interactions and immobilizes TFSI – anions via Mg 2+ coordination. This dual action prevents space charge accumulation caused by local anion depletion, enabling smooth and compact Li deposition, even under a demanding areal current of 10 mA cm –2 . Consequently, the Li/Mg-Por-COF-Cu cell achieves an extended cycle life of 400 cycles with a high average CE of 98.3%, outperforming the bare Cu counterpart by ∼400%. Furthermore, the LiFePO 4 /Mg-Por-COF-Li full cell demonstrates remarkable cycling stability with an average CE of 99.1% over 324 cycles. Simulations corroborate the dual role of Mg-Por-COF in modulating Li + transport and immobilizing TFSI – anions, providing unique atomic control for Li uniform deposition. These findings highlight the potential of structurally designed COFs as superior protective layers for high-performance energy storage, offering high chemical designability and sustainability.}, archive = {J_JACS}, author = {Shuang Zheng and Yubin Fu and Cheng Song and Chunlei Wang and Yang Wu and Shenggang Li and Qing Xu and Joseph S. Francisco and Gaofeng Zeng}, doi = {10.1021/jacs.5c10386}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31249--31259}, shortjournal = {J. Am. Chem. Soc.}, title = {Anode-protective covalent organic framework layer with synergistic Cation–Anion regulation for dendrite-free lithium metal batteries}, volume = {147}, year = {2025}, }
• (2025). Dynamic pore space partition in zinc Metal–Organic frameworks. JACS, 147(34), 31239--31248. (www)

  @article{ , abstract = {Increasing the framework connectivity is a useful strategy to tune pore geometry and properties such as gas separation selectivity. Although highly connected frameworks are common for iconic clusters such as M 3 (O/OH) trimers and Zr 6 (O/OH) 8 hexamers, they are rarely seen for Zn 4 O tetramers, one of the most famed MOF building blocks that predates both M 3 and Zr 6 in the MOF field. Here, we demonstrate that pore space partition (PSP) can unlock the potential of Zn 4 O for higher connectivity (>6). We show that on the pore-space-partitioned acs (pacs) platform, zinc-cluster chemistry is diverse and dynamic, yet it can be mapped out semiquantitatively. A large family of Zn x –pacs materials ( x = 2, 3, 4) with 3 different pore-partition mechanisms has been synthesized by applying PSP to the MOF-5-type system. We propose that the difference in the steric effect around 9-connected Zn 3 (OH) and Zn 4 O, exacerbated when the hexagonal c/a ratio is compressed, plays a key role in the discovery of a new pacs family based on 9-connected Zn 4 O. This work significantly broadens the scope of PSP because it no longer requires preoriented open-metal sites. New pacs materials show much better aqueous stability and greatly enhanced C 2 H 2 /C 2 H 4 separation performance than the corresponding nonpartitioned MOF-5-type materials.}, archive = {J_JACS}, author = {Wei Wang and Yichong Chen and Khai X. Phan and Ziyang Jia and Yuchen Xiao and Xianhui Bu and Pingyun Feng}, doi = {10.1021/jacs.5c10414}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31239--31248}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic pore space partition in zinc Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Metastable clusters and competitive solvation tune ion pairing at liquid interfaces. JACS, 147(34), 31228--31238. (www)

  @article{ , abstract = {The balance of hydrophobic and hydrophilic interactions underlies emergent phenomena in complex multicomponent chemical systems. Here, we show that a supposedly ‘non–interacting’ nonpolar phase can be used to competitively solvate amphiphilic molecules at an oil/aqueous interface. This solvation, as probed by surface specific nonlinear spectroscopy and simulations, results in a molecularly thin corrugated phase boundary featuring metastable assemblies that alter the hydrogen bonding networks of water and the apparent ‘hard/soft’ descriptors used to describe ionic interactions. We show that competitive solvation enhances amphiphile mobility, opening up otherwise energetically inaccessible complexes that transiently interact with aqueous phase ions. These transient species impact ensemble binding affinities and may represent the molecular agents responsible for aspects of ionic transport and function. The result of this work highlights how seemingly unrelated nonpolar interactions feedback onto aqueous phase chemical phenomena, providing a pathway to tune phase separation and self-assembly to access new reaction pathways using interfaces for a range of chemical and biological systems.}, archive = {J_JACS}, author = {Pan Sun and Robert L. Sacci and Uvinduni I. Premadasa and Jan-Michael Y. Carrillo and Santanu Roy and Benjamin Doughty}, doi = {10.1021/jacs.5c10295}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31228--31238}, shortjournal = {J. Am. Chem. Soc.}, title = {Metastable clusters and competitive solvation tune ion pairing at liquid interfaces}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of the nominal structure of (+)-talaromyolide d. JACS, 147(34), 31221--31227. (www)

  @article{ , abstract = {We describe a convergent and stereoselective total synthesis of the nominal structure of (+)-talaromyolide D ( 4 ), a recently isolated secondary metabolite. This meroterpenoid features a unique pentacyclic skeleton distinguished by a fused 6/6/6 dihydroisocoumarin core and an unusual pendant dimethylcyclobutanol embedded within a sequence of four contiguous stereocenters. Our synthetic strategy was enabled by a stereoretentive, nickel-catalyzed electrochemical sp 2 –sp 3 decarboxylative cross-coupling, a two-fold bidirectional stitching sequence comprised of an oxime-directed β-C(sp 3 )–H arylation and S N Ar to establish the central ring system of the target as well as a series of two late-stage carboxylic-acid-directed C(sp 2 )–H oxidation reactions to ultimately access the isocoumarin lactone substructure. This asymmetric synthesis provides the first access to the reported structure of talaromyolide D ( 4 ). Comparison of the spectral data showed that the structure of this natural product had been misassigned, and our strategy may present an opportunity for further structural elucidation of the talaromyolide family isolates.}, archive = {J_JACS}, author = {Bo Qin and Alex Szyperek and Martin Tomanik}, doi = {10.1021/jacs.5c10325}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31221--31227}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of the nominal structure of (+)-talaromyolide d}, volume = {147}, year = {2025}, }
• (2025). Experimental evidence of room-temperature ferromagnetism in semiconducting MnS2. JACS, 147(34), 31212--31220. (www)

  @article{ , abstract = {The discovery of two-dimensional (2D) ferromagnetic semiconductors holds significant promise for advancing Moore’s law and spintronics in-memory computing, sparking tremendous interest. However, the Curie temperature of explored 2D ferromagnetic semiconductors is much lower than room temperature. Although plenty of 2D room-temperature ferromagnetic semiconductors have been theoretically predicted, there have been formidable challenges in preparing such metastable materials with ordered structures and high stability. Here, utilizing a novel template-assisted chemical vapor deposition strategy, we synthesized layered MnS 2 microstructures within a ReS 2 template. The high-resolution atomic structure representation revealed that monolayer MnS 2 microstructures well crystallize into a distorted T-phase. Room-temperature ferromagnetism was confirmed through vibrating sample magnetometer measurements, microzone magnetism imaging techniques, and transport characterization. Theoretical calculations indicated that the room-temperature ferromagnetism originates from the Mn–Mn short-range interaction. Our observation not only offered the experimental confirmation of the intrinsic room-temperature ferromagnetism in layered MnS 2 , but also provided an innovative strategy for the growth of 2D metastable functional materials.}, archive = {J_JACS}, author = {Yibin Zhao and Yi Wan and Chengxi Huang and Pingfan Gu and Xiaomin Zhang and Yucong Wu and Mingyan Liu and You Li and Kaiyou Wang and Erjun Kan}, doi = {10.1021/jacs.5c10107}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31212--31220}, shortjournal = {J. Am. Chem. Soc.}, title = {Experimental evidence of room-temperature ferromagnetism in semiconducting MnS2}, volume = {147}, year = {2025}, }
• (2025). Sln-topological covalent organic frameworks with shape dimorphism and dipolar rotors. JACS, 147(34), 31204--31211. (www)

  @article{ , abstract = {We report herein the first (i) covalent organic frameworks (COFs) with sln topology, (ii) drastic control of the shape of COF crystals with the same topology and chemical composition, (iii) insight that these different shapes are accompanied by conformational isomerism, and (iv) installation of dipolar rotors into three-dimensional (3D) COFs. We used a new building block, hexaarylbenzene with three dipolar 1,2-difluorophenyls. Depending on the solution composition, we generated two types of COF crystals with different shapes: hexagonal prism ( TK-COF-P ) and membrane ( TK-COF-M ). Although they exhibit distinctly different powder X-ray diffraction patterns, they are chemically identical. The structural determinations revealed that they have a low-symmetric, low-density sln topology that is yet to be reported for COFs. The two distinct shapes─shape dimorphism─is found to accompany conformational isomerism. Temperature-dependent dielectric and 19 F NMR relaxation-time measurements reveal that the rotor motion is suppressed at room temperature, but the rotors respond to an external electric field at elevated temperatures owing to the high activation energy for rotation (∼20 kcal mol –1 ), which is desired for room-temperature applications including molecular memories. These outcomes have not only expanded the diversity of COFs but have also provided a foundation for installing external-field-responsive functions into COFs that have high thermal stability, which is expected to invoke broad applications.}, archive = {J_JACS}, author = {Xiaohan Wang and Syunto Goto and Takejiro Ogawa and Takuya Miyazaki and Kouki Kawamura and Atsuko Kosaka and Hiroaki Suzuki and Wang Zhang and Koji Yazawa and Yutaro Ogaeri and Takayuki Kamihara and Kiyohiro Adachi and Daisuke Hashizume and Yukihito Kondo and Takumi Sannomiya and Hidehiro Uekusa and Masaki Kawano and Ryosuke Takehara and Yoshiaki Shoji and Takanori Fukushima and Yoichi Murakami}, doi = {10.1021/jacs.5c10010}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31204--31211}, shortjournal = {J. Am. Chem. Soc.}, title = {Sln-topological covalent organic frameworks with shape dimorphism and dipolar rotors}, volume = {147}, year = {2025}, }
• (2025). Chiral porous sheet assembly for multiple chirality induction in macrocycle formation. JACS, 147(34), 31198--31203. (www)

  @article{ , abstract = {The stereochemistry of chiral macrocycles bearing multiple chirality has a crucial influence on their physical and biological properties. Nevertheless, the multiple chirality induction in macrocyclizations remains largely unexplored in the synthetic community. Here we report that confined macrocyclizations in single-layer chiral porous sheets can generate macrocyclic products bearing multiple chirality with excellent stereoselectivity. To induce multiple chirality in a confined macrocyclization, we used chiral porous sheet structures formed through the self-assembly of a planar aromatic amphiphile including a tilt rod. The chiral interior of the porous sheet imprints its stereochemistry on the conformation of a linear substrate, enabling the ring closing reaction to simultaneously induce multiple chirality, including a stereocenter and strain-induced chirality.}, archive = {J_JACS}, author = {Yongsheng Li and Tianyi Zheng and Zhanting Li and Young Yong Kim and Myongsoo Lee}, doi = {10.1021/jacs.5c09981}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31198--31203}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral porous sheet assembly for multiple chirality induction in macrocycle formation}, volume = {147}, year = {2025}, }
• (2025). Heteropolynuclear Lanthanide(III) complexes for cooperative sensitization upconversion in water. JACS, 147(34), 31187--31197. (www)

  @article{ , abstract = {We report the synthesis of a tritopic ligand, L 2 , composed of two strongly binding lanthanide (Ln) sites using tris-functionalized triazacyclononane (tacn) scaffolds bridged by a weaker Ln binding triethylene glycol chain. Coordination chemistry of Ln 3+ (Ln = Eu, Tb, Yb, Lu) was investigated by using NMR and photoluminescent spectroscopies. The first two Ln 3+ ions are coordinated by the tacn scaffolds to form [Ln L 2 ] and [Ln 2 L 2 ] species, followed by tri- and tetranuclear complexes, [Ln(Ln 2 L 2 )] and [Ln 2 (Ln 2 L 2 )]. The third and fourth exomacrocyclic binding events occur at the polyethylene glycol binding site, buttressed by a synergistic interaction of the phosphonate arms, confirmed by DFT modeling. [Ln 2 L 2 ] (Ln = Tb, Eu, Yb, and Lu) homobimetallic complexes were prepared, and characterized and their spectroscopic properties determined in H 2 O and D 2 O. Titration of the [Yb 2 L 2 ] dinuclear complex by Tb salts in D 2 O confirmed the formation of the tri- and tetranuclear species. Upon excitation into the 2 F 5/2 ← 2 F 7/2 absorption band of Yb at 980 nm, a cooperative sensitization upconversion process is evidenced, displaying visible Tb emission bands. Heating resulted in Ln scrambling in the tacn coordination sites, increasing the UC efficiency by ca. 10 3 . The most efficient emitter for UC is the tetranuclear [TbYb(TbYb L 2 )], with one of each Ln 3+ species in the tacn scaffolds and one of each Ln 3+ species coordinated by the polyethylene glycol chain. Optimization on the pD led to an overall 9.0 × 10 –7 UC quantum yield (λ exc = 980 nm, P = 10.8 W·cm –2 ). The same experiment was repeated in water, affording UC at the molecular level.}, archive = {J_JACS}, author = {Léna Godec and Richard C. Knighton and Nadège Hamon and Waygen Thor and Ka-Leung Wong and Raphaël Tripier and Loïc J. Charbonnière}, doi = {10.1021/jacs.5c09915}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31187--31197}, shortjournal = {J. Am. Chem. Soc.}, title = {Heteropolynuclear Lanthanide(III) complexes for cooperative sensitization upconversion in water}, volume = {147}, year = {2025}, }
• (2025). A data science-guided approach for the development of nickel-catalyzed homo-Diels–Alder reactions. JACS, 147(34), 31175--31186. (www)

  @article{ , abstract = {The Ni-catalyzed homo-Diels–Alder (hDA) reaction represents a convergent but under-investigated approach to preparing bridged bicyclic ring systems. Using the kraken monophosphine descriptor library, Ni-catalyzed hDA reactions of acyclic and cyclic electron deficient olefins were investigated, and key ligand effects required for reactivity were identified using classification models. This analysis guided the discovery of the monophosphine ( S )-AntPhos as a chiral ligand for the enantioselective hDA of acyclic dienophiles. However, these conditions were not compatible with cyclic substrates. Further mechanistic and computational studies revealed a putative role of Ni(I) species and mechanistic divergence between cyclic and acyclic enone dienophiles. Using reaction space design and Bayesian optimization, conditions were developed that expanded the scope to cyclic dienophiles. The resultant cycloadducts were transformed into bicycloheptane structures via cyclopropane cleavage reactions, demonstrating the ability to rapidly access structurally complex scaffolds using this method.}, archive = {J_JACS}, author = {Jamie A. Cadge and Cedric Lozano and Morgan T. Merriman and Paul Oblad and Matthew S. Sigman and Sarah E. Reisman}, doi = {10.1021/jacs.5c09948}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31175--31186}, shortjournal = {J. Am. Chem. Soc.}, title = {A data science-guided approach for the development of nickel-catalyzed homo-Diels–Alder reactions}, volume = {147}, year = {2025}, }
• (2025). Surface FeIV═O induced highly selective phenol polymerization via proton-coupled electron transfer. JACS, 147(34), 31165--31174. (www)

  @article{ , abstract = {Organic polymerization offers a sustainable alternative for water decontamination and resource recovery; however, its popularization is bottlenecked by the unsatisfactory selectivity of traditional electron transfer processes. In this study, we demonstrate that surface high-valent iron-oxo species (≡Fe IV ═O) on nanoscale zerovalent iron (nZVI), characterized by an unoccupied d z 2 orbital and a terminal-oxo moiety, can realize highly efficient phenol recovery via a proton-coupled electron transfer (PCET) pathway for phenol transformation into phenoxyl radicals with final polymers of 3231 g mol –1 in average molecular weight and an impressive polymeric selectivity of 92.6%, surpassing those reported in free radical-/catalyst-oxidant complex-based systems driven by electron transfer (below 77.0%). This PCET-induced polymerization was facilitated by the hydrogen bond formed between ≡Fe IV ═O and phenol, and kinetically obeyed a dual descriptor model comprising p K a and vertical ionization potential, as unveiled by using representative para-substituted phenolic compounds. Furthermore, the high-performance treatment of real phenol wastewater in continuous-flow operations underscores the significant potential of ≡Fe IV ═O for sustainable water decontamination. This study proposes a prospective strategy for pollutant removal and highlights the significance of ≡Fe IV ═O in resource utilization through selective organic polymerization.}, archive = {J_JACS}, author = {Meiqi Li and Cancan Ling and Long Zhao and Lufa Hu and Hao Li and Lizhi Zhang}, doi = {10.1021/jacs.5c09972}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31165--31174}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface FeIV═O induced highly selective phenol polymerization via proton-coupled electron transfer}, volume = {147}, year = {2025}, }
• (2025). Structural role of Nb2O5 in phosphate glasses: An advanced solid-state NMR protocol for the glass system xNb2O5–(100–x)NaPO3. JACS, 147(34), 31147--31164. (www)

  @article{ , abstract = {The structural role of Nb 2 O 5 in oxide glasses remains poorly understood, despite the unique linear and nonlinear optical properties that it bestows. Here, advanced solid-state NMR methods can yield valuable insight, but their full potential has been underutilized for niobium-containing systems, especially in respect of the dipolar techniques that provide quantitative information on the interatomic connectivity and distance distributions. This study presents a new NMR-strategy and applies it to the model glass system x Nb 2 O 5 –(100– x )NaPO 3 (0 ≤ x ≤ 40). The number of P–O–P linkages per P atom is estimated from the 31 P– 31 P dipole–dipole interactions using spin echo decay (SED) and double-quantum based dipolar recoupling effecting nuclear alignment reduction (DQ-DRENAR). The number of P–O–Nb linkages is obtained from the 31 P– 93 Nb dipolar coupling using 93 Nb{ 31 P} rotational echo double resonance (REDOR) and, for the first time, 31 P{ 93 Nb} rotational echo saturation pulse double resonance (RESPDOR). Constrained by these interaction-selective experiments, which also include 31 P/ 23 Na double resonance spectroscopy, the poorly resolved 31 P MAS NMR spectra are quantitatively decomposed into their contributions from the various network-forming units. Additional field dependent 93 Nb MAS NMR experiments provide chemical shift parameters that reveal multiple six-coordinate niobium environments with varying degrees of distortion. Overall, the results demonstrate that Nb 2 O 5 assumes a network former role, increasing the overall network connectivity. They also demonstrate an advanced solid-state NMR protocol for characterizing the structural role of Nb 2 O 5 , an important intermediate oxide, in multicomponent glasses.}, archive = {J_JACS}, author = {Laureano Ensuncho and Henrik Bradtmüller and Philip S. Salmon and Hellmut Eckert}, doi = {10.1021/jacs.5c09793}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31147--31164}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural role of Nb2O5 in phosphate glasses: An advanced solid-state NMR protocol for the glass system xNb2O5–(100–x)NaPO3}, volume = {147}, year = {2025}, }
• (2025). Ru single atom and nanoparticle tandem catalyst unlocking high-efficiency ammonia synthesis under mild conditions. JACS, 147(34), 31136--31146. (www)

  @article{ , abstract = {The development of highly efficient catalysts that enable Haber–Bosch ammonia (NH 3 ) synthesis under mild conditions remains critically challenging since the competitive activation of coadsorbates, particularly excessive N 2 or H 2 binding at active sites, is a trade-off and detrimental to NH 3 synthesis. Herein, we design a novel Ru tandem catalyst that combines Ru single atom (Ru 1 ) with nanoparticle sites (Ru NP ) on CeO 2 nanoislands, leveraging cascade hydrogen catalysis between functionally distinct Ru sites to realize highly efficient NH 3 synthesis under mild conditions. Our studies reveal that Ru NP sites suffer from hydrogen poisoning, whereas Ru 1 sites exclusively adsorb N 2 . The hydrogen spillover from Ru NP to Ru 1 sites reduces hydrogen coverage on Ru NP sites to effectively decrease the N 2 dissociation barrier and also greatly facilitates N 2 hydrogenation at Ru 1 sites for NH 3 synthesis, thus overcoming the trade-off in the dynamic N 2 /H 2 activation equilibrium. As a result, the Ru single atom and nanoparticle tandem catalyst achieves a remarkable NH 3 synthesis rate of 59.0 mmol g cat –1 h –1 with 600 h long-term operational stability at 400 °C and 1 MPa, possessing an exceptionally high specific rate among reported Ru-based catalysts. This catalyst structure design paves a new path for NH 3 synthesis under mild conditions.}, archive = {J_JACS}, author = {Yanliang Zhou and Bo Yang and Lu Wang and Kailin Su and Ben Liu and Hongpeng Fang and Kexin Yue and Xiuyun Wang and Haifeng Qi and Lirong Zheng and Wei Li and Lilong Jiang}, doi = {10.1021/jacs.5c09736}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31136--31146}, shortjournal = {J. Am. Chem. Soc.}, title = {Ru single atom and nanoparticle tandem catalyst unlocking high-efficiency ammonia synthesis under mild conditions}, volume = {147}, year = {2025}, }
• (2025). Development of highly active catalysts for low-temperature CO2 hydrogenation to methanol using a machine learning approach. JACS, 147(34), 31121--31135. (www)

  @article{ , abstract = {The conversion of CO 2 into methanol through hydrogenation represents a promising approach for the utilization of CO 2 and sustainable chemical production. However, current industrial methods rely on copper-based catalysts, which exhibit low CO 2 conversion and limited methanol yields and require high temperatures and pressures. In this study, we utilized a machine-learning (ML) approach to develop low-temperature CO 2 hydrogenation catalysts. By employing iterative ML model predictions and experimental validation in batch reactors, we screened 580 distinct catalysts and identified 33 catalysts that outperformed the previously reported highly active catalyst (Pt(3)/Mo(20)/TiO 2 ). The best catalyst, Pt(5)/Mo(8)–Re(1)–W(0.7)/TiO 2 , exhibited a methanol production rate of 1.46 mmol g –1 h –1 in a batch reactor and a high production rate of 1.8 mmol g –1 h –1 in a flow reactor at 150 °C under 4 MPa (H 2 /CO 2 = 3). In situ/operando spectroscopic analysis was conducted to elucidate the function of each catalyst component in the methanol synthesis. Detailed analysis revealed that in the best catalyst, Pt primarily facilitated H 2 dissociation, partially reduced Mo oxides were crucial in generating oxygenated species, and the presence of acidic W promoted methanol desorption from the catalyst surface. Re promoted the formate conversion to methanol, thus accelerating the overall methanol formation.}, archive = {J_JACS}, author = {Shirun Zhao and Shinya Mine and Gang Wang and Weiyang Zhang and Abdellah Ait El Fakir and Bin Yang and Zengwei Qin and Nazmul Hasan MD Dostagir and Koichi Matsushita and Ichigaku Takigawa and Ken-ichi Shimizu and Takashi Toyao}, doi = {10.1021/jacs.5c09727}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31121--31135}, shortjournal = {J. Am. Chem. Soc.}, title = {Development of highly active catalysts for low-temperature CO2 hydrogenation to methanol using a machine learning approach}, volume = {147}, year = {2025}, }
• (2025). The electronic structure of the superatom au3+. JACS, 147(34), 31111--31120. (www)

  @article{ , abstract = {At the heart of large gold clusters lies Au 3 + , a key three-ring structure that plays a fundamental role in many gold assemblies. Studying this smallest unit provides valuable insight into the photocatalytic mechanisms of larger gold systems. This study presents the first high-resolution, vibrationally resolved optical spectra of mass-selected Au 3 + clusters obtained through photodissociation spectroscopy. The spectra, spanning 2.7–5.0 eV, reveal five band systems with complex and irregular structures. To interpret these spectra, we employ ab initio calculations at the CASSCF level, incorporating spin–orbit coupling to characterize the electronic structure of Au 3 + . These calculations reveal that the observed spectral features arise from the interplay of closely spaced excited states dominated by d-orbital excitations, a small s–d orbital gap, and significant vibronic and spin–orbit coupling. Our findings emphasize that accurate characterization of the excited states of Au 3 + , a seemingly simple triatomic molecule with a valence configuration and orbital structure similar to that of the strontium atom, requires sophisticated multireference calculations. Simplified theoretical methods, such as density functional theory (DFT) and those utilizing small HOMO–LUMO active spaces, fail to capture the strong multireference effects driven by d-orbital contributions, underscoring the complexity of excited-state interactions in gold clusters.}, archive = {J_JACS}, author = {Nikita Kavka and Marko Förstel and Kai Pollow and Taarna Studemund and Roland Mitric and Otto Dopfer}, doi = {10.1021/jacs.5c09486}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31111--31120}, shortjournal = {J. Am. Chem. Soc.}, title = {The electronic structure of the superatom au3+}, volume = {147}, year = {2025}, }
• (2025). Green kilogram-scale MOF synthesis and acetone-induced structural evolution for sieving benzene from cyclohexane. JACS, 147(34), 31102--31110. (www)

  @article{ , abstract = {The separation of benzene/cyclohexane represents a crucial yet challenging process in the petrochemical industry, as their azeotropic mixture cannot be effectively separated through simple distillation. Herein, we report a facile kilogram-batch synthesis of a metal–organic framework (JNU-81-A) in a water/ethanol solution at room temperature. When wetted by acetone, JNU-81-A undergoes a single-crystal-to-single-crystal structural evolution, yielding JNU-81-B with altered coordination environments. Interestingly, further structural evolution was observed upon removal of acetone, resulting in JNU-81-C with one-dimensional channels in the a -axis direction. JNU-81-C exhibits benzene-induced gate-opening flexibility, enabling a sieving effect of benzene from cyclohexane. Liquid-phase column breakthrough experiments demonstrate the ability of JNU-81-C to collect ultrahigh-purity (99.9%) cyclohexane from benzene/cyclohexane mixtures. Moreover, liquid-phase extraction experiments were carried out at a 1000 mL scale using the fabricated JNU-81-C pellets, allowing for increasing the cyclohexane purity from 95% to 99.5% with an average recovery rate of 95% for ten cycles. This work presents an energy-efficient adsorption-based separation of benzene/cyclohexane mixtures, providing an alternative approach for this challenging industrial process.}, archive = {J_JACS}, author = {Zhi-Jie Jiang and Ying Wang and Weigang Lu and Dan Li}, doi = {10.1021/jacs.5c09482}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31102--31110}, shortjournal = {J. Am. Chem. Soc.}, title = {Green kilogram-scale MOF synthesis and acetone-induced structural evolution for sieving benzene from cyclohexane}, volume = {147}, year = {2025}, }
• (2025). Ultrabright 1650 nm-emitting biodegradable organic luminophores for NIR-IIbc fluorescence imaging. JACS, 147(34), 31091--31101. (www)

  @article{ , abstract = {Near-infrared IIbc (NIR-IIbc, 1500–2000 nm) fluorescence imaging permits unprecedented resolution for deep-tissue visualization, driving the high demand for organic NIR-IIbc materials due to their tunable optical properties, versatile functionalization, and excellent biocompatibility. However, nearly all existing organic probes emit peaks below 1500 nm in H 2 O with emission tails extending only to 1600 nm and raise biosafety concerns due to slow hepatobiliary clearance. These limitations hinder the full potential of NIR-IIbc imaging. Herein, we report a planar ambipolar unit-acceptor design to develop biodegradable organic semiconducting polymer (PTZ) nanoprobes emitting a peak at ∼1650 nm in H 2 O. PTZ nanoprobes enable ultrahigh-resolution imaging of near-single-cell cancer (as few as approximately 20 cells), tiny blood vessels (∼100 μm), and ultradeep-seated bone marrow in vivo. Furthermore, the PTZ permits the development of NIR-IIbc molecular probes for ultrahigh-resolution imaging of deep-seated orthotopic liver tumors as small as ∼1.5 mm in vivo. Importantly, PTZ-based probes are biodegradable and can be cleared through hepatobiliary and renal pathways within 18 days, alleviating long-term toxicity concerns. Our work reveals the molecular design toward ultrabright organic NIR-IIbc fluorophores and highlights new opportunities for high-resolution deep-tissue imaging.}, archive = {J_JACS}, author = {Yufu Tang and Yuanyuan Li and Chunxu He and Zongliang Xie and Jianwu Tian and Bowen Li and Yincai Xu and Quli Fan and Bin Liu}, doi = {10.1021/jacs.5c09462}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31091--31101}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrabright 1650 nm-emitting biodegradable organic luminophores for NIR-IIbc fluorescence imaging}, volume = {147}, year = {2025}, }
• (2025). Improving catalytic enantioselectivity of hydrogenation through swelling-induced molecular tension in polymer networks. JACS, 147(34), 31085--31090. (www)

  @article{ , abstract = {Herein, we report that molecular tension generated by the swelling of a polyacrylate network containing a chiral [Biphep]Rh(I) catalyst as a tension-bearing, bis-tethered cross-linker enhances the enantioselectivity of hydrogenation of methyl 2-acetamidoacrylate. Differential swelling of the network is achieved by changing the relative concentrations of toluene (low swelling) and dichloromethane (high swelling) cosolvents. Swelling is characterized by the ratio of final to initial length in a single dimension of the network (λ = l f / l i ), noting that changes are the same in all dimensions; λ x = λ y = λ z . The enantiomeric excess (ee) of the hydrogenation reaction increases monotonically with λ, from 22% ee at λ = 1.53 to 39% ee at λ = 1.77. Control networks in which the catalyst is appended as a tension-free pendant side chain functionality display a minor change in ee as a function of swelling (ee = −0.7 ± 3.1%) with no obvious correlation between the two. The change in enantioselectivity due to swelling of the mechanically coupled network for a given λ is greater than when the same λ x and λ y are generated from the uniaxial compression along the normal z -axis, a result that is attributed to the isotropic strain associated with swelling in three dimensions rather than stretching in two dimensions. The results suggest that solvent swelling may provide a previously untapped modality for exploiting force-coupled catalysis in practical and scalable platforms, including those adapted from current polymer-supported catalysts.}, archive = {J_JACS}, author = {Xujun Zheng and Chenghao Duan and Ross A. Widenhoefer and Stephen L. Craig}, doi = {10.1021/jacs.5c09442}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31085--31090}, shortjournal = {J. Am. Chem. Soc.}, title = {Improving catalytic enantioselectivity of hydrogenation through swelling-induced molecular tension in polymer networks}, volume = {147}, year = {2025}, }
• (2025). A radical-cationic covalent organic framework to accelerate polysulfide conversion for long-durable Lithium–Sulfur batteries. JACS, 147(34), 31073--31084. (www)

  @article{ , abstract = {Covalent organic frameworks (COFs) have emerged as promising metal-free sulfur hosts to facilitate the conversion kinetics and suppress the shuttling effect of lithium polysulfides (LiPSs) in lithium–sulfur (Li–S) batteries. However, constructing COFs with stable and high electrocatalytic functionality for LiPS conversion remains unexplored. Herein, we develop a radical-cationic COF (R-TTF •+ -COF) with superior electrical conductivity of 3.9 S m –1 at room temperature, which features both nucleophilic and electrophilic sites for effective LiPS chemisorption and conversion. With this novel radical-based catalyst, the Li–S battery achieves superior longevity of 1500 cycles with a capacity fading of 0.027% per cycle at a current density of 0.5 C. The capacity retention of the Li–S battery based on R-TTF •+ -COF at the current density of 2.0 C is nearly twice as high compared to a COF without radicals. The crucial role of radical cations in catalyzing LiPS conversion has been systematically elucidated through solid-state nuclear magnetic resonance spectroscopy, electron paramagnetic resonance spectroscopy, and theoretical simulations, which verify the reversible interactions between LiPSs and [TTF] 2 •+ moieties. This intriguing radical-assisted mechanism opens a new avenue for designing efficient catalytic sulfur hosts using organic molecules, offering a significant step toward the practical application of Li–S batteries.}, archive = {J_JACS}, author = {Sijia Cao and Pouya Partovi-Azar and Jin Yang and Dongjiu Xie and Timo Held and Gianluca Marcozzi and Joseph E. McPeak and Wei Zhang and Xia Zhang and Markus Osenberg and Zdravko Kochovski and Changxia Li and Daniel Sebastiani and Johannes Schmidt and Moritz Exner and Ingo Manke and Arne Thomas and Wenxi Wang and Yan Lu}, doi = {10.1021/jacs.5c09421}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31073--31084}, shortjournal = {J. Am. Chem. Soc.}, title = {A radical-cationic covalent organic framework to accelerate polysulfide conversion for long-durable Lithium–Sulfur batteries}, volume = {147}, year = {2025}, }
• (2025). Systematic synthesis of large porous organic cages driven by steric hindrance. JACS, 147(34), 31060--31072. (www)

  @article{ , abstract = {Large organic cages (>3 nm) hold great promise for enhancing gas adsorption capacity and encapsulating bulky guests, such as nanoparticles and biomolecules. However, their synthesis remains challenging due to entropic penalties favoring smaller cages and interlocked byproducts during self-assembly. Here, we present a steric hindrance-driven strategy to systematically construct a series of stable [6 + 12] cages via imine condensation between tetratopic and ditopic synthons. Introducing bulky substituents to the tetratopic building blocks effectively suppressed entropic competition, directing assembly exclusively toward Tet 6 Di 12 topologies. Notably, enhanced steric crowding induced an unprecedented triangular orthobicupola (Johnson solid J 27 ) geometry─the first report of this topology in organic cages. Molecular dynamics and density functional theory calculations confirmed that the increased steric bulk thermodynamically favors Tet 6 Di 12 over smaller analogs ( Tet 3 Di 6 and Tet 4 Di 8 ). Single-crystal structures revealed that the large-sized cages self-assemble into unique spatial arrangements of alternating ultramicro-mesoporous three-dimensional pore networks, with intrinsic frustration in close packing conferring permanent porosity.}, archive = {J_JACS}, author = {Yuanhan Liu and Siyuan Yang and Jinjin Zhang and Junkai Sun and Yaoyi Su and Jiarui Hu and Xiaoyan Wang and Ming Liu}, doi = {10.1021/jacs.5c09357}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31060--31072}, shortjournal = {J. Am. Chem. Soc.}, title = {Systematic synthesis of large porous organic cages driven by steric hindrance}, volume = {147}, year = {2025}, }
• (2025). Locating organocatalysts at pickering droplet interfaces enables promotion of their catalytic enantioselectivity. JACS, 147(34), 31049--31059. (www)

  @article{ , abstract = {Catalytic reactions at aqueous microdroplet interfaces can be remarkably different from those occurring in bulk water due to the unique interfacial microenvironment that enables possible modification of the transition states. However, current research of microdroplet chemistry is mainly focused on reaction acceleration or future scale-up; the promoted catalytic selectivity, especially stereoselectivity, is still in its infancy. In this work, we present our findings that both the reaction rate and the enantioselectivity of chiral organocatalysts can be drastically promoted by locating them at the water–oil interfaces of Pickering droplets. As impressed by the natural cinchonidine-driven asymmetric Mannich reaction and l -proline-catalyzed Aldol reaction, the Pickering droplet-based interfacial system exhibited 1.94–2.22-fold and 2.37–3.74-fold enhanced catalysis efficiency in comparison to their bulk organic and biphasic counterparts, together with the desired enantioselectivities improved from 26–60 to 94% ee and 64–88 to 99% ee, respectively. Interestingly, the observed activity and chirality enhancement were found to be significantly dependent on droplet size. Insight into the origin of these promoted rates and enantioselectivities at the molecular level was further elucidated by using molecular dynamics simulation and density functional theory calculations. This study highlights a new paradigm of a highly reactive and stereoselective water-medium catalytic system, providing an exemplary pathway to access optically active compounds.}, archive = {J_JACS}, author = {Yuwei Wang and Hu Shi and Yue Sun and Xiaoming Zhang and Yanfang Li and Hengquan Yang}, doi = {10.1021/jacs.5c09197}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31049--31059}, shortjournal = {J. Am. Chem. Soc.}, title = {Locating organocatalysts at pickering droplet interfaces enables promotion of their catalytic enantioselectivity}, volume = {147}, year = {2025}, }
• (2025). Reversible electron transfer in the formation of radical anionic and dianionic 1,4-diborabutatrienes. JACS, 147(34), 31042--31048. (www)

  @article{ , abstract = {One- and two-electron reductions of diborylacetylene 1 with potassium graphite (KC 8 ) yielded radical anionic and dianionic 1,4-diborabutatrienes 1 •– K + (thf) 2 and 1 2– (K + ) 2 , respectively. X-ray diffraction, electron paramagnetic resonance, and computational studies indicated the π electron delocalization over the B–C–C–B cumulene skeleton. 1 2– (K + ) 2 possesses a relatively small HOMO–LUMO gap and exhibits a significantly red-shifted UV–vis absorption at λ max = 578 nm, compared to the all-carbon tetraarylbutatrienes. 1 2– (K + ) 2 could undergo a formal 1,4-addition with the C sp –H bond of phenylacetylene to produce 2 , while the reaction with an organic azide led to the cleavage of B═C bonds with the formation of anionic iminoborane 3 . This work showcases a potential method for the facile construction of boracumulenes.}, archive = {J_JACS}, author = {Lizhao Zhu and Chengze Du and Yin Yang and Chunming Cui}, doi = {10.1021/jacs.5c09195}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31042--31048}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible electron transfer in the formation of radical anionic and dianionic 1,4-diborabutatrienes}, volume = {147}, year = {2025}, }
• (2025). Direct synthesis of bicyclo[1.1.1]pentanes by sequential C═C, C–C functionalization reactions. JACS, 147(34), 31034--31041. (www)

  @article{ , abstract = {2-Substituted bicyclo[1.1.1]pentane carboxylates have been synthesized using two sequential carbene reactions. A dirhodium-catalyzed intramolecular cyclopropanation to form a bicyclo[1.1.0]butane is followed by a photoinduced formation of a triplet carbene, which undergoes a diradical addition into the strained C–C bond of the bicyclo[1.1.0]butane. A variety of novel 2-substituted bicyclo[1.1.1]pentanes have been synthesized in good to moderate yields, offering rapid access to these valuable scaffolds. Additionally, a one-pot, two-reaction sequence was developed in which the bicyclo[1.1.1]pentanes were afforded starting from two distinct diazo compounds. Computational analysis supports the triplet carbene intermediate addition into the bicyclo[1.1.0]butane C–C bond. Additionally, computational analysis shows the importance of an aryl substituent to stabilize the diradical intermediate, which is required for the productive formation of the bicyclo[1.1.1]pentanes.}, archive = {J_JACS}, author = {Joshua K. Sailer and Duc Ly and Djamaladdin G. Musaev and Huw M. L. Davies}, doi = {10.1021/jacs.5c09039}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31034--31041}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct synthesis of bicyclo[1.1.1]pentanes by sequential C═C, C–C functionalization reactions}, volume = {147}, year = {2025}, }
• (2025). A unified picture of radical anion photoredox chemistry. JACS, 147(34), 31025--31033. (www)

  @article{ , abstract = {Radical anions are competent reagents for supporting photoredox transformations of exceptionally strong chemical bonds. However, the excited states of radical anions are extremely short-lived, making them impractical for directly accomplishing photochemical transformations with meaningful quantum yields. Herein, we examine the radical anion of 9,10-dicyanoanthracene (DCA •– ), which has previously been reported to activate aryl chloride substrates. We show that 10-cyanoanthrolate (10-CA), the product of the reaction of DCA •– with oxygen, is a competent photocatalyst for reductive transformations of select aryl chlorides but not electron-rich aryl chlorides, suggesting another mode of photoreactivity. We show that DCA •– yields highly reducing solvated electrons via photodetachment when excited with blue light. Near-infrared femtosecond transient absorption spectroscopy measurements show that spectral features assigned to solvated electrons are quenched by electron-rich aryl chlorides that cannot be reduced by 10-CA. Moreover, we demonstrate the generality of solvated electron generation using other previously reported photoactive radicals, such as naphthalene monoimide radical anion and a 9-mesityl-3,6-di- tert -butyl-10-phenylacridinium radical. Taken together, we now present a unified picture of radical anion photoredox chemistry in which the radical anion is susceptible to react with electrophiles by an ECE (electron-chemical-electron) process to furnish a closed shell super-reducing photoreagent. Alternatively, radical anions are sufficiently reduced that a solvated electron may be produced by charge transfer to solvent (CTTS) under sufficiently energetic excitation. Both pathways result in super-reducing reagents that can activate exceptionally strong chemical bonds.}, archive = {J_JACS}, author = {Brandon Johnston and Kristopher G. Reynolds and Brandon M. Campbell and Alexander Li and Daniel G. Nocera}, doi = {10.1021/jacs.5c09029}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31025--31033}, shortjournal = {J. Am. Chem. Soc.}, title = {A unified picture of radical anion photoredox chemistry}, volume = {147}, year = {2025}, }
• (2025). Direct synthesis of amide-linked COFs via ester-amine exchange reaction. JACS, 147(34), 31016--31024. (www)

  @article{ , abstract = {Achieving both crystallinity and stability is challenging for covalent organic frameworks (COFs) as the reversible reaction required for enhancing crystallinity compromises stability. Amide linkages, a type of chemically stable bond for COF construction, are predominantly synthesized via postmodifications. This work presents a direct and convenient method for synthesizing highly crystalline amide-linked COFs via the ester-amine exchange reaction. The reaction is irreversible, as demonstrated by the investigation of model reactions and COF TAPT-TTPF polymerization process. The water absorption capacity of COF TAPT-TTPF was 0.56 g/g at 25 °C and 94% relative humidity. Meanwhile, via direct synthesis, we grew COF TAPT-TTPF on anodized aluminum oxide membranes to form COF@AAO composite membranes. The composite membrane achieved an output power density of 7.70 W/m 2 under a 50-fold salinity gradient in osmotic energy conversion. This direct polymerization protocol improves the convenience and accessibility of amide-linked COFs.}, archive = {J_JACS}, author = {Rui-Zhi Li and Song-Chen Yu and Wei Jiang and Jiale Zhou and Zi-Cong Wang and Xiao-Rui Ren and Wei Feng and Yahong Zhou and Dong Wang and Li-Jun Wan}, doi = {10.1021/jacs.5c08823}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31016--31024}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct synthesis of amide-linked COFs via ester-amine exchange reaction}, volume = {147}, year = {2025}, }
• (2025). Photocontrolled programmable enzymatic cascade for robust CRISPR diagnostics. JACS, 147(34), 31004--31015. (www)

  @article{ , abstract = {CRISPR–Cas12a-based diagnostic technologies have revolutionized nucleic acid detection, but their broader application remains constrained by the protospacer adjacent motif (PAM) requirement and limited multiplexing capabilities due to reliance on trans -cleavage. Here, we present a photocontrolled programmable enzymatic cascade strategy that enables temporal regulation of three sequential reactions─nucleic acid amplification, photoactivated lambda exonuclease (λ-exon)-mediated single-stranded DNA (ssDNA) generation, and PAM-independent Cas12a detection─all within a one-pot system, effectively overcoming the PAM constraint. We further exploit the orthogonal trans -cleavage activity of Cas12a and Cas13a to enable simultaneous dual-gene detection within the one-pot system, thereby circumventing multiplexing limitations. Applied to clinical Mycobacterium tuberculosis (MTB) samples, the method allows detection of both the IS6110 gene of MTB and the human ACTB (β-actin) internal control gene. This photocontrolled one-pot CRISPR diagnostic technology enhances flexibility in target site selection and overcomes the limitations of conventional CRISPR diagnostics, which cannot simultaneously detect both target genes and internal controls. This approach holds promise for advancing the clinical application of CRISPR-based diagnostics.}, archive = {J_JACS}, author = {Menglu Hu and Yihui Wang and Weiwei Qi and Yuqing Zhang and Jiachen Sun and Meng Cheng and Xiaoming Zhou}, doi = {10.1021/jacs.5c08704}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {31004--31015}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocontrolled programmable enzymatic cascade for robust CRISPR diagnostics}, volume = {147}, year = {2025}, }
• (2025). NIR-switched DNA shutter enables reversible intermittent cGAS-STING activation for enhanced antitumor immunity. JACS, 147(34), 30989--31003. (www)

  @article{ , abstract = {With their remarkable activation efficiency, cGAS-STING agonists have emerged as a promising strategy to promote immunotherapy. However, continuous activation of the STING pathway may induce resistance and immune evasion, thus impairing the therapeutic effect. Considering repetitive transient rest could restore immune system function and avoid side effects, here we develop an intermittent STING agonist to reversibly activate the cGAS-STING pathway with “stimulation-suspension” patterns, which induce repetitive “activation-rest” intervals in immunotherapy with enhanced efficiency. Near infrared (NIR) switchable reversible DNA shutter (NIR-DNA shutter), as the intermittent STING agonist, is synthesized by conjugating a pair of segmented complementary DNA strands that incorporated Azobenzene (Azo) to the surface of upconversion nanoparticles (UCNPs). Low power 808 nm irradiation generates a high Vis/UV ratio for UCNPs upconversion emission, which induces trans -Azo isomerization and assembles dsDNA chain along UCNPs surface to activate STING pathway, while high power 808 nm irradiation generates a high UV/Vis ratio for UCNPs upconversion emission, which induces cis -Azo isomerization and disassembles dsDNA chain to pause STING pathway. Switching NIR irradiation powers reversibly converts the NIR-DNA shutter between “ON/OFF” statuses and programs the cGAS-STING pathway with repetitive “activation-rest” interval mode, which demonstrates superior therapeutic efficacy by remodeling the immune-environment and enhancing tumor cell killing compared with the constant STING agonist.}, archive = {J_JACS}, author = {Shiyi Bi and Ruowen Yang and Yulin Cong and Huangxian Ju and Ying Liu}, doi = {10.1021/jacs.5c08583}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30989--31003}, shortjournal = {J. Am. Chem. Soc.}, title = {NIR-switched DNA shutter enables reversible intermittent cGAS-STING activation for enhanced antitumor immunity}, volume = {147}, year = {2025}, }
• (2025). A chemo-enzymatic platform for furanolide synthesis and functional exploration. JACS, 147(34), 30979--30988. (www)

  @article{ , abstract = {Furanolides represent an emerging class of natural products known for their structural diversity and potent bioactivities, including antibiotic, cytotoxic, or algicidal effects. The systematic exploration of their biological activity profiles for the discovery of new hits for drug development thus constitutes a promising endeavor. However, their low natural abundance and the resulting difficulty in obtaining sufficient quantities have limited further in-depth investigations into their biological activity and structure–activity relationships (SARs). Building on our recent discovery of biosynthetic enzymes catalyzing furanolide core-structure assembly, we herein developed a cost-effective, one-pot enzymatic toolbox that enables the fast generation of hundreds of furanolide structural analogs. We systematically evaluated antimicrobial activities and cytotoxicity against the A549 lung cancer cell line for a representative selection of library congeners and explored their SARs. Several derivatives demonstrated significant cytotoxicity, particularly against lung cancer stem cells, offering promising insights into the development of furanolides as potential anticancer agents. Additionally, some analogs displayed promising antibacterial activity against important Gram-positive pathogens such as Staphylococcus aureus .}, archive = {J_JACS}, author = {Xiaoqi Ji and Manuel Einsiedler and Paul M. D’Agostino and Jennifer Herrmann and Rolf Müller and Tobias A.M. Gulder}, doi = {10.1021/jacs.5c08354}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30979--30988}, shortjournal = {J. Am. Chem. Soc.}, title = {A chemo-enzymatic platform for furanolide synthesis and functional exploration}, volume = {147}, year = {2025}, }
• (2025). Antiferromagnetic dimanganese catalase mimics: Targeting oxidative stress to mitigate corneal neovascularization post-alkali injury. JACS, 147(34), 30967--30978. (www)

  @article{ , abstract = {Corneal alkali-burn injury is a common ophthalmic emergency that elevates oxidative stress in the ocular microenvironment, leading to cellular apoptosis and corneal neovascularization. To address this challenge, we report a binuclear manganese complex ( Mn-2 ) featuring a catalase-mimetic antiferromagnetic Mn–O–Mn core, which efficiently scavenges hydrogen peroxide, a key contributor to oxidative damage. This structure enables effective hydrogen peroxide scavenging while concurrently suppressing the Fenton reaction, a major driver of oxidative injury. In comparison to a mononuclear manganese complex (MnSalen, Mn-1 ) and a tri-MnSalen cryptand complex ( Mn-3 ), Mn-2 demonstrated significantly enhanced cytoprotection in human corneal epithelial cells (HCECs). Mechanistic studies revealed that Mn-2 modulates the expression of antioxidant-related proteins, including NQO1 and catalase, as well as both pro- and antiapoptotic proteins such ascleaved caspase 3, cytochrome c, and Bcl-2. In murine models of alkali-burn, topical administration of Mn-2 effectively reduced pathological corneal damage, alleviating corneal inflammatory edema, opacity, and neovascularization, to levels comparable to those achieved with clinically available dexamethasone. Importantly, the eye drops containing Mn-2 exhibited minimal ocular surface toxicity, highlighting their safety for therapeutic use. These findings position Mn-2 as a promising therapeutic option for vision-threatening corneal injuries, thereby addressing a critical gap in ocular regenerative medicine.}, archive = {J_JACS}, author = {Hang Zhang and Kan Xu and Jia-Hui Wu and Dijie Qiao and Xiang-Yu Tan and Sun Rong and Bingwu Wang and Xi-Long Leng and Ke Wang and Hao-Ling Sun and Song Gao and Wei Chi and Jun-long Zhang}, doi = {10.1021/jacs.5c08110}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30967--30978}, shortjournal = {J. Am. Chem. Soc.}, title = {Antiferromagnetic dimanganese catalase mimics: Targeting oxidative stress to mitigate corneal neovascularization post-alkali injury}, volume = {147}, year = {2025}, }
• (2025). Accelerating the pace of oxygen evolution reaction catalyst discovery through megalibraries. JACS, 147(34), 30956--30966. (www)

  @article{ , abstract = {Iridium (Ir) catalysts are essential for the acidic oxygen evolution reaction (OER) in proton-exchange membrane water electrolyzers (PEMWEs), but their high cost, scarcity, and geographical concentration limit large-scale adoption. In addition, the discovery of non-Ir alternatives is slow due to the vast design space possible. Here, a “megalibrary” is used to explore the catalytic activity of ∼156 million distinct nanostructures comprised of Ru, Co, Mn, and Cr to find alternatives to Ir catalysts for OER. Over 40 RuCoMnCr oxides, ranging from low to high activity, were selected, scaled to milligram levels, and studied for their catalytic performance. The activities measured within the megalibrary closely correlated ( r = 0.84) with those of the macroscopic samples. In a PEMWE, the most active catalyst, Ru 52 Co 33 Mn 9 Cr 6 oxide, demonstrated a voltage of 1.58 V at 1 A/cm 2 and 1.77 V at 3 A/cm 2 . At 1 A/cm 2 , it operated continuously for over 1000 h with an average voltage increase rate of 57 μV/h. This study establishes a roadmap to accelerate catalyst discovery for energy conversion, and the platform is a route to large data sets that will facilitate the development of AI and machine learning algorithms that can identify key catalyst design features.}, archive = {J_JACS}, author = {Jin Huang and Zhe Wang and Jiashun Liang and Xiao-Yan Li and Jacob Pietryga and Zihao Ye and Peter T. Smith and Alp Kulaksizoglu and Connor R. McCormick and Jaerim Kim and Bosi Peng and Zeyan Liu and Ke Xie and Steven B. Torrisi and Joseph H. Montoya and Gang Wu and Edward H. Sargent and Chad A. Mirkin}, doi = {10.1021/jacs.5c08326}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30956--30966}, shortjournal = {J. Am. Chem. Soc.}, title = {Accelerating the pace of oxygen evolution reaction catalyst discovery through megalibraries}, volume = {147}, year = {2025}, }
• (2025). Grain boundary oxygen improving the acidic oxygen evolution reaction of zn-RuO2@ZnO. JACS, 147(34), 30943--30955. (www)

  @article{ , abstract = {The lattice oxygen evolution reaction (OER) is the currently predominant mechanism, while the grain boundary (GB) OER is still the enigma. This study proposes the grain boundary oxygen mechanism (GBOM) and validates it using Zn-RuO 2 @ZnO in OER. An optimal GB density in Zn-RuO 2 @ZnO achieves an overpotential of 170 mV and 600 h durability at 10 mA cm –2 . As an anode catalyst in proton-exchange membrane water electrolyzers (PEMWEs), Zn-RuO 2 @ZnO exhibits exceptional stability (>300 h at 500 mA cm –2 ) and high efficiency, requiring only 1.68 V to deliver 1 A cm –2 under 60 °C. Notably, the reduced symmetry at GBs enhances the Ru 4 d xy -O 2 p hybridization, manifested as a distinct antiferromagnetic state, which activates the GBOM pathway and stabilizes its operation through electron transfer into lower-energy orbitals. Our findings highlight that GBs with antiferromagnetic characteristics offer an intriguing design strategy for developing highly active and stable OER catalysts.}, archive = {J_JACS}, author = {Yin Qin and Sihao Deng and Xiao-Ye Zhou and Zilin Yan and Lunhua He and Kaikai Li and Tong-Yi Zhang}, doi = {10.1021/jacs.5c08187}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30943--30955}, shortjournal = {J. Am. Chem. Soc.}, title = {Grain boundary oxygen improving the acidic oxygen evolution reaction of zn-RuO2@ZnO}, volume = {147}, year = {2025}, }
• (2025). Probiotic–Drug conjugates achieve synchronized site-specific probiotic colonization and on-demand drug release against ulcerative colitis and its complication. JACS, 147(34), 30924--30942. (www)

  @article{ , abstract = {The oral surface-modified probiotic therapy, capable of maintaining activity and adhesion of probiotics under harsh gastrointestinal conditions, is effective in treating ulcerative colitis (UC). However, the currently reported surface-modified probiotics suffer from poor selective colonization at a lesion site and limited codelivery capability with other treatment modalities due to different physicochemical properties. Herein, we develop triggerable probiotic–drug conjugates that enable synchronous site-specific probiotic colonization and on-demand drug release for the treatment of UC and its complication. Specifically, the conjugates are composed of probiotic Escherichia coli Nissle 1917 encapsulated with the adhesive tannic acid-ferric inner layer and the reactive oxygen species (ROS)-responsive thioether-bridged pterostilbene-lipid outer coating. Following oral administration, the pathological high-level ROS can trigger the adaptable release of anti-inflammatory pterostilbene and adhesive probiotics from conjugates in the inflamed colon. The targeted colonization of adhesive probiotics, combined with pterostilbene at the lesion site in a synchronous manner, achieves inflammation suppression and sustained gut microbiota modulation. In both mouse models of UC and associated complications, this conjugate demonstrates significant therapeutic and prophylactic efficacy, highlighting its translational potential for clinical combined applications in gastrointestinal disorders.}, archive = {J_JACS}, author = {Linzhou Yin and Shuwen Han and Jiang Xiaowen and Jie Liu and Zhichao Chen and Xi Yang and Zhonggui He and Mengchi Sun and Jin Sun and Huiyuan Gao}, doi = {10.1021/jacs.5c08094}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30924--30942}, shortjournal = {J. Am. Chem. Soc.}, title = {Probiotic–Drug conjugates achieve synchronized site-specific probiotic colonization and on-demand drug release against ulcerative colitis and its complication}, volume = {147}, year = {2025}, }
• (2025). MRNA-based FRET-FLIM imaging platform for quantifying lipid nanoparticle endosomal escape and membrane damage. JACS, 147(34), 30907--30923. (www)

  @article{ , abstract = {Efficient endosomal escape and membrane damage are crucial for mRNA-lipid nanoparticle (LNPs) delivery but remain challenging to quantify. Here, we develop FRET-lifetime imaging for mRNA-LNP tracking (FLINT), an intramolecular FRET-FLIM platform to dynamically monitor mRNA release kinetics and endosomal damage in live cells. Capitalizing on the 50- to 100-fold higher concentration of glutathione (GSH) in the cytosol relative to endocytic vesicles, the FLINT employs disulfide-linked fluorophores conjugated to mRNA uridines, enabling precise tracking of cytosolic mRNA via GSH-activated signal amplification (20–50×). Using FLINT, we find that LNPs with escape-favorable lipid compositions (e.g., C12–200) exhibit rapid FRET signal diffusion, while uptake-driven LNPs (e.g., MC3) accumulate in endosomes with limited release. FLINT further reveals GSH influx during endosomal damage and correlates membrane rupture patterns with mRNA expression. Additionally, FLINT uncovers the influence of lipid organization within LNPs─in addition to endosomal membrane damages─on mRNA delivery efficiency. This FLINT platform decouples uptake, escape, and structural determinants of delivery efficiency, offering a transformative tool for LNP optimization and mechanistic studies both in vivo and in vitro.}, archive = {J_JACS}, author = {Yian Fang and Bin Ma and Zhiqiang Zhao and Ziyan Xuan and Yu Wang and Chuping Huang and Mi Zhang and Lei Zhou and Feng Yao and Kailong Li and Wei You and Xinglin Yang and Jiajia Guo and Yifan Ge and Chenzhong Liao and Yiguang Wang and Lei Miao}, doi = {10.1021/jacs.5c07897}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30907--30923}, shortjournal = {J. Am. Chem. Soc.}, title = {MRNA-based FRET-FLIM imaging platform for quantifying lipid nanoparticle endosomal escape and membrane damage}, volume = {147}, year = {2025}, }
• (2025). Photon-primed organic electrosynthesis enabled by oxidation of photon-induced intermediates. JACS, 147(34), 30897--30906. (www)

  @article{ , abstract = {We present a catalyst-free strategy that combines photochemical and electrochemical activation to unlock unique reactivity in otherwise less reactive molecules. Photochemical excitation generates intermediates that can undergo electrochemical oxidation to form highly electrophilic species that can engage weak nucleophiles, enabling the synthesis of diverse heterocycles under mild conditions. Mechanistic studies, including voltammetric, spectroscopic, and computational analyses, suggest that a light-driven redox chain mechanism plays a crucial role, significantly enhancing the apparent Faradaic efficiency (>100%). The broad substrate scope including bioactive scaffolds highlights the potential of this approach to expand the reactivity landscape in electrochemical synthesis.}, archive = {J_JACS}, author = {Ahhyeon Choi and Doyeon Kim and Daniel Yim and Jungjin Park and Arun Sharma and Woojae Kim and Hyungjun Kim and Hyunwoo Kim}, doi = {10.1021/jacs.5c07822}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30897--30906}, shortjournal = {J. Am. Chem. Soc.}, title = {Photon-primed organic electrosynthesis enabled by oxidation of photon-induced intermediates}, volume = {147}, year = {2025}, }
• (2025). Structure–Function relationships in sequence-controlled copolymers for rare earth element chelation. JACS, 147(34), 30885--30896. (www)

  @article{ , abstract = {The ability to tune material function through primary sequence is a defining feature of biological macromolecules, enabling precise control over structure and target interactions in complex aqueous environments. However, translating sequence–structure–function relationships to synthetic macromolecules is challenging due to their dispersity in sequence, conformation, and composition. Here, we report systematic studies of amphiphilic polymer chelators designed to probe how composition and patterning influence binding affinity and selectivity for rare earth elements (REEs), a series of technologically relevant metals with challenging separation profiles. A library of copolymers varying hydrophobic monomer composition and patterning was synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization, spanning statistical, gradient, and block architectures. REE binding was quantified using a high-throughput colorimetric assay, and reconstruction of polymer ensembles using kinetic stochastic simulations enabled quantitative comparisons of sequence heterogeneity, linking local monomer colocalization to emergent REE binding. Further, we investigated the role of different hydrophobic comonomers in tuning metal coordination, with binding trends linked to structural features that influence binding site desolvation. Complementary dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) measurements showed that both polymer and monomer architecture modulate metal-induced conformational changes, and that multichain assembly behavior emerges beyond critical hydrophobic thresholds. Sequence control also altered REE selectivity, with nonmonotonic differences observed across compositionally identical polymers with different sequence architectures. Together, these findings establish design principles that connect polymer sequence and structure to binding performance, guiding the design of macromolecular chelators with enhanced affinity and selectivity for applications in separations, sensing, and catalysis.}, archive = {J_JACS}, author = {Matthew P. Bogen and William M. Swofford and Supraja S. Chittari and Abigail S. Knight}, doi = {10.1021/jacs.5c07853}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30885--30896}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure–Function relationships in sequence-controlled copolymers for rare earth element chelation}, volume = {147}, year = {2025}, }
• (2025). Revealing performance-limiting buried interfaces in layered Dion–Jacobson Lead–Iodide perovskites. JACS, 147(34), 30873--30884. (www)

  @article{ , abstract = {Dion–Jacobson (DJ) two-dimensional (2D) perovskites have emerged as promising photovoltaic materials due to their superior structural and chemical stability compared to three-dimensional (3D) perovskites. However, their optoelectronic performance remains limited by imperfections at interfaces and a fundamental understanding of these interfacial properties is missing. Herein, we present interfacial structure–property relationships in DJ perovskites by directly probing buried interfaces using combined spectroscopic and microscopic characterization techniques. Multiscale heterogeneities, including phase polydispersity, structural disorder, and nonemissive domains, are more concentrated at buried interfaces than at the top surfaces, limiting overall photophysical performance. A sulfate-based inner-sphere complexation strategy is exploited to homogenize crystal growth and passivate crystal termination, specifically at buried interfaces. This approach suppresses nonradiative recombination and promotes ultrafast interphase carrier transfer within DJ perovskite films. DJ perovskite solar cells achieve a record power conversion efficiency of 20.7% while exhibiting improved environmental stability relative to their 3D counterparts. These findings establish the critical link between the buried interface heterogeneity and the optoelectronic performance of DJ 2D perovskites.}, archive = {J_JACS}, author = {Jiaqi Zhang and Nan Gan and Fangzhou Liu and Xixi Xie and Xian Zhang and Cuncun Wu and Dongchang Shi and Tengyu Xu and Shaogeng Cai and Huichao Guo and Deao Li and Guoxin Shi and Yilin Wei and Jian Li and Mingyang Wei and Yan Guan and Yangyang Zhang and Shijian Zheng and Bohan Li and So Min Park}, doi = {10.1021/jacs.5c07850}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30873--30884}, shortjournal = {J. Am. Chem. Soc.}, title = {Revealing performance-limiting buried interfaces in layered Dion–Jacobson Lead–Iodide perovskites}, volume = {147}, year = {2025}, }
• (2025). Bimolecular nucleophilic substitution (SN2) reaction catalyzed by l-threonine aldolase. JACS, 147(34), 30863--30872. (www)

  @article{ , abstract = {The bimolecular nucleophilic substitution (S N 2) and aldol reactions are cornerstone transformations in organic and biochemical synthesis, yet they operate through fundamentally distinct mechanisms, substrates, and product frameworks. Nature has evolved dedicated enzyme families to catalyze these reactions separately, namely, aldolases for aldol condensations and methyltransferases or similar enzymes for S N 2 pathways. Aldolases have not been reported to catalyze S N 2 reactions. We herein report the unprecedented repurposing of l -threonine aldolase to catalyze an S N 2 reaction. This new activity enables direct asymmetric alkylation of the sp 3 -hybridized Cα–H bond in glycine using readily accessible α-halide carbonyl compounds. Mechanistic and computational analyses elucidate how the active site of the enzyme precisely aligns substrates into a geometry that facilitates the S N 2 transition state. The developed biocatalytic platform provides efficient access to diverse enantiomerically enriched α-amino acids (29 examples), achieving yields up to 95% and exceptional stereocontrol (e.r. > 99:1). This discovery not only expands the catalytic repertoire of aldolases but also underscores the potential for repurposing aldolases to unlock non-native reactivities in sustainable synthesis.}, archive = {J_JACS}, author = {Huijun Yang and Qinrou Li and Shiping Wang and Rui Zhang and Xiang Sheng and Cangsong Liao}, doi = {10.1021/jacs.5c07660}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30863--30872}, shortjournal = {J. Am. Chem. Soc.}, title = {Bimolecular nucleophilic substitution (SN2) reaction catalyzed by l-threonine aldolase}, volume = {147}, year = {2025}, }
• (2025). Impact of the atomic structure at the BiVO4/TiO2 interface on the electronic properties and performance of BiVO4/TiO2 photoanodes. JACS, 147(34), 30851--30862. (www)

  @article{ , abstract = {In photoelectrochemical cells, semiconductor electrodes are usually interfaced with protection layers to extend their stability. Ideally, the protection layer should not decrease photocurrent generation. Hence, the conduction band minimum (CBM) and valence band maximum (VBM) of the protection layer should appropriately align with those of the underlying semiconductor electrode to facilitate the desired interfacial charge transfer with minimal interfacial recombination. However, predicting interfacial band alignment can be challenging, as it may vary depending on the detailed interfacial atomic structure. Investigating the effect of the atomic structure at the semiconductor/protection layer junction on the band alignment is also challenging as it requires samples with varied interfaces without altering the semiconductor and protection layers. Here, we considered TiO 2 , the most widely used material as a protection layer, interfaced with a BiVO 4 photoanode, and we fabricated two n-type BiVO 4 (010)/TiO 2 photoanodes where a thin (∼4 nm) amorphous TiO 2 layer was deposited by atomic layer deposition (ALD). While the individual BiVO 4 (010) and TiO 2 layers were identical in these two samples, we modified the interfacial atomic structure at the BiVO 4 /TiO 2 junction by changing which precursor, Ti or O, was introduced first upon deposition of TiO 2 . By experimentally and computationally investigating the differences in these two samples, we show that the band alignments between BiVO 4 and TiO 2 at the interface may not be straightforwardly predicted by the CBM and VBM of bulk BiVO 4 and TiO 2 and that interfacial atomic arrangements can have a marked impact on the electronic properties and photoelectrochemical performance of the BiVO 4 (010)/TiO 2 photoanode.}, archive = {J_JACS}, author = {Dae Han Wi and Kana Ishisone and Zhaoyi Xi and Zifan Ye and Daye Seo and Jiawei Zhan and Xiao Tong and Mingzhao Liu and Giulia Galli and Kyoung-Shin Choi}, doi = {10.1021/jacs.5c07695}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30851--30862}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of the atomic structure at the BiVO4/TiO2 interface on the electronic properties and performance of BiVO4/TiO2 photoanodes}, volume = {147}, year = {2025}, }
• (2025). A dynamic Silver(I) nanocluster holds together a 3 × 3 self-assembled grid. JACS, 147(34), 30842--30850. (www)

  @article{ , abstract = {Metal ions with well-defined coordination geometries can serve as fixed joints within self-assembled architectures, defining the relative orientations of ligands within higher-order superstructures. The exchange of ligands and metal ions between different positions is slow, involving disruption or distortion. Here we report a series of Ag I 12 X 4 L 6 3 × 3 metal–organic grid-like structures, where the core Ag I 12 X 4 nanocluster is in dynamic motion, with Ag I ions moving between different binding sites, with concomitant conformational changes of the organic ligands, which continue to occupy well-defined positions nevertheless. The identity of the incorporated halide anion governs the activation barrier for silver ion exchange, thus enabling rate control in response to two distinct stimuli: by changing the temperature, and by exchanging one halide for another. The dynamic nanocluster within these grids thus provides a new mode of using metal ions in coordination-driven self-assembly, establishing that the mobile Ag I ions behave in similar ways to Ag 0 atoms in surface-bound clusters and in silver nanoparticles. The kinetic parameters determined in this work, and the techniques developed to measure them, could serve the scientific community to provide additional insight into dynamic metal nanoclusters.}, archive = {J_JACS}, author = {Andrew W. Heard and Luca Pesce and Peter T. Gierth and Simone Adorinni and Tanya K. Ronson and Barbara Rossi and John D. Thoburn and Tomas Deingruber and Martin Welch and David R. Spring and Silvia Marchesan and Giovanni M. Pavan and Jonathan R. Nitschke}, doi = {10.1021/jacs.5c07271}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30842--30850}, shortjournal = {J. Am. Chem. Soc.}, title = {A dynamic Silver(I) nanocluster holds together a 3 × 3 self-assembled grid}, volume = {147}, year = {2025}, }
• (2025). Reactive chemical environments control charge carrier selectivity and photovoltage at nanoparticle Electrocatalyst/Semiconductor junctions in solar water splitting. JACS, 147(34), 30829--30841. (www)

  @article{ , abstract = {Interfacial charge transfer at electrocatalyst/semiconductor (EC/SC) junctions is central to the performance of photo(electro)catalysts, yet the influence of the reactive environment on these processes remains poorly understood. This is particularly the case for unburied EC/SC junctions, such as EC nanoparticles anchored on a SC (np-EC/SC), where reacting molecules readily access the EC surface sites and the np-EC/SC interfaces. Herein, we uncover a dynamic, chemically driven mechanism by which the local reaction environment modulates charge transfer at Pt/p-Si interfaces under solar water splitting conditions. We demonstrate that molecular adsorption of H 2 and O 2 at the metal/electrolyte interface induces interfacial dipoles on Pt nanoparticles, effectively tuning their work function and shifting the junction from Ohmic to rectifying behavior. This environment-responsive modulation of the Schottky barrier height governs charge carrier selectivity independently of the commonly cited pinch-off effect, which is found to be negligible. Additionally, a spontaneously evolved thin SiO x interlayer facilitates tunneling-mediated charge transfer while suppressing recombination, providing an additional degree of control over interfacial energetics. These findings reveal that catalytic surface chemistry can serve as a powerful lever for tuning electronic structure and photovoltage in nanoscale photoelectrode architectures, opening new design strategies for high-efficiency solar fuel systems.}, archive = {J_JACS}, author = {Ahmet Sert and Aarti Mathur and Suljo Linic}, doi = {10.1021/jacs.5c07369}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30829--30841}, shortjournal = {J. Am. Chem. Soc.}, title = {Reactive chemical environments control charge carrier selectivity and photovoltage at nanoparticle Electrocatalyst/Semiconductor junctions in solar water splitting}, volume = {147}, year = {2025}, }
• (2025). Dissolution inhibition via intramolecular N···I halogen bond enables high-loading zn-organic battery. JACS, 147(34), 30820--30828. (www)

  @article{ , abstract = {The development of aqueous zinc-ion batteries faces persistent challenges in reconciling high mass-loading capabilities with extreme tolerance, particularly for organic cathodes prone to dissolution in aqueous electrolyte. Here, we present a halogen-bonded azo-based cathode material, 4,4′-azopyridine-iodide (AZPY-I), engineered through iodine-mediated molecular stabilization of pyridinic nitrogen sites. Analyses reveal that AZPY-I adopts a robust π–π conjugated framework stabilized by directional N···I halogen bonds, achieving ultralow solubility (<0.5 mg mL –1 in H 2 O) while introducing dual redox-active sites with six-electron transfer capability (N═N and I 2 moieties). The Zn||AZPY-I cell delivers a near-theoretical capacity of 202 mAh g –1 with a high mass loading of 22.8 mg cm –2 at 0.5 A g –1 , sustaining a 92% capacity retention over 150 cycles. At an ultrahigh current density (8 A g –1 , ∼34.5 C), the cell demonstrates exceptional cyclability for 150,000 cycles with 0.00032% capacity decay per cycle. This work establishes halogen-bonded molecular engineering as a universal paradigm for designing dissolution-resistant organic electrodes, bridging molecular crystallography with practical battery metrics.}, archive = {J_JACS}, author = {Peng Yang and Jiahao Guo and Silong Lin and Yongzhu Fu and Wei Guo}, doi = {10.1021/jacs.5c07277}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30820--30828}, shortjournal = {J. Am. Chem. Soc.}, title = {Dissolution inhibition via intramolecular N···I halogen bond enables high-loading zn-organic battery}, volume = {147}, year = {2025}, }
• (2025). Structural heterogeneity of proteoform-ligand complexes in adenosine monophosphate-activated protein kinase uncovered by integrated top-down mass spectrometry. JACS, 147(34), 30809--30819. (www)

  @article{ , abstract = {Adenosine monophosphate-activated protein kinase (AMPK) is a heterotrimeric complex (αβγ) that serves as a master regulator of cellular metabolism, making it a prominent drug target for various diseases. Post-translational modifications (PTMs) and ligand binding significantly affect the activity and function of AMPK. However, the dynamic interplay of PTMs, noncovalent interactions, and higher-order structures of the kinase complex remains poorly understood. Herein, we report for the first time the structural heterogeneity of the AMPK complex arising from ligand binding and proteoforms─protein products derived from PTMs, alternative splicing, and genetic variants─using integrated native and denatured top-down mass spectrometry (TDMS). The fully intact AMPK heterotrimeric complex exhibits heterogeneity due to phosphorylation and multiple adenosine monophosphate (AMP) binding states. Native TDMS delineates the subunit composition, AMP binding stoichiometry, and higher-order structure of AMPK complex, while denatured TDMS comprehensively characterizes the proteoforms and localizes the phosphorylation site. Notably, by integrating native TDMS and AlphaFold, we elucidate a flexibly connected regulatory region of AMPK β subunit that was previously unresolvable with traditional structural biology tools. Our findings offer new perspectives on protein kinase regulation and establish a versatile framework for comprehensive characterization of proteoform-ligand complexes.}, archive = {J_JACS}, author = {Hsin-Ju Chan and Boris Krichel and Liam J. Bandura and Emily A. Chapman and Holden T. Rogers and Matthew S. Fischer and David S. Roberts and Zhan Gao and Man-Di Wang and Jingshing Wu and Charlotte Uetrecht and Song Jin and Ying Ge}, doi = {10.1021/jacs.5c06950}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30809--30819}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural heterogeneity of proteoform-ligand complexes in adenosine monophosphate-activated protein kinase uncovered by integrated top-down mass spectrometry}, volume = {147}, year = {2025}, }
• (2025). Tuning the electrical properties through metal-ion-mediated assembly in au25 nanocluster-based frameworks. JACS, 147(34), 30803--30808. (www)

  @article{ , abstract = {Au nanoclusters (NCs), with discrete electronic structures and tunable properties, are promising building blocks for nanoelectronics. However, maximizing their potential requires a deeper understanding of precise control over intercluster interactions, which is crucial for charge transport. Here, we leverage coordination chemistry to fine-tune intercluster distances in NC-based frameworks by incorporating coordinating metal ions (Mg 2+ , Co 2+ , Ni 2+ , or Cu 2+ ) into [Au 25 ( p -HMBA) 18 ] − NCs. Single-crystal X-ray diffraction reveals that four isostructural frameworks have systematic lattice parameter variations, driving a 31-fold enhancement in the electrical conductivity. Density functional theory calculations further reveal semiconductor-like electronic structures and highlight that Cu 2+ -coordinated frameworks exhibit more efficient charge transport due to the presence of Cu 3d states near the Fermi level. This atomic-level investigation of intercluster distance effects and electrical property tuning through coordinating ion incorporation establishes design principles for engineering electronic properties in NC frameworks, enabling the development of precisely tunable and high-performance nanoelectronic materials.}, archive = {J_JACS}, author = {Sinhyeop Kim and Hanna Jääskö and Kyoung Chul Park and Sami Malola and Hannu Häkkinen and Sarah S. Park}, doi = {10.1021/jacs.5c06695}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30803--30808}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the electrical properties through metal-ion-mediated assembly in au25 nanocluster-based frameworks}, volume = {147}, year = {2025}, }
• (2025). Shortwave infrared hemicyanine-6 for cancer-activated and shaving-free preclinical imaging of lung metastasis. JACS, 147(34), 30794--30802. (www)

  @article{ , abstract = {Fluorescence imaging in the shortwave infrared (SWIR) window enables deeper tissue and higher-contrast visualization of pathological events compared to that in the conventional near-infrared (NIR) window. However, specific SWIR detection of biomarkers of interest remains challenging because few fluorophore scaffolds are available to be further modified into biomarker-activatable SWIR probes. Herein, we employ a highly efficient approach to synthesize six hemicyanine derivatives with emissions extending to the SWIR region and structural amenability for construction of activatable probes. The bathochromic shifts of these dyes are driven by the extension of the central polymethine bridge and the substitution of the xanthene endocyclic oxygen atom with a heavier sulfur atom. Among all fluorophores, HCS6, featuring three central methine–methine bonds, has the longest emission maximum at 1010 nm along with superior photostability and high SWIR brightness. These properties enable HCS6 to achieve lung imaging in haired mouse models without the need for shaving. Furthermore, HCS6 is constructed into an activatable probe that selectively turns on its SWIR fluorescence in response to a cancer-associated biomarker, allowing for the highly sensitive identification of metastatic lung lesions in unshaved mice. These hemicyanine scaffolds offer a promising platform for developing versatile activatable probes, highlighting their potential for SWIR microscopy and deep-tissue biological imaging.}, archive = {J_JACS}, author = {Hanyu Yang and Donghao Li and Jiayan Wu and Kanyi Pu}, doi = {10.1021/jacs.5c06682}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30794--30802}, shortjournal = {J. Am. Chem. Soc.}, title = {Shortwave infrared hemicyanine-6 for cancer-activated and shaving-free preclinical imaging of lung metastasis}, volume = {147}, year = {2025}, }
• (2025). Mapping excited-state decay mechanisms in acetylacetone by sub-20 fs time-resolved photoelectron spectroscopy. JACS, 147(34), 30785--30793. (www)

  @article{ , abstract = {Excited-State Intramolecular Hydrogen Transfer (ESIHT) is one of the fastest chemical reactions, occurring on the order of tens of femtoseconds and playing a critical role in light-driven biological processes and technological applications. Here, we investigate the early stages of coupled nuclear-electron dynamics using acetylacetone (AcAc) as a model system exhibiting ESIHT. We employ ultraviolet-extreme ultraviolet (UV-XUV) time-resolved photoelectron spectroscopy (tr-PES) with sub-20 fs resolution in combination with high-level dynamically correlated simulations (CASPT2) to map the electronic relaxation pathways and vibrational modes driving this process. Our results provide distinct spectroscopic signatures of ESIHT occurring within the first 20 fs and resolve the active vibrational modes, showing the intricate evolution of the electronic and nuclear degrees of freedom. Moreover, the analysis reveals the key role of ultrafast intersystem crossing (ISC) to triplet states in modulating the excited-state dynamics and its implications for the overall relaxation pathways. These findings refine our understanding of the photochemistry of AcAc and suggest general principles that can be applied to similar conjugated systems.}, archive = {J_JACS}, author = {Stefano Severino and Flavia Aleotti and Lorenzo Mai and Aurora Crego and Fabio Medeghini and Fabio Frassetto and Luca Poletto and Matteo Lucchini and Francesco Segatta and Maurizio Reduzzi and Mauro Nisoli and Artur Nenov and Rocío Borrego-Varillas}, doi = {10.1021/jacs.5c06327}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30785--30793}, shortjournal = {J. Am. Chem. Soc.}, title = {Mapping excited-state decay mechanisms in acetylacetone by sub-20 fs time-resolved photoelectron spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Microcavity-enhanced directional electrochemiluminescence output from single molecular crystals. JACS, 147(34), 30777--30784. (www)

  @article{ , abstract = {Molecular crystal-based electrochemiluminescence (ECL) waveguides can output directional optical signal. However, an optical loss still exists, suppressing the output strength. Herein, we report an approach of achieving enhanced ECL output by ingeniously designing microrod-shaped molecular crystals with microcavities at both terminals, termed as mMCs. A combined use of band electrode array and ECL microscopy allows both the spatially selective electrochemical excitation of single mMCs to generate ECL and the imaging study of light propagation along the crystals. When triggering ECL reactions at one terminal of mMCs, the light can be transmitted to the other. Compared with solid molecular crystals with an ECL loss of up to 93%, the optical loss in mMCs can be reduced to 15% (left to right) and 81% (right to left). Furthermore, when ECL is triggered at the middle of mMCs, the ECL propagation is lossless and even remarkably improved by 1.7–6.8 times, thus realizing the enhanced directional optical output, thanks to the open microcavities that favor the out-coupling of light from the molecular crystal. This finding demonstrates a controllable approach for the microcavity-enhanced directional ECL output and holds great promise in remote and intercellular imaging through ECL waveguiding.}, archive = {J_JACS}, author = {Xiaojin Huang and Li Shen and Weiyu Qu and Yingying Xu and Wenxuan Fu and Weiliang Guo and Zhihui Dai and Bin Su}, doi = {10.1021/jacs.5c05944}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30777--30784}, shortjournal = {J. Am. Chem. Soc.}, title = {Microcavity-enhanced directional electrochemiluminescence output from single molecular crystals}, volume = {147}, year = {2025}, }
• (2025). Tandem catalysis to mitigate coke formation in the upcycling of mixed polyolefin wastes. JACS, 147(34), 30768--30776. (www)

  @article{ , abstract = {Postconsumer plastic waste is commonly made up of various types of polymers, and the compositional heterogeneity complicates their recycling. A notable example is polyethylene/ethylene vinyl acetate (PE/EVA) blends, which are widely used as multilayer packaging materials, films, and cable coatings. Chemical recycling of PE/EVA blends often yields low-value short-chain alkanes, especially methane, and suffers from coke formation. Here, we demonstrate a tandem hydrodeoxygenation-hydrogenolysis process for the valorization of PE/EVA waste into long-chain hydrocarbons using Ru-MoO x /CeO 2 . Mechanistic investigations reveal that the introduction of MoO x into the Ru catalyst facilitates the hydrodeoxygenation of the acetate group in EVA, thereby abating coke formation, while Ru subsequently catalyzes the hydrogenolysis of the carbon backbone. The system achieves near-complete conversion for mixed PE/EVA, yielding over 65% fuels and waxes with an exceptional high specific activity of 782 g PE/EVA g Ru –1 h –1 . Moreover, Ru-MoO x /CeO 2 displays high efficiencies across various PE/EVA products and over a wide range of hydrogen pressures (0.5–2.0 MPa). This versatility underscores the potential of this tandem process for the upcycling of mixed polyolefin wastes.}, archive = {J_JACS}, author = {Jiayang Zhao and Qikun Hu and Yuqi Wang and Yizhen Che and Zhiqiang Niu}, doi = {10.1021/jacs.5c05824}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30768--30776}, shortjournal = {J. Am. Chem. Soc.}, title = {Tandem catalysis to mitigate coke formation in the upcycling of mixed polyolefin wastes}, volume = {147}, year = {2025}, }
• (2025). Enhanced proton transport in nb-doped rutile TiO2: A highly useful class of proton-conducting mixed ionic electronic conductors. JACS, 147(34), 30757--30767. (www)

  @article{ , abstract = {Mixed protonic and electronic conductors are essential materials as electrodes for electrochemical devices that use hydrogen as a reactant or product, such as fuel cells and steam electrolyzers. As the demand for devices operating at intermediate temperatures (<500 °C) is increasing, it has become highly desirable to develop optimized mixed protonic and electronic conductors for this temperature range. In this study, we investigated hydrogen dissolution and proton transport in Nb-doped rutile TiO 2 (Ti 0.96 Nb 0.04 O 2 ), an oxide semiconductor. Ti 0.96 Nb 0.04 O 2 dissolved hydrogen at 450 °C in a hydrogen atmosphere, incorporating 2.1 × 10 20 cm –3 of protons to the semiconductor, which is 10–100 times higher than that in undoped TiO 2 . This resulted in a proton conductivity of 4 × 10 –3 S cm –1 at 250 °C. Given its electronic conductivity of 2 S cm –1 at 250 °C, Ti 0.96 Nb 0.04 O 2 has been identified as an excellent mixed protonic and electronic conductor. The proton diffusion coefficient reached ∼1 × 10 –5 cm 2 s –1 at 250 °C, which is over 1000 times higher than that of undoped TiO 2 and 10–1000 times higher than those of well-known perovskite-type proton conductors represented by Ba(Zr,Y)O 3 . This enhanced proton density and diffusion is attributed to Nb doping, which stabilizes and delocalizes the electrons introduced by hydrogen dissolution while shielding negative charge centers. This previously unreported mechanism for improving proton conductivity provides a novel design guideline for mixed protonic and electronic conductors, paving the way for the development of future materials in hydrogen-related electrochemical applications.}, archive = {J_JACS}, author = {Takuma Shiraiwa and Tomoyuki Yamasaki and Kizuku Kushimoto and Junya Kano and Takahisa Omata}, doi = {10.1021/jacs.5c05805}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30757--30767}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced proton transport in nb-doped rutile TiO2: A highly useful class of proton-conducting mixed ionic electronic conductors}, volume = {147}, year = {2025}, }
• (2025). Carbene-catalyzed intramolecular cyclization to access inherently chiral saddle-shaped lactones: Achiral bases alternate product chirality. JACS, 147(34), 30747--30756. (www)

  @article{ , abstract = {Enantiodivergent synthesis using a single catalyst or catalysts with the same chiral scaffold has evolved as a particularly attractive tool to access both enantiomers of chiral molecules. Progress in this field mainly comes from the enantiodivergent construction of central chirality as well as axial chirality. We report herein a carbene-catalyzed base-controlled enantiodivergent synthesis of saddle-shaped eight-membered lactones with inherent chirality. With the use of the same carbene catalyst or the carbene catalysts with the same chiral scaffold, both enantiomers of the inherently chiral eight-membered lactones could be obtained under different base conditions in high yields with good to excellent enantioselectivities. The resulting inherently chiral eight-membered lactones allow further stereospecific derivatizations and exhibit notable antibacterial activity. Preliminary DFT calculations unraveled the origins of this base-controlled enantiodivergent process.}, archive = {J_JACS}, author = {Liwen Wei and Yuhang Chen and Qinglong Zhou and Zhikang Wei and Ting Tu and Shichao Ren and Yonggui Robin Chi and Xinglong Zhang and Xing Yang}, doi = {10.1021/jacs.5c05380}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30747--30756}, shortjournal = {J. Am. Chem. Soc.}, title = {Carbene-catalyzed intramolecular cyclization to access inherently chiral saddle-shaped lactones: Achiral bases alternate product chirality}, volume = {147}, year = {2025}, }
• (2025). Air-stable ferrocene-based catholytes for improved performance in pH-neutral aqueous organic redox flow batteries. JACS, 147(34), 30737--30746. (www)

  @article{ , abstract = {Aqueous pH-neutral organic redox flow batteries are emerging as viable solutions for sustainable grid-scale energy storage. However, their advancement is hindered by the limited availability of catholytes that maintain stable cyclability in both ambient air and inert environments, as well as challenges related to low-cost synthesis and achieving high volumetric capacity. Here, we present the design and synthesis of a series of imidazolium-decorated ferrocene derivatives, culminating in the identification of an ionic liquid-like catholyte that sustains cycling stability in air for over 2000 cycles. At a concentration of 0.5 M, this catholyte exhibits remarkable cycling stability, with no capacity loss observed over a 68-day period in an inert atomosphere. Theoretical calculations and spectroscopic analyses reveal that the methyl imidazolium pendant group enhances compound stability and reduces hydrophilic attacks on ferrocenium through hydrogen-bonding interactions, thereby improving cycling stability. Notably, we have successfully constructed a pH-neutral stacked flow battery that achieves a peak power of 140 W and maintains an unprecedented capacity retention of 95% at 60 mA cm –2 after 20,000 cycles. These findings not only introduce a novel pathway for developing highly stable catholytes but also facilitate assembling high-power-density stacked pH-neutral aqueous organic redox flow batteries.}, archive = {J_JACS}, author = {Bin Liu and Manrong Song and Yu Wang and Youke Chen and Honglin Chen and Jing Sun and Jiayou Ren and Xuan Shen and Xiaocong Zhou and Chao Ji and Shengxin Yao and Liuping Chen and Tianshou Zhao}, doi = {10.1021/jacs.5c05219}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30737--30746}, shortjournal = {J. Am. Chem. Soc.}, title = {Air-stable ferrocene-based catholytes for improved performance in pH-neutral aqueous organic redox flow batteries}, volume = {147}, year = {2025}, }
• (2025). Distal mutations in a designed retro-aldolase alter loop dynamics to shift and accelerate the rate-limiting step. JACS, 147(34), 30723--30736. (www)

  @article{ , abstract = {Amino acid residues distant from an enzyme’s active site are known to influence catalysis, but their mechanistic contributions to the catalytic cycle remain poorly understood. Here, we investigate the structural, functional, and mechanistic impacts of distal and active-site mutations discovered through directed evolution of the computationally designed retro-aldolase RA95. Active-site mutations improve catalytic efficiency by 3,600-fold, while distal mutations alone offer no improvement. When combined with active-site mutations, distal mutations further increase efficiency by 6-fold, demonstrating an epistatic effect. X-ray crystallography and molecular dynamics simulations reveal that distal mutations promote active site opening by altering loop dynamics. Kinetic solvent viscosity effects and electric field calculations show that distal mutations accelerate the chemical transformation by 100-fold, shifting the rate-limiting step to product release, which is further accelerated by the increased opening of the active site. These findings establish the critical role of distal residues in shaping the active-site environment and facilitating the structural dynamics essential for efficient progression through the catalytic cycle, offering valuable insights for enzyme design.}, archive = {J_JACS}, author = {Serena E. Hunt and Cindy Klaus and Aqza E. John and Niayesh Zarifi and Alec Martinez and Ferran Feixas and Marc Garcia-Borràs and Michael C. Thompson and Roberto A. Chica}, doi = {10.1021/jacs.5c05134}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30723--30736}, shortjournal = {J. Am. Chem. Soc.}, title = {Distal mutations in a designed retro-aldolase alter loop dynamics to shift and accelerate the rate-limiting step}, volume = {147}, year = {2025}, }
• (2025). Ir(hkl) surface electrochemistry in a nonadsorbing acidic medium. JACS, 147(34), 30708--30722. (www)

  @article{ , abstract = {The fundamental properties of electrochemical materials depend on the multiple and often complex interactions between electrode surface sites and electrolyte species at the electrochemical interface. Despite the use of iridium in electrolyzer systems, much of its surface electrochemistry remains underexplored. This study investigates the surface electrochemistry of the Ir(111), Ir(100), and Ir(110) surfaces in acidic media. Using cyclic voltammetry and CO charge displacement experiments, we establish the charge states and adsorbate coverages as a function of the electrode potential, revealing the presence of hydrogen and hydroxyl coadsorption at low potentials on (111), and almost no coverage of H ad on the (110) facet. In situ Shell Isolated Nanoparticle Enhanced Raman Spectroscopy experiments provide direct evidence of the formation of key adsorbate species, such as hydrogen, hydroxyl, and oxygen, but most importantly, their interactions with interfacial water, confirmed by Density Functional Theory calculations. Our findings highlight the role of coadsorption with microkinetic adsorption voltammetry simulations, corroborating the influence of lateral interactions on adsorption dynamics. These insights help us understand the trends in hydrogen oxidation and evolution and oxygen reduction reactions, where both adsorbate coverage and the interfacial water network determine Ir( hkl ) reactivity. Our results underscore the importance of interfacial water and hydrogen bonding networks in shaping the electrochemical behavior on Ir surfaces, refining our baseline understanding of the Ir surface electrochemistry necessary for the targeted use of advanced Ir-based electrochemical materials.}, archive = {J_JACS}, author = {Kaline Nascimento da Silva and Kavyasree Anjanarambath and Caroline Katherine Williams and Haiying He and Peter Zapol and Pietro Papa Lopes}, doi = {10.1021/jacs.5c04909}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30708--30722}, shortjournal = {J. Am. Chem. Soc.}, title = {Ir(hkl) surface electrochemistry in a nonadsorbing acidic medium}, volume = {147}, year = {2025}, }
• (2025). Unraveling the relaxation dynamics of uracil: Insights from time-resolved X-ray photoelectron spectroscopy. JACS, 147(34), 30694--30707. (www)

  @article{ , abstract = {We report a study of the electronic and nuclear relaxation dynamics of the photoexcited RNA base uracil in the gas phase using time-resolved core-level photoelectron spectroscopy together with high-level calculations. The dynamics was investigated by trajectory surface hopping calculations, and the core ionization energies were calculated for geometries sampled from these. The molecule was excited by a UV laser and dynamics probed on the oxygen, nitrogen, and carbon sites by core electron spectroscopy. We find that the main de-excitation channel of the initially excited S 2 (ππ*) state involves internal conversion to the S 1 (nπ*) state with a time constant of 17 ± 4 fs, while a portion of S 2 (ππ*) population returns directly to the ground state by internal conversion. We find no evidence that the S 1 (nπ*) state decays to the ground state; instead, it decays to triplet states with a time constant of 1.6 ± 0.4 ps. Oscillations of the S 1 (nπ*) state O 1s intensity as a function of time correlate with those of calculated C4═O8 and C5═C6 bond lengths, which undergo a sudden expansion following the initial π → π* excitation. Our calculations support our interpretation of the data and provide detailed insight into the relaxation processes of uracil.}, archive = {J_JACS}, author = {Davide Faccialà and Matteo Bonanomi and Bruno Nunes Cabral Tenorio and Lorenzo Avaldi and Paola Bolognesi and Carlo Callegari and Marcello Coreno and Sonia Coriani and Piero Decleva and Michele Devetta and Nađa Došlić and Alberto De Fanis and Michele Di Fraia and Fabiano Lever and Tommaso Mazza and Michael Meyer and Terry Mullins and Yevheniy Ovcharenko and Nitish Pal and Maria Novella Piancastelli and Robert Richter and Daniel E. Rivas and Marin Sapunar and Björn Senfftleben and Sergey Usenko and Caterina Vozzi and Markus Gühr and Kevin C. Prince and Oksana Plekan}, doi = {10.1021/jacs.5c04874}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30694--30707}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the relaxation dynamics of uracil: Insights from time-resolved X-ray photoelectron spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Design of antigen-targeting fluorogenic probes utilizing intramolecular addition reaction of protein-dye hybrids. JACS, 147(34), 30684--30693. (www)

  @article{ , abstract = {Fluorogenic probes for antigens are useful for various purposes, including medical diagnostics and imaging, but achieving a rapid, large fluorescence increase is difficult. Here, we report a new class of fluorogenic probes for antigens based on a conjugate of an antibody-mimetic DARPin bearing a site-specifically incorporated cysteine and silicon-pyronine (SiP), which reacts reversibly with thiols. By using a library-screening approach, we found that the fluorescence of SiP conjugated to a DARPin is quenched via π-deconjugating addition reaction of the cysteine installed in the DARPin to SiP. Upon antigen binding, the equilibrium of this reaction is shifted to dissociation, restoring π-conjugation in the SiP and resulting in a large increase in fluorescence. As proof of concept of this chemical design principle, we constructed fluorogenic probes targeting GFP and EpCAM, which showed 25- and 12-fold fluorescence increases upon binding, respectively. The latter probe enabled wash-free cancer cell imaging with a low background.}, archive = {J_JACS}, author = {Mamiko Nakadate and Ryosuke Kojima and Naoki Seike and Ryo Tachibana and Kyohhei Fujita and Reiko Tsuchiya and Mako Kamiya and Andreas Plückthun and Yasuteru Urano}, doi = {10.1021/jacs.5c04193}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30684--30693}, shortjournal = {J. Am. Chem. Soc.}, title = {Design of antigen-targeting fluorogenic probes utilizing intramolecular addition reaction of protein-dye hybrids}, volume = {147}, year = {2025}, }
• (2025). Vortex-flow-directed chiral macroscopic ordering of platelet nanostructures formed via the supramolecular assembly of platinum complexes with bis(phenylisoxazolyl)benzene. JACS, 147(34), 30674--30683. (www)

  @article{ , abstract = {To understand the vortex flow-directed circular dichroism (CD) effect observed in homogeneous solutions containing supramolecular structures, the macroscopic order formed by supramolecular structures oriented within a flow must be visualized. In this study, a bis(phenylisoxazolyl)benzene-attached platinum complex was found to self-assemble to form uniform anisotropic platelet nanostructures that are oriented within a flow, thereby generating a chiral macroscopic order that is responsible for CD and linear dichroism (LD) effects only in the vortex flow regime. Cooperative self-assembly of a bis(phenylisoxazolyl)benzene-attached platinum complex via controlled supramolecular polymerization produced anisotropic platelet nanostructures with a narrow polydispersity index. The orientational order parameter of the nanostructures correlated with the flow velocity; thus, the nanostructures were oriented along the flow direction. Furthermore, the vortex flow of the dilute nanostructure solution broke the symmetry of the flow, thereby generating a chiral macroscopic order. As a result, CD and LD effects were observed in the vortex flow regime of the dilute nanostructure solution. These results can be generalized to the formation of chiral macroscopic order in solutions containing anisotropic nanostructures.}, archive = {J_JACS}, author = {Masaya Yoshida and Kyota Yasuda and Takuma Matsumoto and Yudai Ono and Naoyuki Hisano and Mao Kawasaki and Takehiro Hirao and Ye Yuan and Shin-ichi Tate and Martin Vacha and Takeharu Haino}, doi = {10.1021/jacs.5c03761}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30674--30683}, shortjournal = {J. Am. Chem. Soc.}, title = {Vortex-flow-directed chiral macroscopic ordering of platelet nanostructures formed via the supramolecular assembly of platinum complexes with bis(phenylisoxazolyl)benzene}, volume = {147}, year = {2025}, }
• (2025). Catalytic markovnikov hydrothiolation of dehydroamino acids: Unified total synthesis of enteropeptin sactipeptides. JACS, 147(34), 30661--30673. (www)

  @article{ , abstract = {Sactipeptides are a class of antimicrobial cyclic peptides that possess thioaminoketal functional groups. This class defining motif is formed by a carbon–sulfur bond between the cysteine thiol and the α carbon of another amino acid in the peptide. In this work, we report the catalytic intermolecular Markovnikov addition of thiols to dehydroamino acids (Dhaa) to access thioaminoketals directly. Central to our reaction design is the use of a dithiophosphoric acid catalyst, which gives exclusive α-selective addition of thiols to Dhaa residues. The Markovnikov hydrothiolation of cysteine derivatives to Dhaa forms the thioaminoketals found in sactipeptide natural products. This strategy was utilized for the unified synthesis of the enteropeptin sactipeptides and allowed for the evaluation of their structure–activity relationship.}, archive = {J_JACS}, author = {Yiwei Zhang and Shuvendu Saha and Yesen Cheng and Yannik C. C. Esser and Chi P. Ting}, doi = {10.1021/jacs.5c03669}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30661--30673}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic markovnikov hydrothiolation of dehydroamino acids: Unified total synthesis of enteropeptin sactipeptides}, volume = {147}, year = {2025}, }
• (2025). Formation and reactivity of an elusive monomeric Mn(IV)-oxo species inside a cavitand pore. JACS, 147(34), 30647--30660. (www)

  @article{ , abstract = {Metal-functionalized cavitands are promising platforms for mimicking the chemical environments of hydrophobic pockets in natural metalloenzymes. However, successfully combining the unique supramolecular capabilities of cavitand scaffolds with the high reactivities of transition metal complexes still remains a major challenge. In this study, we present an original cavitand architecture featuring a coordinatively unsaturated Mn(II) center embedded deep within its pore. This metallocavitand was employed to generate a Mn(IV)-oxo species inside a molecular cavity. This elusive intermediate was fully characterized spectroscopically (UV–vis, EPR, X-ray photoelectric spectroscopy (XPS), and HRMS) and, for the first time for a pseudo-octahedral Mn(IV)-oxo species, also by XRD. The experimental data was corroborated by detailed ab initio /time-dependent density functional theory (TDDFT) and natural bond orbital (NBO) calculations, confirming the Mn(IV)-oxo (rather than Mn(III)-oxyl) electronic character of this species. Reactivity and mechanistic studies, including monitoring the decay of this complex in various chlorinated solvents and its reactions with representative substrates, revealed that, despite the steric protection provided by the cavitand scaffold, its Mn(IV)-oxo core remains highly reactive in both H atom abstraction (HAA) and O atom transfer (OAT) reactions. Moreover, this reactivity is subject to a high degree of steric control imposed by the cavitand framework capable of discriminating between potential substrate molecules based on their size and shape. This was further demonstrated by the regioselective oxidation of a bisphosphine substrate, emulating the regioselectivity of natural metalloenzymes.}, archive = {J_JACS}, author = {Galon Green and Kamal Uddin Ansari and Thejasree Munikrishna and Sagi Ezov and Donia Shamali and Laxmi-Narayan Nanda and Vitaly Gutkin and Orit Cohen and Daphna Shimon and Yuri Tulchinsky}, doi = {10.1021/jacs.5c02637}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30647--30660}, shortjournal = {J. Am. Chem. Soc.}, title = {Formation and reactivity of an elusive monomeric Mn(IV)-oxo species inside a cavitand pore}, volume = {147}, year = {2025}, }
• (2025). Solvation free energies of anions: From curated reference data to predictive models. JACS, 147(34), 30626--30646. (www)

  @article{ , abstract = {Predicting the physicochemical properties of ionizable solutes, including solubility and lipophilicity, is of broad significance. Such predictions rely on the accurate determination of solvation free energies for ions. However, the limited availability of high-quality reference data poses a challenge in developing accurate, inexpensive computational prediction methods. In this study, we address both issues of data quality and availability. We present three databases and models related to ionic phenomena: (1) 8,241 p K a data points across 8 solvents, (2) 5,536 gas-phase acidities from DLPNO–CCSD(T) QM calculations, and (3) 6,090 solvation free energies of anions across 8 solvents obtained from a thermodynamic cycle. We also report 6,088 solvation free energies of neutral conjugate solutes computed using the COSMO-RS method. The p K a data were obtained from the iBonD database, cleaned, and combined with a separate compilation of trustworthy reference p K a data. Gas-phase acidities were computed for most of the acids present in the p K a corpus. Leveraging these data, we compiled values for solvation free energies of anions. We then trained several graph neural network models, which can be used as an alternative to QM approaches to quickly estimate these properties. The p K a and gas-phase acidity models accept reaction SMILES strings of the acid dissociation as inputs, whereas the solvation energy model accepts the SMILES string of the anion. Our microscopic p K a model achieves good accuracy, with an overall test mean average error of 0.58 units on unseen solutes and 0.59 on the SAMPL7 challenge (the lowest error so far among multisolvent models). Our gas-phase acidity model had mean absolute errors slightly above 2 kcal mol –1 when evaluated against experimental data. The anionic solvation free energy model had mean absolute errors of less than 3 kcal mol –1 in several test evaluations, comparable to (though less reliable than) several widely used QM-based solvation models. The models and data are free and publicly available at doi.org/10.5281/zenodo.13987781.}, archive = {J_JACS}, author = {Thomas Nevolianis and Jonathan W Zheng and Simon Müller and Matthias Baumann and Sofja Tshepelevitsh and Ivari Kaljurand and Ivo Leito and Irina Smirnova and William H Green and Kai Leonhard}, doi = {10.1021/jacs.5c02578}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30626--30646}, shortjournal = {J. Am. Chem. Soc.}, title = {Solvation free energies of anions: From curated reference data to predictive models}, volume = {147}, year = {2025}, }
• (2025). Identifying active sites of IrOx catalysts for OER: A combined operando XAS, SEIRAS, and theoretical study. JACS, 147(34), 30613--30625. (www)

  @article{ , abstract = {Iridium oxide is a benchmark catalyst for anodic oxygen evolution reactions due to its high activity and durability. However, debates persist regarding the short lifespan of reaction intermediates and whether amorphous phases exhibit higher activity in comparison to crystalline ones. Herein, we examined IrO x catalysts with different degrees of crystallinity (SA3.5, SA58, SA103, and SA14.6, named after their BET surface area) and revealed the relation between their structures and OER activities. The atomic pair distribution function analyses show that the amorphous IrO x (SA3.5, SA103, and SA14.6) possesses monoclinic and orthorhombic-like structural phases or motifs, which differ from the typical tetragonal symmetry of crystalline IrO 2 . Operando X-ray absorption spectroscopy (XAS) and operando surface-enhanced infrared absorption spectroscopy (SEIRAS) revealed that the SA3.5 sample, with higher monoclinic content, exhibits a structure containing corner- and edge-sharing octahedra with highly undercoordinated sites, leading to structural defects. These defects generate active electrophilic O I– species, facilitating the generation of *OOH intermediates and enhancing OER activity. Theoretical studies reveal that they also lower the energy barrier for the monoclinic crystal structure. These findings offer a fundamental understanding of amorphous iridium oxides and provide inspiration for developing new OER catalysts.}, archive = {J_JACS}, author = {Neha Thakur and Yadan Ren and Mukesh Kumar and Tomoki Uchiyama and Mitsuharu Fujita and Ikkei Arima and Minoru Ishida and Yingkai Wu and Yuta Tsuji and Hideto Imai and Masashi Matsumoto and Yu Zhuang and Kentaro Yamamoto and Toshiyuki Matsunaga and Koji Ohara and Mitsuhiro Matsumoto and Yuki Orikasa and Yoshiyuki Kuroda and Shigenori Mitsushima and Yoshiharu Uchimoto}, doi = {10.1021/jacs.4c18510}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30613--30625}, shortjournal = {J. Am. Chem. Soc.}, title = {Identifying active sites of IrOx catalysts for OER: A combined operando XAS, SEIRAS, and theoretical study}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of (±)-crokonoid a. JACS, 147(34), 30606--30612. (www)

  @article{ , abstract = {We report the first total synthesis of (±)-crokonoid A, a highly oxidized and rearranged ent -kauranoid featuring a novel tricyclo[4.4.1.1 1,4 ]dodecane scaffold. The unique double bridged carbon skeleton was assembled by synthesis of the bicyclo[4.3.1]decane via nitrile-oxide dipolar cycloaddition. Salient features of this strategy are the effective construction of the bridged system and masking the twofold aldol motif as an isoxazoline. An unconventional bridgehead propargylation set the key quaternary stereocenter concomitant with the installation of the side chain. Subsequent cycloalkenylation led to construction of the bicyclo[3.2.1]octane, completing the carboskeleton. Strategic orchestration involving regio- and diastereoselective reactions furnished the unique oxidation pattern, thus completing the total synthesis.}, archive = {J_JACS}, author = {Tristano Martini and Nobel Saab and Jonathan Muschietti and Erick M. Carreira}, doi = {10.1021/jacs.5c11026}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30606--30612}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of (±)-crokonoid a}, volume = {147}, year = {2025}, }
• (2025). Concise syntheses of harziane diterpenoids by merging local desymmetrization and radical retrosynthesis. JACS, 147(34), 30599--30605. (www)

  @article{ , abstract = {Harziane diterpenoids possess a highly caged 6/5/7/4 core framework and four contiguous stereocenters, including two quaternary ones, and present significant challenges to chemical synthesis. Herein, we report an efficient strategy to rapidly access harziane diterpenoids by merging local desymmetrization and radical retrosynthesis. The strained bicyclo[5.2.0]nonene motif was installed using a local desymmetrizing intramolecular aldol reaction with high diastereotopic group selectivity, while the bridged [3.2.1] ring system and three contiguous stereocenters were rapidly forged by means of three strategic radical fragment couplings, i.e., Baran reductive olefin coupling, photocatalytic deoxygenative alkylation, and acyl radical cyclization.}, archive = {J_JACS}, author = {Jiang Wu and Jiajing Bao and Jiachen Deng and Hailong Tian and Jinghan Gui}, doi = {10.1021/jacs.5c09579}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30599--30605}, shortjournal = {J. Am. Chem. Soc.}, title = {Concise syntheses of harziane diterpenoids by merging local desymmetrization and radical retrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Nitrogen-centered organic salts enable stable lithium-ion supply for high-energy-density batteries. JACS, 147(34), 30591--30598. (www)

  @article{ , abstract = {Compensating lithium (Li) ions for high-energy-density batteries is essential, as the anodes such as silicon-based materials present up to 20% Li-ion loss in the initial cycle. Current Li-ion supply molecules present side reactions with battery components and lead to undesirable gas generation due to the intrinsic electrochemical mechanism. To address this, we report the design of a nitrogen (N)-centered organic salt, lithium-benzimidazol-2-one (Li 2 N 2 C 7 H 4 O), capable of supplying Li-ions without damaging the battery chemical environment and effectively protecting the Ni-rich cathode surface. This molecule, discovered through semisupervised machine learning, undergoes a two-step anodic reaction through a free radical pathway, releasing Li-ions and forming an electrolyte additive, benzimidazolone (C 7 H 4 N 2 O), to suppressing transition metal dissolution of the LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) cathode. No gases were generated in this process. The complete conversion of Li 2 N 2 C 7 H 4 O and effective protection of NCM811 were confirmed by spectroscopic and microscopic characterizations. The utilization of Li 2 N 2 C 7 H 4 O effectively increased the capacity of a silicon monoxide (SiO)/C|NCM811 pouch cell from 186.7 to 205.5 mAh g –1 , and the cell delivered an 84.1% capacity retention after 500 cycles, opening up an avenue to design a N-centered oxidation reaction mechanism for Li-ion supply in high-energy-density batteries.}, archive = {J_JACS}, author = {Ziyang Kang and Shengfei Wang and Guanbin Wu and Shu Chen and Zilong Zheng and Wenwen Wang and Xinwei Du and Huajing Li and Mengyao Zhu and Huisheng Peng and Yue Gao}, doi = {10.1021/jacs.5c09300}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30591--30598}, shortjournal = {J. Am. Chem. Soc.}, title = {Nitrogen-centered organic salts enable stable lithium-ion supply for high-energy-density batteries}, volume = {147}, year = {2025}, }
• (2025). Catalyst-enabled chemoselective metalloradical activation for molecular rearrangement via ester migration and allylic C(sp3)–H amination. JACS, 147(34), 30582--30590. (www)

  @article{ , abstract = {An iron-based metalloradical activation concept is developed for an intramolecular molecular rearrangement via ester migration and an allylic C(sp 3 )–H amination using tetrazole as a nitrene precursor. It has been shown that an appropriate choice of catalyst can switch the chemoselectivity of a particular substrate from molecular rearrangement toward allylic C(sp 3 )–H amination. The scope of the reactions has been demonstrated by the use of a wide number of tetrazoles and aryl azides. Preliminary mechanistic studies revealed that while molecular rearrangement proceeds via an electrophilic nitrene transfer mechanism, C(sp 3 )–H amination follows a distinctive metalloradical activation mechanism controlled by the electronic properties of the iron–porphyrin catalysts. Collectively, this discovery highlights the advancement of chemoselective metalloradical catalysis, which should find wide application in medicinal chemistry and drug discovery.}, archive = {J_JACS}, author = {Sima Patra and Subrata Das and Souvik Nandi and Hillol Khatua and Buddhadeb Chattopadhyay}, doi = {10.1021/jacs.5c07955}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30582--30590}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalyst-enabled chemoselective metalloradical activation for molecular rearrangement via ester migration and allylic C(sp3)–H amination}, volume = {147}, year = {2025}, }
• (2025). Unexpected generation of singlet oxygen at the Air–Water interface of aqueous microdroplets. JACS, 147(34), 30574--30581. (www)

  @article{ , abstract = {Singlet oxygen ( 1 O 2 ) is a classical nonradical reactive oxygen species (ROS), which is of great significance in both natural and engineering environments. Here, we found that 1 O 2 can be generated spontaneously at the air–water interface of microdroplets under dark conditions. 18 O isotope labeled O 2 ( 18 O 2 ) and water (H 2 18 O) were used to identify the source and formation pathway of 1 O 2 and previously reported ROS produced in microdroplets. The results showed that 1 O 2 and superoxide anions (•O 2 – ) were sourced from O 2 , •OH was sourced from H 2 O, while H 2 O 2 can be produced from both H 2 O and O 2 . Moreover, the excited hydrated electron (e – (aq)) induced indirect energy transfer is responsible for exciting O 2 from the ground state to the singlet state. The findings of this work provide an important complement to the construction of a complete ROS chemistry in microdroplets.}, archive = {J_JACS}, author = {Feifei Li and Jitao Lv and Anen He and Jin Xu and Lixia Zhao and Xianwei Wang and Li Mao and Shasha Li and Hailin Wang and Yawei Wang and Guibin Jiang}, doi = {10.1021/jacs.5c02431}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30574--30581}, shortjournal = {J. Am. Chem. Soc.}, title = {Unexpected generation of singlet oxygen at the Air–Water interface of aqueous microdroplets}, volume = {147}, year = {2025}, }
• (2025). Local symmetry breaking and hidden spin polarization in 2D hybrid perovskites with nonprimary ammonium cations. JACS, 147(34), 30545--30573. (www)

  @article{ , abstract = {Two-dimensional hybrid perovskites (2DHPs) have attracted interest as potential platforms for spin-optoelectronic technologies, including spin filtering and polarized light-emitting diodes. When coupling 2DHPs with strong spin–orbit coupling effects, inversion symmetry breaking has often provided an effective indicator/descriptor for screening spintronic materials within the vast prospective organic–inorganic compositional space. Despite the importance of global symmetry, recent studies have revealed that hidden physical effects such as spin and valley polarization can arise due to local symmetry breaking within 2DHP structures that maintain global inversion symmetry. Since many experimental techniques (e.g., some optical probes) are sensitive to such local effects, a chemical understanding of the material design rules for local symmetry breaking is crucial for rationally developing functional spin-optoelectrotnic materials. In this perspective, we propose that such symmetry breaking in 2DHPs may naturally follow from the low symmetry of associated organic cation fragments and thus can be deliberately engineered. Specifically, we focus on 2DHP crystal structures comprising conformationally restricted nonprimary ammonium cations, wherein the local inversion symmetry is broken and spin polarization-related properties might be extracted. By comparing with inorganic materials, we propose a framework targeted at experimental and computational understanding of such physical effects in 2DHPs, for which the compositional flexibility may allow greater control over exotic spin and topological properties that have so far remained hidden.}, archive = {J_JACS}, author = {Rayan Chakraborty and David B. Mitzi}, doi = {10.1021/jacs.5c05250}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30545--30573}, shortjournal = {J. Am. Chem. Soc.}, title = {Local symmetry breaking and hidden spin polarization in 2D hybrid perovskites with nonprimary ammonium cations}, volume = {147}, year = {2025}, }
• (2025). Polymer mechanochemistry: Where is it going?. JACS, 147(34), 30529--30544. (www)

  @article{ , abstract = {Mechanical force can induce and perturb chemical reactivity. By embedding force-responsive molecules, known as mechanophores, within polymer chains, forces can be precisely applied at specific locations within the molecules. Significant advances in polymer mechanochemistry over the past two decades have enhanced our understanding of how to design and control mechanical reactivity of molecular structures, enabled new types of (macro)molecular transformations that are inaccessible via thermal or photochemical manifolds, and led to the development of stress-sensing and toughening materials. In this Perspective, we aim to highlight significant developments in polymer mechanochemistry, discuss the current limitations, and offer our insights into where this dynamic field is headed.}, archive = {J_JACS}, author = {Maggie Horst and Vittal Bhat and Yan Xia}, doi = {10.1021/jacs.5c03945}, journal = {Journal of the American Chemical Society}, month = {8}, number = {34}, pages = {30529--30544}, shortjournal = {J. Am. Chem. Soc.}, title = {Polymer mechanochemistry: Where is it going?}, volume = {147}, year = {2025}, }
• (2025). Chemical synthesis of oligosaccharides derived from streptococcus pneumoniae serotype 35B and d provides molecular insight in l-ficolin binding. JACS, 147(33), 30518--30527. (www)

  @article{ , abstract = {The wide use of Streptococcus pneumoniae capsular polysaccharide (CPS) conjugate vaccines is causing serotype replacement, and the emergence of serotype 35B is concerning because of multidrug resistance. CPS of 35B is composed of pentasaccharide repeating units that are linked through phosphodiester linkages. One of the galactofuranose residues of the pentasaccharide is acetylated, which distinguishes it from invasive serotype 35D, lacking the acetyl ester. Here, we describe a synthetic approach that can provide oligosaccharides derived of CPS 35B and 35D composed of up to 15 monosaccharides using a pentasaccharide building block equipped with four orthogonal protecting groups. The synthetic compounds were used to examine binding properties of l -ficolin, which is a protein that can activate the lectin pathway of the complement system. Solution-phase NMR experiments and computational modeling demonstrate that Galf(OAc)-1,1-Ribitol of the repeating unit of 35B CPS constitutes the minimal motif for binding to l -ficolin, and the acetyl ester is a key recognition motif. Microarray binding experiments confirmed that O -acetylation is essential for recognition and that oligosaccharides composed of 2 or 3 repeating units bind avidly due to ficolin’s multimeric structures. The data provide a rationale why 35D may escape immune detection and be more invasive. The oligosaccharides were employed to investigate binding to pneumococcal serum factors 35a and 29b, which indicates that immunization with 35B CPS will not provide protection against 35D. Antibodies that can bind 35D can, however, recognize 35B, and thus, 35D CPS may provide cross-protection.}, archive = {J_JACS}, author = {Ivan A. Gagarinov and Lin Liu and Francesco Torricella and John N. Glushka and Alpeshkumar K. Malde and Mark von Itzstein and Geert-Jan Boons}, doi = {10.1021/jacs.5c12005}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30518--30527}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemical synthesis of oligosaccharides derived from streptococcus pneumoniae serotype 35B and d provides molecular insight in l-ficolin binding}, volume = {147}, year = {2025}, }
• (2025). Lattice oxygen-mediated CO2 photothermal reduction with tunable CO/H2 ratio on K-doped Nb2O5 nanoribbons. JACS, 147(33), 30508--30517. (www)

  @article{ , abstract = {Thermocatalytic or photocatalytic CO 2 reduction to CO─without H 2 or sacrificial hole scavengers─remains challenging due to prohibitively high energy barriers or the lack of coupled oxidation half-reactions. Photothermal catalysis enables autonomous CO 2 dissociation via synergistic photon-thermal activation under mild conditions. However, it remains a grand challenge to design high-performance catalysts that achieve rapid lattice oxygen dynamic equilibrium by harmonizing photogenerated carriers with thermal lattice vibrations. Here, we report K-doped Nb 2 O 5 nanoribbons (K–Nb 2 O 5 NRs) that synergistically integrate photothermal energy and lattice oxygen redox cycling to effect direct CO 2 decomposition under mild photothermal conditions (50–250 °C). The K–Nb 2 O 5 NRs achieve CO production rates of 4.1–405 μmol·g –1 ·h –1 with 100% selectivity, outperforming undoped Nb 2 O 5 by 6.3-fold at 250 °C. Mechanistic studies reveal that K doping optimizes the electronic structure of Nb 2 O 5 , accelerating oxygen vacancy regeneration and enhancing CO 2 adsorption. At the same time, the photothermal effect decouples lattice oxygen oxidation (photogenerated holes) and CO 2 reduction (photogenerated electrons), thereby suppressing electron–hole recombination. By introducing H 2 O as a dynamic oxygen chemical potential modulator, the H 2 /CO ratio is continuously tuned from 1.4 to 0.3 through competitive adsorption at oxygen vacancy sites. Remarkably, the catalyst maintains syngas production for 50 h in a flow reactor. This study provides new ideas for the design of catalysts for photothermal CO 2 conversion.}, archive = {J_JACS}, author = {Xuanyu Yue and Zhijie Wang and Wengkang Ni and Ke Wang and Yanran Cui and Zhenglong Li}, doi = {10.1021/jacs.5c11625}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30508--30517}, shortjournal = {J. Am. Chem. Soc.}, title = {Lattice oxygen-mediated CO2 photothermal reduction with tunable CO/H2 ratio on K-doped Nb2O5 nanoribbons}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic asymmetric oxidation of phosphines with water. JACS, 147(33), 30499--30507. (www)

  @article{ , abstract = {P-chiral tertiary phosphine oxides (TPOs) hold significant synthetic value due to their capacity to serve as versatile precursors for a wide range of valuable P-chiral phosphorus-containing compounds. However, the direct asymmetric oxidation of readily available phosphines into these TPOs remains a substantial challenge, as no efficient and practical methods have been reported to date. In this study, we present the first catalytic asymmetric approach to access P-chiral TPOs through a photoredox-mediated radical process. This strategy is conceptually inspired by a known photoredox catalytic system employed in phosphine-mediated deoxygenation reactions, wherein TPOs are typically formed as side products. The method utilizes an azaarene-substituted ketone-based oxidant, which, upon single-electron reduction, generates a highly reactive radical anion base. This key intermediate facilitates the activation of a chiral phosphoric acid (CPA), releasing a CPA anion that plays a critical role in stereocontrol during the hydration of phosphine radical cations. The reaction proceeds with high efficiency (up to 96% yield) and excellent stereoselectivity (up to 99% ee), employing water as a sustainable oxygen source. The operational simplicity and atom economy of this methodology are further demonstrated through successful application in 18 O-isotopic labeling experiments using H 2 18 O, thereby enabling the efficient synthesis of isotopically labeled P-chiral TPOs. Beyond exemplifying an innovative transformation that converts byproducts into valuable chemical entities, this work significantly expands the synthetic potential of Brønsted base catalysis in controlling radical reactivity with precise stereochemical outcomes.}, archive = {J_JACS}, author = {Yating Dai and Yinwa Huang and Yuxia Wang and Yufei Lin and Yurong Liu and Qingcong Wei and Xiaowei Zhao and Yanli Yin and Zhiyong Jiang}, doi = {10.1021/jacs.5c11656}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30499--30507}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic asymmetric oxidation of phosphines with water}, volume = {147}, year = {2025}, }
• (2025). Catalytic oxidation of Carbon–Halogen bonds by water with h2 liberation. JACS, 147(33), 30490--30498. (www)

  @article{ , abstract = {The unprecedented catalytic oxidation of carbon–halogen bonds to carboxylic acids using water as the oxidant is disclosed. Compared to previous traditional oxidation reactions, this transformation avoids the use of sacrificial oxidants and liberates useful hydrogen gas as byproduct, presenting an efficient method. Catalyzed by an acridine-based PNP-Ru pincer complex, a series of primary aliphatic and benzylic halides were successfully converted into carboxylic acids in high yields. The oxidation of secondary halides, which yields ketones, was also accomplished efficiently. Moreover, the oxidation of challenging C–F bonds, aliphatic chlorides, and bromides has been achieved for the first time. With further improvement, this method could be effectively utilized in the efficient scale-up synthesis of the phenoxybutyric herbicide, MCPB. Furthermore, a formal anti-Markovnikov oxidation of nonactivated olefins to carboxylic acids has also been demonstrated through a two-step sequence involving anti-Markovnikov hydrobromination followed by oxidation of the resulting alkyl halides.}, archive = {J_JACS}, author = {Cai You and Lijun Lu and David Milstein}, doi = {10.1021/jacs.5c11295}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30490--30498}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic oxidation of Carbon–Halogen bonds by water with h2 liberation}, volume = {147}, year = {2025}, }
• (2025). Probing the mechanism of selective phosphate adsorption from wastewater using aqueous and synchrotron X-ray characterization. JACS, 147(33), 30475--30489. (www)

  @article{ , abstract = {Ion exchange shows promise for recovering phosphate from wastewater as value-added products but requires high phosphate selectivity to compete with conventional treatment. Hybrid anion exchange (HAIX) resins, which contain nonselective basic functional groups and selective iron oxide nanoparticles (FeOnp), can remove phosphate from wastewater. However, knowledge gaps remain regarding the mechanisms of phosphate selectivity and influence of competing ions, hindering efforts to model adsorption dynamics and design adsorption processes for varying wastewaters. To address these gaps, we integrated aqueous-phase adsorption analysis with solid-phase, synchrotron-based X-ray characterization; this integration facilitated elucidation of the distribution and speciation of iron, phosphate, and competing anions on HAIX resins. We compared a quaternary ammonium-functionalized HAIX resin (strong base anion exchange, SBA) to a tertiary amine version (weak base anion exchange, WBA) to determine the role of functional groups. X-ray radiography revealed differences in FeOnp speciation (goethite vs ferrihydrite) and distribution (peripheral vs homogeneous) between the resins, resulting in varied phosphate affinity and intraparticle diffusion resistance. Using micro-X-ray fluorescence (μ-XRF) and micro-X-ray absorption near-edge structure (μ-XANES) spectroscopy, we identified differences in where and how phosphate binds across resin types and wastewaters. Across wastewater compositions, FeOnp sites in WBA contribute more to phosphate adsorption than in SBA, possibly due to variations in Fe distribution and speciation. Phosphate adsorption densities calculated from quantitative μ-XRF maps matched those from aqueous analysis, demonstrating the effectiveness of this integrated approach. Overall, results demonstrate the use of synchrotron-based X-ray characterization for investigating adsorption mechanisms and advance HAIX as a phosphate recovery technology from wastewaters.}, archive = {J_JACS}, author = {Neha Sharma and Edward Apraku and Hannah E. Holmes and Meili Gong and Diego Bustamante and Ashley N. Martinez and Johanna Nelson Weker and Sharon Bone and William A. Tarpeh}, doi = {10.1021/jacs.5c10899}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30475--30489}, shortjournal = {J. Am. Chem. Soc.}, title = {Probing the mechanism of selective phosphate adsorption from wastewater using aqueous and synchrotron X-ray characterization}, volume = {147}, year = {2025}, }
• (2025). Diastereomeric iridium catalysts for enantioselective C(sp3)–H borylation: Roles of two chiralities at the metal center and ligand. JACS, 147(33), 30455--30474. (www)

  @article{ , abstract = {The enantioselective functionalization of inert C(sp 3 )–H bonds is one of the most significant challenges in modern synthetic chemistry, especially when it is applied to structurally complex compounds. To achieve success, we require a comprehensive understanding of the mechanisms involved in controlling enantioselectivity, but such knowledge is currently limited. Herein, we systematically investigated the catalysis of chiral iridium complexes for the C(sp 3 )–H borylation of tetrahydroisoquinoline (THIQ) using DFT calculations with a careful conformational search of transition states. Our results reveal that the active species are iridium(III) tris(boryl) diastereomers bearing chiralities at both the Ir center (Λ or Δ) and ( S , S )-pyridyl-boryl ligand (CBL). This reaction proceeds via enantioselective C(sp 3 )–H activation at the α-methylene position of THIQ, changes in hydride and boryl coordination sites, and B–C reductive elimination as the rate-determining step. R -product is calculated to be produced more than S -one, as experimentally observed. The difference in activation energy between Λ- and Δ-Ir catalysts is 3.60 kcal mol –1 (99% ee ), which agrees with the experimentally observed ee value (94%). Crucially, neglecting Ir-centered Λ/Δ chirality leads to unrealistic 100% ee predictions regardless of CBL substituents, whereas incorporating both metal and ligand chiralities successfully reproduces the substituent-dependent ee trends observed experimentally. The greater selectivity of the R -product over the S -one is attributed to the larger reaction pocket of the transition state of the B–C reductive elimination in the R -product formation than that in the S -one. This work provides fundamental insights into the cooperative stereochemical roles of metal and ligand chiralities in asymmetric C–H borylation.}, archive = {J_JACS}, author = {Jian-Sen Wang and Xiao-Xia You and Zhong-Min Su and Shigeyoshi Sakaki and Rong-Lin Zhong}, doi = {10.1021/jacs.5c10820}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30455--30474}, shortjournal = {J. Am. Chem. Soc.}, title = {Diastereomeric iridium catalysts for enantioselective C(sp3)–H borylation: Roles of two chiralities at the metal center and ligand}, volume = {147}, year = {2025}, }
• (2025). The action of plastic degrading enzyme is accelerated mainly due to an increase in thermal stability rather than by an inherent catalytic effect. JACS, 147(33), 30447--30454. (www)

  @article{ , abstract = {Polyethylene terephthalate (PET) hydrolases offer a promising enzymatic route to plastic waste degradation under mild conditions. Among these, the engineered FAST-PETase variant exhibits superior catalytic efficiency and thermostability compared to the wild-type Is PETase, yet the molecular origins of these enhancements remain debated. In this work, we employ empirical valence bond simulations in conjunction with semimacroscopic PDLD/S-LRA calculations to investigate the rate-determining acylation step in PET dimer hydrolysis catalyzed by both wild-type and FAST-PETase. Our results successfully reproduce the experimentally observed trend in catalytic rate enhancement between the two systems. While prior interpretations attribute the improved activity to a strengthened hydrogen-bond network involving Asp106 and His237, we demonstrate that the distal N233K mutation in FAST-PETase induces long-range electrostatic changes that enhance catalytic efficiency by modulating the active site dipolar environment. More importantly, we show that the elevated performance of FAST-PETase at higher temperatures is not due to reduced flexibility in the mutant region but arises from enhanced thermal stability, which allows the enzyme to operate effectively at elevated temperatures and thus accelerate reaction rates. These findings underscore the central role of electrostatics and stability in enzyme engineering and suggest that data-driven methods, such as maximum entropy models, may enable the rational identification of further stability-enhancing mutations for improved PET depolymerization.}, archive = {J_JACS}, author = {Ashim Nandi and Arieh Warshel}, doi = {10.1021/jacs.5c10598}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30447--30454}, shortjournal = {J. Am. Chem. Soc.}, title = {The action of plastic degrading enzyme is accelerated mainly due to an increase in thermal stability rather than by an inherent catalytic effect}, volume = {147}, year = {2025}, }
• (2025). Dual photoluminescence in low-temperature phase of CsSnI3 nanocrystals. JACS, 147(33), 30436--30446. (www)

  @article{ , abstract = {The expression of metal lone-pair electrons is hypothesized to underpin many of the interesting properties of inorganic halide perovskite semiconductors. Recently, a stable low-temperature monoclinic polar phase was predicted for CsSnBr 3 and CsSnI 3 , opening the possibility of direct investigation of a ferroelectric distorted structure compared to the undistorted structure. To date, there have been no experimental reports of such a structure in CsSnI 3 , and the low-temperature optical properties of CsSnI 3 nanocrystals have remained unexplored. Here we report optical and structural evidence of a phase transition around 240 K in 8.9 nm CsSnI 3 nanocrystals. Several changes in optical behavior occur below this transition point, including high-energy photoluminescence (PL) that emits concurrently with the exciton PL. The emergence of this high-energy PL is correlated with X-ray diffraction (XRD) and differential scanning calorimetry (DSC) supporting a phase transition from the orthorhombic structure between 240–200 K. Transient absorption measurements show an increase in the excited state lifetimes, i.e., slowed carrier cooling, at 200 K when photoexciting with photon energies above the high-energy state, consistent with slowed carrier cooling and emergence of high-energy PL. We hypothesize that the slowed carrier cooling is distinctive to this phase transition that modifies both the electronic and phonon structures that dictate excited-state carrier dynamics, and we discuss these changes.}, archive = {J_JACS}, author = {Kyle T. Kluherz and Jacob L. Shelton and Nicholas J. Weadock and Noemi Leick and Peter C. Sercel and Matthew C. Beard}, doi = {10.1021/jacs.5c10595}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30436--30446}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual photoluminescence in low-temperature phase of CsSnI3 nanocrystals}, volume = {147}, year = {2025}, }
• (2025). Alkene-activating effect in molybdenum-catalyzed asymmetric hydrogenation of arenes: Insights into activity and selectivity. JACS, 147(33), 30423--30435. (www)

  @article{ , abstract = {The asymmetric hydrogenation of substituted benzenes with oxazoline imino(pyridine) (OIP) molybdenum precatalysts is described. A comparison of the hydrogenation activities between alkylbenzenes and the corresponding styrenes revealed an alkene-activating effect, where the introduction of an alkene substituent resulted in the hydrogenation of both the alkene and the arene. Distinct reaction pathways for alkene and arene hydrogenation were observed with the outcomes dependent on the hydrogen pressure, the substitution pattern of the arene, and the placement of the alkene tethered to the arene. The most efficient arene hydrogenation occurred when the alkene was in conjugation with the aromatic ring and the reaction was conducted with 80 atm of H 2 . Hydrogenation of a series of disubstituted styrenes established trends in chemo-, diastereo-, and enantioselectivity and provided insights into the nature of the catalyst–substrate interaction. To gain insight into the mechanistic origins of these trends, OIP-supported molybdenum η 6 -arene complexes with substituted benzenes were synthesized and characterized by X-ray diffraction and NMR spectroscopy. Subsequent hydrogenation demonstrated a correlation between the site selectivity of arene coordination and the diastereo- and enantioselectivity of the hydrogenation reaction. The data informed a stereochemical model for arene coordination and established that coordination of the substrate to the molybdenum center is the stereodetermining step in the hydrogenation reaction.}, archive = {J_JACS}, author = {Julia C. Greenbaum and Andrew J. King and Matthew V. Pecoraro and Paolo Tosatti and Kurt Puentener and Paul J. Chirik}, doi = {10.1021/jacs.5c10499}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30423--30435}, shortjournal = {J. Am. Chem. Soc.}, title = {Alkene-activating effect in molybdenum-catalyzed asymmetric hydrogenation of arenes: Insights into activity and selectivity}, volume = {147}, year = {2025}, }
• (2025). Chiral symmetry breaking in gold stellated nanoicosahedrons. JACS, 147(33), 30412--30422. (www)

  @article{ , abstract = {The integration of high-order symmetry with chiral geometry on individual nanoparticles is intriguing and would provide exciting insights into the chirality transfer from molecules to bulk materials; however, it remains a challenge yet to be addressed. Here we report the synthesis of chiral stellated nanoicosahedrons (SNIs), starting from Au nanoicosahedrons with a high-order ( I h ) symmetry. A chirality transfer strategy based on the synergistic manner of glutathione and copper ions was employed to drive the chiral symmetry breaking in Au SNIs. Chiral Au SNIs with the I point group display highly twisted edges with 532 rotational symmetry and remarkably high chiroptical responses. Benefiting from the highly stellated geometry and intrinsic plasmonic characteristics, chiral Au SNIs also exhibit superior single-particle chiroptical and surface-enhanced Raman scattering properties, which hold great significance for applications in sensing and photonics. Our work provides an important knowledge framework that guides the synthesis of chiral materials with increasing architectural diversity toward chirality-dependent applications.}, archive = {J_JACS}, author = {Xuehao Sun and Binbin Zhang and Yunlong Tao and Jinling Wan and Yahui Yang and Zixu Wang and Chuang Liu and Guizeng Yang and Bintao Tang and Lichao Sun and Qingfeng Zhang}, doi = {10.1021/jacs.5c10355}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30412--30422}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral symmetry breaking in gold stellated nanoicosahedrons}, volume = {147}, year = {2025}, }
• (2025). Efficient electrocatalytic nitrate-to-ammonia enabled by reversible lattice-oxygen control. JACS, 147(33), 30401--30411. (www)

  @article{ , abstract = {Understanding the fundamentals governing reactivity and leveraging this knowledge to achieve optimal catalytic performance have long been a core objective in catalysis study. This challenge is particularly pressing for sustainable nitrogen cycle via nitrate reduction (NO 3 – RR) due to its inherent trade-off between high Faradaic efficiency (FE) and low overpotential. Here, we propose a novel strategy to enhance the NO 3 – RR performance by quantitatively regulating surface oxygen activity of transition metal oxides (TMOs) via tuning the metal–oxygen covalency. Using a series of A-site-substituted La 1– x Sr x CoO 3 perovskites, we conduct comprehensive experimental and modeling studies, revealing that NH 3 yield rate and Faradaic efficiency exhibit distinct “volcano” and “W-shaped” dependencies on surface oxygen activity. Notably, La 0.5 Sr 0.5 CoO 3 , characterized by balanced metal–oxygen covalency, achieves exceptional activity and selectivity for NO 3 – RR. Mechanistic studies uncover a switchable active site that transitions from a lattice-oxygen vacancy to a nonstoichiometric Co on La 1– x Sr x CoO 3 during NO 3 – RR, accompanied by a dynamic and reversible lattice-oxygen refilling process. This mechanism circumvents the potential-limiting step (PLS) and blocks byproduct formation, driving superior catalytic performance. Our discoveries provide insights for designing advanced TMOs for not only NO 3 – RR but also other oxygen-sensitive reactions, while deepening the understanding of surface dynamics during electrocatalysis.}, archive = {J_JACS}, author = {Qian Wu and Dongsheng Shao and Chencheng Dai and Jiarui Wang and Xiaoning Li and Pengfei Song and Wen Xie and Shibo Xi and Longcheng Zhang and Xiu Lin and Songzhu Luo and Shirong Sun and Li An and Pinxian Xi and Zhichuan J. Xu}, doi = {10.1021/jacs.5c10362}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30401--30411}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient electrocatalytic nitrate-to-ammonia enabled by reversible lattice-oxygen control}, volume = {147}, year = {2025}, }
• (2025). Electrochemical annulation of phenothiazines with alkynes: Access to anti-kasha triple-emission, light-sensitive, and room-temperature phosphorescent materials. JACS, 147(33), 30390--30400. (www)

  @article{ , abstract = {Novel anti-Kasha triple-emission materials, light-sensitive materials, and ultralong room-temperature phosphorescent materials were synthesized by an efficient electrochemical synthesis method for the first time. The experimental data and theoretical calculations demonstrate the anti-Kasha triple-emission characteristics of the phenothiazinium salts. These characteristics enable three-channel emission intensity ratio imaging for visualizing intercellular architectures and endow the ability to specifically target the mitochondria of living cells. Furthermore, the novel light-sensitive materials demonstrate a pronounced red shift upon light irradiation. Additionally, the novel phenothiazine-based ultralong room-temperature phosphorescent materials exhibit an extraordinarily long lifetime and a distinctive afterglow, highlighting significant potential for encryption applications in binary coding systems.}, archive = {J_JACS}, author = {Xianhui Yang and Danni Yang and Bijin Li}, doi = {10.1021/jacs.5c09956}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30390--30400}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical annulation of phenothiazines with alkynes: Access to anti-kasha triple-emission, light-sensitive, and room-temperature phosphorescent materials}, volume = {147}, year = {2025}, }
• (2025). Construction of a chiral click chemistry platform via enantioselective F/Cl exchange at S(VI) centers. JACS, 147(33), 30380--30389. (www)

  @article{ , abstract = {Sulfonimidoyl fluorides have emerged as versatile click linkers, where the construction of sulfur-centered chirality plays a pivotal role in chiral recognition, stereoselective binding, and spatial interactions. However, the enantioselective formation of S(VI)–F bonds faces a significant challenge due to facile racemization from low activation barriers. Herein, we introduce inorganic sodium bifluoride (NaHF 2 ), which enables a three-dimensional hydrogen-bonding network to promote stereoinversion of the S–Cl bond via dynamic kinetic asymmetric fluorination, thereby delivering excellent yields and enantioselectivities. Mechanistic studies reveal that a robust hydrogen-bonding catalytic complex with the HF 2 – anion is essential for enantiocontrol. This strategy paves the way for chiral click bioconjugation.}, archive = {J_JACS}, author = {Daming Zeng and Xinyu Zhang and Hanliang Zheng and Ming Wang and Xuefeng Jiang}, doi = {10.1021/jacs.5c09937}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30380--30389}, shortjournal = {J. Am. Chem. Soc.}, title = {Construction of a chiral click chemistry platform via enantioselective F/Cl exchange at S(VI) centers}, volume = {147}, year = {2025}, }
• (2025). Exploring three-dimensional porphyrin-based covalent organic frameworks with outstanding solar energy conversion. JACS, 147(33), 30369--30379. (www)

  @article{ , abstract = {As an emerging class of porous aromatic polymers, porphyrin-based covalent organic frameworks (COFs) have been widely employed in assorted applications due to their unique electronic configurations and properties. Notably, three-dimensional (3D) COFs, characterized by porphyrin cores exposed along steric ordered nanochannels, exhibit great promise for solar energy conversion. However, the development of 3D porphyrin-based COFs continues to present a synthetic challenge, stemming from the scarcity of appropriate topotactic designs and appropriate building blocks. In this study, a series of 3D Por-An-COFs with a reasonable 2-fold lvt-b topology have been synthesized. The 3D architecture enables the periodic alignment of porphyrin units within the conjugated backbones, facilitating light harvesting and interactions between guest species and active centers. Consequently, the 3D Por-An-COF features superior photoresponsive characteristics, including high solar-to-chemical and solar-to-thermal conversion capabilities. In particular, the interfacial water evaporation system based on 3D Por-An-COF achieved an evaporation rate of 1.64 kg m –2 h –1 , and the related thermoelectric device generates an output voltage of 195 mV. This research not only extends the structural diversity of 3D porphyrin-based COFs for photoenergy conversion but also elucidates the intrinsic dimensionality-dependent photoresponsive behaviors, providing valuable insights for the development of advanced porphyrin-based photosensitizers for a wide range of applications.}, archive = {J_JACS}, author = {Jiaqi Guo and Yunyu Guo and Mingxuan Zhang and Hongde Yu and Haohao Bi and Jingyi Feng and Jiahuan Wang and Keyu Geng and Thomas Heine and Junliang Sun and Di Li and Donglin Jiang and Enquan Jin}, doi = {10.1021/jacs.5c09844}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30369--30379}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploring three-dimensional porphyrin-based covalent organic frameworks with outstanding solar energy conversion}, volume = {147}, year = {2025}, }
• (2025). Rare-earth substitution of La3Si2S8I for efficient and color-tunable phosphor converted white light emitting diodes. JACS, 147(33), 30347--30368. (www)

  @article{ , abstract = {Mixed-anion compounds enable properties to be controlled to a greater degree by chemical substitution than single-anion compounds. La 3 Si 2 S 8 I was investigated as a host to develop phosphors based on solid solutions (La 1– x RE x ) 3 Si 2 S 8 I ( RE = Ce, Pr, Tb, Dy, Ho; x = 0–0.33) and (La 1– x – y Ce x RE y ) 3 Si 2 S 8 I ( RE = Tb, Dy; x , y = 0–0.33) that exhibit wide color tunability and white emission. Upon excitation with a 364 nm UV laser source, the phosphors emit through a down-conversion process over a wide visible color gamut. Depending on the RE 3+ concentration, the spectra featured broad emission (cyan for Ce 3+ ) or sharp 4f–4f emission peaks (red for Ho 3+ ; green for Tb 3+ ; cyan-green and red for Pr 3+ ; yellow and cyan for Dy 3+ ) which can be fine-tuned to a wider gamut. The cosubstituted (La 1– x – y Ce x RE y ) 3 Si 2 S 8 I phosphors showed even more intense photoluminescence and wider color palettes within the cyan to green regions (Ce 3+ –Tb 3+ ) and cool to warm white (Ce 3+ –Dy 3+ ). The photometric parameters were appropriate for backlighting display and near UV-pumped phosphor-converted white light-emitting diodes (pc-wLEDs). Photoluminescence decay profiles follow biexponential behavior with lifetimes ranging from a few ns (for Ce 3+ ) to 3–450 μs (for other RE 3+ ). Most of the optimized phosphors were moderately stable at 80–100 °C before the onset of thermal quenching effects. They gave absolute quantum yields up to 50%, which are favorable for efficient energy conversion. Prototype pc-wLEDs fabricated from a blend of three phosphors or from single-phase phosphors showed promising performance.}, archive = {J_JACS}, author = {Trinanjan Dey and Dundappa Mumbaraddi and Razieh Firouzi-Haji and Dmitry Vrublevskiy and Zhongqi Lin and Alkiviathes Meldrum and Arthur Mar}, doi = {10.1021/jacs.5c09863}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30347--30368}, shortjournal = {J. Am. Chem. Soc.}, title = {Rare-earth substitution of La3Si2S8I for efficient and color-tunable phosphor converted white light emitting diodes}, volume = {147}, year = {2025}, }
• (2025). Ultrasensitive biosensing by a plasmonic nanolaser with a record-low threshold at room temperature. JACS, 147(33), 30339--30346. (www)

  @article{ , abstract = {Plasmonic nanolasers are proposed as one of the most promising tools in biosensing due to their high energy density, narrow spectral bandwidth, and feature sizes down to nanometers. However, the high threshold value greatly inhibits the widespread application of nanolasers. Researchers have made many efforts, among which the preparation of low-loss plasmonic nanocavities is the most fundamental approach. Herein, we used UV holographic lithography to prepare optical nanocavities with both a high quality factor ( Q -factor) and strong resonance intensity ( I ), pairing with the LDS 751 dye as the gain material, to construct a plasmonic nanolaser with a record ultralow threshold of 0.49 mW/cm 2 at room temperature. Thus, we could display the first ultrasensitive DNA sensing of nanolaser in a biological environment by using a commercial laser pointer as the pumping source, achieving an ultralow detection limit of 1.91 nM for the Brucella genetic detection in serum. This work not only provides a universal strategy for constructing ultralow threshold nanolasers but also fully demonstrates the enormous advantages of nanolasers for biosensing.}, archive = {J_JACS}, author = {Baoying He and Ning Zeng and Yao Yang and Chao Zhan and Qiaosheng Pu and Bowen Liu}, doi = {10.1021/jacs.5c09622}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30339--30346}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrasensitive biosensing by a plasmonic nanolaser with a record-low threshold at room temperature}, volume = {147}, year = {2025}, }
• (2025). Atomic-level design and understanding of hydroxyl-mediated ag sites with catalytic versatility. JACS, 147(33), 30326--30338. (www)

  @article{ , abstract = {Regulating the size of active centers in catalysts exerts a profound effect on their activity and selectivity. Here, we demonstrate a strategy for precise control over the size of Ag species on Al 2 O 3 , enabling the 2%Ag/Al 2 O 3 catalyst to be tailored for various catalytic reactions. Building on the mechanism wherein hydroxyl groups serve as anchoring sites for Ag, we synthesized hydroxyl-rich Al 2 O 3 supports and subsequently reduced the hydroxyl content through roasting. This approach allowed Ag species to exist on the Al 2 O 3 surface as isolated atoms, clusters, or nanoparticles. As the Ag size increased from single atoms to clusters and nanoparticles, the catalyst’s O 2 activation ability was progressively enhanced, leading to significant performance variations in the O 2 -involved reactions. Notably, the synthesis of this hydroxyl-rich support is facile and reproducible. Our findings offer valuable insights into the rational design of supported Ag catalysts with controllable active center sizes for diverse catalytic applications.}, archive = {J_JACS}, author = {Zhao Li and Yuxuan Xie and Chunxue Wang and Jiayu Feng and Yixing Ma and Xin Sun and Changbin Zhang and Shaohua Xie and Fei Wang and Kai Li and Fudong Liu and Hong He and Ping Ning}, doi = {10.1021/jacs.5c09620}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30326--30338}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic-level design and understanding of hydroxyl-mediated ag sites with catalytic versatility}, volume = {147}, year = {2025}, }
• (2025). Catalytic nitrous oxide degradation with group 15 clusters. JACS, 147(33), 30317--30325. (www)

  @article{ , abstract = {Nitrous oxide (N 2 O) is sometimes referred to as the forgotten greenhouse gas, but ignoring it would be a mistake. N 2 O has a greenhouse warming potential 300× that of CO 2 , and anthropogenic emissions are increasing. Yet, compared to CO 2 , homogeneous catalysts that mediate its reduction are scarce. We present a range of cluster catalysts based on abundant and inexpensive p-block elements that mediate the conversion of N 2 O to environmentally benign N 2 . The catalysts studied offer many critical advantages, and systems can be tuned for performance, recyclability, selectivity, air stability, and commercial availability. Pnictogen clusters present themselves as a general platform in N 2 O reduction chemistry, and control reactions confirm that these clusters offer access to reactivity that simple monopnictogen molecules do not. Mechanistic investigations reveal that the low-valent clusters can access a –1/+1 redox couple, which goes beyond classical main group redox couples and will unlock a vault of hitherto unknown chemical space.}, archive = {J_JACS}, author = {Bono van IJzendoorn and Reece Lister-Roberts and Nikolas Kaltsoyannis and Meera Mehta}, doi = {10.1021/jacs.5c09618}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30317--30325}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic nitrous oxide degradation with group 15 clusters}, volume = {147}, year = {2025}, }
• (2025). Hydrogen bonding activates ferric porphyrin hydroperoxo species and drives the regioselective heme oxygenase reaction. JACS, 147(33), 30304--30316. (www)

  @article{ , abstract = {Heme oxygenase (HO) is responsible for the controlled breakdown of heme in most living organisms, which avoids heme toxicity and provides essential biochemical components like biliverdin and the signaling molecule CO. The reactive oxidant in HO is proposed to be a ferric hydroperoxide species, which attacks a specific meso carbon center of the heme. Both site-directed mutagenesis and density functional theory (DFT) calculations have suggested a dominant role of the hydrogen bonding present in the second sphere of the HO active site in the reactivity of HO. An iron porphyrin with a guanidine group in the second sphere, mimicking the arginine group present in the distal site of HO, is used to generate a ferric hydroperoxide species by sequential electron and proton transfer to a ferrous dioxygen (or ferric superoxide) adduct in a fashion similar to that of HO. Spectroscopic data on these species indicate that the hydroperoxide ligand is in direct hydrogen-bonding interaction with the distal guanidine residue. This ferric hydroperoxide species of this porphyrin is found to regioselectively hydroxylate the meso carbon adjacent to the guanidine group, which gradually degrades further to generate verdoheme and biliverdin, mimicking the function of HO. Experimental data and DFT calculations indicate that the hydrogen bonding from the second sphere guanidine group (1) activates the O–O bond of the ferric hydroperoxide for homolytic cleavage and (2) directs the resultant hydroxyl radical to the closest meso carbon by stabilizing it through hydrogen bonding with the second sphere guanidine group.}, archive = {J_JACS}, author = {Triparna Roy and Soumya Samanta and Souvik Dinda and Pritam Baidya and Abhishek Dey}, doi = {10.1021/jacs.5c09566}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30304--30316}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen bonding activates ferric porphyrin hydroperoxo species and drives the regioselective heme oxygenase reaction}, volume = {147}, year = {2025}, }
• (2025). Fluorinated twists: A pathway to a stable Pd8L16 square antiprism. JACS, 147(33), 30296--30303. (www)

  @article{ , abstract = {Within the extensive family of Pd n L 2 n metal–organic cages, some structures are much easier to access than others. Ligands are generally constructed from planar aromatic linkers. While small structures (Pd 2 L 4 to Pd 6 L 12 ) and large pseudospherical structures (≥Pd 12 L 24 ) can be readily obtained from these flat aryl-based ligands, strategies to intermediate-sized structures have remained elusive as the required angle between metal–ligand coordination vectors (90–120°) is hard to construct from the common toolkit of organic molecules. Herein, we report the Pd 8 L 16 square antiprism as a new addition to the Pd n L 2 n family, a structure shown as thermodynamically stable in both solution and the solid state, for the first time. The ligand achieves close to the ideal angle of 105.1° needed for the square antiprism through the incorporation of a perfluorobiphenyl backbone. The substantial dihedral twist induced by the fluorines diverges the coordination vectors compared to nonfluorous examples while crucially maintaining ligand rigidity to avoid the formation of mixtures of structures─a strategy we believe will have widespread applications in (metallo)supramolecular chemistry.}, archive = {J_JACS}, author = {Soumalya Bhattacharyya and Stephen P. Argent and Ben S. Pilgrim}, doi = {10.1021/jacs.5c09573}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30296--30303}, shortjournal = {J. Am. Chem. Soc.}, title = {Fluorinated twists: A pathway to a stable Pd8L16 square antiprism}, volume = {147}, year = {2025}, }
• (2025). Engineering imine carbon catalytic sites in covalent organic frameworks for enhanced overall H2O2 photosynthesis. JACS, 147(33), 30287--30295. (www)

  @article{ , abstract = {Covalent organic frameworks (COFs) have emerged as ideal photocatalysts for hydrogen peroxide (H 2 O 2 ) photosynthesis from oxygen and water due to their broad light harvesting and programmable structures. However, their catalytic efficiency remains constrained by undefined electron transfer pathways caused by redundant inactive sites around the catalytic sites. Herein, we report a polarization engineering strategy that converts the imine unit from an electronic recombination-prone center into a catalytic center for the oxygen reduction reaction. Ultrafast spectroscopy and theoretical calculations reveal that reducing imine polarization could simultaneously inhibit excited-state deactivation, promote O 2 adsorption and activation, and achieve direct electron transfer from the triphenylbenzene photosensitizer units to the imine catalytic center via the proximity effect. Consequently, azine-linked COF with low polarization of imine units delivers high H 2 O 2 production yields of 2311 μmol g –1 from O 2 and H 2 O for 2 h, which is 3.8 and 2.9 times higher than that of the imine-linked COF with medium polarization and hydrazone-linked COF with high polarization, respectively. This work pioneers a paradigm for engineering imine catalytic sites in COFs, providing a molecular blueprint for designing high-efficiency photocatalytic systems with spatially optimized photosensitizer centers and active sites.}, archive = {J_JACS}, author = {Shuailong Yang and Duanhui Si and Lei Zou and Minghao Shi and Yuanbiao Huang and Rong Cao}, doi = {10.1021/jacs.5c09327}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30287--30295}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering imine carbon catalytic sites in covalent organic frameworks for enhanced overall H2O2 photosynthesis}, volume = {147}, year = {2025}, }
• (2025). Intersegment transfer and the dynamical architecture of fis Protein–DNA multimer complexes. JACS, 147(33), 30277--30286. (www)

  @article{ , abstract = {Gene regulation often entails a cooperative dynamic interplay among several protein molecules and several distinct DNA segments. Intersegment transfer of the Fis protein stimulates DNA inversion during DNA recombination. Individual DNA segments have been found to facilitate the dissociation of Fis proteins already bound to DNA and also allow for the transfer of the Fis between segments. Here, we use the hybrid coarse-grained AWSEM/3SPN.2C model to simulate the Fis protein intersegment transfer and explore its mechanism. We show that entropic effects within the Fis protein–DNA complex dictate the transfer pathway through specific structural configurations, involving specific grooves and consequent orientation constraints on the DNA segments. Multiple copies of the Fis protein facilitate intersegment transfer, explaining how changes in protein–DNA stoichiometry and concentration influence how the Fis–DNA complex architecture is established. This orientational dependence indicates that the assembly of the Fis–DNA complex mimics the interlocking of screws, functioning as a molecular machine that may couple to DNA supercoiling and torsional stress in the DNA generated by motor proteins, thus offering a potential regulatory mechanism for chromosomal organization and gene expression.}, archive = {J_JACS}, author = {Xun Chen and Shikai Jin and Cheng-Han Liu and Yaakov Levy and Min-Yeh Tsai and Peter G. Wolynes}, doi = {10.1021/jacs.5c09262}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30277--30286}, shortjournal = {J. Am. Chem. Soc.}, title = {Intersegment transfer and the dynamical architecture of fis Protein–DNA multimer complexes}, volume = {147}, year = {2025}, }
• (2025). High-efficiency hydrocracking of polyolefin plastics by controlling intimacy between pt clusters and zeolite acid sites. JACS, 147(33), 30268--30276. (www)

  @article{ , abstract = {Hydrocracking of polyolefins using metal-zeolite catalysts offers a promising route for upcycling plastic waste into valuable fuels. However, achieving high-efficiency hydrocracking remains a significant challenge due to the complex depolymerization mechanisms, which hinder the optimization of catalyst structures. Here, we present a novel catalyst design strategy that achieves precise spatial control of Pt and acid sites by strategically positioning Pt clusters on the external surfaces and within the channels of H-Beta (Hβ) zeolite. This synergistic dual-site architecture enables a stepwise reaction pathway: surface Pt-acid sites initiate isomerization and primary cracking to form branched intermediates, which then migrate into the channels, where internal Pt-acid sites drive secondary cracking. This design maximizes the reaction efficiency, achieving unprecedented hydrocracking rates of 30,000 g LDPE ·g Pt –1 ·h –1 for low-density polyethylene (LDPE) and 92,000 g PP ·g Pt –1 ·h –1 for polypropylene (PP) at 250 °C, surpassing state-of-the-art Pt-based catalysts by 5-fold. Remarkably, a 98% yield of short-chain alkanes is achieved even at a mild temperature of 180 °C, with C 5 –C 12 selectivity about 80%, highlighting the advantage of the catalyst’s low-temperature activity and industrial potential. By correlating reaction outcomes with the structural evolution of LDPE/PP, we propose a new isomerization-cracking mechanism that elucidates the critical roles of the surface and internal active sites. This work not only provides a rational design strategy for bifunctional metal-zeolite catalysts but also offers fundamental insights into polyolefin hydrocracking mechanisms, paving the way for scalable and sustainable plastic waste valorization.}, archive = {J_JACS}, author = {Shuheng Tian and Risheng Bai and Zirui Gao and Zhiwei Chen and Maolin Wang and Haoyi Tang and Siyu Lin and Bingjun Xu and Xi Liu and Jihong Yu and Ding Ma}, doi = {10.1021/jacs.5c09153}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30268--30276}, shortjournal = {J. Am. Chem. Soc.}, title = {High-efficiency hydrocracking of polyolefin plastics by controlling intimacy between pt clusters and zeolite acid sites}, volume = {147}, year = {2025}, }
• (2025). Sustainable and orthogonally closed-loop recyclable acetal-based long-chain polyesters. JACS, 147(33), 30259--30267. (www)

  @article{ , abstract = {It is an emerging trend to develop biobased polymers to mimic commodity plastics. New physical and chemical functions are critically needed. We report a strategy for synthesizing long-chain aliphatic poly(ester)acetals (PEAc) with orthogonal degradability. The synthesis involves a two-step process: polycondensation of C18-diester with aliphatic diols to yield telechelic polyester oligomers, followed by polytransacetalization with diethoxymethane. The resulting polymers exhibit mechanical properties comparable to low-density polyethylene. Furthermore, orthogonal depolymerization is selectively controlled by varied conditions: acetal cleavage under acidic conditions, ester hydrolysis under basic conditions, and complete degradation under neutral conditions. Repolymerization largely confirmed the feasibility of closed-loop recycling. The orthogonally addressable architecture enables a distinctive “oligomer–polymer–oligomer” recycling pathway, circumventing the high-energy input and purification demands of conventional “monomer–polymer–monomer” cycles. In addition to recyclability, the poly(ester)acetals exhibit strong adhesion and adhesive reusability on polar substrates such as steel and wood, with shear strength up to 17 MPa, a property that polyethylene does not have. This study provides a promising route for manufacturing high-performance, orthogonally recyclable polymers mimicking polyethylene and beyond.}, archive = {J_JACS}, author = {Xiaomeng Li and Zhitao Hu and Mengxue Zhang and Morgan Stefik and Colleen Scott and Chuanbing Tang}, doi = {10.1021/jacs.5c09003}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30259--30267}, shortjournal = {J. Am. Chem. Soc.}, title = {Sustainable and orthogonally closed-loop recyclable acetal-based long-chain polyesters}, volume = {147}, year = {2025}, }
• (2025). Entropy or enthalpy? second harmonic generation from liquid sheets reveals different ion adsorption mechanisms for Air–Water and Oil–Water interfaces. JACS, 147(33), 30248--30258. (www)

  @article{ , abstract = {The mechanism by which ions adsorb to immiscible liquid–liquid interfaces is central to our understanding of heterogeneous aerosol chemistry, “on-water” catalysis, and biological systems. However, the microscopic details regarding ion adsorption to such interfaces have primarily come from theoretical efforts, owing to several experimental difficulties, viz., reliable preparation of experimentally accessible and contamination-free liquid–liquid interfaces and the absence of spectroscopic tools to unambiguously probe buried surfaces. To overcome these challenges and reveal vital details of ion adsorption to a prototypical hydrophobic liquid–liquid interface, we combine free-flowing planar liquid sheets with deep UV second harmonic generation spectroscopy. The micrometer-thick, layered free-flowing sheets enable the simultaneous measurement of ion adsorption to both the air–water and water–heptane interfaces, and interference of the signal between multiple interfaces permits the retrieval of valuable phase information that is normally not accessible with this technique. Specifically, we measure temperature-dependent Langmuir isotherms of the thiocyanate anion at both interfaces and disentangle the entropic and enthalpic contributions to the Gibbs free energy of adsorption. We find that anion adsorption to these two surfaces has opposite thermodynamic driving forces, with ions being stabilized at the air–water interface by a favorable enthalpy change, whereas ions are stabilized at the water–heptane interface by a favorable entropy change.}, archive = {J_JACS}, author = {Shane W. Devlin and David J. Hoffman and Jake D. Koralek and Richard J. Saykally}, doi = {10.1021/jacs.5c09036}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30248--30258}, shortjournal = {J. Am. Chem. Soc.}, title = {Entropy or enthalpy? second harmonic generation from liquid sheets reveals different ion adsorption mechanisms for Air–Water and Oil–Water interfaces}, volume = {147}, year = {2025}, }
• (2025). Unveiling long-range wavelike alternately competitive and cooperative bond coupling modes in single-atom catalysis. JACS, 147(33), 30239--30247. (www)

  @article{ , abstract = {Supports can critically influence or even dominate the chemical state, adsorption property, and catalytic performance of single-atom catalysts (SACs), but the fundamental physicochemical principles driving adsorbate–M 1 –ligand–support bond interactions have not been fully understood yet. Here, we reveal the orbital–level interaction modes underlying the long-range bond couplings in SACs by using single-atom Ru (Ru 1 ) supported on rutile-type oxides (TiO 2 , SnO 2 , and MnO 2 ) in CO adsorption and oxidation as a model system. Our results show that Ru 1 –support binding strength and catalytic activity for CO oxidation increase in the following order: Ru 1 /TiO 2 < Ru 1 /SnO 2 < Ru 1 /MnO 2 , while CO–Ru 1 adsorption strength oppositely decreases as Ru 1 /TiO 2 > Ru 1 /SnO 2 > Ru 1 /MnO 2 . These interaction trends are overall controlled by the reactivity of surface lattice oxygen atoms (O sl ) on supports. We further discover an alternating competitive and cooperative bond coupling mode in the heteroatomic chains of adsorbate–M 1 –ligand–support systems, in which the strengths of adjacent bonds competitively suppress, while alternating bonds cooperatively enhance. This wavelike bond coupling mode provides a new point to understand support effects on SAC–support interactions and structure–function relationships in SACs.}, archive = {J_JACS}, author = {Jun Zhou and Jiani Jiang and Yangyang Li and Yuefeng Wu and Wenyu Jia and Yuqing Ling and Xiaoyang Wang and Shengqi Chu and Lei Zheng and Xin Liang and Weixin Huang and Dingsheng Wang and Guolei Xiang}, doi = {10.1021/jacs.5c08955}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30239--30247}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling long-range wavelike alternately competitive and cooperative bond coupling modes in single-atom catalysis}, volume = {147}, year = {2025}, }
• (2025). In situ raman spectroscopy reveals the multifunctional role of interfacial water in CO2-to-c2 electroreduction on cu(hkl) surfaces. JACS, 147(33), 30230--30238. (www)

  @article{ , abstract = {Interfacial water serves as both a proton donor and a competitor for active sites at the copper–catalyst interface in the electrochemical CO 2 reduction reaction (CO 2 RR). However, its precise impact on C 2+ product selectivity remains debatable. Here, through the utilization of in situ Raman spectroscopy and theoretical calculations, we have discovered that the population of K + cation hydrated water (K-H 2 O) rises concurrently with the increase of C 2 yield on atomically flat model Cu( hkl ) single crystal surfaces. The K + not only stabilizes the *CO + *CO intermediate by direct coordination but also reshapes the configuration of solvated interfacial water to create a hydrogen-bond-absent environment. This prevents surrounding hydrogen from interacting with the *CO species, ingeniously suppressing its hydrogenation along the C 1 pathway while promoting C–C coupling toward C 2 products. Our results further clarify the CO 2 RR mechanism and provide definitive evidence that cationic hydrated water is critical to tuning the product selectivity.}, archive = {J_JACS}, author = {Yu Zhao and Qiong-Qiong Li and Quan-Feng He and Pei-Wen Ren and Dong-Ao Zhang and Yao-Hui Wang and Jin-Chao Dong and Shisheng Zheng and Yue-Jiao Zhang and Zhi-Lin Yang and Jian-Feng Li}, doi = {10.1021/jacs.5c08922}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30230--30238}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ raman spectroscopy reveals the multifunctional role of interfacial water in CO2-to-c2 electroreduction on cu(hkl) surfaces}, volume = {147}, year = {2025}, }
• (2025). Boosting electrochemical ethylene epoxidation via ruthenium valence state stabilization. JACS, 147(33), 30222--30229. (www)

  @article{ , abstract = {Halide-mediated olefin epoxidation using renewable electricity offers a sustainable route for ethylene oxide (EO) production. However, catalyst deactivation due to excessive oxidation and degradation in halide-rich environments hinders industrial scalability. This paper describes an electron reservoir strategy to stabilize a ruthenium oxide-based catalyst in chloride-rich environments through iridium doping. The electronegativity difference between ruthenium and iridium enables bidirectional electron transfer, mitigating catalyst degradation at high current densities. This strategy achieves a Faradaic efficiency of EO up to 85.1% and stable operation for over 120 h at 150 mA cm –2 . In situ Raman spectroscopy reveals that iridium doping reduces the vibrational frequency disparity between Cl–O and Ru–O bonds, lowering the activation energy for M–O bond cleavage and promoting direct HOCl formation while preventing Cl 2 production. These findings demonstrate the importance of electronic modulation for catalyst design and may inspire new strategies for the sustainable production of chemical feedstocks.}, archive = {J_JACS}, author = {Hongyi Wang and Gong Zhang and Xiao Ma and Hao Dong and Jiachang Liu and Dehui Luo and Zhi-Jian Zhao and Tuo Wang and Peng Zhang and Jinlong Gong}, doi = {10.1021/jacs.5c08317}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30222--30229}, shortjournal = {J. Am. Chem. Soc.}, title = {Boosting electrochemical ethylene epoxidation via ruthenium valence state stabilization}, volume = {147}, year = {2025}, }
• (2025). The heme oxygenase-like diiron enzyme HrmI reveals altered regulatory mechanisms for dioxygen activation and substrate N-oxygenation. JACS, 147(33), 30210--30221. (www)

  @article{ , abstract = {Nonheme diiron enzymes activate dioxygen (O 2 ) to affect various biochemical outcomes. HrmI, a member of the recently discovered and functionally versatile heme oxygenase-like dimetal oxidase/oxygenase (HDO) superfamily, catalyzes the N-oxygenation of L -Lysine to yield 6-nitronorleucine for the biosynthesis of the antibiotic hormaomycin. Unlike other characterized HDO N-oxygenases that have an additional carboxylate ligand thought to be key for regulating dioxygen activation and ensuing N-oxygenation, the predicted primary coordination sphere of HrmI resembles those of HDOs that instead perform C–C fragmentation of substrates. We show that diferrous HrmI reacts with O 2 in a substrate-independent manner to form a presumptive μ-1,2 (Fe 3+ ) 2 peroxo (or P ) intermediate common to the catalytic scheme of many HDOs. P is rapidly converted to a second species with both optical and Mössbauer properties that resemble an activated peroxodiferric adduct ( P’ ). The substrate-dependent acceleration of P’ decay suggests that it, rather than P , initiates l -Lysine metabolism. X-ray crystallographic studies of HrmI in several redox and ligand-bound states provide a stepwise view of structural changes during catalysis and, together with analytical approaches, capture a hydroxylamino metabolic intermediate en route to 6-nitronorleucine formation. The activation of peroxo species provides a key strategy that enables functional adaptation within the widely distributed HDO structural scaffold.}, archive = {J_JACS}, author = {Sydney S. Skirboll and Medha Gangopadhyay and Han N. Phan and Joshua Hartsell and Aditi Mudireddy and Dalton Hilovsky and Paul D. Swartz and Xiaojing Liu and Yisong Guo and Thomas M. Makris}, doi = {10.1021/jacs.5c08814}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30210--30221}, shortjournal = {J. Am. Chem. Soc.}, title = {The heme oxygenase-like diiron enzyme HrmI reveals altered regulatory mechanisms for dioxygen activation and substrate N-oxygenation}, volume = {147}, year = {2025}, }
• (2025). Solid-state packing controls exciton delocalization and photophysics in nonfullerene acceptors. JACS, 147(33), 30199--30209. (www)

  @article{ , abstract = {We engineer molecular packing in five derivatives of the nonfullerene acceptor Y6. Using transient absorption spectroscopy, we find evidence of the formation of a delocalized exciton in addition to the local exciton in neat films of the acceptors. Following selective photoexcitation of the acceptors in donor/acceptor blends with D18, we observe anion formation on the same timescale as in neat acceptor films, suggesting that D18 is a bystander to charge generation after photoexcitation of the acceptors. We quantify the recombination kinetics of the delocalized excitons with the monomolecular recombination constant ( a ) and find that both the hole transfer yield and the internal quantum efficiency in photovoltaic devices increase for acceptor films with lower a . In A1, relatively localized excitons with a limited charge transfer character have fast recombination kinetics ( a = 3.2 × 10 10 s –1 ), leading to the lowest IQE (83.7%). In T1, more delocalized excitons with stronger charge transfer character have slower recombination kinetics ( a = 5.3 × 10 9 s –1 ), leading to a higher IQE (97.2%). Grazing incidence wide-angle X-ray scattering of π–π stacking regions reveals that the tendency to pack face-on is a key driver of exciton delocalization across acceptors with similar molecular packing. We anticipate that this newly identified structural lever will help propel organic photovoltaics toward 20% efficiency.}, archive = {J_JACS}, author = {Robert J. E. Westbrook and Andrew J. Levin and Wei Gao and Urvashi Bothra and Saied Md Pratik and Baobing Fan and Francis R. Lin and Qian-Qian Zhang and Khoa Ngo and Werner Kaminsky and Jean-Luc Brédas and Veaceslav Coropceanu and Alex K.-Y. Jen and Michael F. Toney and David S. Ginger}, doi = {10.1021/jacs.5c08244}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30199--30209}, shortjournal = {J. Am. Chem. Soc.}, title = {Solid-state packing controls exciton delocalization and photophysics in nonfullerene acceptors}, volume = {147}, year = {2025}, }
• (2025). Nickel-catalyzed regio- and enantioselective hydroalkenylation of aldehydes with 2-azadienes. JACS, 147(33), 30190--30198. (www)

  @article{ , abstract = {The development of new methods for the utilization of aldehydes has garnered much attention because their addition products, chiral alcohols, are common structural elements in the pharmaceutical industry. Despite significant progress in the catalytic asymmetric synthesis of secondary allylic alcohols, the synthesis of derivatives bearing amino functionalities remains challenging. Herein, we report a highly regio- and enantioselective nickel-catalyzed direct hydrovinylation of aldehydes with 2-azadienes, delivering a series of 2-azadiene-substituted alcohols in good yields (up to 96%) with high enantioselectivities (up to 99%) under mild conditions. These high-value γ-amino alcohols can be incorporated into natural products and bioactive molecules and are readily transformed into a variety of useful structural motifs.}, archive = {J_JACS}, author = {Ya Du and Lening Zhang and Shengzu Duan and Xiang Yang and Sina Liu and Hongbin Zhang and Patrick J. Walsh and Xiaodong Yang}, doi = {10.1021/jacs.5c08602}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30190--30198}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-catalyzed regio- and enantioselective hydroalkenylation of aldehydes with 2-azadienes}, volume = {147}, year = {2025}, }
• (2025). Synergizing Pd1Sb2 site with neighboring near-surface pd site to break the trade-off between selectivity and activity of alkyne semihydrogenation. JACS, 147(33), 30178--30189. (www)

  @article{ , abstract = {Catalytic hydrogenation of trace alkynes in excess alkenes is essential for producing polymer-grade olefins from steam cracking and alkane dehydrogenation, but achieving high selectivity without sacrificing activity remains a significant challenge. Herein, we report a catalyst design that synergistically integrates computationally proposed surface Pd 1 Sb 2 trimer sites with near-surface Pd sites (Pd ns ) on the P 6 3 / mmc PdSb intermetallic catalyst to achieve the semihydrogenation of alkynes with both high activity and selectivity. Alkynes can be readily activated through strong σ-bonding on the Pd 1 Sb 2 trimer sites, whereas alkenes are only weakly adsorbed via π-interactions due to their matched electronic structures and spatial configurations. Moreover, the neighboring Pd ns cooperates with the Pd 1 Sb 2 sites to achieve spontaneous dissociation of H 2 for subsequent hydrogenation. Consequently, the fabricated PdSb intermetallic catalyst exhibits ethylene and propylene selectivities of 96.50% and 98.65%, respectively, at nearly complete conversions of acetylene and propyne, under industrially relevant conditions, outperforming state-of-the-art catalysts. This study demonstrates a promising strategy that synergizes near-surface and surface ensemble sites to spatially and energetically match with the target reaction pathway, enabling the overcoming of the trade-off between activity and selectivity in hydrogenation.}, archive = {J_JACS}, author = {Xiaohu Ge and Yundao Jing and Wenjie Wang and Yueqiang Cao and Jing Zhang and Gang Qian and Hao Jiang and Xinggui Zhou and De Chen and Weikang Yuan and Xuezhi Duan}, doi = {10.1021/jacs.5c08564}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30178--30189}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergizing Pd1Sb2 site with neighboring near-surface pd site to break the trade-off between selectivity and activity of alkyne semihydrogenation}, volume = {147}, year = {2025}, }
• (2025). Unusual O–H activation-initiated C–C bond cleavage reaction by a nonheme fe enzyme in antifungal nucleoside biosynthesis. JACS, 147(33), 30163--30177. (www)

  @article{ , abstract = {Fe(II)- and α-ketoglutarate (α-KG)-dependent enzymes catalyze diverse reactions, generally initiated by Fe IV =O mediated cleavage of C–H bonds with bond dissociation energies (BDE) of up to ∼100 kcal/mol. Here, we report the discovery of a novel reaction initiated by a significantly more challenging O–H bond cleavage (>100 kcal/mol). This activity was identified in PolD, an enzyme that regulates the sugar size in antifungal nucleoside biosynthesis by catalyzing the transformation of a bicyclic eight-carbon sugar substrate, 5′-amino-6′-hydroxy-octosyl acid 2′-phosphate (AHOAP), into a monocyclic six-carbon product, aminohexuronic acid 2′-phosphate (AHAP). Our studies demonstrate that PolD catalyzes a two-step reaction, in which AHOAP is first oxidized to 5′-amino-6′-keto-octosyl acid 2′-phosphate (AKOAP) via typical C–H activation, followed by a unique C–C bond cleavage on AKOAP to AHAP initiated by O–H activation. X-ray crystal structures of PolD and its homologue, PasI, the latter solved in complex with AHOAP, succinate, and vanadyl, a structural mimic of the Fe IV -oxo intermediate, reveal a substrate binding mode that is consistent with both C–H and O–H homolysis. A comparison of the three enzymes, PasI, PolD, and MalI, all of which exhibit distinct C–C bond cleavage activities, suggests that precise substrate positioning to bring the target OH group of AKOAP close to the Fe IV -oxo intermediate is critical for hydrogen atom transfer from this functional group. These results indicate a novel reactivity of the Fe IV ═O intermediate in Fe/α-KG enzymes, thereby expanding the reaction scope of this enzyme superfamily. The results also reveal the molecular mechanism of the divergent biosynthesis of antifungal nucleosides.}, archive = {J_JACS}, author = {Yanan Du and Julian Dong and Matthew M. Draelos and Laura N. Collazo-Perez and Sean H. Majer and Amie K. Boal and Kenichi Yokoyama}, doi = {10.1021/jacs.5c08400}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30163--30177}, shortjournal = {J. Am. Chem. Soc.}, title = {Unusual O–H activation-initiated C–C bond cleavage reaction by a nonheme fe enzyme in antifungal nucleoside biosynthesis}, volume = {147}, year = {2025}, }
• (2025). Photoelectrochemical asymmetric epoxidation of alkenes with water as an oxygen source in a biphasic system. JACS, 147(33), 30154--30162. (www)

  @article{ , abstract = {Photoelectrochemical (PEC) oxidation of organics to value-added chemicals presents a sustainable alternative to conventional anodic oxygen evolution reactions. While significant progress has been made in PEC organic transformations, asymmetric PEC organic conversions remain underexplored. In this study, we report the chloride-mediated PEC enantioselective epoxidation of alkenes at a mesoporous BiVO 4 photoanode in a CH 2 Cl 2 /aqueous NaCl biphasic system using water as an oxygen source. The NaCl electrolyte serves as a redox mediator and chlorine precursor, where photo-oxidation generates reactive chlorine species (Cl 2 /HClO) that migrate into the organic phase to enable asymmetric catalysis via chiral Mn-salen catalysts. Spectroelectrochemical analysis verified the photogenerated Mn V ═O species as the key intermediate. A key innovation of this study lies in the use of a pendant alkyl chain-modified pyridine N-oxide additive, which uniquely stabilizes the Mn V ═O intermediate through axial coordination while simultaneously acting as a phase-transfer catalyst to facilitate hypochlorous acid migration, dramatically boosting the epoxidation efficiency. This approach achieves high yields (up to 95%) and enantioselectivities (up to 88% enantiomeric excess), even in a challenging artificial seawater/CH 2 Cl 2 biphasic system. By utilizing water as a green oxygen source and coupling with solar fuel production, this work presents a practical and efficient route for asymmetric PEC synthesis.}, archive = {J_JACS}, author = {Zhi Chen and Yong Zhu and Xiaona Li and Zhibing Wen and Hua Gao and Ran Zhao and Siyao Wang and Shuanglin He and Yingjuan Guo and Licheng Sun and Fei Li}, doi = {10.1021/jacs.5c08112}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30154--30162}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoelectrochemical asymmetric epoxidation of alkenes with water as an oxygen source in a biphasic system}, volume = {147}, year = {2025}, }
• (2025). Tungsten-enabled Diels–Alder cycloaddition and cycloreversion of arenes and alkynes: Divergent synthesis of highly functionalized barrelenes and arenes. JACS, 147(33), 30146--30153. (www)

  @article{ , abstract = {The Diels–Alder reaction of benzenes remains a significant synthetic challenge, owing to their highly stabilized aromatic cores. In this work, the dearomatization agent {WTp(NO)(PMe 3 )} is used to promote Diels–Alder reactions of dihapto-coordinated (η 2 ) benzenes with alkynes. The resulting η 2 -barrelene complexes can be oxidized to liberate intact barrelenes. Alternatively, mild pyrolysis leads to the extraction of the corresponding tungsten-acetylene complex and concomitant formation of new arenes possessing substituents originating from the acetylene dienophiles.}, archive = {J_JACS}, author = {Jeremy M. Bloch and Evan Savelson and Alvin Q. Meng and Megan N. Ericson and Ishaan U. Patel and Diane A. Dickie and Jetze J. Tepe and W. Dean Harman}, doi = {10.1021/jacs.5c08320}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30146--30153}, shortjournal = {J. Am. Chem. Soc.}, title = {Tungsten-enabled Diels–Alder cycloaddition and cycloreversion of arenes and alkynes: Divergent synthesis of highly functionalized barrelenes and arenes}, volume = {147}, year = {2025}, }
• (2025). Controlled dimerization of cellular nanodiscs via click chemistry to enhance immune compatibility. JACS, 147(33), 30136--30145. (www)

  @article{ , abstract = {Cellular nanodiscs (CNDs), assembled from cell membrane fragments and stabilized with scaffold molecules, have emerged as a promising biomimetic platform for drug delivery, countermeasures, and vaccination. However, the exposure of inner membrane components in the current CND constructs, such as phosphatidylserine (PS) can trigger immune recognition and rapid clearance, thereby limiting their therapeutic efficacy. To address this issue, here we report on a unique approach to dimerizing CNDs in a precisely controlled, back-to-back manner by covalently linking two monomeric CNDs via click chemistry, aiming to shield the immunogenic inner membrane components. Compared with monomeric CNDs, the resulting dimeric CNDs showed reduced PS exposure, decreased macrophage uptake, and prolonged circulation in vivo. In mouse models of acute lung injury and systemic inflammation, dimeric CNDs achieved superior cytokine suppression and favorable biodistribution with minimal short-term toxicity. These findings demonstrate that CND dimerization can effectively enhance immune compatibility and greatly improve in vivo performance, advancing the application potential of cell membrane-derived CND technology.}, archive = {J_JACS}, author = {Lei Sun and Yiyan Yu and Jiayuan Alex Zhang and Wei-Ting Shen and Kailin Feng and Dean Bai and Zhidong Zhou and Weiwei Gao and Liangfang Zhang}, doi = {10.1021/jacs.5c07920}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30136--30145}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlled dimerization of cellular nanodiscs via click chemistry to enhance immune compatibility}, volume = {147}, year = {2025}, }
• (2025). Discovery and synthesis of a family of boride altermagnets. JACS, 147(33), 30117--30135. (www)

  @article{ , abstract = {Borides are a rich material family. To push the boundaries of borides’ properties and applications into broader fields, we have conducted systematic theoretical and experimental searches for synthesizable phases in ternary borides TM 2 B 2 ( T = 3 d , M = 4 d /5 d transition metals). We find that TM 2 B 2 in the FeMo 2 B 2 -type and CoW 2 B 2 -type structures form a large family of stable/metastable materials of 120 members. Among them, we identify 40 materials with stable magnetic solutions. Further, we discover 11 altermagnets in the FeMo 2 B 2 -type structure. So far, boride altermagnets are rare. In these altermagnets, T = Fe or Mn atoms are arranged in parallel T -chains with strong ferromagnetic intrachain couplings and antiferromagnetic interchain couplings. They simultaneously exhibit electronic band spin splitting, typical of ferromagnetism, and zero net magnetization, typical of antiferromagnetism. They also exhibit magnonic band chiral splitting. Both effects originate from the unique altermagnetic symmetries crucially constrained by the nonmagnetic atoms in the structure. Transport properties of relevance to spintronic applications, including the strain-induced spin-splitter effect and anomalous Hall effect, are predicted. An iodine-assisted synthesis method for TM 2 B 2 is developed, using which 7 of the predicted low-energy phases are experimentally synthesized and characterized, including 4 altermagnets. This work expands the realm of borides by offering new opportunities for studying altermagnetism and altermagnons in borides. It also provides valuable insights into the discovery and design of altermagnets. By demonstrating that altermagnets can exist as families sharing a common motif, this work paves a feasible route for discovering altermagnets by elemental substitutions and high-throughput computations.}, archive = {J_JACS}, author = {Zhen Zhang and Eranga H. Gamage and Genevieve Amobi and Subhadip Pradhan and Andrey Kutepov and Kirill D. Belashchenko and Yang Sun and Kirill Kovnir and Vladimir Antropov}, doi = {10.1021/jacs.5c07874}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30117--30135}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery and synthesis of a family of boride altermagnets}, volume = {147}, year = {2025}, }
• (2025). Spontaneous surface charging and janus nature of the hexagonal boron Nitride–Water interface. JACS, 147(33), 30107--30116. (www)

  @article{ , abstract = {Boron, nitrogen, and carbon are neighbors in the periodic table and can form strikingly similar twin structures─hexagonal boron nitride (hBN) and graphene─yet nanofluidic experiments demonstrate drastically different water friction on them. We investigate this discrepancy by probing the interfacial water and atomic-scale properties of hBN using surface-specific vibrational spectroscopy, atomic-resolution atomic force microscopy (AFM), and machine learning-based molecular dynamics. Spectroscopy reveals that pristine hBN acquires significant negative charges upon contacting water at neutral pH, unlike hydrophobic graphene, leading to interfacial water alignment and stronger hydrogen bonding. AFM supports that this charging is not defect-induced. pH-dependent measurements suggest OH – chemisorption and physisorption, which simulations validate as two nearly equally stable states undergoing dynamic exchange. These findings challenge the notion of hBN as chemically inert and hydrophobic, revealing its spontaneous surface charging and Janus nature, and providing molecular insights into its higher water friction compared to carbon surfaces.}, archive = {J_JACS}, author = {Yongkang Wang and Haojian Luo and Xavier R. Advincula and Zhengpu Zhao and Ali Esfandiar and Da Wu and Kara D. Fong and Lei Gao and Arsh S. Hazrah and Takashi Taniguchi and Christoph Schran and Yuki Nagata and Lydéric Bocquet and Marie-Laure Bocquet and Ying Jiang and Angelos Michaelides and Mischa Bonn}, doi = {10.1021/jacs.5c07827}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30107--30116}, shortjournal = {J. Am. Chem. Soc.}, title = {Spontaneous surface charging and janus nature of the hexagonal boron Nitride–Water interface}, volume = {147}, year = {2025}, }
• (2025). A material platform based on dissociative CO2-derived N,O-acetals for tunable degradation of 3D printable materials. JACS, 147(33), 30095--30106. (www)

  @article{ , abstract = {Modern-day thermosetting polymers should be designed with circular economy principles in mind, considering both their recyclability and end-of-life options. Covalent adaptable networks (CANs) have the potential to address the environmental challenges we face today as, in spite of being thermosets, they can be reprocessed by conventional thermoprocessing methods and are thus recyclable. While in the last years intensive efforts have been devoted to the preparation of CANs using sustainable sources, less attention has been paid to their end-of-life options in case they escape from plastic sorting. Herein, we report the development of a new type of dynamic bond, the N , O -acetal bond based on the coupling between CO 2 -based oxazolidone moieties and abundant, potentially biobased polyols. Computational and kinetic studies revealed that this bond underwent rapid dissociative exchange and, crucially, was also susceptible to hydrolytic degradation. We then prepared a range of thermoset materials endowed by double end-of-life features, i.e., CAN behavior and hydrolytic degradation. This was achieved by radical thiol–ene photo-cross-linking of a diallyl monomer bearing the N , O -acetal moiety with another alkene-functionalized monomer that did not bear this dynamic bond. CANs with tunable mechanical properties and hydrolytic degradation features were easily obtained by modulating the monomer compositions. The fast-photocuring of the N , O -functionalized monomer was then exploited for producing three-dimensional (3D) printed objects, offering the potential for on-demand hydrolytic behavior.}, archive = {J_JACS}, author = {Marco Caliari and Jacopo Teotonico and Mikel Irigoyen and Anje Mujika and Tommaso Isolabella and Daniele Mantione and Lourdes Irusta and Bruno Grignard and Fernando Vidal and Christophe Detrembleur and Haritz Sardon}, doi = {10.1021/jacs.5c07767}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30095--30106}, shortjournal = {J. Am. Chem. Soc.}, title = {A material platform based on dissociative CO2-derived N,O-acetals for tunable degradation of 3D printable materials}, volume = {147}, year = {2025}, }
• (2025). Tailoring artificial hydration microenvironments in covalent organic frameworks for enhanced enzymatic catalysis in organic media. JACS, 147(33), 30084--30094. (www)

  @article{ , abstract = {Hydration at biological interfaces plays a crucial role in enzyme function by stabilizing structures and driving conformational dynamics essential for catalysis. However, preserving these delicate hydration microenvironments in organic solvents remains challenging, undermining nonaqueous enzymatic catalysis and impeding industrial biocatalytic applications. Here, we tailored artificial hydration-like microenvironments for enzymes by integrating flexible oligo(ethylene oxide) chains, rich in hydrogen-bonding acceptors, into the confined channels of covalent organic frameworks (COFs). These engineered microenvironments promote multiple hydrogen-bond interactions between the encapsulated enzyme and the pore walls, significantly enhancing enzyme activity and stability in organic media. Notably, the encapsulated enzyme exhibited approximately 13-fold higher conversion than the free enzyme under 0% relative humidity (RH), while maintaining high performance across a wide humidity range. Unlike the fragile natural hydration layer, this hydration-like environment engineered within the confined nanochannels is stable, effectively preserving enzyme activity in polar solvents, while also resisting elevated temperature. Molecular dynamics (MD) simulations reveal that the multiple hydrogen bond-mediated microenvironment enhances the local conformational flexibility of enzyme and stabilizes its catalytic active center. Furthermore, the versatility of this approach is demonstrated in the lipase-catalyzed regioselective synthesis of active pharmaceutical intermediates. This work establishes an effective strategy for constructing robust hydration-like microenvironments, advancing the design of efficient biocatalysts in nonaqueous systems.}, archive = {J_JACS}, author = {Chunyan Xing and Zhenjie Mu and Bixiao Li and Jianwei Yang and Xiao Feng and Yuanyuan Zhang and Bo Wang}, doi = {10.1021/jacs.5c07600}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30084--30094}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailoring artificial hydration microenvironments in covalent organic frameworks for enhanced enzymatic catalysis in organic media}, volume = {147}, year = {2025}, }
• (2025). Diversity-oriented synthesis of diaza-polycyclic aromatic hydrocarbons coupled with virtual screening for OLED applications. JACS, 147(33), 30072--30083. (www)

  @article{ , abstract = {The development of organic light-emitting diode (OLED) materials requires precisely engineered molecular architectures with tailored optoelectronic properties. Here, we present a strategy that synergistically integrates diversity-oriented synthesis (DOS) with virtual screening to systematically explore the chemical space of diaza-polycyclic aromatic hydrocarbons (diaza-PAHs) for OLED applications. DOS, originally developed for drug discovery, serves as a powerful tool to generate structurally diverse molecular libraries, granting access to previously unexplored diaza-PAHs with potential OLED functionality. Complementing this synthetic approach, virtual screening enables the rapid identification of optimal candidates from an extensive library of computationally generated structures, thereby streamlining the material discovery process. In this work, we introduce a rhodium-catalyzed method that combines sequential C–H activation and annulation, offering a modular synthetic protocol for diaza-PAH scaffolds with tunable electronic properties. By computationally screening 1,061 core structures, we identified two lead frameworks─2,6-diazaanthracene and 2,8-dipyridylthiophene─as potential prototypes for OLED applications. Guided by these computational insights, we synthesized four diaza-PAH derivatives, which exhibited exceptional performance as electron-transporting and host materials in high-efficiency phosphorescent OLEDs. This integrated experimental and computational approach not only accelerates the identification of functional materials but also significantly reduces experimental time and resource consumption. This paradigm shift underscores the potential of merging synthetic diversity with data-driven molecular discovery to advance optoelectronic materials research.}, archive = {J_JACS}, author = {Junjie Liu and Yudong Yang and Zhengyang Bin and Jingsong You}, doi = {10.1021/jacs.5c07594}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30072--30083}, shortjournal = {J. Am. Chem. Soc.}, title = {Diversity-oriented synthesis of diaza-polycyclic aromatic hydrocarbons coupled with virtual screening for OLED applications}, volume = {147}, year = {2025}, }
• (2025). Long–Short-arm acridine ru-pincer catalysts for reversible hydrogen storage based on ethylene glycol. JACS, 147(33), 30060--30071. (www)

  @article{ , abstract = {Liquid organic hydrogen carriers (LOHCs) offer an attractive strategy for efficient hydrogen storage and release, thereby facilitating the effective use of hydrogen as a carbon-neutral energy carrier. The advancement of LOHC technology is highly dependent on the innovation of the catalysts. Herein, based on a strategy combining rigidity and flexibility in a single molecular catalyst, a novel class of PNP-pincer ligands, called long–short-arm acridine ligands, and their Ru complexes have been developed and successfully used in the LOHC system based on ethylene glycol (EG). In comparison to previously reported catalytic systems, which suffered from low conversions or insufficient H 2 release due to the dual challenge of catalyst stability and catalytic activity in the acceptorless dehydrogenative coupling of EG, this new catalytic system overcomes these challenges and achieves high conversion (up to >99%) with high H 2 yield (up to 96%), achieving a hydrogen storage capacity of 6.2 wt %. Mechanistic and computational studies reveal that the special coordination mode, one 5-membered metallacycle and one 6-membered metallacycle, is essential for the high reactivity and late-stage dehydrogenative coupling. Moreover, both dehydrogenation and hydrogenation can be achieved under solvent- and additive-free conditions, highlighting the robustness and application potential of this new catalytic system. This advances the promising liquid-to-liquid paired LOHC systems based on inexpensive, widely accessible, and biobased EG toward practical application.}, archive = {J_JACS}, author = {Cai You and Lijun Lu and Jie Luo and Yael Diskin-Posner and David Milstein}, doi = {10.1021/jacs.5c07428}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30060--30071}, shortjournal = {J. Am. Chem. Soc.}, title = {Long–Short-arm acridine ru-pincer catalysts for reversible hydrogen storage based on ethylene glycol}, volume = {147}, year = {2025}, }
• (2025). Organocatalytic meta-C–H hydroxylation of azaarene N-oxides. JACS, 147(33), 30050--30059. (www)

  @article{ , abstract = {The chemoselective and site-selective molecular editing of azaarenes presents significant potential, as it allows for the precise construction of complex molecules with diverse applications in pharmaceuticals and materials science. Nevertheless, the most substantial challenge lies in the meticulous control of reaction selectivity, primarily due to the complex electronic properties and multiple reactive sites inherent in azaarenes. In this regard, the development of efficient and practical catalysts, especially organocatalysts for these selective transformations, is of the utmost significance and represents a formidable challenge. Against this backdrop, we report an organocatalytic thermodynamically driven cyclizative rearrangement that enables highly site-specific meta -hydroxylation of azaarenes with excellent chemoselectivities. Specifically, a structurally specific nitrilium ion, formed in situ from the reaction of N -methylacetamide with oxalyl chloride, serves as a highly efficient catalyst, enabling a diverse range of azaarene 1-oxides to undergo a unique stepwise 1,3-oxygen transfer. This process ultimately leads to the formation of their corresponding 3-hydroxylated derivatives. Remarkably, this transformation features column-free operation, scalability, a broad scope, high yields, and an inexpensive catalyst system. Applications in the late-stage meta -hydroxylation of pharmaceutically relevant compounds are also demonstrated.}, archive = {J_JACS}, author = {Zhuo-Chen Li and Di Tian and Zi-Qi Wang and Peng Yuan and Hua Wu}, doi = {10.1021/jacs.5c07423}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30050--30059}, shortjournal = {J. Am. Chem. Soc.}, title = {Organocatalytic meta-C–H hydroxylation of azaarene N-oxides}, volume = {147}, year = {2025}, }
• (2025). Regulated electronic and ionic conductive framework for high energy density Lithium–Sulfur batteries. JACS, 147(33), 30042--30049. (www)

  @article{ , abstract = {Achieving high energy density in lithium–sulfur (Li–S) batteries necessitates thick cathodes with high sulfur loadings and a lean electrolyte. However, these configurations introduce critical challenges, including low conductivity, polysulfide shuttling, volume expansion, and mechanical instability, which significantly impede battery performance. In this study, we present a regulated electronic and ionic conductive framework that integrates carbon nanotubes (CNTs) and sulfur onto the surface of air plasma-treated aramid fibers (APAF) in a layer-by-layer fashion (denoted as CNT/S/APAF). This composite framework is then incorporated into a CNT network to form free-standing sulfur cathodes for high energy density Li–S batteries. The resulting structure promotes efficient electron transport, improves electrolyte wettability, suppresses polysulfide diffusion, and mitigates volume expansion. These synergistic effects lead to superior sulfur utilization and cycling stability. The Li–S cells with CNT/S/APAF cathodes exhibit an impressive initial specific capacity of 1437.6 mAh g –1 and areal capacity of 11.3 mAh cm –2 , with a sulfur loading of 7.83 mg cm –2 and an electrolyte-to-sulfur (E/S) ratio of 5 μL mg –1 . Furthermore, they achieve a high energy density of 468.6 Wh kg –1 and maintain excellent cycling stability, retaining a capacity of 6.5 mAh cm –2 after 100 cycles. This scalable approach provides a practical, high-performance solution for next-generation batteries.}, archive = {J_JACS}, author = {Xueting Feng and Xuanguang Ren and Huahui Tian and Mingwei Cui and Guoxin Lu and Jin Zhang and Xin Gao}, doi = {10.1021/jacs.5c07454}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30042--30049}, shortjournal = {J. Am. Chem. Soc.}, title = {Regulated electronic and ionic conductive framework for high energy density Lithium–Sulfur batteries}, volume = {147}, year = {2025}, }
• (2025). Quasi-planar π-extended cycloparaphenylenes: On-surface synthesis, characterization, and electronic properties. JACS, 147(33), 30030--30041. (www)

  @article{ , abstract = {Cycloparaphenylenes (CPPs), hoop-shaped conjugated macrocycles composed of para -linked phenyl units, have attracted significant interest due to their curved aromatic frameworks and para -conjugation, which give rise to unique (opto)electronic properties. Full planarization of their π-systems is structurally inaccessible, as it would further increase the inherent ring strain. However, partial planarization can be achieved by π-extension through incorporation of rigid bending units. Here, we report the on-surface synthesis of quasi-planar π-extended [2n]CPPs (n = 8–11) on Au(111), achieved via a bottom-up surface-assisted strategy, and their characterization by scanning tunneling microscopy/spectroscopy (STM/STS) and density functional theory (DFT). These π-extended CPPs are macrocycles with para -connected phenylenes forming the inner backbone and perylenyl groups bridging the phenylene units. The n = 8 CPP adopts a planar geometry on the surface, while the n = 9 to n = 11 homologues remain nonplanar. Nevertheless, substrate-induced flattening enhances π-orbital overlap and leads to a progressive reduction of the HOMO–LUMO gap with increasing ring size. This behavior is specific for planarized CPPs and contrasts with conventional, nonplanar CPPs. Moreover, π-extension results in a reduced gap compared to the unsubstituted planar parent [2n]CPP. dI/dV maps reveal orbital confinement at the edges and fjord regions, attributed to slower wave function decay. In larger CPPs, the tilted perylenyl groups modulate this confinement and affect the STM contrast in fjord regions. The unique structure of these strained, quasi-planar CPPs provides a well-defined platform for studying the interplay of curvature, conjugation, and electronic structure in bent benzenoid macrocycles.}, archive = {J_JACS}, author = {Dong Han and Jakob Schramm and Zilin Ruan and Tim Naumann and Nour-Eddine El Alaoui and Konstantin Y. Amsharov and Ralf Tonner-Zech and J. Michael Gottfried}, doi = {10.1021/jacs.5c07471}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30030--30041}, shortjournal = {J. Am. Chem. Soc.}, title = {Quasi-planar π-extended cycloparaphenylenes: On-surface synthesis, characterization, and electronic properties}, volume = {147}, year = {2025}, }
• (2025). CO2 fixation and release mediated by carbonate-based coordination polymers. JACS, 147(33), 30022--30029. (www)

  @article{ , abstract = {We demonstrate the synthesis of 11 carbonate (CO 3 2– )-based coordination polymers (CPs) from CO 2 and reveal the structure–property correlation of CO 2 release upon decarbonation. The decarbonation temperatures ( T CO2 ) are tunable as factors of the electronegativity of metal ions and the coordination numbers of CO 3 2– within the CP lattices. The structural tunability of CO 3 2– -based CPs enables high gravimetric CO 2 contents (25–30 wt %) and T CO2 in the low-temperature range where low-grade waste heat can be utilized (170–230 °C). The decarbonation mechanism of CO 3 2– -based CPs, which produces a discrete metal complex, is revealed by 3D electron diffraction and variable-temperature synchrotron X-ray diffraction.}, archive = {J_JACS}, author = {Kentaro Kadota and Sae Matsui and Ayoub Traverson and Yuta Hori and Kanchana Sotho and Kei Morisato and Yoshitaka Aoyama and Yasuteru Shigeta and Yusuke Nishiyama and Satoshi Horike}, doi = {10.1021/jacs.5c07425}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30022--30029}, shortjournal = {J. Am. Chem. Soc.}, title = {CO2 fixation and release mediated by carbonate-based coordination polymers}, volume = {147}, year = {2025}, }
• (2025). Hydrophobic, acid-free zeolite-confined Pt–Cu nanoalloys break Activity–Selectivity limits in low-temperature methane-to-methanol oxidation. JACS, 147(33), 30009--30021. (www)

  @article{ , abstract = {The direct oxidation of methane (CH 4 ) to methanol (CH 3 OH) remains a formidable challenge due to the inertness of CH 4 and the tendency of CH 3 OH to overoxidize. Here, we report Pt–Cu nanoalloys encapsulated within hydrophobic, acid-free silicalite-1 (S-1) zeolite that breaks activity–selectivity limits in CH 4 oxidation to CH 3 OH. The best catalyst exhibits a CH 3 OH productivity of 134 mol of CH 3 OH per mol of Pt per hour and a selectivity of 95% at 150 °C. Kinetic and spectroscopic studies revealed a sequential oxidation mechanism: CH 4 is first oxidized to methyl hydroperoxide (CH 3 OOH) by in situ generated hydrogen peroxide, which subsequently converts to CH 3 OH. The catalytic reaction proceeds with an apparent activation energy of only 42 kJ/mol, the lowest reported to date. The outstanding performance arises from the synergy of the Pt–Cu alloy sites and the hydrophobic pore of S-1. Pt–Cu alloy sites specifically generate oxidizing species and selectively form CH 3 OH, which was not achieved by single metal catalysts and other bimetallic catalysts. A confined hydrophobic, acid-free environment enables rapid extraction of the CH 3 OH from the reaction field and thereby prevents overoxidation. These findings highlight how precious control over both the composition and the local environment of Pt–Cu nanoalloys can markedly enhance the catalytic oxidation of CH 4 to CH 3 OH.}, archive = {J_JACS}, author = {Akira Oda and Koyo Ichino and Yuta Yamamoto and Takeshi Ohtsu and Wei Shi and Yoshiharu Sawada and Jun Kumagai and Kyoichi Sawabe and Atsushi Satsuma}, doi = {10.1021/jacs.5c07414}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {30009--30021}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrophobic, acid-free zeolite-confined Pt–Cu nanoalloys break Activity–Selectivity limits in low-temperature methane-to-methanol oxidation}, volume = {147}, year = {2025}, }
• (2025). Dimensional reduction guides electronic structure evolution in the AnCu4–nSnS4 semiconductor series. JACS, 147(33), 29994--30008. (www)

  @article{ , abstract = {The search for new functional materials with tunable properties remains a central challenge in chemistry, particularly for applications in energy and electronics. In this work, we present a framework for predictive crystal design in alkali metal chalcogenides that enables controlled dimensional reduction of a parent covalent motif, yielding a broad range of electronic structures, which systematically evolve from one parent to the other. We present 11 new members of the A n Cu 4– n SnS 4 family (A = alkali metal; n = 0–4), which reduce the three-dimensional (3D) covalent network of Cu 4 SnS 4 into various 3D, 2D, 1D, and 0D [Cu 4– n SnS 4 ] n − motifs through the substitution of Cu with alkali metals of various radii. The end members of the family set the range in achievable band gaps at 0.99 eV for fully covalent Cu 4 SnS 4 ( n = 0) and 3.38 eV for K 4 SnS 4 ( n = 4) with 0D [SnS 4 ] n − tetrahedra. As the dimensionality of [Cu 4– n SnS 4 ] n − systematically reduces within A n Cu 4– n SnS 4 ( n = 1–3), a stepwise increase in band gap energy occurs through a gradual decrease in the energy of the valence band maximum and an increase in the conduction band minimum, with an increase in the effective masses of charge carriers. Furthermore, irrespective of the alkali metal, the thermal stability decreases with decreasing [Cu 4– n SnS 4 ] n − dimensionality within the quaternary members. Most importantly, we demonstrate that predictable crystal structure and property evolution for a given composition space is possible by deriving a general formula based on substituting the covalent metals of a parent structure with alkali metals.}, archive = {J_JACS}, author = {Michael A. Viti and Zhi Li and Christopher Wolverton and Mercouri G. Kanatzidis}, doi = {10.1021/jacs.5c07366}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29994--30008}, shortjournal = {J. Am. Chem. Soc.}, title = {Dimensional reduction guides electronic structure evolution in the AnCu4–nSnS4 semiconductor series}, volume = {147}, year = {2025}, }
• (2025). Unveiling an ultrareduced state of heme in myoglobin. JACS, 147(33), 29983--29993. (www)

  @article{ , abstract = {Heme proteins are essential metalloproteins with diverse biological roles, and these functions are facilitated by the heme’s ability to adopt multiple oxidation states, with Fe(II), Fe(III), and Fe(IV) being the most commonly observed. While highly reduced heme states beyond Fe(II) have been studied in synthetic complexes, their presence and characterization in native hemoproteins have remained largely unexplored. In this study, we report a full conversion of sperm whale myoglobin (Mb) to an ultrareduced state through chemical reduction under physiologically relevant conditions. Extensive spectroscopic analyses reveal a concerted proton-coupled two-electron reduction of the porphyrin macrocycle, forming a novel ultrareduced species. The identity of this ultrareduced Mb was determined to be a two-electron reduced product of deoxyMb, Por(2e)Fe(II)-Mb. These experimental data indicate that the reduction reaction is porphyrin ligand-centered, and proton transfer might also be involved, generating a high-spin ( S = 2) Fe(II) species in a native heme protein. The electron-rich nature of Por(2e)Fe(II)-Mb enables it to perform a two-electron reduction of NO to N 2 O via a ferrous-nitrosyl intermediate state. These findings expand our understanding of ultrareduced heme iron states in hemoproteins and their potential applications in biochemical and biotechnological fields.}, archive = {J_JACS}, author = {Yunling Deng and Therese Albert and Casey Van Stappen and Philip M. Palacios and Maria L. Amador and Sudharsan Dwaraknath and Yisong Guo and Pierre Moënne-Loccoz and Yi Lu}, doi = {10.1021/jacs.5c07257}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29983--29993}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling an ultrareduced state of heme in myoglobin}, volume = {147}, year = {2025}, }
• (2025). Tuning the hydrogen evolution reaction activity and mechanism on pt via nano-confinement of interfacial water. JACS, 147(33), 29977--29982. (www)

  @article{ , abstract = {Water structuring critically influences reactivity in aqueous electrocatalysis, yet the roles of interfacial water networks in electrode kinetics remain poorly defined. Here, we use the hydrogen evolution reaction (HER) on Pt in acidic media to investigate how modifications to the bulk and interfacial water networks, achieved through the introduction of dimethyl sulfoxide (DMSO), alter HER kinetics. Ultramicroelectrode measurements, with high mass transfer rate and low solution resistance, isolate intrinsic HER kinetics at the DMSO-free regions of the Pt surface. DMSO adsorption blocks HER, but activity on water-rich regions remains stable until the water-covered area drops below 30%, where HER kinetics sharply decline, and the hydrogen adsorption step becomes rate-limiting. Molecular dynamics (MD) simulations reveal that the adsorbed DMSO confines the interfacial water clusters and disrupts the hydrogen bonding. When the resulting interfacial water clusters become sufficiently small, interfacial proton delivery is impeded, retarding the overall HER kinetics. These findings demonstrate how interfacial water confinement offers a strategy to modulate electrocatalysis beyond conventional surface modifications.}, archive = {J_JACS}, author = {Yang Tao and Keegan A. Lorenz-Ochoa and Lei Pan and Ziareena A. Al-Mualem and Carlos R. Baiz and Hang Ren}, doi = {10.1021/jacs.5c07325}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29977--29982}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the hydrogen evolution reaction activity and mechanism on pt via nano-confinement of interfacial water}, volume = {147}, year = {2025}, }
• (2025). Pushing sensitivity and specificity limits in native structural biology: 19F multinuclear dynamic nuclear polarization with magic angle spinning. JACS, 147(33), 29970--29976. (www)

  @article{ , abstract = {Understanding protein structures and their interactions within natural cellular environments is essential for deciphering cellular processes and advancing therapeutic development. Obtaining atomic-level information about protein structural changes in cellular contexts poses a significant challenge. Here, we introduce a 19 F-based, 1 H-assisted dynamic nuclear polarization (DNP) magic angle spinning (MAS) NMR approach that offers exceptionally high sensitivity and specificity, enabling background-free detection of target proteins in mammalian cells for atomic-level structural analysis. We demonstrate this methodology in A2780 cells for the human Cyclophilin A (CypA) protein, with a single fluorine atom incorporated in the sole tryptophan residue. We achieved significant sensitivity gains through 1 H– 19 F cross-polarization (CP), with subsequent 19 F– 13 C double CP providing unique structural information. Remarkably, using 1 H– 19 F– 13 C magnetization transfer allowed the selective detection of 13 C signals from CypA residues up to 6 Å away from the fluorine label. Taken together, our study establishes a framework for investigating protein structure, dynamics, and interactions in mammalian cells by DNP MAS NMR.}, archive = {J_JACS}, author = {Kumar Tekwani Movellan and Daniel Banks and Christian Reiter and James G. Kempf and Angela M. Gronenborn and Tatyana Polenova}, doi = {10.1021/jacs.5c06739}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29970--29976}, shortjournal = {J. Am. Chem. Soc.}, title = {Pushing sensitivity and specificity limits in native structural biology: 19F multinuclear dynamic nuclear polarization with magic angle spinning}, volume = {147}, year = {2025}, }
• (2025). Multiple catalytic branch points in the mechanism of pyrrolidine formation during kainoid biosynthesis leads to diverse reaction outcomes. JACS, 147(33), 29961--29969. (www)

  @article{ , abstract = {The biosynthesis of neuroexcitatory kainoids requires radical-mediated cyclization of N -isoprenylated derivatives of l -glutamate catalyzed by nonheme iron and 2-oxoglutarate-dependent enzymes. While KabC and DabC from species of red algae catalyze this reaction during the biosynthesis of kainic acid and domoic acid, respectively, KabC can also produce a bicyclic lactone as an alternative reaction product. Herein, the radical-mediated catalytic pathways of KabC and DabC with the substrate N -dimethylallyl l -glutamate are fully mapped demonstrating as many as three different product determining steps and competing processes of hydroxylation, C–C bond formation, intramolecular nucleophilic addition, desaturation and C–C bond cleavage leading to four different products including kainic acid, a bicyclic lactone, a hydroxylated product and oxidative rearrangement concomitant with elimination of formaldehyde. The reaction proceeds via stereoselective abstraction of the pro-R H atom from C3 of the substrate followed by radical cyclization that outcompetes canonical hydroxy rebound. Evidence of radical triggered cyclization is provided by the observation of a ring-opened product when a cyclopropyl analogue is assayed. Measurement of primary deuterium kinetic isotope effects less than 2 on the product determining step of desaturation versus lactonization suggests the former involves proton coupled electron transfer (PCET) rather than an acid-base reaction. Furthermore, involvement of a cationic species is supported by detection of a rearrangement product. Collectively, these observations not only reveal the complexity of pyrrolidine formation during kainoid biosynthesis but also its amenability to changes in reaction outcome, which is of use for understanding the control of unstable intermediates during radical-mediated enzymatic reactions.}, archive = {J_JACS}, author = {Tzu-Yu Chen and Mark W. Ruszczycky and Angela Yao and Xiaojun Li and Tun-Cheng Chien and Wei-chen Chang}, doi = {10.1021/jacs.5c07226}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29961--29969}, shortjournal = {J. Am. Chem. Soc.}, title = {Multiple catalytic branch points in the mechanism of pyrrolidine formation during kainoid biosynthesis leads to diverse reaction outcomes}, volume = {147}, year = {2025}, }
• (2025). Unlocking a water coordination environment in co-based Metal–Organic frameworks for advanced nitrate-to-ammonia electroreduction. JACS, 147(33), 29949--29960. (www)

  @article{ , abstract = {Electrochemical nitrate reduction to ammonia ( e -NO 3 RR) offers a promising and sustainable alternative to the traditional Haber–Bosch process, enabling decentralized ammonia production under ambient conditions. However, the efficiency of e -NO 3 RR is limited by the sluggish reaction kinetics due to the high activation energy barriers, poor mass transport, and the weaker adsorption affinity of the catalyst surface. In this study, we report the design and synthesis of a stable three-dimensional cobalt-based metal–organic framework (HUST-38), constructed from benzene-1,4-dicarboxylate ligand and DABCO, featuring water coordination within its framework. Impressively, the as-prepared HUST-38 delivers a high NH 3 Faradaic efficiency of 95.7% and a high NH 3 yield rate of 13.38 mg h –1 mg cat –1 at −0.6 V vs RHE, significantly outperforming the control sample of HUST-39 (3.98 mg h –1 mg cat –1 , nonwater coordination) and the mostly reported single-site solid electrocatalysts. Various in situ measurements disclose that the labile solvent coordination in HUST-38 promotes water molecule accessibility to the catalytically active metal centers, hence augmenting localized *H enrichment and enhancing NO 3 – reduction. The theoretical calculations further substantiate the essential function of metal coordination microenvironments in modulating the electrocatalytic process, specifically by reducing free energy barriers associated with key reaction intermediates and enhancing the adsorption and desorption kinetics of reactants and products, ultimately leading to improved electrocatalytic activity and efficiency. The present work provides a foundation for the structural design of metal organic frameworks to develop efficient electrocatalysts.}, archive = {J_JACS}, author = {Pandi Muthukumar and Zakir Ullah and Xia Zhang and Habib Ullah and Yuxiao Liu and Linfeng Li and Shengji Tian and Xianlong Zhou and Savarimuthu Philip Anthony and Yunpeng Zuo and Chade Lv and Xin Wang and Chundong Wang}, doi = {10.1021/jacs.5c07066}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29949--29960}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking a water coordination environment in co-based Metal–Organic frameworks for advanced nitrate-to-ammonia electroreduction}, volume = {147}, year = {2025}, }
• (2025). Ion–Dipole interactions modulated anion-reinforced solvation chemistry for advanced wide-temperature sodium-ion full batteries. JACS, 147(33), 29939--29948. (www)

  @article{ , abstract = {Wide-temperature sodium-ion batteries (SIBs) are considered promising candidates for large-scale energy storage systems under extreme temperature conditions. However, SIBs generally suffer from an unstable electrode–electrolyte interface (EEI) at high temperature and sluggish interfacial kinetics at low temperature, resulting in poor temperature tolerance with fast capacity degradation. Herein, a weakly coordinated carboxylate ester cosolvent, methyl butyrate, is employed to modulate the ion–dipole interactions in fluorine-free ester-based electrolyte for the anion-reinforced solvation chemistry. The unique solvent chemistry enables the construction of stable anion-derived inorganic-rich EEI on both cathode and anode surfaces while simultaneously reducing the desolvation energy barrier, thereby significantly enhancing the interfacial stability and kinetics. Therefore, the Prussian blue||hard carbon (PB||HC) full cell demonstrates a stable operation at a wide temperature range from −20 to 100 °C. Noticeably, the PB||HC 18650 cylindrical cell delivers a superior capacity retention of 91.41% after 230 cycles at an elevated temperature of 55 °C. This work provides valuable guidance for designing fluorine-free ester-based electrolytes through rational modulation of ion–dipole interactions, paving a promising pathway for wide-temperature sodium-ion full batteries.}, archive = {J_JACS}, author = {Yun Wan and Xiaoyan Shi and Zhiming Zhou and Wenxi Kuang and Xu Xu and Xiaosa Zhang and Xinhui Zeng and Xunzhu Zhou and Junxiang Liu and Shu-Lei Chou and Lin Li}, doi = {10.1021/jacs.5c07004}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29939--29948}, shortjournal = {J. Am. Chem. Soc.}, title = {Ion–Dipole interactions modulated anion-reinforced solvation chemistry for advanced wide-temperature sodium-ion full batteries}, volume = {147}, year = {2025}, }
• (2025). Intrastrand peptide staples that promote β-sheet folding, self-assembly, and amyloid seeding. JACS, 147(33), 29930--29938. (www)

  @article{ , abstract = {Side chain stapling of cysteine (Cys) residues offers convenient entry into constrained peptides with enhanced bioactivity and bioavailability. Despite its widespread application in the constraint of α-helical, PPII, and loop conformations, the stabilization of β-sheet folds via intrastrand side chain Cys stapling remains largely unexplored. Here, we demonstrate that i → i +2 stapling with E -butenyl, butynyl, and m -xylyl linkers significantly enhances the folded population of two distinct β-hairpin model peptides. High-resolution NMR structures reveal that these staples support canonical β-sheet backbone torsions and stabilize cross-strand interactions. Leveraging the maintenance of intact backbone hydrogen-bonding edges, we employed i → i +2 side chain macrocyclization in the design of constrained β-arch peptides derived from the tau protein. We show that intrastrand stapling of a nonaggregation-prone segment promotes self-assembly into β-sheet-like filaments. The resulting filaments also seed the aggregation of endogenous tau in a cell-based assay in a macrocycle- and sequence-dependent manner. These findings establish di-Cys i → i +2 stapling as a versatile and synthetically accessible method to stabilize β-sheet structure and modulate the self-assembly of seed-competent amyloidogenic peptides.}, archive = {J_JACS}, author = {Abha Dangi and Isaac J. Angera and Juan R. Del Valle}, doi = {10.1021/jacs.5c06944}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29930--29938}, shortjournal = {J. Am. Chem. Soc.}, title = {Intrastrand peptide staples that promote β-sheet folding, self-assembly, and amyloid seeding}, volume = {147}, year = {2025}, }
• (2025). Tailoring solvent-mediated CO2 reservoirs at heterointerfaces for enhanced electrochemical CO2-to-C2H4 conversion. JACS, 147(33), 29919--29929. (www)

  @article{ , abstract = {Transforming waste CO 2 into value-added fuels and chemicals, while simultaneously enabling renewable electricity storage, presents a viable strategy for achieving a sustainable energy economy. However, efficient conversion to C 2+ products remains challenging, primarily due to the low CO 2 concentration at the catalyst surface in aqueous environments. Herein, we addressed this issue by designing Cu 2 O-MgO catalysts with abundant nanointerfaces serving as effective CO 2 reservoirs under aqueous conditions. Ab initio molecular dynamics simulations demonstrated that these interfaces substantially enhanced the CO 2 stabilization at the surface, effectively inhibiting their displacement by interfacial water molecules. This localized CO 2 enrichment facilitated C–C coupling kinetics and selectively promoted the formation of target products. Building on these findings, we synthesized a model catalyst featuring abundant Cu 2 O-MgO nanointerfaces and evaluated its performance in aqueous media. Remarkably, flowing electrolyzer tests demonstrated a Faradaic efficiency of 67% for ethylene at a current density of ∼ 240 mA·cm –2 . Subsequent mechanistic investigations combining spectroscopy experiments and theoretical calculation simulations demonstrated that the surface-enriched CO 2 enhanced the CO* coverage at the Cu active sites, thereby promoting ethylene production through facilitated C–C coupling. This study pioneers the rational design of heterogeneous catalysts for selective CO 2 RR toward value-added chemicals with potential applications extending to diverse electrocatalytic processes.}, archive = {J_JACS}, author = {Jing Yang and Chengkai Jin and Di Si and Fusong Kang and Fen Qiao and Junfeng Wang and Dongjing Liu and Lilin Zhang and Tian Tian and Xunhua Zhao and Zhou Yu and Kang Chen and Heng-Quan Chen and Xiao-Shun Zhou}, doi = {10.1021/jacs.5c06799}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29919--29929}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailoring solvent-mediated CO2 reservoirs at heterointerfaces for enhanced electrochemical CO2-to-C2H4 conversion}, volume = {147}, year = {2025}, }
• (2025). Surface entropy mediated hydrogen spillover on Au/TiO2: Influences of strongly adsorbed water on h2 adsorption thermodynamics. JACS, 147(33), 29908--29918. (www)

  @article{ , abstract = {Hydrogen spillover, a poorly understood adsorption phenomenon, plays an important role in hydrogen storage, catalytic hydrogenation, and energy conversion processes. While widely invoked to explain anomalous observations, the fundamental mechanisms underlying spillover remain under debate, particularly regarding the influence of surface adsorbates, such as water. In this study, we investigate how strongly adsorbed water (SAW) impacts hydrogen spillover (H*) on Au/TiO 2 catalysts using in situ Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). By carefully correlating IR and TGA data, we quantify the relationship between water coverage and spillover. At low to moderate temperatures (<200 °C), SAW resides primarily on Ti Lewis acid sites, while hydrogen spillover is associated with surface hydroxyl groups. Our findings reveal that even though H* and SAW do not directly compete for surface adsorption sites, SAW suppresses H*. Van’t Hoff studies indicate SAW suppresses spillover by modifying the surface entropy of the titania, presumably by perturbing multiple proton transfer equilibria across the support surface. Maintaining constant water and hydroxyl coverage over a modest temperature range allowed for the determination of reliable thermodynamic parameters for hydrogen spillover on titania, yielding a slightly exothermic heat of adsorption (−7 ± 1 kJ/mol H*). These insights highlight the indirect role that surface water can play in catalytic reactions involving hydrogen spillover and offer a new perspective on catalyst design and optimization for hydrogen-involved reactions. This work also highlights the importance of considering the entropy of oxide surfaces in understanding catalysis over oxides.}, archive = {J_JACS}, author = {Tae Yong Yun and Audrey M. Battiste and Angela Pathickal Abraham and Kelle D. Hart and Bert D. Chandler}, doi = {10.1021/jacs.5c06813}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29908--29918}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface entropy mediated hydrogen spillover on Au/TiO2: Influences of strongly adsorbed water on h2 adsorption thermodynamics}, volume = {147}, year = {2025}, }
• (2025). Precise chemical lithiation: A pathway to superior li-enriched Li1+xNCM523 cathodes for long life anode-free li metal batteries. JACS, 147(33), 29895--29907. (www)

  @article{ , abstract = {Developing lithium-enriched cathodes, such as Li 1+ x NCM523 ( x ≥ 0), offers a promising approach to boost the cycling life of anode-free lithium metal batteries (AFLMBs). However, the traditional electrochemical prelithiation method is confined to laboratory studies, while conventional chemical prelithiation using highly reductive reagents like biphenyllithium (0.25 V vs Li + /Li) often causes severe surficial excessive-lithiation and structural degradation, compromising battery performance. Herein, we propose a precise chemical lithiation strategy using 9-fluorenone lithium (FL-2Li) as an optimal lithiation reagent to achieve controllable and uniform lithium insertion in Li 1+ x NCM523 cathodes. The redox potential of FL-2Li reagent (1.32 V vs Li + /Li) is strategically matched─slightly below the lithiation potential of Li 1.7 NCM523 (1.50 V) to allow tolerable overlithiation, yet above that of Li 2.0 NCM523 (1.0 V) to avoid excessive-lithiation, and significantly higher than Li 4.0 NCM523 (Li 2 O/TM, 0.75 V) to prevent irreversible structural collapse. This design yields a superior Li 1.7 NCM523 cathode with a homogeneous bulk-lithiated structure, thereby eliminating the core–shell effects typically observed with conventional reagents. Consequently, the chemically prelithiated Li 1.7 NCM523 exhibits superior electrochemical performance, achieving 86.16% capacity retention after 100 cycles at 1C in Cu||Li 1.7 NCM523 anode-free cells. Our findings established a versatile framework for the rational selection of lithiation reagents, providing critical theoretical insights and practical guidance for designing high-performance, scalable lithium-enriched cathodes, which may potentially advance battery technology for electric vehicles and energy storage systems.}, archive = {J_JACS}, author = {Tingcan Li and Ruimin Gao and Xuanze Wang and Mingyu Zhang and Mingyuan Jiang and Juzheng Zhang and Ran Tan and Jike Wang and Xinping Ai and Pei Xiong and Liumin Suo and Jiangfeng Qian}, doi = {10.1021/jacs.5c06681}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29895--29907}, shortjournal = {J. Am. Chem. Soc.}, title = {Precise chemical lithiation: A pathway to superior li-enriched Li1+xNCM523 cathodes for long life anode-free li metal batteries}, volume = {147}, year = {2025}, }
• (2025). Multistate structure determination and dynamics analysis reveals a unique ubiquitin-recognition mechanism in ubiquitin C-terminal hydrolase. JACS, 147(33), 29884--29894. (www)

  @article{ , abstract = {Despite accumulating evidence that protein dynamics is indispensable for understanding the structural basis of biological activities, it remains challenging to visualize the spatial description of the dynamics and to associate transient conformations with their molecular functions. We have developed a new NMR protein structure determination method for the inference of multistate conformations using multiple types of NMR data, including paramagnetic NMR and residual dipolar couplings, as well as conventional NOEs. Integration of these data in the structure calculation permits delineating accurate ensemble structures of biomacromolecules. Applying the method to yeast ubiquitin hydrolase 1, we find large dynamics of its N-terminus (gating lid) and crossover loop surrounding the active site for ubiquitin-recognition and proteolysis. The N-terminus (gating lid) moves into and out of the crossover loop, suggesting their underlying functional significance. Our results, including those from biochemical analysis, show that large motion surrounding the active site contributes strongly to the efficiency of the enzymatic activity.}, archive = {J_JACS}, author = {Mayu Okada and Yutaka Tateishi and Eri Nojiri and Tsutomu Mikawa and Sundaresan Rajesh and Hiroki Ogasa and Takumi Ueda and Hiromasa Yagi and Toshiyuki Kohno and Takanori Kigawa and Ichio Shimada and Peter Güntert and Yutaka Ito and Teppei Ikeya}, doi = {10.1021/jacs.5c06502}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29884--29894}, shortjournal = {J. Am. Chem. Soc.}, title = {Multistate structure determination and dynamics analysis reveals a unique ubiquitin-recognition mechanism in ubiquitin C-terminal hydrolase}, volume = {147}, year = {2025}, }
• (2025). Deubiquitinase-targeting chimeras mediated stabilization of tumor suppressive e3 ligase proteins as a strategy for cancer therapy. JACS, 147(33), 29875--29883. (www)

  @article{ , abstract = {Targeted protein stabilization has emerged as a promising therapeutic strategy to combat various human diseases linked to aberrant protein degradation. However, the deubiquitinase-targeting chimera (DUBTAC) technology is still in its infancy, with only a few proteins being successfully stabilized. To this end, the stabilization of tumor suppressor proteins represents a critical therapeutic strategy to combat cancer, as their loss-of-function mutations and reduced expression are frequently implicated in the pathogenesis of diverse types of human cancer. In this study, we present an innovative PRO–DUBTAC platform that, for the first time, stabilizes tumor-suppressive E3 ubiquitin ligases as a novel anticancer therapeutic approach. Through the conjugation of E3 ligase ligands with a small-molecule ligand of the deubiquitinase OTUB1 via a linker, we developed two series of PRO–DUBTACs─VHL-DUBTAC and KEAP1-DUBTAC─that effectively stabilize the tumor-suppressive E3 ligases VHL and KEAP1 in cells, respectively, in an OTUB1-dependent manner to retard tumor cell growth. PRO–DUBTAC could be a versatile and generalizable platform for the selective stabilization of tumor-suppressor E3 ligases, thereby opening new therapeutic avenues for targeted cancer therapies by harnessing the tumor-suppressive potential of E3 ligases.}, archive = {J_JACS}, author = {Li Chen and Zhijie Deng and Yan Xiong and Jing Liu and Daoyuan Huang and Jingchao Wang and Yong Chen and Hiroyuki Inuzuka and Ling Xie and Xian Chen and Jian Jin and Wenyi Wei}, doi = {10.1021/jacs.5c06306}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29875--29883}, shortjournal = {J. Am. Chem. Soc.}, title = {Deubiquitinase-targeting chimeras mediated stabilization of tumor suppressive e3 ligase proteins as a strategy for cancer therapy}, volume = {147}, year = {2025}, }
• (2025). Breaking the birefringence barrier in B–O crystals via B–C π-scaffolding. JACS, 147(33), 29864--29874. (www)

  @article{ , abstract = {Optically anisotropic crystals exhibiting large birefringence (Δ n ) are crucial for manipulating polarized light in optical technologies. While traditional borates offer structural diversity and inherent anisotropy, achieving large Δ n (>0.3) combined with short-wave UV transparency remains challenging, and surpassing the Δ n = 0.5 threshold has been unrealized in this material class. Herein, we employ a B–C π-scaffolding strategy to introduce 2-halogen-pyridine-5-boronic acid, PyXB(OH) 2 , as novel π-conjugated B–O functional modules. Combining these with either oxalate (C 2 O 4 ) or nitrate (NO 3 ) anions yielded four new birefringent crystals: HPyXB(C 2 O 4 )(OH) (X = Cl, Br) and [HPyXB(OH) 2 ]·(NO 3 ) (X = Cl, Br). Crucially, the crystal packing differs significantly between the two series. In HPyXB(C 2 O 4 )(OH), the constituent π-units (PyX and C 2 O 4 ) adopt a noncoplanar arrangement with a large dihedral angle. In contrast, specific intermolecular interactions (dominated by hydrogen bonds and electrostatic interactions) within [HPyXB(OH) 2 ]·(NO 3 ) enforce a highly synergistic, near-coplanar alignment of the [HPyXB(OH) 2 ] + moiety and the NO 3 anion. This optimized structural arrangement leads to exceptionally large birefringence for the [HPyXB(OH) 2 ]·(NO 3 ) series, with measured Δ n values reaching 0.533 for X = Cl (calculated 0.554) at 546 nm. These values drastically exceed those of the HPyXB(C 2 O 4 )(OH) counterparts (Δ n = 0.182–0.194) and are more than four times larger than that of the commercial benchmark α-BaB 2 O 4 (Δ n = 0.12@546 nm). Significantly, [HPyXB(OH) 2 ]·(NO 3 ) represents the first B–O containing crystal to surpass the 0.5 birefringence threshold, validating B–C π-scaffolding as a powerful strategy for designing ultrahigh-performance birefringent materials.}, archive = {J_JACS}, author = {Jia-Jia Li and Miao-Bin Xu and Ming-Chang Wang and Zhi Lin and Yuan Lin and Yun-Xia Hu and Jia-Min Lian and Jin Chen and Ke-Zhao Du}, doi = {10.1021/jacs.5c06328}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29864--29874}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking the birefringence barrier in B–O crystals via B–C π-scaffolding}, volume = {147}, year = {2025}, }
• (2025). Application of solid higher-order zincates enables a Ni/Lassaletta-ligand-catalyzed, atroposelective negishi cross-coupling reaction. JACS, 147(33), 29852--29863. (www)

  @article{ , abstract = {A novel atroposelective Negishi cross-coupling reaction employing recently discovered solid higher-order zincates as highly transmetalating-active reagents has been developed. Applying an earth-abundant Ni/Lassaletta-ligand-based catalyst, highly useful atropoisomeric biaryls were prepared in generally high yields and enantiomeric purities. The catalyst showed high activity toward a large variety of (pseudo)halide substrates and higher-order zincates of different synthetic origins, as well as significant catalyst control, even when employing a chiral sulfoxide substrate. To highlight the synthetic value of our method described herein, a novel atropoisomeric phosphasilinane ligand and a naphthylisoquinoline alkaloid were synthesized. The corresponding reaction mechanism has been investigated based on control experiments, proceeding via a traditional closed-shell cycle involving Ni 0/II species.}, archive = {J_JACS}, author = {Damian Groß and Lennart Kirchhoff and Benedikt Schiller and Lukas Bucher and Oliver Trapp and Dino Berthold}, doi = {10.1021/jacs.5c06296}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29852--29863}, shortjournal = {J. Am. Chem. Soc.}, title = {Application of solid higher-order zincates enables a Ni/Lassaletta-ligand-catalyzed, atroposelective negishi cross-coupling reaction}, volume = {147}, year = {2025}, }
• (2025). Stable Metal–Organic electrocatalysts for anion-exchange membrane water electrolyzers by defect engineering. JACS, 147(33), 29838--29851. (www)

  @article{ , abstract = {Developing efficient and durable catalysts for the alkaline oxygen evolution reaction (OER) is vital to achieving practical anion-exchange membrane water electrolyzers (AEMWEs) for green hydrogen production. Here, we break the activity–stability trade-off of electrocatalysis by defect engineering of Ni-based metal–organic electrocatalysts (Ni-benzenedicarboxylate; Ni-BDC) through coordinating ferrocenecarboxylates (Fc) to the metal sites. Experimental results collectively reveal that the defect MOF (Ni-BDC:Fc_5:1) exhibits a high OER turnover frequency of 0.75 O 2 s –1 at 300 mV overpotential. Operando Raman spectroscopy and isotope-labeling electrochemical mass spectrometry measurements indicate the structure of Ni-BDC:Fc_5:1 is also more stable in service than that of pure Ni-BDC. The high activity and stability could be attributed to the moderate defects (i.e., unsaturated Ni sites) in the structure that not only increase the intrinsic activity and stability of the local active environment by inhibiting lattice oxygen exchange but also electrochemically activate the bulk of the catalysts by creating a porous network that facilitates internal H 2 O/OH – conduction with enhanced electronic conduction. Accordingly, an AEMWE employing Ni-BDC:Fc_5:1 as the OER catalyst delivers an industrial-level current density of 1 A cm –2 at 1.73 V cell and can be steadily operated for more than 120 h.}, archive = {J_JACS}, author = {Hongbin Xu and Daniel J. Zheng and Shuo Wang and Ethan Yupeng Zheng and Yilin Zhang and Tongchao Liu and Junxiang Liu and Davide Menga and Junghwa Kim and Jen-Hung Fang and Xiao Wang and Zhen Zhang and Lena Schröck and Jiaqi Wang and Sungsik Lee and Sunmoon Yu and Haldrian Iriawan and Guanzhou Zhu and Yuriy Román-Leshkov and Ju Li and Yang Shao-Horn}, doi = {10.1021/jacs.5c06156}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29838--29851}, shortjournal = {J. Am. Chem. Soc.}, title = {Stable Metal–Organic electrocatalysts for anion-exchange membrane water electrolyzers by defect engineering}, volume = {147}, year = {2025}, }
• (2025). α-synuclein drives SNARE-dependent tubular remodeling of vesicles. JACS, 147(33), 29829--29837. (www)

  @article{ , abstract = {α-Synuclein (α-syn) disrupts synaptic vesicle architecture in Parkinson’s disease (PD), yet the underlying mechanisms remain unclear. Here, we identify a previously unrecognized phenomenon in which α-syn (≥20 μM) rapidly induces SNARE-dependent tubular protrusions on highly curved small unilamellar vesicles (∼45 nm in diameter). This process requires functional v- and t-SNAREs, as neither v-SNARE nor t-SNARE alone, nor predocked SNARE complexes or CDV-treated SNARE liposomes, support tubulation. Notably, the familial PD-associated mutations A30P and E46K enhance tubule formation, whereas A53T exhibits minimal activity. Disrupting the α-syn–VAMP2 interaction abolishes tubulation, directly linking this interface to vesicle remodeling. Tubule formation increases with α-syn concentration, impairs SNARE-mediated membrane fusion, and significantly modulates α-syn liquid–liquid phase separation (LLPS), underscoring its pathological relevance. These findings reveal a novel mechanism by which α-syn remodels vesicle architecture, providing deeper insights into synaptic dysfunction in PD.}, archive = {J_JACS}, author = {Qun Li and Tao Hu and Fan Li and Yutong Xing and Zhenyong Wu}, doi = {10.1021/jacs.5c06021}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29829--29837}, shortjournal = {J. Am. Chem. Soc.}, title = {α-synuclein drives SNARE-dependent tubular remodeling of vesicles}, volume = {147}, year = {2025}, }
• (2025). High-luminescence efficiency NIR-II nanocrystals via hierarchical confinements for imaging-guided surgery of acute intestinal ischemia. JACS, 147(33), 29815--29828. (www)

  @article{ , abstract = {Among the diverse challenges encountered by fluorescence imaging in the second near-infrared region (NIR-II, 1000–1700 nm), achieving high quantum yields (QYs) for contrast agents is critical yet rarely addressed. Herein, we demonstrate an approach to overcoming this issue through rational structural design that leverages hierarchical confinements at both molecular and aggregate levels. Through an alteration of methyl substituents, the rotational freedom of aromatic rings is effectively reduced, facilitating the formation of rigid mortise-and-tenon joints within the crystal lattice. As a result, an absolute QY of 9.7% is achieved in the crystal state. Moreover, the abundant intermolecular noncovalent interactions endow B-ToMeT with crystallization ability, enabling the assembly of nanocrystals (NCs) formed in aqueous solution, whose emission peak is 970 nm with an exceptionally high relative QY of 28.2%. This underscores the remarkable advantage of the hierarchical confinement strategy. By using the ultrabright NCs for real-time monitoring of intestinal vessels in the living system, early diagnosis and surgical treatment of acute intestinal ischemia can be realized, indicating the great potential of this molecular design for high-performance NIR-II materials in in vivo imaging and surgery navigation.}, archive = {J_JACS}, author = {Fulong Ma and Rongyuan Zhang and Bingzhe Wang and Zongwen Liang and Siwei Zhang and Jinhui Jiang and Haozhe Tan and Guichuan Xing and Ryan T. K. Kwok and Jacky W. Y. Lam and Zheng Zhao and Ben Zhong Tang}, doi = {10.1021/jacs.5c05981}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29815--29828}, shortjournal = {J. Am. Chem. Soc.}, title = {High-luminescence efficiency NIR-II nanocrystals via hierarchical confinements for imaging-guided surgery of acute intestinal ischemia}, volume = {147}, year = {2025}, }
• (2025). Eyes on the prize: Tracking electron transfer in G-rich duplex and quadruplex DNA using enantiopure ruthenium polypyridyl infrared redox probes. JACS, 147(33), 29801--29814. (www)

  @article{ , abstract = {Photosensitized damage by the mechanism of direct 1e – transfer from a nucleobase to the metal complex is a complementary approach to type I and type II methods of photodynamic therapy. In this ultrafast spectroscopic study we report the ability of a nitrile infrared redox probe to report on the photo-oxidation of guanine-rich DNA, comprising persistent runs of guanine, by the dppz-10-CN containing complex [Ru(TAP) 2 (dppz-10-CN)] 2+ ( 1 2+ ), dppz-10-CN = 10-cyano-dipyrido[3,2-a:2′,3′-c]phenazine and TAP = 1,4,5,8-tetraazaphenanthrene. Our study reveals the ability of the enantiomers of 1 2+ to photo-oxidize guanine in double-stranded and quadruplex DNA. Transient visible absorption reveals a high yield of the formation of the photoreduced metal complex due to photo-oxidation of guanine in the quadruplex-bound 1 2+ systems, and that this is greater for the Λ enantiomer. Spectro-electrochemical and computational studies indicate the role of the dppz-10-CN as the preferred site of reduction, while time-resolved electronic absorption (TrA) spectroscopy highlights the impact of the enantiomers on the yield of photo-oxidation in the DNA systems. Notably, time-resolved infrared (TRIR) spectroscopy allows comprehensive tracking of the photo-oxidation dynamics by monitoring four key components, namely: (1) the transient band of the Ru/TAP-based lowest 3 MLCT excited state, (2) bleach bands associated with DNA bases in close proximity to the excited state “site effect”, (3) the guanine radical cation band at ca. 1700 cm –1 and (4) the amplification of the red-shifted nitrile stretching vibration of the transient dppz-reduced complex. Together, these results allow detailed profiling of photoinduced electron transfer in DNA-bound ruthenium(II) polypyridyl complex systems and highlight the potential of such redox probes. Overall, this study presents an important insight regarding the nature of charge transfer in a Hoogsteen-bound guanine quadruplex compared to Watson-Crick GC base pairings.}, archive = {J_JACS}, author = {Mark Stitch and Martin Pižl and Niamh Lehane and Gregory M. Greetham and František Hartl and Michael Towrie and Susan J. Quinn}, doi = {10.1021/jacs.5c05736}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29801--29814}, shortjournal = {J. Am. Chem. Soc.}, title = {Eyes on the prize: Tracking electron transfer in G-rich duplex and quadruplex DNA using enantiopure ruthenium polypyridyl infrared redox probes}, volume = {147}, year = {2025}, }
• (2025). Metal–Organic Framework/Au Core/Shell nanocubes for spatially aligned molecular analysis and molecular-fingerprint sensing with surface-enhanced raman scattering. JACS, 147(33), 29792--29800. (www)

  @article{ , abstract = {The spatial configuration of molecules on metal surfaces is a key parameter in reliably modulating the surface-enhanced Raman scattering (SERS) signals quantitatively, but the methods and platforms for controlling this configuration are not well established. Here, we utilized metal–organic frameworks (MOFs) to periodically and spatially arrange molecules in synthesizing zeolite imidazole framework-8 (ZIF-8)/Au core/shell nanocubes (ZACS NCs) for quantitative SERS. The uniform plasmonic Au nanoshell deposition onto ZIF-8 NCs was accomplished by the (100) facets of ZIF-8 and the use of cetyltrimethylammonium chloride (CTAC). In ZACS NCs, an interfacial Au/Zn alloy layer is between the AuNC core and ZIF-8 shell, which can modulate the plasmonic properties of the ZACS NCs. Single-particle Raman analysis suggests that characteristic vibrational Raman moieties of 2-methylimidazole (2-mIM) ligands have a clear laser polarization angle dependence. Importantly, the micro-Raman analysis results from all of the eight different vibrational moieties of ZIF-8 display highly linear relationships between particle concentration and SERS intensity, verifying that the spatially aligned configuration and periodicity of these moieties within ZIF-8 generate quantitative SERS signals. Finally, it was shown that the characteristic Raman peaks of 2-mIM ligands from the ZACS NCs can be used to detect and differentiate various targets of interest. This opens a new paradigm for versatile plasmonic porous materials.}, archive = {J_JACS}, author = {Hyeon-Jeong Shin and Kyungin Choi and Jiwoong Son and Munjeong Kim and Sarah S. Park and Jwa-Min Nam}, doi = {10.1021/jacs.5c05420}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29792--29800}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal–Organic Framework/Au Core/Shell nanocubes for spatially aligned molecular analysis and molecular-fingerprint sensing with surface-enhanced raman scattering}, volume = {147}, year = {2025}, }
• (2025). Synergistic engineering of electronic structure and interfacial field via a 3D heterostructure for stable sodium metal batteries. JACS, 147(33), 29779--29791. (www)

  @article{ , abstract = {Uneven distribution of electric field and sodium ion on the sodium metal anode surface is identified as the key factor triggering dendrite growth, which severely compromises the energy density and cycle life of batteries. Herein, a sodiophilic heterostructure with Sn 4 P 3 nanoparticles encapsulated in N/P codoped graphene-like nanotubes (Sn 4 P 3 /NPGTs) is synthesized through the integration of chemical vapor deposition and in situ phosphorization. Rich active sites constructed by N/P codoping modulate the local electronic structure effectively, facilitating uniform Na + distribution and adsorption while reducing the nucleation overpotential. The interfacial electric field formed at the heterogeneous interface exerts electrostatic forces on Na + , inducing ionic rectification, directional migration, and confined deposition of Na + within the channels. In addition, the synergistic mechanism for improved Na + deposition behavior is unraveled in-depth through in situ optical microscopy characterization, COMSOL simulations, in situ XRD analysis, and density functional theory calculations at multiple scales. Asymmetric cells remain stable for 1500 cycles at 3.0 mA cm –2 and 1.0 mAh cm –2 , and the corresponding symmetric cells display a lifespan exceeding 2000 h. Pairing with either low-voltage (NaTi 2 (PO 4 ) 3 ) or high-voltage (Na 3 V 2 (PO 4 ) 3 ) cathodes, the full cells exhibit excellent cycling stability.}, archive = {J_JACS}, author = {Hui Zong and Shang-Qi Li and Xiaoyang Zheng and Xue-Yan Wu and Se−Si Li and Qian-Qian Hao and Xing-He Zhao and Yao-Wen Zhang and Kai-Xue Wang and Xiaowei Song and Jie-Sheng Chen}, doi = {10.1021/jacs.5c05156}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29779--29791}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic engineering of electronic structure and interfacial field via a 3D heterostructure for stable sodium metal batteries}, volume = {147}, year = {2025}, }
• (2025). Overcoming the activity-stability trade-off in electrocatalysts via unconventional two-step structural reconstructions of amorphous oxides. JACS, 147(33), 29767--29778. (www)

  @article{ , abstract = {The activation of lattice oxygen in oxide catalysts via structural reconstruction is critical for optimizing the catalytic performance in oxidation–reduction systems. However, in electrochemical O 2 evolution, the structural transformations preceding electrochemical reconstruction and their impact on the resulting structural inhomogeneity have long remained insufficiently understood. Here, we activate the lattice oxygen of the W-doped Co–Fe amorphous oxide through spontaneous and electrochemical bulk reconstructions. Chemical state evolution studies reveal that the reconstructed active γ-layered double hydroxide (LDH), characterized by local structural inhomogeneity, promotes the formation of reactive nonbonding oxygen states, achieving Co 3+ -catalyzed O 2 evolution. The catalyst demonstrates a cell voltage of 1.69 V at 1 A cm –2 with stable operation for 600 h in anion-exchange membrane water electrolyzers. Using in situ spectroscopic techniques, we establish dynamic correlations among Co ion oxidation states, phase structure, and lattice oxygen activation during reconstruction. Notably, we provide the first experimental evidence of a potential-dependent mechanistic transition governing both the activity and the stability of the catalyst. These findings deepen our understanding of structure-performance relationships in electrocatalysts and highlight the pivotal role of the chemical state evolution in catalytic processes.}, archive = {J_JACS}, author = {Guichen Gao and Guangshe Li and Taotao Huang and Jiawei Wan and Zhibin Geng and Haitong Tang and Xu Zhao and Shilong Fu and Luyi Sun and Jiong Li and Liping Li}, doi = {10.1021/jacs.5c04970}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29767--29778}, shortjournal = {J. Am. Chem. Soc.}, title = {Overcoming the activity-stability trade-off in electrocatalysts via unconventional two-step structural reconstructions of amorphous oxides}, volume = {147}, year = {2025}, }
• (2025). A symbol of immortality: Evidence of honey in bronze jars found in a paestum shrine dating to 530–510 BCE. JACS, 147(33), 29756--29766. (www)

  @article{ , abstract = {This study re-examines a 2500-year-old residue found in bronze jars at an underground shrine in Paestum (Italy), previously identified as a wax/fat/resin mixture excluding honey from its composition. Our multianalytical approach detected lipids, saccharide decomposition products, hexose sugars, and major royal jelly proteins supporting the hypothesis that the jars once also contained honey/honeycombs. The research highlights the value of reinvestigating archeological residues in museums with advanced biomolecular techniques and offers a more specific method for detecting bee products in ancient contexts.}, archive = {J_JACS}, author = {Luciana da Costa Carvalho and Elisabete Pires and Kelly Domoney and Gabriel Zuchtriegel and James S. O. McCullagh}, doi = {10.1021/jacs.5c04888}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29756--29766}, shortjournal = {J. Am. Chem. Soc.}, title = {A symbol of immortality: Evidence of honey in bronze jars found in a paestum shrine dating to 530–510 BCE}, volume = {147}, year = {2025}, }
• (2025). DNA-templated spatially controlled proteolysis targeting chimera for cyclin D1–CDK4/6 complex protein degradation. JACS, 147(33), 29742--29755. (www)

  @article{ , abstract = {Constraining proximity-based drugs, such as proteolysis targeting chimeras (PROTACs), into their bioactive conformation can significantly impact their selectivity and potency. However, traditional methods for achieving this often involve complex and time-consuming synthetic procedures. Here, we introduced an alternative approach by demonstrating DNA-templated spatially controlled PROTACs (DTACs), which leverage the programmability of nucleic acid-based self-assembly for efficient synthesis and offer precise control over inhibitors’ spacing and orientation. The resulting constructs revealed distance- and orientation-dependent selectivity and degradation potency for the Cyclin D1–CDK4/6 protein complex in cancer cells. Notably, the optimal construct DTAC-V1 demonstrated unprecedented synchronous degradation of the entire Cyclin D1–CDK4/6 complex, leading to robust G1-phase cell cycle arrest and effective inhibition of cancer cell proliferation. Furthermore, in a xenograft mouse model, DTAC-V1 exhibited potent therapeutic efficacy by effectively degrading Cyclin D1–CDK4/6 and suppressing tumor growth, underscoring its potential as an anticancer agent. Overall, our findings demonstrate the feasibility of DTAC as a rapid, scalable, and modular platform for the spatial control of functional inhibitors for optimal effectiveness, making it a promising method for proximity-based therapeutics.}, archive = {J_JACS}, author = {Rong Zheng and Abhay Prasad and Deeksha Satyabola and Yang Xu and Subhajit Roy and Yichen Yan and Petr Šulc and Hao Yan}, doi = {10.1021/jacs.5c04918}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29742--29755}, shortjournal = {J. Am. Chem. Soc.}, title = {DNA-templated spatially controlled proteolysis targeting chimera for cyclin D1–CDK4/6 complex protein degradation}, volume = {147}, year = {2025}, }
• (2025). Origins of tetrahedral order in ice. JACS, 147(33), 29732--29741. (www)

  @article{ , abstract = {The many-body decomposition of the lattice energies in seven ice polymorphs (ice Ih, II, VIII, IX, XIII, XIV, XV) reveals an intriguing correlation between the polymorph’s local tetrahedral order, its density, and the inherent cooperativity of its hydrogen bond network. Low-pressure ice phases demonstrate significant cooperative effects, accounting for up to approximately 25% of the lattice energy and exhibit nearly perfect local tetrahedral order. In contrast, high-pressure ice phases exhibit smaller cooperative effects (around 6%) and local structures that are less tetrahedral. The distinct local tetrahedral order encompassing nearest neighbors in these ice polymorphs is attributed to the hydrogen bond cycles in the extended network (heterodromic, antidromic and homodromic), which represents a unifying feature that profoundly influences cooperativity based on cycle size and connectivity. These findings facilitate the establishment of a novel causality between structure and stability while they further identify cooperativity as the key descriptor of hydrogen bonding characteristics across the ice phase diagram.}, archive = {J_JACS}, author = {Kristina M. Herman and Sotiris S. Xantheas}, doi = {10.1021/jacs.5c04844}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29732--29741}, shortjournal = {J. Am. Chem. Soc.}, title = {Origins of tetrahedral order in ice}, volume = {147}, year = {2025}, }
• (2025). Monocyclic azetidines via a visible-light-mediated aza paternò-büchi reaction of ketone-derived sulfonylimines. JACS, 147(33), 29722--29731. (www)

  @article{ , abstract = {The recent rise in popularity of azetidines in pharmaceutical chemistry has inspired the development of visible-light-mediated aza Paternò-Büchi reactions as direct transformations to form these desirable products. Despite these advancements, successful reports of accessing monocyclic azetidines from acyclic imines remain scarce. Here, we report a visible-light-mediated aza Paternò-Büchi reaction of acyclic ketone-derived sulfonylimines, which are previously unexplored substrates in this transformation, with activated alkenes (i.e., styrenes and dienes) to form 2,2-disubstituted monocyclic azetidines that can be further modified to reveal free N – H azetidines. Computational and experimental mechanistic studies reveal that in contrast to aldehyde-derived oximes, the use of ketone-derived sulfonylimines enables tuning of the reaction mechanism to favor initial formation of the C–N rather than C–C bond, thus enabling access to 2,2-disubstituted monocyclic azetidine scaffolds.}, archive = {J_JACS}, author = {Cody H. Ng and Emily R. Wearing and Dominique E. Blackmun and Gianmarco G. Terrones and Jessica Toigo and Ka-Ming Tong and Kaid C. Harper and Julia C. Donovan and Madeleine A. Gonley and Eric A. Voight and Benjamin D. Bergstrom and Michael O. Wolf and Heather J. Kulik and Corinna S. Schindler}, doi = {10.1021/jacs.5c04692}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29722--29731}, shortjournal = {J. Am. Chem. Soc.}, title = {Monocyclic azetidines via a visible-light-mediated aza paternò-büchi reaction of ketone-derived sulfonylimines}, volume = {147}, year = {2025}, }
• (2025). Direct generation of carboxyl radicals from carboxylic acids catalyzed by photoactivated ketones. JACS, 147(33), 29711--29721. (www)

  @article{ , abstract = {Carboxyl radicals are reactive intermediates, which potentially offer opportunities to develop unique transformations in radical chemistry, yet their straightforward generation from carboxylic acids has largely relied on the use of environmentally less benign methods, and their application has been mainly limited to decarboxylative functionalizations. Here, we present a photoactivated ketone-catalyzed direct generation of carboxyl radicals via hydrogen atom transfer (HAT) from the O–H bond of carboxylic acids. An integrated approach combining theoretical predictions and experimental validation guided the development of this simple, chemoselective O–H HAT catalysis, which is facilitated by hydrogen-bonding interaction between the ketone photocatalyst and the carboxylic acid and leaves weaker C–H bonds intact. Our protocol has a broad substrate scope with high functional group tolerance and is applicable to direct decarboxylative functionalization of primary, secondary, and tertiary aliphatic carboxylic acids, including bioactive molecules. Benzoyloxy radicals were also prepared, enabling site-selective C(sp 3 )–H alkylation of ortho -alkyl-substituted benzoic acids via a 1,5-HAT process.}, archive = {J_JACS}, author = {Kenji Yamashita and Hayate Sano and Yuki Goto and Hiroki Hayashi and Yoshitaka Hamashima}, doi = {10.1021/jacs.5c04571}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29711--29721}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct generation of carboxyl radicals from carboxylic acids catalyzed by photoactivated ketones}, volume = {147}, year = {2025}, }
• (2025). The water-mediated reaction pathway for catalytic opening of the furanic ring on platinum catalysts. JACS, 147(33), 29702--29710. (www)

  @article{ , abstract = {The fundamental understanding of C–O bond activation in bioheterogeneous catalysts is essential for the lignocellulosic upgrading reaction in the liquid phase. Yet, multifaceted solvent effects complicate the analysis of the atomistic reaction mechanism. The use of protic solvents in the conversion of biomass-derived furanics into chain alcohols, carboxylic acids, and amines can lead to high rates, but the origin of the solvent-mediated rate enhancements remains largely unknown. Here, we consider 2,5-bis(hydroxymethyl)furan (BHMF) as a model substrate and elucidate the significant role of water-mediated protonation in selectively cleaving particular C–O–C bonds through insight from quantum mechanics (QM) theory combined with solid experimental kinetic evidence. Depending on the solvent, we observe that the initial product formation rate in water is about 2 orders of magnitude larger than that in dioxane. We show that water participates directly in reductive C–O–C bond scission via assisted proton transfer, activating a low-energy barrier path. We find that a water molecule acting as a nucleophile then subsequently attacks the C(2) carbon atom to initiate a hydroxyl shift process in the intermediate, which then undergoes stepwise hydrogenation to produce a chain alcohol. Throughout this catalytic cycle, hydronium ions are generated spontaneously at the metal/water interface to indirectly impact the mechanism and kinetics of the reactions. Furthermore, we reveal how substituent groups (e.g., hydroxymethyl) affect the direct nucleophilic attack of the furan ring by water, a finding that rationalizes long-standing selectivity challenges in biomass conversion. Our QM calculations provide new insights into C–O bond activation in the liquid phase, highlighting the influence of the microsolvation environment on controlling the reaction path.}, archive = {J_JACS}, author = {Mingxin Lv and Liyuan Huai and Zhilin Chen and Hongfeng Yin and William A. Goddard, III and Jian Zhang}, doi = {10.1021/jacs.5c02521}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29702--29710}, shortjournal = {J. Am. Chem. Soc.}, title = {The water-mediated reaction pathway for catalytic opening of the furanic ring on platinum catalysts}, volume = {147}, year = {2025}, }
• (2025). The role of ethanol in lithium-mediated nitrogen reduction. JACS, 147(33), 29687--29701. (www)

  @article{ , abstract = {Although the Haber–Bosch process for industrial ammonia production is hailed by many as one of the most influential breakthroughs of the 20th century, its decarbonization and decentralization remain a critical challenge. One of the most promising and fast improving approaches is electrochemical nitrogen reduction mediated by lithium. However, the impact of electrolyte configuration on the formation of the solid electrolyte interphase (SEI) and its effect on selective nitrogen reduction is still elusive. In particular, the role of commonly added, supposedly sacrificial, proton donors on SEI chemistry and morphology remains a mystery. In this work, the impact of ethanol concentration in a 1 M LiNTf 2 in THF electrolyte on SEI properties and nitrogen reduction is analyzed via a multipronged characterization approach. Post-mortem surface analysis via X-ray photoelectron spectroscopy shows a dependence in the relative proportion of LiF and Li 2 O on ethanol concentration, while depth profiling measurements via cluster source time-of-flight secondary ion mass spectrometry reveal increasing SEI electrolyte permeability at higher ethanol concentrations. Cryogenic electron microscopy measurements show a reduction in SEI thickness with increased ethanol concentration, as well as increased SEI homogeneity. Lithium metal is also observed only in the ethanol-free condition. Analysis of bulk SEI components via titration corroborates the observation of lithium metal in cryo-microscopy measurements, as well as showing an increase in bulk Li 2– x OH x content with ethanol concentration. A narrow ‘Goldilocks’ region is revealed, where the SEI has just the right properties for efficient nitrogen reduction.}, archive = {J_JACS}, author = {Olivia Westhead and Romain Tort and James O. Douglas and Michele Conroy and Bethan J. V. Davies and Anna Winiwarter and Aishah Faisal and Matthew Spry and Artem Khobnya and Mary P. Ryan and Maria-Magdalena Titirici and Rhodri Jervis and Ifan E. L. Stephens}, doi = {10.1021/jacs.5c03389}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29687--29701}, shortjournal = {J. Am. Chem. Soc.}, title = {The role of ethanol in lithium-mediated nitrogen reduction}, volume = {147}, year = {2025}, }
• (2025). Enhancing hydrogen production from bioenergy crops via photoreforming. JACS, 147(33), 29679--29686. (www)

  @article{ , abstract = {Photoreforming perennial bioenergy crops (willow, Miscanthus , and poplar) has the potential to produce H 2 with reduced environmental impacts. To understand the compositional effects of the biomass on the average rate of H 2 production over the first 30 min of reaction ( r H 2 ), the r H 2 values of model biomass component (i.e., cellulose, hemicellulose, and lignin) mixtures were compared with those from the raw biomass. The higher cellulose or hemicellulose content in multicomponent mixtures resulted in higher r H 2 , whereas lignin reduced the hydrogen production rate. However, with raw biomass, the ratio of biomass components alone did not determine the r H 2 via photoreforming, with rates of hydrogen production for different varieties of willow ranging between 1.9 μmol h –1 and 12.3 μmol h –1 , 11.8 μmol h –1 for a poplar, and 6.8 μmol h –1 for a miscanthus biomass. In addition, comparable r H 2 values of raw poplar and its extracted cellulose via an IonoSolv treatment indicated the possibility of using raw biomass materials without delignification for generating H 2 via photoreforming. Importantly, r H 2 was positively correlated with the interaction between water and the biomass, as assessed by NMR relaxation via an examination of the T 1 / T 2 ratio. A stronger water-biomass interaction resulted in a higher r H 2 . Genetic modification of biomass has been suggested as a putative way to improve the r H 2 of biomass with an enhanced interaction with water. This research enhances the understanding of factors influencing H 2 production from lignocellulosic biomass by photoreforming and supports the breeding and management of perennial biomass crops to maximize H 2 yields while minimizing land area requirements.}, archive = {J_JACS}, author = {Meshal Aljohani and Lan Lan and Helen Daly and Pedro Verdía Barbará and Min Hu and Suhaib Nisar and Shengzhe Ding and Jason Hallett and Neil Watkins and William J. Macalpine and Rebecca Rowe and Agnieszka Brandt-Talbot and Gregg Sanford and John Ralph and Shawn D. Mansfield and Carmine D’Agostino and Xiaolei Fan and Christopher Hardacre}, doi = {10.1021/jacs.5c01871}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29679--29686}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing hydrogen production from bioenergy crops via photoreforming}, volume = {147}, year = {2025}, }
• (2025). Nitric oxide-to-ammonia synthesis with nearly 100% yield by ambient-pressure thermocatalysis under mild temperature. JACS, 147(33), 29673--29678. (www)

  @article{ , abstract = {This study discovered a new thermocatalytic reaction of NO-to-NH 3 synthesis to solve nitric oxide pollution and low NH 3 synthesis efficiency. Solid-solution Os x Pt 1– x /γ-Al 2 O 3 exhibited an outstanding performance in NO-to-NH 3 synthesis under mild temperatures and ambient pressure. Os 0.1 Pt 0.9 /γ-Al 2 O 3 yielded up to 97% NH 3 at 200 °C, with remarkably higher yield and milder conditions than that of the Haber-Bosch process. The high NO-to-NH 3 synthesis activities and NH 3 yields were attributed to the synergistic effect of ultrafast NO and H 2 dissociations.}, archive = {J_JACS}, author = {Ying Qin and Junyun Gao and Bo Huang}, doi = {10.1021/jacs.5c11515}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29673--29678}, shortjournal = {J. Am. Chem. Soc.}, title = {Nitric oxide-to-ammonia synthesis with nearly 100% yield by ambient-pressure thermocatalysis under mild temperature}, volume = {147}, year = {2025}, }
• (2025). Iron-catalyzed asymmetric reductive cross-coupling of ketimines with alkyl iodides. JACS, 147(33), 29666--29672. (www)

  @article{ , abstract = {We report herein an Fe-catalyzed asymmetric reductive cross-coupling of carbonyl-containing ketimines with unactivated alkyl halides, enabling the efficient synthesis of enantioenriched α-tertiary amino esters and amides. This transformation is promoted by a commercially available iron(II) triflate catalyst in combination with a chiral bisoxazoline–phosphine (NPN) ligand and inexpensive manganese as the reductant. A broad range of primary and secondary alkyl iodides are compatible, affording the desired products in high yields with excellent enantioselectivities and exceptional functional group tolerance. The protocol is amenable to the late-stage decoration of complex molecules and the construction of heterocycles bearing quaternary stereocenters. Mechanistic investigations, including radical clock experiments and high-resolution mass spectrometry, support a single-electron-transfer (SET) pathway involving Fe(I)/Fe(II)/Fe(III) redox cycling and alkyl radical species. This work not only expands the toolbox for asymmetric C(sp 3 )–C bond formation but also showcases the untapped potential of chiral iron catalysis in stereoselective radical transformations.}, archive = {J_JACS}, author = {Jiaxin Wang and Haohao Bai and Xinping Xi and Rui He and Xinjie Dong and Guodong Ju and Chao Wang}, doi = {10.1021/jacs.5c11470}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29666--29672}, shortjournal = {J. Am. Chem. Soc.}, title = {Iron-catalyzed asymmetric reductive cross-coupling of ketimines with alkyl iodides}, volume = {147}, year = {2025}, }
• (2025). Halogen bonding in solution: Under pressure. JACS, 147(33), 29659--29665. (www)

  @article{ , abstract = {The first study of the high-pressure behavior of organic halogen bond donors in solution is presented: HP-NMR titrations were performed in various solvents, primarily with a neutral tridentate halogen bond donor and an orthoamide or halides as Lewis bases. While the orthoamide showed stronger binding upon increased pressure in CDCl 3 , CD 2 Cl 2 , acetone- d 6 , and THF- d 8 , the halides unexpectedly featured decreased association constants for the first three solvents. For comparison, bromide was also titrated against dicationic halogen and chalcogen bond donors as well as a thiourea as a representative hydrogen bond donor, with the latter showing weaker binding at elevated pressure. Qualitative agreement with this data was achieved via thermodynamic modeling using PC-SAFT. These findings stress the important role of the solvent in halogen-bonded complexes involving charged species and are expected to provide the basis for a rational application of high pressure in applications of halogen bonding in solution.}, archive = {J_JACS}, author = {Saber Mehrparvar and Marcel Klinksiek and Richard M. Gauld and Julian Wolf and Meghana Poliyodath Mohanan and Christoph Vonnemann and Jan Haase and Raffaella Papagna and Martin H. H. Völkel and Viktoria H. Gessner and Christoph Held and Stefan M. Huber}, doi = {10.1021/jacs.5c11036}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29659--29665}, shortjournal = {J. Am. Chem. Soc.}, title = {Halogen bonding in solution: Under pressure}, volume = {147}, year = {2025}, }
• (2025). Isolation and reactivity of a BN-embedded heterocumulene. JACS, 147(33), 29653--29658. (www)

  @article{ , abstract = {The incorporation of B═N units into cumulenes offers a promising strategy to modulate their electronic structures and chemical properties, yet free hybrid heterocumulenes containing both C═C and B═N bonds remain elusive. Herein, we report the synthesis of a hybrid [4]heterocumulene achieved through the strategic use of an N-heterocyclic-substituted diazoalkene and an N-heterocyclic imino-substituted borane as precursors. Single-crystal X-ray diffraction analysis and DFT calculations unequivocally confirm that the BN-embedded heterocumulene features a bent C═C═B═N═C framework, exhibiting exceptional π-delocalization along the cumulenic backbone. Notably, this hybrid system exhibits remarkable reactivity toward unsaturated substrates, including isocyanide, carbon dioxide, and organic azide, leading to the selective formation of three-, four-, and five-membered boron-containing heterocycles. These transformations highlight the unique electronic properties imparted by the BN incorporation and underscore the potential of such heterocumulenes as versatile synthons in boron chemistry.}, archive = {J_JACS}, author = {Xuyang Wang and Chuangchuang Xu and Fanshu Cao and Yilin Sun and Chunming Cui and Zhenbo Mo}, doi = {10.1021/jacs.5c10390}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29653--29658}, shortjournal = {J. Am. Chem. Soc.}, title = {Isolation and reactivity of a BN-embedded heterocumulene}, volume = {147}, year = {2025}, }
• (2025). Anionic reversible Addition–Fragmentation chain-transfer polymerization of methacrylates. JACS, 147(33), 29648--29652. (www)

  @article{ , abstract = {Anionic polymerizations of methacrylates are controlled processes that give well-defined materials; however, these polymerizations require reactive and pyrophoric organolithium reagents for initiation and must be run at low temperatures to maintain control. The ability to run these reactions closer to room temperature and limit the amount of pyrophoric reagents necessary to carry out these polymerizations would increase the practicality, safety, and scalability of these reactions. Herein, we present an anionic reversible addition–fragmentation chain-transfer (RAFT) polymerization that reduces the amount of reactive alkyl lithium required for initiation and is performed at elevated temperatures compared to traditional anionic processes. By using ethyl 2-formyl-2-phenylbutanoate as a chain-transfer agent, we leverage reversible aldol reactions with the propagating enolate chain ends to achieve chain-transfer and subsequent control over the polymerization. Through the proposed anionic RAFT mechanism, a variety of methacrylates were polymerized in a controlled manner. The resulting polymers had stable, isolable aldehyde chain ends, which could be reinitiated to form block polymers.}, archive = {J_JACS}, author = {Paige E. Jacky and Madison A. Neukirch and Brett P. Fors}, doi = {10.1021/jacs.5c10586}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29648--29652}, shortjournal = {J. Am. Chem. Soc.}, title = {Anionic reversible Addition–Fragmentation chain-transfer polymerization of methacrylates}, volume = {147}, year = {2025}, }
• (2025). Iterative synthesis of intrinsically disordered protein mimics. JACS, 147(33), 29642--29647. (www)

  @article{ , abstract = {Artificial intrinsically disordered proteins (IDPs) are often biosynthesized in cells by repeating low-complexity sequences derived from native IDPs through rational engineering. Herein we report the chemical synthesis of stereocontrolled linear and cyclic IDP mimics with up to 640 amino acids (∼52 kDa) via an iterative exponential growth (IEG) strategy. Following a known sequence originating from the disordered region of natural tropoelastin, linear elastin-like polypeptides (ELPs) were synthesized by conjugating monomeric pentapeptides via IEG, which transferred the sequence and chiral features of pentapeptides to the resultant polypeptides, thereby achieving robust control of their molecular weights and stereochemistry. Cyclic ELPs with different molecular weights were further synthesized via intramolecular amidation. Distinct lower critical solution temperature phase transition behaviors were observed with varying molecular weights, stereochemistry, and topology of ELPs. Our work demonstrates a new synthetic route toward chemically complex ELPs and the profound impact of chemical parameters on their properties.}, archive = {J_JACS}, author = {Jian Wan and Zhenhai Tang and Qinmeng Zhong and Tianjin Wang and Rui Tan and Shoupeng Cao and Zhengbiao Zhang and Dongdong Zhou and Hao Su}, doi = {10.1021/jacs.5c09156}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29642--29647}, shortjournal = {J. Am. Chem. Soc.}, title = {Iterative synthesis of intrinsically disordered protein mimics}, volume = {147}, year = {2025}, }
• (2025). Isolation and characterization of an organobismuth dihydride. JACS, 147(33), 29636--29641. (www)

  @article{ , abstract = {We report the synthesis, isolation, and structural characterization of an elusive organobismuth(III) dihydride (Ar*–Bi(III)–H 2 , 1 ). The complex features a bulky and rigid t Bu-M s Fluind ligand that permits complete spectroscopic characterization and SC-XRD. The compound is thermally unstable and decomposes to quantitatively form H 2 and Ar*–Bi(I) in a chemoselective intramolecular process. In addition to H 2 formation, the presence of a Bi–H bond is supported by comparative spectroscopy (NMR and IR) with its deuterated analogue 1 - d 2 .}, archive = {J_JACS}, author = {Satoshi Kurumada and Nils Nöthling and Yue Pang and Nijito Mukai and Markus Leutzsch and Richard Goddard and Josep Cornella}, doi = {10.1021/jacs.5c09023}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29636--29641}, shortjournal = {J. Am. Chem. Soc.}, title = {Isolation and characterization of an organobismuth dihydride}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of (+)-pierisketone b. JACS, 147(33), 29631--29635. (www)

  @article{ , abstract = {We report herein the first total synthesis of (+)-pierisketone B, a bioactive diterpene that possesses a unique tetracyclic 7/5/6/5 carbocyclic framework that is punctuated with numerous stereocenters, two of which are quaternary and five of which are contiguous. The synthesis features an unusual Pauson Khand cyclization to generate the bridged tricyclic core. Creation of the requisite cis -fused hydrindanone moiety was achieved by hydroxyl directed hydrogenation of an allylic alcohol, and the A-ring of the natural product was formed by a Mukaiyama aldol reaction followed by a cyclization involving addition of a vinyl anion to a proximal ketone group. The resulting tetracyclic intermediate was then elaborated in six steps to complete the first total synthesis of (+)-pierisketone B in a longest linear sequence of 20 steps from (−)-linalool.}, archive = {J_JACS}, author = {Qi Gu and Grant D. Walby and Michael D. Wood and Stephen F. Martin}, doi = {10.1021/jacs.5c08617}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29631--29635}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of (+)-pierisketone b}, volume = {147}, year = {2025}, }
• (2025). Directed evolution of copper-substituted nonheme enzymes for enantioselective alkene oxytrifluoromethylation. JACS, 147(33), 29624--29630. (www)

  @article{ , abstract = {Trifluoromethylation is a coveted transformation due to the unique properties of the trifluoromethyl (−CF 3 ) group and the importance of organofluorine compounds. Enzymes that can catalyze the formation of C−CF 3 bonds would therefore be highly desirable. However, such “trifluoromethylases” are rare. Here, we report a biocatalytic platform for constructing CF 3 -substituted lactones via intramolecular alkene oxytrifluoromethylation based on hydroxymandelate synthase from Amycolatopsis orientalis ( Ao HMS), a nonheme iron enzyme. The key feature that enabled the development of this enzymatic system was the substitution of the native catalytic iron center with copper. This modification retained the ability of the Ao HMS protein scaffold to facilitate CF 3 radical generation while harnessing the exceptional catalytic activity of copper for alkene oxyfunctionalizations. Directed evolution of copper-substituted Ao HMS resulted in an engineered variant capable of producing β-, γ-, and δ-lactones bearing quaternary stereocenters with high efficiency and enantiocontrol (up to 99% yield and 98.5:1.5 e.r.). This work not only expands the biocatalytic toolbox for organofluorine synthesis but also highlights the immense potential of metal-substituted nonheme iron enzymes for evolving new-to-nature transformations.}, archive = {J_JACS}, author = {James G. Zhang and Xiongyi Huang}, doi = {10.1021/jacs.4c18532}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29624--29630}, shortjournal = {J. Am. Chem. Soc.}, title = {Directed evolution of copper-substituted nonheme enzymes for enantioselective alkene oxytrifluoromethylation}, volume = {147}, year = {2025}, }
• (2025). London dispersion as a design element in molecular catalysis. JACS, 147(33), 29611--29623. (www)

  @article{ , abstract = {This Perspective describes the role of London dispersion (LD) interactions as a key factor controlling chemical selectivity. LD arises from the correlated motion of electrons, leading to subtle yet significant stabilization (“steric attraction”), and counterbalances, together with other noncovalent interactions, Pauli exchange repulsion (“steric hindrance”). While chemists have largely relied on the latter to rationalize selectivities in catalyzed reactions, we emphasize here the role LD plays as a key design element in chemical reactions, in particular, for catalyst development.}, archive = {J_JACS}, author = {Marvin H. J. Domanski and Michael Fuhrmann and Peter R. Schreiner}, doi = {10.1021/jacs.5c09212}, journal = {Journal of the American Chemical Society}, month = {8}, number = {33}, pages = {29611--29623}, shortjournal = {J. Am. Chem. Soc.}, title = {London dispersion as a design element in molecular catalysis}, volume = {147}, year = {2025}, }
• (2025). Nanographene-oxy radical stabilized by a carbaporphyrin framework. JACS, 147(32), 29602--29610. (www)

  @article{ , abstract = {Stable organic radicals are garnering increased attention due to the unusual properties of open-shell electronic systems. However, there are limitations associated with their preparation. For instance, hexa-peri-hexabenzocoronene (HBC), a representative nanographene, has armchair edges and shows good stability, reflecting the presence of Clar sextet rings. This renders HBC-based organic radicals challenging to prepare. Here, we report HBC-based organic radicals that are stabilized within a recently reported carbaporphyrin-like dipyrromethene-fused nanographene hybrid ( HBCP ). Using a straightforward process involving acetoxylation followed by hydrolysis, an inner-hydroxy-substituted HBCP , termed HBCP-OH , is obtained. Oxidation of HBCP-OH with MnO 2 gives the HBC-oxy radical HBCP-O . This radical is highly stable and is tolerant to air, moisture, and silica gel column chromatography. As prepared, HBCP-O displays organic π radical character, as confirmed by electron paramagnetic resonance (EPR) spectroscopy, cyclic voltammetry, femtosecond transient absorption measurements, and density functional theory (DFT) calculations. Furthermore, this HBC-oxy radical can act as a ligand to coordinate Cu(III) and Pd(II) as representative metal cations. The resulting Cu(III) ( HBCP-OCu ) and Pd(II) ( HBCP-OPd ) complexes show distinct electronic features. While the former is a closed-shell nonradical complex, the latter exists as an open-shell organic radical. The present study demonstrates a new way to access stable nanographene-based organic radicals that can be further functionalized through metal complexation.}, archive = {J_JACS}, author = {Haodan He and Jaehyeok Ryu and Zhaohui Zong and Jiyeon Lee and Tae Hun Heo and Juwon Oh and Jiwon Kim and Jonathan L. Sessler and Xian-Sheng Ke}, doi = {10.1021/jacs.5c11048}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29602--29610}, shortjournal = {J. Am. Chem. Soc.}, title = {Nanographene-oxy radical stabilized by a carbaporphyrin framework}, volume = {147}, year = {2025}, }
• (2025). Effect of chirality on ultrafast triplet exciton formation in electron Donor–Acceptor cocrystals. JACS, 147(32), 29592--29601. (www)

  @article{ , abstract = {Triplet excitons formed in organic donor–acceptor cocrystals are desirable for solar energy, optoelectronic, and quantum information applications, and recent work on chirality-induced spin selectivity (CISS) provides an indication that chirality may influence triplet exciton formation in potentially useful ways. Here, we investigate the effect of a chiral electron acceptor on the charge transfer dynamics and triplet exciton formation in a series of donor–acceptor cocrystals, each having a coronene donor paired with one of three acceptors: achiral N , N -bis(3′-pentyl)perylene-(3,4:9,10)-bis(dicarboximide) and two enantiomeric chiral PDIs, N , N ′-bis(( R )- or ( S )-3′- sec -butyl)perylene-(3,4:9,10)-bis(dicarboximide). X-ray diffraction of the three cocrystals confirms that they have nearly identical structures. Transient absorption microscopy shows that photoexcitation of the cocrystals results in charge-transfer (CT) state formation in <0.3 ps followed by triplet exciton formation in ∼100 ps, with yields of 38 ± 2, 51 ± 5, and 50 ± 6% for the achiral, ( R )-, and ( S )-cocrystals, respectively. Time-resolved electron paramagnetic resonance spectroscopy confirms that the triplet excitons form by spin–orbit CT intersystem crossing. The increase in triplet yield of the cocrystals with the chiral acceptor relative to that of the achiral acceptor is attributed to CISS increasing the triplet character of the CT state.}, archive = {J_JACS}, author = {Georgia C. Mantel and Kyle T. Kairys and Malik L. Williams and Matthew D. Krzyaniak and Ryan M. Young and Roel Tempelaar and Michael R. Wasielewski}, doi = {10.1021/jacs.5c10851}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29592--29601}, shortjournal = {J. Am. Chem. Soc.}, title = {Effect of chirality on ultrafast triplet exciton formation in electron Donor–Acceptor cocrystals}, volume = {147}, year = {2025}, }
• (2025). Epoxide stereochemistry controls regioselective ketoreduction in epoxyquinoid biosynthesis. JACS, 147(32), 29582--29591. (www)

  @article{ , abstract = {Epoxyquinoids possess multiple contiguous chiral centers and reactive functional groups, offering valuable opportunities for drug discovery and chemical biology. Despite their structural diversity, the biosynthetic pathways of these species remain poorly understood. Here, we fully elucidate the biosynthesis of (−)-asperpentyn ( 2 ) through heterologous reconstitution in Aspergillus oryzae , chemical synthesis, chiral analysis, and biochemical assays. We identify critical pathway enzymes, including the FAD-binding monooxygenase AtyG, cupin domain-containing protein AtyE, and ketoreductases AtyD and AtyC. AtyE performs oxidation and stereoselective (2 R ,3 S )-epoxidation, converting siccayne ( 4 ) to (2 R ,3 S )-β-epoxyquinone ( 6 ). AtyD and AtyC control S - and R -stereochemistry, respectively, for ketoreductions at C-4 and C-1 positions, with the regioselectivity of AtyD influenced by substrate epoxide configuration. Specifically, AtyD regioselectively reduces the C4-keto group on 6 but cannot further reduce the C1-keto group on (+)-harveynone ( 8 ), whereas (2 S ,3 R )-α-epoxyquinone ( 10 ) undergoes reduction at both C-1 and C-4 positions. Subsequent AtyC-mediated reduction installs opposite stereochemistry at C-1, yielding 2 . Kinetic analyses confirm the biosynthetic sequence from 6 to 8 (AtyD) and 8 to 2 (AtyC). Mutagenesis demonstrates that residue F97 in AtyD critically determines regioselectivity, while mutations at L137A and Q246A shift the regioselectivity. Four new epoxyquinols ( 7 , 11 , 15, and 16 ) and four new epoxyhydroquinones ( 9 , 12 , 14, and 17 ) were generated, enhancing mechanistic insights into AtyD and AtyC catalyses. Notably, an in vitro one-pot reaction using AtyD_F97A and AtyC successfully converted 10 to (+)-asperpentyn ( 1 ). This comprehensive characterization of stereochemistry control in 2 biosynthesis expands enzymatic tools for generating chemical complexity among epoxyquinoid natural products.}, archive = {J_JACS}, author = {Szu-Yu Wang and Kuei-Wei Chiu and Ke-Li Lin and Hsin-Yu Wei and Yu-Rong Chen and Zhijay Tu and Yi-Tzu Lin and Chun-Hung Lin and Rong-Jie Chein and Hsiao-Ching Lin}, doi = {10.1021/jacs.5c10778}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29582--29591}, shortjournal = {J. Am. Chem. Soc.}, title = {Epoxide stereochemistry controls regioselective ketoreduction in epoxyquinoid biosynthesis}, volume = {147}, year = {2025}, }
• (2025). Enantioselective construction of aza-bicyclo[3.2.1]octane skeletons via substituted π-allyl palladium dipoles originated from neutral η3-propargyl palladium species. JACS, 147(32), 29568--29581. (www)

  @article{ , abstract = {A catalytic strategy for insitu generation of substituted π-allyl palladium dipoles from neutral η 3 -propargyl palladium complexes has been disclosed, enabling the construction of enantiomerically enriched aza-bicyclo[3.2.1]octane frameworks through cascade cyclization reactions based on neutral zwitterionic π-propargyl palladium species derived from vinylidenecyclopropane-diesters (VDCP-diesters) and their analogues. This protocol demonstrates remarkable synthetic efficiency under mild reaction conditions, achieving moderate to good yields (42 examples) with excellent stereochemical control (>90% ee in most cases). This asymmetric catalytic reaction can be applied in a series of semigram-scale manipulations, and the obtained cycloadducts can be transformed into diverse functionalized products while retaining excellent enantioselectivities. On the basis of mechanistic investigations and DFT calculations, the critical “ palladacyclobutenization-protonolysis ” sequence has been elucidated as the pivotal chirality-determining step in the whole plausible reaction pathway.}, archive = {J_JACS}, author = {Yong-Jie Long and Yin Wei and Min Shi}, doi = {10.1021/jacs.5c10764}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29568--29581}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective construction of aza-bicyclo[3.2.1]octane skeletons via substituted π-allyl palladium dipoles originated from neutral η3-propargyl palladium species}, volume = {147}, year = {2025}, }
• (2025). Arene activation by calcium Hydride/Zinc amide equilibration. JACS, 147(32), 29554--29567. (www)

  @article{ , abstract = {The β-diketiminato calcium hydride, [(BDI)CaH] 2 (BDI = HC{(Me)CNDipp} 2 , where Dipp = 2,6- i -Pr 2 C 6 H 3 ), reacts with [Zn{N(SiMe 3 ) 2 } 2 ] and [Zn(TMP) 2 ] (TMP = 2,2,6,6-tetramethylpiperidide) to provide labile species and complex equilibria with a degree of commonality in ultimately providing the products of calcium to zinc β-diketiminate transmetalation. The silazide system provides the known [(BDI)Ca{N(SiMe 3 ) 2 }] and the heterobimetallic, [(BDI)Ca{N(SiMe 3 ) 2 }(μ-H)Zn] 2 , as a viable instrument for ligand transfer to yield [(BDI)ZnH] as the final reaction product. In contrast, the TMP-derived system evidences an enhancement in Brønsted basicity, yielding [(BDI)Zn(C 6 H 5 )] by deprotonation of the benzene solvent. This process occurs via the heterobimetallic [(BDI)Ca(μ-N{C(CH 3 ) 2 CH 2 } 2 CH)(μ-H)Zn(μ-H)] 2 and the previously unreported calcium amide [(BDI)Ca(TMP)]. The [(BDI)Zn(C 6 H 5 )] produced by this reaction may be exploited in biphenyl synthesis by a telescoped palladium-catalyzed cross-coupling with bromobenzene, which is unaffected by the presence of the other residual reaction products. This protocol has also been extended to the deprotonation of several further nonactivated arenes to yield the corresponding β-diketiminato arylzinc reagents with only mesitylene providing 3,5-dimethylbenzyl formation by C(sp 3 )-H deprotonation. Although [(BDI)Ca(TMP)] reacts with both benzene and toluene, with the latter reaction providing the calcium benzyl, [(BDI)Ca(CH 2 C 6 H 5 )], and it is plausible that the latter species arises from initial C(sp 2 )-H deprotonation and subsequent isomerization, density functional theory (DFT) calculations identify arene deprotonation to be kinetically and thermodynamically disfavored. The bimetallic derivative, [(BDI)Ca(μ-N{C(CH 3 ) 2 CH 2 } 2 CH)(μ-H)Zn(μ-H)] 2 , cannot be definitively identified as the agent of arene deprotonation. We conclude, however, that the zinc arylation process requires the synergic cooperation of both metals.}, archive = {J_JACS}, author = {Kyle G. Pearce and Agustín Morales and Michael S. Hill and Mary F. Mahon and Claire L. McMullin}, doi = {10.1021/jacs.5c10735}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29554--29567}, shortjournal = {J. Am. Chem. Soc.}, title = {Arene activation by calcium Hydride/Zinc amide equilibration}, volume = {147}, year = {2025}, }
• (2025). Atomic off-centering driven phonon-glass electron-crystal-like thermoelectric transport in entropy-stabilized quinary telluride. JACS, 147(32), 29542--29553. (www)

  @article{ , abstract = {Entropy engineering offers innovative design opportunities for synthesizing new thermoelectric materials by integrating conflicting physical parameters. Optimization of configurational entropy holds the potential to simultaneously reduce the thermal conductivity through inherent disorder and enhance the Seebeck coefficient by symmetrizing the crystal lattice, both of which are crucial to augmenting the thermoelectric performance of a crystalline solid. Here, we synthesized an entropy-stabilized quinary metal telluride single crystal, AgGeSnSbTe 4 , exhibiting an intriguing phonon-glass electron-crystal (PGEC)-like thermoelectric transport. Synchrotron X-ray pair distribution function (X-PDF) analysis infers that entropy-driven stabilization generates a highly symmetric rock-salt average structure but is accompanied by cation distortion in the local structure, which further enhances with temperature, reminiscent of emphanisis . Local lattice distortion-induced anharmonicity with considerable atomic disorder leads to glass-like lattice thermal conductivity, where the phonon mean free path approaches the interatomic distance. Phonon dispersion analysis corroborates the presence of local symmetry breaking, primarily driven by the off-centering displacement of Ge atoms due to the stereochemical expression of the 4 s 2 lone pair, which results in local ferroelectric lattice instability. Notably, the glassy thermal conductivity is complemented by good electrical conductivity and a high Seebeck coefficient, enabled through long-range atomic order within the average cubic framework. The realization of the PGEC paradigm results in a promising thermoelectric figure-of-merit (zT) of ∼1.2 at 670 K in the Bridgman-grown AgGeSnSbTe 4 crystal.}, archive = {J_JACS}, author = {Animesh Bhui and Shuva Biswas and Sayan Paul and Subarna Das and Adrija Ghosh and Diptikanta Swain and Tapas Kumar Maji and Swapan Kumar Pati and Kanishka Biswas}, doi = {10.1021/jacs.5c10635}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29542--29553}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic off-centering driven phonon-glass electron-crystal-like thermoelectric transport in entropy-stabilized quinary telluride}, volume = {147}, year = {2025}, }
• (2025). In situ quantification of directional rotation by a catalysis-driven azaindole-N-Oxide–Phenoic acid molecular motor. JACS, 147(32), 29534--29541. (www)

  @article{ , abstract = {We report the in situ quantification of directional rotation of a new type of catalysis-driven rotary motor featuring a phenyl carboxylic acid rotor attached to a 7-azaindole- N -oxide stator through a biaryl C–N bond. Continuous directional rotation of the rotor about the stator is driven by the achiral motor’s rotary catalysis of carbodiimide hydration in the presence of a chiral pyrrolidinylpyridine- N -oxide. The catalytic cycle features an intermediate O -acyl-azaindole- N -oxide ester tether formed between the carboxylic acid of the rotor and the N -oxide of the stator. Face-selective cleavage of the tether by the chiral pyrrolidinylpyridine- N -oxide additive generates relatively long-lived diastereomeric pyridine- N -oxide esters of the phenyl carboxylic acid. These are hydrolyzed during the catalytic cycle to reform the carboxylic acid resting state of the motor, completing net directional 360° rotation. In contrast to previous catalysis-driven motor-molecules, the motor’s directionality could be determined directly from the transient concentrations of the diastereomeric intermediates formed during rotary catalysis. This avoids reliance on restricted rotation models to assess motor directionality and provides direct access to other key performance indicators such as motor speed and catalytic, coupling and fuel efficiency. The in situ-determined directionality of the motor was found to be in excellent agreement with the directionality determined from a restricted rotation model, supporting both the efficacy of the new approach and the validity of using appropriately designed restricted rotation models. The results establish a straightforward method for the in situ quantification of various aspects of motor behavior, aiding the design and optimization of artificial molecular motors.}, archive = {J_JACS}, author = {Hua-Kui Liu and Axel Troncossi and Benjamin M. W. Roberts and Stefan Borsley and David A. Leigh}, doi = {10.1021/jacs.5c10520}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29534--29541}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ quantification of directional rotation by a catalysis-driven azaindole-N-Oxide–Phenoic acid molecular motor}, volume = {147}, year = {2025}, }
• (2025). Postsynthetic construction of single-crystal formamide-linked covalent organic frameworks. JACS, 147(32), 29526--29533. (www)

  @article{ , abstract = {Postsynthetic modification (PSM) of covalent organic frameworks (COFs) provides a powerful strategy to promote the development of this emerging class of crystalline reticular materials. However, obtaining precise structural information regarding the postsynthetic installation of functional groups into the skeletons of COFs remains a significant challenge, primarily because of the loss of crystallinity of the parent crystals during the PSM process. Herein, by carefully selecting the starting COF crystal and optimizing the reaction conditions, we report the first example of a multistep single-crystal-to-single-crystal chemical transformation for COFs, in which imine-linked COFs are successfully transformed into novel formamide-linked COFs. The structural details of these COFs are precisely characterized via single-crystal X-ray diffraction analysis, revealing a mechanical contraction of up to 13.4% in volume for the formamide-linked COF compared with the parent amine-linked COF. Moreover, the chemical stability of the resulting COFs toward strong acids was significantly enhanced. This protocol opens a door for the design of novel COFs and presents a potential pathway for exploring their properties and applications.}, archive = {J_JACS}, author = {Yukun Li and Yue Wan and Xinyue Deng and Meiting Zhao and Bin Zhang and Zhifang Wang}, doi = {10.1021/jacs.5c10341}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29526--29533}, shortjournal = {J. Am. Chem. Soc.}, title = {Postsynthetic construction of single-crystal formamide-linked covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Supertough and multirecyclable cross-linked polyurethane enabled by supramolecular chain extenders and noncovalent cross-linkers. JACS, 147(32), 29517--29525. (www)

  @article{ , abstract = {Cross-linked polyurethane is widely used as a high-performance elastomer, owing to its excellent mechanical properties and superior durability. However, a critical challenge remains in integrating its in-use stability with dynamic behavior during recycling. Herein, supertough and multirecyclable cross-linked polyurethanes were developed through the cooperation of supramolecular chain extenders and noncovalent cross-linkers. This strategy, leveraging both a robust covalent network and a high-density hydrogen-bonded network, achieves enhanced mechanical strength and solvent resistance for in-use stability. The rapid and reversible dynamic exchange of the high-density hydrogen-bonded network endows polyurethane with excellent processability and recovery, exhibiting a distinct macroscopic flow at an elevated processing temperature. The resulting material exhibits a remarkable tensile stress of 50 MPa, an exceptional toughness of 300 MJ/m 3 , and maintains above 96% recycling efficiency after six recycling cycles, significantly outperforming conventional polyurethanes. Therefore, the integration of in-use durability and dynamic recyclability in cross-linked polyurethanes is successfully achieved, providing a promising pathway toward sustainability goals for cross-linked polymers with tailor-made mechanical properties.}, archive = {J_JACS}, author = {Weiheng Lai and Bo Qin and Xiao Cao and Quan Chen and Jiang-Fei Xu and Xi Zhang}, doi = {10.1021/jacs.5c10178}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29517--29525}, shortjournal = {J. Am. Chem. Soc.}, title = {Supertough and multirecyclable cross-linked polyurethane enabled by supramolecular chain extenders and noncovalent cross-linkers}, volume = {147}, year = {2025}, }
• (2025). Support-accelerated proton transfer for enhanced oxygen evolution catalysis. JACS, 147(32), 29505--29516. (www)

  @article{ , abstract = {Catalyst supports are conventionally regarded as inert substrates for dispersing and stabilizing active species. Here we show that supports can be deliberately engineered to actively participate in catalytic reactions by accelerating interfacial proton transfer in oxygen evolution reaction (OER). IrO 2 clusters were supported on hydroxyl- and methyl-functionalized zirconium phosphate, yielding IrO 2 /OH-ZrP and IrO 2 /CH 3 -ZrP, respectively. In-situ spectroscopy, electrochemical measurements and theoretical calculations reveal that, different from IrO 2 /CH 3 -ZrP, which follows the conventional adsorbate evolution mechanism (AEM), the −OH groups in IrO 2 /OH-ZrP directly participate in OER by lowering *OOH deprotonation barrier and significantly facilitating proton transfer, leading to a Support-Accelerated Proton Transfer AEM (SAEM). Notably, rotation-dependent OER activity studies coupled with local pH measurements provide direct and compelling evidence of the support-mediated proton transfer process. Consequently, IrO 2 /OH-ZrP achieves a turnover frequency of 3.35 s –1 at an overpotential of 300 mV, 2.99 times higher than that of IrO 2 /CH 3 -ZrP. This study underscores the significance of support engineering in proton-transfer limiting reactions and provides new insights into electrocatalyst design beyond active site engineering.}, archive = {J_JACS}, author = {Wenrui Li and Jianning Lv and Xianchun Chen and Bo Wang and Lu Wang}, doi = {10.1021/jacs.5c10092}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29505--29516}, shortjournal = {J. Am. Chem. Soc.}, title = {Support-accelerated proton transfer for enhanced oxygen evolution catalysis}, volume = {147}, year = {2025}, }
• (2025). Enzyme-mimicking copper single-atom catalyst for selective oxidation of methane to liquid oxygenates. JACS, 147(32), 29496--29504. (www)

  @article{ , abstract = {Direct methane conversion (DMC) to oxygenates with high reactivity and selectivity represents one of the greatest challenges in catalysis. Herein, we report an enzyme-mimicking Cu 1 single-atom catalyst for efficient DMC using H 2 O 2 and O 2 as the oxidant. Upon oxidation with H 2 O 2 , Cu 1 single atoms are stabilized in the form of N 2 –Cu 1 -O at the zigzag edge of carbon nitride, endowing highly covalent Cu–O pair for homolytic C–H cleavage of methane (diameter of 3.78 Å) with a low barrier of 0.58 eV. Importantly, the formed methyl radicals could be captured by O 2 and generate CH 3 OOH (diameter >4.2 Å) as the primary product, whose back diffusion and overoxidation over Cu 1 are retarded via the steric hindrance of the zigzag edge that holds a “V-type” configuration with an entrance width of 3.87 Å. Such synergy between active centers and the specific steric hindrance of the surrounding geometric structure, analogous to the gating mechanism of methane monooxygenase, gives a high turnover frequency of 405.3 ± 8.2 h –1 with ∼100% selectivity at 50 °C.}, archive = {J_JACS}, author = {Li Zhang and Yike Huang and Yuehan Wang and Zhen Wang and Chuande Huang and Xiaofeng Yang and Botao Qiao and Xiaodong Wang and Tao Zhang}, doi = {10.1021/jacs.5c10016}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29496--29504}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzyme-mimicking copper single-atom catalyst for selective oxidation of methane to liquid oxygenates}, volume = {147}, year = {2025}, }
• (2025). C(sp3)–H amination with an ammonia-derived Copper(III) amide. JACS, 147(32), 29489--29495. (www)

  @article{ , abstract = {Metal-ammine (NH 3 ) and metal-amide (NH 2 ) species are common intermediates in ammonia oxidation, typically designed with weak N–H bonds to facilitate the sequential breakage of N–H bonds. Since the σ-bonding interaction between a metal center and an NH 3 ligand weakens the N–H bonds, M–NH 3 complexes with high N–H bond dissociation free energy (BDFE) are rare. However, we are particularly interested in M–NH 3 complexes with high BDFE N–H for their potential in the conversion of C(sp 3 )–H bonds to C(sp 3 )–NH 2 bonds. Herein, we report the synthesis and characterization of copper(II) and formal copper(III) NH 3 and NH 2 complexes derived from ammonia (NH 3 ). The N–H bond dissociation free energy (BDFE) of the copper(II) ammine complex ( L Cu II NH 3 , L = [ N , N ′-bis(2,6-diisopropylphenyl)-2,6-pyridine-dicarboxamido] 2– ) was measured to be 92.8(1.5) kcal/mol, the highest N–H bond strength reported for an M–NH 3 species. The copper(III) amide congener (LCu III NH 2 ) is reactive toward C(sp 3 )–H functionalization, efficiently mediating the C(sp 3 )–H activation and C(sp 3 )–N bond formation, producing a range of functionalized hydrocarbon products, including nitriles, ketones, and primary amines.}, archive = {J_JACS}, author = {Maxwell S. Reese and Joshua A. Queener and Curtis E. Moore and Shiyu Zhang}, doi = {10.1021/jacs.5c09977}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29489--29495}, shortjournal = {J. Am. Chem. Soc.}, title = {C(sp3)–H amination with an ammonia-derived Copper(III) amide}, volume = {147}, year = {2025}, }
• (2025). Harnessing BET-bromodomain assisted nuclear import for targeted subcellular localization and enhanced efficacy of antisense oligonucleotides. JACS, 147(32), 29478--29488. (www)

  @article{ , abstract = {Antisense oligonucleotides (ASOs) are a promising class of therapeutics designed to modulate gene expression. Both key mechanisms of action for ASOs operate in the nucleus: splice-switching ASOs modify pre-mRNA, processed in the nucleus, and mRNA-degrading ASOs require RNase H, an enzyme predominantly active in the nucleus. Therefore, to achieve maximal therapeutic efficacy, ASOs require efficient nuclear delivery. In this work, we have synthesized ASO conjugates for active nuclear import, by covalent conjugation with a potent and proven small-molecule nuclear importer, (+)-JQ1. (+)-JQ1 is a well-characterized high-affinity binder for members of the BET bromodomain family of proteins and was recently shown to transport cytoplasmic proteins into the nucleus. Our (+)-JQ1-ASO conjugates outperformed their unmodified counterparts for both splice-switching and mRNA knockdown in the nucleus, across different molecular targets, backbone chemistries, and cell lines. In addition, we show that the improvement in on-target efficacy correlates with increased nuclear localization of the (+)-JQ1-modified ASOs by subcellular fractionation and immunocytochemistry. Notably, we improved the performance of Oblimersen, a BCL-2 ASO drug that failed in phase-III clinical trials. (+)-JQ1-Oblimersen showed increased effectiveness in an acute myeloid leukemia cell model, showing that this therapeutic may merit re-evaluation. This work demonstrates that the covalent modification of ASOs with a small-molecule nuclear importer can significantly improve target engagement and pave the way for more effective therapeutics.}, archive = {J_JACS}, author = {Disha Kashyap and Martina Cadeddu and Peter L. Oliver and Thomas A. Milne and Michael J. Booth}, doi = {10.1021/jacs.5c09544}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29478--29488}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing BET-bromodomain assisted nuclear import for targeted subcellular localization and enhanced efficacy of antisense oligonucleotides}, volume = {147}, year = {2025}, }
• (2025). Unveiling the angstrom-scale interfacial electron spillover through the Metal/Electrolyte interface. JACS, 147(32), 29468--29477. (www)

  @article{ , abstract = {The behaviors of solid–liquid interfacial electron spillovers under negative potentials are crucial for understanding heterogeneous reactions and catalysts. The missing experimental details at the angstrom scale leave the current understanding of interfacial electron spillovers largely conceptual. Herein, we demonstrated interfacial electron spillover at electrode–electrolyte interfaces by combining in situ electrochemical plasmon-enhanced Raman spectroscopy (PERS) with a plasmonic molecular ruler strategy. Using a series of molecules adsorbed on or proximate to metallic electrodes (Pt, Pd, Au, and Ag) as molecular rulers, the electron spillover from electrodes to electrolytes was experimentally and theoretically correlated to the PERS bands of the functional groups of rulers, which provided a spatial resolution down to the angstrom scale. The electron spillover length was highly dependent on the potentials, metals, and electrolytes. An electron spillover with a length of up to 4 Å was observed at the Ag electrode–organic electrolyte interface. These results provide quantitative measurements of the fundamental details of electronic behaviors in metal–liquid interfaces, which may guide efforts to tailor the physical and chemical properties of metals under electrochemical polarization and prospectively enable active control of quantum plasmonics for angstrom-scale interfacial sensing.}, archive = {J_JACS}, author = {Jun Yi and Yue-Jiao Zhang and Yi-Fan Huang and Jun-Rong Zheng and En-Ming You and Xiang Wang and Wei Lu and Petar M. Radjenovic and Meng Zhang and Sai Duan and Jian-Feng Li and Bing-Wei Mao and De-Yin Wu and Bin Ren and Wolfgang Schmickler and Alexei A. Kornyshev and Xin Xu and Xiang Zhang and Zhong-Qun Tian}, doi = {10.1021/jacs.5c09908}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29468--29477}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling the angstrom-scale interfacial electron spillover through the Metal/Electrolyte interface}, volume = {147}, year = {2025}, }
• (2025). Dendritic membranized coacervate microdroplets: A robust platform for synthetic-living cell consortia. JACS, 147(32), 29457--29467. (www)

  @article{ , abstract = {Bottom-up synthetic biology seeks to construct artificial cells with biomimetic or novel functionalities to uncover the fundamental principles of cellular evolution and drive advances in medicine and bioengineering. Among them, membranized coacervate microdroplets (MCM) uniquely combine a molecularly crowded aqueous interior with a surrounding membrane, both hallmarks of eukaryotic cells. Replicating cellular functions requires synthetic cells to remain structurally stable in biological environments, where ionic strength presents a significant threat to the integrity of complex coacervates. By leveraging the globular and rigid architecture of dendrimers, MCM, composed of oppositely charged small dendrimers and polypeptides─further stabilized by a charged PEG-dendritic copolymer assembled at the periphery─exhibits a critical salt concentration more than twice that of coacervates formed from polypeptides or branched polyelectrolytes with significantly higher degrees of polymerization. This highlights the enhanced robustness of dendritic MCM under physiological conditions and their suitability as synthetic cells in biological media. By mimicking key cell-like behavior such as efficient enzyme encapsulation (irrespective of the isoelectric point), fast internal dynamics, and chemical communication, dendritic MCM emerge as a promising synthetic cell platform for the selective delivery of therapeutic enzymes. In addition, their ability to engage in signal transduction pathways within synthetic-natural cell consortia, enabling responses to extracellular cues via chemical signaling, paves their way in tissue engineering and regenerative medicine.}, archive = {J_JACS}, author = {Celia Jimenez-Lopez and Lucas Garcia-Abuin and Eduardo Fernandez-Megia}, doi = {10.1021/jacs.5c09772}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29457--29467}, shortjournal = {J. Am. Chem. Soc.}, title = {Dendritic membranized coacervate microdroplets: A robust platform for synthetic-living cell consortia}, volume = {147}, year = {2025}, }
• (2025). Structural control of metal-centered excited states in Cobalt(III) complexes via bite angle and π–π interactions. JACS, 147(32), 29444--29456. (www)

  @article{ , abstract = {Co III complexes have recently become an important focus in photophysics and photoredox catalysis due to metal-centered excited states with strong oxidizing properties. Optimizing chelate ligand bite angles is a widely used strategy to strengthen metal–ligand interactions in coordination complexes, with the resulting enhanced ligand fields often contributing to extended excited-state lifetimes that are advantageous for photochemical applications. We demonstrate that bite-angle optimization exerts the opposite effect on Co III polypyridines compared to previously studied transition metal complexes, as polypyridine ligands function as π-donors to Co III rather than π-acceptors. Our findings reveal two counterintuitive paradigms: while bite-angle optimization weakens the ligand field in Co III complexes, the resulting lower-energy metal-centered excited states can be accompanied by extended excited-state lifetimes, driven by increased rigidification through intramolecular π–π interactions. These insights, along with additional experiments investigating the possibility of photoreactions from higher excited states, advance the current understanding of the photophysics and photochemistry of first-row transition metal complexes and highlight key distinctions from the more extensively studied photoactive complexes of second- and third-row transition metals.}, archive = {J_JACS}, author = {Polina Yaltseva and Tamar Maisuradze and Alessandro Prescimone and Stephan Kupfer and Oliver S. Wenger}, doi = {10.1021/jacs.5c09616}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29444--29456}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural control of metal-centered excited states in Cobalt(III) complexes via bite angle and π–π interactions}, volume = {147}, year = {2025}, }
• (2025). Decoding chirality transfer strengths and Structure–Property relationships in bismuth-containing chiral hybrid Organic–Inorganic semiconductors. JACS, 147(32), 29431--29443. (www)

  @article{ , abstract = {Chiral hybrid organic–inorganic semiconductors (CHOIS), which integrate chiral organic cations by hydrogen-bonding interactions with anionic metal halide subunits, have recently emerged as cutting-edge materials with the potential to revolutionize energy-efficient information processing, particularly in the realms of spintronics. By harnessing the inherent chirality of organic cations, CHOIS can effectively manipulate spin dynamics, a crucial factor for enhancing the device performance in next-generation electronics. However, the challenge lies in the limited understanding of structure–property relationships, which hinders the ability to control and fine-tune the chirality within these materials. To address this gap, we developed a systematic approach that provides rational chemical control over the structural characteristics of bismuth (Bi)-containing CHOIS by incorporating chiral organic cations with adjustable hydrogen-bonding interactions. Our work, which combines in-depth crystallographic analysis with advanced spectroscopic techniques, uncovers a clear correlation between specific local structural features and enhanced chiroptical responses, as well as spin-related phenomena, such as the Rashba–Dresselhaus effects. Our findings not only pave the way for the design of advanced chiral materials with precisely tailored chiroptical and spin-related properties, but also open new frontiers for their application in optoelectronic and spintronic devices, offering unprecedented potential for future technologies.}, archive = {J_JACS}, author = {Nilave Chakraborty and Tu Anh Ngo and Alexis Dominguez Montero and Thilanka Liyanage and Gregory T. McCandless and Julia Y. Chan and Tho D. Nguyen and Luisa Whittaker-Brooks}, doi = {10.1021/jacs.5c09713}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29431--29443}, shortjournal = {J. Am. Chem. Soc.}, title = {Decoding chirality transfer strengths and Structure–Property relationships in bismuth-containing chiral hybrid Organic–Inorganic semiconductors}, volume = {147}, year = {2025}, }
• (2025). N-heterocyclic carbene-ligated mixed-valent linear cu3 cluster for enhanced electrocatalytic nitrite reduction. JACS, 147(32), 29423--29430. (www)

  @article{ , abstract = {Multinuclear copper centers play a crucial role in biological electron transfer processes, with the CuA site in cytochrome c oxidase and nitrous oxide reductase exemplifying efficient mixed-valence copper cycling. However, the challenges of mimicking these biological systems for multielectron catalysis, such as nitrite reduction to ammonia, remain largely underexplored. Herein, we present the design and synthesis of a stable, mixed-valent linear Cu 3 cluster coordinated by an N-heterocyclic carbene (NHC) ligand. This NHC ligand stabilizes the Cu 3 core and facilitates an efficient electron transfer. Structural and electronic characterizations reveal temperature-dependent electron delocalization within the cluster. The Cu 3 cluster efficiently catalyzes the electrochemical reduction of nitrite to ammonia with a high selectivity under mild conditions. These findings provide valuable insights into the role of mixed-valence copper clusters in catalysis, offering a promising approach for sustainable nitrite reduction.}, archive = {J_JACS}, author = {Haozhe Dong and Xuejie Wang and Pingsen Shi and Nian Chen and Zhiqiang Zhang and Jia Yan and Aiwen Lei and Hong Yi}, doi = {10.1021/jacs.5c09431}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29423--29430}, shortjournal = {J. Am. Chem. Soc.}, title = {N-heterocyclic carbene-ligated mixed-valent linear cu3 cluster for enhanced electrocatalytic nitrite reduction}, volume = {147}, year = {2025}, }
• (2025). Synthesis and structural analysis of an emissive colloidal argyrodite nanocrystal: Canfieldite Ag8SnS6. JACS, 147(32), 29413--29422. (www)

  @article{ , abstract = {We resolve a phase identification controversy in the Ag–Sn–S material system by unraveling the polymorphic structure of nanocrystals within the argyrodite material family. Argyrodites are a class of superionic materials used in their bulk form for applications in solid-state batteries and thermoelectrics, where their advantageous properties relate to their polymorphism. However, despite their well-studied bulk applications, the limited exploration at the nanoscale has left considerable potential for the discovery of emerging properties due to size effects. Further, phase identification presents a prominent challenge to the study of polymorphs in superionic conductors and related materials. In this work, we synthesize canfieldite-like (Ag 8 SnS 6 ) nanocrystals to understand their formation and structural behavior at the nanoscale. We observe the emergence of emissive, metastable, cluster-like species. Then, high-resolution transmission electron microscopy reveals indistinguishable polymorphs of canfieldite due to identical heavy-atom frameworks. However, using synchrotron X-ray total scattering for pair distribution function analysis, we uncover structural distortions, showing a pseudo-orthorhombic configuration that likely gives rise to the red emission. Further, we investigate the optical properties and structure of Ag 8 SnS 6 nanocrystals upon the addition of Zn 2+ , the cation of interest in the canfieldite vs pirquitasite (Ag 2 ZnSnS 4 ) phase identification controversy. We show that Zn 2+ is incorporated in the canfieldite-like structure through the replacement of Ag + , boosting the emission. Our results solve a standing phase identification challenge and uncover fundamental insights for the synthesis and structure of canfieldite nanocrystals, laying the ground for the exploration of other argyrodite materials with emerging properties at the nanoscale.}, archive = {J_JACS}, author = {Francisco Yarur Villanueva and Victor Quezada Novoa and Pascal Rusch and Stefano Toso and Maxwell W. Terban and Yurii P. Ivanov and Joaquin Carlos Chu and Maxine J. Kirshenbaum and Ehsan Nikbin and Maria J. Gendron Romero and Mirko Prato and Giorgio Divitini and Jane Y. Howe and Mark W. B. Wilson and Liberato Manna}, doi = {10.1021/jacs.5c09495}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29413--29422}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis and structural analysis of an emissive colloidal argyrodite nanocrystal: Canfieldite Ag8SnS6}, volume = {147}, year = {2025}, }
• (2025). Electrostatic fields induce accelerated proton coupled electron transfer rates in chlorophyll model compounds. JACS, 147(32), 29399--29412. (www)

  @article{ , abstract = {Chlorophyll-based pigments are crucial mediators of redox processes in photosynthesis, serving as the primary electron donors in photosystems I and II. Despite their structural similarities, these pigments exhibit a wide range of redox potentials (0.5–1.3 V vs SHE), and little experimental insight into the origins of this variation is available. To address this deficit, we have synthesized two crown ether-appended Mg-porphyrin complexes as chlorophyll model compounds and demonstrated their ability to bind redox-inactive metal cations. Cation binding to the Mg-porphyrin complexes was found to increase their redox potentials in a manner that depends linearly on the total cationic charge felt by the complex, implicating a through-space electrostatic field effect. The corresponding 1-electron oxidized π-cation radical complexes were then prepared and characterized by UV–vis, FT-IR, and EPR spectroscopies and ESI-MS. The π-cation radical species were found to be competent for the PCET oxidation of a phenolic substrate, mimicking the reaction between photo-oxidized chlorophyll and tyrosine in photosystem II. Cation binding to the π-cation radical complexes was found to increase the rates of their PCET and ET reactions in a charge-dependent manner which could be rationalized using Marcus theory. This work provides direct experimental evidence that electrostatic fields can tune the redox potentials of chlorophyll model compounds, leading to an increase in their oxidative reactivity.}, archive = {J_JACS}, author = {Oscar Reid Kelly and Brendan Twamley and Marcel Swart and Aidan R. McDonald}, doi = {10.1021/jacs.5c09511}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29399--29412}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrostatic fields induce accelerated proton coupled electron transfer rates in chlorophyll model compounds}, volume = {147}, year = {2025}, }
• (2025). Synthesis of high-entropy gradient crystals via the soret effect during bridgman growth. JACS, 147(32), 29389--29398. (www)

  @article{ , abstract = {Functionally gradient materials exhibit compositional or structural gradient changes, creating new functional materials for diverse application domains. High-entropy crystals containing multiple elements hold the promise of continuous elemental regulation, facilitating the realization of functionally gradient materials. However, intrinsic property studies of high-entropy gradient crystals remain limited, and the synthesis of high-entropy gradient crystals is challenging due to the strong inherent disorder. Herein, we propose a general approach to synthesize high-entropy gradient crystals via the Soret effect in Bridgman growth. Based on the polycrystalline AgSbPbSnGeTe 5 , we integrate the concepts of gradient crystals and high-entropy crystals, culminating in the first successful synthesis of high-entropy gradient crystals via the Soret effect during crystal growth. The macroscopic temperature gradient in the Bridgman method drives the growth of dense, intact millimeter-sized single crystals, while the microscopic temperature gradient induces the Soret effect, leading to a compositional gradient in the high-entropy ingot. As a demonstration of its thermoelectric utility, an intrinsically high ZT ∼1.44 at 673 K was achieved in high-entropy gradient crystals. This work establishes a general paradigm for designing high-entropy gradient crystals via the Soret effect in the Bridgman method, providing a new man-made material for emerging functional needs and shedding useful light on the synthesis of large-sized high-entropy single crystal.}, archive = {J_JACS}, author = {Kai Li and Liang Sun and Qingqing Liu and Ni Ma and Wei Bai and Chong Xiao and Yi Xie}, doi = {10.1021/jacs.5c09415}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29389--29398}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of high-entropy gradient crystals via the soret effect during bridgman growth}, volume = {147}, year = {2025}, }
• (2025). Asymmetric cobalt single-atom catalysts with engineered hydrophobic microenvironment: A reaction-transport coupled strategy for efficient methyl oleate epoxidation. JACS, 147(32), 29377--29388. (www)

  @article{ , abstract = {The depletion of fossil resources and the urgent demand for biodegradable alternatives drive innovations in transforming renewable vegetable oils into high-value chemicals. Despite substantial progress in epoxidized vegetable oils (EVOs) as green alternatives to petrochemicals, this process remains hindered by low activity and/or selectivity. Herein, we present an effective strategy coupling intrinsically active asymmetric single-atom Co–N 2 –O 2 sites with an engineered hydrophobic microenvironment to overcome these challenges in methyl oleate epoxidation, a model reaction for vegetable oil conversion. This rationally designed catalyst achieves a record turnover frequency of 1356 h –1 and 99% selectivity under ambient conditions by using O 2 as the terminal oxidant. Mechanistic studies reveal that the asymmetric Co–N 2 –O 2 coordination markedly enhances O 2 activation by creating a modulated electronic structure that up-shifts the d-band center of the Co atom, thereby boosting electronic reactivity toward O 2 compared to symmetric Co–N 4 sites. Crucially, the alkyl anhydride-grafted hydrophobic surface engineers a unique microenvironment that facilitates the partitioning of the lipophilic methyl oleate substrate and creates “oxygen-enriched surfaces” that increase local O 2 concentration near the active sites, leading to a more than 3-fold activity enhancement over its hydrophilic counterpart. This performance is achieved by finally realizing a “reaction–transport coupled” mechanism, which synergistically leverages the enhanced O 2 activation capability of the asymmetric Co sites with the improved mass transport of reactants conferred by the engineered hydrophobic microenvironment. This work not only provides a scalable and energy-efficient pathway for industrial EVO production but also offers a generalizable molecular engineering paradigm that synergistically integrates active site design─specifically leveraging asymmetric single-atom sites─with microenvironment engineering.}, archive = {J_JACS}, author = {Huiling Feng and Yanyan Li and Yu Guan and Jiasheng Huang and Yujing Ren and Wengang Liu}, doi = {10.1021/jacs.5c09407}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29377--29388}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric cobalt single-atom catalysts with engineered hydrophobic microenvironment: A reaction-transport coupled strategy for efficient methyl oleate epoxidation}, volume = {147}, year = {2025}, }
• (2025). Directed halogen atom transfer (DIXAT): A powerful tool for chemoselective generation of aryl radicals toward remote C(sp3)–H functionalization of aliphatic amines. JACS, 147(32), 29367--29376. (www)

  @article{ , abstract = {Halogen atom transfer (XAT) and single electron transfer (SET) have emerged as versatile tools for the generation of aryl radicals. The intrinsic reactivity of these methods is governed by bond dissociation energies (BDEs) and reduction potentials, respectively, which typically favor activation of an aryl iodide over an aryl bromide. To date, no existing methods have overturned these inherent reactivity trends. The newly developed strategy, a directed halogen atom transfer (DIXAT), overcomes the above reactivity trends by enabling a chemoselective activation of aryl bromides bearing an ortho directing group, even in the presence of otherwise more reactive aryl iodides. This approach allows for precise control over aryl radical generation based on spatial orientation rather than redox or bond strength considerations. We have harnessed this novel technique to conduct nickel-catalyzed arylation and cascade carboarylation of the remote C(sp 3 )–H bonds of aliphatic amines. The site-selectivity of C–H functionalization is governed by a tethered auxiliary via 1,6- or 1,7-HAT processes. This transformation features operational simplicity, high functional group tolerance, a broad scope, and applicability to late-stage C(sp 3 )–H functionalization.}, archive = {J_JACS}, author = {Sidhant Wagulde and Kevin P. Quirion and Turki M. Alturaifi and Peng Liu and Vladimir Gevorgyan}, doi = {10.1021/jacs.5c09218}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29367--29376}, shortjournal = {J. Am. Chem. Soc.}, title = {Directed halogen atom transfer (DIXAT): A powerful tool for chemoselective generation of aryl radicals toward remote C(sp3)–H functionalization of aliphatic amines}, volume = {147}, year = {2025}, }
• (2025). Absolute configuration control in covalent organic frameworks. JACS, 147(32), 29359--29366. (www)

  @article{ , abstract = {Reticular materials constructed from chiral building blocks have garnered significant attention; however, the influence of their absolute configurations on framework structures and properties has yet to be elucidated. Herein, we report the stereoselective synthesis of covalent organic frameworks (COFs) through precise manipulation of the absolute configurations of chiral precursors. By selectively linking axially chiral binaphthalene-functionalized precursors with defined stereochemistry, we synthesized four ultrastable, highly crystalline isomeric three-dimensional COFs. Remarkably, two COFs are enantiomeric and adopt a chiral quartz ( qtz ) topology, while the other two exhibit an achiral diamondoid ( dia ) topology─both outcomes governed solely by the specific pairing of absolute configurations. Moreover, these structural distinctions, particularly in framework chirality and pore environments, result in divergent chiral separation behaviors: the qtz COFs effectively resolve racemates, whereas the dia COFs show no chiral separation ability. Our findings provide direct experimental evidence that absolute configuration can dictate not only framework chirality but also topology and function, offering new insights into the stereochemical control of reticular materials.}, archive = {J_JACS}, author = {Huimin Ding and Ya Zhang and Zixing Wang and Honglin Du and Mengsi Li and Xinyi Huang and Xu Zhou and Zeyue Zhang and Zi-Han Wu and Weixu Li and Bo Gui and Weiguang Zhang and Songliang Cai and Junliang Sun and Cheng Wang}, doi = {10.1021/jacs.5c09266}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29359--29366}, shortjournal = {J. Am. Chem. Soc.}, title = {Absolute configuration control in covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Phase behavior of light-responsive lyotropic liquid crystals for molecular solar thermal energy storage. JACS, 147(32), 29349--29358. (www)

  @article{ , abstract = {Molecular solar thermal energy storage (MOST) materials are a promising method for renewable energy storage that captures solar energy and releases it on demand as heat. Azobenzene is attractive for MOST applications due to its photoreversible E–Z isomerization. Recently, phase-change materials have been formed using azobenzene to increase their energy-storage capacity; however, these condensed phases often lower the isomerization degree, which is only recovered on dissolution. In this work, sparing solvent addition is used to drive the self-assembly of azobenzene photosurfactants (AzoPS) into lyotropic liquid crystal (LLC) phases, which are explored for MOST applications for the first time. Using small-angle X-ray scattering (SAXS), polarized optical microscopy, and differential scanning calorimetry (DSC), we show that the structure-isomerization behavior, and energy-storage properties of these light-responsive LLCs can be systematically tuned by adjusting the photosurfactant structure, solvent, and concentration. Furthermore, by developing a method that combines SAXS with in situ DSC, we directly correlate the isomerization-induced LLC phase transitions to their energy-storage contributions. The formation of LLC phases through solvent addition both enhances the degree of isomerization (by up to 20%) and amplifies the structural disordering on isomerization, resulting in energy-storage densities of up to 123 J g –1 . The ability to tune both the structure and isomerization properties in LLC materials suggests significant promise for MOST applications. In addition, the combination of advanced characterization methods used to establish the structure–isomerization–enthalpy (LLC-photoswitch-phase change) relationships provides unique insight into these multicomponent systems and accelerates the design pathways to future iterations for competitive solar energy storage devices.}, archive = {J_JACS}, author = {Beatrice E. Jones and Zhihang Wang and Martijn A. Zwijnenburg and Charlotte J. C. Edwards-Gayle and Kasper Moth-Poulsen and Nathan Cowieson and Rachel C. Evans}, doi = {10.1021/jacs.5c09267}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29349--29358}, shortjournal = {J. Am. Chem. Soc.}, title = {Phase behavior of light-responsive lyotropic liquid crystals for molecular solar thermal energy storage}, volume = {147}, year = {2025}, }
• (2025). Ultraconjugated Electron–Proton transfer mechanism in the product selectivity-controllable electrocatalytic oxidation of binary primary alcohols. JACS, 147(32), 29340--29348. (www)

  @article{ , abstract = {Controllable conversion of reactants to desired products in electrocatalytic reactions is of inherent significance but faces fundamental challenges, such as the oxidation upgrading of polyhydric alcohols. To date, the reaction mechanism, especially the selectivity-determining step (SDS), is still unclear in electrocatalytic alcohol oxidation. Herein, a unique ultraconjugated electron–proton transfer mechanism has been proposed to elucidate the oxidation behavior of the far-end hydroxyl groups from the catalyst surface in the electrocatalytic oxidation of binary primary alcohols (BPAs) as a paradigm. It has been revealed that the desorption/oxidation of hydroxy acids is the SDS in the electrocatalytic oxidation of ultraconjugated structure-containing BPAs according to the proposed mechanism. Accordingly, the selectivity to target products can be effectively and elaborately regulated by, for example, altering the electrochemical reaction parameters such as potentials. This study clarifies the critical role of the inherent molecular structure of reactants in determining the final product distribution, therefore not only helping to gain useful knowledge for the controlled electrocatalytic conversions of polyhydric alcohols but also providing new insights into product distribution regulations in the electrocatalytic conversions of a broad spectrum of complex organic molecules containing conjugated structures.}, archive = {J_JACS}, author = {Jiabiao Yan and Yuwei Ren and Bingji Huang and Zelin Li and Chen Zhao and Lisong Chen and Jianlin Shi}, doi = {10.1021/jacs.5c09163}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29340--29348}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultraconjugated Electron–Proton transfer mechanism in the product selectivity-controllable electrocatalytic oxidation of binary primary alcohols}, volume = {147}, year = {2025}, }
• (2025). Lattice-nitrogen-mediated chemistry suppresses hydrogen evolution for record faradaic efficiency in ammonia synthesis. JACS, 147(32), 29327--29339. (www)

  @article{ , abstract = {Ammonia (NH 3 ) production using air, water, and electricity offers a transformative route to carbon-free chemical synthesis, addressing global sustainability challenges. However, the hydrogen evolution reaction (HER) in aqueous systems significantly hinders NH 3 selectivity, limiting the Faradaic efficiency (FE) to below ∼15%. Herein, we report an FE of approximately 48% for aqueous NH 3 synthesis, using two-dimensional (2D) nitride catalysts. These catalysts enable lattice nitrogen protonation through the Mars-van Krevelen (MvK) mechanism, effectively suppressing HER. Using operando spectroelectrochemistry, we identified active sites and tracked nitrogen vacancy cycles, providing unprecedented insights into the reaction pathways. Our findings, supported by advanced computational techniques and complementary spectroscopic analyses, highlight the stability and efficiency of the MvK cycle, setting a new benchmark for sustainable NH 3 production.}, archive = {J_JACS}, author = {David Kumar Yesudoss and Hao-En Lai and Denis Johnson and Mark Lee and Benjamin Reinhart and Perla B. Balbuena and Abdoulaye Djire}, doi = {10.1021/jacs.5c09104}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29327--29339}, shortjournal = {J. Am. Chem. Soc.}, title = {Lattice-nitrogen-mediated chemistry suppresses hydrogen evolution for record faradaic efficiency in ammonia synthesis}, volume = {147}, year = {2025}, }
• (2025). Bumps on the road: The way to clean relaxation dispersion magic-angle spinning NMR. JACS, 147(32), 29315--29326. (www)

  @article{ , abstract = {Microsecond-to-millisecond motions are instrumental for many biomolecular functions, including enzymatic activity and ligand binding. Bloch-McConnell Relaxation Dispersion (BMRD) Nuclear Magnetic Resonance (NMR) spectroscopy is a key technique for studying these dynamic processes. While BMRD experiments are routinely used to probe protein motions in solution, the experiment is more demanding in the solid state, where dipolar couplings complicate the spin dynamics. It is believed that high deuteration levels are required and sufficient to obtain accurate and quantitative data. Here we show that even under fast magic-angle spinning and high levels of deuteration artifactual “bumps” in 15 N R 1ρ BMRD profiles are common. The origin of these artifacts is identified as a second-order three-spin Mixed Rotational and Rotary Resonance (MIRROR) recoupling condition. These artifacts are found to be a significant confounding factor for the accurate quantification of microsecond protein dynamics using BMRD in the solid state. We show that the application of low-power continuous wave (CW) decoupling simultaneously with the 15 N spin-lock leads to the suppression of these conditions and enables quantitative measurements of microsecond exchange in the solid state. Remarkably, the application of decoupling allows the measurement of accurate BMRD even in fully protonated proteins at 100 kHz MAS, thus extending the scope of μs dynamics measurements in MAS NMR.}, archive = {J_JACS}, author = {Ben P. Tatman and Vidhyalakshmi Sridharan and Motilal Uttarkabat and Christopher P. Jaroniec and Matthias Ernst and Petra Rovó and Paul Schanda}, doi = {10.1021/jacs.5c09057}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29315--29326}, shortjournal = {J. Am. Chem. Soc.}, title = {Bumps on the road: The way to clean relaxation dispersion magic-angle spinning NMR}, volume = {147}, year = {2025}, }
• (2025). Rethinking the excited-state redox properties of Iron(III) complexes for LMCT photoredox catalysis. JACS, 147(32), 29304--29314. (www)

  @article{ , abstract = {The reduction potentials of electronically excited states are crucial input values for photoredox reaction design. Since they are not directly measurable, they are typically estimated from the corresponding ground-state potentials and excited-state energies. Here, we demonstrate that this commonly applied approach breaks down for low-spin d 5 complexes of iron(III) with photoactive ligand-to-metal charge transfer (LMCT) excited states. Stern–Volmer luminescence quenching, photocatalytic experiments, and detailed thermodynamic analyses demonstrate that the true potentials for the oxidation of excited-state iron(III) complexes are up to 0.7 V lower than anticipated, resulting in a nearly 70 kJ/mol change in the driving forces of photoinduced electron transfer reactions. Our analysis further indicates that other complexes with LMCT-excited states and partially filled d-orbitals are likely to exhibit the same behavior, because LMCT-excited-state quenching removes the highest-energy electron from the t 2g orbital but results in a formally ligand-centered oxidation, whereas the first ground-state oxidation is typically metal-centered. These findings have significant implications for the use of the emerging class of complexes with photoactive LMCT-excited states as well as for the broader field of LMCT photoredox catalysis in synthetic chemistry.}, archive = {J_JACS}, author = {Joël Wellauer and Michael L. Pattuwage and Egan H. Doeven and Timothy U. Connell and Oliver S. Wenger and Paul S. Francis}, doi = {10.1021/jacs.5c08841}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29304--29314}, shortjournal = {J. Am. Chem. Soc.}, title = {Rethinking the excited-state redox properties of Iron(III) complexes for LMCT photoredox catalysis}, volume = {147}, year = {2025}, }
• (2025). Modular synthetic platform for the elaboration of fragments in three dimensions for fragment-based drug discovery. JACS, 147(32), 29292--29303. (www)

  @article{ , abstract = {Fragment-based drug discovery (FBDD) is a key strategy employed in the hit-to-lead phase of pharmaceutical development. The rate-limiting step of this process is often identifying and optimizing synthetic chemistry suitable for fragment elaboration, especially in three dimensions (3-D). To address this limitation, we herein present a modular platform for the systematic and programmable elaboration of two-dimensional (2-D) fragment hits into lead-like 3-D compounds, utilizing nine bifunctional building blocks that explore a range of vectors in 3-D. The building blocks comprise (i) rigid sp 3 -rich bicyclic cyclopropane-based structures to fix the vectors and (ii) two synthetic handles─a protected cyclic amine and a cyclopropyl N- methyliminodiacetic acid (MIDA) boronate. To validate our approach, we present (i) multigram-scale synthesis of each 3-D building block; (ii) Suzuki-Miyaura cross-coupling reactions of the cyclopropyl BMIDA functionality with aryl bromides; and (iii) N -functionalization (via commonplace medicinal chemistry toolkit reactions) of arylated products to deliver 3-D lead-like compounds. Each building block accesses a distinct 3-D exit vector, as shown by analysis of the lowest energy conformations of lead-like molecules using RDKit, and by X-ray crystallography of pyrimidine methanesulfonamide derivatives. Since the synthetic methodology is established in advance of fragment screening and utilizes robust chemistry, the elaboration of fragment hits in 3-D for biochemical screening can be achieved rapidly. To provide proof-of-concept, starting from the drug Ritlecitinib, the development of inhibitors of Janus kinase 3 (JAK3) around a putative pyrrolopyrimidine 2-D fragment hit was explored, streamlining the discovery of a novel and selective JAK3 inhibitor with IC 50 = 69 nM.}, archive = {J_JACS}, author = {Andres R. Gomez-Angel and Hanna F. Klein and Stephen Y. Yao and James R. Donald and James D. Firth and Rebecca Appiani and Cameron J. Palmer and Joshua Lincoln and Simon C. C. Lucas and Lucia Fusani and R. Ian Storer and Peter O’Brien}, doi = {10.1021/jacs.5c08786}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29292--29303}, shortjournal = {J. Am. Chem. Soc.}, title = {Modular synthetic platform for the elaboration of fragments in three dimensions for fragment-based drug discovery}, volume = {147}, year = {2025}, }
• (2025). Dipole-tailored isomeric linker enables decoupling of aggregation and crystallinity in conjugated polymers for stretchable transistors and photodiodes. JACS, 147(32), 29282--29291. (www)

  @article{ , abstract = {The microstructure of conjugated polymers critically influences their mechanical and electronic properties. Reducing crystallinity is a common approach to improve stretchability but often leads to diminished chain aggregation, which impairs charge transport. To address this trade-off, we introduce a dipole modulation strategy to decouple aggregation from crystallinity in conjugated polymers. A series of dipole-tailored isomeric linkers (DTLs), namely, 2,6-DTL, 3,5-DTL, and 2,4-DTL, are synthesized by varying the position of an alkoxy substituent on a benzene core and flanked by thiophene units, yielding linkers with increasing dipole moments. These linkers are incorporated into a diketopyrrolopyrrole (DPP)-based polymer backbone to regulate dipole moment and chain packing. The PDPP-(2,4)-DTL polymer, whose linker possesses the highest dipole moment and most asymmetric geometry, exhibits reduced long-range crystallinity and enhanced short-range aggregation. This optimized microstructure leads to a 4-fold increase in crack onset strain and a 1.5-fold enhancement in field-effect mobility compared to the reference polymer. Subsequently, PDPP-(2,4)-DTL is blended with the nonfullerene acceptor Y7 to form the bulk heterojunction layer of a stretchable organic photodiode. The resulting device exhibits higher external quantum efficiency (EQE) and detectivity ( D *) relative to the control, maintains a D * above 10 11 Jones under 80% strain, and retains a stable photoresponse after hundreds of stretching cycles. These findings highlight dipole modulation as an effective strategy to tailor polymer microstructure and simultaneously enhance mechanical and electronic properties.}, archive = {J_JACS}, author = {Chung-Chieh Kang and Tzu-Ming Hung and Shi-Ting Lu and Ta-Chung Lu and Chien-Chung Shih}, doi = {10.1021/jacs.5c08831}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29282--29291}, shortjournal = {J. Am. Chem. Soc.}, title = {Dipole-tailored isomeric linker enables decoupling of aggregation and crystallinity in conjugated polymers for stretchable transistors and photodiodes}, volume = {147}, year = {2025}, }
• (2025). Scalable and versatile fabrication of free-standing covalent organic framework membranes with tunable microstructure for molecular separation. JACS, 147(32), 29271--29281. (www)

  @article{ , abstract = {Covalent organic framework (COF) membranes hold significant promise for applications in separation, catalysis, and energy conversion; however, their industrial adoption has been hindered by the lack of scalable and efficient fabrication methods. Here, we present a fast, versatile, and broadly applicable strategy for fabricating free-standing and flexible COF membranes by casting precursor suspensions, followed by heat treatment under controlled humidity. This approach enables the fabrication of COF membranes with lateral dimensions up to several square decimeters and thicknesses that are tunable down to submicron levels within 1 h. It demonstrates remarkable versatility for producing a family of ketoenamine-linked COF membranes through the condensation of 1,3,5-triformylphloroglucinol with various amine monomers differing in length, side groups, and geometry. The resulting crack-free COF membranes exhibit high mechanical strength, with ultimate tensile strength up to 60 MPa and Young’s modulus up to 1.7 GPa, as well as exceptionally high porosity, with Brunauer–Emmett–Teller (BET) surface areas reaching up to 2226 m 2 g –1 . More importantly, the morphology, porosity, and crystallinity of the membranes can be finely tuned by modulating the heating conditions. The membranes with optimized microstructures demonstrate excellent separation performance, achieving over 99% rejection in nanofiltration of aqueous dye solutions, and a separation factor of 11 with an H 2 permeance of 2857 GPU in H 2 /CO 2 gas separation. This approach provides a scalable and effective pathway toward large-scale COF membrane manufacturing for advanced molecular separations and other membrane-based technologies.}, archive = {J_JACS}, author = {Kasper Eliasson and Fanfan Jiang and Michelle Åhlén and Maria Strømme and Chao Xu}, doi = {10.1021/jacs.5c08788}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29271--29281}, shortjournal = {J. Am. Chem. Soc.}, title = {Scalable and versatile fabrication of free-standing covalent organic framework membranes with tunable microstructure for molecular separation}, volume = {147}, year = {2025}, }
• (2025). Two-in-one flexible Metal–Organic framework: One-step C2H4 purification via inverse C2H6–C2H4 and C2H2–CO2 separations. JACS, 147(32), 29255--29270. (www)

  @article{ , abstract = {Flexible metal–organic frameworks (FMOFs) with “S-shaped” stepped isotherms are stimuli-responsive smart materials that exhibit dynamic structural changes in response to guests, offering intrinsic thermal management and excellent regenerability compared to the classical rigid adsorbents. Herein, a 2-fold interpenetrated 3D flexible MOF (FMOF): IITKGP-39 is reported whose gate-opening behavior is synchronously intertwined with the pore functionalization strategy, which served as a fascinating tool for simultaneous redressal of highly demanding one-step ethylene (C 2 H 4 ) purification via inverse ethane-ethylene (C 2 H 6 /C 2 H 4 ) separation (i.e., C 2 H 6 trapping) as well as acetylene-carbon dioxide (C 2 H 2 /CO 2 ) separation through one-step sorbent separation technology (OSST). Notably, IITKGP-39 represents the first FMOF to exhibit inverse C 2 H 6 /C 2 H 4 sorption behavior with outstanding breakthrough separation selectivity of ∼2.3 at room temperature (298 K), accompanied by one-step C 2 H 4 purification from ternary C 2 gas mixtures. Further, it excels in C 2 H 2 /CO 2 separation with a remarkable uptake ratio of ∼18 and high breakthrough selectivity of 8.3. A detailed elucidation into structural dynamics is revealed through in situ X-ray diffraction analysis that manifested the sorbate-induced structural transformation among three distinct phases: as-synthesized (phase-α), activated (phase-β), and gas sorption/gate opened phase (phase-γ). Thus, IITKGP-39 is a unique industrially compatible two-in-one physisorbent that serves as a multipurpose molecular separator by virtue of reversible flexibility with outstanding separation performances.}, archive = {J_JACS}, author = {Debolina Mukherjee and Shyam Chand Pal and Jia-Xin Wang and Volodymyr Bon and Santanu Chand and Stefan Kaskel and Bin Li and Dirk Volkmer and Madhab C. Das}, doi = {10.1021/jacs.5c08726}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29255--29270}, shortjournal = {J. Am. Chem. Soc.}, title = {Two-in-one flexible Metal–Organic framework: One-step C2H4 purification via inverse C2H6–C2H4 and C2H2–CO2 separations}, volume = {147}, year = {2025}, }
• (2025). Phenoxyimine iron aryl and alkoxide complexes as reactive intermediates in iron-catalyzed C(sp2)–C(sp3) suzuki-miyaura cross-coupling. JACS, 147(32), 29241--29254. (www)

  @article{ , abstract = {The mechanism of phenoxyimine iron-catalyzed C(sp 2 )–C(sp 3 ) Suzuki-Miyaura cross-coupling (SMC) mediated by alkoxide bases has been investigated through a combination of catalytic and stoichiometric experiments, focusing on the synthesis of catalytically relevant iron intermediates. Phenoxyimine (FI) iron bromide, alkoxide, and aryl complexes bearing pyridine and 4-dimethylaminopyridine (DMAP) ligands were synthesized and characterized by a combination of 57 Fe Mössbauer spectroscopy, 1 H NMR spectroscopy, magnetometry, and X-ray diffraction. Resting-state analysis supports turnover-limiting transmetalation from neutral aryl boron nucleophiles to high-spin, tetrahedral iron(II) alkoxide complexes to yield the corresponding iron(II) aryl derivatives. Based on the experimental data, these high-spin, tetrahedral iron complexes likely both capture the electrophile-derived C(sp 3 ) radical and initiate the radical chain responsible for C(sp 2 )–C(sp 3 ) bond formation. High-spin iron(II) aryl complexes with both electron-donating and -withdrawing substituents were isolated, contrasting the scope limitations of the catalytic cross-coupling, where only aryl boronate nucleophiles with electron-deficient groups afforded a high yield of cross-coupled product. The iron alkoxide complexes converted to catalytically inactive bis(chelate) iron complexes and iron alkoxide aggregates over time through a pathway involving dissociation of the pyridine ligand. Thus, the success of the catalytic cross-coupling reaction is dependent on the relative rates of two competing processes: (i) the rate of transmetalation of the aryl organoboron nucleophile versus (ii) the rate of deactivation of the iron alkoxide resting state through conversion to the bis(chelate) iron complex. Addition of DMAP to both stoichiometric and catalytic reactions suppressed catalyst deactivation and improved cross-coupling performance.}, archive = {J_JACS}, author = {Adam D. Bass and Paul O. Peterson and Matthew V. Pecoraro and Matthew V. Joannou and Eric M. Simmons and Steven R. Wisniewski and Tianyi Zhang and Junho Kim and Paul J. Chirik}, doi = {10.1021/jacs.5c08508}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29241--29254}, shortjournal = {J. Am. Chem. Soc.}, title = {Phenoxyimine iron aryl and alkoxide complexes as reactive intermediates in iron-catalyzed C(sp2)–C(sp3) suzuki-miyaura cross-coupling}, volume = {147}, year = {2025}, }
• (2025). Binuclear metal-based covalent organic framework mimicking metallohydrolases for direct photoreforming of PET plastic. JACS, 147(32), 29232--29240. (www)

  @article{ , abstract = {Direct photoreforming of waste poly(ethylene terephthalate) (PET) plastic into high-value-added chemicals is a promising method that improves resource utilization. However, the traditional method for PET depolymerization was mostly harsh alkali pretreatment (C OH – = 5–10 M), which largely impeded direct reforming due to the diversity of the conditions and thus caused inefficiency and discontinuity for plastic upgrading. Binuclear metallohydrolases have been proven to cause maximal acceleration of hydrolytic processes via the proximity effect under mild conditions but are unable to realize further reforming reaction due to monofunctionality. Integrating binuclear metallohydrolases and reforming active units into covalent organic frameworks (COFs) will be a promising solution to resolve the above issues. Herein, we develop two Robson-type binuclear metal-based COFs (ZnZn-Salen-Ni COF and CuCu-Salen-Ni COF) by introducing binuclear mimicking enzymatic sites and water photolysis sites to realize direct photoreforming of PET under mild alkaline conditions without chemical pretreatment. The integrated system successfully utilized ethylene glycol intermediates from depolymerization to promote high-value-added chemicals (formic acid, 421.46 μmol g cat –1 h –1 ) and hydrogen (923.25 μmol g cat –1 h –1 ) production with the one-pot–one-catalyst method over ZnZn-Salen-Ni COF and achieved an overall specific activity of 0.125 g PET g cat –1 h –1 , with ∼100% conversion toward PET photoreforming. The mechanism of PET depolymerization and intermediates promoting hydrogen evolution was studied through density functional theory calculations. This work provides a new idea and a sustainable route for the rational design and development of function-integrated materials for upgrading plastic waste into value-added chemicals.}, archive = {J_JACS}, author = {Ming-Hao Qin and Pei Huang and Mi Zhang and Cheng Xiao and Jia-Yi Chen and Yi-Da Zhou and Meng Lu and Ji-Yang Li and Ya-Qian Lan}, doi = {10.1021/jacs.5c08549}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29232--29240}, shortjournal = {J. Am. Chem. Soc.}, title = {Binuclear metal-based covalent organic framework mimicking metallohydrolases for direct photoreforming of PET plastic}, volume = {147}, year = {2025}, }
• (2025). Tuning entanglement molecular weights with ultrahigh-molecular-weight polystyrenics. JACS, 147(32), 29223--29231. (www)

  @article{ , abstract = {We report a method to produce ultrahigh-molecular-weight (UHMW, >10 6 Da) styrenic polymers with tunable entanglement molecular weights ( M e ). The high number of primary chain entanglements (≫10) results in good mechanical strength and dimensional stability at elevated temperatures while maintaining melt and solution reprocessability over multiple cycles with no change in the viscoelastic behavior or molecular weight distributions. We use mild photoiniferter polymerization to synthesize copolymers of alkoxy-functionalized styrenics and pentafluorostyrene (PFS). The electronic mismatch of the electron-rich styrenics with electron-deficient PFS provided enhanced cross-propagation rates, which enabled access to UHMWs under reasonable reaction times. We tune M e by pre- and postpolymerization modification of the styrenic repeat units with n -alkyl pendants of variable lengths. This enables modulation of M e over a range of 40,000–160,000 Da, which provides tunable Young’s moduli over a range of 0.04–69 MPa. Moreover, the UHMW polymers possess good creep recovery (>50%) up to 125 °C, despite glass transition temperatures ( T g ) ranging from −14 to 52 °C. Specifically, this side-chain tunability enables various unique thermomechanical behaviors, including room-temperature shape memory. Furthermore, the high solution viscosity of the UHMW polymers allows the processing of these materials into fibers, which is not possible in lower-molecular-weight counterparts of identical chemical composition and concentration. This study establishes a novel route to UHMW polymers comprised solely of styrenic backbones, with readily tunable viscoelastic and thermomechanical properties through the systematic engineering of M e .}, archive = {J_JACS}, author = {Joshua D. Marquez and Kevin A. Stewart and Kaden C. Stevens and Benjamin J. Ryder and Thi H. Le and Nathan B. Wei and Won J. Choi and Yong Huang and Brent S. Sumerlin and Austin M. Evans}, doi = {10.1021/jacs.5c08357}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29223--29231}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning entanglement molecular weights with ultrahigh-molecular-weight polystyrenics}, volume = {147}, year = {2025}, }
• (2025). HOCl/ClONO2 catalytic cycle: Promotion of the reactive uptake of N2O5 at the Air–Water interface. JACS, 147(32), 29215--29222. (www)

  @article{ , abstract = {Changes in the reactive uptake of dinitrogen pentoxide (N 2 O 5 ) by aerosols play important roles in regulating the levels of O 3 , OH, NO x , and CH 4 . However, a quantitative understanding of the uptake mechanism remains incomplete. Herein, we show that a HOCl/ClONO 2 catalytic cycle facilitates the reactive uptake of N 2 O 5 at the air–water interface. Our ab initio molecular dynamics (AIMD) simulations reveal that the (N 2 O 5 )N···O(HOCl) dipole–dipole interaction is the primary interaction between HOCl and N 2 O 5 at the air–water interface. This interaction promotes the formation of an N–O bond and leads to the generation of NO 3 – , ClONO 2 , and H 3 O + . Free-energy calculations further reveal that this reaction is both kinetically and thermodynamically more favorable at the air–water interface than in bulk water and has an energy barrier of ∼5.3 kcal/mol. Additionally, the generated ClONO 2 rapidly hydrolyzes at the interface and forms HOCl, NO 3 – , and H 3 O + . The net reaction is as follows: N 2 O 5 + 3H 2 O → 2NO 3 – + 2H 3 O + . This mechanism allows a single HOCl molecule to participate in multiple HOCl/ClONO 2 cycles, thereby enhancing the reactive uptake of N 2 O 5 by aerosols. This study provides insights for interpreting experimental results and has broader implications for understanding the chemistry of aerosols and clouds at the air–water interface.}, archive = {J_JACS}, author = {Xiangyu Chen and Zhengyi Wan and Qi Bai and Chongqin Zhu and Joseph S. Francisco}, doi = {10.1021/jacs.5c08347}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29215--29222}, shortjournal = {J. Am. Chem. Soc.}, title = {HOCl/ClONO2 catalytic cycle: Promotion of the reactive uptake of N2O5 at the Air–Water interface}, volume = {147}, year = {2025}, }
• (2025). Elucidating the biosynthetic pathway and mechanisms of retrochalcones. JACS, 147(32), 29205--29214. (www)

  @article{ , abstract = {Chalcone is a privileged natural product skeleton for drug discovery, and retrochalcone represents a group of nonclassical chalcones with a distinctive oxygen substitution pattern. Echinatin, a hepatoprotective agent, is a retrochalcone derived from Glycyrrhiza inflata . Despite their initial discovery half a century ago, the biosynthetic mechanisms of retrochalcones have remained elusive. In this work, we identified a ketoreductase, GinKR1, which selectively catalyzes the reduction of the 1″-carbonyl group of the dibenzoylmethane precursor 2′- O -methyllicodione, followed by spontaneous dehydration to form the retrochalcone skeleton. Our findings reveal that the A and B rings of retrochalcones are derived from the shikimate and polyketide pathways, respectively, which are reversed to normal chalcones. In addition, 18 O isotope labeling verifies that the carbonyl oxygen of retrochalcones is derived from the hydroxyl group introduced by a flavanone 2-hydroxylase. The complete biosynthetic pathway of echinatin was elucidated by identifying six enzymes from G. inflata . Moreover, we determined the crystal structure of GinKR1 and identified a critical α10 helix responsible for its regioselectivity. With this α10 helix as a marker, we further discovered homologous genes of GinKR1 from 185 plant species. This study elucidates the biosynthetic pathway and underlying mechanisms of retrochalcones.}, archive = {J_JACS}, author = {Lei Ye and Zi-Long Wang and Zi-Qi Xu and Yun-Gang Tian and Meng Zhang and Ikuro Abe and Min Ye}, doi = {10.1021/jacs.5c08070}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29205--29214}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating the biosynthetic pathway and mechanisms of retrochalcones}, volume = {147}, year = {2025}, }
• (2025). Piezoelectrically enhanced charge carriers transfer in a highly conjugated Nickel(II)-acetylide framework for photocatalytic CO2 reduction. JACS, 147(32), 29192--29204. (www)

  @article{ , abstract = {The piezoelectric field within two-dimensional (2D) piezo-photocatalysts offers a promising strategy for enhancing charge carrier kinetics to convert CO 2 into valuable chemicals. However, the diversity of available 2D piezo-photocatalysts remains limited. Here, we present a highly conjugated Ni II -acetylide framework (HETP-Ni-GY) featuring triangular atomic pores arranged in a hexagonal symmetry, constructed by incorporating Ni II -complex into the graphdiyne (GDY) framework via Ni II -bis(acetylide) linkages (–C≡C–Ni(PEt 3 ) 2 –C≡C–). The triangular topology induces a densely packed yet ordered π-structure that facilitates efficient electron transfer. The synergistic interplay of light and piezoelectric field in the HETP-Ni-GY/triethanolamine (TEOA) catalytic system enables the efficient production of CO (129.80 μmol g –1 h –1 ) and CH 4 (10.08 μmol g –1 h –1 ), with a total selectivity of 78.44%. Experimental and theoretical studies reveal that the Ni II -(PEt 3 ) 2 units within the framework significantly enhance piezoelectric polarization ( e 11 = 2.46 × 10 –10 C m –2 , d 33 = 4.91 pm V –1 ) due to increased structural distortion and noncentrosymmetry, facilitating the conversion of CO 2 . The triphenylene π-columns function as electron reservoirs, while Ni II -bis(acetylide) blocks serve as CO 2 capture and activation centers through π-d-π interactions. This study provides fundamental insights into the functionality of low-cost metal-acetylide frameworks and offers guidance for the rational design of efficient 2D piezocatalysts.}, archive = {J_JACS}, author = {Mude Zhu and Hua Su and Fangzhou Yang and Yingying Qin and Fuku Chung-Hei Hui and Runzhe Zhang and Jianxin Geng and Kai Wang and Xiaoyun Fan and Wai-Yeung Wong and Linli Xu}, doi = {10.1021/jacs.5c08037}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29192--29204}, shortjournal = {J. Am. Chem. Soc.}, title = {Piezoelectrically enhanced charge carriers transfer in a highly conjugated Nickel(II)-acetylide framework for photocatalytic CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). Molecular-scale asymmetry nanochannels for high-efficiency osmotic energy generation. JACS, 147(32), 29179--29191. (www)

  @article{ , abstract = {Osmotic power, as an example of iontronics, can convert an ion gradient to electrical energy by the membrane-based reverse electrodialysis technique. However, its efficiency in harvesting osmotic energy is mostly dependent on ion permeability and selectivity during transmembrane diffusion. The two-dimensional (2D) heterogeneous interface establishes molecular-scale asymmetric structure and charge that is expected to exert a crucial effect on the ion permeability and selectivity but remains unexplored. Here, we designed a 2D nanofluidic membrane with molecular-level asymmetric channels that can achieve high cation selectivity while maintaining outstanding ion conductivity. When applied to osmotic energy generators, this membrane can exhibit a high cation selectivity coefficient of 0.985 and a superior energy conversion efficiency of up to 47.1%, coupled with an excellent output power density of over 20 W m –2 in mixing the artificial seawater and river water. The Na + ions transport through a 2D heterostructured membrane via an interface-induced contiguous ion adsorption-diffusion mechanism is uncovered. The asymmetric pore structure and negative charge distribution enable highly selective adsorption of Na + ions and subsequently fast transport in the molecular-scale asymmetric nanochannels. This work provides an in-depth understanding of ion transport in asymmetric nanochannels and further inspires their applications in other advanced energy-harvesting devices.}, archive = {J_JACS}, author = {Chao Liu and Caichao Ye and Jiali Wang and Ting Yang and Anqi Ni and Tianning Zhang and Kunpeng Mao and Long Chen and Shijian Wang and Jingwen Sun and Wenqing Zhang and Xin Wang and Jianfei Che and Pan Xiong and Guoxiu Wang and Junwu Zhu}, doi = {10.1021/jacs.5c08016}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29179--29191}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular-scale asymmetry nanochannels for high-efficiency osmotic energy generation}, volume = {147}, year = {2025}, }
• (2025). Preparation of 1,4-diamines by enantio- and diastereoselective Cu–Josiphos-catalyzed reductive couplings of azatrienes and imines: Regiodivergence enabled by catalyst structure and reagent tailoring. JACS, 147(32), 29162--29178. (www)

  @article{ , abstract = {We introduce a method for the 6,5-hydrofunctionalization of 2-azatrienes with N -phosphinoyl imine electrophiles under CuH catalysis to prepare 1,4-diamines bearing two stereogenic centers with excellent regio-, diastereo-, and enantiocontrol. In comparison to previously disclosed 6,3-hydrofunctionalizations of azatrienes with (Ph-BPE)CuH or ( t -Bu-BDPP)CuH, the use of Josiphos SL-J001–1 as the supporting ligand facilitates regiodivergent introduction of the electrophile. We identify the electronic character of each phosphine of the ligand as critical to the observed regioselectivity and the utilization of an N -phosphinoyl group on the imine to be essential. Steric modification of the azatriene’s activating group may enhance regioselectivity in challenging cases. Electronic modification of the N -phosphinoyl group can improve chemoselectivity to favor reductive coupling over imine reduction in several instances, a discovery that translates to couplings with other copper catalysts in forming 1,2-diamines. Experiments illustrate the delicate balance in favoring 1,4-diamine formation over all other processes and, along with density functional theory (DFT) calculations, lead us to a mechanistic proposal for this catalytic reaction.}, archive = {J_JACS}, author = {Pengfei Zhou and Jiaqi Zhu and Annie Zhang and Hanggai Nuomin and Steven J. Malcolmson}, doi = {10.1021/jacs.5c08095}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29162--29178}, shortjournal = {J. Am. Chem. Soc.}, title = {Preparation of 1,4-diamines by enantio- and diastereoselective Cu–Josiphos-catalyzed reductive couplings of azatrienes and imines: Regiodivergence enabled by catalyst structure and reagent tailoring}, volume = {147}, year = {2025}, }
• (2025). Diblock copolypeptoid micelles as platform for aqueous photoredox cyanation of arenes. JACS, 147(32), 29152--29161. (www)

  @article{ , abstract = {Micellar catalysis offers a sustainable and effective alternative to traditional systems. This study introduces a micellar platform based on the amphiphilic diblock copolypeptoid poly( N -methyl glycine)- block -poly( N -n-propyl glycine) for direct arene cyanation in water. The polymer was used to encapsulate the photoredox catalyst 3,6-di- tert -butyl-9-mesityl-10-phenylacridinium tetrafluoroborate (Mes-Acr-Ph + ), forming core–shell nanostructures, as confirmed by dynamic light scattering (DLS) and cryogenic transmission electron microscopy (cryo-TEM). Under visible light irradiation, micellar core confinement activates the catalytic performance of Mes-Acr-Ph + , enabling selective C–H cyanation of diverse arenes in water. Recycling experiments demonstrate the stability and reusability of the micelles, highlighting their potential for scalable photoredox applications. This strategy advances aqueous photoredox catalysis by addressing longstanding challenges in catalyst solubility, reactivity, aggregation, close proximity, and reaction control.}, archive = {J_JACS}, author = {Afshin Nabiyan and Mitra Esfandiari and Jakob Ruickoldt and Petra Wendler and Nora Kulak and Helmut Schlaad}, doi = {10.1021/jacs.5c07882}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29152--29161}, shortjournal = {J. Am. Chem. Soc.}, title = {Diblock copolypeptoid micelles as platform for aqueous photoredox cyanation of arenes}, volume = {147}, year = {2025}, }
• (2025). Tailoring nanostructures through precise architectural engineering: Insights from cyclic block copolymer self-assembly. JACS, 147(32), 29142--29151. (www)

  @article{ , abstract = {A comprehensive understanding of the unique self-assembly potential of cyclic block copolymers has long been obscured by inherent molecular uncertainties, such as linear impurities and chain-length dispersity. This study addresses these challenges through meticulous design of discrete cyclic block copolymers and their precisely matched linear counterparts. Unconventional complex spherical packings, including Frank–Kasper A15 phase, σ phase, and a quasicrystalline phase, are captured, significantly broadening the structural diversity accessible in cyclic block copolymers. Direct comparisons among the topological isomers reveal substantially deflected phase boundaries and unexpected domain size expansion in cyclic block copolymers compared to their triblock counterparts, a trend that contradicts long-standing consensus. The discrepancies arise from a competition between two opposing factors: the enhanced conformational flexibility due to the elimination of chain ends and the steric hindrance imposed by the cyclic topology. When steric effects dominate, the increased conformational asymmetry in cyclic block copolymers stabilizes unconventional spherical phases and enlarges overall domain sizes. The precisely engineered macromolecules eliminate disruptive effects from confounding chemical defects, offering an ideal platform for systematic and quantitative investigation into how chain architecture governs self-assembly and molecular packing.}, archive = {J_JACS}, author = {Zhanhui Gan and Yue Zeng and Shuai Wang and Zhuoqi Xu and Shilong Zha and Xue-Hui Dong}, doi = {10.1021/jacs.5c07759}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29142--29151}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailoring nanostructures through precise architectural engineering: Insights from cyclic block copolymer self-assembly}, volume = {147}, year = {2025}, }
• (2025). Polyhedral crystal films of covalent organic frameworks. JACS, 147(32), 29130--29141. (www)

  @article{ , abstract = {Porous crystal films offer great potential for tackling energy and environmental challenges. However, despite over a decade of intensive research, covalent organic framework (COF) films exhibiting polyhedral textures reflective of their crystalline nature remain exceedingly rare. Here we present a scalable and adaptable biphasic strategy to synthesize pyrene (Py)-COF polyhedral crystal films with exceptional crystalline order under ambient conditions. This method enables precise control over polycrystal formation in solution and crystal growth on substrates, yielding Py-COF polyhedral films with tunable nanometer-scale thicknesses on a 4 in. wafer scale. Among them, a Py-1P film achieves a record-high Brunauer–Emmett–Teller surface area reported for COF films with comparable pore sizes alongside remarkable chemical stability. Real-space electron microscopy reveals previously unreported details of the growth of COF crystal films. These polyhedral crystal films show anisotropic thermal responses along the [001] lattice direction, with dynamically adaptive thermal expansion coefficients of (1.64–2.15) × 10 –4 K –1 . Through sensor testing, we correlate film crystallinity with device performance and longevity. This research expands the boundaries of COF films, revealing tremendous possibilities to advance film science and its applications.}, archive = {J_JACS}, author = {Xiansong Shi and Qixing Liu and Haipei Shao and Chengjun Kang and He Li and Wen-Hua Li and Anwesha Mukherjee and Junyu Ren and Nengxiu Zhu and Wei Zhao and Dongchen Shi and Zhaoqiang Zhang and Yong Wang and Ming Lin and Dan Zhao}, doi = {10.1021/jacs.5c07737}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29130--29141}, shortjournal = {J. Am. Chem. Soc.}, title = {Polyhedral crystal films of covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Organoarsine Metal–Organic framework as a solid-state ligand for Rhodium(I) olefin hydroformylation catalysis. JACS, 147(32), 29119--29129. (www)

  @article{ , abstract = {A new triaryl arsine (Ar 3 As)-based metal–organic framework (MOF) named AsCM-102 has been prepared by the reaction of As(C 6 H 4 -4-CO 2 H) 3 with Co(BF 4 ) 2 and 4,4′-bipyridine. AsCM-102 contains pairs of staggered As donors that function as trans- chelators for the facile incorporation of organometallic Rh I species via a single crystal-to-single crystal transformation. Coordination of Rh I is achieved by soaking crystals in a solution of [Rh(CO) 2 Cl] 2 at 70 °C. The originally closed and offset As 2 pockets expand to facilitate the trans- As 2 chelation of Rh I . The resulting metalated MOF displays trans -[(Ar 3 As) 2 Rh(CO)Cl n ] (1– n )+ complexes inside uniquely confined micropore reaction environments. Installation of the As–Rh–As moieties significantly enhances the internal porosity of the MOF. Crystalline Rh I –AsCM-102 is an air-stable and recyclable hydroformylation catalyst, which is more active than its phosphine-based analogue. It is also selective toward the formation of iso -aldehydes over n -aldehydes with various C 6 –C 8 olefin feedstocks. By leveraging the absolute atomic coordinates of Rh I –AsCM-102 obtained from single-crystal X-ray diffraction analysis, density functional theory (DFT) explains the experimentally observed iso -favored hydroformylation regioselectivity due to pore confinement. Rh I –AsCM-102 is resistant toward leaching of As into solution under forcing reaction conditions (40 atm of CO/H 2 , 70 °C). This work demonstrates the premise that incorporation of organo(arsines) into MOF scaffolds is a safer and more convenient strategy for their deployment in catalysis, by alleviating M–As bond lability and As toxicity issues, which prevents their widespread use in homogeneous catalysis.}, archive = {J_JACS}, author = {Venkatesh Piradi and Wenrui Chai and Samuel K. Emslie and R. Eric Sikma and Chuning Zhang and Serhii Vasylevskyi and Graeme Henkelman and Simon M. Humphrey}, doi = {10.1021/jacs.5c07706}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29119--29129}, shortjournal = {J. Am. Chem. Soc.}, title = {Organoarsine Metal–Organic framework as a solid-state ligand for Rhodium(I) olefin hydroformylation catalysis}, volume = {147}, year = {2025}, }
• (2025). Electrochemical oxygen reduction reaction-coupled dechlorination promoting acylation reaction for aromatic ester synthesis. JACS, 147(32), 29109--29118. (www)

  @article{ , abstract = {Aromatic ester compounds are one of the most versatile chemicals in many applications. Acylation reactions using acyl chlorides as building blocks are of great significance for their synthesis. However, novel and efficient strategies for acyl chlorides formation are limited. Here, we propose a cascaded route for aromatic ester synthesis via the oxygen reduction reaction (ORR)-coupled electrochemical dechlorination of trichloromethyl compounds, followed by the chemical acylation reaction. A selectivity of 93.2% and a yield of 92.5% for methyl 6-chloronicotinate (MCN) generation are obtained by electrochemical reduction of 2-chloro-5-trichloromethylpyridine over the activated Ag electrode in an O 2 -saturated methanol solution. Electrochemical in situ characterizations, femtosecond transient absorption spectra, isotope labeling, and theoretical calculations elucidate that the formation of 6-chloronicotinoyl chloride (CNC) is an important step, which is derived from the coupling of in situ generated reactive oxygen species by ORR with a dechlorination intermediate in the electrochemical process. The involvement of O 2 alters the electrochemical reaction pathway from conventional hydrodechlorination to an oxygenation–dechlorination process, which is attributed to the preferentially occurring ORR rather than the hydrogen evolution reaction. Subsequently, the in situ generated CNC sparks a chemical acylation reaction with methanol for MCN synthesis. This work provides an efficient electrochemical–chemical cascade strategy for generating a series of aromatic esters, showing promising application potential.}, archive = {J_JACS}, author = {Zhefei Zhao and Linlin Zhang and Minhao Chen and Ruopeng Yu and Runtao Jin and Fengjiao Jian and Shengyin Shui and Wenjie Yan and Yinghua Xu and Xinbiao Mao and Youqun Chu and Huajun Zheng}, doi = {10.1021/jacs.5c07666}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29109--29118}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical oxygen reduction reaction-coupled dechlorination promoting acylation reaction for aromatic ester synthesis}, volume = {147}, year = {2025}, }
• (2025). Acidic additives enable tunable low temperature side chain cleavage and performance enhancement in organic photovoltaics. JACS, 147(32), 29098--29108. (www)

  @article{ , abstract = {Thermal elimination of alkyl side chains from solution-processed organic semiconductors is a proven technique to maximize desirable properties such as conductivity, optical density, and thermal stability. However, conventional thermolysis (>200 °C, 10–30 min) of tertiary butyloxycarbonyl (Boc)-based side chains has consistently resulted in poor performance metrics across various types of devices (such as organic photovoltaics), which is often attributed to uncontrolled/undesired morphology from high annealing temperatures. To circumvent high temperatures while retaining benefits associated with removing alkyl chains, we present a new acid-catalyzed cleavage (ACC) method where acidic additives coprocessed with organic semiconductors enable alkyl-chain removal at mild annealing temperatures (90–140 °C within 30 min). Based on our mechanistically derived kinetic model, we demonstrate that both acid strength and concentration can effectively tune the temperature required for rapid thermolysis. Furthermore, we find the ACC method to be highly adaptable to numerous Boc-based functionalities. Finally, bulk heterojunction organic solar cells were chosen to showcase the benefits of lowering the cleavage temperature via ACC. With only 5 wt % diphenyl phosphate additive, the required cleavage temperature was lowered by 80 °C to a more amenable 140 °C for the cleavable side chain-based conjugated polymers POET-T2 and PffBT-T4-TCS60. The reduced annealing temperature improves the achievable power conversion efficiency of side chain-cleaved polymer-based organic photovoltaics with appreciable stability.}, archive = {J_JACS}, author = {Jordan Shanahan and Jiyeon Oh and Sung Yun Son and Wei You}, doi = {10.1021/jacs.5c07639}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29098--29108}, shortjournal = {J. Am. Chem. Soc.}, title = {Acidic additives enable tunable low temperature side chain cleavage and performance enhancement in organic photovoltaics}, volume = {147}, year = {2025}, }
• (2025). Formation of lactic acid (CH3CH(OH)COOH), a metabolic keystone for the molecular origins of life, in interstellar ice analogues. JACS, 147(32), 29088--29097. (www)

  @article{ , abstract = {Lactic acid (CH 3 CH(OH)COOH)–a key biorelevant hydroxycarboxylic acid–is ubiquitous in living organisms and critically linked to the molecular origins of life due to its fundamental role in metabolic pathways. With the anoxic conditions of early Earth, anaerobic metabolic pathways such as lactic acid fermentation may have served as an essential mechanism for primordial cellular metabolisms. Although lactic acid has been detected in high abundances in carbonaceous asteroid Ryugu and various meteorites like Murchison, its formation pathways under extreme conditions of the interstellar medium (low temperature, radiation) have remained elusive. Here, we report the first bottom-up formation of racemic lactic acid via a barrierless radical–radical recombination between the hydroxycarbonyl (HOĊO) radical and the 1-hydroxyethyl (CH 3 ĊHOH) radical in interstellar analog ices composed of carbon dioxide (CO 2 ) and ethanol (CH 3 CH 2 OH). These results provide a first step toward a fundamental understanding of the abiotic formation of biorelevant hydroxycarboxylic acids via nonequilibrium reactions from ubiquitous precursor molecules in extraterrestrial environments. Utilizing isomer-selective vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry and isotopic substitution experiments, lactic acid and its isomer monoethyl carbonate (CH 3 CH 2 OCOOH) were identified in the gas phase during temperature-programmed desorption. These findings suggest that they can likely form in interstellar ices containing carbon dioxide and ethanol in cold molecular clouds via galactic cosmic rays-mediated nonequilibrium chemistries.}, archive = {J_JACS}, author = {Jia Wang and Chaojiang Zhang and Alexandre Bergantini and Oleg V. Kuznetsov and Mikhail M. Evseev and Anastasia S. Shishova and Ivan O. Antonov and Ralf I. Kaiser}, doi = {10.1021/jacs.5c07637}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29088--29097}, shortjournal = {J. Am. Chem. Soc.}, title = {Formation of lactic acid (CH3CH(OH)COOH), a metabolic keystone for the molecular origins of life, in interstellar ice analogues}, volume = {147}, year = {2025}, }
• (2025). Regulating the acidity of HF/Pyridine media to control the chemodivergent fluoro- and hydro-heteroalkylation of olefins. JACS, 147(32), 29079--29087. (www)

  @article{ , abstract = {Oxocarbenium ions are important reactive intermediates with many applications in organic synthesis. Among them, primary oxocarbenium ions have been much less explored, in part due to the difficulty of controlling their reactivity under standard conditions. Here, we show that the reactivity of such species can be finely modulated in strongly acidic HF/pyridine media. By leveraging the tunable acidity of HF/pyridine solutions, their reaction with olefins can be diverted toward either fluoro- or hydro-oxyalkylation. Additional spectroscopic and computational investigations provide insights into the mechanism.}, archive = {J_JACS}, author = {Mélissa Longuet and Fabien Naullet and Alexandre Pérochon and Agnès Martin-Mingot and Frédéric Guégan and Bastien Michelet and Sébastien Thibaudeau}, doi = {10.1021/jacs.5c07526}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29079--29087}, shortjournal = {J. Am. Chem. Soc.}, title = {Regulating the acidity of HF/Pyridine media to control the chemodivergent fluoro- and hydro-heteroalkylation of olefins}, volume = {147}, year = {2025}, }
• (2025). Structural and electronic tuning of luminescent ZnII complexes based on an o-terphenyl ligand motif. JACS, 147(32), 29065--29078. (www)

  @article{ , abstract = {The structural and photophysical properties of five chiral Zn complexes incorporating a carbazolate (Cz) donor that is electronically decoupled from a pyridyl acceptor by an ortho -connection to a bridging phenylene group are presented. The bidentate ligand in the unsubstituted bis-ligated parent complex was methylated at key positions to constrain the torsional freedom of the donor/acceptor moieties, resulting in three structurally modified bis-ligated derivatives, all exhibiting energy gaps between the singlet and triplet excited states (Δ E ST ) between 22 and 27 meV. Methylation improves the photoluminescence quantum yield (up to 30% in solution), while the low Δ E ST of these complexes allows for dual-emission properties in all of the bis-ligated derivatives. Structural modification of the Cz/pyridyl ligand was also investigated by linking the unsubstituted bidentate ligand to generate a tetradentate, tetrapodal ligand. The solution-state structure of the tetradentate ligand is similar in its free and ligated forms, featuring a binding site reminiscent of enzymes and metal-sequestering ligands. The resulting tetradentate complex [Zn( N 2 R 2 )] shows enhanced through-bond conjugation, increasing the Δ E ST to 89 meV, thereby eliminating the dual-emission characteristics of the bis-ligated complexes. Furthermore, this complex shows a 50-fold improvement in hydrolytic stability in organic solution relative to the parent complex. These compounds and their analyses are intended to enrich the understanding of compounds exhibiting through-space charge transfer and guide the search for earth-abundant metal complexes for applications in photosensitization and luminescence.}, archive = {J_JACS}, author = {Darius A. Shariaty and Peter I. Djurovich and Mark E. Thompson}, doi = {10.1021/jacs.5c07162}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29065--29078}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural and electronic tuning of luminescent ZnII complexes based on an o-terphenyl ligand motif}, volume = {147}, year = {2025}, }
• (2025). Directly oxidizing ethanol to glycolic acid over a single-rh-site catalyst via water-mediated oxygen shuttle. JACS, 147(32), 29052--29064. (www)

  @article{ , abstract = {Direct oxidation of ethanol to glycolic acid in aqueous solutions under mild conditions offers opportunities for sustainable chemistry. Herein, we report a water-mediated oxygen-shuttle mechanism on S/N/I atoms synergistically coordinated single-Rh-site catalysts (Rh 1 /AC-SNI 400 ) to enable the direct production of glycolic acid from ethanol oxidation with 93% selectivity in liquid products and a TOF of 250 h –1 at 160 °C. Comprehensive characterizations including isotope labeling experiments and theoretical calculations reveal that hydroxyl radicals (•OH), generated via O 2 /I-triggered H 2 O dissociation, insert into C–I bonds to form hydroxyl groups and meanwhile, replace the original OH in ethanol to form C═O, ensuring that all oxygen atoms of glycolic acid directly originate from H 2 O. O 2 enters the system through the decomposition and regeneration of HIO intermediates, completing the oxygen-shuttle cycle driven by sustainable regeneration of water. Furthermore, the optimized S/N/I atoms’ synergistical coordination enhances electron delocalization around single-Rh sites, substantially reducing the activation barriers of critical reaction steps and outperforming Rh nanoparticles by 16-fold in activity.}, archive = {J_JACS}, author = {Bin Li and Jiali Mu and Guifa Long and Xiangen Song and Yang Zhao and Ende Huang and Siyue Liu and Yao Wei and Fanfei Sun and Siquan Feng and Qiao Yuan and Xingju Li and Yutong Cai and Yue Zhang and Wenrui Dong and Weiqing Zhang and Xueming Yang and Dehui Deng and Li Yan and Yunjie Ding}, doi = {10.1021/jacs.5c07150}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29052--29064}, shortjournal = {J. Am. Chem. Soc.}, title = {Directly oxidizing ethanol to glycolic acid over a single-rh-site catalyst via water-mediated oxygen shuttle}, volume = {147}, year = {2025}, }
• (2025). Collinear Jahn–Teller ordering induces monoclinic distortion in “Defect-free” LiNiO2. JACS, 147(32), 29042--29051. (www)

  @article{ , abstract = {Lithium nickel oxide, LiNiO 2 (LNO), and its doped derivatives are promising battery cathode materials with high gravimetric capacity and operating voltages. They are also of interest to the field of quantum magnetism due to the presumed S = 1/2 triangular lattice and associated geometric frustration. However, the tendency for Li/Ni substitutional defects and off-stoichiometry makes fundamental studies challenging. In particular, there is still a discrepancy between the rhombohedral ( R 3̅ m ) bulk structure and the Jahn–Teller (JT) distortions of the NiO 6 octahedra inferred on the basis of local structural probes. Karger et al . ( Chem. Mater. 2023 , 35 , 648–657) recently used Na/Li ion exchange to synthesize “defect-free” LNO by exploiting the absence of antisite disorder in NaNiO 2 (NNO). Here we characterize the short- and long-range structure of this ion-exchanged material and observe splittings of key Bragg reflections at 100 K in X-ray and neutron diffraction (XRD and NPD), indicative of a monoclinic distortion induced by a cooperative collinear JT distortion, similar to that seen in NNO. Variable temperature XRD reveals a second-order phase transition from the monoclinic ( C 2/ m ) low-temperature structure to a rhombohedral ( R 3̅ m ) structure above ∼400 K. We propose that this collinear JT ordering is also present in solid-state synthesized LNO with the domain size and extent of monoclinic distortion controlled by defect concentration. This new structural description of LNO will help advance our understanding of its electronic and magnetic properties and the series of phase transformations that this material undergoes upon electrochemical cycling in Li-ion batteries.}, archive = {J_JACS}, author = {George S. Phillips and James M. A. Steele and Farheen N. Sayed and Leonhard Karger and Liam A. V. Nagle-Cocco and Annalena R. Genreith-Schriever and Gabriel E. Pérez and David A. Keen and Jürgen Janek and Torsten Brezesinski and Joshua D. Bocarsly and Siân E. Dutton and Clare P. Grey}, doi = {10.1021/jacs.5c07435}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29042--29051}, shortjournal = {J. Am. Chem. Soc.}, title = {Collinear Jahn–Teller ordering induces monoclinic distortion in “Defect-free” LiNiO2}, volume = {147}, year = {2025}, }
• (2025). Titanium-, nitrogen-doped carbon flowers catalyze electrochemical nitrate reduction reaction to ammonia. JACS, 147(32), 29026--29041. (www)

  @article{ , abstract = {An emerging design heuristic for electrochemical nitrate reduction (NO 3 RR) catalysts is synthesizing electron-deficient sites to facilitate binding of electron-rich NO 3 – . However, this rule has rarely been applied to metal-, nitrogen-doped carbon (MNC) catalysts. Titanium (Ti), with low electronegativity and high NO 3 RR reactivity, is a compelling MNC candidate. To date, atomically dispersed TiN x motifs have eluded synthesis due to the strong oxophilicity of Ti. Here, we leverage nitrogen-rich carbon flowers (CF) to overcome synthetic challenges and produce Ti-, N-doped carbon flower (TiCF) catalysts. Advanced materials characterization demonstrates that TiCF catalysts are a mixed phase material with 3/4 of Ti atoms in TiO 2 -like nanoparticles and 1/4 of Ti atoms in novel, atomically dispersed TiN x sites. TiCF achieves 61 ± 7% NH 3 -selectivity at −0.70 V vs RHE and 14 ± 5 mA/cm 2 to NH 3 formation (| j NH 3 |) at −0.85 V vs RHE in (0.1 M NaOH + 0.1 M NaNO 3 + 0.45 M Na 2 SO 4 ) electrolyte. Control studies show both CF morphology and Ti sites are essential for high NO 3 RR activity. Density functional theory calculations attribute the NO 3 RR reactivity to TiN x , which facilitates multiple bond formation with surface intermediates to promote favorable NH 3 synthesis pathways. Thus, TiCF exhibits 60× higher | j NH 3 | values than bulk Ti and NH 3 yield rates (>0.06 mmol NH 3 /h/cm 2 ) that are competitive with state-of-the-art MNC catalysts (e.g., FeNC, CuNC). TiCF introduces a new class of Ti electrocatalysts, advancing the MNC design space and sustainable NH 3 production.}, archive = {J_JACS}, author = {Matthew J. Liu and Carlos A. Fernández Otero and Diego Uruchurtu Patino and Huaxin Gong and Md Delowar Hossain and Jesse E. Matthews and Kindle S. Williams and Alfred Vargas and Michael J. Zachman and Adam S. Hoffman and Dennis Nordlund and Michal Bajdich and Simon R. Bare and Michaela Burke Stevens and Thomas F. Jaramillo and Zhenan Bao and William A. Tarpeh}, doi = {10.1021/jacs.5c07334}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29026--29041}, shortjournal = {J. Am. Chem. Soc.}, title = {Titanium-, nitrogen-doped carbon flowers catalyze electrochemical nitrate reduction reaction to ammonia}, volume = {147}, year = {2025}, }
• (2025). Structural elucidation of nucleophilic compounds through synergistic coordination and hydrogen bonding in a Metal–Organic framework. JACS, 147(32), 29013--29025. (www)

  @article{ , abstract = {This study presents the development of a novel metal–organic framework (MOF) denoted as APF-80, suitable for the structural analysis of nucleophilic compounds that have traditionally been challenging to analyze using the crystalline sponge method. It was synthesized using a new mixed-substituent hexaazaphenalene ligand (344-TPHAP) featuring both 3-pyridyl and 4-pyridyl groups. This framework demonstrated remarkable stability toward nucleophilic molecules, which could be captured inside the pores through a synergistic combination of coordination and hydrogen-bonding interactions. APF-80 was successfully applied to determine the structures of 12 bioactive molecules, including naturally occurring alkaloids and pharmaceutical compounds. The host–guest interaction modes observed inside the resulting structures were classified into five distinct types. Binding energy calculations revealed that the guest site energies positively correlated with the crystallographic occupancies and the corresponding interaction types. This multimodal capture mechanism enabled the precise structural analysis of nucleophilic compounds under mild conditions, expanding the scope of molecules that can be analyzed by the crystalline sponge method.}, archive = {J_JACS}, author = {Tomoki Nakagawa and Yuki Wada and Bun Chan and Taichi Baba and Kengo Hanaya and Yuta Koseki and Ryuji Asano and Katsuyuki Aoki and Pavel M. Usov and Masaki Kawano}, doi = {10.1021/jacs.5c07192}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29013--29025}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural elucidation of nucleophilic compounds through synergistic coordination and hydrogen bonding in a Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Molecular engineering of a conductive Metal–Organic framework for ultrasensitive, rapid, selective, and reversible sensing of nitric oxide. JACS, 147(32), 29003--29012. (www)

  @article{ , abstract = {The selective, sensitive, low power, and portable detection of nitric oxide (NO) is important for environmental monitoring, industrial safety, and medical diagnostics. While tremendous progress has been made in detecting NO, existing technologies exhibit significant trade-offs in sensitivity, selectivity, portability, and power requirements for broad implementation. This paper presents the first synthesis of a novel class of two-dimensional conductive tetrapyrazinoporphyrazine-based metal–organic frameworks (MOFs) interconnected with Cu ( DC-100 and DC-102 ) and Zn ions ( DC-101 ) with unprecedented chemiresistive performance toward NO detection. DC-100 achieves an ultralow detection limit (0.47 parts-per-trillion (ppt)), rapid response (within seconds), high selectivity of NO over H 2 S, SO 2 , CO, NH 3 , and NO 2 , excellent reversibility, operation at room temperature, and low power requirements. The novel structural features and material–analyte interactions of DC-100 with NO represent a significant conceptual advance in molecular engineering of materials for NO detection, with potential applications in environmental monitoring, industrial safety, and medical diagnostics.}, archive = {J_JACS}, author = {Joseph Y. M. Chan and Elissa O. Shehayeb and Doran L. Pennington and Christopher H. Hendon and Katherine A. Mirica}, doi = {10.1021/jacs.5c07229}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {29003--29012}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular engineering of a conductive Metal–Organic framework for ultrasensitive, rapid, selective, and reversible sensing of nitric oxide}, volume = {147}, year = {2025}, }
• (2025). Automated electroanalysis accelerates the discovery of concerted Proton–Electron transfer. JACS, 147(32), 28993--29002. (www)

  @article{ , abstract = {Electroanalysis of reaction kinetics is a time-tested method for the mechanistic inquiry of proton-coupled electron transfer (PCET), yet the tedious manual nature of its experimental operation reduces the analytical tool’s research throughput and impedes its broader application. Here we report an automated, high-throughput electrochemical platform for reliable electroanalysis of PCET reactions with [Os II (bpy) 2 (py)(H 2 O)] 2+ as the model system. The automated system increases the research throughput by more than 10-fold and accelerates our discovery of a concerted PCET pathway facilitated by a proposed adduct formation between the redox center and phosphate as a proton donor/acceptor. As opposed to at least 3 years of manual experimentation, automated electroanalysis completed the inquiry within 1,580 h (66 days) by analyzing more than 43,800 voltammograms and quantifying approximately 730 kinetic rate constants. Such experimental “big data” opens up new lines of inquiry that were not feasible before. Automating electroanalysis accelerates discoveries for a wide range of critical applications in energy conversion and storage.}, archive = {J_JACS}, author = {Jingwen Sun and Yi-An Lai and Jiangtian Sun and Yifan Du and Brandon J. Jolly and Hongyuan Sheng and Tai Ying Lai and Hao Ming Chen and Cyrille Costentin and Matthew Nava and Chong Liu}, doi = {10.1021/jacs.5c07228}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28993--29002}, shortjournal = {J. Am. Chem. Soc.}, title = {Automated electroanalysis accelerates the discovery of concerted Proton–Electron transfer}, volume = {147}, year = {2025}, }
• (2025). Leveraging data science to elucidate ligand features for pd-catalyzed enantioretentive N-arylations of cyclic α-substituted amines in aqueous media. JACS, 147(32), 28981--28992. (www)

  @article{ , abstract = {The combination of high-throughput experimentation (HTE) and data science offers a promising solution for the optimization of challenging chemical reactions, although current data science approaches to deal with highly skewed data sets resulting from typical HTE campaigns are limited. One such attractive yet challenging reaction is the preparation of chiral tertiary anilines via palladium-catalyzed N -arylation of enantioenriched, α-substituted secondary amines. While enantioenriched tertiary anilines are highly valuable motifs in medicinal chemistry, their synthesis remains challenging to accomplish in high yields and enantiospecificity. Herein, we disclose a method for the enantioretentive N -arylation of cyclic secondary amines. After an extensive HTE campaign, a novel phosphorinane ligand for palladium, ‘NiniPhos,’ was found to demonstrate high yields (up to 96%) and enantiospecificity (96 to >99% es) across a range of amines with diverse aryl halides under aqueous conditions. Despite screening more than 120 ligands, only 31 demonstrated catalytic activity (>10% yield), resulting in a highly skewed data set. By applying data science-driven hotspot analysis and machine learning (linear support vector machines), the structural features of ligands leading to the activity cliff were identified, pinpointing di -tert -butylphosphines and phosphorinanes as privileged ligand classes in this reaction. This workflow offers a generalizable strategy for extracting mechanistic insights from skewed data sets, which can be leveraged for reaction design and optimization.}, archive = {J_JACS}, author = {Andrew R. Ickes and Jordan P. Liles and Niginia Borlinghaus and Jeremy Henle and Rafal Swiatowiec and Niharika Prakash Kaushik and Wilfried M. Braje and Kaid C. Harper and Shashank Shekhar and Matthew S. Sigman}, doi = {10.1021/jacs.5c07224}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28981--28992}, shortjournal = {J. Am. Chem. Soc.}, title = {Leveraging data science to elucidate ligand features for pd-catalyzed enantioretentive N-arylations of cyclic α-substituted amines in aqueous media}, volume = {147}, year = {2025}, }
• (2025). Atomic trajectories of a bimolecular reaction visualized by ultrafast electron diffraction. JACS, 147(32), 28973--28980. (www)

  @article{ , abstract = {Bimolecular reactions are ubiquitous in chemistry, but it is exceptionally difficult to resolve the motion of atoms for such processes on the ultrafast time scales that the breaking and creation of chemical bonds occur. Detecting small changes in atom positions requires high temporal and spatial resolution and reliable signal-to-noise characteristics. Here, we have exploited solid-state alignment to track a photoinduced bimolecular disproportionation reaction that transforms two pairs of adjacent triiodide anions (I 3 – ) into the metastable tetraiodide molecule and the diiodide fragment. We use ultrafast electron diffraction and dynamical structure refinement, where the atomic displacements are directly reconstructed from the diffraction data with plausible restraints on the atomic trajectories starting from the known ground-state structure. The excited-state structures are supported by theoretical calculations in the solid state and the reaction courses show clear site dependence on the ultrafast time scale. Our results provide a close-up view of the atomic motions involved in this classic reaction in real time, from bond elongation to breaking at the parent ion, to collision and subsequent bond formation of the liberated I atom with the neighboring I 3 – , all within a picosecond.}, archive = {J_JACS}, author = {R. Patrick Xian and Stuart A. Hayes and Gastón Corthey and Carole A. Morrison and Alexander Marx and Hazem Daoud and Cheng Lu and R. J. Dwayne Miller}, doi = {10.1021/jacs.5c07077}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28973--28980}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic trajectories of a bimolecular reaction visualized by ultrafast electron diffraction}, volume = {147}, year = {2025}, }
• (2025). In situ quantitative imaging of nonuniformly distributed molecules in zeolites. JACS, 147(32), 28965--28972. (www)

  @article{ , abstract = {Accurate assessment of molecular uptake and interactions at pore surfaces is crucial for advancing functional porous materials. However, these processes are governed by the intricate interplay of geometry constraints, local electric fields, and operational conditions, requiring in situ atomic-resolution characterization. Here, we present sub-angstrom-resolution (0.76 Å) and linear-phase-response imaging of zeolites and adsorbed benzene molecules across varying atmospheric conditions using in situ electron ptychography. Environment-induced crystal mis-tilts and low electron beam coherence were effectively corrected to maintain high resolution. We established a linear relationship between image phase changes and the number of adsorbed molecules, enabling molecule quantification within individual pores under varying benzene vapor pressures. Depth analysis revealed nonuniform molecular adsorption along pore channels, with guest molecules preferentially accumulated near Al-enriched regions. Our findings provide a general strategy for investigating localized molecular behaviors on the atomic scale in complex environments relevant to industrial catalysis and separation processes.}, archive = {J_JACS}, author = {Hao Xiong and Yi-Chi Wang and Xiaoyu Liang and Mingyu Zhao and Guo Tian and Guowei Wang and Lin Gu and Xiao Chen and Fei Wei}, doi = {10.1021/jacs.5c07054}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28965--28972}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ quantitative imaging of nonuniformly distributed molecules in zeolites}, volume = {147}, year = {2025}, }
• (2025). Two-state, nonvolatile memristors and light-assisted logic-in operation from diarylethene-based single-molecule junctions. JACS, 147(32), 28955--28964. (www)

  @article{ , abstract = {Single-molecule junctions (SMJs) were fabricated incorporating photochromic diarylethene units, which are covalently bonded to a bottom electrode by diazonium electro-reduction. The scanning-tunneling-microscopy break-junction (STM-BJ) and conductance versus time (STM- G ( t )) techniques characterize the different conductance states upon light irradiation, whereas the STM current versus voltage ( I / V ) measurement at room temperature allows electric-field-stimulated conductance switching. We observe that the Au–[DAE] 1 –Pt SMJs appear with a single conductance state. The Au–[DAE] 2 –Pt SMJs show two distinct high- and low-conductance states under UV or visible light irradiation. Most importantly, hysteresis I / V loops, emerging with a yield as high as 60%, reveal an electric-field-generated conductance switching with a memory effect. Cycles of successive “reading, writing, and erasing” processes are practiced at different applied voltages between the “0” (LC) and “1” (HC) states such that a Au–[DAE] 2 –Pt SMJ functions as a fully electric nonvolatile memristor. Statistical I / t and I / V heatmaps indicate that the memory properties are highly reproducible. Considering light and electric-field stimulus as two different inputs and the resulting HC or LC as output signals, the Au–[DAE] 2 –Pt memristor shows an XOR logic-in operation.}, archive = {J_JACS}, author = {Xinlei Yao and Lihao Guan and François Maurel and Fréderic Lafolet and Xiaonan Sun and Jean-Christophe Lacroix}, doi = {10.1021/jacs.5c06991}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28955--28964}, shortjournal = {J. Am. Chem. Soc.}, title = {Two-state, nonvolatile memristors and light-assisted logic-in operation from diarylethene-based single-molecule junctions}, volume = {147}, year = {2025}, }
• (2025). The structure of human IAPP fibrils reflects membrane and pH conditions. JACS, 147(32), 28943--28954. (www)

  @article{ , abstract = {Physiologically relevant in vitro models of amyloid aggregation are essential for linking structural insights to disease pathology. In type 2 diabetes, aggregation of human islet amyloid polypeptide (hIAPP) into fibrils is a hallmark of β-cell dysfunction, yet structural data on ex vivo hIAPP fibrils remain unavailable. Most models use solution-grown fibrils, overlooking membrane interactions and native pH, which underscores the need for more realistic in vitro models. Here, we use solid-state NMR spectroscopy to determine the structure of phospholipid membrane-mediated hIAPP fibrils formed under extracellular (pH 7.4) conditions. These fibrils are homogeneous and adopt an L-shaped protofilament architecture with an extended N-terminal β-strand─a region often unresolved in cryo-EM. The fibril core (N14–L27) adopts the CF1 fold, a conserved β-arch also seen in nonlipidic fibrils, suggesting its relevance in disease. In contrast, fibrils formed at intracellular pH (5.3) are structurally heterogeneous and show distinct structural differences in the C-terminus. hIAPP must exhibit substantial structural plasticity in the membrane environment, transitioning from helical monomers to β-hairpin oligomers and ultimately to β-arch-rich fibrils─transitions that may introduce energy barriers stabilizing toxic intermediates. Our findings provide the first high-resolution structure of membrane-mediated hIAPP fibrils highlighting the need to model aggregation under physiologically relevant conditions.}, archive = {J_JACS}, author = {Venus Singh Mithu and Karin Giller and Evgeny Nimerovsky and Kerstin Overkamp and Loren B. Andreas and Stefan Becker and Christian Griesinger}, doi = {10.1021/jacs.5c06971}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28943--28954}, shortjournal = {J. Am. Chem. Soc.}, title = {The structure of human IAPP fibrils reflects membrane and pH conditions}, volume = {147}, year = {2025}, }
• (2025). Unshielded ino decahedral core copper nanoclusters enable efficient photocatalytic sulfonylation of aryl halides. JACS, 147(32), 28932--28942. (www)

  @article{ , abstract = {The synthesis of metal nanoclusters (NCs) having decahedral cores is challenging, with only a few reports primarily focusing on systems containing gold (Au) and silver (Ag). Herein, we present the synthesis, characterization, and catalytic activities of a copper (Cu) NC featuring a centered Ino decahedral core: Cu 19 ( t BuPhCH 2 S) 12 (PPh 3 ) 6 H 6 Br ( Cu 19 ). Unlike typical core–shell structured NCs, Cu 19 exhibits a unique structure with a core capped by four motifs from four directions, where two square faces and both apexes of the Ino decahedron core are capped, leaving three square faces of the core exposed, acting as highly efficient catalytic active sites. This distinctive design opens new possibilities for catalytic applications of Cu NCs, as demonstrated experimentally in the sulfonylation of aryl halides under visible light irradiation at room temperature. Density functional theory (DFT) and experimental results suggest that the catalytic cycle proceeds through a single-electron transfer (SET) process between the photoexcited Cu 19 NC-sulfinates and the aryl halide, enabling efficient C–S arylation of sulfinates. The unshielded Cu 19 NC catalysts can be converted into a heterogeneous recyclable catalyst and are compatible with a wide range of aryl halides and sulfinate nucleophiles for producing sulfones.}, archive = {J_JACS}, author = {Mohammed Faihan Alotaibi and Arunachalam Sagadevan and Peng Yuan and Mohammad Bodiuzzaman and Kathiravan Murugesan and Renqian Zhou and Jun Yin and Simil Thomas and Ren-Wu Huang and Naveen M. Halappa and Chunwei Dong and Mutalifu Abulikemu and Husam N. Alshareef and Omar F. Mohammed and Magnus Rueping and Osman M. Bakr}, doi = {10.1021/jacs.5c06846}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28932--28942}, shortjournal = {J. Am. Chem. Soc.}, title = {Unshielded ino decahedral core copper nanoclusters enable efficient photocatalytic sulfonylation of aryl halides}, volume = {147}, year = {2025}, }
• (2025). Time-domain observation of ultrafast self-trapped exciton formation in lead-free double halide perovskites. JACS, 147(32), 28923--28931. (www)

  @article{ , abstract = {Self-trapped excitons (STEs), which have one or both carriers spatially trapped by a lattice distortion, are associated with broadband emission and a large Stokes shift that is desirable for many applications. The fundamental physical processes that lead to their formation are difficult to observe, mainly due to the ultrafast time scales involved and the low oscillator strength of STE transitions. Here, we employ ultrafast transient absorption spectroscopy with sub-20 fs temporal resolution in the ultraviolet to study the STE formation process in a pair of lead-free double perovskites, Cs 2 AgInCl 6 and Cs 2 (Ag 0.6 Na 0.4 )InCl 6 . Using first-principles calculations, we assign a broad photoinduced absorption band in Cs 2 AgInCl 6 to an intraband transition in the valence band that tracks the initial 70 fs hot-hole cooling step. Furthermore, exciton–phonon coupling calculations unravel the phonon modes that couple strongly with excitons in the lowest absorption peak to cause self-trapping. The transient absorption data shows the buildup of a stimulated emission band from the STE on a 200 fs time scale and long-lived coherent oscillations corresponding to the phonons of the lattice modified by the STE formation process.}, archive = {J_JACS}, author = {Ana Maria de Paula and Shunran Li and Bowen Hou and Srikrishnaa Vadivel and Danielle C. Teles-Ferreira and Andrea Iudica and Piotr Kabacinski and Hemen Hosseini and Jack McArthur and Giulio Cerullo and Diana Y. Qiu and Peijun Guo and Franco V. A. Camargo}, doi = {10.1021/jacs.5c06628}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28923--28931}, shortjournal = {J. Am. Chem. Soc.}, title = {Time-domain observation of ultrafast self-trapped exciton formation in lead-free double halide perovskites}, volume = {147}, year = {2025}, }
• (2025). Spin sensor-integrated covalent organic frameworks reveal the effect of Host–Guest interactions on the catalytic activity of immobilized enzymes. JACS, 147(32), 28912--28922. (www)

  @article{ , abstract = {Encapsulating enzymes within covalent organic frameworks (COFs) offers a promising strategy to enhance enzyme stability and facilitate their separation and recycling. However, the complex host–guest interactions in such hybrid systems substantially affect enzyme conformation flexibility, which can dominate key catalytic processes such as substrate binding and catalytic conversion. Understanding these molecular interplays is crucial but remains challenging. In this work, we present a spin sensor-integrated COF (SSICOF) strategy to probe host–guest interactions across diverse enzyme@COF systems. This approach leverages the highly programmable reticular framework of structurally stable COFs, wherein pore channels are atomically engineered to integrate spin probes via a click chemistry reaction. The spin–lattice interactions between the spin probes and the encapsulated enzyme generate interpretable variations in electron paramagnetic resonance (EPR) signals, delivering the host–guest interactions that cannot be probed by traditional spectroscopic techniques. Using the SSICOF approach combined with computational simulations, we demonstrate that the catalytic activity of immobilized enzymes is closely linked to their degree of freedom and structural flexibility under COF pore confinement. This strategy offers a versatile and powerful tool for probing underlying interactions in complex host–guest systems and predicting the catalytic activity of enzyme@COF hybrid biocatalysts.}, archive = {J_JACS}, author = {Jingru Feng and Xiaohui Liu and Siming Huang and Hankang Zhong and Can Xue and Guosheng Chen and Xiantai Zhou and Gangfeng Ouyang}, doi = {10.1021/jacs.5c06528}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28912--28922}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin sensor-integrated covalent organic frameworks reveal the effect of Host–Guest interactions on the catalytic activity of immobilized enzymes}, volume = {147}, year = {2025}, }
• (2025). Regulating the assembly of γ-cyclodextrin host and polyoxometalate-based guests toward light-responsive hybrid rotaxanes. JACS, 147(32), 28903--28911. (www)

  @article{ , abstract = {The rational design of hybrid organic–inorganic rotaxanes is crucial for advancing molecular machines and functional nanomaterials, yet the integration of metal-oxo clusters into interlocked systems remains challenging. Herein, we present a precision synthesis strategy for hybrid rotaxanes combining γ-cyclodextrin (γ-CD) hosts with Anderson-type polyoxometalate (POM)-based guests. This approach utilizes covalent POM modification coupled with strategically anchored organic functionalities to control supramolecular assembly, enabling the construction of pseudo -[2]-, [3]-, and [4]rotaxanes with controlled structural variations. Significantly, we achieved the first single-crystal examples of supramolecular pseudo -[4]rotaxanes featuring γ-CD dimers threaded by two organo-POM units. A key breakthrough was achieved through light-induced single-crystal-to-single-crystal transformation of these pseudo -[4]rotaxanes, producing hybrid [3]rotaxanes containing uniquely arranged anti -head-to-tail anthracene dimers─the first reported photoresponsive architecture of this type. These structural transformations demonstrate the dynamic, stimuli-responsive character of these hybrid systems. This work establishes a new paradigm for the precision engineering of rotaxanes using organo-POM building blocks, revealing their remarkable potential for creating smart materials with programmable structural changes. The successful integration of covalent modification, supramolecular templating, and photoresponsive components provides a powerful platform for developing next-generation multifunctional molecular machines and adaptive nanomaterials with precisely controlled properties.}, archive = {J_JACS}, author = {Wu-Ji Chen and Chun-Yan Liu and Yun-Jing Mu and Yi-An Yin and Chang-Gen Lin and De-Liang Long and Leroy Cronin and Yu-Fei Song}, doi = {10.1021/jacs.5c06495}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28903--28911}, shortjournal = {J. Am. Chem. Soc.}, title = {Regulating the assembly of γ-cyclodextrin host and polyoxometalate-based guests toward light-responsive hybrid rotaxanes}, volume = {147}, year = {2025}, }
• (2025). Supramolecular complexation of quenched rosamines with Cucurbit[7]Uril: Fluorescence turn-ON effect for super-resolution imaging. JACS, 147(32), 28893--28902. (www)

  @article{ , abstract = {Here, we present a fluorogenic supramolecular host–guest system comprising cucurbit[7]uril (CB7) and a rationally designed rosamine fluorescent dye ( P-ARose ) tailored for super-resolution imaging applications. By strategically designing the meso -aryl moiety of the guest, we concomitantly quenched the dye’s emission in its free form and achieved strong binding with the host. The formation of the complex suppresses quenching and encompasses a large fluorescence turn-ON effect. Experimental and theoretical studies revealed that CB7 complexation significantly improved the photophysical properties of P-ARose , with a 6.4-fold fluorescence increase and 4.2-fold enhanced emission quantum yield. Further functionalization of P-ARose with a HaloTag ligand or an NHS reactive group rendered it suitable for live-cell and immunofluorescence labeling, yielding specificity, negligible background, and a minimal fluorescence signal in the unbound state. The addition of CB7 drastically increased fluorescence, enabling conventional and stimulated emission depletion (STED) imaging with subdiffraction resolution. Furthermore, the turn-ON ability of the host–guest complex facilitated pseudo two-color sequential imaging of different protein combinations within the same acquisition channel. These results demonstrate the potential of this supramolecular system to enable an additional super-resolution imaging multiplexing modality through noncovalent chemistry.}, archive = {J_JACS}, author = {Dušan Kolarski and Mariano L. Bossi and Richard Lincoln and Juan C. Fuentes-Monteverde and Vladimir N. Belov and Stefan W. Hell}, doi = {10.1021/jacs.5c06406}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28893--28902}, shortjournal = {J. Am. Chem. Soc.}, title = {Supramolecular complexation of quenched rosamines with Cucurbit[7]Uril: Fluorescence turn-ON effect for super-resolution imaging}, volume = {147}, year = {2025}, }
• (2025). Ternary interactions balance enabled sequential assembly toward the synthesis of hierarchically mesoporous metal hydroxide nanoparticles. JACS, 147(32), 28882--28892. (www)

  @article{ , abstract = {Materials with spatially orthogonal hierarchically mesoporous structures exhibit intriguing physical and chemical properties due to the synergistic integration of bimodal pores. The introduction of porosity with an extra dimension via multiple soft templates is highly flexible, but it remains a challenge for metal hydroxide materials. Here, we report a ternary interaction balance-enabled sequential assembly (TESA) strategy to construct hierarchically mesoporous metal hydroxide (HM-M) nanoparticles with tunable morphologies. This facile fabrication involves a sequential assembly process, including heterogeneous nucleation and monomicelle assembly, during which ingenious regulations on surface tension at the ternary interface are required. The balance among metal precursors, small surfactants, and block copolymers can be extended to obtain HM-M nanoparticles with various morphologies and compositions that possess enormous potential in catalysis, sensing, and energy. This study not only provides a versatile synthesis platform for novel HM-M materials but also offers new insights and inspiration for investigating multicomponent interactions during the assembly process.}, archive = {J_JACS}, author = {Yuanzhao Xie and Wenhe Xie and Jiarong Li and Yonghui Deng and Xiaowei Cheng}, doi = {10.1021/jacs.5c06417}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28882--28892}, shortjournal = {J. Am. Chem. Soc.}, title = {Ternary interactions balance enabled sequential assembly toward the synthesis of hierarchically mesoporous metal hydroxide nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Enantioselective synthesis of spirocyclic nitrogen-containing heterocycles catalyzed by an iridium-containing cytochrome. JACS, 147(32), 28875--28881. (www)

  @article{ , abstract = {In the past decade, thousands of synthetic building blocks, intermediates, and drug candidates containing a spirocyclopropane core with at least one nitrogen atom have been investigated for a range of biological activities. These compounds create three-dimensional architectures that maintain the rigidity of their more sp 2 -rich analogs. Most examples contain simple core structures with unsubstituted cyclopropyl moieties, and only one has been made enantioselectively. Therefore, a straightforward method to produce more complex spirocyclic amines with high stereoselectivity would be of great synthetic utility. Here, we report the stereoselective cyclopropanation of methylene-substituted saturated heterocycles catalyzed by an iridium-containing cytochrome. After just four rounds of mutagenesis, we identified a variant that forms spiroazetidines, spiropyrrolidines, and spiropiperidines with enantioselectivities up to 99%. These results demonstrate an expeditious route to valuable, rigid, sp 3 -rich amino acid linchpins.}, archive = {J_JACS}, author = {Jingtong Xu and Brandon J. Bloomer and John N. Brunn and Andrew P. Quest and Sukriyo Chakraborty and Joseph E. Schneider and Douglas S. Clark and John F. Hartwig}, doi = {10.1021/jacs.5c06239}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28875--28881}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective synthesis of spirocyclic nitrogen-containing heterocycles catalyzed by an iridium-containing cytochrome}, volume = {147}, year = {2025}, }
• (2025). Catalytic photooxygenation demonstrates therapeutic efficacy in transthyretin amyloidosis. JACS, 147(32), 28860--28874. (www)

  @article{ , abstract = {The escalating global trend of aging populations has brought attention to the rising prevalence of late-onset amyloid disorders. Among them, amyloid transthyretin (ATTR) amyloidosis presents a growing area of unmet medical needs. While current treatment modalities have demonstrated efficacy in preventing or delaying amyloid generation, methodology to selectively modify and neutralize existing amyloid burdens remains inadequately addressed, leaving the fundamental irreversibility and hence the fatality of these conditions, a long-standing medical challenge. Here, we report the first demonstration of therapeutic efficacy in ATTR amyloidosis via dynamic control of ATTR aggregation and toxicity, enabled by small-molecule organophotocatalysis. Selective incorporation of hydrophilic oxygen atoms into the hydrophobic amyloid core reshapes the aggregation landscape, neutralizing proteotoxicity, and mitigating cellular damage. Additionally, this targeted covalent modification significantly reduces in vivo ROS levels, correlating with the observed therapeutic effects in Caenorhabditis elegans , the only experimental model replicating key clinical manifestations of the disease. Docking simulations elucidated the molecular basis of catalyst performance, providing the foundational blueprint for amyloid-neutralizing organophotocatalysis. Collectively, this study provides a scalable approach to overcoming a persistent barrier in amyloidosis therapy.}, archive = {J_JACS}, author = {Mina Yamane and Hiroki Umeda and Moe Toyobe and Atsushi Iwai and Kuraudo Ishihara and Genki Kudo and Harunobu Mitsunuma and Yukiko Hori and Taisuke Tomita and Mineyuki Mizuguchi and Masamitsu Okada and Mitsuharu Ueda and Yukio Ando and Shigehiro A. Kawashima and Youhei Sohma and Hironori Kaji and Takatsugu Hirokawa and Kunitoshi Yamanaka and Motomu Kanai}, doi = {10.1021/jacs.5c06205}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28860--28874}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic photooxygenation demonstrates therapeutic efficacy in transthyretin amyloidosis}, volume = {147}, year = {2025}, }
• (2025). Stable and accurate orbital-free density functional theory powered by machine learning. JACS, 147(32), 28851--28859. (www)

  @article{ , abstract = {Hohenberg and Kohn have proven that the electronic energy and the one-particle electron density can, in principle, be obtained by minimizing an energy functional with respect to the density. While decades of theoretical work have produced increasingly faithful approximations to this elusive exact energy functional, their accuracy is still insufficient for many applications, making it reasonable to try and learn it empirically. Using rotationally equivariant atomistic machine learning, we obtain for the first time a density functional that, when applied to the organic molecules in QM9, yields energies with chemical accuracy relative to the Kohn–Sham reference while also converging to meaningful electron densities. Augmenting the training data with densities obtained from perturbed potentials proved key to these advances. This work demonstrates that machine learning can play a crucial role in narrowing the gap between theory and the practical realization of Hohenberg and Kohn’s vision, paving the way for more efficient calculations in large molecular systems. The trained STRUCTURES25 model is made available along with full source code and data for training and inference.}, archive = {J_JACS}, author = {Roman Remme and Tobias Kaczun and Tim Ebert and Christof A. Gehrig and Dominik Geng and Gerrit Gerhartz and Marc K. Ickler and Manuel V. Klockow and Peter Lippmann and Johannes S. Schmidt and Simon Wagner and Andreas Dreuw and Fred A. Hamprecht}, doi = {10.1021/jacs.5c06219}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28851--28859}, shortjournal = {J. Am. Chem. Soc.}, title = {Stable and accurate orbital-free density functional theory powered by machine learning}, volume = {147}, year = {2025}, }
• (2025). Unveiling the role of chirality in the oxidation of monoterpenes. JACS, 147(32), 28842--28850. (www)

  @article{ , abstract = {Monoterpene oxidation is a major contributor to the formation and growth of a secondary organic aerosol (SOA) in the atmosphere. Although most monoterpenes naturally exist in two enantiomeric forms, the impact of their molecular chirality on SOA formation has been neglected, in part due to the hypothesis that a precursor’s chirality will not impact gaseous oxidation processes when considering achiral oxidants (e.g., O 3 , OH radicals). Within this study, we systematically investigated the gas-phase oxidation of the enantiomers of two common monoterpenes, (±)-α-pinene and (±)-limonene, at atmospherically relevant concentrations. We demonstrate greater formation (15 ± 0.3% and 19 ± 0.2%) of oxidized organic molecules (OOMs) for (+)-α-pinene and (+)-limonene, respectively, compared to their (−) enantiomers. We propose these observations are due to differences in key intermediate steps within the oxidation process that correlate with RO 2 lifetime and bimolecular reactions. For example, oxidation of (+)-limonene promotes the formation of alkoxy radicals, which predominately undergo isomerization and subsequent radical propagation, leading to enhanced OOM production. In contrast, (−)-limonene oxidation favors the scission of the carbon skeleton, producing more volatile products. The observed differences in product yields between the enantiomer populations are expected to have atmospheric repercussions on SOA formation due to shifting enantiomer compositions from vegetation stress events (e.g., drought due to climate change) and the use of volatile chemical products.}, archive = {J_JACS}, author = {Linyu Gao and Sébastien Perrier and Siddharth Iyer and Laurent Vanoye and Fabienne Fache and Megan S. Claflin and Theo Kurten and Matthieu Riva}, doi = {10.1021/jacs.5c06118}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28842--28850}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling the role of chirality in the oxidation of monoterpenes}, volume = {147}, year = {2025}, }
• (2025). Cu nanocluster size effect inducing the transformation of polysulfides to Cu2S/CuS for durable sodium storage. JACS, 147(32), 28831--28841. (www)

  @article{ , abstract = {The limited conversion efficiency of polysulfides (PSs) in sodium–sulfur batteries remains a critical bottleneck to achieving optimized sulfur utilization and stable cycling. While copper-based materials present promise in anchoring PSs, the dynamic evolution of Cu nanostructures during cycling and their size-dependent interaction with PSs are poorly understood. Herein, we reveal a size-governed electrochemical mechanism in which Cu nanoclusters (<1 nm) dynamically regulate the phase transition between Cu 2 S and CuS to enable reversible sulfur redox chemistry. Operando analysis demonstrates that Cu foil-derived nanoclusters form single-crystalline Cu 2 S via strong electrostatic coupling with long-chain PSs, effectively suppressing shuttling. As cycling progresses, Cu nanocluster refinement lowers the energy for Cu 2 S-to-CuS conversion, creating a kinetically favorable dual-phase structure (Cu 2 S outer/CuS inner) that accelerates solid-phase sulfur regeneration. Simultaneously, the Cu nanoclusters and CuS synergistically catalyze PSs-to-S conversion, achieving near-theoretical sulfur utilization. The S-loaded carbon on the Cu foil (S@C–Cu) cathode delivers ultrastable cycling (1164.9 mAh g –1 after 3000 cycles at 5 A g –1 ) and high areal capacity (3.68 mAh cm –2 in pouch cell). This size-effect-driven phase evolution is generalizable to Cu 9 S 5 , Cu 2 S, NiS 2 , and CoS 2 . Our work bridges nanoscale metal dynamics with macroscopic battery performance, offering atomic-level insights into sulfur electrochemistry for practical energy storage.}, archive = {J_JACS}, author = {Canpei Wang and Mengting Zheng and Tiefeng Liu and Liguang Wang and Jun Lu}, doi = {10.1021/jacs.5c05478}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28831--28841}, shortjournal = {J. Am. Chem. Soc.}, title = {Cu nanocluster size effect inducing the transformation of polysulfides to Cu2S/CuS for durable sodium storage}, volume = {147}, year = {2025}, }
• (2025). Balanced iodophilicity and solvophilicity unlocks fast iodine conversion chemistry. JACS, 147(32), 28820--28830. (www)

  @article{ , abstract = {The shuttling of polyiodides and sluggish redox kinetics greatly hinder the implementation of an aqueous Zn–I 2 battery. Despite numerous catalysts have been implemented to improve the iodine cathode stability, an important aspect, the balance between polyiodide adsorption and interfacial mass transport kinetics at the cathode surface, has been overlooked. It is known that insufficient intermediate trapping ability will cause low iodine utilization and fast capacity decay. However, excessive adsorption of iodine species will block the ion transport and lead to passivation of the catalyst, which is particularly serious under lean-electrolyte and high mass loading conditions. To tackle this challenge, we employ a dual single atomic catalyst encompassing NiN 4 P and FeN 4 P sites to promote a catalytic interface with well-balanced solvophilicity and iodophilicity. Specifically, the FeN 4 and NiN 4 sites primarily enhance polyiodide immobilization and mass transport, respectively. The P ligands further strengthen these functions by tuning the Fe site from low to medium spin state and creating the anion-rich inner Helmholtz plane at Ni sites. Benefiting from this dual-metal atomic catalyst, the iodine cathode exhibits high cycling stability and ultralow self-discharge rate under a low E/I ratio. This work provides insights into regulating the aqueous halogen cathode interface for long cycle life.}, archive = {J_JACS}, author = {Tao Xiao and Jin-Lin Yang and Ruo Jie Xu and Hengyue Xu and Huan Liu and Jia Li and Haoming Bao and Xiaoyan Jin and Seong-Ju Hwang and Zhe Wang and Hong Jin Fan}, doi = {10.1021/jacs.5c05786}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28820--28830}, shortjournal = {J. Am. Chem. Soc.}, title = {Balanced iodophilicity and solvophilicity unlocks fast iodine conversion chemistry}, volume = {147}, year = {2025}, }
• (2025). Tunable formal photocycloaddition of 1-naphthol derivatives. JACS, 147(32), 28810--28819. (www)

  @article{ , abstract = {Although three different modes of photocycloaddition between arenes and alkenes are well-known, the control of reaction selectivity remains a long-standing challenge. In this study, we present the first tunable photocycloaddition of 1-naphthol derivatives under visible light irradiation, affording ortho , meta , and para cycloadducts, respectively. The success of the reaction hinges on a rational design of naphthalene substrates and the judicious selection of solvents and sensitizer. The reaction mechanism is further elucidated through a combination of control experiments and density functional theory (DFT) calculations.}, archive = {J_JACS}, author = {Qinqin Wu and Shuo Yang and Minyan Wang and Ping Lu}, doi = {10.1021/jacs.5c05463}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28810--28819}, shortjournal = {J. Am. Chem. Soc.}, title = {Tunable formal photocycloaddition of 1-naphthol derivatives}, volume = {147}, year = {2025}, }
• (2025). A dynamically induced phase transition in Na4P2S6─Ultrafast na+ mobility triggering rotor phase formation. JACS, 147(32), 28799--28809. (www)

  @article{ , abstract = {The physical properties of any crystalline solid, such as the irregular movement of ions or atoms, are closely linked to its structure. Changes in local structure or local defect chemistry are typically attributed to changes in ion hopping. Conversely, one might also ask whether fast ionic diffusion can cause structural changes, finally initiating an overall phase transition. By using high-resolution 23 Na and 31 P nuclear magnetic resonance (NMR) carried out at temperatures as high as 650 °C, we show that changes of the local Na + environment in the Na + -conducting model compound Na 4 P 2 S 6 indeed precede the transition of the anionic framework from β-Na 4 P 2 S 6 to the fast-conducting γ-phase. While rapid 2D Na + diffusion governs ionic conductivity in the β-phase of Na 4 P 2 S 6 , the high-temperature γ-phase has been theoretically predicted and experimentally shown to be a rotor phase with high dynamics of both the mobile Na + cations and the anionic framework. Here, we provide evidence that Na + diffusion and the initial transformation of the Na substructure precede the transition of the P 2 S 6 units to a rotating framework. NMR spectra and relaxation times of both 23 Na and 31 P reveal that rapid P 2 S 6 4– motions occur in a molten Na + substructure, but these motions do not influence Na + hopping much. Hence, we suggest that Na + hopping while first initiating the transformation to the rotor phase is indeed uncoupled from polyanion rotations at high temperatures. Our study provides a new perspective on the details governing phase transitions in fast-ion conductors and may lead to a deeper understanding of these phenomena.}, archive = {J_JACS}, author = {Katharina Hogrefe and Bernhard Gadermaier and Christian Schneider and Sebastian Bette and Bettina V. Lotsch and H. Martin R. Wilkening}, doi = {10.1021/jacs.5c05339}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28799--28809}, shortjournal = {J. Am. Chem. Soc.}, title = {A dynamically induced phase transition in Na4P2S6─Ultrafast na+ mobility triggering rotor phase formation}, volume = {147}, year = {2025}, }
• (2025). Targeting the SARS-CoV-2 RNA translation initiation element SL1 by molecules of low molecular weight. JACS, 147(32), 28783--28798. (www)

  @article{ , abstract = {We present the development of low molecular weight inhibitors that target the 5′-terminal RNA stem-loop 1 (SL1) of the SARS-CoV-2 genome. SL1 is crucial for allowing viral protein synthesis in the context of global translational repression in infected cells. We applied compound- and RNA-detected nuclear magnetic resonance spectroscopy (NMR) experiments to guide a fragment-growth strategy based on two primary NMR screening hits from a diverse fragment library poised for follow-up chemistry. These primary hits with molecular weights of around 200 Da were derivatized with the aim of improving the initial solubility, binding affinity, and target specificity. We used NMR to monitor solubility changes, binding affinity, and specific binding to the SL1 binding pocket during the fragment derivatization campaign. Compounds scoring the best in all three categories were further tested for their inhibitory effect on SL1 in a cell-free translation assay, where the best two compounds, A.2 and A.13, showed both significant and selective inhibition. Our results demonstrate that small molecules targeting translation initiation of SARS-CoV-2 can be rapidly obtained using NMR-guided medicinal chemistry, and that the correlation between affinity, selectivity, and in situ function of the derived compounds is still to be explored.}, archive = {J_JACS}, author = {Sabrina Toews and Francesca Donà and Marco Keller and Jürgen Krauß and Franz Bracher and Úrsula López-García and Jörg Pabel and Daniel Merk and Marcel J. J. Blommers and Jan Ferner and Anna Wacker and Christian Richter and Harald Schwalbe}, doi = {10.1021/jacs.5c05264}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28783--28798}, shortjournal = {J. Am. Chem. Soc.}, title = {Targeting the SARS-CoV-2 RNA translation initiation element SL1 by molecules of low molecular weight}, volume = {147}, year = {2025}, }
• (2025). Facile synthesis of polyhydroperoxides from ethylene and carbon monoxide. JACS, 147(32), 28773--28782. (www)

  @article{ , abstract = {A synthetic strategy for preparing on-chain polyhydroperoxides is reported, utilizing the postpolymerization functionalization of polyketone. Alternating polyketones, derived from the copolymerization of ethylene and carbon monoxide, were quantitatively and selectively transformed into solid polyperoxides using aqueous hydrogen peroxide at room temperature. The complete conversion of carbonyl into peroxy groups made the resulting polyperoxide ideal for free radical graft copolymerization. As a functional polymer, polyperoxide was employed as a macroinitiator to prepare densely grafted copolymers, polyethylene- g -poly(4-methylstyrene) and polyethylene- g -poly(methyl methacrylate). Moreover, the degradability of the graft copolymer was demonstrated, further highlighting the sustainability of polyperoxide from production to application.}, archive = {J_JACS}, author = {Hyuk-Joon Jung and Hootan Roshandel and Yin-Pok Wong and Paula L. Diaconescu}, doi = {10.1021/jacs.5c05143}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28773--28782}, shortjournal = {J. Am. Chem. Soc.}, title = {Facile synthesis of polyhydroperoxides from ethylene and carbon monoxide}, volume = {147}, year = {2025}, }
• (2025). Ultrahigh-throughput multiplexed screening of purified protein from cell-free expression using droplet microfluidics. JACS, 147(32), 28758--28772. (www)

  @article{ , abstract = {Screening large libraries is essential for protein engineering, but traditional approaches are limited by low throughput and biological variability. Here, we present an ultrahigh-throughput droplet microfluidics platform utilizing cell-free expression to screen libraries of purified proteins. We use bifunctional agarose beads to capture both DNA and encoded proteins, facilitating complete reagent exchange between incompatible reaction steps. This enhances the signal-to-noise ratio compared to live-cell expression systems. We introduce multiplexed screening to increase the loading per drop, enhancing the throughput by ∼100 times to 10 million variants in under 1 h of sorting. We use this platform to engineer Bacillus subtilis Lipase A (BsLipA) for improved thermotolerance. We screen a combinatorial library where 15 residues are saturated and identify multiple variants with 9–12 substitutions and >40 °C improvement in thermotolerance after a single round of mutagenesis. This platform offers a robust, scalable solution for protein engineering.}, archive = {J_JACS}, author = {Anqi Chen and Wentao Xu and Xinge Diana Zhang and Junming Lao and Xing Zhao and Karla Milcic and David A. Weitz}, doi = {10.1021/jacs.5c04962}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28758--28772}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrahigh-throughput multiplexed screening of purified protein from cell-free expression using droplet microfluidics}, volume = {147}, year = {2025}, }
• (2025). Simulation evidence of nanobubble clusters of gas in water: A nanoscale solvation mechanism. JACS, 147(32), 28748--28757. (www)

  @article{ , abstract = {Previous experiments have shown that when water is mixed with dissolvable organic molecules (DOMs), it can lead to insoluble gas-containing nanoclusters. However, molecular insights into the gas-containing nanoclusters are still lacking. Herein, we show the first large-scale simulation evidence of stable nanobubble (NB) clusters (∼2 nm radius) of insoluble gas in water mixed with DOMs by using electrically neutral interface models. Notably, our molecular dynamics simulations demonstrate a dissolution–nanobubble–dissolution transition for the (insoluble) gas in the water/DOM solutions (as the mole fraction of DOMs is increased), a phenomenon observed across most DOM types excluding extreme polarity cases. The latter evidence suggests that the formation of gas-containing NB clusters is likely a generic phenomenon for water mixed with a modest amount of DOMs. The re-entrant dissolution behavior can be attributed to the dual roles of DOMs, i.e., for promoting and stabilizing NB clusters at low gas mole fraction and generating continuous nanostructures of the gas beyond the NB formation threshold. Our independent theoretical analysis confirms the stability of NB clusters in water/DOM solutions. Akin to micelle formation, NB formation results in increased solubility of insoluble gas in water/DOM solutions. From a fundamental solution chemistry perspective, the formation of NB clusters can be viewed as a nanoscale solvation mechanism that differs markedly from the conventional molecular solvation mechanism for the insoluble gas in water.}, archive = {J_JACS}, author = {Jing Li and Hongguang Zhang and Zhenjiang Guo and Jian Jiang and Xianren Zhang and Dapeng Cao and Xiao Cheng Zeng}, doi = {10.1021/jacs.5c04560}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28748--28757}, shortjournal = {J. Am. Chem. Soc.}, title = {Simulation evidence of nanobubble clusters of gas in water: A nanoscale solvation mechanism}, volume = {147}, year = {2025}, }
• (2025). Amplifying engineered bacterial outer membrane vesicle production using functional peptidoglycan inhibitors. JACS, 147(32), 28735--28747. (www)

  @article{ , abstract = {Outer membrane vesicles (OMVs) are promising candidates for biomedical applications. However, their widespread use has been limited by low productivity and suboptimal therapeutic effects. In this study, we introduce an effective chemical method using designed boosters to enhance endogenous OMV generation, achieving up to a 65-fold increase through a simple one-step coculture process. These boosters are formed by conjugating 4-(naphthalen-2-yl)-4-oxobutanoic acid (NA) with different compounds, allowing for the customizable production of either natural or functionalized OMVs. Furthermore, the resulting functionalized OMVs exhibit good photodynamic treatment potential for both in vitro and in vivo experiments. Detailed mechanism study suggests that upon the entry of boosters into bacteria, the synthesis of peptidoglycan was inhibited, leading to membrane protrusion and OMV release. Importantly, this strategy is successfully validated across five classical bacterial strains, demonstrating the versatility of the boosters. This work provides a simple, effective, and universal method to enhance the generation of OMVs, offering new insights for the development of biomanufacturing platforms in cancer therapy.}, archive = {J_JACS}, author = {Dandan Wang and Bowen Li and Dongfeng Zhang and Jiahao Zhuang and Siqin Chen and Jianwu Tian and Zhiyao Li and Chongzhi Wu and Weidong Pan and Bin Liu}, doi = {10.1021/jacs.5c04132}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28735--28747}, shortjournal = {J. Am. Chem. Soc.}, title = {Amplifying engineered bacterial outer membrane vesicle production using functional peptidoglycan inhibitors}, volume = {147}, year = {2025}, }
• (2025). Elucidation of the Structure–Activity relationship for cu-erionite in the direct conversion of methane to methanol: An operando XAS study. JACS, 147(32), 28723--28734. (www)

  @article{ , abstract = {The partial oxidation of methane to methanol over copper-exchanged zeolites offers a promising avenue for methane valorization. Numerous zeolites have been demonstrated to be active for the selective oxidation of methane, with the methanol yield varying significantly depending on the zeolite framework, Si/Al ratio, and copper loading. Herein, we present a comprehensive study of one of the most active Cu-erionite (Cu-ERI) zeolites with different compositions for the stepwise conversion of methane to methanol, aiming to elucidate the relationship between the methanol yield and the nature of copper species in Cu-ERI zeolites. Operando X-ray absorption spectroscopy (XAS), combined with Fourier-transform infrared spectroscopy (FTIR), allows us to establish a correlation that reveals the dependence of the methanol yield on the reduction rate of copper species. Our findings demonstrate that the Cu/Al ratio plays a crucial role in determining the reducibility of copper species in Cu-ERI zeolites, which in turn governs methanol yield normalized to the copper content. While the Si/Al ratio of the parent zeolite determines the achievable copper loading and the maximal methanol yield, it does not influence the normalized methanol yield. This work suggests that controlling the Cu/Al ratio is essential for maximizing copper efficiency and achieving selective methane partial oxidation. At a fixed optimal Cu/Al ratio, increasing the Al content enhances the total methanol yield by providing more copper exchange sites. The structure–activity relationship of Cu-ERI zeolites in the direct conversion of methane to methanol offers valuable insights into the interplay between the zeolite host and copper species, highlighting the importance of both Cu/Al and Si/Al ratios in designing selective, high-performance materials for this challenging reaction.}, archive = {J_JACS}, author = {Jie Zhu and Vitaly L. Sushkevich and Amy J. Knorpp and Mark A. Newton and Toru Wakihara and Tatsuya Okubo and Zhendong Liu and Jeroen A. van Bokhoven}, doi = {10.1021/jacs.5c03554}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28723--28734}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidation of the Structure–Activity relationship for cu-erionite in the direct conversion of methane to methanol: An operando XAS study}, volume = {147}, year = {2025}, }
• (2025). Nano-Bi@Hard carbon composite anode for sodium-ion batteries with 385 wh l–1 volumetric energy density and durability. JACS, 147(32), 28714--28722. (www)

  @article{ , abstract = {Sodium-ion batteries (SIBs) are promising alternatives to lithium-ion batteries (LIBs) for sustainable energy storage, yet their adoption in compact applications is hindered by a low volumetric energy density (VED) or relatively poor structural instability. Herein, we present a nano-Bi@hard carbon (nano-Bi@HC) composite featuring densely packed microspheres with uniformly dispersed Bi nanoparticles (6–18 nm) embedded in a hard carbon matrix, achieving a remarkable VED of 385 Wh L –1 , with exceptional cycling stability (97% retention over 4000 cycles). Utilizing pectin’s carboxyl functional groups, Bi 3+ ions were homogeneously coordinated to enable a high Bi content (86.2 wt %) without agglomeration during carbonization. The nano-Bi@HC anode exhibits an unparalleled volumetric capacity of 1950 mAh cm –3 under a high areal loading (12.3 mg cm –2 ) and compaction density (4.8 g cm –3 ). Paired with a Na 3 V(PO 4 ) 3 cathode, the full cell demonstrates a superior performance across temperature ranges, highlighting its practical potential. This study establishes a scalable strategy for designing high-VED and durable alloy-based anodes, bridging critical gaps in SIB technology.}, archive = {J_JACS}, author = {Zhiyu Lu and Haolei Yu and Yunhong Wei and Chengcheng Cao and Rong Liang and Guolei Cai and Song Jin and Hongchang Jin and Yong Ni and Yue Lin and Hengxing Ji}, doi = {10.1021/jacs.5c03507}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28714--28722}, shortjournal = {J. Am. Chem. Soc.}, title = {Nano-Bi@Hard carbon composite anode for sodium-ion batteries with 385 wh l–1 volumetric energy density and durability}, volume = {147}, year = {2025}, }
• (2025). Understanding twisted triarylboranes from single crystals to heterojunction blends and their applications in organic photovoltaics. JACS, 147(32), 28694--28713. (www)

  @article{ , abstract = {The triarylborane family has expanded rapidly as valuable π electron-accepting moieties in organic materials, yet the performance and application of triarylboranes in organic photovoltaics (OPVs) have thus far been limited. Herein, we present a comprehensive platform of 17 distinct triarylboranes to investigate their structure–property relationships from single crystals to heterojunction blends and further to OPV device performance. We show that twisted triarylboranes exhibit distinct molecular packing behavior in the solid state, characterized by limited π–π stacking and the lack of the face-on orientation required for efficient light-to-electric conversion, in contrast to state-of-the-art OPV materials. However, when incorporated as a third component, triarylboranes induce red-shifted absorption and blue-shifted photoluminescence spectra in OPV materials, thereby reducing reorganization energies in blends. Furthermore, triarylboranes possessing high dipole moments and trap-free energetics enhance power conversion efficiencies (PCEs) in devices. Notably, careful molecular design of triarylboranes is essential, as strong donor moieties lead to high-lying HOMOs in triarylboranes, creating energetic traps in OPV blends and significantly reducing PCEs. Finally, we demonstrate the application of triarylboranes in semitransparent OPVs, achieving improved PCEs and stability without losing semitransparent performance, and in state-of-the-art PM6/L8-BO-based blends, achieving impressive PCEs of 19.56%. These findings offer valuable guidance for the rational design of triarylboranes for OPVs and related organic electronic applications, reducing reliance on trial-and-error approaches.}, archive = {J_JACS}, author = {Jianhua Han and Han Xu and Anirudh Sharma and Jesika Asatryan and Florian Rauch and Alexandra Friedrich and Johannes Krebs and Lukas Swoboda and Julia Schuster and Sudhakar Pagidi and Neena K. Kalluvettukuzhy and Maryam Alqurashi and Pakkirisamy Thilagar and Nils Schopper and Ivo Krummenacher and Vladimir Stepanenko and Maik Finze and Holger Braunschweig and Jaime Martín and Frank Würthner and Derya Baran and Todd B. Marder}, doi = {10.1021/jacs.5c02308}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28694--28713}, shortjournal = {J. Am. Chem. Soc.}, title = {Understanding twisted triarylboranes from single crystals to heterojunction blends and their applications in organic photovoltaics}, volume = {147}, year = {2025}, }
• (2025). π–π stacking and structural configurations in aromatic thiophene and fluorobenzene dimers revealed by rotational spectroscopy. JACS, 147(32), 28684--28693. (www)

  @article{ , abstract = {Understanding the structures and bonding interactions between aromatic systems is crucial for interpreting the properties of biological molecules and materials. In this study, we employed chirp-polarization Fourier-transform microwave spectroscopy to investigate the structures and noncovalent interactions in both homogeneous and heterogeneous dimers formed by thiophene and fluorobenzene molecules. Our findings reveal that the thiophene dimer adopts a T-shaped structure, while the fluorobenzene dimer predominantly exhibits a parallel-displaced arrangement. For the heterogeneous dimer, both T-shaped and parallel-displaced structures are observed. Isotopic substitution spectra were utilized to obtain precise structural information on the π–π stacking configurations, with their stability further verified via the observation of the helium-doped clusters. Theoretical calculations indicate that dispersion interactions dominate the binding energies of these dimers. The study reveals that due to the small barriers for configurational transitions, only one isomer, either parallel or T-shaped, is likely to persist in the gas phase, unless the two isomers have nearly equal binding energies, as seen in the C 4 H 4 S-PhF complex.}, archive = {J_JACS}, author = {Xinlei Chen and Guanjun Wang and Xiaoqing Zeng and Weixing Li and Mingfei Zhou}, doi = {10.1021/jacs.5c02401}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28684--28693}, shortjournal = {J. Am. Chem. Soc.}, title = {π–π stacking and structural configurations in aromatic thiophene and fluorobenzene dimers revealed by rotational spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Carbon reduction powered by natural electrochemical gradients under submarine hydrothermal vent conditions. JACS, 147(32), 28674--28683. (www)

  @article{ , abstract = {Energy metabolism at the emergence of life has been the topic of intense theoretical and experimental study. Alkaline hydrothermal vents (AHVs) may have facilitated energy transfer and carbon fixation at life’s emergence. Specifically, pH separation across vent walls could have been the forerunner to pH separation across cell membranes, with inorganic barriers containing [Ni-]FeS minerals as precursors of metalloenzymes in potentially ancient biological reductive acetyl-CoA Wood–Ljungdahl (WL) and other metabolic pathways. We previously demonstrated pH-gradient-dependent reduction of CO 2 to formate by H 2 in AHV interface conditions. Here, we address the same problem of CO 2 reduction using a macroscale reactor with minerals synthesized via protocols meant to mimic the natural processes of hydrothermal chimney formation. This reactor also allowed us to probe more variables and explore longer experimentation time frames. These results elucidate how different aspects of the hydrothermal–vent interface (e.g., different minerals and/or temperature gradients) affect the observed CO 2 electrochemical reduction as well as the flow of electrons under passive vs induced currents and potentials. Using experimental simulations and electrochemistry techniques, we detected two key steps of the WL pathway (CO 2 to formic acid and the formation of acetic acid). We explored effects of Ni incorporation in the mineral catalyst, as well as temperature and the effects of these variables on the production of formate. Currents as small as 10 nanoamps to 10 microamps were enough to efficiently carry out CO 2 reduction. In this work, we electrochemically explore energy protometabolism in vent–ocean interfaces, specifically focusing on [Ni-]FeS minerals as precursors of metalloenzymes.}, archive = {J_JACS}, author = {T. Altair and E. Dragoti and V. Sojo and Y. Li and S. Skiffington and W.A. Sullivan and G.T. Drozd and S.E. McGlynn and D. Galante and H. Varela and R. Hudson}, doi = {10.1021/jacs.5c01948}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28674--28683}, shortjournal = {J. Am. Chem. Soc.}, title = {Carbon reduction powered by natural electrochemical gradients under submarine hydrothermal vent conditions}, volume = {147}, year = {2025}, }
• (2025). Carbonate-bearing ionizable lipids for mRNA delivery to splenic NK cells. JACS, 147(32), 28665--28673. (www)

  @article{ , abstract = {mRNA immunotherapies targeting natural killer (NK) cells hold substantial potential for treating cancer and viral diseases. However, achieving functional delivery of mRNA to splenic NK cell subsets remains a formidable challenge. Herein, we rationally design a library of 161 carbonate-bearing ionizable lipids (CAILs) and formulate lipid nanoparticles (LNPs) for functional mRNA delivery to the spleen and NK cells following intravenous administration. Unlike traditional LNPs that primarily target the liver, CAIL-based four-component LNPs predominantly deliver mRNA to the spleen. Notably, the removal of cholesterol from CAIL LNPs further enhances the spleen-targeting specificity and efficacy, significantly surpassing those of previous spleen-targeted LNPs. As a result, the optimized CAIL LNPs achieve robust mRNA translation in splenic NK cells, inducing encouraging transfection of 21% of splenic NK cells in an Ai9 mouse model. The lipid structural design and LNP formulation optimization pave the way to address the challenge of efficient mRNA delivery to NK cells, presenting opportunities for the development of NK cell-based mRNA therapies.}, archive = {J_JACS}, author = {Shiqi Wu and Lu Shi and Kexin Su and Lixin Lin and Xinxin Yan and Yiran Zhang and Tianrui Gu and Zichuan Wang and Tengfei Xu and Shuai Liu}, doi = {10.1021/jacs.5c01389}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28665--28673}, shortjournal = {J. Am. Chem. Soc.}, title = {Carbonate-bearing ionizable lipids for mRNA delivery to splenic NK cells}, volume = {147}, year = {2025}, }
• (2025). Control of indodicarbocyanine dimer geometry using variable-length linkers to DNA scaffolds. JACS, 147(32), 28651--28664. (www)

  @article{ , abstract = {In recent years, DNA scaffolds have been utilized to organize dye molecules into aggregates with tailored optical and photophysical properties. While dye separation can be controlled with nanometer-scale accuracy, controlling the relative dye orientation in an aggregate on DNA remains challenging. In this work, we investigate varying the length of the two-point linker between indodicarbocyanine (Cy5) dyes and the DNA template as a method to better control the resulting dimer geometry. To test this approach, we synthesize Cy5 with either 2-carbon or 4-carbon two-point linkers and compare their behavior to commercially available Cy5 with 3-carbon two-point linkers. Using experimental spectroscopy, theoretical modeling, and molecular dynamics simulations, we demonstrate that shortening the linker from 3-carbon to 2-carbon limits the π–π interactions between dyes, thereby promoting the formation of J-like Cy5 dimers. Conversely, increasing the linker length provides the dye more freedom of motion, allowing greater π–π interactions and yielding dimers with greater H-like character. Furthermore, shorter linkers can restrict dye accessible volume, which, under the driving force of π–π interactions, suppresses heterogeneity in dye packing for specific placements of Cy5 on double stranded DNA and DNA Holliday junction scaffolds. These results emphasize the importance of dye linker chemistry in determining important optical and photophysical properties of DNA-scaffolded dye aggregates. They also suggest that tuning the length of the dye linker is an effective strategy to overcome two challenges that currently limit DNA-scaffolded dye aggregates in photonics applications: gaining control of dye aggregate geometry and suppressing heterogeneity in dye packing.}, archive = {J_JACS}, author = {Adam A. Meares and Sara R. Ansteatt and Sebastián A. Díaz and Young C. Kim and Paul D. Cunningham and Smriti Thomas and Victoria Segal and Angelica Rose Galvan and Gissela Pascual and Simon K. Roy and Lance K. Patten and Bernard Yurke and William B. Knowlton and Jeunghoon Lee and Igor L. Medintz and Joseph S. Melinger}, doi = {10.1021/jacs.5c00128}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28651--28664}, shortjournal = {J. Am. Chem. Soc.}, title = {Control of indodicarbocyanine dimer geometry using variable-length linkers to DNA scaffolds}, volume = {147}, year = {2025}, }
• (2025). Intersystem crossing outcompetes triplet-pair separation from 1(TT) below 270 k in anthradithiophene films. JACS, 147(32), 28638--28650. (www)

  @article{ , abstract = {Singlet fission (SF) and triplet–triplet annihilation (TTA) are processes which may be exploited to boost the efficiency of solar energy technology. Despite being studied since the late 1960s, the mechanism of singlet fission is still not fully understood. This is partly because the main technique used to study singlet fission, optical or visible/near-IR transient absorption spectroscopy, cannot distinguish between the strongly coupled triplet-pair state 1 (TT), weakly interacting triplet pairs (T..T), and independent triplet states T 1 + T 1 . To solve this problem, we combine transient optical spectroscopy performed as a function of magnetic field and transient electron spin resonance (ESR) spectroscopy to probe the different steps involved in the singlet fission mechanism. By using transient photoluminescence spectroscopy performed as a function of magnetic field to selectively probe the second step of singlet fission: 1 (TT) ⇌ (T..T), we show that in a well-studied model system, anthradithiophene (diF-TES-ADT), this step is highly temperature-dependent, even though the first step, 1 S → 1 (TT), is not. Transient ESR measurements confirm the absence of singlet fission at temperatures between 40 and 250 K for this system, with clear signatures of triplets generated by intersystem crossing and evidence for decay by triplet–triplet annihilation, further supported by magnetic field effect measurements. We conclude that in polycrystalline diF-TES-ADT, intersystem crossing outcompetes triplet hopping at temperatures below 270 K, enabling direct intersystem crossing from the bound triplet pair 1 (TT) to an independent triplet state T 1 localized on a single chromophore. The generated triplets can re-encounter and decay through triplet–triplet annihilation.}, archive = {J_JACS}, author = {Eman M. Bu Ali and Arnau Bertran and Gabriel Moise and Shuangqing Wang and Rachel C. Kilbride and John E. Anthony and Claudia E. Tait and Jenny Clark}, doi = {10.1021/jacs.5c00001}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28638--28650}, shortjournal = {J. Am. Chem. Soc.}, title = {Intersystem crossing outcompetes triplet-pair separation from 1(TT) below 270 k in anthradithiophene films}, volume = {147}, year = {2025}, }
• (2025). Reversible C–H bond activation of unactivated arenes by a nickel-silylene complex. JACS, 147(32), 28632--28637. (www)

  @article{ , abstract = {A nickel-silylene complex is shown to reversibly activate benzene via C–H bond activation at ambient temperature. The benzene C–H bond formally adds across the Ni–Si core to form a nickel-silyl complex with an H–Si–Ni–Ph linkage bearing a highly covalent Ni–Si bond (2.2363(6) Å). Dissolution of this product in neat arene solvent, e.g., toluene, trifluorotoluene, or anisole, resulted in the complete conversion to the aryl C–H activated product of the solvent and, thereby, demonstrates the facile reversibility of C–H bond activation across the Ni–Si core. The various arene C–H bond activations by the reactive Ni(0)-silylene species were investigated using density functional theory calculations. In all cases, the arene initially forms an η 2 -adduct to Ni(0), and then C–H activation proceeds via a concerted oxidative addition at only the Ni center. The Si center assists C–H bond activation by sharing the redox burden with Ni while stabilizing the resultant hydride.}, archive = {J_JACS}, author = {Leon Gomm and Hui Zhu and Gregor Schnakenburg and Senada Nozinovic and Stefan Grimme and Connie C. Lu}, doi = {10.1021/jacs.5c10922}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28632--28637}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible C–H bond activation of unactivated arenes by a nickel-silylene complex}, volume = {147}, year = {2025}, }
• (2025). A bifunctional sulfone reagent for asymmetric aminomethylative sulfonylation of dienes. JACS, 147(32), 28624--28631. (www)

  @article{ , abstract = {Sulfone reagents have emerged as highly versatile coupling partners in transition-metal catalysis, owing to their exceptional reactive flexibility. However, current C–SO 2 activation strategies in sulfone reagents remain constrained to introducing single- or double-electron acceptors onto the departing sulfonyl moieties, which inadvertently diminishes the reactivity of the resulting sulfinate and prevents its reutilization. To tackle the long-standing dichotomy between C–SO 2 bond cleavage and reconstruction, we report a neighboring nitrogen-directed C–SO 2 activation strategy, thereby inventing a novel aminomethyl sulfone reagent. The application of this aminomethyl sulfone reagent was showcased by the palladium-catalyzed asymmetric aminomethylative sulfonylation of dienes to forge a variety of chiral 1,3-amino sulfones. The extensive substrate compatibility, unparalleled reactivity, and unprecedented high stereoselectivity demonstrated the great potential of this reagent in synthetic chemistry.}, archive = {J_JACS}, author = {Shoule Cai and Zeyu Zhao and Guoqing Yang and Hanmin Huang}, doi = {10.1021/jacs.5c09837}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28624--28631}, shortjournal = {J. Am. Chem. Soc.}, title = {A bifunctional sulfone reagent for asymmetric aminomethylative sulfonylation of dienes}, volume = {147}, year = {2025}, }
• (2025). Co-assembly of covalent organic framework particles into binary ordered superstructures. JACS, 147(32), 28617--28623. (www)

  @article{ , abstract = {Colloidal particles can co-assemble into multicomponent ordered superstructures, with their properties determined by the individual building blocks. Here, we demonstrate that covalent organic framework (COF) particles can co-assemble into binary ordered superstructures through solvent evaporation within confined spaces. By adjusting the particle size ratio, we prepare 2D COF-COF binary ordered superstructures with different stoichiometries (LS 2 and LS 6 ), underscoring entropic control over the assembly process. We further report the first example of co-assembly between COF and metal–organic framework (MOF) particles, presenting a 2D COF-MOF binary ordered superstructure with LS 2 stoichiometry. These results expand the design space for hybrid porous materials by enabling the construction of complex binary superstructures from COF particles of diverse sizes, shapes, porosities, and chemical compositions.}, archive = {J_JACS}, author = {Javier Fonseca and Tingchuan Zhou and Bingyang Lu and Jinlong Yang and Xu Deng}, doi = {10.1021/jacs.5c09498}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28617--28623}, shortjournal = {J. Am. Chem. Soc.}, title = {Co-assembly of covalent organic framework particles into binary ordered superstructures}, volume = {147}, year = {2025}, }
• (2025). Regiodivergent interrupted ni-catalyzed chain-walking of unsaturated alcohol side-chains via traceless activating groups. JACS, 147(32), 28610--28616. (www)

  @article{ , abstract = {Herein, we describe a regiodivergent interrupted chain-walking of unsaturated aliphatic alcohols. The method leverages the potential of traceless groups to forge C(sp 3 )–C(sp 3 ) and C(sp 3 )–nitrogen bonds at distal methylene sp 3 C–H sites, with site selectivity dictated by a judicious choice of the ligand. The protocol is distinguished by its broad applicability, offering unconventional disconnections to access β/γ-substituted aliphatic alcohols that are difficult to reach otherwise.}, archive = {J_JACS}, author = {Hao Wang and Huihui Zhang and Marta Martínez-Belmonte and Jordi Benet-Buchholz and Ruben Martin}, doi = {10.1021/jacs.5c09426}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28610--28616}, shortjournal = {J. Am. Chem. Soc.}, title = {Regiodivergent interrupted ni-catalyzed chain-walking of unsaturated alcohol side-chains via traceless activating groups}, volume = {147}, year = {2025}, }
• (2025). Directed evolution of class i aldolases for cooperative photobiocatalytic enantioselective radical α-alkylation of aldehydes. JACS, 147(32), 28601--28609. (www)

  @article{ , abstract = {By harnessing the synergy between enzymes and photoredox catalysts, cooperative photobiocatalysis has recently emerged as a promising strategy for developing stereoselective radical reactions. While various cofactor-dependent enzymes have been repurposed, the use of cofactor-independent enzymes in such cooperative catalysis without requiring expensive cofactors remains rare. Herein, we report the successful repurposing of class I aldolases, a prominent family of naturally occurring, cofactor-independent enzymes, to catalyze unnatural radical α-alkylation of aldehydes in a highly enantioselective fashion. Through directed evolution of Escherichia coli 2-deoxy- d -ribose-5-phosphate aldolase ( Ec DERA), we developed an effective radical alkylase bearing five mutations and inverted π-facial selectivity relative to wild-type Ec DERA, allowing a range of aldehydes to couple with α-iodoesters, α-iodoketones, and α-iodonitriles with excellent enantiocontrol. This study represents the first demonstration of leveraging the nucleophilic enamine intermediate in class I aldolases for radical-mediated stereoselective C–C bond formation. Mechanistic investigations suggested that when irradiated at 440 nm, cooperative catalysis with an exogenous Ir photocatalyst more effectively induces enzymatic enamine radical activity than charge-transfer complex photochemistry. Together, these findings underscore the potential of class I aldolases to enable general and stereoselective new-to-nature radical transformations.}, archive = {J_JACS}, author = {Quanquan Wang and Zhiyu Bo and Michael S. Bratslavsky and Yang Yang}, doi = {10.1021/jacs.5c08477}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28601--28609}, shortjournal = {J. Am. Chem. Soc.}, title = {Directed evolution of class i aldolases for cooperative photobiocatalytic enantioselective radical α-alkylation of aldehydes}, volume = {147}, year = {2025}, }
• (2025). The overlooked stereoisomers of the ionizable lipid ALC315. JACS, 147(32), 28595--28600. (www)

  @article{ , abstract = {Lipid nanoparticles (LNPs) are a powerful delivery platform for nucleic acid therapeutics such as mRNA vaccines and gene therapies. Central to their success are ionizable lipids, which facilitate the cellular uptake and endosomal escape of nucleic acids. However, achieving a high delivery efficiency often comes with the drawback of increased cytotoxicity. Here, we report a chemical, biological, and toxicological investigation into the three stereoisomers of ALC315, a mixture of which constitutes one of the most successful marketed ionizable lipids for LNPs. We demonstrate that the individual stereoisomers of ALC315 can be accessed by either the asymmetric chemical synthesis or chromatography of an intermediate. An LNP formulation based on a single stereoisomer of ALC315 enhances mRNA transfer efficiency while reducing the associated cytotoxicity in human cell lines. Our results underscore the potential of stereochemically pure ionizable lipids as key components in the development of next-generation nucleic acid therapies, offering an enhanced delivery performance and better safety profiles.}, archive = {J_JACS}, author = {Chandra Kanta De and Masumi Tsuda and Chendan Zhu and Stefanie Dehn and Heike Hinrichs and Nobuya Tsuji and Hui Jin and Hisashi Arase and Shinya Tanaka and Benjamin List}, doi = {10.1021/jacs.5c08345}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28595--28600}, shortjournal = {J. Am. Chem. Soc.}, title = {The overlooked stereoisomers of the ionizable lipid ALC315}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of (−)-neocucurbol c enabled by pattern recognition and MHAT cyclization. JACS, 147(32), 28589--28594. (www)

  @article{ , abstract = {We report an asymmetric total synthesis of (−)-neocucurbol C, a diterpene natural product possessing a unique and complex 6/6/5/5/6 polycyclic skeleton and nine stereocenters. Pattern-recognition analysis led us to the chiral pool molecule (+)-nootkatone as the starting material, already containing the AB ring system and two key stereocenters encoded by the target molecule. The extra isopropenyl group of (+)-nootkatone was removed by Kwon’s hydrodealkenylative bond fragmentation. Other key steps include a Suzuki–Miyaura cross coupling to introduce an aromatic ring as the E ring precursor, an oxidative dearomatization cyclization to form the key oxa-bridge, and a metal-catalyzed hydrogen atom transfer (MHAT)-initiated reductive radical cyclization to complete the entire framework for subsequent peripheral decorations, which eventually delivered (−)-neocucurbol C in 24 steps for the first time. In addition, the cytotoxicity evaluation of (−)-neocucurbol C and its synthetic intermediates against multiple cancer cell lines identified new lead compounds with promising anticancer activity for further development.}, archive = {J_JACS}, author = {Li-Ping Zhong and Cyrus Gudeman and Jingsong Zhen and Oshani A. Wanasinghe and Jacob Hellmig and Michael J. E. Collins and John Bacsa and Alexander Adibekian and Mingji Dai}, doi = {10.1021/jacs.5c08224}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28589--28594}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of (−)-neocucurbol c enabled by pattern recognition and MHAT cyclization}, volume = {147}, year = {2025}, }
• (2025). Radical-initiated photodissociation at tryptophan residues within intact proteins in the gas phase. JACS, 147(32), 28583--28588. (www)

  @article{ , abstract = {Controlling selective fragmentation at particular residues in the gas phase could greatly improve our ability to characterize intact proteins by mass spectrometry and reveal proteoforms crucial to human biology. However, the chemical homogeneity and size of proteins frustrates characterization because fragmentation inevitably leads to thousands of product ions and highly complex spectra that resist complete interpretation. Herein, we report a method for the selective, photochemical cleavage of whole proteins in the gas phase via the photolysis of alpha-peptidyl radicals. The activation process results in predictable and selective dissociation of the peptide bond N-terminal to the initiating radical. Alpha peptidyl radicals are readily introduced in a residue specific manner via the nitrosation of tryptophan, which enables an easily triggered side chain loss. This approach affords highly controlled fragmentation of intact proteins in the gas phase, producing results analogous to those obtained by tryptic digests in solution. The smaller fragment ions produced by selective dissociation are abundant and can be further analyzed to facilitate characterization by providing more detailed information about sequence and modification sites.}, archive = {J_JACS}, author = {Lin He and Aidan G. Purcell and Gregory J. O. Beran and Yixuan Zhu and Karen R. Coronado and Samuel I. Mann and W. Hill Harman and Ryan R. Julian}, doi = {10.1021/jacs.5c07784}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28583--28588}, shortjournal = {J. Am. Chem. Soc.}, title = {Radical-initiated photodissociation at tryptophan residues within intact proteins in the gas phase}, volume = {147}, year = {2025}, }
• (2025). Proteomic tracking extracellular vesicle RNA interactors in recipient immune cells through orthogonal labelings. JACS, 147(32), 28577--28582. (www)

  @article{ , abstract = {RNA cargos in extracellular vesicles (EVs) mediate intercellular communication by engaging RNA-binding proteins (RBPs) in recipient cells. Here, we introduce extracellular RNA interactome capture through orthogonal labelings (ERICOL), a targeted cross-linking and quantitative chemical proteomic strategy based on metabolic labeling of RNAs and stable isotope labeling of proteins for systematic profiling of EV RBPs in recipient cells. Time-resolved analysis of tumor-derived EVs in Jurkat T cells revealed dynamic patterns of EV RNA uptake and RBP engagement. Further profiling in primary human CD8+ T cells treated with wild-type or IDH1 mutant intrahepatic cholangiocarcinoma (ICC)-derived EVs uncovered IDH1 mutation-driven alterations in the EV RBP landscape. ERICOL offers a powerful strategy for comprehensive profiling of EV RNA interactome dynamics and provides mechanistic insights into EV-mediated immune modulation.}, archive = {J_JACS}, author = {Zheng Zhang and Zhuojun Luo and Yikai Liu and Subhransu Sekhar Sahoo and Vamara Dembele and Meng-Ju Wu and Nabeel Bardeesy and Fang Huang and Majid Kazemian and Kyle A. Cottrell and W. Andy Tao}, doi = {10.1021/jacs.5c07631}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28577--28582}, shortjournal = {J. Am. Chem. Soc.}, title = {Proteomic tracking extracellular vesicle RNA interactors in recipient immune cells through orthogonal labelings}, volume = {147}, year = {2025}, }
• (2025). Macrocycle side chain crowding enables tunable curvature from planar to wrinkled and wavy hydrogen-bonded sheets. JACS, 147(32), 28570--28576. (www)

  @article{ , abstract = {We report a side chain-crowding strategy to direct the self-assembly of hydrogen-bonded semicarbazone macrocycles into porous organic frameworks with tunable curvatures and exceptional acetone uptake and selectivity. Three triangular macrocycles bearing isopropyl, isobutyl, and isopentyl side chains were synthesized and self-assembled through hydrogen-bonding arrays into planar, wrinkled, and square-octagonal wavy sheets, driven by steric congestion. After activation, the distorted frameworks retain permanent porosity and exhibit record-high acetone vapor uptake (up to 617 cm 3 /g STP at 298 K) with high acetone/methanol selectivity (up to 7.2:1). Single-crystal X-ray diffraction reveals multivalent hydrogen bonding between acetone and the intrinsic binding sites, underpinning both high uptake and selectivity. This work establishes a general design for encoding curvature, guest-binding affinity, and structural robustness into hydrogen-bonded frameworks via macrocycle-side chain crowding.}, archive = {J_JACS}, author = {Javed R. Pathan and Xinyu Pang and Sarah C. Olsen and A. Mercy Abarna and Richard J. Staples and Jayanta Samanta and Vladimir B. Birman and Chenfeng Ke}, doi = {10.1021/jacs.5c07383}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28570--28576}, shortjournal = {J. Am. Chem. Soc.}, title = {Macrocycle side chain crowding enables tunable curvature from planar to wrinkled and wavy hydrogen-bonded sheets}, volume = {147}, year = {2025}, }
• (2025). Asymmetric deoxygenative formal [3 + 2] cycloaddition of carboxylic acids and vinylcyclopropanes. JACS, 147(32), 28564--28569. (www)

  @article{ , abstract = {We report an iridium-catalyzed asymmetric formal [3 + 2] cycloaddition between carboxylic acids and vinylcyclopropanes to access highly enantioenriched tetrahydrofurans. This reaction proceeds under mild conditions with excellent stereoselectivity and a broad substrate scope. A key feature of the method is the in situ formation of mixed anhydrides, which modulate the reactivity of carboxylic acids and prevent undesired O-nucleophilic pathways. The transformation is compatible with diverse functional groups, complex bioactive molecules, and late-stage carbon isotope labeling using [ 13 C]CO 2 . This work expands the utility of carboxylic acids in enantioselective cycloaddition chemistry.}, archive = {J_JACS}, author = {Ying Liu and Guorong Xiao and Zhuofan Bai and Yun Sa and Mengjiao Yang and Duanyang Kong}, doi = {10.1021/jacs.5c07376}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28564--28569}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric deoxygenative formal [3 + 2] cycloaddition of carboxylic acids and vinylcyclopropanes}, volume = {147}, year = {2025}, }
• (2025). A charge-driven strategy for covalent modification and modulation of biomolecular condensates. JACS, 147(32), 28558--28563. (www)

  @article{ , abstract = {Small-molecule modulation of biomolecular condensates has emerged as a novel and attractive therapeutic modality. Increasing evidence implicates dysregulated condensate formation in neurodegenerative diseases and cancer. However, the proteins that mediate condensate formation are typically difficult to drug directly with small molecules. Here, we present a charge-driven strategy and demonstrate its implementation on Ras GTPase-activating protein-binding protein 1 (G3BP1) to inhibit G3BP1-mediated stress granule (SG) formation. Small-molecule SG inhibitors were developed from the carbonylacrylic amide covalent functionality and were used to modify the folded domain of G3BP1 with surface charges, leading to an alteration of the conformational dynamics of intrinsically disordered regions. Cellular experiments using HeLa cells expressing cysteine-mutated G3BP1, together with structure–activity relationship studies, support the proposed charge-driven mechanism of action. Molecular dynamics simulations further suggest that the small-molecule G3BP1 modification promotes a shift toward more compact conformations, comparable to that induced by an ∼26% increase in IDR1-IDR3 interaction. Together, our findings establish a new strategy for the rational modulation of biomolecular condensates.}, archive = {J_JACS}, author = {Zhewei Chen and Lu Liu and Jerome Cattin and Tuomas P. J. Knowles and Gonçalo J. L. Bernardes}, doi = {10.1021/jacs.5c06625}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28558--28563}, shortjournal = {J. Am. Chem. Soc.}, title = {A charge-driven strategy for covalent modification and modulation of biomolecular condensates}, volume = {147}, year = {2025}, }
• (2025). Photon-by-photon fluorescence lifetime analysis of within-burst state transitions of single proteins in lipid membranes. JACS, 147(32), 28552--28557. (www)

  @article{ , abstract = {Understanding rapid, nonequilibrium dynamics of single proteins in lipid membranes is crucial but challenging. This study advances fluorescence lifetime analysis by developing a computationally efficient variational Bayesian framework for photon-by-photon hidden Markov modeling. It enables robust and accurate model selection, facilitating real-time tracking of state evolution of a molecule within a brief time frame. We applied the method to investigate nonequilibrium membrane insertion of a model peptide, revealing that unsaturated bonds in acyl chains not only merely modulate the fluidity of lipid membranes but also directly interact with transmembrane proteins, answering a long-standing question about unsaturated bonds’ roles in membrane–protein interactions.}, archive = {J_JACS}, author = {Hao Wang and Hang Fu and Ye Yuan and Chenguang Yang and Zhao Lin and Tongsheng Chen and Chunhua Xu and Shuxin Hu and Ming Li and Ying Lu}, doi = {10.1021/jacs.5c06452}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28552--28557}, shortjournal = {J. Am. Chem. Soc.}, title = {Photon-by-photon fluorescence lifetime analysis of within-burst state transitions of single proteins in lipid membranes}, volume = {147}, year = {2025}, }
• (2025). Direct editing of cysteine to electrophilic alkyl halides in peptides. JACS, 147(32), 28546--28551. (www)

  @article{ , abstract = {Functional group conversion is a cornerstone of modern synthetic chemistry. Many strategies routinely employed for small-molecule transformations are unsuitable for modifying biomacromolecules, including peptides. Here, we describe a simple but chemoselective approach that directly converts the nucleophilic cysteine carbon–thiol side chain into an electrophilic carbon–halogen bond under mild conditions, compatible with diverse peptides. The incorporation of this versatile synthetic handle facilitates a range of subsequent transformations that are rarely, if ever, applied to complicated peptides. We envision that this side-chain editing methodology will open a broad expanse of unexplored peptide chemical space, which will concomitantly unlock applications for an entire class of new biomacromolecules.}, archive = {J_JACS}, author = {Daniel S. Honeycutt and Waldo Salgado-Bello and Harlan S. Greenberg and William K. McCarthy and Jason M. Mrosla and Brian Pallares and Jacob M. Goldberg and Fang Wang}, doi = {10.1021/jacs.5c06200}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28546--28551}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct editing of cysteine to electrophilic alkyl halides in peptides}, volume = {147}, year = {2025}, }
• (2025). Tech-enhanced synthesis: Exploring the synergy between organic chemistry and technology. JACS, 147(32), 28523--28545. (www)

  @article{ , abstract = {Recent years have witnessed growing interest in integrating enabling technologies into synthetic organic chemistry to address long-standing challenges in reproducibility, sustainability, and scalability. This perspective showcases how modern tools, ranging from continuous-flow reactors and electrochemical cells to photochemical technologies, biocatalysis, mechanochemistry, and self-driving laboratories, are reshaping the way chemists design, perform, and optimize reactions. Through selected case studies, we highlight how these technologies not only solve specific reactivity and process issues but also open new avenues for reactivity discovery and chemical innovation. Rather than viewing technology as a complication, we advocate for its adoption as a natural extension of synthetic creativity, capable of enhancing safety, reducing waste, and expanding accessible chemical space. Our aim is to inspire broader implementation and interdisciplinary training to equip the next generation of chemists with the tools to rethink how synthesis is performed in the 21st century.}, archive = {J_JACS}, author = {Stefano Bonciolini and Antonio Pulcinella and Timothy Noël}, doi = {10.1021/jacs.5c10303}, journal = {Journal of the American Chemical Society}, month = {8}, number = {32}, pages = {28523--28545}, shortjournal = {J. Am. Chem. Soc.}, title = {Tech-enhanced synthesis: Exploring the synergy between organic chemistry and technology}, volume = {147}, year = {2025}, }
• (2025). Design and synthesis of hetero-bicephalic detergents for native mass spectrometry of membrane proteins. JACS, 147(31), 28513--28522. (www)

  @article{ , abstract = {Native mass spectrometry is playing a central role in characterizing the noncovalent interactions of membrane proteins, enabling the discovery of lipids that regulate membrane protein function and modulate interactions with other molecules. The use of specialized charge-reducing detergents and/or molecular additives is critical to mitigate overactivation during native MS to facilitate proper analysis. Here, we present the design and synthesis of a new class of dual-headgroup detergents featuring two distinct hydrophilic moieties. One headgroup, the spermine moiety, is designed to promote lower charge states of membrane proteins, thereby enhancing the preservation of labile complexes in the mass spectrometer. The other hydrophilic headgroup─either a maltoside or a tetraethylene glycol moiety─is commonly found in traditional detergents used for the extraction and solubilization of membrane protein complexes. Using a diverse set of membrane proteins varying in size, topology, and oligomeric state, we demonstrate that these novel dual-headgroup detergents exhibit exceptional charge-reducing properties, particularly when introduced to membrane proteins solubilized in different detergents. Additionally, we highlight their effectiveness in preserving the complex of a G-protein-coupled receptor with a nanobody that selectively binds to its active state. Collectively, these high-performance detergents advance the rational design of detergents for native MS and expand the capabilities for studying membrane proteins in diverse biochemical environments.}, archive = {J_JACS}, author = {Jing-Yuan Chang and Djavdat Azizov and Vikki N. Shinde and Sangho D. Yun and Robert L. Rider and Yun Zhu and Hanieh Bahramimoghaddam and Michael Lynn and David H. Russell and Lei Fang and Arthur Laganowsky}, doi = {10.1021/jacs.5c10841}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28513--28522}, shortjournal = {J. Am. Chem. Soc.}, title = {Design and synthesis of hetero-bicephalic detergents for native mass spectrometry of membrane proteins}, volume = {147}, year = {2025}, }
• (2025). Symmetric boron-bridged carbon quantum frameworks for light-emitting diodes with over 20% external quantum efficiency. JACS, 147(31), 28504--28512. (www)

  @article{ , abstract = {The development of eco-friendly solution-processed quantum dots plays an important role in the fabrication of electroluminescent light-emitting diodes (LEDs) for large-area display applications. However, the efficiency of these eco-friendly devices is still significantly lower than that of heavy metal-based state-of-the-art alternatives. Herein, we demonstrate metal-free carbon-based quantum materials: symmetric boron-bridged carbon quantum frameworks ( sym -B-CQFs) composed of four dibenzo[fg,op]tetracene blocks bonded by boron atoms to form a rigid nonplanar conjugated framework. The sym -B-CQFs can deliver high-efficiency delayed fluorescence with a reverse intersystem crossing rate ( k RISC ) of 1.04 × 10 6 s –1 and 98 ± 0.6% total photoluminescence quantum yield. Experimental and theoretical analyses reveal that the nonplanar frameworks, originating from symmetric boron-bridges, lead to an alternate distribution of the frontier orbitals on different blocks and result in a small energy gap between the singlet and triplet excited states; this, in turn, increases k RISC . Solution processable LEDs based on sym -B-CQFs exhibit a record-high external quantum efficiency (EQE) of 20.4% and low efficiency roll-off (EQE = 18.0% at 1000 cd m –2 ). We anticipate that these high-performance carbon-based LEDs are highly suitable for next-generation large-area displays.}, archive = {J_JACS}, author = {Ting Yuan and Guimin Zhao and Diandong Tang and Xianzhi Song and Jiameng Du and Zhaoxi Yu and Yang Zhang and Laizhi Sui and Xiaohong Li and Yunchao Li and Lin Shen and Fanglong Yuan and Wei Jiang and Louzhen Fan}, doi = {10.1021/jacs.5c10746}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28504--28512}, shortjournal = {J. Am. Chem. Soc.}, title = {Symmetric boron-bridged carbon quantum frameworks for light-emitting diodes with over 20% external quantum efficiency}, volume = {147}, year = {2025}, }
• (2025). Mono or di? a potential-controlled electrochemical halogenation of anilines. JACS, 147(31), 28492--28503. (www)

  @article{ , abstract = {In organic reactions, controlling the degree of substitution, such as monosubstitution or disubstitution, typically necessitates the use of varied reagents, reaction conditions, and temperatures, often leading to increased separation costs. Simplifying this complexity while developing more direct and efficient methods for controlling reaction outcomes remains a long-standing challenge. In this work, we present a novel and efficient electrochemical strategy that leverages the precise control of electrode potential to selectively halogenate aniline derivatives, offering a breakthrough in the reaction selectivity. By manipulating the electrode potential, we control the generation of different intermediates and, therefore, the reaction mechanisms. At a lower electrode potential (1.38 V vs SHE), the formation of X • facilitates selective para -halogenation, whereas at a higher electrode potential (2.88 V vs SHE), the formation of X + is the primary reason for obtaining dihalides. This method eliminates the need for oxidants, transition metals, or external bases, utilizing the unique ability of electrode activation to enhance the substrate reactivity and reaction efficiency. The approach provides an alternate perspective in organic or electrochemical synthesis.}, archive = {J_JACS}, author = {Baijing Wu and Hongliang Fan and Xiaoxue Luo and Yufeng Wang and Dan He and Minhua Shao and Cunpu Li and Zidong Wei}, doi = {10.1021/jacs.5c10514}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28492--28503}, shortjournal = {J. Am. Chem. Soc.}, title = {Mono or di? a potential-controlled electrochemical halogenation of anilines}, volume = {147}, year = {2025}, }
• (2025). DNA framework nanoruler-directed surface fluorescence enhancement as a sensing platform for MicroRNA detection. JACS, 147(31), 28484--28491. (www)

  @article{ , abstract = {Surface-enhanced fluorescence can occur when fluorophores approach a rough or nanoscopic metallic surface, owing to the enhanced local electric field. However, revealing the surface fluorescence enhancement mechanism remains an important concern, primarily due to the lack of a nanoruler for precisely tuning the distance between the fluorophores and the substrate. Importantly, the precise distance is also critical as the heterogeneous size of spacers can lead to differentiated enhancement, resulting in low reproducibility. Herein, we propose a tetrahedral DNA framework (TDF) nanoruler strategy. Three vertexes of TDFs are thiolated for their immobilization on the Au matrix, while the fourth vertex is labeled with fluorophores. Therefore, the distance between the fluorophores and the Au substrate is governed by the size of TDFs. Various TDFs are combined as the nanoruler, and thus, we reveal the distance-dependent emission efficiency. We clearly observed the gradually enhanced and subsequently decreased emission along with the increased distance with the nanoruler. The maximum fluorescence enhancement was achieved at a critical distance of 5–7 nm with a narrow range for the labeled fluorophores on the Au substrate. Moreover, their rigid structure also realizes the uniform size of TDFs for homogeneous signal enhancement. Thus, sensitive detection of microRNA biomarkers of prostate cancer (PCa) was realized with a detection limit of 1 aM and used for early diagnosis of PCa. Furthermore, the TDF nanoruler strategy can be easily extended to other distance-dependent systems, enabling the optimization of their performance.}, archive = {J_JACS}, author = {Fangfei Yin and Shuyang Zhang and Hui Chen and Qian Li and Xiaolei Zuo and Chunhai Fan}, doi = {10.1021/jacs.5c10210}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28484--28491}, shortjournal = {J. Am. Chem. Soc.}, title = {DNA framework nanoruler-directed surface fluorescence enhancement as a sensing platform for MicroRNA detection}, volume = {147}, year = {2025}, }
• (2025). Surface acidity of oxygen evolution intermediates by excited state optical spectroscopy. JACS, 147(31), 28474--28483. (www)

  @article{ , abstract = {While the protonation of homogeneous metal-oxide catalysts is quite relevant for mechanisms in aqueous solution, the relevance of surface acidity to catalytic mechanisms of heterogeneous metal oxides is far less understood. Without a distinguishing metric ascribed to transient intermediates, invoking surface acidity is limited to rationalizing pH-dependent product evolution. Recently, the emissive population associated with intermediates of electron and proton transfer at a titanium oxide surface demonstrated an isotherm with pH whose half-rise occurred at pH = 11.8. As detected by a time-resolved visible broadband probe, the intermediates formed within <2 ps upon photoexcitation of the oxygen evolution reaction (OER) at an electron-doped (0.1% Nb) SrTiO 3 /aqueous interface. Here, we demonstrate how the pH dependence of the <2 ps population is preserved such that when the intermediate population finally decays with a time constant of 10 μs, it does so with a pH onset at 11.4. The distinctive pH associated with a metastable population ascribes a surface acidity to the first intermediate of water oxidation, interpreted as favoring Ti–OH • below and Ti–O •– above an acid dissociation constant ( i . e ., p K a ). The work shows that the excited state optical spectroscopy is sensitive to protonation over the lifetime of metastable intermediates. Further, it shows that the details of the hydration layer prior to excitation are important for stabilizing intermediate populations of different acidities that then affect the chemical steps of water oxidation catalysis at longer time scales, e . g ., bond formation.}, archive = {J_JACS}, author = {Michael Paolino and Suryansh Singh and Cassius Boyd and Moritz Lang and Tanja Cuk}, doi = {10.1021/jacs.5c10001}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28474--28483}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface acidity of oxygen evolution intermediates by excited state optical spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Self-assembled ion transport channels in block copolymer electrolytes for dendrite-free all-solid-state sodium batteries. JACS, 147(31), 28464--28473. (www)

  @article{ , abstract = {Sodium metal batteries are a promising low-cost alternative to lithium-based systems, offering abundant raw materials and high energy density. However, their development is hindered by challenges such as dendrite growth and interfacial instability, which compromise safety and cycling performance. To address these issues, we report a new class of fluorinated, ion conducting block copolymer electrolytes designed to self-assemble into well-defined ion transport channels. These block copolymers, composed of perfluoropolyether (PFPE) segments and charged polyethylene oxide (PEO) blocks, self-assemble into a variety of nanostructures. A three-dimensional interconnected body-centered cubic (BCC) morphology forms across a broad PFPE volume fraction range ( f PFPE ≈ 0.15–0.30). Among the observed morphologies, the BCC phase stands out for its superior performance, enabling high ion conductivity (up to 1.42 × 10 –4 S cm –1 at 80 °C) and forming robust electrode/electrolyte interfaces that support stable cycling in symmetric sodium cells for over 5000 h at 0.1 mA cm –2 . Furthermore, in full-cell configurations using Na 3 V 2 (PO 4 ) 3 (NVP) cathodes, the block copolymer-based sodium metal battery retains >91% of its initial capacity after 1000 cycles at 0.5 C and a high Coulombic efficiency at >99.8%. This study highlights the potential of morphological control through block copolymer design to overcome key limitations in sodium metal batteries and presents a viable path toward safe, high-performance, and sustainable energy storage technologies.}, archive = {J_JACS}, author = {Zhou Chen and Zhuojing Yang and Xiao Tan and Yiqing Wang and Bin Luo and Xiaoen Wang and Maria Forsyth and Craig J. Hawker and Debra J. Searles and Cheng Zhang}, doi = {10.1021/jacs.5c09890}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28464--28473}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-assembled ion transport channels in block copolymer electrolytes for dendrite-free all-solid-state sodium batteries}, volume = {147}, year = {2025}, }
• (2025). Stimulated emission from below the bandgap in giant quantum shells. JACS, 147(31), 28454--28463. (www)

  @article{ , abstract = {Colloidal semiconductor nanocrystals (NCs) have emerged as promising candidates for developing solution-processable optical gain media with potential applications in integrated photonic circuits and lasers. However, the deployment of NCs in these technologies has been hindered by the nonradiative Auger recombination of multiexciton states, which shortens the optical gain lifetime and reduces its spectral range. Here, we demonstrate that these limitations can be overcome by using giant colloidal quantum shells (g-QSs), comprising a quantum-confined CdSe shell grown over a large (∼14 nm) CdS bulk core. Such bulk-nanoscale architecture minimizes exciton–exciton interactions, leading to suppressed Auger recombination and one of the broadest gain bandwidths reported for colloidal nanomaterials, spanning energies both above and, remarkably, below the bandgap. Ultrafast transient absorption and photoluminescence measurements demonstrate that the high-energy portion of optical gain arises from states containing more than 15 excitons per particle, while the unusual sub-bandgap gain behavior results from an Auger-assisted radiative recombination, a mechanism that has traditionally been viewed as a loss pathway. Collectively, these results reveal a unique gain regime associated with bulk-nanocrystal hybrid systems, which offers a promising path toward solution-processable light sources.}, archive = {J_JACS}, author = {Amelia D. Waters and Mykhailo V. Bondarchuk and Christopher M. Hicks and Sean Smith and Divesh Nazar and Maxwell Marshal Kannen and Dulanjan Harankahage and Siddhartha Thennakoon and Jiamin Huang and Edison Anzenbacher and Pavel Anzenbacher and Alexander N. Tarnovsky and Anton V. Malko and Mikhail Zamkov}, doi = {10.1021/jacs.5c09795}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28454--28463}, shortjournal = {J. Am. Chem. Soc.}, title = {Stimulated emission from below the bandgap in giant quantum shells}, volume = {147}, year = {2025}, }
• (2025). Counterion-driven long-term imaging of cell membranes and migrasomes using dicationic NIR AIEgens. JACS, 147(31), 28442--28453. (www)

  @article{ , abstract = {Tracking migrasome formation and dynamics is challenging due to the limited specificity and stability of existing membrane dyes for long-term imaging. Here, we develop a series of aggregation-induced emission (AIE) probes featuring a dicationic donor–π–acceptor structure (CDPP-2X) with NIR emission for selective long-term membrane and migrasome labeling. Among the synthesized ( Z )-4-(4-(1-cyano-2-(4-(diphenylamino)phenyl)vinyl)phenyl)pyridine-1-ium (CDPP) derivatives, CDPP-2PF 6 exhibited superior performance, with the PF 6 counterion enhancing lipophilicity for dual-mode membrane anchoring via electrostatic and hydrophobic interactions. This mechanism, combined with restricted intramolecular motion, enables strong fluorescence enhancement and up to 3 h of membrane retention. CDPP-2PF 6 selectively accumulates in phosphoinositide-rich migrasomes within 5 min, showing a preferential and strong affinity for phosphatidylinositol 4,5-bisphosphate (PIP2), a key lipid involved in migrasome biogenesis and cell migration. Comparative analyses with wheat germ agglutinin (WGA) and 3,3′-dioctadecyloxacarbocyanine perchlorate (DiO) confirm CDPP-2PF 6 ’s superior specificity and phospholipid-dependent localization. Pharmacological studies with blebbistatin and methyl-β-cyclodextrin (MβCD) reveal that actin polymerization is essential for migrasome formation. At the same time, lipid microdomain integrity is crucial for both biogenesis and probe localization, as evidenced by the complete loss of fluorescence upon cholesterol depletion. Confocal fluorescence lifetime imaging captures a distinctive fluorescence lifetime shift from 1.8 to 0.9 ns during migrasome formation, enabling real-time membrane remodeling tracking. CDPP-2PF 6 ’s sensitivity to phospholipid composition provides insights into lipid remodeling during migrasome formation and cell migration. These features establish CDPP-2PF 6 as a robust platform for long-term membrane and migrasome imaging, offering new opportunities to investigate lipid remodeling, cellular signaling, and phospholipid-rich organelles in physiological and pathological processes.}, archive = {J_JACS}, author = {Ziyue Ye and Chengpeng Qiu and Zonghang Liu and Haifei Wen and Feng Gao and Yue Zhang and Wen-Jin Wang and Jianquan Zhang and Zijie Qiu and Wan Zhang and Parvej Alam and Zheng Zhao and Ben Zhong Tang}, doi = {10.1021/jacs.5c09607}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28442--28453}, shortjournal = {J. Am. Chem. Soc.}, title = {Counterion-driven long-term imaging of cell membranes and migrasomes using dicationic NIR AIEgens}, volume = {147}, year = {2025}, }
• (2025). Chemically inducible cyclic dinucleotides as self-deliverable STING agonists with enhanced antitumor immunity. JACS, 147(31), 28429--28441. (www)

  @article{ , abstract = {The stimulator of interferon genes (STING) has emerged as a promising therapeutic target in cancer immunotherapy. Cyclic dinucleotide (CDN)-based agonists are known to activate the STING signaling pathway; however, their clinical applications are largely hindered by challenges such as poor stability, low cell penetrability, and the lack of spatiotemporal controls that can result in off-target inflammatory responses. Here, we reported a novel design of chemically inducible CDNs (iCDNs) for efficient cellular uptake and on-demand STING activation through the installation of bio-orthogonal chemical groups onto the phosphodiester sites of CDNs. We demonstrated that iCDNs could effectively self-deliver into cells and enable bio-orthogonal activation of STING signaling via Staudinger reduction or the inverse-electron-demand Diels–Alder (IEDDA) reaction. This strategy was further extended to respond to light and endogenous enzymes, allowing for spatiotemporal and cell-specific control of STING activation. In a poorly immunogenic tumor model, the bio-orthogonal iCDNs were demonstrated to conditionally activate the STING signaling pathway upon chemical induction, with enhanced antitumor immunity and reduced systemic cytokine release in serum. We further showed that the bio-orthogonal iCDNs with a targeting moiety boosted antitumor efficacy and sensitized tumor responses to an immune checkpoint blockade (ICB). The iCDNs provide a useful strategy for the efficient delivery of CDNs and spatiotemporal control of CDN-mediated STING activation, underscoring their potential in drug development for cancer immunotherapy.}, archive = {J_JACS}, author = {Yang Hai and Zhen Xun and Linlin Yang and Zimu Cai and Zhenkun Wu and Jian-Hui Jiang}, doi = {10.1021/jacs.5c09626}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28429--28441}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemically inducible cyclic dinucleotides as self-deliverable STING agonists with enhanced antitumor immunity}, volume = {147}, year = {2025}, }
• (2025). Super-resolution imaging of semiconductor nanopatterns using the non-bridging-oxygen-hole-center-based photoluminescence enhancement effect. JACS, 147(31), 28419--28428. (www)

  @article{ , abstract = {Precise metrology and defect characterization are essential for ensuring device performance and yield as semiconductor manufacturing pushes critical dimensions into the nanoscale regime. In this regard, super-resolution fluorescence microscopy (SRM) has recently gained attention as a powerful tool, providing nanoscale resolution essential for advanced device fabrication. However, conventional SRM techniques often rely on fluorescent labeling, which could introduce chemical complexity, alter material properties, and limit semiconductor-processing compatibility while also imposing resolution constraints owing to the size of the fluorescent tag. To address these challenges, we introduce a new super-resolution label-free imaging approach for silica-based nanomaterials based on the photoluminescence generated from the formation of nonbridging oxygen hole centers (NBOHCs) in silica. These intrinsic defects exhibit strong photoluminescence that is significantly enhanced through electron illumination and thiol treatment, thereby enabling subdiffraction imaging without the need for complex molecular labels. Furthermore, we reconstructed super-resolution images of silica nanostructures with significantly improved spatial resolution through the use of fluctuation-based super-resolution image analysis. We show that this method effectively resolves silica-based semiconductor nanopatterns in a manner that delivers high contrast and spatial resolution by highlighting the NBOHC-regeneration potential for advancing semiconductor metrology. Also, we demonstrate that our method enables high-contrast and highly sensitive visualization of various nanoscale defects on patterned silica surfaces, highlighting its strong potential as a powerful, nondestructive tool for nanoscale defect detection in semiconductor pattern inspection. Ultimately, the developed method is expected to provide a promising approach that can be broadly used to structurally characterize various inorganic nanomaterials at the nanoscale.}, archive = {J_JACS}, author = {Li Hung Hung and Uidon Jeong and Ga-eun Go and Doory Kim}, doi = {10.1021/jacs.5c09567}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28419--28428}, shortjournal = {J. Am. Chem. Soc.}, title = {Super-resolution imaging of semiconductor nanopatterns using the non-bridging-oxygen-hole-center-based photoluminescence enhancement effect}, volume = {147}, year = {2025}, }
• (2025). Emerging complex behavior driven by self-organization: Dynamic covalent libraries of acylhydrazones in water. JACS, 147(31), 28408--28418. (www)

  @article{ , abstract = {The generation of self-organized phases drives the emergence of states of matter of higher complexity. Herein, we study in situ generated self-assembled systems based on the condensation between different aldehydes and hydrazides in water. The resulting acylhydrazones can self-organize into turbid hydrogels or bigger microcrystals depending on the component substituents. The generation of the organized phases was investigated by nuclear magnetic resonance (NMR) and ultraviolet–visible (UV–vis) spectroscopy as well as by microscopy, rheology and solid-state X-ray analyses. Polar substituents like imidazole rings, carboxylic acids and alcohols still lead to hydrogels due to the high propensity of the hydrophobic aromatic cores to self-assemble. The microcrystalline gels containing acidic and basic groups displayed pH-responsiveness. Such behavior allowed for adaptive scrambling-sorting transitions and sorting selectivity switching within 1 × 2 dynamic covalent libraries driven by self-organization in response to environmental conditions. Moreover, the generation of hydrophobic microenvironments in the self-assembled three-dimensional (3D)-network promoted selective imine formation made of apolar components as a result of the stabilization and protection of the reversible covalent bond from hydrolysis. Thus, the dynamic systems described here exhibit up to five levels of adaptive behaviors governed by self-organization (see conclusions).}, archive = {J_JACS}, author = {Ferran Esteve and Zhaozheng Yang and Jean-Marie Lehn}, doi = {10.1021/jacs.5c09521}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28408--28418}, shortjournal = {J. Am. Chem. Soc.}, title = {Emerging complex behavior driven by self-organization: Dynamic covalent libraries of acylhydrazones in water}, volume = {147}, year = {2025}, }
• (2025). Mechanical-bond-enabled highly efficient charge separation in a light-harvesting Hetero[2]Catenane. JACS, 147(31), 28399--28407. (www)

  @article{ , abstract = {Photodriven charge separation is a key process for converting solar energy into chemical energy. However, it remains a challenge to develop artificial light-harvesting materials that can simultaneously achieve ultrafast charge separation and a long-lived charge-separated state with low energy loss. In contrast to conventional strategies based on covalent or noncovalent interactions, we employed a mechanical bond to forcibly assemble two strongly electron-deficient cationic chromophores ( TTzBox 4+ and PDI-C 2+ ), which have very similar reduction potentials and exhibit limited noncovalent interactions, into a hetero[2]catenane ( TTzPCat 6+ ). This design provides efficient π electronic couplings, enabling ultrafast charge separation (<2.3 ps) even with a low driving force (|Δ G CS | ≈ 160 meV). Furthermore, the adaptive molecular conformation of TTzPCat 6+ , in combination with the Marcus inverted region effect, successfully prolongs the charge-separated state lifetime ( k CS / k CR > 1000), surpassing the conventional trade-off between driving force and charge separation efficiency in heterogeneous donor–acceptor systems. The photocatalytic system based on TTzPCat 6+ exhibits an over 2-fold enhancement in selective oxidation of aryl sulfides under mild conditions, demonstrating the potential of mechanical bonding for preparing photocatalytic materials. This investigation not only highlights a strategy for achieving highly efficient charge separation with low energy loss but also offers fresh insights into developing efficient solar energy conversion systems.}, archive = {J_JACS}, author = {Xueze Zhao and Guangcheng Wu and Bai-Tong Liu and Han Han and Huang Wu and Bohan Tang and Shuai Fang and Chun Tang and Ruihua Zhang and Sheng-Nan Lei and Enxu Liu and Yi-Kang Xing and Ryan M. Young and Michael R. Wasielewski and J. Fraser Stoddart}, doi = {10.1021/jacs.5c09425}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28399--28407}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanical-bond-enabled highly efficient charge separation in a light-harvesting Hetero[2]Catenane}, volume = {147}, year = {2025}, }
• (2025). Enantio- and diastereoselective reductive propargylic sulfinamidation enabled by synergistic bimetallic catalysis. JACS, 147(31), 28389--28398. (www)

  @article{ , abstract = {In this manuscript, we present a groundbreaking strategy for the efficient synthesis of S-propargyl sulfinamides, featuring both stereogenic sulfur(IV) centers and alkyne motifs, through the asymmetric addition of racemic propargyl acetates to sulfinylamines. Our innovative approach leverages a synergistic nickel/copper dual-catalytic system, wherein each metal center is coordinated by a distinct chiral ligand. This system demonstrates unparalleled control over chiral sulfur centers, accommodating both primary and tertiary propargylic acetates. Notably, reactions involving secondary propargylic acetates achieve exceptional enantio- and diastereoselectivity for both the carbon and sulfur stereocenters. Comprehensive mechanistic studies reveal the distinct and complementary roles of nickel and copper catalysis in facilitating this high degree of stereoselective control, offering new insights into the design of complex catalytic systems for asymmetric synthesis.}, archive = {J_JACS}, author = {Linlin Ding and Junshan Chen and Hongjian Lu and Zhuangzhi Shi}, doi = {10.1021/jacs.5c09416}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28389--28398}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantio- and diastereoselective reductive propargylic sulfinamidation enabled by synergistic bimetallic catalysis}, volume = {147}, year = {2025}, }
• (2025). Construction of a de novo nucleotide biosynthesis pathway in artificial cells for RNA transcription. JACS, 147(31), 28378--28388. (www)

  @article{ , abstract = {The reconstitution of the de novo nucleotide synthesis pathway from inorganic compounds for RNA transcription is essential for an autonomous artificial cell. Here, a de novo uridine triphosphate (UTP) synthesis pathway is successfully constructed starting from NH 4 HCO 3 , involving eight enzymes of carbamoyl phosphate synthetase (CPS), aspartate transcarbamoylase (ATC), dihydroorotase (DHO), dihydroorotate dehydrogenase (DHODH), ribose-phosphate pyrophosphokinase (RPPK), uridine 5′-monophosphate synthase (UMPs), uridylate kinase (UK), and nucleoside diphosphate kinase (NDK). ATP regeneration system composed of creatine kinase (CK) and creatine phosphate is incorporated to drive this pathway. 0.85 mM UTP is produced within 180 min under the optimized conditions, which is further used for RNA transcription along with preadded CTP, GTP, regenerated ATP, and T7 RNA polymerase. The de novo UTP synthesis pathway and RNA transcription components are encapsulated into giant unilamellar vesicles to build artificial cells capable of nucleotide de novo production for subsequent RNA transcription. The successful RNA transcription inside artificial cells is visualized using pyronin Y. The successful reconstitution of the de novo UTP synthesis pathway for RNA transcription inside artificial cells lays a solid foundation for the reproduction of an autonomous artificial cell.}, archive = {J_JACS}, author = {Yiming Liu and Mingrui Zhang and Jingjing Zhao and Yongshuo Ren and Shubin Li and Weichen Wang and Wei Mu and Xiaojun Han}, doi = {10.1021/jacs.5c09375}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28378--28388}, shortjournal = {J. Am. Chem. Soc.}, title = {Construction of a de novo nucleotide biosynthesis pathway in artificial cells for RNA transcription}, volume = {147}, year = {2025}, }
• (2025). Anti-diastereo- and enantioselective ruthenium-catalyzed C–C coupling-oxidative lactonization of 1,4-butanediol: Alkynes as allylmetal pronucleophiles. JACS, 147(31), 28370--28377. (www)

  @article{ , abstract = {Reported methods for enantioselective oxidative lactonization affect desymmetrization of prochiral or meso -diols, and processes where C–C bond formation accompanies oxidative lactonization are undescribed. Here, using the ruthenium catalyst assembled from RuHCl(CO)(PPh 3 ) 3 , JOSIPHOS SL-J009-1 and KI, allylative oxidative lactonizations of 1,4-butanediol (10 6 tons/yr) are described that occur with high levels of anti -diastereo- and enantioselectivity. As corroborated by deuterium labeling experiments, these processes merge three distinct catalytic events: (a) alkyne-to-allene isomerization, (b) transfer hydrogenative carbonyl (α-aryl)allylation of the allene pronucleophile, and (c) oxidative lactonization of the resulting enantiomerically enriched 1°,2°-diol.}, archive = {J_JACS}, author = {Catherine G. Santana and Peyton W. Meares and Zachary J. Dubey and Michael J. Krische}, doi = {10.1021/jacs.5c09358}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28370--28377}, shortjournal = {J. Am. Chem. Soc.}, title = {Anti-diastereo- and enantioselective ruthenium-catalyzed C–C coupling-oxidative lactonization of 1,4-butanediol: Alkynes as allylmetal pronucleophiles}, volume = {147}, year = {2025}, }
• (2025). Accelerated discovery of energy transfer-catalyzed dearomative cycloadditions through a data-driven three-layer screening strategy. JACS, 147(31), 28359--28369. (www)

  @article{ , abstract = {Visible-light-mediated energy transfer (EnT) photocatalysis has emerged as a highly appealing strategy for converting planar (hetero)arenes into complex, medicinally relevant, three-dimensional (3D) architectures. Current methodologies for intermolecular dearomative photocycloadditions, however, are restricted to bicyclic (hetero)aromatic systems, while the more abundant monocyclic (hetero)arenes remain vastly underexplored. Accessing the triplet state of the ubiquitous monocyclic (hetero)arenes poses a formidable challenge due to their high triplet energy barriers. Herein, we report several EnT-catalyzed intermolecular dearomative cycloadditions of monocyclic heteroarenes with alkenes and bicyclo[1.1.0]butanes. To overcome the intrinsic limitations in triplet-state reactivity and accelerate reaction discovery, we introduced a data-driven three-layer screening strategy that integrates predictive data science tools for mapping excited-state properties with luminescence quenching and reaction-based screening. This synergistic three-layer screening strategy uncovers structure-reactivity relationships between substituted monocyclic heteroarenes and biradical acceptors, facilitating the accelerated discovery of new reactivity. Utilizing this data-driven approach, we developed the EnT-catalyzed intermolecular dearomative cycloaddition of thiophenes, oxazoles, and thiazoles with alkenes/bicyclo[1.1.0]butanes, providing access to unprecedented C(sp 3 )-rich 3D molecular scaffolds.}, archive = {J_JACS}, author = {Debanjan Rana and Carla Hümpel and Ranjini Laskar and Leon Schlosser and Sophie Korgitzsch and Subhabrata Dutta and Constantin G. Daniliuc and Frank Glorius}, doi = {10.1021/jacs.5c09249}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28359--28369}, shortjournal = {J. Am. Chem. Soc.}, title = {Accelerated discovery of energy transfer-catalyzed dearomative cycloadditions through a data-driven three-layer screening strategy}, volume = {147}, year = {2025}, }
• (2025). Dipole characteristics of polymers with main-chain polar rings: Impact of dipole strength and orientation on reactivity and material properties. JACS, 147(31), 28350--28358. (www)

  @article{ , abstract = {Dipole–dipole interactions arising from polar side chains are known to modify polymer properties (e.g., thermal, rheological) compared to their nonpolar analogues. Incorporating polar functionality into the main chain should similarly influence material properties while keeping the side chains available for further diversification. However, studies of main-chain dipole–dipole interactions are less common and limited to fairly weak dipoles (∼1 Debye, D). Herein, we leverage the tunability of oxazolidine and oxazolidinone rings to systematically characterize structure–property relationships of main-chain dipoles in terms of dipole strength, backbone flexibility, and dipole orientation. Changing the dipole strength of the repeat unit from 1.6 to 4.7 D raised the glass transition temperature ( T g ) by ∼50 °C and the activation energy of flow ( E a ) by 49 kJ/mol. Increasing the backbone flexibility through hydrogenation had smaller and contradictory effects of slightly raising T g and lowering E a . When controlling for strength and backbone flexibility, changing the dipole orientation further affected both the T g by 12 °C and the E a by 26 kJ/mol. These results reveal the relative influence of multiple structural features in modulating the formation of dipole–dipole interactions that impact thermal and rheological properties. Additionally, the structural differences between the heterocycles altered the polymerization reactivity, which we attribute to different chelation modes of the ruthenium catalyst during ring-opening metathesis polymerization. This work establishes for the first time the importance of the strength and orientation of noncovalent interactions from polar backbone rings on polymer synthesis and properties, informing strategies for controlling material properties by leveraging tunable dipoles.}, archive = {J_JACS}, author = {Allison R. Wong and Jorge Barroso and Luc G. Wetherbee and Bess Vlaisavljevich and Jessica R. Lamb}, doi = {10.1021/jacs.5c09178}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28350--28358}, shortjournal = {J. Am. Chem. Soc.}, title = {Dipole characteristics of polymers with main-chain polar rings: Impact of dipole strength and orientation on reactivity and material properties}, volume = {147}, year = {2025}, }
• (2025). Isolation of diamond spin chains in a layered halide perovskite heterostructure. JACS, 147(31), 28340--28349. (www)

  @article{ , abstract = {The halide perovskite heterostructure (CuCl 4 ) 2 (MTPA) 4 Cu 3 Cl 6 (Cu_Cu; MTPA = 3-(methylthio)-propylammonium) forms from solution as single crystals consisting of alternating layers of 2D Cu II –Cl perovskite and 1D Cu II –Cl diamond chain intergrowth. Using magnetometry, heat capacity, and electron paramagnetic resonance measurements, we interrogate the magnetic ordering of the 2D perovskite and 1D intergrowth layers at temperatures down to 0.055 K. As with other Cu–Cl perovskites, the perovskite-layer spins order ferromagnetically at 10 K. Magnetization data of Cu_Cu feature a multicomponent curve, consistent with magnetization of the perovskite layers and one of the three additional Cu II sites in the intergrowth layer, suggesting antiferromagnetic coupling of the remaining two intergrowth-layer spins. A broad feature in AC susceptibility measurements at 6 K and an anomalous heat capacity feature at 0.3 K suggest that local ordering events occur at dramatically different energy scales with decreasing temperature. EPR spectra indicate that these local orderings occur within the 1D chains. Notably, no long-range magnetic ordering event in the intergrowth is evident down to 0.055 K, suggesting that the geometric constraints imposed by the perovskite framework and the steric bulk of the MTPA ligands physically separate and magnetically isolate the diamond chains. In contrast, well-studied diamond-spin-chain materials such as azurite show long-range magnetic order at low temperatures due to interchain interactions. Thus, Cu_Cu provides an ideal platform for studying isolated, anisotropic spin chains. More generally, this study illustrates the capability of halide perovskite heterostructures to serve as vehicles for the scalable synthesis of complex magnetic materials.}, archive = {J_JACS}, author = {Caravaggio D. Caniglia and Yuntian Li and Jiajia Wen and Magdalene T. Brueggemeyer and Young S. Lee and Edward I. Solomon and Ian R. Fisher and Hemamala I. Karunadasa}, doi = {10.1021/jacs.5c08981}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28340--28349}, shortjournal = {J. Am. Chem. Soc.}, title = {Isolation of diamond spin chains in a layered halide perovskite heterostructure}, volume = {147}, year = {2025}, }
• (2025). Observation of *N2H3 intermediates by in situ electrochemical SERS: New pathway of ammonia oxidation on high-durability PtIr catalysts. JACS, 147(31), 28331--28339. (www)

  @article{ , abstract = {The electrochemical ammonia oxidation reaction (AOR) is a cornerstone technology for sustainable on-site hydrogen production and clean energy conversion. While Pt-based alloys such as PtIr have emerged as promising AOR electrocatalysts to address the rapid deactivation of pure Pt systems, the atomic-level mechanisms governing their superior stability remain unresolved. Here, we employ in situ electrochemical surface-enhanced Raman spectroscopy to directly track the evolution of intermediates on Pt and PtIr catalysts during the AOR. On pure Pt electrodes, increasing potential drives sequential oxidation of *NH 2 to *N 3 – , ultimately forming surface-bound *NO x species that poison active sites and degrade performance. In stark contrast, PtIr alloys bypass this detrimental pathway by enabling an unconventional *N 2 H 3 -centered mechanism. Through N–N coupling of *NH and *NH 2 intermediates at Pt–Ir integrative catalytic sites, *N 2 H 3 is generated and dehydrogenated to N 2 without the formation of toxic byproducts. Therefore, PtIr alloy catalysts exhibit significantly enhanced durability compared to monometallic Pt catalysts. This work highlights the paramount importance of directly observing key reaction intermediates via in situ spectroscopy for elucidating catalytic mechanisms.}, archive = {J_JACS}, author = {Maodi Zhang and Teng Wang and Xiaomeng Du and Yue Mao and Aonan Zhu and Aoxuan Du and Lingbo Tong and Wei Xie}, doi = {10.1021/jacs.5c09123}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28331--28339}, shortjournal = {J. Am. Chem. Soc.}, title = {Observation of *N2H3 intermediates by in situ electrochemical SERS: New pathway of ammonia oxidation on high-durability PtIr catalysts}, volume = {147}, year = {2025}, }
• (2025). Dihapto-coordinated conjugated carbocycles (η2-CnHn n = 5–8): Blurring the line between aromatic and antiaromatic hydrocarbons. JACS, 147(31), 28322--28330. (www)

  @article{ , abstract = {The tungsten fragment {WTp(NO)(PMe 3 )} (Tp = trispyrazolylborate) is an effective dearomatization agent for benzene and its derivatives. The dihapto-coordination of this system to an arene disrupts its aromatic stability, thereby promoting facile electrophilic additions to the hydrocarbon, which can then be followed by the addition of nucleophiles. This preliminary study endeavors to extend this conceptual approach to other aromatic and antiaromatic carbocycles. Dihapto-coordinated complexes of η 2 -tropylium, η 2 -cyclopentadienyl cation, and η 2 -cyclooctatetraene have been synthesized and characterized using SC-XRD, DFT, CV, and 1 H, 31 P, and 13 C NMR (including COSY, NOESY, HSQC, HMBC). Their fluxional behavior and reactivity toward electrophilic/nucleophilic additions, such as protonation and methylation, are also demonstrated.}, archive = {J_JACS}, author = {Megan N. Ericson and Josh K. Heman-Ackah and Rachel F. Lombardo and Alvin Q. Meng and Mason R. Ortiz and Sofia E. Megert and Diane A. Dickie and W. Dean Harman}, doi = {10.1021/jacs.5c09111}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28322--28330}, shortjournal = {J. Am. Chem. Soc.}, title = {Dihapto-coordinated conjugated carbocycles (η2-CnHn n = 5–8): Blurring the line between aromatic and antiaromatic hydrocarbons}, volume = {147}, year = {2025}, }
• (2025). Nickel-catalyzed enantioconvergent cross-electrophile coupling of benzylic alcohols with alkenyl electrophiles. JACS, 147(31), 28313--28321. (www)

  @article{ , abstract = {Enantioconvergent cross-coupling is a powerful strategy for asymmetric synthesis, but its application to alcohols remains challenging. Here, we demonstrate the potential of the dynamic kinetic cross-electrophile coupling (DK-XEC) strategy to enable the enantioconvergent coupling of alcohols. This nickel-catalyzed approach directly couples benzylic alcohols with alkenyl electrophiles, providing access to enantioenriched alkenes bearing allylic stereogenic centers. The reaction proceeds under mild conditions, exhibits a broad substrate scope and high enantioselectivity, and eliminates the need for separate preactivation of alcohols.}, archive = {J_JACS}, author = {Jun-Dan Fang and Xiaobo Pang and Xing-Zhong Shu}, doi = {10.1021/jacs.5c09072}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28313--28321}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-catalyzed enantioconvergent cross-electrophile coupling of benzylic alcohols with alkenyl electrophiles}, volume = {147}, year = {2025}, }
• (2025). Direct cellular screening of pd-mediated arylation of cyclic peptide binders targeting ubiquitin chains: Toward modulating NEMO Liquid–Liquid phase separation. JACS, 147(31), 28303--28312. (www)

  @article{ , abstract = {Ubiquitination is a critical post-translational modification that regulates key cellular processes such as protein degradation and DNA damage repair. Targeting a specific type of ubiquitin chain (e.g., Lys48 or Lys63-linked ubiquitin chain) via cyclic peptides presents a new strategy to modulate biological processes with therapeutic potential for various diseases. However, such a strategy remains challenging due to the obstacles of cell permeability and bioactivity. Here, we present a new method that directly assesses these parameters by integrating palladium-mediated Cys arylation with direct cellular screening. Using CP4 , a previously identified cyclic peptide modulator of Lys63-linked ubiquitin chains, we generated a focused library of arylated analogues and optimized the Pd-mediated arylation for direct cellular screening. We discovered a new analog, CP-P12-Ar H , that demonstrated enhanced binding affinity and robust bioactivity, as evidenced by increased γ-H2AX phosphorylation and apoptosis induction in cancer cells. Furthermore, CP-P12-Ar H effectively inhibited the in vitro formation of NF-κB essential modulator (NEMO) biomolecular condensates by disrupting the elongation of Lys63-linked ubiquitin chains, offering a novel way to modulate NF-κB signaling. This work establishes a generalizable platform for the rapid optimization of cyclic peptide therapeutics targeting protein–protein interactions.}, archive = {J_JACS}, author = {Mahdi Hasan and Nagaraju Vodnala and Yuri Glagovsky and Yakop Saed and Julia Kriegesmann and Hiroaki Suga and Ashraf Brik}, doi = {10.1021/jacs.5c09059}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28303--28312}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct cellular screening of pd-mediated arylation of cyclic peptide binders targeting ubiquitin chains: Toward modulating NEMO Liquid–Liquid phase separation}, volume = {147}, year = {2025}, }
• (2025). BNB-modified perylene, terrylene, and quaterrylene diimides: Introduction of the π-accepting and aggregation-suppressing diborinic imide group in rylene dyes. JACS, 147(31), 28289--28302. (www)

  @article{ , abstract = {Rylene diimides are among the most intensively researched classes of functional organic dyes. They are characterized by outstanding photoabsorption and -emission properties in combination with excellent photostability and thermal stability. Due to strong intermolecular π–π interactions, the larger, peri -extended rylene diimides, in particular, require the complex attachment of solubilizing substituents to enable their handling and processing in the solution phase. Herein, we introduce the diborinic imide functional group as a substitute for the commonly used dicarboximide moiety at the peri -termini of rylenes, thus leading to a new class of well-soluble rylene dyes with excellent optoelectronic properties. We synthesized borinic diimides of perylene (PD B I 5 ), terrylene (TD B I 7 ), and quaterrylene (QD B I 9 ) starting from a BNB-modified phenalenyl ( 1 ). These compounds show progressively bathochromically shifted absorption and emission characteristics with increasing system size, with fluorescence quantum yields up to Φ F = 0.92 for 5 , and extended NIR (near-infrared) emission for 9 . Single-crystal X-ray diffraction (XRD) studies reveal modified molecular packing in the solid state, pointing to a reduced tendency to aggregation. The new compounds undergo two reversible successive reductions, which were monitored by UV–vis–NIR spectroelectrochemistry. We performed the chemical reduction of 5 to obtain the potassium salts of the mono- and the dianion, K[ 5 ] and K 2 [ 5 ], respectively. Both the dianion and, in contrast to common rylene diimide dyes, also the monoanion show fluorescence emission, which extends into the NIR region. Quantum chemical ACID and 2D-NICS ZZ calculations reveal a transition from mainly local aromaticity to global aromaticity upon reduction.}, archive = {J_JACS}, author = {Michael Müller and Jonas Klopf and Alexandra Friedrich and Sarah Lutz and Manuel Buckel and Ivo Krummenacher and Holger Braunschweig and Bernd Engels and Holger Helten}, doi = {10.1021/jacs.5c09035}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28289--28302}, shortjournal = {J. Am. Chem. Soc.}, title = {BNB-modified perylene, terrylene, and quaterrylene diimides: Introduction of the π-accepting and aggregation-suppressing diborinic imide group in rylene dyes}, volume = {147}, year = {2025}, }
• (2025). Dynamic modulation of multicellular interactions via ATP-dissipative DNA assembly. JACS, 147(31), 28277--28288. (www)

  @article{ , abstract = {Living cells exhibit dynamic adaptability through ATP-fueled processes that are crucial for tissue development and immune responses. Conventional methods for controlling cell assembly lack the nonequilibrium, reversible behavior of natural systems. Here, we present an ATP-dissipative DNA assembly system that leverages DNA’s programmability to enable adaptive, hierarchical structures with spatiotemporal control. By utilizing various DNA monomers, including double-stranded DNA (dsDNA), tetrahedral DNA frameworks, and branched DNA frameworks, we achieve the precise regulation of cell assembly in response to ATP-driven enzymatic reactions. BDF-based condensates, formed through multivalent liquid–liquid phase separation (LLPS), dynamically modulate intercellular interactions, mimicking the extracellular matrix adaptability. This system was successfully applied to regulate cell assembly in Ramos, PC-12, and natural killer (NK) cells. By harnessing endogenous ATP secreted by cells, we enabled real-time reversible control over cell assembly. Furthermore, the ATP-dissipative assembly system enhanced the tumor-killing efficacy of NK cells by modulating their interactions with cancer cells. This work highlights the potential of DNA-based dissipative self-assembly for precise spatiotemporal regulation of cellular interactions, shedding light on advanced applications in intelligent materials and immunotherapy.}, archive = {J_JACS}, author = {Yi Xu and Yao Luo and Xiaoyun Lu and Jingyi Ye and Zeyu Chen and Yao Hu and Chen Shen and Bin Zhao and Erfeng Kou and Jie Deng and Chunhai Fan and Huan Zhang and Honglu Zhang}, doi = {10.1021/jacs.5c08925}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28277--28288}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic modulation of multicellular interactions via ATP-dissipative DNA assembly}, volume = {147}, year = {2025}, }
• (2025). Nontrivial spin dynamics synergy in a weakly coupled heteroanisotropic dysprosium chain-based array. JACS, 147(31), 28268--28276. (www)

  @article{ , abstract = {Spin chains (SCs) are fascinating due to their exotic quantum effects and promising applications. Despite the significant challenges in chemically aligning heteroanisotropic spins into weakly coupled chains, it is essential for advancing molecular spin engineering and exploring novel quantum behaviors. As well-defined, highly anisotropic, and two-level quantum systems, single-molecule magnet (SMM) units provide an excellent platform for the bottom-up approach to constructing heteroanisotropic spin chains. Herein, we successfully linked Ising-like dysprosium into one-dimensional (1D) spin chains via coordination bonds, resulting in three novel 1D arrays of homo/heteroanisotropic dysprosium ( SC-α , SC-β , and SC-αβ ) built from two kinds of pro-SMM units (α and β) connected by hydroquinone along the easy axes. Unlike the homodysprosium chains ( SC-α and SC-β ) and traditional single-chain magnets (SCMs) with strong coupling, the weakly coupled hetero-SMM chain ( SC-αβ ) revealed nontrivial synergistic spin dynamics between magnetic anisotropy and temperature-dependent spin polarization, leading to a unique two-stage magnetic quantum tunneling phenomena occurring at high and low temperatures. Furthermore, we demonstrated unprecedented control of spin orientation between the heterodysprosium units by manipulating magnetizing paths. These findings highlight the significant potential of weakly coupled heteroanisotropic spin chains, with distinct relaxation lifetimes, for novel applications in quantum information storage and processing.}, archive = {J_JACS}, author = {Wei Deng and Shan-Nan Du and Yan-Cong Chen and Jun-Liang Liu and Ming-Liang Tong}, doi = {10.1021/jacs.5c08875}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28268--28276}, shortjournal = {J. Am. Chem. Soc.}, title = {Nontrivial spin dynamics synergy in a weakly coupled heteroanisotropic dysprosium chain-based array}, volume = {147}, year = {2025}, }
• (2025). Ammonia evolution in glycine pyrolysis via ionic-pair reaction mechanisms. JACS, 147(31), 28259--28267. (www)

  @article{ , abstract = {Amino acids are key contributors to nitrogenous emissions during biomass pyrolysis, yet the underlying reaction mechanisms governing their thermal degradation remain only partially understood. In this study, we combine systematic reaction path search algorithms with chemical insight and density functional theory (DFT) simulations to investigate the thermal decomposition of glycine (Gly), the simplest amino acid, with a focus on the formation of ammonia (NH 3 ), a major precursor of environmentally harmful NO x species. We derive a comprehensive reaction network for the thermal decomposition of Gly. Notably, we show that, at variance with water (H 2 O) that can be generated via simple dimerization in the gas phase, NH 3 evolution is kinetically unfavorable at moderate temperatures and low-pressure conditions, while it can proceed with much smaller barriers in the condensed phase via many-body mechanisms involving ionic-pair proton-exchange-driven polymerization pathways. Under such conditions, we predict that NH 3 evolution competes with H 2 O formation, reconciling theoretical predictions with experimental observations.}, archive = {J_JACS}, author = {Jacopo Lupi and Thantip Roongcharoen and Luca Sementa and Francesca Cicogna and Alessandro Nanni and Alessandro Fortunelli}, doi = {10.1021/jacs.5c08868}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28259--28267}, shortjournal = {J. Am. Chem. Soc.}, title = {Ammonia evolution in glycine pyrolysis via ionic-pair reaction mechanisms}, volume = {147}, year = {2025}, }
• (2025). Spinning top-like nanoprobes for direct visualization of cooperative ca2+-binding-induced conformational switching in single calmodulin molecules. JACS, 147(31), 28251--28258. (www)

  @article{ , abstract = {Understanding the rapid, domain-specific conformational dynamics of single calmodulin (CaM) molecules remains a major challenge due to the limited temporal resolution of existing single-molecule techniques. Here, we present a mechano-responsive strategy using high-speed nanoscale spinning tops (NSTs) as nanoprobes to directly resolve these dynamics. By constructing a single-molecule CaM protrusion on a protein corona-coated gold nanorod, we enabled stochastic thermally driven rotation, whose speed is sensitively modulated by conformational changes in CaM. Distinct hydrophilic and hydrophobic states of apo-CaM and Ca 2+ -bound CaM, respectively, give rise to characteristic rotational signatures, allowing millisecond-resolved detection of conformational switching. Kinetic analysis across single CaM molecules reveals the cooperative binding of two Ca 2+ ions to the C-terminal domain, supported by a Hill coefficient of 1.81 and a binding stoichiometry of 2.43. This platform provides an approach for quantifying protein–ligand interactions and conformational kinetics at the single-molecule level, offering new insights into calcium-mediated signaling and dynamic protein function.}, archive = {J_JACS}, author = {Rui Liu and Zhuodong Tang and Qing Xia and Zixuan Chen and Jun-Jie Zhu}, doi = {10.1021/jacs.5c08829}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28251--28258}, shortjournal = {J. Am. Chem. Soc.}, title = {Spinning top-like nanoprobes for direct visualization of cooperative ca2+-binding-induced conformational switching in single calmodulin molecules}, volume = {147}, year = {2025}, }
• (2025). Near-infrared to visible photon upconversion with gold quantum rods and aqueous photo-driven polymerization. JACS, 147(31), 28241--28250. (www)

  @article{ , abstract = {Converting near-infrared (NIR) photons into visible light via triplet–triplet annihilation upconversion (TTA-UC) is a promising strategy for advancing energy, biomedical, and materials science. However, the development of efficient NIR sensitizers remains a major challenge. Here, we report an atomically precise gold quantum rod, Au 42 (PET) 32 (PET = 2-phenylethanethiolate), as a high-performance photosensitizer for NIR-to-visible TTA-UC. Paired with TES-ADT as an annihilator, the system exhibits a 6.7% quantum yield, a 0.5 eV anti-Stokes shift, and a low threshold intensity of 90 mW/cm 2 . To enable aqueous compatibility, the upconversion nanodroplets are encapsulated with a silica shell, yielding Au 42 /TES-ADT@SiO 2 nanoparticles (NPs) capable of driving efficient photoinduced atom-transfer radical polymerization (photo-ATRP) and forming hydrogels in water. This system offers a versatile platform for the next generation photopolymerization with NIR light, solar energy utilization and noninvasive biomedical applications.}, archive = {J_JACS}, author = {Zhongyu Liu and Xiaolei Hu and Lianshun Luo and Guiying He and Abhrojyoti Mazumder and Ece Gunay and Yitong Wang and Elizabeth C. Dickey and Linda A. Peteanu and Krzysztof Matyjaszewski and Rongchao Jin}, doi = {10.1021/jacs.5c08826}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28241--28250}, shortjournal = {J. Am. Chem. Soc.}, title = {Near-infrared to visible photon upconversion with gold quantum rods and aqueous photo-driven polymerization}, volume = {147}, year = {2025}, }
• (2025). Pushing the thermodynamic and kinetic limits of near-infrared emissive CrIII complexes in photocatalysis. JACS, 147(31), 28226--28240. (www)

  @article{ , abstract = {Photoactive Cr III complexes are typically based on polypyridine coordination environments, exhibit red luminescence, and are good photo-oxidants but have modest photoreducing properties. We report new Cr III complexes with anionic chelate ligands that enable color-tunable near-infrared luminescence and red-light-driven photoreduction reactions involving elementary steps that are endergonic up to 0.5 eV. Improving the metal–ligand bond covalency rather than more established approaches such as optimizing ligand field strength and coordination geometry is the underlying molecular design concept to achieve this favorable behavior. Our analysis suggests an intricate interplay between productive but slow endergonic photoinduced electron transfer and energy-wasting charge recombination rooted in cage escape effects, which could be generally important for photocatalysis. Our work also suggests the occurrence of doublet–doublet annihilation, a process that seems to have been largely neglected in current research on photoactive Cr III complexes but which could provide a mechanistic entry point into the widely used process of photochemical upconversion, typically based on triplet–triplet annihilation. Overall, this work conceptually advances the current state of the art of photoactive Cr III complexes in terms of molecular design, luminescence, and photoredox behavior. More generally, it informs photochemistry in terms of elucidating the limits of light-to-chemical energy conversion efficiency and the value of long-lived excited states in complexes of earth-abundant transition metals.}, archive = {J_JACS}, author = {Giacomo Morselli and Tim H. Eggenweiler and Marco Villa and Alessandro Prescimone and Oliver S. Wenger}, doi = {10.1021/jacs.5c08541}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28226--28240}, shortjournal = {J. Am. Chem. Soc.}, title = {Pushing the thermodynamic and kinetic limits of near-infrared emissive CrIII complexes in photocatalysis}, volume = {147}, year = {2025}, }
• (2025). Triptycene-based 2.5-dimensional Metal–Organic frameworks: Atomically accurate structures and anisotropic physical properties from hydrogen-bonding bridged protonated building units. JACS, 147(31), 28215--28225. (www)

  @article{ , abstract = {Recent advances in two-dimensional (2D) π-d conjugated conductive metal–organic frameworks (2D cMOFs) have highlighted their potential as sophisticated, active materials in electrochemical energy storage devices, electrocatalysis, and sensors. However, a lack of high-quality structural characterization severely limits our understanding of their physical properties. Specifically, rapid and irreversible nucleation and aggregation, induced by strong interlayer π-π interactions, have hindered crystal growth in these cMOFs. In this study, by utilizing triptycene-based ligands, 2,3,6,7,14,15-hexahydroxy triptycene (HHTripH 2 ) and 9,10-dimethyl-2,3,6,7,14,15-hexahydroxy triptycene (HHTripMe 2 ), we successfully mitigated interlayer π-π interactions and achieved SCXRD quality crystals of two triptycene-based 2D MOFs/Cu 3 (TripH 2 ) 2 and Cu 3 (TripMe 2 ) 2 . The crystal structures reveal a protonated catechol ligand and an interlayer hydrogen-bonding-guided stacking motif, with density functional theory (DFT) calculations confirming their semiconducting nature. The steric effect of the two axial methyl groups in the TripMe 2 ligand modifies the structure of Cu 3 (TripMe 2 ) 2 from regular AB stacking to interpenetration, significantly enhancing the stability of the crystals. These high-quality crystals enabled the direct measurement of anisotropic dual proton–electron conduction, governed by thermally activated hopping through hydrogen-bonding networks. ESR and susceptibility measurements indicate that these modifications facilitate hydrogen-bonding-guided One-dimensional (1D) antiferromagnetic behavior in the Cu(cat) 2 secondary building units (SBUs). This study reveals the critical roles of high-quality crystal structures and protonation–deprotonation of coordinating atoms in understanding the properties of 2D MOFs.}, archive = {J_JACS}, author = {Qi Chen and Amos Afugu and Yoshiaki Shuku and Zhen-Fei Liu and Kunio Awaga and Zhongyue Zhang}, doi = {10.1021/jacs.5c08703}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28215--28225}, shortjournal = {J. Am. Chem. Soc.}, title = {Triptycene-based 2.5-dimensional Metal–Organic frameworks: Atomically accurate structures and anisotropic physical properties from hydrogen-bonding bridged protonated building units}, volume = {147}, year = {2025}, }
• (2025). Enantioselective carbonylative coupling reactions: Merging nickel-based selectivity and photoredox reactivity. JACS, 147(31), 28206--28214. (www)

  @article{ , abstract = {Transition metal-catalyzed carbonylative coupling reactions play a crucial role in the synthesis of functional molecules of use throughout pharmaceutical development, natural products, and material science. This utility is driven by both the efficiency of carbonylation chemistry and the broad presence of the carbonyl functionality in most synthetic materials. Unfortunately, the development of enantioselective carbonylative coupling reactions of alkyl halides and nucleophiles to access the α-chiral motif found in most drugs is, to date, not viable. This has been attributed to the inhibitory influence of carbon monoxide, which blocks the activation of C(sp 3 )-halides and limits the efficacy of chiral ligand environments in modulating selectivity. Here, we show how this challenge can be addressed via a conceptually alternative approach to such reactions, where the coupling of photoredox and chiral nickel catalysis can be employed to separate reactivity from stereocontrol. This combined strategy has enabled the first asymmetric carbonylative coupling of benzylic and related C(sp 3 )-halides with amines and the preparation of a diverse array of chiral amides with excellent enantioselectivity. These findings expand the scope of enantioselective catalysis and offer new possibilities for synthesizing chiral carbonyl-containing compounds with wide-ranging implications for drug discovery and synthetic chemistry.}, archive = {J_JACS}, author = {Ling Li and Zhen Hu and Shuaikang Ren and Bruce A. Arndtsen and Lingling Chu}, doi = {10.1021/jacs.5c08527}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28206--28214}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective carbonylative coupling reactions: Merging nickel-based selectivity and photoredox reactivity}, volume = {147}, year = {2025}, }
• (2025). Efficient kinetic-resolution copolymerization of epoxides and CO2 achieved via computation-guided catalyst design. JACS, 147(31), 28198--28205. (www)

  @article{ , abstract = {The enantioselective resolution copolymerization of racemic terminal epoxides and CO 2 is a powerful strategy for preparing isotactic polycarbonates. However, no catalytic system to date has enabled both high chemo- and stereoselectivity in this transformation. Herein, a computation-guided strategy was conducted to understand the key factors governing the activity, chemoselectivity, and stereoselectivity of chiral bimetallic cobalt complexes. Computational fine-tuning of bimetallic synergy allowed accelerated copolymerization, suppression of epoxide homopolymerization, and enhanced chiral induction. Ultimately, a privileged chiral bimetallic catalyst bearing 6,6-ditriflate substituents was computationally designed and experimentally synthesized, which exhibited unprecedented enantioselectivity ( s -factor up to over 300) and high chemoselectivity (>95% carbonate units) for various racemic epoxides during resolution copolymerization with CO 2 . This study is expected to serve as a theoretical framework for broadly guiding the design of privileged chiral catalysts for asymmetric catalytic polymerizations.}, archive = {J_JACS}, author = {Bai-Hao Ren and Sarah M. Severson and Si-Nuo Wang and Zheng-Fei Liu and Lin-Di Zhang and Zi-Cong Wang and Ye Liu and Wei-Min Ren and Geoffrey W. Coates and Xiao-Bing Lu}, doi = {10.1021/jacs.5c08366}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28198--28205}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient kinetic-resolution copolymerization of epoxides and CO2 achieved via computation-guided catalyst design}, volume = {147}, year = {2025}, }
• (2025). Solvent-induced morphology control of polymer assemblies with improved photothermal features. JACS, 147(31), 28189--28197. (www)

  @article{ , abstract = {Organic photothermal agents (OPTAs) are extensively utilized in applications such as therapy and imaging. However, enhancing their photothermal performance often depends on complex molecular designs, which are limited by the challenges of chemical synthesis. Herein, we present a straightforward strategy to optimize the optical absorbance of OPTAs by adjusting the morphology of assemblies of an amphiphilic block copolymer (PEG 44 -PTA 5 ), leading to enhanced photothermal conversion efficiency. By changing the polarity of the organic solvent in which the polymer was dissolved, addition of water to induce assembly led to the exclusive formation of polymersomes or bicontinuous nanospheres. The morphological variations were confirmed using a range of electron microscopy techniques and small-angle X-ray scattering. Due to their mesoporous structure, the bicontinuous nanospheres exhibited superior light-harvesting capabilities, achieving a high absorption coefficient of 1.1 × 10 5 M –1 cm –1 and a photothermal conversion efficiency of 45% when irradiated with a 808 nm laser. Our work introduces a facile solvent-induced assembly strategy for precisely controlling the morphology of OPTAs while simultaneously tuning their light absorption properties to enhance photothermal conversion.}, archive = {J_JACS}, author = {Yingtong Luo and Jianhong Wang and Yudong Li and Işıl Yeşil Gür and Marco M.R.M. Hendrix and Yiğitcan Sümbelli and Alexander Fusi and Ilja K. Voets and Loai K. E. A. Abdelmohsen and Jingxin Shao and Jan C. M. van Hest}, doi = {10.1021/jacs.5c08355}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28189--28197}, shortjournal = {J. Am. Chem. Soc.}, title = {Solvent-induced morphology control of polymer assemblies with improved photothermal features}, volume = {147}, year = {2025}, }
• (2025). Mechanisms and synthetic applications of cyclic, nonstabilized isodiazenes: Nitrogen-atom insertion into pyrrolidines and related rearrangements. JACS, 147(31), 28179--28188. (www)

  @article{ , abstract = {Reactive intermediates that can promote nonintuitive bond disconnections underpin advancements in skeletal editing methodologies. Accordingly, a detailed understanding of their reactivity and its underlying mechanisms is central to progress in this space. Herein, we catalog and study the reactivity of nonstabilized cyclic isodiazene intermediates generated via the reaction of cyclic secondary amines with an anomeric amide reagent. Depending on the amine structure, distinct and predictable product classes can be accessed: cyclic hydrazones are formed from pyrrolidines, N -amino indoles from indolines, orthoquinodimethane intermediates from isoindolines, cyclopropanes from azetidines, and cyclic tetrazines from piperidines. Mechanistic experiments and density functional theory calculations suggest that many of these transformations proceed through an azomethine imine intermediate. In most cases, this reactive species subsequently rearranges to a cyclic hydrazone by an unusual self-catalysis mechanism proceeding through a dimeric tetrazine. This oxidative nitrogen insertion was leveraged in several subsequent synthetic applications. Redox diversification of the cyclic hydrazones enables access to pyridazines and cyclic hydrazines, including the synthesis of an orthogonally protected l -piperazic acid from the readily available chiral pool l -prolinol.}, archive = {J_JACS}, author = {Cecile Elgindy and Achyut R. Gogoi and Ángel Rentería-Gómez and Bumsu Park and Deborshee Das and Carys E. Obertone and Balu D. Dherange and Osvaldo Gutierrez and Mark D. Levin}, doi = {10.1021/jacs.5c08361}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28179--28188}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanisms and synthetic applications of cyclic, nonstabilized isodiazenes: Nitrogen-atom insertion into pyrrolidines and related rearrangements}, volume = {147}, year = {2025}, }
• (2025). Deciphering the photochemistry of thionylimide (HNSO): Isomers and tunneling-controlled reactions. JACS, 147(31), 28173--28178. (www)

  @article{ , abstract = {Thionylimide (HNSO) and its isomer thionitrous acid (HSNO) are important intermediates in atmospheric chemistry and biology, respectively. However, the chemical network linking HNSO and HSNO is not fully understood due to the absence of some high-energy isomers. Herein, we report the identification of trans -HNSO and cis -HONS during the photochemistry of cis -HNSO in a solid Ne matrix at 3 K. The characterization of both species with matrix-isolation IR spectroscopy is supported by D- and 15 N-isotope labeling experiments and quantum chemical calculations at the CCSD(T)-F12B/VTZ-F12 level of theory using configuration-selective vibrational configuration interaction theory (VCI). Interestingly, spontaneous reactions via quantum mechanical tunneling (QMT) have been observed at 3 K for the trans → cis conformational rotation in HNSO and HOSN, as well as for the 1,3-hydrogen migration in cis -HONS (→ cis -HSNO). The QMT mechanism by the hydrogen atom is consistent with the kinetic isotope effects (KIEs) and the multidimensional instanton theory calculations.}, archive = {J_JACS}, author = {Xin Jiang and Yiding Fan and Longtian Huang and Yixin Guo and Wei Fang and Lina Wang and Guntram Rauhut and Xiaoqing Zeng}, doi = {10.1021/jacs.5c08291}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28173--28178}, shortjournal = {J. Am. Chem. Soc.}, title = {Deciphering the photochemistry of thionylimide (HNSO): Isomers and tunneling-controlled reactions}, volume = {147}, year = {2025}, }
• (2025). Intersected bicyclic N-confused corrole dimers with tunable aromaticity and topological chirality. JACS, 147(31), 28161--28172. (www)

  @article{ , abstract = {Despite the successful syntheses of unique porphyrinoids by oxidative cyclization of oligopyrranes, the development of bicyclic variants with unprecedented topologies, aromaticity, and chirality remains challenging. Herein, we report the syntheses of a class of bicyclic porphyrinoids based on the oxidative cyclization of heptapyrrane P 7 . Thus, a nonsymmetrical intersected bicyclic N-confused corrole dimer 1 was synthesized, wherein two terminal pyrrolic α-C atoms are linked to the β-C atoms of the middle pyrrole ring. Subsequent reduction of dimer 1 afforded dimer 2 by the attachment of two hydrogen atoms. Interestingly, 1 and 2 exhibit 18π aromatic–16π antiaromatic and 18π aromatic–18π aromatic structures, respectively, and the aromaticity of 2 can be effectively modulated by solvent polarity with contribution of the zwitterionic resonance effect. Furthermore, both 1 and 2 can chelate copper ions to form 18π aromatic–nonaromatic mono-Cu(III) complex 1-Cu and nonaromatic–nonaromatic bis-Cu complex 1-Cu 2 , with the absorption band edge extended to ca. 1800 nm. In addition, the distinctive structures of these compounds enable their separation into a pair of enantiomers, with ( M , M )-2 and ( P , P )-2 achieving the largest dissymmetry factor | g abs | of 0.015. These results indicate that oxidative cyclization of long-chain oligopyrranes holds promise for the syntheses of novel bicyclic porphyrinoids with unprecedented topologies, tunable aromaticity, and photophysical properties as well as persistent chirality.}, archive = {J_JACS}, author = {Yanping Huang and Bin Zhu and Shijun Li and Glib Baryshnikov and Hailong Wang and Chengjie Li and Hans Ågren and Jianzhuang Jiang and Yongshu Xie and Qizhao Li}, doi = {10.1021/jacs.5c08284}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28161--28172}, shortjournal = {J. Am. Chem. Soc.}, title = {Intersected bicyclic N-confused corrole dimers with tunable aromaticity and topological chirality}, volume = {147}, year = {2025}, }
• (2025). Electron donors in the intertwined interface restore oxy-substituted selenides. JACS, 147(31), 28151--28160. (www)

  @article{ , abstract = {Nature chose selenium as the antioxidant element center in proteins, permitting the reversible conversion of organic bioenzymes between oxidized and selenized forms. Despite the importance of such antielectronegativity reversibility, it has not yet been demonstrated in inorganic selenides. We report an unexpected example showing that oxy-substituted sites in metal selenides can be restored to selenized forms reversibly by mild electrochemical manipulation in a copper aqueous solution. Synchrotron measurements of the localized lattice and bond structure suggest that copper as an electron donor can transfer extra electrons to oxidized metal centers via the O–V–Se–Cu-bonded bridge path in the deep-intertwined interface to confer rare reversibility. We demonstrate that such reversibility is generalized in vanadium diselenide and manganese diselenides/selenides, offering the possibility of applying promising selenides in widespread aqueous systems.}, archive = {J_JACS}, author = {Yuanhe Sun and Junwei Yang and Wei Zhang and Haitao Li and Mengru Lin and Hao Shi and Yi Gao and Wen Wen and Chunyi Zhi and Xiaolong Li and Daming Zhu}, doi = {10.1021/jacs.5c08194}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28151--28160}, shortjournal = {J. Am. Chem. Soc.}, title = {Electron donors in the intertwined interface restore oxy-substituted selenides}, volume = {147}, year = {2025}, }
• (2025). Facilitating anodic ammonia oxidation over trace cobalt-substituted solid solution of platinum to boost direct ammonia fuel cell up to 853.75 mW cm–2. JACS, 147(31), 28137--28150. (www)

  @article{ , abstract = {Low-temperature direct ammonia fuel cell (DAFC) is a key technology for decarbonized electric generation on a large scale and with high safety. However, as the core of DAFC, the anodic ammonia oxidation reaction (AOR) still suffers from unsatisfactory activity and an ambiguous reaction mechanism. Herein, inspired by homogeneously catalyzed oxidation of ammonia, a nucleophilic attack mechanism that loosens the steric and charge constraints in heterogeneous catalysis is theoretically predicted and experimentally verified by a three-stage isotope-labeling experiment. Guided by this more practical mechanism, a highly efficient AOR process is realized over trace cobalt-substituted solid solution of platinum, delivering a superior current density of 83.96 A g –1 at 5 mV s –1 . The assembled DAFC exhibits a remarkable power density of up to 853.75 mW cm –2 at 60 °C and can operate steadily for 300 h with a performance retention rate of 95.14%, propelling the application of low-temperature DAFC to a more practical era.}, archive = {J_JACS}, author = {Yanzheng He and Sisi Liu and Qiyang Cheng and Yunfei Huan and Lifang Zhang and Wenjun Shi and Weiyi Shen and Fengchun Zhou and Xiaolei Yuan and Mengfan Wang and Chenglin Yan and Tao Qian}, doi = {10.1021/jacs.5c08228}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28137--28150}, shortjournal = {J. Am. Chem. Soc.}, title = {Facilitating anodic ammonia oxidation over trace cobalt-substituted solid solution of platinum to boost direct ammonia fuel cell up to 853.75 mW cm–2}, volume = {147}, year = {2025}, }
• (2025). Nickel-assisted dehydration of DNA-engineered colloidal crystals. JACS, 147(31), 28127--28136. (www)

  @article{ , abstract = {In colloidal crystal engineering, DNA has enabled precise control over crystal symmetry and architecture through programmable interparticle interactions in aqueous environments. However, practical applications typically require dry-state operation, necessitating robust strategies to transform these assemblies into free-standing solid-state metamaterials. As direct dehydration often induces structural collapse due to DNA deformation and capillary forces, the preservation of structural integrity becomes a critical challenge, particularly for large crystals with macroscopic functionality. Here, we introduce a nickel ion-assisted freeze-drying strategy that combines reversible Ni 2+ -DNA phosphate coordination for stress mitigation with lyophilization to reduce interfacial damage. This approach enables rapid fabrication (within 2 h) of solid-state colloidal crystals while maintaining hierarchical order from nanoscale to macroscale. Structural characterization confirms retention of crystallographic symmetry despite up to 45% lattice contraction, and surface analysis reveals multidimensional defects analogous to those in atomic crystals. Notably, this approach facilitates the fabrication of monolithic single crystals spanning tens of micrometers, featuring flat surfaces and enhanced metallic reflectivity. This work overcomes the rigidity-adaptability trade-off in existing processes, offering a scalable route to colloidal metamaterials for applications in photonic circuits and near-field optical devices.}, archive = {J_JACS}, author = {Wenhe Ma and Tianyi Lu and Soumia Cheddah and Bochen Li and Kun Dai and Xiaoliang Chen and Kai Xia and Chunhai Fan and Jichao Zhang and Guangbao Yao}, doi = {10.1021/jacs.5c08215}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28127--28136}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-assisted dehydration of DNA-engineered colloidal crystals}, volume = {147}, year = {2025}, }
• (2025). An expedient synthesis of the antimitotic natural products sarcodictyin and eleutherobin, and carbohydrate analogues. JACS, 147(31), 28117--28126. (www)

  @article{ , abstract = {The eleutherobins and sarcodictyins are diterpenoids that belong to an elite family of microtubule-stabilizing natural products that includes the frontline cancer therapy Taxol. To date, members of this family of natural products have been overlooked as clinical candidates in large part, owing to a lack of material available from natural sources (rare marine invertebrates) or through chemical synthesis. Here, we report a concise synthesis of several members of the eleutherobin and sarcodictyin natural products using an approach that parallels Nature’s strategy, with the assembly of a eunicellin intermediate followed by regio- and diastereoselective oxidations. Additionally, we report a collection of eleutherobin carbohydrate analogues that shed light on the relationship between carbohydrate structure and anticancer activity. These efforts should support and inspire the discovery of next-generation microtubule-stabilizing drugs.}, archive = {J_JACS}, author = {Daniel Driedger and Anthony Fers-Lidou and Megan Schroeder and Ingrid Elisia and Gerald Krystal and Robert Britton}, doi = {10.1021/jacs.5c08176}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28117--28126}, shortjournal = {J. Am. Chem. Soc.}, title = {An expedient synthesis of the antimitotic natural products sarcodictyin and eleutherobin, and carbohydrate analogues}, volume = {147}, year = {2025}, }
• (2025). Protein recognition and assembly by a phosphocavitand. JACS, 147(31), 28107--28116. (www)

  @article{ , abstract = {Controlled protein assembly is an enabling technology, in particular, for biomaterials fabrication. Here, we report protein recognition and assembly by a phosphate-containing macrocycle ( pctx ). We show that the C 3 -symmetric phosphocavitand is a versatile receptor for N-terminal residues or arginine but not lysine. Using atomic resolution X-ray diffraction data, we reveal the precise details of N-terminal complexation in the β-propeller protein Ralstonia solanacearum lectin (RSL). In some cocrystal structures, a tetrahedral cluster of the phosphocavitand occupies one end of the β-propeller fold, providing a node for protein assembly. The macrocycle cluster is compatible with different types of precipitants, a broad pH range, and zinc complexation. We demonstrate system control with an arginine-enriched RSL that alters the overall assembly due to selective arginine complexation by pctx . A lysozyme– pctx cocrystal structure also demonstrates arginine complexation by the macrocycle. An alternative macrocycle cluster occurs with an engineered RSL bearing an extended N-terminus. In this structure, involving zinc ligation at the N-terminus, the macrocycle forms trimeric clusters and four such clusters form cage-like substructures within the tetrahedral protein framework. Thus, N-terminal complexation in combination with phosphocavitand self-assembly provides new routes to protein crystal engineering.}, archive = {J_JACS}, author = {Colin P. Wren and Ronan J. Flood and Niamh M. Mockler and Martin Savko and Maura Malinska and Qiang Shi and Peter B. Crowley}, doi = {10.1021/jacs.5c08121}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28107--28116}, shortjournal = {J. Am. Chem. Soc.}, title = {Protein recognition and assembly by a phosphocavitand}, volume = {147}, year = {2025}, }
• (2025). Asymmetric C–H functionalization of N-boc-2,5-dihydro-1H-pyrrole and its application as a key step in the synthesis of (−)-dragocin d. JACS, 147(31), 28098--28106. (www)

  @article{ , abstract = {Dirhodium tetracarboxylate-catalyzed reaction of aryldiazoacetates with N -Boc-2,5-dihydro-1 H -pyrrole results in a highly enantio- and diastereoselective C–H functionalization exclusively at the α- N C2 position. This result is a sharp contrast to the reaction with ethyl diazoacetate, which results in cyclopropanation of the olefinic site. Rh 2 ( S - or R -PTAD) 4 is the optimal chiral catalyst and is capable of generating the C–H functionalization products in up to 87% yield with high levels of diastereoselectivity (>20:1 d.r.) and enantioselectivity (97% ee) with a low catalyst loading (0.05 mol %). Computational studies were conducted to rationalize the reactivity difference between donor/acceptor carbenes and acceptor carbenes. The utility of the C–H functionalization chemistry was illustrated by its application to the synthesis of (−)-dragocin D and a variety of pharmaceutically relevant pyrrolidines.}, archive = {J_JACS}, author = {Terrence-Thang H. Nguyen and Kristin Shimabukuro and Djamaladdin G. Musaev and John Bacsa and Antonio Navarro and Huw M. L. Davies}, doi = {10.1021/jacs.5c08080}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28098--28106}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric C–H functionalization of N-boc-2,5-dihydro-1H-pyrrole and its application as a key step in the synthesis of (−)-dragocin d}, volume = {147}, year = {2025}, }
• (2025). Enhancing chiral site density in covalent organic frameworks enables efficient SERS-based enantioselective discrimination. JACS, 147(31), 28085--28097. (www)

  @article{ , abstract = {Surface-enhanced Raman scattering (SERS) enables simultaneous molecular identification and chiral discrimination, yet its broader application is often restricted by the limited availability of robust, reproducible, and universally applicable chiral sensing platforms. Herein, we demonstrate that covalent organic frameworks (COFs) offer a versatile platform for constructing stable and highly enantioselective SERS substrates. A three-dimensional chiral COF ( SU-1 ) was synthesized via a “two-in-one” strategy using a single enantiopure binaphthol-derived monomer bearing both aldehyde and amine functionalities. This self-condensation approach eliminates achiral components and achieves the highest reported density of chiral binaphthyl units (2.05 mmol/g) among the known COFs. For comparison, a structurally analogous COF ( SU-2 ) with lower chiral site density was synthesized via conventional co-condensation of a chiral binaphthol-based tetrabenzaldehyde and p -phenylenediamine. Upon incorporation of gold nanoparticles, both frameworks were evaluated as SERS-active platforms for the enantioselective sensing of a variety of small aromatic molecules. SU-1 exhibited significantly enhanced enantioselectivity and signal reproducibility relative to SU-2 , highlighting the effectiveness of the “two-in-one” strategy in amplifying chiral recognition. This work presents a generalizable approach for constructing high-performance chiral COF-based SERS substrates and advances the application of crystalline porous materials in enantiomeric analysis.}, archive = {J_JACS}, author = {Ji Yang and Siqi Wei and Tong Zhang and Li Wu and Lei Jia and Jinqiao Dong and Chen Yuan and Yong Cui and Xiandeng Hou}, doi = {10.1021/jacs.5c08040}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28085--28097}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing chiral site density in covalent organic frameworks enables efficient SERS-based enantioselective discrimination}, volume = {147}, year = {2025}, }
• (2025). Carbonylmetallated palladium nanoclusters for visible-light-driven carbonylation under 1 atm of CO. JACS, 147(31), 28073--28084. (www)

  @article{ , abstract = {Palladium nanoclusters (Pd NCs) hold great promise in organic synthesis; however their controlled synthesis via direct reduction remains challenging due to kinetically favored formation of nanoparticles. In this study, we employ carbonylmetallate ligands to regulate the reduction reaction kinetics and successfully achieve three [Co(CO) 4 ] − terminated Pd 14 NCs. Magnetic studies, in conjunction with quantum chemical calculations, suggest that the Pd 14 cluster exhibits a quartet ground state and open-shell superatomic character with 1S 1 jellium configuration, representing the first open-shell palladium superatom containing one free electron. The high stability of the clusters is largely attributed to significant electron transfer from the [Co(CO) 4 ] − ligand to the Pd 14 core, facilitated by polarized Pd(δ – )–Co(δ + ) bonds, along with pronounced Co→Pd σ-, π-, and δ-donor, as well as δ-acceptor, interactions between the [Co(CO) 4 ] − ligands and the Pd 14 core. Remarkably, the Pd 14 NC exhibits exceptional catalytic activity in carbonylative cross-couplings under mild conditions (1 atm CO and 30 W of 450 nm LEDs), owing to enhanced nucleophile activation by the [Co(CO) 4 ] moieties. This protocol tolerates a broad range of challenging aryl and alkyl halides and is applicable to complex derivatization and the targeted synthesis of bioactive pharmaceuticals. Our findings demonstrate the potential of carbonylmetallate ligands in Pd cluster synthesis and enable further exploration of metal NCs with unique polar heterometallic components for synergistic catalytic applications.}, archive = {J_JACS}, author = {Lin-Mei Zhang and Hui-Zhi Wei and Hao Zhang and Xu-Hang Zhong and Shang-Fu Yuan and Bingzhe Wang and Jianyu Wei and Qixia Bai and Zhe Zhang and Kuan-Guan Liu and Tao Wu and Dan Li}, doi = {10.1021/jacs.5c08034}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28073--28084}, shortjournal = {J. Am. Chem. Soc.}, title = {Carbonylmetallated palladium nanoclusters for visible-light-driven carbonylation under 1 atm of CO}, volume = {147}, year = {2025}, }
• (2025). Crystallizing the uncrystallizable: Insights from extensive screening of PROTACs. JACS, 147(31), 28056--28072. (www)

  @article{ , abstract = {PROTACs are new drug molecules in the beyond Rule of Five (bRo5) chemical space with extremely poor aqueous solubility and intrinsically poor crystallizability due to their structure, which comprises two distinct ligands covalently linked by a flexible linker. This makes PROTACs particularly challenging to understand from a solid-state preformulation perspective. While several X-ray structures have been reported of PROTACs in ternary complexes, to date no structures have been published of single component densely packed PROTACs, from which an understanding of PROTACs’ intermolecular interactions, and therefore physical properties, can be developed. An extensive crystallization protocol was applied to grow single crystals of a cereblon-recruiting PROTAC “AZ1” resulting in structures of an anhydrous form and a nonstoichiometric p -xylene solvate using 3D electron diffraction and synchrotron X-ray crystallography, respectively. The lattice energies are dominated by dispersive interactions between AZ1 molecules despite the presence of multiple hydrogen-bond donors and acceptors and planar aromatic groups, and both structures are built on similar intermolecular interactions. Thermal and spectral characterization revealed another solvate form containing dichloromethane. Amorphous solids produced by mechanochemical grinding of anhydrous AZ1 crystals also differed in dissolution characteristics from an amorphous solid produced by desolvating the dichloromethane solvate crystals, indicating that AZ1 may demonstrate pseudo -polyamorphism. This study paves the way for solid form screening and understanding in pharmaceutical systems that are far bRo5.}, archive = {J_JACS}, author = {Martin A. Screen and James F. McCabe and Sean Askin and Jamie L. Guest and Paul Hodgkinson and Aurora J. Cruz-Cabeza and Toby J. Blundell and Daniel N. Rainer and Simon J. Coles and Alexandra Longcake and Michael R. Probert and Clare S. Mahon and Mark R. Wilson and Jonathan W. Steed}, doi = {10.1021/jacs.5c07977}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28056--28072}, shortjournal = {J. Am. Chem. Soc.}, title = {Crystallizing the uncrystallizable: Insights from extensive screening of PROTACs}, volume = {147}, year = {2025}, }
• (2025). Ultra-narrow homogeneous photoluminescence line width of zinc-blende CdSe-based Core/Shell nanocrystals: Dominating role of Lattice–Ligands interface. JACS, 147(31), 28044--28055. (www)

  @article{ , abstract = {Homogeneous photoluminescence (PL) line width of semiconductor nanocrystals is usually much greater than thermal broadening at room temperature (∼25 meV), limiting their applications as optical and optoelectronic materials. Here, homogeneous PL line width of zinc-blende CdSe nanocrystals with epitaxially grown CdS, ZnSe, and ZnS shells is studied using single-molecular spectroscopy, confirming that delocalization of electron and hole wave functions to the lattice–ligands interface dictates their PL homogeneous line width. Specially, epitaxial ZnSe (or ZnSe inner and ZnS outer) shells form type-I band offsets with CdSe cores, colocalizing both electron and hole wave functions within the ordered core lattice with minimum lattice strain. Without delocalization to the disordered lattice–ligands interface, these epitaxial shells reduce the homogeneous PL line width of CdSe nanocrystals by ∼70%. Exceptionally narrow homogeneous PL (∼25 meV) allows observation of the energy splitting (20∼60 meV) of two lowest optically active states of the ground-state exciton for 2–6 nm CdSe in right-triangular-bipyramidal shape. This energy splitting does not play a decisive role in determining the PL homogeneous line width but leads to dual-peak and polarized emission.}, archive = {J_JACS}, author = {Yuqing Wang and Jiakuan Zhang and Zihang Chen and Xionglin Zhou and Haixin Lei and Haiyan Qin and Xiaogang Peng}, doi = {10.1021/jacs.5c08004}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28044--28055}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultra-narrow homogeneous photoluminescence line width of zinc-blende CdSe-based Core/Shell nanocrystals: Dominating role of Lattice–Ligands interface}, volume = {147}, year = {2025}, }
• (2025). Unveiling water-vapor-promoted oxidation of palladium nanoparticles via atomic-scale transmission electron microscopy at atmospheric pressure. JACS, 147(31), 28035--28043. (www)

  @article{ , abstract = {Water vapor plays a critical role in metal oxidation, profoundly impacting structural integrity and functional performance. However, its effects on metal oxidation dynamics under realistic temperatures and pressures remain poorly understood. In this study, we utilized Cs-corrected transmission electron microscopy (TEM) in combination with atmospheric-pressure techniques to investigate the oxidation dynamics of Pd nanoparticles in water vapor, and systematically compared their behavior to that in oxygen, both under atmospheric conditions. Atomic-resolution TEM images reveal that protruding PdO nucleates on the Pd{110} surface in a water vapor atmosphere, with PdO(1̅1̅2) aligned parallel to Pd(22̅0), or rotated within 7.4° around the consistently parallel directions of PdO[111] and Pd[001]. In contrast, PdO nucleates and grows on the Pd{100} surface in oxygen to form continuous films with a fixed epitaxial relationship, i.e., PdO(001)//Pd(100), PdO[1̅10]//Pd[001]. Density functional theory (DFT) calculations combined with crystallographic analysis demonstrate that facet-dependent adsorption energy and interfacial mismatch govern the distinct nucleation and growth behaviors. Particularly, the self-enhanced adsorption capability for water vapor during the oxidation, along with the presence of interstitial hydrogen in the oxide, facilitates accelerated overall oxidation in water vapor. This work bridges the pressure gap in study of metal oxidation dynamics in the presence of water vapor and offers mechanistic insights into oxidation processes under practical environmental conditions.}, archive = {J_JACS}, author = {Ruiyang You and Meiliang Ma and Zihan Wang and Xiaoyun Guo and Songda Li and Yang Ou and Wentao Yuan and Zhong-Kang Han and Ying Jiang and Yong Wang}, doi = {10.1021/jacs.5c07765}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28035--28043}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling water-vapor-promoted oxidation of palladium nanoparticles via atomic-scale transmission electron microscopy at atmospheric pressure}, volume = {147}, year = {2025}, }
• (2025). O-induced diatomic Fe–Mo mimetic enzyme for efficient electrocatalytic nitrogen reduction at universal pH. JACS, 147(31), 28024--28034. (www)

  @article{ , abstract = {Electrochemical nitrogen reduction reaction (ENRR) provides a sustainable route for the NH 3 synthesis. However, designing catalysts that facilitate efficient electron/proton transfer and the hydrogenation of multiple intermediates remains a challenge. In this study, inspired by the natural nitrogenase proteins, a biomimetic Fe–Mo diatomic catalyst (FeMo-CDW(CT-3h)) was designed for efficient ENRR. The microenvironment of Fe–Mo diatomic sites was precisely tuned using the O-induced atomic confinement effect, where O atoms modulate the activity of the sites. FeMo-CDW(CT-3h) with four O atoms achieves a record-breaking NH 3 yield at universal pH as well as high stability (250 h and 10 cycles) due to its optimal electron transfer efficiency. In particular, the NH 3 yield of 336.03 μg h –1 cm –2 in 0.1 M HCl was over three times higher than the previously reported maximum. Theoretical calculations reveal that the hybridization of Fe–Mo d orbitals with N 2 * antibonding orbitals enhances electron transfer, extends and weakens the N≡N bond, and accelerates proton transfer and hydrogenation, thereby increasing NH* antibonding orbitals enhances electron transfer, extends and weakens the N≡N bond, and accelerates proton transfer and hydrogenation, thereby increasing NH 3 generation.}, archive = {J_JACS}, author = {Yuanyuan Yu and Qingtong Zhang and Simin Wei and Guangfu Qian and Qian He and Wenyan Yin and Douyong Min and Shuangfei Wang and Yuliang Zhao}, doi = {10.1021/jacs.5c07762}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28024--28034}, shortjournal = {J. Am. Chem. Soc.}, title = {O-induced diatomic Fe–Mo mimetic enzyme for efficient electrocatalytic nitrogen reduction at universal pH}, volume = {147}, year = {2025}, }
• (2025). Janus palladium membrane electrode enables competent hydrodehalogenation via hydride transfer. JACS, 147(31), 28015--28023. (www)

  @article{ , abstract = {Efficient and selective electrochemical hydrodehalogenation of organic halides remains a significant challenge in electrocatalysis due to competing side reactions, low Faradaic efficiency, and stringent solubility requirements. Herein, we introduce a design of Janus palladium membrane electrode (J-Pd m ) that enables the direct generation and transfer of hydride species from water reduction in a dual-cell configuration. This design facilitates heterogeneous hydride transfer in an aprotic environment, achieving rapid reaction rate and superior Faradaic efficiency compared to conventional electrochemical hydrogenation systems and traditional electrochemical palladium membrane reactors. Notably, J-Pd m efficiently catalyzes the hydrodehalogenation of unactivated alkyl halides, a challenging transformation that suffers from poor efficiency in traditional electrocatalytic systems. Furthermore, J-Pd m enables the site-selective deuteration of pharmaceutical molecules, as demonstrated in the gram-scale synthesis of deuterated ibuprofen using D 2 O as the deuterium source. This work demonstrates J-Pd m as a powerful and versatile platform for electrocatalytic hydrogenation, hydrogenolysis, and isotopic labeling, offering a competent alternative to conventional electrochemical strategies and exhibiting broad industrial and pharmaceutical applications.}, archive = {J_JACS}, author = {Xiaosong Hu and Minling Zhong and Feihu Wang and Yujie Sun}, doi = {10.1021/jacs.5c07689}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28015--28023}, shortjournal = {J. Am. Chem. Soc.}, title = {Janus palladium membrane electrode enables competent hydrodehalogenation via hydride transfer}, volume = {147}, year = {2025}, }
• (2025). Breaking bonds with short-wave infrared light: BODIPY photocages for two-photon activation in the 900–1500 nm NIR-II window. JACS, 147(31), 28002--28014. (www)

  @article{ , abstract = {Photocages enable light-triggered cargo release in biological systems, but their excitation is often restricted to UV/visible wavelengths, where tissue penetration is limited. Two-photon excitation (2PE) offers a solution by allowing near-infrared (NIR) or short-wave infrared (SWIR) activation within biological windows of maximal tissue transparency. While photocaging in the first biological window (650–950 nm) has been demonstrated, applications in the second biological window (1000–1350 nm) remain unexplored. Here, we investigate the two-photon absorption (2PA) properties of 11 BODIPY photocages featuring single-photon absorption spanning 450–750 nm, focusing on 3- and 5-position substitutions to identify key motifs that enhance 2PA in the 900–1500 nm range. We find that strong charge transfer character and increased vibrational freedom can relax symmetry-related selection rules, significantly enhancing 2PA. Cross sections (δ) exceeded 4000 GM at 900 nm for a bis(styryl)-BODIPY with carbazole units and reached 1110 GM at 1240 nm for its monostyryl analog. Two additional B-methylated molecules with improved uncaging quantum yields were synthesized, yielding uncaging action cross sections (δΦ u ) up to 5.8 GM at 900 nm and around 1 GM at 1300–1400 nm. Notably, these modifications preserve the core photophysical properties of BODIPY, making them ideal for molecular engineering. These findings highlight key design principles for efficient 2P-activatable photoactuators operating in the NIR-II biological window and show that heterolytic C–O bond cleavage can be triggered by two SWIR photons carrying as little as 20 kcal/mol each.}, archive = {J_JACS}, author = {Yagmur Aydogan-Sun and Alexandra Egyed and Arthur H. Winter and Josef Wachtveitl}, doi = {10.1021/jacs.5c07710}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {28002--28014}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking bonds with short-wave infrared light: BODIPY photocages for two-photon activation in the 900–1500 nm NIR-II window}, volume = {147}, year = {2025}, }
• (2025). Highly conjugated porphyrin arrays enable optical resolution of ferromagnetic and antiferromagnetic aligned states of the triplet exciton and an incorporated stable radical. JACS, 147(31), 27992--28001. (www)

  @article{ , abstract = {Well-defined photogenerated molecular spin systems have potential utility in spintronics and quantum information science (QIS). Because molecular magnetic, optical, and electronic properties can be controlled by design, diverse spin systems can be prepared at modest temperatures. Photogenerated molecular spin systems often involve states prepared from the interaction of excitons and charges. Resolving the nature of electron spin alignment in photogenerated spin states described by the coupling of a triplet exciton and a stable radical commonly relies on EPR spectroscopy. We describe ethyne-bridged (porphinato)metal ( PM n ) oligomers that incorporate a macrocycle-bound Cu(II) radical center. Upon photoexcitation of such PM n arrays, a singdoublet ( 2 S 1 ) state is formed; ultrafast internal conversion (IC) then produces a tripdoublet ( 2 T 1 ) state, which undergoes intersystem crossing (ISC) to produce a tripquartet ( 4 T 1 ) state, before relaxation to the ground state ( 2 S 0 ). These highly conjugated Cu(II) radical-containing PM n arrays enable direct observation of copper porphyrin 2 T 1 → 4 T 1 ISC dynamics from the biexponential decay of the near-infrared (NIR) 2,4 T 1 → 2,4 T n transient absorption manifold. Multireference n -electron valence perturbation theory (NEVPT2) computations illuminate how PM n electronic structure controls the relaxation dynamics of these long-lived (>10 ns) electronically excited multiplet states. These studies show that highly conjugated and polarizable porphyrin arrays incorporating stable spin centers provide rare π-delocalized systems where the ferromagnetic and antiferromagnetic alignment between a triplet exciton and a stable radical are both spectrally resolved and addressable using transient optical spectroscopy at wavelengths exceeding 1 μm, providing new opportunities to QIS.}, archive = {J_JACS}, author = {Jiaqi Zhu and Zachary X. W. Widel and Chih-Hung Ko and Peng Zhang and David N. Beratan and Michael J. Therien}, doi = {10.1021/jacs.5c07638}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27992--28001}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly conjugated porphyrin arrays enable optical resolution of ferromagnetic and antiferromagnetic aligned states of the triplet exciton and an incorporated stable radical}, volume = {147}, year = {2025}, }
• (2025). Johnson solid gold nanoclusters as heterogeneous visible-light photocatalysts for fukuyama indole synthesis. JACS, 147(31), 27981--27991. (www)

  @article{ , abstract = {Despite notable advancements in noble metal photocatalysis, improving catalyst efficiency and recyclability remains a key challenge that needs to be addressed to facilitate large-scale synthetic applications. Herein, we have successfully synthesized bisphosphine-protected gold nanoclusters with a distinctive Johnson solid kernel, which serve as efficient and recyclable heterogeneous photocatalysts for visible-light-driven three-component radical couplings in Fukuyama indole synthesis. In contrast to conventional gold complexes, the newly developed cluster-based catalysts can be easily photoexcited to their triplet states by visible light, enabling single-electron transfer with O -acyl oximes, a hitherto unexplored class of electrophiles in gold photocatalysis. Our latest discovery suggests that establishing photocatalytic systems based on atomically precise metal nanoclusters with unique structural and electronic properties represents a promising avenue for advancing chemical synthesis in a sustainable and practical manner.}, archive = {J_JACS}, author = {Li-Juan Liu and Xiaxi Lei and Jun Guo and Xiaoyong Mo and Yuhan Lao and Shengli Zhuang and Hong Zeng and Shun Yang and Yue Zhao and Wen Wu Xu and Jian He}, doi = {10.1021/jacs.5c07580}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27981--27991}, shortjournal = {J. Am. Chem. Soc.}, title = {Johnson solid gold nanoclusters as heterogeneous visible-light photocatalysts for fukuyama indole synthesis}, volume = {147}, year = {2025}, }
• (2025). A protein-centric mass spectrometry approach for species identification within harmful algal blooms. JACS, 147(31), 27974--27980. (www)

  @article{ , abstract = {Harmful algal blooms present severe environmental threats, impacting water quality, aquatic ecosystems, and human health. The frequency and intensity of these blooms are rising, largely driven by global warming and changing climatic conditions. There is an urgent need for innovative methods to monitor blue-green algae, also known as cyanobacteria, to enable the implementation of preventative measures. Here, we show that native mass spectrometry is an effective tool for detecting cyanobacteria directly from lake samples, both prior and during bloom formation. Our approach allows for the rapid characterization of cyanobacterial populations within lakes, offering valuable insights into the dynamics of cyanobacterial species associated with harmful algae blooms. Overall, we highlight the exceptional capability of native mass spectrometry in directly detecting and monitoring cyanobacterial blooms, which will support the development of more effective strategies to mitigate this growing environmental challenge.}, archive = {J_JACS}, author = {Jaspreet K. Sound and Hannah E. Wedgwood and Qonita Afinanisa and Tim W. Overton and Aneika C. Leney}, doi = {10.1021/jacs.5c07419}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27974--27980}, shortjournal = {J. Am. Chem. Soc.}, title = {A protein-centric mass spectrometry approach for species identification within harmful algal blooms}, volume = {147}, year = {2025}, }
• (2025). Tetracene functionalized si(111) achieves enhanced solar-to-chemical energy conversion via molecular acceptor states. JACS, 147(31), 27962--27973. (www)

  @article{ , abstract = {The properties of semiconductor|liquid interfaces play a critical role in determining the efficiency of solar-to-hydrogen (STH) conversion. Here, we investigate how molecular functionalization of Si(111) and Si(111)|TiO 2 surfaces impacts photoelectrochemical (PEC) hydrogen production efficiency. We find that functionalization of ∼3% of the atop sites of Si(111) with either 9-anthracene (Anth) or 5-tetracene (Tet), with the remaining sites passivated by methyl groups, provides substrates with high electronic quality and low surface oxide densities, as determined by X-ray photoelectron spectroscopy (XPS) measurements. Surface photovoltage (SPV) spectroscopy shows that surfaces modified with Anth or Tet exhibit an increased photovoltage, with Tet-functionalized surfaces yielding an additional 192 meV relative to methyl-terminated Si(111), indicating improved charge separation for Si-Tet. Further improvement in onset potential was achieved by replacing a nitrogen-containing TiO 2 atomic layer deposition (ALD) precursor (TDMAT) with a precursor lacking nitrogen (TTIP), which eliminates the parasitic defect band in the TiO 2 overlayer (p-Si(111)-Tet|TTIP-TiO 2 |Pt: V OC = +0.283 ± 0.041 V vs RHE). Density functional theory (DFT) analysis demonstrates that compared with Anth-modified Si(111), the Tet-modified surface exhibits more hybridized Si(111)-Tet states closer to the silicon band edges. Mercury contact current–voltage ( I – V , dark) measurements quantified the relative interfacial density of states of Si-Tet, Si-Anth and Si-Me surfaces─revealing that the interfacial state density was highest for Si-Tet. This suggests that such hybridized interfaces serve to capture better photoexcited charge, which enables facile electron transfer to molecular acceptors in solution. Overall, the data indicate that beneficial hybrid molecular LUMO surface states interacting with the Si conduction band edge results in improved hydrogen evolution (HER) performance for p-Si devices.}, archive = {J_JACS}, author = {Brittany R. Pollok and Jeremy R. M. Brinker and Sina G. Lewis and Sahar Daemi and Sean T. Roberts and Frank E. Osterloh and Joel D. Eaves and Michael J. Rose}, doi = {10.1021/jacs.5c06963}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27962--27973}, shortjournal = {J. Am. Chem. Soc.}, title = {Tetracene functionalized si(111) achieves enhanced solar-to-chemical energy conversion via molecular acceptor states}, volume = {147}, year = {2025}, }
• (2025). Mg-ion conduction in antiperovskite solid electrolytes revealed by 25Mg ultrahigh field NMR and first-principles calculations. JACS, 147(31), 27949--27961. (www)

  @article{ , abstract = {Magnesium-ion batteries hold the potential to outperform the energy density of lithium-ion batteries, given the divalent charge carried by each Mg 2+ cation, but remain in an early stage of development. Here, 25 Mg solid-state nuclear magnetic resonance (ssNMR) is used to gain insight into the local structure and Mg-ion dynamics of candidate Mg-ion solid electrolytes, the antiperovskites Mg 3 SbN and Mg 3 AsN. Using the highest available magnetic field (35.2 T) for high-resolution solid-state NMR, the largest 25 Mg quadrupole coupling constants ( C Q ) yet measured of up to 22 MHz are reported and corroborated by first-principles calculations. Predicted C Q values are shown to correlate with the antiperovskite’s tolerance factor; thus, 25 Mg NMR linewidths can report on lattice distortions and phase stability of these antiperovskites. Variable-temperature 25 Mg NMR spectra demonstrate changes at elevated temperatures, ascribed to Mg-ion motional effects. 25 Mg T 1 relaxometry measurements at ultrahigh field reveal a lower activation energy for the more distorted Mg 3 AsN phase, matching computational predictions of a lower energy barrier for Mg 2+ ion migration and suggesting that additional scrutiny of antiperovskites as Mg-ion conductors is warranted. Given the inherent challenges of 25 Mg NMR, this work demonstrates the benefits of combining ultrahigh field NMR spectroscopy, advanced pulse sequences, modern signal processing, and first-principles calculations to facilitate NMR of quadrupolar nuclei as a tool to probe the local structure and ion dynamics in beyond-Li battery materials.}, archive = {J_JACS}, author = {David M. Halat and Haoyu Liu and Kwangnam Kim and Grant C. B. Alexander and Xiaoling Wang and Amrit Venkatesh and Adam R. Altenhof and Harris E. Mason and Saul H. Lapidus and Jeong Seop Yoon and Ivan Hung and Zhehong Gan and Jordi Cabana and Donald J. Siegel and Jeffrey A. Reimer and Baris Key}, doi = {10.1021/jacs.5c07442}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27949--27961}, shortjournal = {J. Am. Chem. Soc.}, title = {Mg-ion conduction in antiperovskite solid electrolytes revealed by 25Mg ultrahigh field NMR and first-principles calculations}, volume = {147}, year = {2025}, }
• (2025). Flexible double bonds-enhanced photodynamic therapy toward antibacterial resistance. JACS, 147(31), 27932--27948. (www)

  @article{ , abstract = {The relationship between the molecular structure and types of reactive oxygen species (ROS) generated from photosensitizers (PSs) must be understood for advancing photodynamic therapy (PDT). In this study, we synthesized PS-S + , PS-D + , and PS-T + consisting of C–C, C═C, and C≡C bond linkers, respectively, between electron donor and acceptor moieties. Unlike PS-S + and PS-T + , PS-D + containing a flexible C═C bond linker can absorb energy under white light irradiation, which enhances the swing of connected acceptor groups and leads to the formation of a noncoplanar structure. ROS generation experiments and density functional theory (DFT) calculations demonstrated that the formed noncoplanar structure of PS-D + can narrow the energy gap between the singlet and triplet states (Δ E S-T ), which facilitated intersystem crossing, thereby enhancing ROS production, and shifted the generation mechanism from Type II to Type I. PS-S + , PS-D + , and PS-T + antibacterial fibers were synthesized using the wet spinning method. Our developed fibers exhibited long-term, good antibacterial properties in both in vitro ( Escherichia coli and Staphylococcus aureus ) and in vivo (infected mice) wound dressing experiments, showcasing potential as sustainable and biosafe wound dressings to accelerate healing. We herein highlight the (1) guidance for the design strategy of PS and (2) the innovative fibers for medical applications.}, archive = {J_JACS}, author = {Fei Guo and Jiyoung Yoo and Qingqing Zhang and Yu-Ting Zhao and Seokjin Hong and Zi-Ming Zhou and Zhao-Ying Zhu and Hoyeon Jang and Chang-Hai Yi and Zhen Wang and Jong Seung Kim}, doi = {10.1021/jacs.5c07262}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27932--27948}, shortjournal = {J. Am. Chem. Soc.}, title = {Flexible double bonds-enhanced photodynamic therapy toward antibacterial resistance}, volume = {147}, year = {2025}, }
• (2025). Pressure-modulated quantum melting of spin order in the kondo lattice Mn1/4TaS2. JACS, 147(31), 27922--27931. (www)

  @article{ , abstract = {Controlling and understanding the quantum phase transitions (QPTs) of the magnetically ordered phases of strongly correlated systems, such as heavy-Fermion materials, cuprate superconductors, is essential for uncovering the new physical phenomena in condensed matter physics. This study reports the observation of pressure-modulated magnetic QPTs (MQPTs) and heavy-Fermion-like behavior in a manually constructed Kondo lattice─Mn 1/4 TaS 2 . At low temperatures, pressure application induces quantum melting of magnetic order within the helical magnetic configuration of Mn 1/4 TaS 2 . As pressure increases, the system transitions from the heavy-Fermion-like state to a Kondo singlet state, accompanied by a reduction in effective mass. This transition is attributed to the enhanced shielding of local magnetic moments by conduction electrons under pressure, demonstrating the competition between Kondo screening and Ruderman–Kittel–Kasuya–Yosida interactions. This study establishes a framework for creating Kondo lattice phase diagrams featuring in situ complex MQPTs under applied pressure using intercalated TMDs.}, archive = {J_JACS}, author = {Jingyan Song and Xiaoran Zhang and Chutong Zhang and Mengge Zhang and Kewen Zhang and Yitian Guo and Dong Qiu and Jiashuo Liang and Yuqing Liu and Jianwen Huang and Chao Yang and Yong Wang and Chenhui Zhang and Dongxing Zheng and Yan Li and Aitian Chen and Liying Wang and Chao Jin and Xiaobing Liu and Xixiang Zhang and Peng Li}, doi = {10.1021/jacs.5c07281}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27922--27931}, shortjournal = {J. Am. Chem. Soc.}, title = {Pressure-modulated quantum melting of spin order in the kondo lattice Mn1/4TaS2}, volume = {147}, year = {2025}, }
• (2025). Designing pb-free high-entropy relaxor ferroelectrics with machine learning assistance for high energy storage. JACS, 147(31), 27912--27921. (www)

  @article{ , abstract = {High-entropy tactics present exceptional promise in advancing the dielectric energy storage of relaxor ferroelectrics, thereby benefiting various pulsed-power electronic systems. However, their vast composition space poses challenges in the rational design of a high-performance system. Herein, we present a machine learning-supplemented strategy to design high-entropy relaxors, demonstrating an ultrahigh energy-storage density of 17.2 J cm –3 and high efficiency of 87% at a high breakdown strength of 79 kV mm –1 . By integrating six A -site and one B -site critical intrinsic features of constituent ions, deduced from a constructed random forest regression model, the (Bi 2/5 Na 1/5 K 1/5 Ba 1/5 )(Ti,Hf)O 3 high-entropy system is identified. Atomic-level local structural analysis reveals that incorporating these certified cations, with diverse local polar and lattice construction characteristics, results in a highly fluctuating local polarization structure. This favorable structure is characterized by pronounced orientation disorder and a broadly distributed length of unit-cell polarization vectors within the expanded lattice framework. Macroscopically, the optimized relaxor displays high dielectric susceptibility and large resistance. Moreover, a large discharge energy density of 5.8 J cm –3 and power energy density of 447 MW cm –3 , along with outstanding operational stability, are achieved. This study presents a data-driven model to explore complex intrinsic features and facilitate the design of high-performance relaxors.}, archive = {J_JACS}, author = {Banghua Zhu and Xingcheng Wang and Ji Zhang and Huajie Luo and Laijun Liu and Joerg C. Neuefeind and Hui Liu and Jun Chen}, doi = {10.1021/jacs.5c07213}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27912--27921}, shortjournal = {J. Am. Chem. Soc.}, title = {Designing pb-free high-entropy relaxor ferroelectrics with machine learning assistance for high energy storage}, volume = {147}, year = {2025}, }
• (2025). Strain-release-driven synthesis of pentafluorosulfanylated four-membered rings under energy transfer photocatalysis. JACS, 147(31), 27905--27911. (www)

  @article{ , abstract = {Methods to prepare SF 5 -containing molecules are of significant interest, as the pentafluorosulfanyl (SF 5 ) group imparts unique chemical and physical properties─such as high electronegativity, and thermal stability─that are valuable in pharmaceuticals, agrochemicals, and materials science. The use of our shelf-stable reagent, imine-SF 5 , enables selective access to four-membered ring SF 5 -containing molecules under mild reaction conditions via a strain-release approach facilitated by energy-transfer catalysis. Mechanistic investigations provided insight into the reaction pathway. This approach advances pentafluorosulfanylation methodology, paving the way for future development.}, archive = {J_JACS}, author = {Yi Yang and Lulu Han and Louis Canavero and Liza Brettnacher and Lhoussain Khrouz and Cyrille Monnereau and Maurice Médebielle and Anis Tlili}, doi = {10.1021/jacs.5c07138}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27905--27911}, shortjournal = {J. Am. Chem. Soc.}, title = {Strain-release-driven synthesis of pentafluorosulfanylated four-membered rings under energy transfer photocatalysis}, volume = {147}, year = {2025}, }
• (2025). Direct N–SF5 and N–SF4CF3 bond formation through strain-release functionalization of 3-substituted [1.1.0]Azabicyclobutanes. JACS, 147(31), 27892--27904. (www)

  @article{ , abstract = {In comparison to modern methods for carbon–SF 5 bond formation, methods for direct heteroatom–SF 5 bond formation are exceptionally scarce, rendering motifs such as “ N –SF 5 ” virtually unexplored in the context of organic and medicinal chemistry. Herein, we demonstrate that direct N –SF 5 bond formation can be accomplished through strain-release pentafluorosulfanylation of 3-aryl [1.1.0]azabicyclobutanes (ABBs), using an easy-to-access solution of SF 5 Cl. To our surprise, the resultant N –SF 5 azetidines proved to be remarkably chemically stable and amenable to peripheral synthetic modifications (e.g., amination, cross-coupling, oxidation, dehalogenation, S N 1, and S N Ar reactions). The methodology also extends to direct N –SF 4 CF 3 bond formation using trans -CF 3 SF 4 Cl, enabling comparative studies throughout this work. From a mechanistic standpoint, DFT calculations, Hammett analyses, and radical trapping experiments support our proposed radical chain propagation mechanism. From a fundamental standpoint, considering N –SF 5 and N –SF 4 CF 3 azetidines are heretofore unknown molecular motifs, this work analyzes their dynamic, spectroscopic, and crystallographic features, as well as computed properties (e.g., BDE and p K b values), to provide foundational knowledge and inform downstream applications. While the carbon-bound SF 5 group has been employed as a bioisostere for a CF 3 group, we posited the N –SF 5 motif could be a potential replacement for a small sulfonamide. Accordingly, we synthesized an N –SF 5 derivative of a spleen tyrosine kinase inhibitor reported in the patent literature for comparative ADME studies; results from in vitro profiling indicate that an N –SF 5 azetidine could indeed be an alternative for an N –SO 2 Me azetidine, in cases where enhanced lipophilicity is desirable.}, archive = {J_JACS}, author = {Yannick Kraemer and Soojun Park and Wang-Yeuk Kong and Yongxin Chen and Anthony J. Witt and Jón Atiba Buldt and Abbey N. Ragan and Lauren M. Holder and Dean J. Tantillo and Cody Ross Pitts}, doi = {10.1021/jacs.5c07137}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27892--27904}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct N–SF5 and N–SF4CF3 bond formation through strain-release functionalization of 3-substituted [1.1.0]Azabicyclobutanes}, volume = {147}, year = {2025}, }
• (2025). Modulating the binding kinetics of bruton’s tyrosine kinase inhibitors through transition-state effects. JACS, 147(31), 27876--27891. (www)

  @article{ , abstract = {Optimization exercises strive toward increasing the efficacy and selectivity of small molecules toward the target of interest while simultaneously phasing out design elements that lead to off-target interactions. Given the nonequilibrium nature of biological systems, greater reliance should be placed on engineering kinetic selectivity in addition to equilibrium thermodynamic selectivity; however, the rational design of kinetic selectivity is a challenging endeavor. This study presents a systematic knowledge-based approach to the design of inhibitors that vary in their binding kinetics for Bruton’s tyrosine kinase (BTK), a target for treating B-cell malignancies and autoimmune diseases. A detailed kinetic assessment was performed on existing BTK inhibitors, which, together with structural studies, provided critical insights into BTK-inhibitor interactions that control the kinetics of enzyme inhibition. Subsequently, a series of pyrazolopyrimidines was designed with the objective of modifying interactions between the inhibitor and the regulatory (R) spine in the kinase back pocket, which were hypothesized to modulate the stability of the transition state on the binding reaction coordinate. This resulted in the development of BTK inhibitors with extended residence time in which the variation in k on and k off was uncoupled from equilibrium thermodynamic affinity.}, archive = {J_JACS}, author = {Eduardo Bravo, Jr and Yong Li and David Yin-Wei Lin and Bharath Srinivasan and Marco Barone and Stan Xiaogang Li and Francesca DelloRusso and Anza Suneer Rahiyanath and Ana Corrionero and Patricia Alfonso and Niall Prendiville and Dima Kozakov and Amy H. Andreotti and Peter J. Tonge}, doi = {10.1021/jacs.5c07063}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27876--27891}, shortjournal = {J. Am. Chem. Soc.}, title = {Modulating the binding kinetics of bruton’s tyrosine kinase inhibitors through transition-state effects}, volume = {147}, year = {2025}, }
• (2025). A covalent self-reporting peptide degrader enables real-time monitoring of targeted protein degradation in vivo. JACS, 147(31), 27862--27875. (www)

  @article{ , abstract = {Peptides have demonstrated great potential in drug development. However, their broader application in modalities such as proteolysis-targeting chimeras (PROTACs) remains limited by the lack of real-time efficacy feedback and poor pharmacokinetic stability. Herein, we develop a covalent self-reporting peptide degrader (Co-SPeD) by integrating a fluorine-substituted aryl fluorosulfate warhead and a rotor fluorophore derived from stilbene derivatives, which allows for covalent binding to target proteins via sulfur(VI) fluoride exchange chemistry and emitting activatable fluorescence. Co-SPeD is found to covalently bind to the K51 residue of the MDM2 protein, enabling real-time monitoring of targeted MDM2 degradation. By swapping the targeting peptide and screening rotor fluorophores, the Co-SPeD platform is successfully extended to other oncogenic proteins, including BCL-xL, GRP78, and KRAS (G12D). Additionally, Co-SPeD demonstrates significant antitumor efficacy in preclinical tumor models. More importantly, real-time in vivo monitoring of MDM2 degradation using Co-SPeD plays a crucial role in guiding cisplatin combination administration, leading to a 50% increase in tumor growth inhibition compared to nonguided treatment groups. This approach provides a targeted endogenous protein degradation strategy with real-time monitoring, offering a powerful and generalizable platform for next-generation PROTAC design, the advancement of peptide-based therapeutics, and the rational optimization of cancer therapy.}, archive = {J_JACS}, author = {Wei Zhang and Lizhen Yuan and Rui Liu and Yanbo Jing and Shijun Lin and Hao Fang and Yuxuan Li and Xiaohui Zhang and Jun Dai and Tao Liu and Fan Xia and Xiaoding Lou}, doi = {10.1021/jacs.5c07041}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27862--27875}, shortjournal = {J. Am. Chem. Soc.}, title = {A covalent self-reporting peptide degrader enables real-time monitoring of targeted protein degradation in vivo}, volume = {147}, year = {2025}, }
• (2025). Basicity–Controlled C–H bond activation by a structurally characterized Ni(III)–Hydroxo complex. JACS, 147(31), 27855--27861. (www)

  @article{ , abstract = {The selective oxidation of strong C–H bonds remains a central challenge in synthetic chemistry, in part due to the elusive nature of active oxidants and their underlying mechanisms. Herein, we report the isolation and complete characterization of a room–temperature–stable mononuclear Ni(III)–hydroxo complex, [Na(15c5)][Ni(PS3″)(OH)] ([Na(15c5)][ 2 ]), supported by a tris (benzenethiolato)phosphine ligand derivative. The X-ray crystallographic structure of 2 reveals a trigonal bipyramidal Ni(III) center, in which the coordinated hydroxo ligand is stabilized by secondary coordination sphere interactions. Complex 2 displays hydrogen atom transfer (HAT) reactivity toward strong C–H bonds, including that in cyclohexane (BDE = 99.5 kcal mol –1 ). Kinetic studies with various C–H substrates reveal a strong linear correlation between log( k 2 ) and substrate p K a , but a poor correlation with C–H bond dissociation energies, indicating an asynchronous PCET pathway with a transition state predominantly governed by proton transfer (PT). The O–H bond dissociation free energy of a resulting Ni(II)–aqua species was estimated to be 96.6–100.3 kcal mol –1 based on thermodynamic data. A semiempirical free energy analysis following the approach of Barman et al. ( Proc. Natl. Acad. Sci. U.S.A. 2021 , 118, e2108648118) gives a best-fit x value of 0.18 ( R 2 = 0.99), where x = 1 indicates synchronous PCET and lower values reflect greater PT character in the transition state. These findings underscore the critical role of basicity in modulating PCET reactivity and establish complex 2 as a rare, well–defined Ni(III)–OH oxidant capable of strong C–H bond activation at low redox potential.}, archive = {J_JACS}, author = {Hung-Ruei Pan and John Wu and Chun-Ming Tsai and Pei-Juan Liao and Hua-Fen Hsu}, doi = {10.1021/jacs.5c06941}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27855--27861}, shortjournal = {J. Am. Chem. Soc.}, title = {Basicity–Controlled C–H bond activation by a structurally characterized Ni(III)–Hydroxo complex}, volume = {147}, year = {2025}, }
• (2025). Constructing dual-functional organic cuboctahedron cages with two different triangular building units for efficient artificial photosynthesis of hydrogen peroxide from water and oxygen. JACS, 147(31), 27847--27854. (www)

  @article{ , abstract = {Artificial photosynthesis of hydrogen peroxide (H 2 O 2 ) from water and oxygen is a green method, which requires catalysts that can complete oxygen reduction and water oxidation reactions simultaneously. Herein, two cases of organic cage single crystals with an exquisite Archimedean polyhedron configuration (named CityU-40 and CityU-41 ) through the assembly of two different triangle motifs via dative boron ← nitrogen (B ← N) bonds are reported. Both cages possess big cavities (1.5 nm) and large open windows (1 nm * 1.2 nm). Due to the integration of two photosensitive functional motifs into one cage with a short distance, both CityU-40 and CityU-41 have been demonstrated as efficient catalysts for the artificial photosynthesis of H 2 O 2 from pure water and oxygen/air under ambient sunlight.}, archive = {J_JACS}, author = {Lei Zhang and Zihao Chen and Xiao-Xin Li and Xiang Wang and Qianfeng Gu and Zongmin Zheng and Naoki Aratani and Chun-Sing Lee and Ya-Qian Lan and Qichun Zhang}, doi = {10.1021/jacs.5c06974}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27847--27854}, shortjournal = {J. Am. Chem. Soc.}, title = {Constructing dual-functional organic cuboctahedron cages with two different triangular building units for efficient artificial photosynthesis of hydrogen peroxide from water and oxygen}, volume = {147}, year = {2025}, }
• (2025). Thiazole-bimodulated covalent organic frameworks for synergistic water harvesting and photosplitting. JACS, 147(31), 27835--27846. (www)

  @article{ , abstract = {Vapor-phase photocatalytic hydrogen evolution offers a method to alleviate pure water scarcity, minimize mass transfer resistance, and avoid photocatalyst poisoning. Due to the limited research on water sorption kinetics and photogenerated charge carrier dynamics, the interaction mechanism between photocatalysts and water molecules remains unclear. Thus, we herein design covalent organic frameworks (COFs) using different thiazole configurations to enhance the efficiency of water harvesting and photosplitting. Crystallographic studies indicate that increased thiazole fusion in COFs can form one-dimensional open channels via tight π–π stacking to facilitate mass transfer. Electrostatic potential and adsorption energy analyses reveal the semihydrophobic trait of bis-thiazole, which modulates the vapor adsorption capacity of COFs with the hydrophilic ketone structure. Furthermore, transient absorption spectroscopy indicates that the electron-donating bis-thiazole, in conjunction with the keto structure, facilitates the separation of photogenerated charge carriers. Under the modulation of thiazole, water adsorption on COFs narrows their bandgap and optimizes electron transport, thus achieving a vapor-phase hydrogen evolution rate of 866 μmol h –1 g –1 . This study sheds light on the design of vapor-phase photocatalysts and the synergistic effect between water harvesting and photosplitting, marking an advancement toward sustainable energy solutions.}, archive = {J_JACS}, author = {Hanlin Hou and Keming Wu and Xianjie Chen and Xinfeng Liu and Yanli Zhao}, doi = {10.1021/jacs.5c06823}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27835--27846}, shortjournal = {J. Am. Chem. Soc.}, title = {Thiazole-bimodulated covalent organic frameworks for synergistic water harvesting and photosplitting}, volume = {147}, year = {2025}, }
• (2025). Autonomous activation of a gated chemiluminescent photosensitizer enables targeted photodynamic therapy in tumor cells. JACS, 147(31), 27822--27834. (www)

  @article{ , abstract = {Chemiluminescence-based photodynamic therapy (CLPDT) offers a promising solution to the light penetration limits of traditional PDT. However, it lacks spatiotemporal control. Intracellularly activated, self-luminescent PDT agents via a molecular logic gate switch may address this key limitation. We report the synthesis of the self-activating, chemiluminescent photosensitizer (PS) that enables tumor microenvironment-controlled PDT applications. This system integrates a dioxetane-based (Diox) chemiluminescent scaffold with a ruthenium-based (Ru) PS through an oxidation and pH-sensitive linker to enable an AND-gated activation mechanism. The Diox@Ru conjugate is selectively activated by elevated intracellular reactive oxygen species (ROS), characteristic of aggressive cancer phenotypes arising from altered cell metabolism. Upon exposure to ROS (in this case, hydrogen peroxide), the boronic acid ester protecting group of the dioxetane is cleaved, initiating localized chemiluminescence that directly excites the Ru(II) PS to generate cytotoxic singlet oxygen ( 1 O 2 ). Importantly, Diox@Ru remains inert under physiological conditions (neutral pH, low ROS) as well as in the acidic, ROS-rich extracellular tumor milieu (slightly acidic, high ROS). Its activation is confined to the intracellular space of glycolytic cancer cells with mildly alkaline, ROS-rich cytoplasm; and proceeds autonomously, without the need for external light irradiation. In both two-dimensional (2D) monolayer cultures and three-dimensional (3D) tumor spheroid models, Diox@Ru exhibits robust luminescence and efficient 1 O 2 production, resulting in potent cytotoxic effects. These findings present a versatile platform for autonomous activation of self-luminescent PDT agents and highlight the promise of logic-gated chemiluminescence for spatially controlled therapy in complex biological settings.}, archive = {J_JACS}, author = {Wenwu Peng and Tianjiao Zhou and Lifan Hu and Vivien Vankann and Toszka Bohn and Tobias Bopp and Seah Ling Kuan and Tanja Weil}, doi = {10.1021/jacs.5c06761}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27822--27834}, shortjournal = {J. Am. Chem. Soc.}, title = {Autonomous activation of a gated chemiluminescent photosensitizer enables targeted photodynamic therapy in tumor cells}, volume = {147}, year = {2025}, }
• (2025). Self-immolative cationic Iridium(III) complex-encapsulated nanoprodrug for enhanced chemo-photodynamic synergistic therapy of melanomas. JACS, 147(31), 27812--27821. (www)

  @article{ , abstract = {To mitigate off-target drug toxicity, hypoxia-activated prodrugs have been designed for precise tumor treatment. However, their therapeutic efficiency is often constrained by limited drug release and the development of anticancer drug resistance. In this study, we combined hypoxia-activated chemotherapy with photodynamic therapy (PDT) to develop a new hypoxia-activated cationic iridium(III) complex prodrug, Ir-azo-Cl , for enhancing drug release with robust synergistic chemo-photodynamic therapy of tumors. Ir-azo-Cl can be selectively activated by tumor hypoxia to release a cationic iridium(III) complex photosensitizer and chemotherapeutic drug. Two-photon PDT-induced self-immolation of Ir-azo-Cl further accelerates drug release, amplifying the therapeutic effect. To enhance tumor targeting and accumulation, Ir-azo-Cl was encapsulated into folate-functionalized phospholipids, resulting in the formation of a nanoprodrug ( DPF@Ir-azo-Cl ). DPF@Ir-azo-Cl exhibited strong tumor-accumulation capability and high therapeutic efficiency in melanoma-bearing mice. Overall, the present study presents a novel strategy for developing hypoxia-activated prodrugs to enhance drug release and improve synergistic chemo-photodynamic cancer therapy.}, archive = {J_JACS}, author = {Chaolong Liu and Jianqin Yan and Miaomiao Wu and Wenyu Wang and Lu Yuan and Dihua Tian and Yong Sun and Run Zhang}, doi = {10.1021/jacs.5c06657}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27812--27821}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-immolative cationic Iridium(III) complex-encapsulated nanoprodrug for enhanced chemo-photodynamic synergistic therapy of melanomas}, volume = {147}, year = {2025}, }
• (2025). Cosolvent electrolyte design for high-voltage aqueous Zinc–Sulfur batteries. JACS, 147(31), 27802--27811. (www)

  @article{ , abstract = {Aqueous zinc–sulfur batteries (AZSBs) offer cost and safety advantages but face challenges related to severe cell polarization. Herein, we introduce a cosolvent, N , N -diethylformamide (DEF), in the ZnSO 4 electrolyte to facilitate the sulfur cathode conversion reaction. Compared to Zn(H 2 O) 6 2+ , the reconstructed solvated [Zn(H 2 O) 5 DEF] 2+ in the cosolvent electrolyte exhibits a narrower HOMO–LUMO gap (0.74 eV vs 1.31 eV), leading to faster charge transfer kinetics at the electrolyte–electrode interface. Due to the strong interaction between DEF and sulfur electrode, the electrons donated by DEF occupy the antibonding orbitals of sulfur, increasing the electron density and electrostatic repulsion between sulfur atoms, thereby weakening the S–S bond interaction. This electron injection effect also reduces the band gap and enhances the intrinsic electrical conductivity of sulfur. As a result, this cosolvent electrolyte design for AZSBs achieves an elevated discharge plateau of 0.8 V vs Zn 2+ /Zn and reduced cell polarization of 0.32 V, outperforming most reported AZSBs. Additionally, we present design principles for cosolvent electrolytes in AZSBs, with machine learning results suggesting that the donor number and HOMO energy of the cosolvents are critical descriptors for predicting the discharge voltage of AZSBs. This work offers new insights into the development of high-performance AZSBs.}, archive = {J_JACS}, author = {Peng Hei and Ya Sai and Lin Yu and Yulai Lin and Bo Li and Guangxu Hu and Wanlong Wu and Jing Wang and Xiaoqi Sun and Xiao-Xia Liu and Yu Song}, doi = {10.1021/jacs.5c06710}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27802--27811}, shortjournal = {J. Am. Chem. Soc.}, title = {Cosolvent electrolyte design for high-voltage aqueous Zinc–Sulfur batteries}, volume = {147}, year = {2025}, }
• (2025). Enantioconvergent hydrobenzylation of racemic allylic alcohols with aryl hydrazones via bifunctional ruthenium catalysis. JACS, 147(31), 27790--27801. (www)

  @article{ , abstract = {The use of hydrazones as carbanion equivalents for carbon–carbon bond formation reactions has emerged as a versatile tool for organic synthesis. However, the enantioselective formation of carbon–carbon bonds with hydrazones has been underdeveloped. We have developed a Ru-catalyzed enantioconvergent hydrobenzylation of racemic allylic alcohols using aryl hydrazones as latent alkyl nucleophiles. The reaction produces enantioenriched products with two remote chiral centers, achieving high diastereoselectivities (up to 20:1 dr) and excellent enantioselectivities (99% ee in most cases). Notably, the alkyl source originates from the electrophilic sp 2 carbons of hydrazones, which are readily prepared from various aldehydes and depart from the most often employed alkyl nucleophiles derived from organometallic sp 3 carbons, and the reaction releases harmless N 2 as the sole byproduct. Mechanistic investigations suggest a sequential dehydrogenation/conjugate addition/reduction pathway with a single Ru complex catalyzing both the borrowing hydrogen and hydrazone conjugate addition cycles while simultaneously controlling the stereoselectivities of both chiral centers. DFT studies reveal that the Ru complex acts as a metal–ligand bifunctional catalyst, activating the hydrazones, reversing the C═N bond polarity, and facilitating the conjugate addition. The key transition state of the bond formation step features the attack of the activated hydrazone on an α,β-unsaturated ketone in an outer-sphere manner, offering a new catalytic mode for hydrazone chemistry.}, archive = {J_JACS}, author = {Jian Zhang and Ka Key Cheung and Mingyang Song and Weijun Tang and Huaming Sun and Zhenyang Lin and Jianliang Xiao and Chao Wang}, doi = {10.1021/jacs.5c06622}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27790--27801}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioconvergent hydrobenzylation of racemic allylic alcohols with aryl hydrazones via bifunctional ruthenium catalysis}, volume = {147}, year = {2025}, }
• (2025). Distinctive kinetic signatures of surface segregation processes in bimetallic nanoparticle catalysis. JACS, 147(31), 27777--27789. (www)

  @article{ , abstract = {Surface segregation in bimetallic catalysts, driven by reaction conditions, can alter active site distributions and profoundly impact catalytic performance, yet its influence on reaction kinetics is not well understood. Using CO oxidation on bimetallic PtCu nanoparticles as a model system, we show that temperature-dependent, oxygen-induced surface segregation of Cu atoms leads to reversible changes in the concentration and coordination of the catalytically active Pt surface sites and a corresponding increase in apparent activation energy at higher temperatures. This behavior is opposite to that of pure metals, where activation energies typically decrease with the temperature. Our kinetic studies are supported by in situ infrared spectroscopy, density functional theory calculations, and microkinetic modeling. Similar kinetic trends observed in PtCo, which exhibits the surface segregation, but not in PtRu alloys, which do not change under reaction conditions, suggest that atypical variations in kinetic parameters can serve as easily accessible indicators of surface segregation. These results establish a direct link between dynamic surface restructuring and macroscopic kinetics in bimetallic systems.}, archive = {J_JACS}, author = {Rong Ye and Samiha Bhat and Jared R. Arkfeld and Bill Yan and Chenggong Jiang and Bryan R. Goldsmith and Nirala Singh and Eranda Nikolla and Suljo Linic}, doi = {10.1021/jacs.5c06619}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27777--27789}, shortjournal = {J. Am. Chem. Soc.}, title = {Distinctive kinetic signatures of surface segregation processes in bimetallic nanoparticle catalysis}, volume = {147}, year = {2025}, }
• (2025). Specific ion properties induce spontaneous H2O2 production at the Air–Water interface. JACS, 147(31), 27768--27776. (www)

  @article{ , abstract = {Recent studies have reported spontaneous production of OH radicals and H 2 O 2 at the air–water interface of water droplets. However, the mechanism(s) behind this chemistry remain elusive, with the presence of a strong electric field at the interface being considered one reason for this spontaneous chemistry. Here, we provide evidence that in salt-containing aqueous droplets, the amount of oxidant formation is strongly related to the identity and concentration of the ions present in the solution. Anions have a significantly stronger effect on H 2 O 2 formation compared to cations. The effect of the anions’ identity on H 2 O 2 formation follows the Hofmeister series, which describes changes in the solvation properties of a solution due to the presence of ions. We present a quantitative relationship between two Hofmeister parameters and peroxide concentration derived from our experimental results. This link between H 2 O 2 formation and the Hofmeister series suggests that anions disrupt the water structure at the interface, reducing the solvation of OH – anions and promoting their dissociation into OH radicals and free electrons, leading to an increase in H 2 O 2 formation. This study shows that spontaneous formation of H 2 O 2 is driven by the solvation properties at the interface and not necessarily (or exclusively) by the presence of a strong electric field.}, archive = {J_JACS}, author = {Yoan Carreira Mendes Da Silva and Maria Angelaki and D. James Donaldson and Christian George}, doi = {10.1021/jacs.5c06512}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27768--27776}, shortjournal = {J. Am. Chem. Soc.}, title = {Specific ion properties induce spontaneous H2O2 production at the Air–Water interface}, volume = {147}, year = {2025}, }
• (2025). Chiral metallic DM-EDT-TTF radical cation salts: Anion size-dependent structural and electronic transitions, charge ordering, and chirality-induced spin selectivity. JACS, 147(31), 27749--27767. (www)

  @article{ , abstract = {Both enantiomers ( S,S ) and ( R,R ) of the chiral mixed-valence radical cation salts (DM-EDT-TTF) 2 XO 4 (X = Cl or Re) have been prepared by electrocrystallization. Single-crystal high-quality synchrotron radiation data allowed for the very accurate determination of their 298 and 18 K structures. At room temperature, they crystallize in the enantiomorphic space groups P6 2 22 and P6 4 22 for the ( S,S ) and ( R,R ) enantiomers, respectively, while at 18 K, the structures have been solved in the P6 2 and P6 4 space groups, respectively. This symmetry reduction results in a quadrupled unit cell containing four independent donors disordered over two inequivalent positions. In the perrhenate salts, there is strong structural evidence of the occurrence of charge ordering at 18 K as suggested by the alternation of charge-rich and charge-poor donors within the stacks. The easier establishment of charge disproportionation is very likely related to the higher metal-to-insulator transition temperature for perrhenate compared to perchlorate, as observed in the electrical resistance measurements. Spin-polarized DFT band structure calculations support the magnetic ground state of the materials and the activated low-temperature conductivity as a consequence of gap opening. Single-crystal Raman spectroscopy measurements indicate a stronger charge ordering degree at 10 K for the perrhenate than for the perchlorate salts. For the first time in chiral TTF-based conductors, the chirality-induced spin selectivity (CISS) effect is demonstrated through magnetoresistance measurements at room temperature on thin crystals of (DM-EDT-TTF) 2 ClO 4 , with a value of up to 30% for CISS-induced magnetoresistance.}, archive = {J_JACS}, author = {Flavia Pop and Nabil Mroweh and Pascale Auban-Senzier and Geert L. J. A. Rikken and Daichi Hirobe and Hiroshi M. Yamamoto and Arkadiusz Frąckowiak and Iwona Olejniczak and Sébastien Pillet and El-Eulmi Bendeif and Pere Alemany and Enric Canadell and Narcis Avarvari}, doi = {10.1021/jacs.5c06549}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27749--27767}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral metallic DM-EDT-TTF radical cation salts: Anion size-dependent structural and electronic transitions, charge ordering, and chirality-induced spin selectivity}, volume = {147}, year = {2025}, }
• (2025). Sustainable imine production using alkanes as substrates via a plasma-microdroplet approach. JACS, 147(31), 27743--27748. (www)

  @article{ , abstract = {The direct functionalization of alkanes remains a formidable challenge in synthetic chemistry. Herein, we present an integrated plasma-microdroplet approach for the efficient conversion of alkanes into imines under mild conditions. By employing plasma discharge in a nitrogen atmosphere, inert C–H bonds are selectively activated, generating abundant N-insertion intermediates. These species are then captured by electrosprayed microdroplets, where they undergo rapid transimination with gaseous primary amines, yielding imines with high efficiency. Real-time mass spectrometry analysis reveals a two-step mechanism: initial plasma-driven alkane functionalization followed by microdroplet-accelerated transimination. By synergistically combining the high activation capability of nonthermal plasma with the enhanced reaction dynamics of microdroplets, this method establishes a green alternative to conventional thermal catalysis for sustainable chemical transformation from inert substrates.}, archive = {J_JACS}, author = {Shuang Sun and Yijie Fu and Xiangrui Bu and Qinhao Shi and Weilong Wu and Xinghui Li and Xiaohao Wang and Quan Yu}, doi = {10.1021/jacs.5c06426}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27743--27748}, shortjournal = {J. Am. Chem. Soc.}, title = {Sustainable imine production using alkanes as substrates via a plasma-microdroplet approach}, volume = {147}, year = {2025}, }
• (2025). C–H amination of arenes and heteroarenes through a dearomative (3 + 2) cycloaddition. JACS, 147(31), 27731--27742. (www)

  @article{ , abstract = {The C–H amination of arenes offers a path for the synthesis of important arylamines that precludes the need for the prior functionalization of arene substrates, for example through halogenations or metalations. Most often, the direct C–H amination of arenes was achieved using transition metal or photoredox catalysis, through mechanisms ranging from electrophilic substitution to radical additions or nitrene insertions. Here, we report that azidium ions enabled the telescoped C–H amination of unactivated arenes and heteroarenes through a cycloaddition and C–N/N–N bond cleavage sequence. First, a dearomative (3 + 2) cycloaddition reaction between aromatic substrates and azidium ions generated fused triazolinium adducts. Subsequent treatment of the latter with a mild base, followed by thermolysis at moderate temperatures, achieved the synthesis of a diverse range of arylamines with a broad substrate scope. The synthetic versatility of this approach was showcased in the late-stage amination of natural products, pharmaceuticals, agrochemicals, and functional organic materials. Comparison with electrophilic halogenation/Buchwald–Hartwig amination or Ir-catalyzed borylation/Chan–Lam amination sequences revealed that the new C–H amination can provide a regio- or site-selectivity that complements these most widely used approaches for the synthesis of arylamines. Employing this protocol, uniquely regioselective postsynthetic double C–H aminations of coronene and [9]cycloparaphenylene were achieved for the first time.}, archive = {J_JACS}, author = {Sajan Pradhan and Fahimeh Mohammadi and Rikuou Tanase and Kazuma Amaike and Kenichiro Itami and Jean Bouffard}, doi = {10.1021/jacs.5c06390}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27731--27742}, shortjournal = {J. Am. Chem. Soc.}, title = {C–H amination of arenes and heteroarenes through a dearomative (3 + 2) cycloaddition}, volume = {147}, year = {2025}, }
• (2025). From molecular dynamics to the conductivity of sulfuric acid: Ultrafast optical kerr effect experiments and ab initio molecular dynamics simulations. JACS, 147(31), 27720--27730. (www)

  @article{ , abstract = {Extensive use of sulfuric acid in technological applications calls for knowledge of its molecular scale properties. Here, we report a study of aqueous sulfuric acid solutions across a broad concentration range using optical heterodyne-detected optical Kerr effect (OHD-OKE) experiments and ab initio molecular dynamics (AIMD) simulations. The OHD-OKE experiments measured the time derivative of the polarizability–polarizability correlation function (PPCF). By comparison of distinct components of the OKE signal to the excess proton identity correlation functions calculated from AIMD simulations, it was found that the experimental t 3 components quantitatively agreed with the proton hopping time from one water to another, which suggested that the origin of t 3 was associated with proton hopping. The proton hopping distances within the t 3 time scale were used to determine the proton hopping diffusion constants at several concentrations. Using information from the literature and the Nernst–Einstein conductivity equation, it was shown that the vehicular mechanism was insufficient to describe the conductivity. The experimental concentration-dependent conductivities were reproduced by adding the AIMD proton hopping contribution to the conductivity, and proton hopping was shown to be the dominant component of the conductivity. Finally, the experimental concentration-dependent function, C 3 / t 3 , where C 3 is the amplitude coefficient of the third PPCF component, closely tracked the concentration dependence of the hopping component of the conductivity.}, archive = {J_JACS}, author = {Laura Kacenauskaite and Sijia Chen and Max Moncada Cohen and Gregory A. Voth and Michael D. Fayer}, doi = {10.1021/jacs.5c06194}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27720--27730}, shortjournal = {J. Am. Chem. Soc.}, title = {From molecular dynamics to the conductivity of sulfuric acid: Ultrafast optical kerr effect experiments and ab initio molecular dynamics simulations}, volume = {147}, year = {2025}, }
• (2025). Accelerating nitrate electroreduction to ammonia via Metal–Support interactions in ni-WS2 catalysts. JACS, 147(31), 27708--27719. (www)

  @article{ , abstract = {Electrocatalytic nitrate reduction reaction (NO 3 – RR) is a promising route for both treating NO 3 – -containing wastewater and enabling sustainable ammonia (NH 3 ) synthesis. While two-dimensional (2D) transition metal dichalcogenides (TMDs) catalysts have been widely investigated as catalysts in various electrocatalytic reactions, their practical application in NO 3 – RR remains hindered by inherently sluggish kinetics and insufficient stability. Metal–support interaction (MSI), which enhances charge transfer and stabilizes catalytic sites, offers a compelling strategy to address these challenges. Herein, we design an MSI-driven Ni-WS 2 catalyst via a two-step strategy. The Ni-WS 2 catalyst demonstrates outstanding NO 3 – RR performance, achieving a Faradaic efficiency of 91.7% at −0.3 V RHE with an NH 3 yield rate of 23.3 mg h –1 cm –2 at −0.7 V RHE . Significantly, the Ni-WS 2 catalyst maintained an exceptional stability in a membrane electrode assembly (MEA), sustaining ≈32 mg h –1 cm –2 NH 3 production over 100 h, surpassing most previously reported TMD-based catalysts. Density functional theory (DFT) calculations reveal that MSI between Ni metal and WS 2 support induces interfacial charge redistribution, optimizes adsorption energy of key intermediates and lowers the energy barrier for the rate-determining step (*NH 2 → *NH 3 ). Furthermore, the Zn-NO 3 – battery assembled with Ni-WS 2 cathode exhibits remarkable performance. This work advances a two-step synthesis strategy for high-performance NO 3 – RR electrocatalysts through targeted MSI modulation.}, archive = {J_JACS}, author = {Jiangnan Lv and Qianwen Yang and Tingting Liang and Xiaoting Sun and Wanting Rong and Qiqi Dai and Yizhi Gao and Lanfang Wang and Xiaohong Xu and Yang Liu}, doi = {10.1021/jacs.5c06333}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27708--27719}, shortjournal = {J. Am. Chem. Soc.}, title = {Accelerating nitrate electroreduction to ammonia via Metal–Support interactions in ni-WS2 catalysts}, volume = {147}, year = {2025}, }
• (2025). Heme-like {CoNO}9, (STTP•–2){CoNO}9, and {CoNO}10 complexes supported by 21-thiaporphyrin macrocycle. JACS, 147(31), 27698--27707. (www)

  @article{ , abstract = {Using a weaker ligand field thiaporphyrin macrocycle (STTP) as a heme-like ligand, we succeeded in the isolation of an unprecedented complete series of {CoNO} n ( n = 9 and 10 in the Enemark–Feltham notation) and a (STTP •–2 ){CoNO} 9 species. Specifically, electrochemical or chemical reduction of a {CoNO} 9 ( S T = 1/2) species by potassium graphite (KC 8 ) results in first ligand-based reduction leading to a {CoNO} 9 moiety antiferromagnetically coupled to a thiaporphyrin dianionic radical yielding an overall S T = 0 ground state, and subsequent metal-based reduction affording an S T = 1/2 complex comprised of a genuine {CoNO} 10 unit ligated by a thiaporphyrin radical. Multiple analytical and spectroscopic measurements using SXRD, IR, NMR, SQUID, and EPR coupled to detailed DFT calculations support the assignment of a high-spin Co II center in {CoNO} 9 and (STTP •–2 ){CoNO} 9 and a high spin Co I center in {CoNO} 10 . Furthermore, the reaction of the {CoNO} 9 complex with Ph 3 CSNO and PhNO was found to furnish cobalt C -diazeniumdiolate heme-like complexes, which provides an alternative route to accessing a hyponitrite-like intermediate in heme models.}, archive = {J_JACS}, author = {Xiao-Rui Ren and Shengfa Ye and Fang Wang and Gao-Xiang Wang and Zi-Bin Zhong and Xuebin Jiang and Wang Chen and Ronghui Cao and Feng Bai and Peng-Cheng Duan}, doi = {10.1021/jacs.5c06334}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27698--27707}, shortjournal = {J. Am. Chem. Soc.}, title = {Heme-like {CoNO}9, (STTP•–2){CoNO}9, and {CoNO}10 complexes supported by 21-thiaporphyrin macrocycle}, volume = {147}, year = {2025}, }
• (2025). Entropy-driven structural evolution in ceramic oxides. JACS, 147(31), 27685--27697. (www)

  @article{ , abstract = {High-entropy ceramics, with five or more elements randomly occupying the same cation crystallographic sites, offer vast compositional diversity and unique properties for material design and applications. However, for many dissimilar elements, entropic stabilization cannot overcome the enthalpic barrier to cation substitution. As a result, most high-entropy ceramics incorporate only a few similar elements, limiting the in-depth exploration of the effect of entropy on ceramic properties. Here, we first use density functional theory to model fluorite crystal structures composed of 1–10 elements and then experimentally present practical fluorite oxide nanostructures containing 1, 3, 8, and 15 metals, as well as a record-breaking 25-element high-entropy ceramic incorporating a diverse palette of rare-earth, transition, alkaline, p -block, and noble metals. As entropy increases, structural and configurational disorder in the solid solution rises, altering structural features such as lattice distortion, crystallinity, homogeneity, defect density, and thermal stability. This research provides new insights and understanding of the role of entropy in stabilizing compositionally complex ceramics.}, archive = {J_JACS}, author = {Shuo Liu and Chaochao Dun and Lin Xiong and Shaon Das and Sanjit Ghose and Dominik Wierzbicki and Kaiwen Chen and Zhengxi Xuan and Kun Wang and Feipeng Yang and Baishakhi Mazumder and Xinyi Wang and Wei Chen and Zhou Lin and Jeffrey J. Urban and Mark T. Swihart}, doi = {10.1021/jacs.5c06254}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27685--27697}, shortjournal = {J. Am. Chem. Soc.}, title = {Entropy-driven structural evolution in ceramic oxides}, volume = {147}, year = {2025}, }
• (2025). Writing with molecules: Tip-induced local chemisorption of N-heterocyclic olefins on cu(111). JACS, 147(31), 27676--27684. (www)

  @article{ , abstract = {N-Heterocyclic olefins (NHOs), possessing highly polarizable electron-rich double bonds, have recently received increased attention as promising ligands to modify the properties of various surfaces such as Cu, Au, and Si. This work demonstrates the precise “writing” of molecules on a Cu(111) surface by using the electric field of a scanning tunneling microscope (STM) tip. This selectively switches the molecules from a mobile, physisorbed state to a chemisorbed state with molecular, nanoscale spatial resolution under ultrahigh vacuum conditions. We utilize STM and high-resolution electron energy-loss spectroscopy supported by density-functional theory to investigate adsorption and orientation of the molecules on the Cu(111) surface. We find that IPr-NHO adopts two distinct adsorption states on Cu(111): a mobile, physisorbed state and a chemisorbed state. We can distinguish between the two states using X-ray photoelectron spectroscopy and show that the mobile species can be transformed into the immobile species via interaction with the STM tip with molecular precision. This enables “writing” of IPr-NHO on Cu(111) as the molecules can be chemisorbed in a predefined assembly in intentionally designed shapes, opening new possibilities for nanofabrication, molecular electronics, and tunable surface chemistry.}, archive = {J_JACS}, author = {Felix Landwehr and Ankita Das and Sergio Tosoni and Juan J. Navarro and Mowpriya Das and Frank Glorius and Markus Heyde and Beatriz Roldan Cuenya}, doi = {10.1021/jacs.5c06188}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27676--27684}, shortjournal = {J. Am. Chem. Soc.}, title = {Writing with molecules: Tip-induced local chemisorption of N-heterocyclic olefins on cu(111)}, volume = {147}, year = {2025}, }
• (2025). Identification of Ni–N4 active sites in atomically dispersed ni catalysts for efficient chlorine evolution reaction. JACS, 147(31), 27664--27675. (www)

  @article{ , abstract = {Chlorine (Cl 2 ) is one of the most important chemicals in the chemical industry, which is primarily produced by the electrochemical chlorine evolution reaction (CER) in the chlor–alkali process. While platinum-group metal (PGM)-based dimensionally stable anodes (DSAs) have dominated over the last half century, atomically dispersed catalysts (ADCs) have recently emerged as a promising class of CER catalysts; however, they still rely on PGMs. In this work, we prepared a series of non-PGM (Fe, Co, Ni, and Cu)-based ADCs and investigated their CER reactivity trends. Among these, the Ni ADC exhibited the best CER activity and kinetics. Notably, its CER activity exceeded those of commercial DSA and reported non-PGM-based catalysts. In situ X-ray absorption spectroscopy and X-ray photoelectron spectroscopy analyses combined with density functional theory calculations revealed that the Ni–N 4 motif serves as a major active site for the CER. The Ni-loading-controlled Ni ADCs confirmed the involvement of Ni–N 4 sites as active sites in the formation of Cl 2 . Overall, our findings pave the way for extending ADC-based CER catalysts to non-PGM compositions.}, archive = {J_JACS}, author = {Jinjong Kim and Taejung Lim and David Hernández-Castillo and June Sung Lim and Jihyun Park and Dayeon Kim and Jaehwan Kim and Jaeyune Ryu and Young Jin Sa and Jong Hoon Lee and Yun Jeong Hwang and Hoi Ri Moon and Kai S. Exner and Sang Hoon Joo}, doi = {10.1021/jacs.5c06097}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27664--27675}, shortjournal = {J. Am. Chem. Soc.}, title = {Identification of Ni–N4 active sites in atomically dispersed ni catalysts for efficient chlorine evolution reaction}, volume = {147}, year = {2025}, }
• (2025). Redox-induced microstructure and phase dynamics in nickel: Insights from in situ synchrotron X-ray diffraction. JACS, 147(31), 27651--27663. (www)

  @article{ , abstract = {Using in situ synchrotron X-ray diffraction, we interrogate the microstructural and phase evolution of polycrystalline nickel (Ni) during redox cycling in O 2 , H 2 , and H 2 O environments. Oxidation in O 2 promotes strong (111) texturing in both the NiO overlayer and the underlying Ni substrate. However, this crystallographic alignment is lost following reduction in H 2 and subsequent reoxidation, demonstrating irreversible microstructural changes. H 2 exposure leads to proton dissolution into the Ni lattice, triggering a localized phase transition from face-centered cubic (FCC) to hexagonal close-packed (HCP) Ni in hydrogen-saturated regions. In H 2 O-containing atmospheres, dissociative H 2 O adsorption produces protons that permeate the NiO layer, forming γ-NiOOH within the NiO lattice and HCP Ni beneath the NiO overlayer as protons accumulate. Kinetic analysis via the Johnson-Mehl-Avrami–Kolmogorov model uncovers distinct growth mechanisms: preoxidized Ni surfaces follow one-dimensional (1D) kinetics for NiO, γ-NiOOH, and HCP growth, whereas pristine Ni exhibits three-dimensional (3D) kinetics due to island-like nucleation and growth of NiO. These results highlight the critical interplay between H 2 O dissociation, hydrogen permeation, and redox-driven phase transformations, with practical implications in engineering nickel-based catalysts and hydrogen storage systems through controlled microstructural and phase evolution.}, archive = {J_JACS}, author = {Shyam Bharatkumar Patel and Jianyu Wang and Xiaobo Chen and Yupeng Wu and Raul Acevedo-Esteves and Kenneth Evans-Lutterodt and Randall L. Headrick and Guangwen Zhou}, doi = {10.1021/jacs.5c06066}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27651--27663}, shortjournal = {J. Am. Chem. Soc.}, title = {Redox-induced microstructure and phase dynamics in nickel: Insights from in situ synchrotron X-ray diffraction}, volume = {147}, year = {2025}, }
• (2025). Well-aligned liquid crystal interface and expanded solvation sheath accelerate zn2+ desolvation kinetics for stable zinc batteries. JACS, 147(31), 27640--27650. (www)

  @article{ , abstract = {The straightforward processing and assembly of zinc batteries enable large-scale production and cost-effective energy storage solutions. However, nonuniform Zn plating and parasitic reactions impede practical deployment, which can be addressed through advanced interfacial modifications and enhanced Zn 2+ transport kinetics. Herein, we developed a trace additive based on a tailored liquid crystal molecule (4-pentyl-4′-cyanobiphenyl, 5CB), which preferentially adsorbs onto the zinc surface to form a dynamic ordered interfacial layer and modulate the Zn 2+ solvation shell due to its self-assembling and anisotropic properties. The interfacial layer inhibits solvent decomposition and side reactions, while the expanded solvation shell weakens Zn 2+ interactions with both solvents and anion, lowering the desolvation barrier and enabling fast, uniform Zn 2+ transport. Consequently, the Zn 2+ transfer number increases from 0.29 to 0.71, and epitaxial deposition of Zn 2+ along the (002) crystal plane is promoted, ensuring uniform zinc deposition. Benefiting from the liquid crystal interfacial layer, the Zn∥Zn symmetric cell demonstrates exceptional cycling stability for up to 2000 h, surpassing that without 5CB (only 400 h) while asymmetric Zn∥Ti cells with 5CB maintain >99.1% Coulombic efficiency after 1100 cycles, compared to rapid degradation without 5CB. The Zn∥PANI full cells deliver 157.6 mAh g –1 at 0.1 A g –1 , retaining 130.1 mAh g –1 at a high current density of 5 A g –1 , and achieves 86% capacity retention over 500 cycles. These findings highlight the effectiveness of liquid crystal interfacial engineering in improving Zn-ion transport kinetics and stabilizing Zn anodes, paving the way for high-performance, long-lifetime zinc batteries.}, archive = {J_JACS}, author = {Chen Li and Yuxuan Liu and Jiangwen Liu and Mili Liu and Yulong Gao and Xinyu Wang and Yongshuo Zheng and Jun Liu and Longtao Ma and Liuzhang Ouyang and Min Zhu}, doi = {10.1021/jacs.5c06049}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27640--27650}, shortjournal = {J. Am. Chem. Soc.}, title = {Well-aligned liquid crystal interface and expanded solvation sheath accelerate zn2+ desolvation kinetics for stable zinc batteries}, volume = {147}, year = {2025}, }
• (2025). Electronic modification of a reduced mononuclear nonheme iron nitrosyl complex leads to HNO release. JACS, 147(31), 27624--27639. (www)

  @article{ , abstract = {A new pentadentate-fluorinated N 4 S(thiolate) ligand was synthesized. Reaction with Fe(BF 4 ) 2 ·6H 2 O gives a new thioether complex, [Fe II (CH 3 CN)(N3Py pF SEtCN)][BF 4 ] 2 ( 1 ), and on-metal deprotection gives the thiolate complex, [Fe II (CH 3 CN)(N3Py pF S)][BF 4 ] ( 2 ). Reaction of 2 with NO forms a low-spin ground state ( S = 1/2) {FeNO} 7 complex ( 3 ). Chemical reduction of 3 with cobaltocene gives a metastable intermediate spin S = 1 {FeNO} 8 complex ( 4 ). Protonation of 4 releases nitroxyl (HNO), as observed by ESI-MS and 31 P NMR trapping experiments with PPh 3 . Complexes 1 and 2 were characterized by single-crystal X-ray crystallography, complexes 2 – 4 were characterized by EPR and FT-IR spectroscopies, and all iron complexes were characterized by 19 F NMR, UV–vis, and 57 Fe Mössbauer spectroscopies. These results show that a nonheme iron complex can generate and release HNO, suggesting that nonheme iron centers could be endogenous or exogenous sources of HNO in biological systems. Additionally, the fluorine-substituted N 4 S(thiolate) ligand provides a unique spectroscopic handle to monitor the reactivity of the iron center several bonds away from the fluorine substituent.}, archive = {J_JACS}, author = {Jacob A. Wade and Aniruddha Dey and Alex Confer and Sudha Yadav and Maxime A. Siegler and Therese Albert and Pierre Moënne-Loccoz and Yisong Guo and V. Sara Thoi and David P. Goldberg}, doi = {10.1021/jacs.5c05977}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27624--27639}, shortjournal = {J. Am. Chem. Soc.}, title = {Electronic modification of a reduced mononuclear nonheme iron nitrosyl complex leads to HNO release}, volume = {147}, year = {2025}, }
• (2025). Developing dynamic ion transport channels in polymer solid electrolytes for high-performance lithium metal batteries. JACS, 147(31), 27611--27623. (www)

  @article{ , abstract = {Solid polymer electrolytes (SPEs) are promising for next-generation solid-state lithium metal batteries owing to their electrochemical stability and high safety. However, limited ionic conductivity and poor interfacial stability have hindered their practical applications. To address these challenges, we propose a novel approach by incorporating trace amounts of sulfone (SL) into polyacrylic-based SPEs, purposely creating “ dynamic ion transport channels .” Molecular dynamics simulations and experimental validation demonstrate that the optimal incorporation of SL ( in situ -SL2) precisely tunes the solvation structure, establishing dense, multipoint coordination networks via gradient ion–dipole interactions . The inherent flexibility of SL facilitates rapid conformational changes and dynamic bridging with Li + ions, reducing energy barriers for Li + elastic hopping and thus enhancing ionic conductivity and lithium-ion transference numbers. Detailed interfacial analysis reveals that in situ SL2 SPE promotes the formation of a stable, inorganic-rich solid electrolyte interphase (SEI), effectively suppressing the metal dendrite growth. The LFP| In situ -SL2|Li cell exhibits over 91.7% capacity retention after 2000 cycles at 3 C, highlighting a superior performance and long-term stability. This work provides valuable insights into designing high-performance SPEs for long-lifetime and safe lithium metal batteries.}, archive = {J_JACS}, author = {Qiang Lv and Li-an Li and Xi Zhang and Runqi Wang and Ning Wen and Lijuan Xue and Haimei Wang and Lei Shen and Dairong Chen and Francesco Ciucci and John Wang}, doi = {10.1021/jacs.5c05911}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27611--27623}, shortjournal = {J. Am. Chem. Soc.}, title = {Developing dynamic ion transport channels in polymer solid electrolytes for high-performance lithium metal batteries}, volume = {147}, year = {2025}, }
• (2025). Elucidating electric field-induced rate promotion of brønsted acid-catalyzed alcohol dehydration. JACS, 147(31), 27599--27610. (www)

  @article{ , abstract = {Applied potentials have been demonstrated as a powerful tool to promote heterogeneous Brønsted acid catalysis by orders of magnitude, leveraging interfacial electric fields to stabilize protonated intermediates. However, the use of flat two-dimensional electrodes with inherently low active site densities limits the application of conventional thermochemical characterization techniques that can probe the nature of catalytic active sites. Here, we use kinetic analyses with an electrostatics-based model to elucidate the intricacies of potential-induced rate promotion, employing liquid-phase dehydration of 1-methylcyclopentanol catalyzed by carboxylic acid groups on carbon nanotubes as a probe system. Using a basket electrode to directly polarize catalyst powder, we demonstrate that thermocatalytic reaction rates can be promoted by 100,000-fold, exhibiting a log–linear dependence on applied potential with rate-potential scalings as high as 125 ± 4 mV per 10-fold rate increase. In agreement with model predictions, we show that lower ionic strengths attenuate potential sensitivity, resulting from a weakening of the interfacial electric field that interacts with the acidic proton. Furthermore, we experimentally confirm the model-predicted “isokinetic potential” (at ∼0.6 V vs Ag/AgCl)─the potential at which all rate scaling lines at various ionic strengths intersect, making the rate independent of ionic strength. Base titrations reveal that only ∼8% of the carboxylic acid sites are catalytically active, yet these same active sites are operational at the highest and lowest potentials. Collectively, our results provide a key methodology for modeling catalytic effects of electric fields, quantifying active sites under applied potential, and demonstrating fundamental principles of electric field-induced rate promotion.}, archive = {J_JACS}, author = {Bhavish Dinakar and Karl S. Westendorff and Juan F. Torres and Mostapha Dakhchoune and Katelyn Groenhout and Nathan Ewell and Yogesh Surendranath and Mircea Dincă and Yuriy Román-Leshkov}, doi = {10.1021/jacs.5c05891}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27599--27610}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating electric field-induced rate promotion of brønsted acid-catalyzed alcohol dehydration}, volume = {147}, year = {2025}, }
• (2025). Ordering bent and straight dicarboxylate linkers in an fcu zirconium Metal–Organic framework. JACS, 147(31), 27586--27598. (www)

  @article{ , abstract = {The ordering of multiple organic linkers with different sizes and geometries on metal–organic frameworks (MOFs) offers structures with advanced complexity and functionality for enhanced properties. The selection of the components and the number of synthesis steps are commonly rationalized to match existing structural motifs in order to increase the probability of producing the designed new frameworks. Alternatively, combining multiple components, without a preconceived structural model, allows for the exploration of unprecedented structural characteristics. However, this approach requires a large number of experiments to identify both the composition and conditions for a successful synthesis. Here, we report a new Zr-MOF containing ordered straight and bent dicarboxylate linkers prepared by a one-pot synthesis. The discovery was made by high-throughput exploration of the chemical space composed of two linkers, the source of Zr, and the modulator. The linkers and the Zr 6 cluster are ordered on an fcu framework that is tetragonally distorted from its typical cubic symmetry. The arrangement of linkers with different sizes and geometries affords cages and windows with shapes that have not been reported previously, despite the plethora of known fcu -based MOFs. The new MOF exhibits chromatographic separation of the n -hexane/benzene/cyclohexane mixture and demonstrates reversible unbinding and rebinding of the bent linkers upon the addition and removal of protic solvents. The unusual structural properties of the new MOF arise from ordering linkers in a non-predetermined manner following high-throughput synthesis exploration.}, archive = {J_JACS}, author = {Grace S. G. Farmer and Daniel J. Cheney and Khai-Nghi Truong and Nusik Gedikoglu and Bhupendra P. Mali and Datta Markad and Dmytro Antypov and Frédéric Blanc and Alexandros P. Katsoulidis and Matthew J. Rosseinsky}, doi = {10.1021/jacs.5c05854}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27586--27598}, shortjournal = {J. Am. Chem. Soc.}, title = {Ordering bent and straight dicarboxylate linkers in an fcu zirconium Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Topochemical reaction involving double-to-single layer conversion: Mo3Ta2O10N with a kagomé lattice. JACS, 147(31), 27576--27585. (www)

  @article{ , abstract = {Topochemical reactions in transition metal oxides, typically involving oxygen removal or anion exchange, provide a versatile platform for creating metastable phases with diverse functionalities. While these reactions often modify the valence and coordination environment of transition metals, the underlying metal frameworks are usually preserved, maintaining a 1:1 structural correspondence. A representative example is SrFeO 3 → SrFeO 2 , in which each octahedral layer transforms into a single square-planar layer. In this study, we report an unprecedented topochemical transformation in Mo 2 Ta 2 O 11 , composed of alternating MoO 4 tetrahedral bilayers and TaO 6 octahedral bilayers. Ammonolysis at 500 °C in the presence of Mo(CO) 6 collapses the MoO 4 tetrahedral bilayer into a single MoO 6 octahedral layer, thereby breaking the conventional 1:1 structural correspondence. This collapse leads to an 18% contraction along the c axis, substantially exceeding the 10% contraction seen in SrFeO 2 . The resulting compound, Mo 3 Ta 2 O 10 N (space group R –3 m ), has an Mo-based kagomé lattice with finite d -electrons (Mo 4.33+ ), in sharp contrast to the d 0 configuration of the precursor (Mo 6+ 2 Ta 5+ 2 O 11 ). Magnetic susceptibility and NMR measurements suggest that Mo 3 Ta 2 O 10 N is an itinerant kagomé system. This study demonstrates that topochemical reactions can induce dynamic and extensive structural reorganizations, pushing the boundaries of what was previously considered accessible by such low-temperature routes.}, archive = {J_JACS}, author = {Ryoya Higuchi and Kohdai Ishida and Cédric Tassel and Baptiste Vignolle and Daichi Kato and Kantaro Murayama and Hsin-Hui Huang and Akihide Kuwabara and Shunsuke Kobayashi and Yusuke Nambu and Hiroyasu Matsudaira and Shunsaku Kitagawa and Kenji Ishida and Congling Yin and Hiroshi Takatsu and Hiroshi Kageyama}, doi = {10.1021/jacs.5c05749}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27576--27585}, shortjournal = {J. Am. Chem. Soc.}, title = {Topochemical reaction involving double-to-single layer conversion: Mo3Ta2O10N with a kagomé lattice}, volume = {147}, year = {2025}, }
• (2025). Electronic textiles based on conductive Metal–Organic frameworks as scavengers and sensors of toxic oxyanions from water. JACS, 147(31), 27561--27575. (www)

  @article{ , abstract = {Water contamination by toxic oxyanions poses a severe threat to ecosystems and human health. While various adsorbents have been developed for oxyanion sequestration, designing a single material that simultaneously achieves high selectivity, rapid adsorption kinetics, and real-time sensing capabilities remains a challenge. This study explores the first use of layered, conductive metal–organic frameworks (cMOFs) based on hexahydroxy- and hexaimino-triphenylene (HHTP and HITP) cores coordinated with nickel and copper for the dual sensing and filtration of oxyanions from water. Systematic investigations of Ni 3 (HHTP) 2 , Cu 3 (HHTP) 2 , Ni 3 (HITP) 2 , and Cu 3 (HITP) 2 reveal that Ni 3 (HITP) 2 exhibits unprecedented adsorption capacities, capturing up to 827 mg of MnO 4 – and 497 mg of Cr 2 O 7 2– per gram of MOF, while filtering up to 99% of these oxyanions within 10 min of exposure. Ni 3 (HITP) 2 also demonstrates high applicability in real-world scenarios, maintaining a remarkable adsorption performance across various water matrices, pH conditions, and competing anion interferences. Spectroscopic and computational investigations reveal a multimechanistic scavenging process involving chemisorption, physisorption, and redox reactions. Grafting Ni 3 (HITP) 2 onto cotton textiles via a layer-by-layer approach yields mechanically robust, easy to handle, and flexible electronic textile capable of filtering oxyanions for up to 32 cycles without performance loss, while allowing their detection with high sensitivity and low detection limits reaching 2.2 ppm for MnO 4 – and 6 ppm for Cr 2 O 7 2– . Taken together, these findings pave the way for MOF-based next-generation water treatment technologies that integrate efficient filtration and real-time sensing capabilities.}, archive = {J_JACS}, author = {Patrick Damacet and Priyanshu Chandra and Emma K. Ambrogi and Hyuk-Jun Noh and Ericka L. Asmus and Elissa O. Shehayeb and Giovanni Barcaro and Susanna Monti and Katherine A. Mirica}, doi = {10.1021/jacs.5c05275}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27561--27575}, shortjournal = {J. Am. Chem. Soc.}, title = {Electronic textiles based on conductive Metal–Organic frameworks as scavengers and sensors of toxic oxyanions from water}, volume = {147}, year = {2025}, }
• (2025). Chiroptical signal amplification in amorphous siloxane network by asymmetric ring distortion. JACS, 147(31), 27552--27560. (www)

  @article{ , abstract = {Understanding the polymorphs and amorphous structures of silicon oxide is an essential issue not only for fundamental science but also for energy and environmental science. In particular, the amplification mechanism of chiroptical signals in amorphous silicon oxide has drawn significant attention. Here, we explore how the chiroptical signal can be amplified in amorphous silicon oxide (silica) having nanoscale helical structures. Our findings reveal that the observed vibrational circular dichroism (VCD) signals originate from the formation of symmetry-broken siloxane ring structures. Furthermore, we demonstrate that the amplification of siloxane VCD signals is driven by an enthalpy-driven asymmetric ring distortion during volumetric shrinkage.}, archive = {J_JACS}, author = {Yutaka Okazaki and Thierry Buffeteau and Naoya Ryu and Kyohei Yoshida and Ju-Yeon Jo and Kan Hachiya and Takashi Sagawa and Reiko Oda}, doi = {10.1021/jacs.5c05168}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27552--27560}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiroptical signal amplification in amorphous siloxane network by asymmetric ring distortion}, volume = {147}, year = {2025}, }
• (2025). Structural transition from closed to open for the influenza a m2 proton channel as observed by proton-detected solid-state NMR. JACS, 147(31), 27537--27551. (www)

  @article{ , abstract = {The influenza A M2 protein is an acid-activated proton channel and an established pharmaceutical target for antiflu drugs. Here, we studied the conductance domain of the tetrameric M2 channel (construct 18–60) using proton-detected solid-state NMR under native-like conditions in lipid bilayers. We obtained results at different pH values relevant to the virus life cycle: pH 7.8 (nonconducting, closed), pH 6.0 (opening), and pH 4.5 (conducting, fully open). In the closed state at pH 7.8, we detected two sets of resonances of the functionally important side chain of H37. Employing quantum mechanics/molecular mechanics (QM/MM) simulations, we assigned them to hydrogen-bonded and free H37 side chains occurring in varying ratios in the tetrameric arrangement. Additionally, some backbone signals also appear twice, suggesting conformational heterogeneity. The arrangement appears rather rigid, explaining the nonconducting nature of the channel. Lowering the pH to 6.0 leads to increased dynamics of the side chains, as manifested by their disappearance in CP based solid-state NMR spectra. This dynamic arrangement, which results from additional protonation of the four H37 side chains, allows for the efficient transport of protons through the channel. Finally, at pH 4.5, the conformational heterogeneity observed at higher pH values disappears completely, and a unique set of highly resolved resonances becomes visible. This suggests a well-defined acid-activated state of the M2 channel. Notably, in this state, the signals of the His37 side chains are absent due to dynamics, as well as the signals of the amphipathic helix (residues 45–52). This study provides strong evidence to a model of proton conduction through M2 which relies on dynamic vs rigid H37 side chains and furthermore lays the basis for an atomic structure of the acid-activated state of M2.}, archive = {J_JACS}, author = {Swantje Mohr and Caspar Schattenberg and Tillmann Utesch and Henry Sawczyc and Veniamin Chevelkov and Sascha Lange and Jacek Kozuch and Han Sun and Adam Lange}, doi = {10.1021/jacs.5c05111}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27537--27551}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural transition from closed to open for the influenza a m2 proton channel as observed by proton-detected solid-state NMR}, volume = {147}, year = {2025}, }
• (2025). Deep learning for bidirectional translation between molecular structures and vibrational spectra. JACS, 147(31), 27525--27536. (www)

  @article{ , abstract = {Two deep learning models, TranSpec and SpecGNN, were developed to establish a bidirectional mapping between molecular vibrational spectra and simplified molecular input line entry system (SMILES) representations, akin to a “translation” between the language of spectra and the language of molecular structures. Initially, TranSpec achieved accuracy rates of 55 and 63% for quantum chemistry (QC)-calculated IR and Raman spectral data sets, respectively, but its performance dropped to 11% for the NIST experimental IR data set. To address this, we combined IR and Raman spectra as input; augmented the data set; employed model fusion, transfer learning, and multisource learning; applied molecular mass filtering; and leveraged SpecGNN for spectral simulation and candidate reordering. These improvements boosted TranSpec’s accuracy to 53.6% for the experimental IR data set. Notably, SpecGNN outperformed traditional QC methods in terms of both spectral accuracy and computational efficiency. Finally, we demonstrated TranSpec’s ability to recognize functional groups and distinguish isomers or homologues. Together, TranSpec and SpecGNN models provide an efficient and accurate AI-driven framework for interpreting molecular structures and spectra, advancing applications in spectroscopy and cheminformatics.}, archive = {J_JACS}, author = {Tianqing Hu and Zihan Zou and Bo Li and Tong Zhu and Shaonan Gu and Jun Jiang and Yi Luo and Wei Hu}, doi = {10.1021/jacs.5c05010}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27525--27536}, shortjournal = {J. Am. Chem. Soc.}, title = {Deep learning for bidirectional translation between molecular structures and vibrational spectra}, volume = {147}, year = {2025}, }
• (2025). Inverse trans influence and uranium-arene σ-bonding drive molecular geometry: Ligand modification from hard to soft flips the oxide from axial to equatorial. JACS, 147(31), 27515--27524. (www)

  @article{ , abstract = {A rare example of an equatorially bound terminal uranium(V) oxo complex in a chelating sulfur-based ligand environment, namely [(mes( Me,Ad ArS) 3 )U V (O eq )(THF)] ( 2 ), is presented. Octahedrally coordinated 2 is obtained by reaction of the mesitylene-anchored tris-thiophenolate-coordinated uranium(III) complex [U III ((SAr Ad,Me ) 3 mes)] ( 1 ) with the oxygen-atom transfer reagent N 2 O. The observed, equatorially bound oxo ligand in 2 is in stark contrast to its known tris-aryloxide analog, [(mes( Me,Ad ArO) 3 )U V (O ax )(THF)] ( A ), where the oxo ligand occupies the typically observed axial coordination site. Complexes 1 and 2 are characterized by single-crystal X-ray diffraction analyses and spectroscopic and magnetochemical methods, including 1 H NMR, UV/vis/NIR electronic absorption, as well as EPR spectroscopy and SQUID magnetometry, thus confirming the C S symmetry and the pentavalent oxidation state of 2 . Encompassing quantum chemical calculations (DFT and CASPT2) on 2 and its tris-phenolate analog A , support and rationalize the structural and electronic differences. The molecular orbital pictures show that a stabilizing σ-bonding interaction arising from the U–O eq inverse trans influence (ITI) is present in 2 but missing in A . In 2 , the sulfur 3p orbitals are closer in energy to the uranium 5f manifold than the arene π-system, leading to an ITI, while U–arene σ- or δ-bonding is not observed. Although the arene orbitals remain separated from the uranium 5f orbitals in A , the absence of an ITI allows the arene a 2u orbital to engage in a σ-type interaction with the metal. Thus, incorporating a tris-thiophenolate to an arene anchor introduces a new design concept in molecular f-element chemistry. This approach stabilizes an equatorially bound U(V) oxo center, contrasting with its tris-phenolate counterpart, where oxo coordination is axial. The observed geometric divergence, driven by competing ITI and U–arene interactions, not only tunes electronic structure but also leads to differentiated reactivity: only the phenolate analogs activate H 2 O, while the thiolates do not.}, archive = {J_JACS}, author = {Benedikt Kestel and Daniel Pividori and Sabyasachi Roy Chowdhury and Frank W. Heinemann and Bess Vlaisavljevich and Karsten Meyer}, doi = {10.1021/jacs.5c05029}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27515--27524}, shortjournal = {J. Am. Chem. Soc.}, title = {Inverse trans influence and uranium-arene σ-bonding drive molecular geometry: Ligand modification from hard to soft flips the oxide from axial to equatorial}, volume = {147}, year = {2025}, }
• (2025). Unveiling phase transition dynamics using cryogenic optical microscopy in a charge-transfer Fe2Co2 switchable molecular material. JACS, 147(31), 27506--27514. (www)

  @article{ , abstract = {Understanding the phase transition mechanism in switchable materials is crucial to optimizing their properties. In this study, we present the thermal electron transfer-coupled spin transition (ETCST) mechanism, revealed through the cryogenic optical microscopy (OM) measurements on a cyanide-bridged square complex, {[Fe(Tp)(CN) 3 ] 2 [Co(vbik) 2 ] 2 }·2ClO 4 ·2CH 2 Cl 2 ( 1·ClO 4 ), where Tp is tris(pyrazolyl)borate and vbik is bis(1-vinylimidazolyl)ketone. A one-step thermal ETCST of 1·ClO 4 is observed using conventional techniques such as single-crystal X-ray diffraction (SC-XRD) and bulk sample magnetic measurements. The ETCST is cooperative, with quite different transition temperatures for the single crystal ( T 1/2 ↑ = 251.5 K for heating and T 1/2 ↓ = 243.5 K) and bulk sample ( T 1/2 ↑ = 273 K and T 1/2 ↓ = 255 K). In contrast, the direct visualization of the thermal ETCST in the single crystal of 1·ClO 4 through OM and the subsequent image analysis disclose for the first time a phase transition of unexpected complexity. The ETCST progresses in three steps along the a , b , and c axes: (i) Initially, the strip domains form and rapidly extend along the a -axis. (ii) These domains then gradually widen in the b -axis covering the entire ab layer. (iii) The final step involves a layer-by-layer extension of ETCST along the c -axis. Structural analysis of 1·ClO 4 reveals that two types of intermolecular interactions govern the two preferential propagation directions of ETCST. The first type, mediated by the ClO 4 – anion, drives the rapid propagation of ETCST along the a axis, occurring so rapidly that conventional methods like magnetometry and SC-XRD are unable to detect it. The second type, along the b axis, involves the π–π stacking of vbik ligands, which contributes to the slower ETCST propagation in this direction. This mechanistic insight into the anisotropic propagation patterns of ETCST in 1·ClO 4 underscores the role of intermolecular interactions in modulating the dynamics of molecular switching.}, archive = {J_JACS}, author = {Buqin Xu and Nour-El-Islam Belmouri and Longhe Li and Sadiya Sadiya and Guillaume Bouchez and Mouhamadou Sy and Geoffrey Gontard and Kamel Boukheddaden and Yanling Li and Rodrigue Lescouëzec}, doi = {10.1021/jacs.5c04906}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27506--27514}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling phase transition dynamics using cryogenic optical microscopy in a charge-transfer Fe2Co2 switchable molecular material}, volume = {147}, year = {2025}, }
• (2025). De novo design of high-performance cortisol luminescent biosensors. JACS, 147(31), 27494--27505. (www)

  @article{ , abstract = {Frequent, reliable cortisol measurement is critical for diagnosing and managing adrenal disorders, stress responses, and circadian rhythm disruptions. However, current cortisol assays or detection methods remain confined to laboratory settings, limiting on-site testing. Protein-based biosensors provide a promising point-of-care (POC) solution, yet no robust, field-ready protein-based cortisol biosensor is available. Here, we de novo design cortisol-inducible dimerization modules and systematically sample their fusions with split luciferase reporters by using a protein structure prediction pipeline. The resulting biosensor, designed straight from the computer, yields over 300-fold luminescent response with picomolar sensitivity and can be rapidly imaged by a standard camera or smartphone. This work highlights the power of computational protein design for developing next-generation protein-based biosensors.}, archive = {J_JACS}, author = {Julie Yi-Hsuan Chen and Xue Peng and Chenggang Xi and Gyu Rie Lee and David Baker and Andy Hsien-Wei Yeh}, doi = {10.1021/jacs.5c05004}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27494--27505}, shortjournal = {J. Am. Chem. Soc.}, title = {De novo design of high-performance cortisol luminescent biosensors}, volume = {147}, year = {2025}, }
• (2025). N-oxide-driven heme-activatable biomolecule labeling for visualization of labile heme in living cells and mouse brain. JACS, 147(31), 27484--27493. (www)

  @article{ , abstract = {Labile heme, a complex comprising protoporphyrin IX coordinated with an iron ion, functions as a critical biological mediator in physiological and pathological processes across diverse organisms. Despite its fundamental importance, both the subcellular dynamics and the systemic trafficking of heme remain inadequately characterized, primarily due to a scarcity of chemical tools capable of detecting labile heme in living systems. Herein, we report the development of innovative chemical probes that enable the detection of labile heme in live cells, fixed specimens, and in vivo models through a novel N -oxide-driven heme-activatable biomolecule labeling strategy. These probes exhibit exceptional selectivity, becoming activated exclusively upon heme interaction to form covalent bonds with neighboring proteins. We demonstrate that the tertiary amine N -oxide moiety triggers heme activation, followed by self-oxidation to generate reactive quinone intermediates responsible for covalent bond formation. This reaction proceeds effectively in living cells and within the brains of live mice. Our probe enables fluorescence imaging of living cells and 3D tissue visualization of mouse brains for labile heme detection, while facilitating multiomics analysis, including proteomics and single-cell RNA sequencing. This comprehensive approach provides unprecedented opportunities for investigating the physiological and pathological roles of labile heme in complex living systems.}, archive = {J_JACS}, author = {Ryo Kakiuchi and Tadanori Fukaya and Satomi Tamakoshi and Shohei Tsuji and Honoka Fujimori and Masamitsu Shimazawa and Tomonori Tamura and Itaru Hamachi and Takeru Ochi and Hiroko Matsunaga and Haruko Takeyama and Hideko Nagasawa and Tasuku Hirayama}, doi = {10.1021/jacs.5c04990}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27484--27493}, shortjournal = {J. Am. Chem. Soc.}, title = {N-oxide-driven heme-activatable biomolecule labeling for visualization of labile heme in living cells and mouse brain}, volume = {147}, year = {2025}, }
• (2025). Lighting up healing: Green light-driven dual gasotransmitters release against MRSA wound infections. JACS, 147(31), 27471--27483. (www)

  @article{ , abstract = {Methicillin-resistant Staphylococcus aureus (MRSA) represents a major clinical challenge as a predominant pathogen causing chronic and difficult-to-treat wound infections. Effective strategies that simultaneously combat bacterial infection and promote tissue regeneration are essential yet challenging for managing MRSA-related wound complications. Herein, we report the design of a novel integrated dual-gas release molecular platform, which enable the phototriggered simultaneous release of NO and CO within a single molecular entity, i.e., an acylhydrazine-caged rhodamine ( AhCR565 ). Green light initiates the cascade release of NO and CO from AhCR565 , with a synchronized fluorescent turn-on signal, serving as an intrinsic calibration mechanism for real-time tracking of the localization, kinetics of dual gas release. The photodriven simultaneous release of NO and CO from AhCR565 demonstrates a superior antimicrobial effect against MRSA, while exhibiting excellent biocompatibility. By harnessing the synergistic and complementary bioactivities of NO and CO, AhCR565 effectively eradicates bacterial infections and promotes wound healing in a marine MRSA-infected skin wound model. This work highlights a promising noninvasive strategy for multigas simultaneous release therapy, providing a potent approach to tackling resistant bacterial infections and addressing broader biomedical challenges.}, archive = {J_JACS}, author = {Yanyan Hou and Yuze Wang and Ping Yang and Zhetao Shen and Xueli Wang and Jinquan Chen and Youjun Yang and Daijie Chen and Xuhong Qian and Xiao Luo}, doi = {10.1021/jacs.5c04824}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27471--27483}, shortjournal = {J. Am. Chem. Soc.}, title = {Lighting up healing: Green light-driven dual gasotransmitters release against MRSA wound infections}, volume = {147}, year = {2025}, }
• (2025). Iridium–Lewis acid bifunctional catalyst-enabled regio- and enantioselective C(sp2)–H meta-borylation of α,α-diarylcarboxamides. JACS, 147(31), 27458--27470. (www)

  @article{ , abstract = {Enantioselective C(sp 2 )–H activation typically relies on forming rigid 5- or 6-membered metallacyclic intermediates. Examples involving direct metalation at remote C(sp 2 )–H bonds, which require larger metallacycles, remain scarce. Herein, we report a series of 1,1′-bi-2-naphthol (BINOL)-derived chiral bipyridine ligands that enable iridium-catalyzed regio- and enantioselective meta -borylation of α,α-diarylcarboxamides, generating an all-carbon quaternary stereocenter in high yields and excellent regio- and enantioselectivities. The chiral side arm, BINOL, holds a Lewis acid aluminum center and interacts with the Lewis basic fragment of the substrate to bring it into proximity with the bipyridine part of the iridium-catalyst for the remote-selective borylation reaction. The chiral pocket enables the effective transfer of the chiral information, overcoming the challenges of long-range asymmetric induction, presumably due to the closer proximity of the chiral scaffold of the ligand and the (pro)stereogenic center of the substrate. The prochiral substrates were desymmetrized with up to an excellent 99% ee. An unprecedented kinetic resolution for such a transformation has also been disclosed with moderate to good selectivity ( s -factor up to 19.5). The synthetic utility was demonstrated through a successful scale-up experiment and subsequent transformation of the boronate ester to various functional groups. Further, mechanistic studies indicate that the catalyst primarily governs the enantioselectivity of the desymmetrization reaction, while the kinetic resolution of the monoborylated product plays a secondary role in further enhancing the product’s enantioselectivity. Finally, density functional theory (DFT) calculations have been performed to understand the reaction mechanism and the crucial noncovalent interactions involved in the transition states that dictate observed enantioselectivity.}, archive = {J_JACS}, author = {Netai Aditya and Shovan Das and Ayan Datta and Biplab Maji}, doi = {10.1021/jacs.5c04877}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27458--27470}, shortjournal = {J. Am. Chem. Soc.}, title = {Iridium–Lewis acid bifunctional catalyst-enabled regio- and enantioselective C(sp2)–H meta-borylation of α,α-diarylcarboxamides}, volume = {147}, year = {2025}, }
• (2025). Selective photochemical conversion of carbon dioxide to formic acid at Gas–Water interface of microbubbles. JACS, 147(31), 27449--27457. (www)

  @article{ , abstract = {We report a selective photochemical conversion of carbon dioxide (CO 2 ) to formic acid (HCOOH, FA) at the gas–water interface (GWI) of microbubbles. The microbubbles with an average diameter of 42 μm are produced by passing CO 2 gas through a porous thermoplastic bubbler immersed in an aqueous solution of the copper(II)-phenanthroline complex [Cu(Phen) 2 ] 2+ . The average FA production rate at room temperature is found to be 47.5 μM h –1 for 5 mM of [Cu(Phen) 2 ] 2+ . When 5 mM iodide (I – ) is added to the system, the FA production rate increases to a maximum value of 63.8 μM h –1 . We also demonstrated that both acidic and alkaline conditions stimulate FA formation. Mechanistic investigations indicate that H • at the GWI plays a crucial role in the reduction of CO 2 via the formation of the • COOH intermediate, which was captured using (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) as a spin trap as well as by the molecular copper catalyst. As microbubbles are continuously formed in water, the reactions at the GWI of microbubbles can be sustained over extended periods, making it easier to scale up production, which often is an issue with droplet-generated products. These findings demonstrate the promising potential of gas microbubbles in water to drive unexpected chemistry, thereby removing a greenhouse gas such as CO 2 by converting it into valuable products. The present study is a first step toward a practical demonstration, but does not constitute an industrial process at present.}, archive = {J_JACS}, author = {Sandeep Bose and Masoud A. Mehrgardi and Richard N. Zare}, doi = {10.1021/jacs.5c04912}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27449--27457}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective photochemical conversion of carbon dioxide to formic acid at Gas–Water interface of microbubbles}, volume = {147}, year = {2025}, }
• (2025). Uncovering the pressure-dependent mechanism of CO2 hydrogenation to methanol on ga-promoted Cu/ZrO2 using operando modulation-excitation DRIFTS. JACS, 147(31), 27438--27448. (www)

  @article{ , abstract = {The synthesis of methanol via CO 2 hydrogenation is attracting significant interest, with Cu-based catalysts currently leading this promising approach. Incorporating Ga and Zr promoters further enhances catalyst performance by suppressing the competing reverse water–gas shift (RWGS) reaction. However, their precise mechanistic roles and the identities of key reaction intermediates remain debated, which may be the key for catalyst design and process optimization. In this study, we extend operando modulation-excitation spectroscopy coupled with diffuse reflectance infrared Fourier transform spectroscopy and mass spectrometry (ME-DRIFTS-MS) to investigate CO 2 hydrogenation over Ga-promoted Cu/ZrO 2 under varying industrially relevant pressures up to 50 bar. Our results indicate that methanol formation proceeds predominately via the formate pathway with formate (HCOO*) and methoxy (CH 3 O*) as pivotal intermediates. Additionally, we demonstrate that the rate-determining step is strongly dependent on the pressure and temperature, ultimately dictated by the local abundance of adsorbed hydrogen (H*) and gaseous H 2 O. Ga facilitates hydrogen adsorption, accelerating HCOO* hydrogenation to CH 3 O* and preventing its decomposition to CO. Notably, CH 3 O* conversion to CH 3 OH occurs via a water-assisted pathway rather than direct hydrogenation, explaining previously unclear correlation between Cu dispersion and catalytic activity. These mechanistic insights highlight the potential of optimizing reaction conditions─especially lower operating temperatures and controlled water cofeed─to significantly enhance methanol selectivity over Cu-based CO 2 hydrogenation catalysts.}, archive = {J_JACS}, author = {Abdullah J. Al Abdulghani and Sudipta Ganguly and Ryan H. Hagmann and Zhuoran Sun and Matias Alvear and Lesli O. Mark and Eranda Nikolla and Yomaira J. Pagán-Torres and Ive Hermans}, doi = {10.1021/jacs.5c04835}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27438--27448}, shortjournal = {J. Am. Chem. Soc.}, title = {Uncovering the pressure-dependent mechanism of CO2 hydrogenation to methanol on ga-promoted Cu/ZrO2 using operando modulation-excitation DRIFTS}, volume = {147}, year = {2025}, }
• (2025). Light-off salient effect: Thermal phase transitions of molecular crystals controlled by photoirradiation. JACS, 147(31), 27431--27437. (www)

  @article{ , abstract = {The ways that molecular crystals respond to various stimuli have attracted much research attention, thus expanding the functional diversity of their response behavior. For example, ever since the reports of luminescent mechanochromic compounds emerged and began to increase in number, a unique class of such materials has been reported, i.e., luminescent mechanochromic materials based on a single-crystal-to-single-crystal phase transition or crystal bending. An elaborate strategy would be required to diversify further the known array of stimulus responses, and such findings would expand the materials applications of molecular crystals. Here, we achieved a light-off salient effect by effectively combining two external stimuli. Benzodifuranone 1 has three distinct polymorphs, and their thermal phase transitions can be modulated using photoirradiation. Two of the polymorphs, i.e., 1A and 1B , undergo a thermal phase transition to high-temperature polymorph 1X . Upon cooling, 1X transforms back to the 1A phase. Notably, the thermal phase-transition temperature can be reduced by approximately 30 °C under illumination by ultraviolet light. Leveraging this strategy to control the phase transition of 1 using two external stimuli, we demonstrated a light-off salient effect.}, archive = {J_JACS}, author = {Tomohiro Seki and Takumi Okada and Masahiro Ikeda and Kaisei Yamamoto and Shotaro Hayashi and Yuko Kishida and Hidehiro Uekusa}, doi = {10.1021/jacs.5c04563}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27431--27437}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-off salient effect: Thermal phase transitions of molecular crystals controlled by photoirradiation}, volume = {147}, year = {2025}, }
• (2025). Mechanochemical solid form screening of zeolitic imidazolate frameworks using structure-directing liquid additives. JACS, 147(31), 27413--27430. (www)

  @article{ , abstract = {We demonstrate a systematic application of the mechanochemical liquid-assisted grinding (LAG) methodology to screen for forms of zinc imidazolate (Zn Im 2 ), of fundamental importance as the simplest member of the zeolitic imidazolate framework materials family. The exploration of 45 different liquid additives, selected based on their molecular structure and physicochemical properties has resulted in eight different Zn Im 2 topological forms, appearing in 13 crystallographically distinct solid forms (including two previously unknown forms of the crb (BCT) topology), amorphous phases, and the interrupted moc -Zn 4 Im 8 H Im . All prepared topological forms were also explored computationally, using dispersion-corrected periodic density functional theory (DFT) calculations, enabling the rationalization of screening outcomes, and setting the stage for future prediction of additive-directed metal–organic framework (MOF) synthesis. This first systematic exploration of LAG in screening for three-dimensional MOFs demonstrates the potential of the liquid additive to not only accelerate materials synthesis, but also to direct it toward topologically different MOFs. The discovery of novel forms of a material that already exhibits at least 21 crystallographically and functionally different forms provides a strong testimony on the power of mechanochemistry in metal–organic materials discovery.}, archive = {J_JACS}, author = {Ivana Brekalo and Katarina Lisac and Joseph R. Ramirez and Petra Pongrac and Andreas Puškarić and Srećko Valić and Yizhi Xu and Michael Ferguson and Joseph M. Marrett and Mihails Arhangelskis and Tomislav Friščić and K. Travis Holman}, doi = {10.1021/jacs.5c04043}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27413--27430}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanochemical solid form screening of zeolitic imidazolate frameworks using structure-directing liquid additives}, volume = {147}, year = {2025}, }
• (2025). NMR-guided studies to establish the binding interaction between a peptoid and protein. JACS, 147(31), 27403--27412. (www)

  @article{ , abstract = {Ligand discovery of nonenzymatic proteins can be accomplished through screening methods utilizing libraries comprising small molecules, peptides, and peptidomimetics. Incorporating peptoids, which are oligomers of N -substituted glycine monomers, into high-throughput screens can produce libraries of large structural diversity. Due to their malleable structures, peptoids can occupy unique protein binding sites, but determination of the peptoid binding pose is challenging. For example, the peptoid KDT-11 is reported to bind with low micromolar binding affinity to the proteasome subunit Rpn-13. Poor solubility of initial compound screening hits, like KDT-11, can greatly hinder progress in drug discovery since it limits in vitro characterization. The work reported here overcomes this hurdle with the addition of a solubility tag to KDT11, enabling elucidation of the biologically relevant surface of the peptoid through a variety of structure–activity relationships and biophysical studies. NMR paramagnetic relaxation data guided a structural modeling protocol using multiple molecular dynamics (MD) trajectories and extensive sampling. The final peptoid-protein structure is conformationally stable in equilibrium MD trajectories for >1 μs time period. KDT-11 binds across the β6/β7/β8 strands and α-helix of Rpn-13, revealing an interface for inhibition that could be targeted in future computational drug discovery efforts to obtain more potent ligands for Rpn-13. It is reasonable that the methodology described here can extend to other flexible peptoid or peptide ligands in complexes with proteins.}, archive = {J_JACS}, author = {Christine S. Muli and Dan Xie and Carol Beth Post and Darci J. Trader}, doi = {10.1021/jacs.5c04064}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27403--27412}, shortjournal = {J. Am. Chem. Soc.}, title = {NMR-guided studies to establish the binding interaction between a peptoid and protein}, volume = {147}, year = {2025}, }
• (2025). Crystalline peptoid nanofibers with a single-unit cell cross section. JACS, 147(31), 27390--27402. (www)

  @article{ , abstract = {Ultranarrow crystalline one-dimensional nanostructures formed from soft materials facilitate precise structural control in nanomaterial design, which is essential for biomedicine and nanotechnology applications. Systematic control of their hierarchical structure is challenging due to the complexities of simultaneously manipulating multiple noncovalent interactions at such small scales. We employed a polypeptoid crystal motif as a supramolecular synthon to engineer ultranarrow crystalline nanofibers constrained to a single lattice axis by incorporating a single ionizable side chain into the hydrophobic core of a nanosheet-forming peptoid. Cryogenic transmission electron microscopy of the nanofibers revealed detailed molecular arrangements of a unit-cell cross-section and the presence of distinct pH-dependent lattice isoforms that resulted in morphological transformations. Molecular dynamics simulations demonstrated that the ionizable side chain plays a critical role in changing the local conformation of the unit cell, which further impacts the dimensionality of hierarchical structures. Moreover, these fibers were readily functionalized with biological ligands to afford one-dimensional (1D) protein arrays. This approach for the high-precision bottom-up assembly of ultranarrow 1D nanostructures offers significant potential for developing novel biomimetic nanostructures.}, archive = {J_JACS}, author = {Yen Jea Lee and Morgan Seidler and Xubo Luo and Glenn L. Butterfoss and Tianyi Yu and Behzad Rad and Sunting Xuan and Chenhui Zhu and David Prendergast and Nitash P. Balsara and Brooks A. Abel and Ronald N. Zuckermann and Xi Jiang}, doi = {10.1021/jacs.5c03996}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27390--27402}, shortjournal = {J. Am. Chem. Soc.}, title = {Crystalline peptoid nanofibers with a single-unit cell cross section}, volume = {147}, year = {2025}, }
• (2025). Achieving efficient electrocatalytic CO2-involved N-methylation on Cu–Ni–Al heterostructured catalysts. JACS, 147(31), 27377--27389. (www)

  @article{ , abstract = {Using CO 2 as the carbon source for electrocatalytic C–N coupling with organic amino compounds to achieve N-methylation reactions offers an appealing route for synthesizing valuable N-containing chemicals, mitigating CO 2 emissions, and storing renewable energy but is challenging. Herein, we report the first work to design heterostructured Cu–Ni–Al electrocatalysts for N-methylation. Using 4-hydroxypiperidine (PD) as a substrate, high electrocatalytic performance with a 1-methyl-4-piperidinol (MPD) faradaic efficiency (FE) of 29.3%, a N-methylation selectivity of 100%, a C-selectivity of 78.3%, and a formation rate of 15.4 mmol g –1 h –1 was achieved in the H-cell. It also showed remarkable recycling stability. Control experiments and in situ measurements confirmed the key role of the CuO/NiAl 2 O 4 heterostructure for the N-methylation reaction. Moreover, a combination of experimental and density functional theory (DFT) calculations demonstrated that CO 2 converted to the *H 2 CO intermediate on the CuO/NiAl 2 O 4 heterostructure, which underwent chemical condensation and subsequent reduction with nucleophilic amino compounds on the CuO/NiAl 2 O 4 heterostructure, leading to high efficiency toward N-methylation. Further investigation showed that this system could also be extended to other amino compounds.}, archive = {J_JACS}, author = {Xiaodong Ma and Xinning Song and Xingxing Tan and Libing Zhang and Shunhan Jia and Limin Wu and Ruhan Wang and Weixiang Li and Chaofeng Zheng and Lihong Jing and Xinchen Kang and Qinggong Zhu and Xiaofu Sun and Buxing Han}, doi = {10.1021/jacs.5c03413}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27377--27389}, shortjournal = {J. Am. Chem. Soc.}, title = {Achieving efficient electrocatalytic CO2-involved N-methylation on Cu–Ni–Al heterostructured catalysts}, volume = {147}, year = {2025}, }
• (2025). Phosphorus-driven dual d-band harmonization for reversible electrocatalysis. JACS, 147(31), 27367--27376. (www)

  @article{ , abstract = {To develop effective electrocatalysts, the d-band center theory has been a reliable predictor of electrocatalytic activity in transition-metal-based catalysts. However, it fails to accurately describe magnetic systems influenced by spin polarization. Herein, phosphorus doping was introduced into cobalt diselenide on a hive-like carbon framework with nitrogen insertion (P-CoSe 2 @NC), which significantly enhances electrocatalytic performance for reversible CO 2 conversion in an advanced Li–CO 2 battery with specific capacities around 17,000 mAh g –1 , high-rate performance, and good longevity exceeding 600 h in a pouch cell. Phosphorus doping induces lattice torsion in CoSe 2 , leading to strain-caused changes in the d-band center across different crystal planes, which are linked with the redistribution of spin states. To address the limitations of the traditional single d-band center model, the dual center model reveals how phosphorus doping effectively harmonizes the competition between spin orbitals, originating from changes in higher spin states. Such equilibrium moderates interactions with electrochemical intermediates to lower reaction energy barriers, enhancing reversible electrocatalysis for Li–CO 2 batteries. Therefore, strain-induced changes in the d-band centers, coupled with alterations in spin states, underline the enhanced electrocatalytic performance observed. This work provides novel insights into regulating bifunctional electrocatalytic activities in spin-polarized systems through a dual d-band center approach, utilizing nonmetal doping to optimize performance.}, archive = {J_JACS}, author = {Yiming Zhang and Lanling Zhao and Jun Wang and Yao Liu and Zidong Zhang and Wenwen Cai and Jizhen Ma and Jintao Zhang}, doi = {10.1021/jacs.5c03061}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27367--27376}, shortjournal = {J. Am. Chem. Soc.}, title = {Phosphorus-driven dual d-band harmonization for reversible electrocatalysis}, volume = {147}, year = {2025}, }
• (2025). Roles of three conserved active site residues of cytochrome c nitrite reductases during the early steps of nitrite reduction. JACS, 147(31), 27355--27366. (www)

  @article{ , abstract = {Cytochrome c nitrite reductases (ccNiRs) catalyze reduction of nitrite to ammonium in a six-electron, eight-proton process. This report explores how the behavior of three active site ccNiR variants differs from that of the wild type enzyme (ccNiR wt ) in the presence of nitrite and a variety of electron donors. While the nitrite-loaded active site of Shewanella oneidensis ccNiR wt could be 2-electron reduced within seconds to yield a 6-coordinate ferrous nitrosyl ({Fe(L)NO} 7 ) at high applied potentials, quantitative reduction of the nitrite-loaded variants R103Q, H257Q, or Y206F required substantially stronger reductants and yielded a different product over several hours. Thus, nitrite-loaded variant reduction by a large excess of hexaammineruthenium(II) yielded quantitatively, within 2 h, a species with UV–visible spectroscopic characteristics distinct from those obtained from nitrite-loaded ccNiR wt reduction. The same species was generated when the nitrite-loaded variants were treated with reduced indigo tetrasulfonate (I4S red ), but under these conditions, the species gradually disappeared unless the nitric oxide generator 1-( N , N -diethylamino)diazen-1-ium-1,2-diolate (DEANO) was also added to the reaction mixture. Characterization by electron paramagnetic resonance (EPR) spectroscopy of the variant species generated by I4S red reduction showed them to have a 5-coordinate {FeNO} 7 active site heme, in which the ligand L trans to the NO • had dissociated from the iron center. By contrast, L did not dissociate in the 2-electron reduced wild type ccNiR. Thus, the ccNiR active site residues R103, H257, and Y206 are all needed to facilitate fast {Fe(L)NO} 7 formation at high applied potentials, and to prevent dissociation of the trans ligand from {Fe(L)NO} 7 .}, archive = {J_JACS}, author = {Shahama Alam and Bradley J. Dimock and Brian Bennett and Steven J. Reinhardt and Shahid Shahid and A. Andrew Pacheco and Jarett Wilcoxen}, doi = {10.1021/jacs.5c03297}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27355--27366}, shortjournal = {J. Am. Chem. Soc.}, title = {Roles of three conserved active site residues of cytochrome c nitrite reductases during the early steps of nitrite reduction}, volume = {147}, year = {2025}, }
• (2025). Distal scaffold flexibility modulates eyring activation parameters in Re(I) substitution reactions: A case for dynamics as the “Thematic third coordination sphere”. JACS, 147(31), 27341--27354. (www)

  @article{ , abstract = {The use of dynamic ligand scaffolds to construct metal complexes with enhanced reactivity has recently emerged as an important research direction. Previous studies on ligand dynamics lay within the context of catalysis; thus, interpretation of the role dynamics in reactivity remained ambiguous among sequential chemical processes. Herein, we circumvent the complexity of catalytic systems by studying “simple” ligand substitution reactions. We previously reported the rigid Anth(py) 2 and dynamic Thianth(py) 2 ligands; in this work, we report two new dynamic ligands derived from the phenoxathiin scaffold, O Phxt(py) 2 and S Phxt(py) 2 . Rhenium tricarbonyl complexes of type [( L ( py 2 )Re(CO) 3 (X))] (where L(py 2 ) = Anth(py) 2 , Thianth(py) 2 , O Phxt(py) 2 , S Phxt(py) 2 ; X = Br, OTf) were synthesized and structurally investigated using IR spectroscopy and X-ray crystallography. Solution dynamics were investigated using variable temperature NMR. The impact of dynamics on reactivity was determined experimentally using Eyring analysis for bromide substitution onto the triflate complexes (OTf – →Br – ): a ∼ 10× enhanced rate constant was observed for the most dynamic complex compared with the least dynamic. Eyring activation parameters for ligand substitution displayed an enthalpy–entropy compensation effect, which we posit can be understood in terms of the conformational flexibility (or rigidity) of the complexes. The energetic landscape of the complexes were investigated computationally with potential energy surface scans and conformational searches (using the Conformer-Rotamer Ensemble Sampling Tool, CREST). Our findings suggest that ligand dynamics in transition metal systems enhance their reactivity, and ─ more generally ─ tuning ligand flexibility can be leveraged as a new design principle for the preparation of metal complexes with enhanced reactivity.}, archive = {J_JACS}, author = {Alec T. Larson and Serhii Vasylevskyi and Michael J. Rose}, doi = {10.1021/jacs.5c02268}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27341--27354}, shortjournal = {J. Am. Chem. Soc.}, title = {Distal scaffold flexibility modulates eyring activation parameters in Re(I) substitution reactions: A case for dynamics as the “Thematic third coordination sphere”}, volume = {147}, year = {2025}, }
• (2025). Strain-distinct α-synuclein and tau cross-seeding uncovered by correlative approach with optical photothermal infrared sub-micron imaging. JACS, 147(31), 27323--27340. (www)

  @article{ , abstract = {The co-occurrence of α-synuclein (αSyn) and Tau in synucleinopathies and tauopathies suggests a complex interplay between these proteins. Their cross-seeding enhances fibrillization, leading to the formation of diverse amyloid-specific structures enriched with β-sheets, which may influence their biological functions. However, existing tools cannot differentiate structural polymorphs directly in cells, as conventional microscopic approaches have limitations in providing structural insights into aggregates. As a result, a structurally relevant characterization of amyloids in their native cellular environment has not yet been achieved. In this study, we characterize the structural rearrangements of newly formed αSyn inclusions cross-seeded by different αSyn and Tau preformed fibrils (PFFs) directly in cells, using a correlative approach that combines submicron optical photothermal infrared (O-PTIR) microspectroscopy and confocal microscopy. We found that hybrid PFFs synthesized from αSyn, and two Tau isoforms (Tau3R and Tau4R) exhibit variations in αSyn and Tau composition. Specifically, structural polymorphs composed of αSyn and Tau3R exhibit the highest β-sheet content and most potent seeding potency, leading to enhanced phosphorylation within cellular inclusions. Importantly, we demonstrate that cellular inclusions inherit structural motifs from their donor seeds and exhibit distinct spatial and structural evolution. By providing subcellular-resolution structural imaging of amyloid proteins, our study uncovers divergent mechanisms of αSyn aggregation induced by αSyn/Tau PFFs in both mixed and hybrid formats.}, archive = {J_JACS}, author = {Xiaoni Zhan and Wen Li and Eric Hatterer and Jean-Philippe Courade and Kristin Piché and Oxana Klementieva and Jia-Yi Li}, doi = {10.1021/jacs.5c02811}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27323--27340}, shortjournal = {J. Am. Chem. Soc.}, title = {Strain-distinct α-synuclein and tau cross-seeding uncovered by correlative approach with optical photothermal infrared sub-micron imaging}, volume = {147}, year = {2025}, }
• (2025). Limestone conversion to cement clinker precursor in a zero-gap electrolyzer. JACS, 147(31), 27314--27322. (www)

  @article{ , abstract = {The carbon intensity of industrial cement production could be reduced by replacing the high-temperature kilns used to decompose limestone (CaCO 3(s) ). One possible solution is to use electrochemical reactors to convert CaCO 3(s) into Ca(OH) 2(s) . The challenge is that most continuous-flow electrochemical reactors reported to date require voltages that are too high (>4 V at 100 mA cm –2 ) to be practical. A key reason for these high voltages is that the reactors contain a chemical chamber inserted between the anode and cathode chambers, which leads to a high Ohmic resistance. In this study, we present an electrolyzer that decomposes CaCO 3(s) into reactive Ca 2+ ions using only two chambers. This cell design, with an anode and cathode chamber separated by a membrane instead of a chemical chamber, follows a “zero-gap” configuration akin to hydrogen-producing electrolyzers and fuel cells. We also engage the reversible redox activity of (hydro)anthraquinones to mediate oxidation and reduction within a narrow electrochemical window. The streamlined “cement electrolyzer” is capable of operating at an initial full cell voltage of 0.38 V at 100 mA cm –2 with 100% proton efficiency.}, archive = {J_JACS}, author = {Tengxiao Ji and Shaoxuan Ren and Gaopeng Jiang and Yumeng Yang and Siwei Ma and Christopher E. B. Waizenegger and Yongwook Kim and Andrew M. L. Jewlal and Monika Stolar and Curtis P. Berlinguette}, doi = {10.1021/jacs.5c02266}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27314--27322}, shortjournal = {J. Am. Chem. Soc.}, title = {Limestone conversion to cement clinker precursor in a zero-gap electrolyzer}, volume = {147}, year = {2025}, }
• (2025). Intermolecular interactions in direct air capture materials: Insights from charge density analysis. JACS, 147(31), 27299--27313. (www)

  @article{ , abstract = {Direct air capture (DAC) materials enable the removal of CO 2 from the atmosphere, but improving their efficiency requires a detailed understanding of the intermolecular interactions that govern CO 2 sorption and release. Here, we present an experimental electron density study of methylglyoxal-bis(iminoguanidine) (MGBIG), a promising DAC material, using high-resolution X-ray and neutron diffraction data combined with quantum crystallographic analysis. This approach bridges theoretical and experimental data by quantifying electron density distributions and revealing how hydrogen bonds stabilize CO 2 -derived carbonate phases and may influence the desorption behavior. We identify distinct hydrogen-bonding environments in two crystalline carbonate phases: P1, a transient kinetic product, and P3, a thermodynamically stable phase. Multipolar refinement and electrostatic potential and multipole moment calculations precisely map electron density distributions, revealing key hydrogen bonds involved in CO 2 capture. Topological analysis of electron density highlights a cooperative hydrogen-bonding network in the thermodynamically favored P3 phase, where enhanced electron density delocalization and water-mediated interactions contribute to a more stable lattice. Energetic analyses confirm that stronger hydrogen bonding networks enhance the stability of P3 with a binding energy of −607.0 kJ/mol and greater lattice stability (−847.3 kJ/mol) compared to P1 (−302.5 and −571.0 kJ/mol, respectively). Electrostatic potential maps further illustrate polarization patterns that may influence the stability of the binding of CO 2 and release conditions. These findings establish a direct experimental framework for linking electron density distributions to intermolecular interactions in DAC materials, providing a rational design strategy for optimizing sorbents with improved CO 2 capture efficiency and reduced energy demands.}, archive = {J_JACS}, author = {Sylwia Pawledzio and Jeffrey Einkauf and Radu Custelcean and Xiaoping Wang}, doi = {10.1021/jacs.5c01946}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27299--27313}, shortjournal = {J. Am. Chem. Soc.}, title = {Intermolecular interactions in direct air capture materials: Insights from charge density analysis}, volume = {147}, year = {2025}, }
• (2025). Enabling ethanol dehydrogenation catalysis by postsynthetic anion exchange of triazolate-based Metal–Organic frameworks. JACS, 147(31), 27289--27298. (www)

  @article{ , abstract = {Materials containing soft, polarizable elements are expanding the boundaries of catalytic properties, offering unique electronic communication and stability characteristics compared with their harder counterparts due to the enhanced covalent nature of metal–ligand interactions. However, integrating soft components like sulfur into metal–organic frameworks (MOFs) for catalytic applications remains a largely underexplored challenge. Here, we report the synthesis of a family of triazole-based MOFs and expand upon established postsynthetic anion exchange methods to incorporate sterically encumbered polarizable elements, such as alkyl thiolates. Single-crystal X-ray diffraction, coupled with elemental analysis, confirms the successful anion exchange within M 2 X 2 BBTA ( M = Co, Ni; X = μ-Cl, μ-OH, μ-SH, μ-SMe, μ-SEt; H 2 BBTA = 1 H ,5 H -benzo(1,2- d :4,5- d ′)bistriazole). We found that the anion identity significantly impacts the catalytic activity and selectivity of the MOFs, especially in nonoxidative ethanol dehydrogenation. Temperature-programmed experiments indicated that the metal single sites act as catalytically active sites below 250 °C. This work not only expands the synthetic toolbox for incorporating polarizable components into MOFs but also provides critical insights into their catalytic potential.}, archive = {J_JACS}, author = {Dawson A. Grimes and Hongjun Park and Courtney S. Smoljan and Haomiao Xie and Justin M. Notestein and Omar K. Farha}, doi = {10.1021/jacs.5c02064}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27289--27298}, shortjournal = {J. Am. Chem. Soc.}, title = {Enabling ethanol dehydrogenation catalysis by postsynthetic anion exchange of triazolate-based Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Chemostructurally stable polyionomer coatings regulate proton-intermediate landscape in acidic CO2 electrolysis. JACS, 147(31), 27278--27288. (www)

  @article{ , abstract = {CO 2 electroreduction (CO 2 R) in acidic media offers a path to high carbon utilization via local carbonate regeneration. However, this proton-rich environment challenges achieving a combined selectivity and rate toward multicarbon (C 2+ ) products due to proton and intermediate competition. Here, we demonstrate a strategy to modulate local protons and intermediates, at these settings, using a polyionomer coating over benchmark copper gas diffusion electrodes. The polyionomer integrates amine (−NH x ) function from branched polyethylenimine (PEI) with sulfonate (−SO 3 – ) and amphiphilic functions from PFSA. We show that their chemical structure enables H-bonding interaction, leading to a stereochemical assembly that retains a structure–property relationship through a wide pH range (2–14). PFSA domains modulate *CO intermediates and local [CO 2 ]/[H 2 O] and K + environment, while partially protonated amines provide further control over proton availability and intermediate stabilization, which in combination enhance C–C coupling. When implemented in a flow cell (0.5 M K 2 /H 2 SO 4 , pH = 2), the optimized polyionomer coating enables a C 2+ Faradaic efficiency of 61% at a single-pass CO 2 utilization of 84%, including a conversion efficiency of 64% toward C 2+ , at a current density of at 0.3 A cm –2 ─an improvement of almost 30% in C 2+ selectivity and 35% in carbon utilization compared to monofunctional coatings. These findings expand the toolbox of strategies to modulate CO 2 R microenvironments toward improved performance.}, archive = {J_JACS}, author = {Bárbara Polesso and Adrián Pinilla-Sánchez and Eman H. Ahmed and Anku Guha and Marinos Dimitropoulos and Blanca Belsa and Viktoria Golovanova and Lu Xia and Ranit Ram and Sunil Kadam and Aparna M. Das and Junmei Chen and Johann Osmond and Adam Radek Martínez and Melanie Micali and Esther Alarcón Lladó and F. Pelayo García de Arquer}, doi = {10.1021/jacs.5c01314}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27278--27288}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemostructurally stable polyionomer coatings regulate proton-intermediate landscape in acidic CO2 electrolysis}, volume = {147}, year = {2025}, }
• (2025). Local cation-ordered superlattice stabilizing ni-rich single-crystalline cathodes. JACS, 147(31), 27265--27277. (www)

  @article{ , abstract = {Ni-rich single-crystalline cathodes are pivotal for advancing lithium-ion battery technology due to their high energy density and mechanical stability. However, Ni-rich single-crystalline particles face intrinsic structural heterogeneity due to excessively high sintering temperature required to shape micron-sized morphologies─typically over 150 °C above the polycrystalline optimum, leading to rapid electrochemical decay and unsatisfied rate performance that hinder their practical application. Here, we propose a lithium-deficient presintering strategy to synthesize cation-ordered single-crystalline LiNi 0.83 Co 0.12 Mn 0.05 O 2 (S-NCM83), effectively minimizing lattice chemical heterogeneity and defect formation. The resulting cation-ordered percolation network enhances the structural stability of the bulk, reduces the energy barrier for Li + migration, and stabilizes Li + diffusion pathways. Consequently, S-NCM83 demonstrates significantly improved cycling stability across various operating temperatures and achieves exceptional rate performance, delivering 206 mAh g –1 at 0.1 C and 170 mAh g –1 at 5 C, without requiring surface coatings or doping. This work introduces a universal strategy to address the long-standing structural instability issues in single-crystalline cathodes, paving the way for simplified and scalable approaches to long-life and high-energy lithium-ion batteries.}, archive = {J_JACS}, author = {Tao Huang and Weiyuan Huang and Pei Liu and Yang Gu and Xiangzhong Ren and Jianhong Liu and Xianghui Xiao and Khalil Amine and Qianling Zhang and Biwei Xiao and Tongchao Liu and Jiangtao Hu}, doi = {10.1021/jacs.5c00615}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27265--27277}, shortjournal = {J. Am. Chem. Soc.}, title = {Local cation-ordered superlattice stabilizing ni-rich single-crystalline cathodes}, volume = {147}, year = {2025}, }
• (2025). Ferromagnetic bimetallic catalysts enhance the overall performance of Lithium–Sulfur batteries under a magnetic field. JACS, 147(31), 27251--27264. (www)

  @article{ , abstract = {Sluggish reaction kinetics and severe dendrite growth are two main obstacles that hinder lithium–sulfur batteries (LSBs) from practical applications. Here, unconventionally d–p hybridized ferromagnetic Fe 3 M (M = Al, Si, Ga, Ge, Sn) materials are studied as the electrocatalysts and conductive scaffolds for LSBs. This reveals that under a magnetic field, the d–p hybridization can be obviously enhanced via the electron cloud overlap between M and Fe atoms around the Fermi level, thereby leading to highly improved kinetics of the entire Li–S reactions. Furthermore, the magnetic field and magnetized Fe 3 M can locally regulate the diffusion pathways of Li + through the Lorentz force, facilitating uniform lithium deposition. With Fe 3 Ga as the optimal option, under a magnetic field of 280 mT, the Fe 3 Ga@CNF/S cathode delivers specific capacities of 1343.3 and 1091.7 mA h g –1 , respectively, at 0.1C and 3.0C, along with an ultralow capacity decay rate of only 0.0065% for 300 cycles at 10.0C, while the Fe 3 Ga@CNF/Li anode maintains a low overpotential of 24.5 mV over 100 days of cycling at 5 mA cm –2 . Consequently, the performances of the Li–S full cell with the Fe 3 Ga@CNF/S cathode and the Fe 3 Ga@CNF/Li anode are significantly improved, producing a capacity of 1027.1 mA h g –1 at 0.2C and 657.5 mA h g –1 at 3.0C, and a Li–S pouch cell with a sulfur loading of 0.146 g delivers a high specific energy density of 317 Wh kg –1 when tested under the magnetic field.}, archive = {J_JACS}, author = {Guowen Sun and Chao Yue Zhang and Mengjing Jin and Jiayue Li and Xiaojun Pan and Andreu Cabot and Gengzhi Sun and Jin Yuan Zhou}, doi = {10.1021/jacs.4c15169}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27251--27264}, shortjournal = {J. Am. Chem. Soc.}, title = {Ferromagnetic bimetallic catalysts enhance the overall performance of Lithium–Sulfur batteries under a magnetic field}, volume = {147}, year = {2025}, }
• (2025). Au-catalyzed aerobic dehydrogenative aromatization to m-phenylenediamine derivatives via product selectivity control. JACS, 147(31), 27238--27250. (www)

  @article{ , abstract = {m -Disubstituted arenes are important in various fields but difficult to be directly synthesized by classical methods in the case of two electron-donating substituents due to the o , p -orientation. Dehydrogenative aromatization from nonaromatic cyclohexenone motifs and nucleophiles via 1,2- and 1,4-addition to produce m -disubstituted arenes is promising as the novel process overcoming the intrinsic problems derived from using aromatic compounds as the substrates; however, there are no reports on tandem oxidation involving dehydrogenative aromatization for one-step synthesis via simultaneous 1,2- and 1,4-addition or m -phenylenediamine derivative synthesis because of the quite difficult product selectivity control. Here, by utilizing the unique dehydrogenation catalysis of CeO 2 -supported Au nanoparticles, we have developed one-step synthesis of various m -phenylenediamine derivatives via selective aerobic dehydrogenative aromatization from cyclohexenone motifs and secondary amines. In addition, the product selectivity switch to enaminones or N , N -disubstituted anilines was also achieved by tuning the reaction conditions.}, archive = {J_JACS}, author = {Heizo Kimura and Takafumi Yatabe and Kazuya Yamaguchi}, doi = {10.1021/jacs.4c12043}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27238--27250}, shortjournal = {J. Am. Chem. Soc.}, title = {Au-catalyzed aerobic dehydrogenative aromatization to m-phenylenediamine derivatives via product selectivity control}, volume = {147}, year = {2025}, }
• (2025). Induced bioconjugation via on-demand isocyanate formation. JACS, 147(31), 27232--27237. (www)

  @article{ , abstract = {Selective bioconjugation reactions, exemplified by bioorthogonal chemistry, constitute a fundamental and broadly applicable tool across diverse fields, enabling precise biomolecular modifications in complex biological environments. Despite significant progress, the application of highly reactive electrophilic warheads, such as isocyanates, remains constrained by a trade-off between reactivity and selectivity, as well as hydrolytic decomposition. Here, we report a novel bioconjugation strategy that generates isocyanates on demand from a stable hydroxamic acid–pyrrolidine conjugate precursor and a sulfonyl fluoride activator. Utilizing rapid and reversible boronic ester formation, this “isocyanate surrogate” approach enables selective protein labeling with reaction rates reaching up to 10 4 M –1 s –1 . Our findings highlight the utility of this strategy as a practical and versatile tool for inducible and selective biomolecular labeling in biological systems.}, archive = {J_JACS}, author = {Yuki Yamanashi and Menghan Xu and Shigehiro A. Kawashima and Motomu Kanai}, doi = {10.1021/jacs.5c11603}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27232--27237}, shortjournal = {J. Am. Chem. Soc.}, title = {Induced bioconjugation via on-demand isocyanate formation}, volume = {147}, year = {2025}, }
• (2025). Cooperative bimetallic radical catalysis enables asymmetric hydrogen-atom transfer. JACS, 147(31), 27224--27231. (www)

  @article{ , abstract = {Achieving precise stereocontrol in asymmetric hydrogen-atom transfer (HAT) reactions is a central challenge in radical chemistry, particularly in nonenzymatic systems. Existing approaches primarily rely on carbon-centered radicals and conventional hydrogen donors with inherently weak X–H bonds, which are prone to racemic background processes and suffer from limited donor diversity. Herein, we report a new conceptual approach: cooperative bimetallic radical catalysis that enables asymmetric HAT without the formation of carbon radicals. This cooperative system employs two titanium catalysts to independently activate both the hydrogen donor and acceptor, facilitating a concerted HAT process with excellent stereochemical communication. This strategy expands the accessible scope of HAT chemistry by unlocking the use of unconventional hydrogen donors, such as imidazole, beyond constraints of weak X–H bonds. Mechanistic studies support the proposed dual activation and concerted HAT pathway. This work represents an intriguing mode in asymmetric HAT, providing a sustainable platform for stereoselective radical transformations.}, archive = {J_JACS}, author = {Jian Shen and Fangkun Wang and Zhiyuan Ma and Jie Jiang and Yong-Qiang Zhang}, doi = {10.1021/jacs.5c10189}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27224--27231}, shortjournal = {J. Am. Chem. Soc.}, title = {Cooperative bimetallic radical catalysis enables asymmetric hydrogen-atom transfer}, volume = {147}, year = {2025}, }
• (2025). Enantioselective total synthesis of bipolarolides a and b. JACS, 147(31), 27219--27223. (www)

  @article{ , abstract = {Bipolarolides A and B are members of the ophiobolin family of sesterterpenes, characterized by their intricate cage-like structures. Herein we report a concise asymmetric total synthesis of bipolarolides A and B enabled by the type-II Diels–Alder reaction. The synthesis features a sequence of key transformations: an iridium-catalyzed enantioselective allylation to establish the first stereocenter, type-II Diels–Alder reaction to rapidly assemble the bicyclo[3.3.1]non-1-ene core, reductive oxy-ring opening with olefin isomerization, aldol cyclization to construct a D ring, and a late-stage electrochemical C–H oxidation to complete the ether ring.}, archive = {J_JACS}, author = {Yufei Liu and Ke Sun and Qi Wei and Jin Chen and Shengling Sun and Yaxin Li and Zhongkai Feng and Yingying Guo and Zhaohong Lu}, doi = {10.1021/jacs.5c09835}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27219--27223}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective total synthesis of bipolarolides a and b}, volume = {147}, year = {2025}, }
• (2025). Interfacial electric fields modulate redox reactions in abiological coacervates. JACS, 147(31), 27213--27218. (www)

  @article{ , abstract = {Biomolecular condensates formed by liquid–liquid phase separation (LLPS) establish gradients of biomolecules and ions across the dilute–dense interface, giving rise to interfacial electric fields (IEFs) that can drive redox reactions. Here, we demonstrate that such electrochemical behavior is not exclusive to biological systems. By using polyelectrolyte–counterion interactions to induce phase separation, we formed synthetic coacervates that exhibit surface electrical potentials. The resulting IEFs liberate reactive species such as hydroxyl radicals and electrons from hydroxide ions, leading to detectable redox activity. These findings reveal that LLPS-driven electrochemical functions are not limited to biology and can be harnessed in designed abiological systems to mimic the biochemical roles of cellular condensates.}, archive = {J_JACS}, author = {Fei Zhang and Yinqi Tian and Hongshuai Wei and Tongqing Yue and Yu Gao and Xiaoxu Li and Richard N. Zare and Xinxing Zhang and Zejun Wang}, doi = {10.1021/jacs.5c09651}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27213--27218}, shortjournal = {J. Am. Chem. Soc.}, title = {Interfacial electric fields modulate redox reactions in abiological coacervates}, volume = {147}, year = {2025}, }
• (2025). Propargylic alcohol as a key substrate motif for achieving enantioselective gold-catalyzed enyne cycloisomerization. JACS, 147(31), 27207--27212. (www)

  @article{ , abstract = {Despite successes in achieving asymmetric induction in enyne cycloisomerization, few systems are applicable to each of the typical 6- endo , 5- exo , and 5- endo cyclization/cycloisomerization modes. By appending a synthetically valuable hydroxymethyl group at the alkyne end, a hydrogen bond between the HO group of the propargyl alcohol moiety and a chiral ligand basic group offers a novel asymmetric induction strategy in gold-catalyzed enyne cycloisomerization reactions. Both 1,5-enynes and 1,6-enynes are suitable substrates, and 5- exo , 5- endo , and 6- exo cyclizations lead to outstanding enantioselectivities. As a valuable reactive moiety, the hydroxymethyl group is converted into a versatile aldehyde moiety in the exo cyclization modes or engages in enantioselective cyclizations in a ligand-dictated chemodivergent process. This strategy may further advance asymmetric gold catalysis.}, archive = {J_JACS}, author = {Yue Li and Xuan Wu and Kaylaa Gutman and Jielin Yang and Liming Zhang}, doi = {10.1021/jacs.5c08821}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27207--27212}, shortjournal = {J. Am. Chem. Soc.}, title = {Propargylic alcohol as a key substrate motif for achieving enantioselective gold-catalyzed enyne cycloisomerization}, volume = {147}, year = {2025}, }
• (2025). Remote-markovnikov hydrobromination and hydrochlorination of allyl carboxylates via dual Photoredox/Cobalt catalysis. JACS, 147(31), 27197--27206. (www)

  @article{ , abstract = {Alkyl halides are ubiquitous motifs in pharmaceuticals, agrochemicals, and materials, yet direct access to regioisomeric variants remains limited. Conventional hydrohalogenation of alkenes proceeds via ionic or radical pathways and is generally confined to 1,2-addition. Here, we report a dual cobalt/photoredox catalytic platform that enables remote -Markovnikov-selective 1,3-hydrobromination and hydrochlorination of allyl carboxylates. The transformation proceeds via a metal–hydride hydrogen atom transfer (MHAT) from a Co–H species, 1,2-radical acyloxy migration (1,2-RAM), and halogen atom transfer (XAT) from a Co–X complex. This strategy delivers β-acyloxy alkyl halides under mild conditions, with broad functional group tolerance, compatibility with complex molecules, and scalability. Mechanistic experiments support a radical relay sequence that diverges from classical regioselectivity to access formal 1,3-addition products. This work establishes a general approach to regioselective C–X bond formation via programmable radical migration and expands the synthetic toolbox for alkene hydrofunctionalization.}, archive = {J_JACS}, author = {Arman Khosravi and Yu Zhang and Gaoyuan Zhao and Kelton J. Radefeld and Sahil Sharma and Nuwan A. Pannilawithana and Yuxiang Zhang and Peng Liu and Ming-Yu Ngai}, doi = {10.1021/jacs.5c08537}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27197--27206}, shortjournal = {J. Am. Chem. Soc.}, title = {Remote-markovnikov hydrobromination and hydrochlorination of allyl carboxylates via dual Photoredox/Cobalt catalysis}, volume = {147}, year = {2025}, }
• (2025). Spotlight on mechanosterics: A bulky macrocycle promotes functional group reactivity in a [2]Rotaxane. JACS, 147(31), 27192--27196. (www)

  @article{ , abstract = {Macrocycles typically hinder the reactivity of adjacent functional groups in mechanically interlocked molecules due to steric shielding. Herein, we report a [2]rotaxane in which a bulky macrocycle in fact accelerates deprotection of a Fmoc-derived stopper by 36-fold compared to a non-interlocked control. We rationalize this by a preorganization of the macrocycle and the stopper, exposing its reactive site for base abstraction. This is evidenced by extensive NMR, SC-XRD, and DFT studies, revealing highly directional CH−π interactions and hydrogen bonding between the interlocked components. Our findings highlight and structurally rationalize how entanglement can instead promote reactivity through precise spatial control. This concept paves the way for designing molecular machines with functional, reactivity-enhancing components.}, archive = {J_JACS}, author = {Thomas Pickl and Claire Stark and Diego Briganti and Massimiliano Curcio and Alexander Pöthig}, doi = {10.1021/jacs.5c08210}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27192--27196}, shortjournal = {J. Am. Chem. Soc.}, title = {Spotlight on mechanosterics: A bulky macrocycle promotes functional group reactivity in a [2]Rotaxane}, volume = {147}, year = {2025}, }
• (2025). Catalytic borylation of poly(vinyl chloride) produces adhesive materials. JACS, 147(31), 27186--27191. (www)

  @article{ , abstract = {Postpolymerization functionalization of polymers can create new applications for existing materials, while retaining their most favorable, intrinsic properties. Polyvinyl chloride (PVC) is a widely used, commodity polymer that is particularly challenging to modify. We report a copper-catalyzed protocol that replaces a small fraction of the C–Cl bonds in PVC with C–B bonds to boronic esters. The reaction occurs with an inexpensive catalyst comprising copper(II) chloride and an NHC ligand derived from a common ionic liquid that is distinct from the N-heterocyclic carbene (NHC) used for the borylation of small alkyl halides. The resulting materials adhere strongly to common surfaces, such as glass and metals, even more strongly than do commercial glues.}, archive = {J_JACS}, author = {Kyan A. D’Angelo and Nathan Sun and Nicodemo R. Ciccia and Isaac F. Yu and Brett A. Helms and John F. Hartwig}, doi = {10.1021/jacs.5c08083}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27186--27191}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic borylation of poly(vinyl chloride) produces adhesive materials}, volume = {147}, year = {2025}, }
• (2025). Fully recyclable and remarkably robust cross-linked polyethylene networks via direct free-radical copolymerization with disulfide dynamic covalent bonds. JACS, 147(31), 27179--27185. (www)

  @article{ , abstract = {Cross-linked polyethylene (XLPE) is a commercially important polyolefin thermoset that suffers from nonrecyclability due to its permanent cross-links. Herein, we report the first in-reactor synthesis of dynamic covalently cross-linked polyethylene or polyethylene covalent adaptable networks (PE CANs) via free-radical copolymerization of ethylene and bis(2,2,6,6-tetramethyl-4-piperidyl methacrylate) disulfide (BTMA). BTMA is a bifunctional comonomer containing a dissociative dynamic disulfide bond. These PE CANs exhibit high crystallinity, outstanding dimensional stability, high-temperature creep resistance, and robust thermomechanical properties comparable to commercial XLPE. Crucially, our PE CANs demonstrate full recovery of cross-link density and thermomechanical performance after recycling. Stress relaxation studies reveal viscoelastic behavior enabled by cross-link exchange but dominated by polymer chain reptation, resulting in activation energies aligned with those of long-chain-branched PE melts. This work presents a novel, scalable method for free-radical copolymerization of recyclable PE CANs, offering a more sustainable alternative to XLPE.}, archive = {J_JACS}, author = {Logan M. Fenimore and Mathew J. Suazo and Sarah Mitchell and Hadi Mohammadi and Kimberly Miller McLoughlin and Cassandra Gallaschun and Patryk Sewruk and Markus Busch and John M. Torkelson}, doi = {10.1021/jacs.5c07720}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27179--27185}, shortjournal = {J. Am. Chem. Soc.}, title = {Fully recyclable and remarkably robust cross-linked polyethylene networks via direct free-radical copolymerization with disulfide dynamic covalent bonds}, volume = {147}, year = {2025}, }
• (2025). Predictions of steady-state photo-CIDNP enhancement by machine learning. JACS, 147(31), 27172--27178. (www)

  @article{ , abstract = {Photochemically induced dynamic nuclear polarization (photo-CIDNP) is a hyperpolarization method used to boost signal sensitivity in NMR spectroscopy. So far, there is no theory to predict the steady-state photo-CIDNP enhancement reliably, and hence, suitable target molecules need to be identified through tedious experimental screenings. Here, we explore the use of machine learning to predict steady-state photo-CIDNP enhancement. For a series of 27 indole-, five amino-acid-, and eight phenol-derivatives, the signal-to-noise enhancement (SNE) of steady-state photo-CIDNP experiments was measured and then connected to a combination of eight molecular features. The nucleophilic Fukui index was identified as a strong qualitative indicator of the site with the highest SNE in each molecule. Furthermore, a semiquantitative machine learning model based on Logistic Regression identified the sites with high enhancements (SNE > 90) in 100% of cases. Among several quantitative machine learning models for enhancement prediction, CatBoost Regressor and K-Nearest Neighbors showed the best performance. The results demonstrate the high potential of machine learning approaches for predictions of photo-CIDNP SNE, which will enable virtual prescreening of compound libraries.}, archive = {J_JACS}, author = {Marta Stefańska and Thomas Müntener and Sebastian Hiller}, doi = {10.1021/jacs.5c07462}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27172--27178}, shortjournal = {J. Am. Chem. Soc.}, title = {Predictions of steady-state photo-CIDNP enhancement by machine learning}, volume = {147}, year = {2025}, }
• (2025). Enzymatic stereodivergent synthesis of azaspiro[2.y]alkanes. JACS, 147(31), 27165--27171. (www)

  @article{ , abstract = {Azaspiro[2.y]alkanes are increasingly valuable scaffolds in pharmaceutical drug discovery; however, an asymmetric catalytic method for their synthesis remains unknown. Here, we present a stereodivergent carbene transferase platform for the cyclopropanation of unsaturated exocyclic N -heterocycles to provide structurally diverse and pharmaceutically relevant azaspiro[2.y]alkanes in high yield (21–>99% yield) and excellent diastereoselectivity and enantioselectivity (diastereomeric ratio (dr) values from 52.5:47.5 to >99.5:0.5; enantiomeric ratio (er) values from 51:49 to >99.5:0.5). These engineered protoglobin-based enzymes operate on gram scale, with no organic cosolvent, at substrate concentrations up to 150 mM (25 g/L) using lyophilized E. coli lysate as the catalyst. This platform represents a practical, scalable, and stereodivergent biocatalytic synthesis of azaspiro[2.y]alkanes, using low-cost engineered protoglobins and their native iron-heme cofactors.}, archive = {J_JACS}, author = {Jennifer L. Kennemur and Yueming Long and Catherine J. Ko and Anuvab Das and Frances H. Arnold}, doi = {10.1021/jacs.5c07015}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27165--27171}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzymatic stereodivergent synthesis of azaspiro[2.y]alkanes}, volume = {147}, year = {2025}, }
• (2025). Cobalt-catalyzed asymmetric reductive coupling of isocyanates with tertiary alkyl halides for sterically bulky chiral amide synthesis. JACS, 147(31), 27155--27164. (www)

  @article{ , abstract = {The ubiquity of amide bonds in pharmaceuticals, agrochemicals, natural products, and peptides underscores the enduring demand for efficient amide synthesis in organic chemistry. Nevertheless, the facile construction of sterically congested chiral amides bearing α-quaternary stereogenic centers remains a formidable synthetic challenge. Herein, we report a catalytic reductive addition strategy that leverages readily accessible and stable isocyanates for stereoselective carbon–carbon bond formation. Enabled by earth-abundant chiral cobalt catalysis, this method achieves the enantioconvergent amidation of racemic tertiary alkyl halides, delivering α-tetrasubstituted amides with sterically demanding quaternary stereocenters. By circumventing the use of organometallic reagents, this unprecedented enantioselective alkylative reductive addition accommodates a broad substrate scope, including structurally diverse isocyanates and α-chloro tertiary amides, while achieving exceptional enantioselectivity (up to 99% ee). Preliminary mechanistic studies demonstrate a radical addition mechanism that is operative in this reductive amidation process.}, archive = {J_JACS}, author = {Wenyu Zhao and Yiwen Shen and Xianqing Wu and Tingting Xia and Jiangtao Hu and Jingping Qu and Yifeng Chen}, doi = {10.1021/jacs.5c06669}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27155--27164}, shortjournal = {J. Am. Chem. Soc.}, title = {Cobalt-catalyzed asymmetric reductive coupling of isocyanates with tertiary alkyl halides for sterically bulky chiral amide synthesis}, volume = {147}, year = {2025}, }
• (2025). Harnessing O-vinylhydroxylamines for ring-annulation: A scalable approach to azaindolines and azaindoles. JACS, 147(31), 27148--27154. (www)

  @article{ , abstract = {We report a convenient and scalable strategy for the synthesis of 7-azaindolines and 7-azaindoles using O -vinylhydroxylamines as ring-annulation reagents. These fused nitrogen-containing heterocycles are prominent in numerous biologically active molecules, including FDA-approved pharmaceuticals. Traditional synthetic approaches to these motifs often rely on costly transition metal catalysts and/or high-temperature conditions, such as those employed in the Larock and Fischer indole syntheses. In our approach, O -vinylhydroxylamines undergo N-arylation with aza-arene N -oxides, triggering a rapid [3,3]-sigmatropic rearrangement. This is followed by rearomatization and cyclization to deliver 7-azaindolines, which can be readily dehydrated to afford the corresponding 7-azaindoles. The method offers a broad substrate scope, enabling access to a diverse array of highly functionalized derivatives. Moreover, the mild reaction conditions facilitate late-stage functionalization of complex molecules, demonstrating their value in both synthetic and medicinal chemistry.}, archive = {J_JACS}, author = {Zachary Grimm and Charlotte Randolph and Oleksandr Buravov and Pavel Mykhailiuk and László Kürti}, doi = {10.1021/jacs.5c06568}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27148--27154}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing O-vinylhydroxylamines for ring-annulation: A scalable approach to azaindolines and azaindoles}, volume = {147}, year = {2025}, }
• (2025). Breaking a lewis acidity trend for rare earths by excited state quenching. JACS, 147(31), 27143--27147. (www)

  @article{ , abstract = {Facilitating different chemistries between the rare earth (RE = La–Lu, Sc, Y) ions is of significant interest for their separations. While the bulk of attention has been on maximizing the small differences in their ground state chemistry, interest is beginning to shift toward the differences in their electronic excited states. In this work, we demonstrate modulation of the photostationary state of an azobenzene derivative, Na 1 , via chelation to a series of RE III DO3A (DO3A = 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) complexes. The extent of photoisomerization of 1 – follows the trend in RE III Lewis acidity with two exceptions: Sm III and Er III . UV–vis spectroscopy, titration experiments, and computational analysis show that these exceptions are a result of energy transfer rather than differences in ground state chemistry. These results open a pathway to differentiate REs by new photochemical means.}, archive = {J_JACS}, author = {Randall K. Wilharm and Michael R. Gau and Dirk Trauner and Eric J. Schelter}, doi = {10.1021/jacs.5c05257}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27143--27147}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking a lewis acidity trend for rare earths by excited state quenching}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of paxdaphnine a and daphlongamine b via an aza-prins cyclization strategy. JACS, 147(31), 27137--27142. (www)

  @article{ , abstract = {Paxdaphnine A ( 1 ) and daphlongamine B ( 2 ) are two heptacyclic Daphniphyllum alkaloids, each containing eight consecutive stereogenic centers. We achieved the first synthesis of these molecules in racemic form by using a biomimetic aza-Prins cyclization strategy. Paxdaphnine B ( 3 ), a putative biogenetic precursor of 1 and 2 , was also obtained in the synthesis. A pentacyclic analogue of 3 was prepared in a scalable manner and served as a common intermediate. The sterically congested cyclopentane moiety of this intermediate was constructed via a nitrone–olefin cycloaddition reaction, and the assembly of its diquinane motif relied on an intramolecular Pauson–Khand reaction. Despite the unsatisfactory outcome of the initial biomimetic aza-Prins reaction of 3 with HCHO, we utilized the N -cyanomethyl derivative of 3 as an alternative substrate in combination with AgTFA as a promoter to rescue the biomimetic route to 1 . On the basis of a similar strategy, an aza-Prins cyclization–lactonization cascade, involving a different terminating nucleophile, was developed for the synthesis of 2 .}, archive = {J_JACS}, author = {Lu Ren and Zhaohong Lu and Dimin Wu and Mingchen Ma and Ang Li}, doi = {10.1021/jacs.4c04779}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27137--27142}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of paxdaphnine a and daphlongamine b via an aza-prins cyclization strategy}, volume = {147}, year = {2025}, }
• (2025). Photocurrent experiments as probes and prods in large-area molecular electronic junctions. JACS, 147(31), 27122--27136. (www)

  @article{ , abstract = {Since its experimental realization in the late 1990s, molecular electronics (ME) has received significant attention due to its unique charge transport behavior that occurs over nanoscale dimensions. The molecular junction (MJ), wherein single molecules or arrays of parallel molecules are oriented between two metallic electrodes is the fundamental building block of ME. Specifically, temperature-independent quantum mechanical tunneling across a few nanometers in MJs is distinct from transport in organic or inorganic semiconductors and may be valuable for next-generation electronics. Although molecular tunneling junctions have been introduced commercially, fundamental questions remain about the control of charge transport in various MJs, including those containing proteins and DNA. Examples include: (i) Does molecular structure play an important role in charge transport? (ii) What is the effective barrier (tunneling or any other) for transport in MJs? (iii) Does the molecular structure remain intact during junction fabrication and operation? (iv) What charge transport mechanisms are present beyond the range of quantum tunneling? We propose a simple yet effective approach to resolve the important questions mentioned above through photocurrent experiments. In this perspective, we are showcasing various capabilities of photocurrent experiments to probe, prod, and investigate various features in MEs including internal energy barriers, in situ monitoring of the molecular structure, activationless transport over long distances, and biological charge transport.}, archive = {J_JACS}, author = {Abhishek S. Shekhawat and Aarti Diwan and Tulika Srivastava and Rajesh Kumar and Shailendra K. Saxena and Richard L. McCreery}, doi = {10.1021/jacs.5c04182}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27122--27136}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocurrent experiments as probes and prods in large-area molecular electronic junctions}, volume = {147}, year = {2025}, }
• (2025). Functionalities of simple and complex electrolytes in confinement. JACS, 147(31), 27105--27121. (www)

  @article{ , abstract = {Understanding simple and molecular electrolytes has advanced the development of various biotechnologies and industrial processes. In recent years, researchers have designed new ion-based architectures that emulate important biomimetic functions such as neural and organelle-like processes to alleviate societal demands. These examples, and many other bioinspired futuristic devices, rely on understanding and controlling electrostatic interactions in nanoscale confinement. For example, information transference and data processing demands have motivated studies toward the development of neuromorphic computers, which could distribute information into many small neuron-like devices that process and store information locally. Another area where the design of biomimetic functions plays a key role is in the need to decompose environmentally harmful chemicals. This has led to the design of synthetic mimics of unstructured proteins to protect enzymes in nonbiological environments, resembling the functions of membraneless organelles. This perspective explores principles aimed to design composite materials involving simple and complex electrolytes in confinement to imitate functional biomaterials. The function of layered materials for the synthesis of ionic machines and of poleylectrolytes to assemble functional enzymatic membranes is discussed, emphasizing new physical chemistry principles and computational methodologies.}, archive = {J_JACS}, author = {Felipe Jiménez-Ángeles and Nicholas Pogharian and Brandon Nicholas Onusaitis and Monica Olvera de la Cruz}, doi = {10.1021/jacs.5c04186}, journal = {Journal of the American Chemical Society}, month = {8}, number = {31}, pages = {27105--27121}, shortjournal = {J. Am. Chem. Soc.}, title = {Functionalities of simple and complex electrolytes in confinement}, volume = {147}, year = {2025}, }
• (2025). Ribosomal incorporation of fluorosulfonyloxy-l-phenylalanine into macrocyclic peptides for de novo target-specific covalent binders. JACS, 147(30), 27095--27104. (www)

  @article{ , abstract = {Macrocyclic peptides are emerging as a promising molecular framework in covalent drug development due to their high specificity, affinity, and low toxicity, addressing challenges such as off-target effects and nonspecific binding associated with traditional covalent binders. Although mRNA display technology has advanced the discovery of covalent peptide binders, it has primarily focused on cysteine residues, thereby limiting the diversity of targetable proteins. In this study, we ribosomally incorporated 4-fluorosulfonyloxy- l -phenylalanine (FSY) into macrocyclic peptides, enabling the construction of a diverse covalent macrocyclic peptide library for de novo screening against human α-thrombin and fibroblast activation protein. This led to the identification of novel peptides with covalent binding capabilities and a distinct dissociation profile, which in turn enabled potent inhibitory activities at concentrations within the low nanomolar range. Notably, FSY-bearing macrocyclic peptides conjugated with a radionuclide chelator demonstrated significantly improved tumor-selective uptake and prolonged retention, outperforming their noncovalent counterparts while underscoring their remarkable potential in targeted radionuclide therapy. This study provided a robust and efficient platform for the de novo discovery of FSY-bearing macrocyclic peptides, broadening the scope of covalent drug development for diverse biomedical applications.}, archive = {J_JACS}, author = {Yawen Yang and Pei Liu and Xi-Yang Cui and Junjie Wu and Wenfeng Cai and Jie Cheng and Chuanjie Lu and Xiaowei Fan and Youming Zhang and Zhibo Liu and Yizhen Yin}, doi = {10.1021/jacs.5c10625}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {27095--27104}, shortjournal = {J. Am. Chem. Soc.}, title = {Ribosomal incorporation of fluorosulfonyloxy-l-phenylalanine into macrocyclic peptides for de novo target-specific covalent binders}, volume = {147}, year = {2025}, }
• (2025). Temperature below 30 mK achieved by adiabatic demagnetization refrigeration. JACS, 147(30), 27089--27094. (www)

  @article{ , abstract = {Adiabatic demagnetization refrigeration (ADR) is the only technique capable of reaching ultralow temperatures without helium-3 and plays a crucial role at the forefront of both fundamental and applied science. However, progress in ADR is constrained by the limited magnetic entropy change (−Δ S m ) of existing refrigerants at ultralow temperatures. This limitation primarily stems from the inherent contradiction of simultaneously attaining a large −Δ S m and a low magnetic ordering temperature ( T 0 ) in magnetic refrigerant design. Here, we show that a magnetic refrigerant exhibiting both a large −Δ S m and a low T 0 can be simultaneously achieved by incorporating weak magnetic exchange and dipolar interactions into the dense frustrated magnet KYb 3 F 10 ( 1 ). Notably, the average −Δ S m of 1 in the 0.05–1.0 K range surpasses those of commercial refrigerants (NH 4 )Fe(SO 4 ) 2 ·12H 2 O and CrK(SO 4 ) 2 ·12H 2 O by 146 and 219%, respectively, while its T 0 is lower than 50 mK. Practical ADR testing confirms that a minimum temperature of 27.2 mK can be reached under a magnetic field of 6 T using 1 as the refrigerant. Thus, this work not only presents a high-performance ultralow-temperature refrigerant but also addresses the long-standing challenge of simultaneously achieving a large −Δ S m and a low T 0 in the design of magnetic refrigerants.}, archive = {J_JACS}, author = {Qiao-Fei Xu and Xin-Yang Liu and Ruo-Tong Wu and Ming-Yang Fu and Man-Ting Chen and Jun-Sen Xiang and Yin-Shan Meng and Tao Liu and Pei-Jie Sun and La-Sheng Long and Lan-Sun Zheng}, doi = {10.1021/jacs.5c10483}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {27089--27094}, shortjournal = {J. Am. Chem. Soc.}, title = {Temperature below 30 mK achieved by adiabatic demagnetization refrigeration}, volume = {147}, year = {2025}, }
• (2025). Monodisperse giant unilamellar niosomes as minimal synthetic cells. JACS, 147(30), 27081--27088. (www)

  @article{ , abstract = {Giant unilamellar vesicles (GUVs) such as liposomes, polymersomes, and fatty acid vesicles are widely studied as synthetic cell models. However, liposomes suffer from limited membrane permeability, instability, and high material cost, while polymersomes lack membrane fluidity, and fatty acid vesicles are sensitive to ions and pH. Here, we introduce giant unilamellar niosomes (GUNs), nonionic surfactant-based vesicles, as a robust, cost-effective platform for synthetic cells. Using droplet microfluidics, we generate monodisperse Span 80-based GUNs that exhibit outstanding membrane fluidity and intrinsic selective permeability to small molecules (<400–500 Da) and protons, without the need for embedded transport proteins. We demonstrate their functional utility by inducing pH-responsive liquid–liquid phase separation to mimic membraneless organelles and by reconstituting a self-sustaining glycolysis–mitochondria cascade to fuel ATP-driven actin polymerization. These results establish GUNs as versatile, cost-effective, and permeable synthetic cell models, with broad potential in biomimetic microsystems, synthetic biology, and drug delivery.}, archive = {J_JACS}, author = {Zhen-Hong Luo and Xuan-Yan He and Nan-Nan Deng}, doi = {10.1021/jacs.5c09950}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {27081--27088}, shortjournal = {J. Am. Chem. Soc.}, title = {Monodisperse giant unilamellar niosomes as minimal synthetic cells}, volume = {147}, year = {2025}, }
• (2025). Regioisomeric engineering of sterically hindered bright near-infrared paraptosis agents for chemo-photodynamic therapy. JACS, 147(30), 27068--27080. (www)

  @article{ , abstract = {Paraptosis emerges as a new promising form of programmed nonapoptotic cell death in chemotherapeutic anticancer therapy. However, current paraptosis agents face critical challenges, including poor targeting specificity, limited imaging capability, and low therapeutic efficacy. To overcome these limitations, we developed a novel approach by functionalizing the tetraphenylethylene (TPE) unit at the meso position of xanthene dyes, enabling the synthesis of two sterically hindered regioisomeric fluorescent paraptosis-inducing agents ( m -TSX and p -TSX) for mitochondria-targeted chemo-photodynamic anticancer therapy. These agents exhibited strong near-infrared (NIR) emissions (∼663 nm) with a quantum yield of up to 82.9%. The TPE substitution, in contrast to the phenyl group, allowed for precise modulation of triplet excited state energy levels, boosting type I/II reactive oxygen species (ROS) generation, and notable enhancement of the paraptotic anticancer activity. Comparative studies of the meta- and para -substituted regioisomers revealed that the meta -substituted m -TSX exhibited superior ROS generation and anticancer behavior. m -TSX effectively induced Alix/ATF4-regulated paraptosis, along with apoptosis and necrosis, while also triggering GPX4/SLC7A11-regulated ferroptosis under low-power 655 nm laser (0.1 W/cm 2 ) irradiation, leading to effective cancer cell growth inhibition. Furthermore, in vivo chemo-photodynamic therapy against HeLa tumor by inducing multiple cell death pathways was successfully achieved. This innovative strategy of steric hindrance regulation represents a breakthrough in developing bright NIR xanthene-based anticancer agents for synergistic cancer therapy.}, archive = {J_JACS}, author = {Xiang Wang and Xiaowan Han and Xiaoyuan Tian and Hosoowi Lee and Caihong Xiang and Chaorui Wang and Liang Luo and Hai-Yu Hu and Guangle Niu and Juyoung Yoon}, doi = {10.1021/jacs.5c10005}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {27068--27080}, shortjournal = {J. Am. Chem. Soc.}, title = {Regioisomeric engineering of sterically hindered bright near-infrared paraptosis agents for chemo-photodynamic therapy}, volume = {147}, year = {2025}, }
• (2025). Symmetry-breaking amplifies lone pair expression and orbital splitting for promising chain-like thermoelectrics. JACS, 147(30), 27059--27067. (www)

  @article{ , abstract = {The relative impact of electronic instability and quantum confinement on lattice dynamics and transport properties remains elusive. Here, we demonstrate that the influence of lone-pair electrons (LPEs) expression on phonon dissipation surpasses that of dimensional reduction using a quasi-low-dimensional Pb-Sn-S-Se system as a prototype. We experimentally observe that quasi-one-dimensional (1D) PbSnS 3 exhibits higher thermal transport than quasi-two-dimensional (2D) PbSnS 2 , attributed to the loss of LPEs. Therefore, we attempt a symmetry-breaking strategy to amplify the expression of LPEs in 1D-Pb 2 Sn 2 S 5 Se. Using first-principles calculations and Boltzmann transport theory, we reveal that amplified LPEs expression in 1D-systems induces more diffuson-like vibrations, as well as enhanced Umklapp and Normal processes. Moreover, phase transition and thermal transport analysis in 2D-PbSnS 2 reveals a stronger correlation between LPEs expression and phonon dissipation compared to the 1D-systems, regardless of variations on structure symmetry and dimension. Apart from the LPEs expression amplification, the symmetry-breaking strategy substantially facilitates orbital splitting in 1D-systems, leading to effective electron-phonon decoupling for promising thermoelectric efficiency. Consequently, our proposed strategy can be extended to optimize other quasi-low-dimensional systems containing LPEs, offering novel physical and chemical insights into the design of advanced thermoelectrics and thermal management materials.}, archive = {J_JACS}, author = {Shulin Bai and Yixuan Hu and Shaoping Zhan and Tian Gao and Bingchao Qin and Li-Dong Zhao}, doi = {10.1021/jacs.5c09889}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {27059--27067}, shortjournal = {J. Am. Chem. Soc.}, title = {Symmetry-breaking amplifies lone pair expression and orbital splitting for promising chain-like thermoelectrics}, volume = {147}, year = {2025}, }
• (2025). Efficient generation of hydrated electrons for organic transformations using manganese-doped cd-free quantum dots. JACS, 147(30), 27049--27058. (www)

  @article{ , abstract = {Photoemission materials, which can emit free electrons under light illumination, hold substantial technological value in diverse fields ranging from advanced electron sources to photochemistry. Spin-exchange Auger interaction, recently discovered in Mn 2+ -doped colloidal quantum dots (QDs), suggests the potential of these low-cost materials for efficient photoemission. However, previous Cd-based QDs suffer from an inherent toxicity issue, and they typically require multistep spin-exchange Auger interaction to achieve free electron ejection. Here, we report Mn 2+ -doped ZnSe QDs as a promising solution to these issues. Besides avoiding toxic materials, ZnSe-based QDs feature a high-energy conduction band that allows for efficient photoemission by absorbing only two photons, as confirmed by our femtosecond transient absorption measurements. The first photon enacts subpicosecond energy transfer from a photoexcited QD to a Mn 2+ -dopant. The second photogenerated electron–hole pair in the QD subsequently undergoes subpicosecond spin-exchange Auger interaction with the excited dopant, which transfers energy to the QD electron and ejects it into the vacuum. In aqueous solution, this leads to hydrated electrons with quantum efficiency exceeding 7%. Importantly, the millisecond excited-state lifetime of Mn 2+ -dopants enables efficient photoemission under continuous-wave illumination, which is leveraged to drive a dechlorination reaction of chloroacetate.}, archive = {J_JACS}, author = {Meng Yao and Xuyang Lin and Jingyi Zhu and Zhaolong Wang and Kaifeng Wu}, doi = {10.1021/jacs.5c09882}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {27049--27058}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient generation of hydrated electrons for organic transformations using manganese-doped cd-free quantum dots}, volume = {147}, year = {2025}, }
• (2025). A redox-active frustrated lewis pair for the activation and N–O scission of nitrosonium cations. JACS, 147(30), 27043--27048. (www)

  @article{ , abstract = {Frustrated Lewis pairs (FLPs) have revolutionized main-group chemistry by enabling reactivity traditionally associated with transition metals. However, existing FLP systems are predominantly restricted to two-electron heterolytic or homolytic bond activation mechanisms. In this work, we present a phosphine functionalized with a peripheral redox-active phenothiazine moiety and explore its unique behavior within an FLP framework. The resulting FLP exhibits unprecedented reactivity, allowing for the activation of the highly oxidizing nitrosonium cation with subsequent N–O bond scission. This reaction is facilitated by the redox-active functionality, first being oxidized by a single electron, then producing a reactive FLP that activates NO, resulting in an overall 3-electron bond activation. This novel transformation underscores the potential of incorporating redox-active groups to expand the scope of FLP chemistry, paving the way for new avenues in main-group bond activations.}, archive = {J_JACS}, author = {Casey A. Lenart and Avik Bhattacharjee and Taylor P. L. Cosby and Guillaume Bélanger-Chabot and Christopher B. Caputo}, doi = {10.1021/jacs.5c09854}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {27043--27048}, shortjournal = {J. Am. Chem. Soc.}, title = {A redox-active frustrated lewis pair for the activation and N–O scission of nitrosonium cations}, volume = {147}, year = {2025}, }
• (2025). Precise distal B–H bond activation of nido-carboranes by copper catalysis: Synthesis of benzene bioisosteres from boron clusters. JACS, 147(30), 27030--27042. (www)

  @article{ , abstract = {The exploration of innovative molecular scaffolds offers an exciting opportunity to venture into a previously unexplored chemical space. Boron clusters, such as carboranes, exhibit three-dimensional (3D) cage structures for exopolyhedral derivatization along multiple directions. This makes carboranes hold great potential as bioisosteric mimetics of benzene. However, the lack of efficient synthetic strategies for the regioselective functionalization of up to ten B–H sites has considerably hampered the broad application of carboranes as benzene bioisosteres. Herein, we report a novel reaction paradigm that involves copper-catalyzed precise carbene insertion into the nucleophilic remote B–H bond of nido -carboranes. The current protocol enables the synthesis of a series of multifunctionalized boron cluster derivatives for the construction of benzene bioisosteres. The reaction proceeds under mild conditions with rapid conversion and exhibits a broad substrate scope and excellent group tolerance. These features render the method highly adaptable for the development of boron-cluster-modified pharmaceuticals and trinity-type boron neutron capture therapy (BNCT) drug candidates. Additionally, high-performance carborane-based luminogens, which were facilely constructed by the developed reaction, exhibit multicolor emissions, high solid-state luminescence efficiency, and aggregation-induced circularly polarized luminescence (AI-CPL). This study not only demonstrates the potential of boron clusters as benzene mimetics but also opens new avenues for drug discovery and materials development.}, archive = {J_JACS}, author = {Ningning Zhou and Hongyuan Ren and Xinrui Li and Jie Peng and Zhaofeng Sun and Houji Cao and Deshuang Tu and Chang-sheng Lu and Hong Yan}, doi = {10.1021/jacs.5c09523}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {27030--27042}, shortjournal = {J. Am. Chem. Soc.}, title = {Precise distal B–H bond activation of nido-carboranes by copper catalysis: Synthesis of benzene bioisosteres from boron clusters}, volume = {147}, year = {2025}, }
• (2025). Single-entity resolution single-cell nanosensor reveals reactive oxygen species at stress granules are formed by interfacial redox chemistry. JACS, 147(30), 27020--27029. (www)

  @article{ , abstract = {The electrochemical activities of biomolecular condensates represent a new fundamental functioning mechanism in biochemistry and cell biology. However, our understanding of the underlying molecular mechanism and the interfacial field-dependent chemical activities remains limited. This is due to the lack of technology to probe such activities in real time and at a single-condensate level. Stress granules (SGs) are membraneless organelles that form in the cytoplasm to adapt to cell stress, which are found to encapsulate reactive oxygen species (ROS) in our lab. Here, we design and implement a collision-based electrochemical nanosensor that enables probing of the redox activities of SGs at a single-condensate level in live cells. We show that ex-vivo separated SGs drive the redox reactions depending on their own interfacial potentials and the constituents of the solution system. Surprisingly, we found that water molecules, rather than solvated oxygen (the main source of ROS produced by a conventional enzyme reaction in cells), are the main chemical origin of the redox activity of SGs. Finally, we demonstrate the application of this electrochemical nanosensor in real-time probing of the generation of hydrogen peroxide from SGs in mammalian cells and show that the electrochemical environment of the cells can regulate the redox activity of SGs. This work uncovers the likely mechanisms encoding nonenzymatic redox activities of SGs and demonstrates a key fundamental technological capability that can be highly useful in exploring the intracellular electroactive pathways of macroscale assemblies.}, archive = {J_JACS}, author = {Hui Gu and Chaoyi Gu and Andre Du Toit and Wen Yu and Michael W. Chen and Heather L. Struckman and Jonathan R. Silva and Yifan Dai and Andrew G. Ewing}, doi = {10.1021/jacs.5c09338}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {27020--27029}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-entity resolution single-cell nanosensor reveals reactive oxygen species at stress granules are formed by interfacial redox chemistry}, volume = {147}, year = {2025}, }
• (2025). Artificial chloroplast nanoarchitectonics through Liquid–Liquid phase separation enables recycled and enhanced photosynthesis. JACS, 147(30), 27011--27019. (www)

  @article{ , abstract = {Biomimetic supramolecular assembly offers a potent strategy to achieve artificial photosynthesis with higher efficiency. We constructed a polyoxometalate (POM)-based artificial chloroplast through liquid–liquid phase separation (LLPS), which efficiently mimics the photocatalytic water oxidation process. Such an architecture shows a greatly enhanced oxygen evolution rate with excellent recyclability in a confined space. To be specific, mixing a positively charged polyelectrolyte with a negatively charged sacrificial electron acceptor (SEA) in a stoichiometric manner creates coacervate droplets so as to entrap POM molecules. A microreactor with an obviously wrinkled structure is assembled. Spontaneously, a homogeneous-to-heterogeneous transformation enables POM to possess excellent recyclability, reusability, and structural stability occurring in an artificially designed microreactor. As a consequence, the efficiency of photocatalytic water oxidation to produce O 2 is remarkably improved compared to that of POM in the homogeneous state. This work opens a new avenue to integrate multiple functionalized components into one system to improve photosynthetic performance, which holds great potential in real applications.}, archive = {J_JACS}, author = {Rong Shu and Yang Xu and Jinbo Fei and Fanchen Yu and Zibo Li and Xuanze Meng and Junbai Li}, doi = {10.1021/jacs.5c09352}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {27011--27019}, shortjournal = {J. Am. Chem. Soc.}, title = {Artificial chloroplast nanoarchitectonics through Liquid–Liquid phase separation enables recycled and enhanced photosynthesis}, volume = {147}, year = {2025}, }
• (2025). Breaking the ion ordering in the perovskite anode for enhanced high-temperature oxygen evolution reaction activity. JACS, 147(30), 27000--27010. (www)

  @article{ , abstract = {Ion ordering in the perovskite oxide plays a crucial role in governing the properties, such as magnetic behavior, electronic and ionic conductivity, and dielectric or ferroelectric characteristics. As the common anodes in solid oxide electrolysis cells (SOECs), perovskites exhibit remarkable high-temperature oxygen evolution reaction (OER) activity. However, the influence of ion ordering in the perovskite anode on the OER activity remains poorly understood. In this study, we demonstrate that the A-site ion in Pr x Ba 2– x Co 2 O 5+δ perovskites transforms from ordered to disordered as the Pr content increases from 1.0 to 1.5. Comprehensive characterizations and density functional theory calculations reveal that this order–disorder transition significantly enhances d – p orbital hybridization, thereby enhancing the rates of oxygen exchange and oxygen ion transport. Electrochemically, the disordered Pr 1.5 Ba 0.5 Co 2 O 5+δ anode exhibits notably reduced ohmic and polarization resistances, achieving superior OER performance with a current density of 2.29 A cm –2 at 1.6 V and 800 °C. This work highlights the critical role of ion ordering in the OER performance and offers new insights into the design of efficient SOEC anode materials.}, archive = {J_JACS}, author = {Lina Yu and Xueyu Hu and Yige Guo and Shaowei Zhang and Jingcheng Yu and Geng Zou and Xiaomin Zhang and Mingrun Li and Zhentao Ma and Xusheng Zheng and Yuefeng Song and Meilin Liu and Guoxiong Wang and Xinhe Bao}, doi = {10.1021/jacs.5c09331}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {27000--27010}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking the ion ordering in the perovskite anode for enhanced high-temperature oxygen evolution reaction activity}, volume = {147}, year = {2025}, }
• (2025). Pressure-activated efficient near-infrared luminescence in atomically precise gold nanoclusters. JACS, 147(30), 26991--26999. (www)

  @article{ , abstract = {Achieving efficient near-infrared (NIR) luminescence in atomically precise gold nanoclusters is challenging due to the strong vibrational freedom of the gold core. Herein, we synthesized two gold nanoclusters, [Au 11 (PPh 3 ) 8 Cl 2 ]Cl ( Au 11 -1 ) and Au 11 (PPh 3 ) 7 Cl 3 ( Au 11 -2 ), with comparable initial NIR photoluminescence quantum yields (PLQY, 0.3% and 0.32%, respectively), and systematically investigated their NIR piezoluminescence behaviors based on the hydrostatic pressure effect. Under high pressure, Au 11 -1 exhibits a significant NIR piezoluminescence enhancement. When the pressure increases to 3.6 GPa, the NIR-PLQY of Au 11 -1 amplifies from the initial 0.3% to 75.6%, which is the highest PLQY reported for solid-state gold nanoclusters. However, Au 11 -2 exhibits only monotonic pressure-induced luminescence quenching under compression. In situ high-pressure angle-dispersive X-ray diffraction experiments and theoretical calculations confirm the existence of distinct anisotropic compressions in Au 11 -1 and Au 11 -2 , which induce differential structural distortion of the gold core. The faster shrinkage along the a -axis exacerbates the structural distortion of the Au 11 -1 core, whereas the more rapid compression along the b -axis in Au 11 -2 suppresses the structural distortion of the gold core. High-pressure femtosecond transient absorption and Raman spectra synergistically demonstrate that pressure-driven directional structural distortion significantly suppresses nonradiative losses caused by low-frequency vibrations of the Au 11 -1 core along the a -axis, resulting in NIR piezoluminescence enhancement of Au 11 -1 . Our study deeply reveals the intrinsic correlation between NIR-PLQY and metal core vibration relaxation at the atomic scale and provides a new approach to design and develop high-performance NIR luminescent materials.}, archive = {J_JACS}, author = {Ya-Ni Yang and Qiu-Yang Wan and Meng-Jie Zhu and Hua-Yang Ru and Ji-Kun Yang and Qi Li and Meng Zhou and Gaosong Chen and Yuchen Wu and Lei Jiang and Shuang-Quan Zang}, doi = {10.1021/jacs.5c09304}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26991--26999}, shortjournal = {J. Am. Chem. Soc.}, title = {Pressure-activated efficient near-infrared luminescence in atomically precise gold nanoclusters}, volume = {147}, year = {2025}, }
• (2025). Enantiodivergent access to acyclic quaternary stereocenters by nitrilase-catalyzed desymmetrizing hydrolysis of malononitriles. JACS, 147(30), 26980--26990. (www)

  @article{ , abstract = {The desymmetrization of fully substituted carbons bearing a pair of enantiotopic functional groups represents a pragmatic approach to the synthesis of quaternary stereocenters. Prochiral α,α-disubstituted malononitriles are of particular interest due to the simplicity of their preparation, the programmable introduction of functional substituents, and the high synthetic value of the resulting enantioenriched nitriles. Nevertheless, the asymmetric catalytic transformation of these malononitriles to all-carbon quaternary stereocenters represents a significant challenge. Here, we present a nitrilase ( Ss NIT)-catalyzed desymmetrizing hydrolysis of α,α-disubstituted malononitriles, resulting in the production of enantioenriched α-cyanocarboxylic acids containing acyclic all-carbon quaternary stereocenters in good yields (up to 99% yield) with excellent enantioselectivities (up to 99% ee). By fine-tuning and reshaping the substrate pockets of the enzyme through Focused Rational Iterative Site-directed Mutagenesis (FRISM), we successfully engineered a pair of enantiocomplementary nitrilases ( M1 and M3 ), thereby providing a divergent synthetic route to assemble both R and S configurations of the quaternary stereocenters. The synthetic robustness and scalability of this strategy were further validated through gram-scale reactions using whole-cell biocatalysts, followed by derivatization into diverse enantioenriched noncanonical amino acid derivatives bearing quaternary stereocenters. This study highlights the potential of biocatalysis in facilitating the efficient synthesis of quaternary centers and their enantiomers through the rational engineering of enzymes.}, archive = {J_JACS}, author = {Yong-Ze Xie and Dong-Sheng Yang and Li-Gang Bai and Jin-Wei Yang and Bo Gu and Meng-Ting Liu and Qi-Yue Wang and Wang Wang and Wen-Bo Liu and Heng Song}, doi = {10.1021/jacs.5c09258}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26980--26990}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantiodivergent access to acyclic quaternary stereocenters by nitrilase-catalyzed desymmetrizing hydrolysis of malononitriles}, volume = {147}, year = {2025}, }
• (2025). Mechanistic insights into methylamine electrosynthesis from CO2 and NO on co-based dual-atom catalysts. JACS, 147(30), 26969--26979. (www)

  @article{ , abstract = {Methylamine (MMA) is a vital raw material in the chemical industry. Recent advances in electrochemical synthesis have enabled new routes for amide production via the coreduction of CO 2 and nitrogen oxides. However, achieving selective C–N coupling with high Faradaic efficiency remains challenging due to the complexity of reaction intermediates and poorly understood mechanisms. In this study, we employed state-of-the-art constant-potential DFT calculations and microkinetic simulations to elucidate the mechanism of MMA electrosynthesis on heterogeneous single-atom/dual-atom catalysts (SACs/DACs) based on Co-phthalocyanine (Co-Pc) frameworks. We identified three critical factors governing C–N coupling selectivity: (i) the adsorption manner of CO 2 and NO, (ii) the energy barrier of the initial Langmuir–Hinshelwood (LH) step, and (iii) the free energy change associated with over-reduction of *NH 2 OH and *HCHO intermediates. Guided by these criteria, we demonstrated the superior catalytic performance of Co-based DACs over that of their SAC counterpart. Furthermore, we highlighted the hydrogen affinity of the transition metal center as a critical parameter for rational DAC design and identified 2D Co–Ir-Pc as a promising electrocatalyst for MMA production, predicted to significantly outperform the experimentally validated Co-Pc monomers. This work not only provides mechanistic insights into C–N coupling on SACs/DACs but also establishes a general framework for the rational design of efficient MMA electrosynthesis catalysts.}, archive = {J_JACS}, author = {Tianze Xu and Zifan Wang and Tianyang Liu and Feifan Wang and Yu Jing}, doi = {10.1021/jacs.5c08979}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26969--26979}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic insights into methylamine electrosynthesis from CO2 and NO on co-based dual-atom catalysts}, volume = {147}, year = {2025}, }
• (2025). Polycrystalline covalent organic frameworks: Multiscale structural insights from morphological diversity to dynamic lattice evolution. JACS, 147(30), 26955--26968. (www)

  @article{ , abstract = {Covalent organic frameworks are a class of crystalline porous materials with covalent skeletons and inherent pores. They are prepared through a topology-directed polymerization process and are usually obtained as polycrystalline materials. Despite rapid progress in materials synthesis and functional expansion, less is known about the structure of polycrystalline frameworks. This situation is ubiquitous in most cases, which complicates comparisons between frameworks, precludes the finding of intrinsic properties, and impedes discrete structure–property correlations. In this work, we report structures of polycrystalline frameworks by uncovering the coexistence of different morphologies and their static and dynamic behaviors, disclosing a realistic picture and multiple-scale insights into structures of the most frequently used polycrystalline frameworks. Visualization with high-resolution transmission electron microscopy revealed four distinct morphologies, i.e., nanoparticle aggregates, nanorod aggregates, ultrathin nanosheets, and parasitic fusion entities. Moreover, direct visualization revealed the existence of different polygons and channels and their contents together with their boundaries and unstructured complements. Our studies revealed new assembly mechanisms via covalent-bond-mediated nanoparticle fusion and amorphous-phase-interconnected crystalline domain formation, providing a foundation for synthesizing high-quality crystalline porous frameworks and exploring their potential properties and functions.}, archive = {J_JACS}, author = {Juan Li and Yukun Liu and Xuezeng Tian and Shulin Chen and Shanshan Tao and Masaki Takeguchi and Donglin Jiang}, doi = {10.1021/jacs.5c09081}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26955--26968}, shortjournal = {J. Am. Chem. Soc.}, title = {Polycrystalline covalent organic frameworks: Multiscale structural insights from morphological diversity to dynamic lattice evolution}, volume = {147}, year = {2025}, }
• (2025). Photoactivated ion transport: Role of intrinsic defects and plasmonics for efficient ionic power harvesting. JACS, 147(30), 26944--26954. (www)

  @article{ , abstract = {The process of photosynthesis in green plants and energy conversion in certain archaea are inseparable from photoregulated ion pumping. Two-dimensional (2D) nanofluidic membranes, emerging as competitive candidates for constructing ion pumps, present intriguing prospects for harvesting light energy. However, the inevitable presence of defects during the synthesis of 2D materials underscores the critical need to understand their impact on ion transport dynamics within nanofluidic systems. Here, we present a chemically engineered asymmetric nanofluidic membrane (ANM) by intercalating molybdenum trioxide (MoO 3 ) with controlled oxygen vacancies into graphene oxide laminates, systematically investigating the defect chemistry-governed photo-activated ion transport. Upon photoexcitation, MoO 3 nanosheets exhibit tunable surface plasmon resonance (SPR) through photochemical H + intercalation, leading to an augmentation of oxygen vacancies and an elevated concentration of free electrons. These vacancies enrich MoO 3 with excess localized surface electrons, enabling tunable SPR that creates negative charge centers and significantly enhances space charge through defect-induced polarization. Density functional theory (DFT) calculations reveal the atomic-level mechanism of vacancy-enhanced cation transport, showing a notable 188% increase in the adsorption energy of K + at MoO 3 surfaces with two vacancy sites compared to one vacancy (−13.66 vs −4.74 eV). Under asymmetric photo irradiation, the system achieves a peak power density of approximately 439.2 W/cm 2 in equilibrium ionic solutions, realizing a photonic-to-ionic energy conversion efficiency of 7.98 × 10 –4 % via synergistic effects of defects and plasmonics. Our research pioneers the elucidation of the regulation and underlying mechanisms of intrinsic defects on active ion transport within nanofluidic membranes, while fostering a novel perspective on photon–electron–ion interplay within nanofluidic environments.}, archive = {J_JACS}, author = {Pei Liu and Mengmeng Zheng and Yue Wang and Xiang-Yu Kong and Yingjie Zhao and Mengru Zhang and Qun Xu and Lei Jiang and Liping Wen}, doi = {10.1021/jacs.5c09051}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26944--26954}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoactivated ion transport: Role of intrinsic defects and plasmonics for efficient ionic power harvesting}, volume = {147}, year = {2025}, }
• (2025). Combinatorial synthesis and evaluation of trialkyl galloyl amidoamine ionizable lipids for mRNA formulation. JACS, 147(30), 26934--26943. (www)

  @article{ , abstract = {Lipid nanoparticles (LNPs), containing ionizable cationic lipids, have attracted widespread interest in recent years, particularly following their use as mRNA delivery systems for COVID-19 vaccines. Here, we report on the combinatorial synthesis of galloyl amidoamine-based ionizable lipids. Starting from methyl gallate, three alkyl tails were substituted onto the aromatic ring, and the carboxylic acid was transformed into an ionizable tertiary amine headgroup. Optimization of the synthetic protocol resulted in a scalable, chromatography-free procedure requiring as few as two transformation steps and yielding a library of 43 different lipids in high yield (>88%). By varying the ionizable amine headgroup and the length, saturation, and branching of the alkyl tails, we found that the length of the lipid tail significantly impacted solubility and mRNA encapsulation efficiency. Trialkyl lipids comprising unsaturated heptyl and octyl tails enabled the formulation of sub-150 nm LNPs with encapsulation efficiencies exceeding 85%. Benchmarking experiments against a commercial MC3 LNP formulation identified four lipids that enabled potent mRNA transfection in vitro. Moreover, in vivo studies in mice with selected LNP formulations indicated that three lipids performed on par with MC3 in terms of luciferase reporter-protein expression in the liver and spleen after intravenous administration. Additionally, these lipids did not show any toxicity in the spleen and liver. These results clearly highlight the translational potential of trialkyl galloyl amidoamine lipids and more particularly for mRNA-based therapies.}, archive = {J_JACS}, author = {Bianka Golba and Irene De Franceschi and Zifu Zhong and Martijn J. Schuijs and Claudia M. Brenis Gomez and Heleen Lauwers and Benoit Louage and Iasona Sheshi and Nezha Badi and Bruno G. De Geest and Filip E. Du Prez}, doi = {10.1021/jacs.5c09030}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26934--26943}, shortjournal = {J. Am. Chem. Soc.}, title = {Combinatorial synthesis and evaluation of trialkyl galloyl amidoamine ionizable lipids for mRNA formulation}, volume = {147}, year = {2025}, }
• (2025). Constructing alkali Metal–Organic frameworks with high porosity utilizing a high-connectivity organic linker. JACS, 147(30), 26926--26933. (www)

  @article{ , abstract = {Alkali metal–organic frameworks (AMOFs) hold considerable promise for a broad spectrum of applications, benefiting from their low toxicity and lightweight. However, the construction of AMOFs with permanent porosity remains a significant challenge due to the tendency of alkali metals to coordinate with polar solvents, thereby forming coordination polymers with low dimensionality. Here, we introduce a connectivity-regulated approach for the synthesis of porous AMOFs by using highly connected organic linkers. Following this strategy, we have constructed AMOFs (denoted as HIAM-112-Li/Na/K/Rb/Cs) using the entire group of alkali metals (Li, Na, K, Rb, and Cs) and an octacarboxylate linker. In particular, HIAM-112 K/Rb/Cs demonstrate record-high porosities among K-, Rb-, and Cs-based coordination networks, respectively. By evaluating their separation performance for the selected gas mixtures, we demonstrate that these highly porous AMOFs hold a strong potential in adsorption-related fields.}, archive = {J_JACS}, author = {Jiafeng Miao and Saif Ullah and Xin Sun and Kang Zhou and Timo Thonhauser and Zuotai Zhang and Jing Li and Manglai Gao and Hao Wang}, doi = {10.1021/jacs.5c08920}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26926--26933}, shortjournal = {J. Am. Chem. Soc.}, title = {Constructing alkali Metal–Organic frameworks with high porosity utilizing a high-connectivity organic linker}, volume = {147}, year = {2025}, }
• (2025). Origin of selectivity in alternating current-enabled partial reduction of (Hetero)Arenes: A case study of two consecutive irreversible electrochemical steps. JACS, 147(30), 26917--26925. (www)

  @article{ , abstract = {Herein, we investigate the origin of selectivity in the alternating current (AC)-enabled partial reduction of (hetero)arenes to cyclic alkenes. Reduction of (hetero)arenes can be considered as a reaction involving two consecutive irreversible electrochemical steps: the first generates the desired cyclic alkene, while the second leads to its undesired overreduction. Conventional constant current or voltage (DC) electrolysis results in poor selectivity toward the partial reduction products, originating from overreduction and base-induced decomposition of the desired product. Fast-scan cyclic voltammetry shows that the rate constant for the first reduction ( k 1 ) exceeds that of the second one ( k 2 ). Finite element simulations based on this experimental finding semiquantitatively capture the frequency-dependent selectivity observed in AC electrolysis experiments (i.e., increasing the AC frequency enhances selectivity). The results further reveal that AC electrolysis mitigates the low selectivity by only collecting the products at the initial stage of the reduction reaction, which is mostly under a kinetically controlled regime. We then extend the finite element model and introduce Δ E FOW , the foot-of-the-wave potential difference between cyclic voltammograms of substrate and partial reduction product, as an accessible proxy for k 2 / k 1 . A Δ E FOW > 80 mV predicts synthetically useful selectivity (>30%) toward the partial reduction product below 100 Hz.}, archive = {J_JACS}, author = {Sreesaila Sreekumar and Joshua A. Beeler and Diptangshu Datta Mal and Henry S. White and Long Luo}, doi = {10.1021/jacs.5c08873}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26917--26925}, shortjournal = {J. Am. Chem. Soc.}, title = {Origin of selectivity in alternating current-enabled partial reduction of (Hetero)Arenes: A case study of two consecutive irreversible electrochemical steps}, volume = {147}, year = {2025}, }
• (2025). Dissecting bioelectrical networks in photosynthetic membranes with electrochemistry. JACS, 147(30), 26907--26916. (www)

  @article{ , abstract = {Photosynthetic membranes contain complex networks of redox proteins and molecules, which direct electrons along various energy-to-chemical interconversion reactions important for sustaining life on Earth. Analyzing and disentangling the mechanisms, regulation, and interdependencies of these electron transfer pathways is extremely difficult, owing to the large number of interacting components in the native membrane environment. While electrochemistry is well established for studying electron transfer in purified proteins, it has proved difficult to wire into proteins within their native membrane environments and even harder to probe on a systems-level the electron transfer networks they are entangled within. Here, we show how photosynthetic membranes from cyanobacteria can be wired to electrodes to access their complex electron transfer networks. Measurements of native membranes with structured electrodes revealed distinctive electrochemical signatures, enabling analysis from the scale of individual proteins to entire biochemical pathways as well as their interplay. This includes measurements of overlapping photosynthetic and respiratory pathways, the redox activities of membrane-bound quinones, along with validation using in operando spectroscopic measurements. Importantly, we further demonstrated extraction of electrons from native membrane-bound Photosystem I at −600 mV versus SHE, which is ∼1 V more negative than from purified photosystems. This finding opens up opportunities for biotechnologies for solar electricity, fuel, and chemical generation. We foresee this electrochemical method being adapted to analyze other photosynthetic and nonphotosynthetic membranes, as well as aiding the development of new biocatalytic, biohybrid, and biomimetic systems.}, archive = {J_JACS}, author = {Joshua M. Lawrence and Rachel M. Egan and Laura T. Wey and Karan Bali and Xiaolong Chen and Darius Kosmützky and Mairi Eyres and Lan Nan and Mary H. Wood and Marc M. Nowaczyk and Christopher J. Howe and Jenny Z. Zhang}, doi = {10.1021/jacs.5c08519}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26907--26916}, shortjournal = {J. Am. Chem. Soc.}, title = {Dissecting bioelectrical networks in photosynthetic membranes with electrochemistry}, volume = {147}, year = {2025}, }
• (2025). A’-site dipole magnitude and direction dominate the ionization energy and electron affinity of layered metal-halide perovskites. JACS, 147(30), 26898--26906. (www)

  @article{ , abstract = {Layered metal halide perovskites (LHPs), often referred to as 2D HPs, are promising materials for developing optoelectronics due to their tunable optoelectronic properties and improved stability compared to nonlayered (3D) metal halide perovskites. For integration into electronic devices, it is critical to appropriately adjust the work function (WF) and transport energies of the LHPs to promote efficient charge transfer between materials in the device stack. The transport energies of LHPs can be modified by changing the A’-site cation structure, inorganic sheet thickness, and the metal cation or halide anion. Here, we investigate how the A’-site cation structure influences the WF, ionization energy (IE), and electron affinity (EA) of n = 1 Sn- and Pb-based LHPs with a series of ortho- and para -functionalized phenethylammonium (PEA) iodide derivatives. To accurately assign the IE and EA, we develop a fitting method where the instrumental broadening, σ IB , in ultraviolet and low-energy inverse photoemission spectroscopy (UPS and LEIPS, respectively) is accounted for. Density functional theory calculations combined with UPS and LEIPS measurements show that the dipole magnitude and direction of the A’-site cation exert a dominant influence on the WF, IE, and EA. Here, the direction and magnitude of the dipole, as manipulated through the strength and position of the electron-withdrawing or -donating substituent on PEA, can tune the WF by up to 1.2 eV, the IE by up to 0.9 eV, and the EA by up to 1.2 eV. The crystal structures indicate that the Sn–I–Sn bond angles have a clear influence over the optical gap; however, the influence of these Sn–I–Sn bond angles on the transport energies is dwarfed by the effect of the A’ dipole. These results provide insight into how to tune the WF and transport energies of LHPs for optoelectronic device integration.}, archive = {J_JACS}, author = {Harindi R Atapattu and Sahar Bayat and Henry Pruett and Anton S Perera and Tareq Hossain and Keerthan R. Rao and Kevin Pedersen and Augustine Yusuf and Sean Parkin and Chad Risko and Kenneth R. Graham}, doi = {10.1021/jacs.5c08621}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26898--26906}, shortjournal = {J. Am. Chem. Soc.}, title = {A’-site dipole magnitude and direction dominate the ionization energy and electron affinity of layered metal-halide perovskites}, volume = {147}, year = {2025}, }
• (2025). Deciphering SN2-type nucleophilic substitution via halogen-free intermediates for high-energy Zinc–Iodine batteries. JACS, 147(30), 26889--26897. (www)

  @article{ , abstract = {High-valence halogen conversion reactions are promising for realizing high-energy-density aqueous batteries. It has been more challenging to realize a stable and reversible I 0 / I + conversion than the facile I – / I 0 conversion. While interhalogen chemistry has been employed to realize a reversible I – /I 0 / I + (i.e., four-electron) redox couple, the introduction of additional halide species raises corrosion and toxicity issues. Herein, we propose an SN2-type nucleophilic substitution mechanism for the activation of the I 0 / I + redox process. A series of halogen-free intermediates containing imide groups is proven effective in promoting four-electron halogen reactions due to conjugation-stabilized nitrogen anions. A structure–kinetics relationship among various imide-containing molecules is elucidated using two descriptors: the hydrogen dissociation energy ( E d ) of the imide group and the local nucleophilicity (LN) of the corresponding nitrogen anion. A Zn–I 2 battery with a theobromine intermediate exhibits stable cycling (a capacity retention of 93.9% at 5 A g –1 over 1000 cycles). This work provides new insights into the mechanism of the I 0 / I + redox process and a new avenue to the development of high-capacity multielectron iodine cathodes.}, archive = {J_JACS}, author = {Zhehan Yi and Hengyue Xu and Jin-Lin Yang and Jia Li and Tao Xiao and Hao Chen and Cheng Jiang and Hong Li and Seok Woo Lee and Hong Jin Fan}, doi = {10.1021/jacs.5c08469}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26889--26897}, shortjournal = {J. Am. Chem. Soc.}, title = {Deciphering SN2-type nucleophilic substitution via halogen-free intermediates for high-energy Zinc–Iodine batteries}, volume = {147}, year = {2025}, }
• (2025). Correlated reaction coordinate motion produces nonadditive rate enhancement for electron and energy transfer in multiacceptor structures. JACS, 147(30), 26877--26888. (www)

  @article{ , abstract = {Molecular structures with multiple donor, bridge, or acceptor units can display quantum interference effects that influence electron and energy transfer (ET and EnT) rates. Recent experiments found a 4–5-fold increase in ET rates for donor–acceptor structures with two acceptors compared to one. This result is surprising: simple classical or quantum analysis suggests a factor of 2 rate enhancement. We analyze the coupling interactions in multi-acceptor systems and find that rate enhancements beyond additive effects arise from acceptor-acceptor interactions that (1) shift the reaction free energy, (2) change the donor–acceptor couplings, and (3) alter the reaction-coordinate motion. Consideration of these effects explains the observed rates in multiacceptor systems and suggests strategies to tailor energy and electron transfer kinetics.}, archive = {J_JACS}, author = {Hanggai Nuomin and Feng-Feng Song and Peng Zhang and David N. Beratan}, doi = {10.1021/jacs.5c08324}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26877--26888}, shortjournal = {J. Am. Chem. Soc.}, title = {Correlated reaction coordinate motion produces nonadditive rate enhancement for electron and energy transfer in multiacceptor structures}, volume = {147}, year = {2025}, }
• (2025). Taming tautomerism in organic crystal structure prediction. JACS, 147(30), 26865--26876. (www)

  @article{ , abstract = {Tautomerism influences the solubility, stability, efficacy, and even toxicity of drug formulations. Computational solid-form screening is increasingly being used to help identify effective drug formulations and derisk against undesirable crystal forms. Here, however, we demonstrate that widely used density functionals predict tautomeric crystal polymorph energetics poorly, largely due to density-driven delocalization error. We first show how these DFT models incorrectly identify the preferred tautomeric polymorphs of 2-thiobarituric acid and the antihelmintic drug mebendazole and that some functionals substantially underestimate the barrier to solid-state tautomerization. Surveying 18 additional examples, we find that tautomeric polymorph energy differences defy conventional wisdom by exceeding the normal 10 kJ/mol energy window associated with crystal polymorphism in ∼40% of the cases, sometimes by tens of kJ/mol. Moreover, the DFT errors in the polymorph energy differences are strikingly large: they can reach tens of kJ/mol and produce the wrong qualitative stability ordering in ∼20–30% of the cases. We address the challenge of predicting tautomeric polymorphs through a general solution that combines periodic hybrid DFT with intramolecular coupled-cluster theory corrections to substantially improve agreement with experiment. Most notably, our refined models reveal that the experimentally reported crystal structure of mebendazole form B features the incorrect tautomer─a prediction that is confirmed via solid-state NMR analysis.}, archive = {J_JACS}, author = {Cody J. Perry and Sebastian A. Ramos and Maria C. Phelps and Leonard J. Mueller and Gregory J. O. Beran}, doi = {10.1021/jacs.5c08442}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26865--26876}, shortjournal = {J. Am. Chem. Soc.}, title = {Taming tautomerism in organic crystal structure prediction}, volume = {147}, year = {2025}, }
• (2025). Hexavalent ru catalyst with both lattice oxygen and metal ion mechanisms coactive for water oxidation. JACS, 147(30), 26854--26864. (www)

  @article{ , abstract = {Green hydrogen from water requires the development of efficient and low-cost catalysts for anodic oxygen evolution reaction (OER), which is the main obstacle for electrochemical water splitting. Herein, we focus on an OER catalyst (Pb 2 CoRuO 7 ) featuring Ru 6+ , which exhibits an ultralow overpotential of 176 mV at 10 mA cm –2 and a Tafel slope of 30.52 mV dec –1 vs 340 mV at 10 mA cm –2 and a Tafel slope of 111.54 mV dec –1 for RuO 2 in 1.0 M KOH solution. In situ X-ray absorption experiments demonstrated the gradual conversion of Ru 5+ ions into high-valence Ru 6+ , while a portion of Co 3+ ions transformed into Co 4+ during the OER process. Density functional theory calculations revealed that the ultrahigh OER activity of Pb 2 CoRuO 7 was contributed by both metal-site adsorbate evolution (MAE) at the Co site and the lattice-oxygen-vacancy-site (LOV) mechanism involving lattice oxygen located between Ru 6+ and Co. Our work presents a new and unusual OER catalyst where both the MAE and LOV mechanisms cooperatively facilitate catalytic activity.}, archive = {J_JACS}, author = {Yanzhuo Li and Jianfa Zhao and Shengjie Zhang and Yalei Fan and Chang-Yang Kuo and Yu-Chieh Ku and Ting-Shan Chan and Cheng-Wei Kao and Yu-Cheng Huang and Chien-Te Chen and Shu-Chih Haw and Changqing Jin and Hongbin Zhao and Daixin Ye and Chao Jing and Zhiwei Hu and Linjuan Zhang}, doi = {10.1021/jacs.5c08425}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26854--26864}, shortjournal = {J. Am. Chem. Soc.}, title = {Hexavalent ru catalyst with both lattice oxygen and metal ion mechanisms coactive for water oxidation}, volume = {147}, year = {2025}, }
• (2025). Controlled solid-state ring-opening polymerization of cyclic carbonates via mechanochemical H-bonding organocatalysis. JACS, 147(30), 26844--26853. (www)

  @article{ , abstract = {Mechanochemical tools offer a sustainable route to solid-state polymerization via unique force-activated mechanisms. However, achieving well-controlled living mechanochemical polymerization has remained a challenge. In this study, we proposed a mechanochemical hydrogen-bond-catalyzed ring-opening polymerization (mechano-HROP) strategy that enabled efficient and controllable solid-state polymerization of cyclic carbonates at room temperature. Mechanical force lowers the activation energy of the ROP, while hydrogen bonding further reduces the energy barrier and governs the polymerization process. As a result, solid-state mechano-HROP exhibited exceptional polymerization reactivity ( k obs 29 °C = 0.0137 min –1 ). Kinetics analysis confirmed a controlled/living process, and DFT calculations supported a hydrogen-bonded bifunctional activation mechanism in the solid state. This method successfully yielded a series of functionalized aliphatic polycarbonates ( M n up to 178.9 kDa, D̵ < 1.18) with complete monomer conversion and a high storage modulus of 1.75 GPa. The resulting polymers exhibited high end-group fidelity and potential for chain extension and copolymerization. Overall, this study underscored the significance of mechanochemical hydrogen-bond catalysis for sustainable polymer synthesis.}, archive = {J_JACS}, author = {Kai Chen and Shuo Li and Zheng Wang and Zuxiang Lin and Zhijun Han and Xin Wang and Zhao Wang and Nikos Hadjichristidis}, doi = {10.1021/jacs.5c08373}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26844--26853}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlled solid-state ring-opening polymerization of cyclic carbonates via mechanochemical H-bonding organocatalysis}, volume = {147}, year = {2025}, }
• (2025). Symmetrization of strong hydrogen bond under high pressure in bihydroxide-ion-containing NaCu2(SO4)2·H3O2 revealed by experimental charge density, single-crystal electron diffraction, and neutron diffraction studies. JACS, 147(30), 26830--26843. (www)

  @article{ , abstract = {In minerals and inorganic compounds, strong hydrogen bonding can lead to the formation of complex ionic species such as the H 3 O 2 – bihydroxide anion and Zundel cation H 5 O 2 + . We studied [NaCu 2 (SO 4 ) 2 ·H 3 O 2 ] natrochalcite, which contains bihydroxide anions and undergoes hydrogen bond symmetrization at the lowest pressure reported so far among inorganic compounds. Hydrogen bond symmetrization leads to changes in the bulk modulus, seismic wave velocities, and proton mobility and plays a primary role in high-temperature superconductivity, but its characteristics are not well understood due to a lack of systematic studies and limitations of experimental methods sensitive to this subtle change. In this work, we applied experimental charge density analysis based on in situ single-crystal X-ray diffraction data, along with the single-crystal neutron and electron diffraction experiments, to probe the behavior of hydrogen atoms during the hydrogen bond symmetrization process under high-pressure conditions. On the way to the symmetrical H-bonding, natrochalcite undergoes a series of complex redistributions of electron density, which we trace with multipole refinement and detailed analysis of changes in the Laplacian of electron density values. Additionally, we deconvoluted the equation of state (volume of the unit cell vs pressure relation) into the atomic equation of states describing dependencies of atomic charges or volumes vs pressure.}, archive = {J_JACS}, author = {Piotr Rejnhardt and Roman Gajda and Magdalena Woińska and Jan Parafiniuk and Gerald Giester and Ronald Miletich and Yan Wu and Tomasz Poręba and Mohamed Mezouar and Szymon Sutuła and Tomasz Góral and Przemysław Dera and Krzysztof Woźniak}, doi = {10.1021/jacs.5c08310}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26830--26843}, shortjournal = {J. Am. Chem. Soc.}, title = {Symmetrization of strong hydrogen bond under high pressure in bihydroxide-ion-containing NaCu2(SO4)2·H3O2 revealed by experimental charge density, single-crystal electron diffraction, and neutron diffraction studies}, volume = {147}, year = {2025}, }
• (2025). Regenerative electroactive self-assembled layers from reversible non-covalent interactions. JACS, 147(30), 26820--26829. (www)

  @article{ , abstract = {Tethering redox-active molecules to electrode surfaces bridges the atomistic control prized in homogeneous systems with the practicality of reusable heterogeneous electrodes. Synthetic strategies for immobilization are traditionally designed to be permanent and thus lack a mechanism for repairing in situ molecular detachment or degradation. A repair mechanism tuned to overcome the rates of molecular detachment and degradation would instead allow continuous regeneration of the desired electrochemical activity. Here, we develop a mechanism-guided strategy for regenerative self-assembled electroactive layers by leveraging electrostatic and van der Waals interactions as dynamic and reversible non-covalent tethers. Using ferrocene-labeled amphiphile monomers as a model system, we quantify the kinetics of molecular self-assembly, disassembly, and induced degradation under electrochemical conditions. We show that non-covalent self-assembly and disassembly dynamics at the electrode interface is tuned by synthetically varying the monomer tail length, and we identify rates that compete with molecular degradation. We assemble our kinetic data into a mechanistic model that predicts the exchange dynamics that allow intentionally degraded molecules to be replaced in situ . Our work unlocks non-covalent, reversible tethering of redox-active molecules at electrode surfaces as a molecularly tunable repair mechanism to enhance durability in electrochemical applications.}, archive = {J_JACS}, author = {Nicholas D. Maldonado and Caroline Hou and Anna Wuttig}, doi = {10.1021/jacs.5c08100}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26820--26829}, shortjournal = {J. Am. Chem. Soc.}, title = {Regenerative electroactive self-assembled layers from reversible non-covalent interactions}, volume = {147}, year = {2025}, }
• (2025). The discovery of complex heterocycles from millipede secretions. JACS, 147(30), 26813--26819. (www)

  @article{ , abstract = {The recent explosion in documented chemistry from Colobognatha, a millipede subterclass with more than 240 species, has rekindled interest in the defensive secretions from these ancient animals. Prior to 2020, studies on defensive secretions by Colobognatha─the only millipedes that produce terpenoid alkaloids─were limited to a single order, Polyzoniida. However, numerous species of the order Platydesmida have recently been shown to produce structurally diverse terpenoid alkaloids with potent biological activities. Platydesmidan defensive secretions encompass multiple natural product scaffolds with greater chemical complexity compared to previously reported millipede-derived alkaloids. Here, we report an analysis of the defensive secretions of Andrognathus corticarius , an evolutionary sister to all other Platydesmida. Analyzing defensive secretions revealed that A. corticarius produces an arsenal of alkaloids dissimilar to all previously reported metabolites. Using various analytical techniques, we accomplished complete structural assignment of two distinct scaffolds: a 5,6-fused heterocycle named the andrognathines and a 6,6,6,5-bridged heterocycle containing seven continuous stereogenic centers named the andrognathanols. Each scaffold contains diverse fatty acids; this leads to an extraordinary number of unique metabolites. These described alkaloids are actively secreted upon physical disturbance and change the behavior of ants that reside in the same environment.}, archive = {J_JACS}, author = {Paige Banks and Carla Menegatti and Lin Du and Paul E. Marek and Emily Mevers}, doi = {10.1021/jacs.5c08079}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26813--26819}, shortjournal = {J. Am. Chem. Soc.}, title = {The discovery of complex heterocycles from millipede secretions}, volume = {147}, year = {2025}, }
• (2025). Field-induced interlayer ion migration and electronic coupling unlock ferroelectricity in centrosymmetric AgInP2Se6 crystals. JACS, 147(30), 26804--26812. (www)

  @article{ , abstract = {The research on two-dimensional (2D) van der Waals (vdW) ferroelectric materials has garnered significant interest due to their novel underlying chemical mechanisms and promising application potential. However, prior studies were largely limited to noncentrosymmetric materials under traditional ferroelectric concepts, hampering the development of vdW ferroelectric systems. Here, we report a centrosymmetric ionic–electronic-coupled vdW ferroelectric semiconductor, AgInP 2 Se 6 , where polarization switching arises from electric field-driven interlayer Ag + migration. Combining density functional theory calculations and in situ second-harmonic generation spectroscopy confirms that at room temperature, the ionic migration barrier prevents spontaneous relaxation, stabilizing the nonvolatile polarization. This discovery expands the landscape of ferroelectric materials beyond symmetry constraints, unlocking new possibilities for low-power, nonvolatile memory and in-memory computing architectures. Using AIPSe as the channel in a ferroelectric semiconductor transistor, we achieve a 69% memory window, an on/off ratio exceeding 10 6 , and exceptional endurance and retention. This study establishes a chemical strategy for modulating polar properties in materials, unveiling unprecedented chemical insights into the ferroelectric regulation of vdW crystals.}, archive = {J_JACS}, author = {Fapeng Sun and Haojie Xu and Qiankun Ju and Wenting Hong and Qian Cai and Zhihua Sun and Wei Liu}, doi = {10.1021/jacs.5c07965}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26804--26812}, shortjournal = {J. Am. Chem. Soc.}, title = {Field-induced interlayer ion migration and electronic coupling unlock ferroelectricity in centrosymmetric AgInP2Se6 crystals}, volume = {147}, year = {2025}, }
• (2025). Highly efficient near-infrared light-driven molecular motor rotation enabled by upconversion nanoparticles as nanoscale light sources. JACS, 147(30), 26797--26803. (www)

  @article{ , abstract = {Powering light-driven molecular motors with visible or near-infrared (NIR) light is essential in the design of molecular machines, bringing dynamic functions to the next generation of responsive materials particularly for biological applications. However, current strategies suffer from heavy molecular substitution and low photoefficiency of excitation, limiting their practical use in bulk materials and biomolecular systems. Here, we report a general and highly efficient strategy to power NIR light-driven molecular motors via a radiative energy transfer mechanism. Taking advantage of spectrally tunable upconversion nanoparticles (UCNPs), the motors powered by continuous wave NIR light can reach photostationary states (PSS) with high efficiency, comparable to those of direct UV/visible light-driven systems, without a deaeration process needed. The concept is validated on various molecular motors with different rotary speeds, providing a general, broadly applicable principle for the future design of highly efficient NIR-powered photodynamic molecular motor systems.}, archive = {J_JACS}, author = {Jinyu Sheng and Youxin Fu and Kefan Wu and Thomas Freese and Hong Zhang and Ben L. Feringa}, doi = {10.1021/jacs.5c07953}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26797--26803}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly efficient near-infrared light-driven molecular motor rotation enabled by upconversion nanoparticles as nanoscale light sources}, volume = {147}, year = {2025}, }
• (2025). 8-quinox cobalt catalyst enables the reductive alkylative addition of sulfinylamines with unactivated alkyl halides. JACS, 147(30), 26786--26796. (www)

  @article{ , abstract = {Sulfur-based chiral centers play a critical role in drug discovery yet pose significant challenges in achieving precise stereochemical control. Sulfinamides, serving as versatile intermediates and chiral auxiliaries, have traditionally required multistep synthesis or auxiliary-dependent strategies. Recent advances using N -sulfinyltritylamine (TrNSO) enabled catalytic arylative additions; however, stereoselective alkylative approaches remain underdeveloped, likely due to the highly reactive alkyl radical intermediate. Herein, we report a cobalt-catalyzed reductive addition strategy for direct enantioselective C(sp 3 )–S bond formation between TrNSO and unactivated alkyl halides. Leveraging an unprecedented 8-Quinox cobalt catalyst, this method delivers alkyl-substituted sulfinamides with broad substrate scope, excellent functional group tolerance, and high enantioselectivity. The protocol is further extended to a cascade addition/cyclization sequence, facilitating the efficient synthesis of enantioenriched sultims. DFT calculations reveal stereochemical control arises from selective alkyl radical addition orchestrated by the chiral cobalt catalyst.}, archive = {J_JACS}, author = {Ning Liu and Hanyu Xia and Yue Shi and Kejie Xu and Zhiying Yu and Xianqing Wu and Genping Huang and Jingping Qu and Yifeng Chen}, doi = {10.1021/jacs.5c07911}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26786--26796}, shortjournal = {J. Am. Chem. Soc.}, title = {8-quinox cobalt catalyst enables the reductive alkylative addition of sulfinylamines with unactivated alkyl halides}, volume = {147}, year = {2025}, }
• (2025). Robust high-spin state in one-dimensional CrX2 (X = cl, br, i) at the single-chain limit. JACS, 147(30), 26776--26785. (www)

  @article{ , abstract = {Low-dimensional magnetic materials have garnered significant interest due to their unique physical properties and potential applications. Nevertheless, the synthesis of one-dimensional (1D) magnetic materials presents challenges, and the properties of these 1D materials at the single-chain limit have not been well investigated. We here explore experimentally and theoretically 1D CrX 2 (X= Cl, Br, I) magnetic single chains residing within carbon nanotubes. Single chains of CrX 2 are confirmed by the atomic-resolution scanning transmission electron microscopy (STEM) imaging and spectroscopy analysis. Electron energy loss spectroscopy clearly reveals the high-spin state of the Cr atoms within the chain. Notably, we present the first precise measurement and analysis of Cr spin state at the single-chain level, revealing that these spin states can be controlled by the local atomic bonding configuration (CrX 2 versus CrX 3 phases). Density functional theory (DFT) calculations support the structural stability and provide the magnetic and electronic properties of the 1D CrX 2 chains.}, archive = {J_JACS}, author = {Yangjin Lee and Linxuan Li and Weihan Zhang and Uje Choi and Kihyun Lee and Young-Min Kim and Wei Ji and Wu Zhou and Kwanpyo Kim and Alex Zettl}, doi = {10.1021/jacs.5c07656}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26776--26785}, shortjournal = {J. Am. Chem. Soc.}, title = {Robust high-spin state in one-dimensional CrX2 (X = cl, br, i) at the single-chain limit}, volume = {147}, year = {2025}, }
• (2025). Convergent total synthesis of erchinines a and b and their c20 epimers. JACS, 147(30), 26769--26775. (www)

  @article{ , abstract = {The total synthesis of two monoterpenoid indole alkaloids (MIAs), erchinines A and B, is described. Isolated from the plant Ervatamia chinensis , both compounds display antimicrobial activity against Trichophyton rubrum and Bacillus subtilis . Their structures are composed of a unique caged system, bearing a 1,4-diazepine fused oxazolidine moiety and containing three successive N , O -acetals. Key features of the synthesis include the construction of the 2-aza-3-oxobicyclo[2.2.2]octene core via an intramolecular pyridone Diels–Alder reaction and a Zr-mediated bisamide reduction that induces a tandem N , O -acetal forming cascade reaction.}, archive = {J_JACS}, author = {Yong Sun Cho and Joseph P. Tuccinardi and John L. Wood}, doi = {10.1021/jacs.5c07636}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26769--26775}, shortjournal = {J. Am. Chem. Soc.}, title = {Convergent total synthesis of erchinines a and b and their c20 epimers}, volume = {147}, year = {2025}, }
• (2025). Characterization of complex-B ([Fe(κ3-cys)(CN)(CO)2]−), biosynthetic precursor to the [FeFe]-hydrogenase active site, and related complexes. JACS, 147(30), 26762--26768. (www)

  @article{ , abstract = {The preparation, spectroscopy, and structure are described for [Fe(κ 3 -cys)(CN)(CO) 2 ] − ([ 2 ] − ). Otherwise known as complex-B, this coordination complex is an early intermediate in the biosynthesis of the active site of the [FeFe]-hydrogenases. As confirmed by X-ray crystallography, the complex is octahedral with a tridentate cysteinate ligand. The octahedron is completed with two CO ligands and CN – , which is trans to thiolate. A second isomer is observed in solution. Complex [ 2 ] − was prepared by treating [Fe(succinimido)(Br)(CN)(CO) 3 ] − ([ 1 ] − ) with cysteinate. From [ 1 ] − the related penicillamine and homocysteine complexes were also prepared. A practical reagent for probing the biosynthetic role of complex-B, called Syn–B–Br, can be produced in good yield from [ 1 ] − . Complex [ 1 ] − is prepared by oxidative addition of N -bromosuccinimide to [Fe(CN)(CO) 4 ] − . The work is complemented by 13 CO exchange experiments and DFT calculations.}, archive = {J_JACS}, author = {Xin Yu and Toby J. Woods and Thomas B. Rauchfuss}, doi = {10.1021/jacs.5c07540}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26762--26768}, shortjournal = {J. Am. Chem. Soc.}, title = {Characterization of complex-B ([Fe(κ3-cys)(CN)(CO)2]−), biosynthetic precursor to the [FeFe]-hydrogenase active site, and related complexes}, volume = {147}, year = {2025}, }
• (2025). PEG-grafted oligolysines stabilize DNA origami while enhancing receptor-specific cell binding. JACS, 147(30), 26748--26761. (www)

  @article{ , abstract = {DNA nanostructures (DNs) offer programmable platforms for targeted biomedical applications, but their limited stability under physiological conditions has hindered their utility. Protective surface modifiers, or “coatings”, can improve DN stability but often impede access of surface-displayed ligands to cell receptors, reducing receptor engagement and target cell binding. Here, we report polyethylene glycol (PEG)-grafted oligolysine coatings that simultaneously enhance DN structural stability and preserve receptor-specific cell binding. We synthesized a 36-member coating library varying in lysine valency, PEG molecular weight, and grafting density, and identified three formulations that bound DNs with ∼ 6-fold higher affinity and conferred ∼ 30-fold greater cargo stability than the widely used K 10 - b -PEG 5k block copolymer. When functionalized with antibodies, coated DNs selectively engaged Fcγ receptors on DC2.4 dendritic cells─a phagocytic cell line prone to nonspecific interactions with uncoated DNs─achieving a 12-fold increase in binding specificity relative to K 10 - b -PEG 5k . Statistical modeling revealed that optimal performance required coordinated tuning of multiple parameters, underscoring the importance of multiparametric design. This work identifies improved protective coatings for DNA origami and establishes a design framework for engineering biostable, receptor-targeted DNA nanodevices for biological applications.}, archive = {J_JACS}, author = {Mohammadamir G. Moghadam and Travis R. Douglas and Shana Alexander and Lindsey K. Fiddes and Grayson Tilstra and Omar F. Khan and Leo Y. T. Chou}, doi = {10.1021/jacs.5c07566}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26748--26761}, shortjournal = {J. Am. Chem. Soc.}, title = {PEG-grafted oligolysines stabilize DNA origami while enhancing receptor-specific cell binding}, volume = {147}, year = {2025}, }
• (2025). Light-driven chemical cascade reduces barriers to hydrogen production. JACS, 147(30), 26739--26747. (www)

  @article{ , abstract = {Photocatalysis offers an opportunity for sustainable hydrogen and chemical production. Traditional systems require semiconductors with very specific conduction-band (CB) properties and expensive noble metal cocatalysts, limiting material availability and increasing costs. Here, we introduce an alternative photocatalytic pathway that bypasses these constraints, producing hydrogen and formic acid via a cascade process. Under illumination, oxygen and methanol are converted to hydrogen peroxide and formaldehyde, which then react in solution to yield hydrogen and formic acid. We demonstrate the viability of the process employing two limited direct photocatalysts, polymeric carbon nitride (which is not active without a cocatalyst) and tungsten oxide (which presents an unsuitable CB). Our method provides significant advantages: bandgap flexibility, reduced energy consumption and environmental impact, and elimination of noble metal cocatalyst costs. This approach expands the range of suitable semiconductor materials for efficient photocatalytic hydrogen production, offering a more economical and practical solution.}, archive = {J_JACS}, author = {Venugopala Rao Battula and Gabriel Mark and Muhammad Saad Naeem and Yash Shah and Michael Volokh and Leanne M. Gilbertson and Núria López and Menny Shalom}, doi = {10.1021/jacs.5c07557}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26739--26747}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-driven chemical cascade reduces barriers to hydrogen production}, volume = {147}, year = {2025}, }
• (2025). Warhead strategy for targeted protein S-nitrosation. JACS, 147(30), 26726--26738. (www)

  @article{ , abstract = {Protein post-translational modifications (PTMs) are critical factors in disease progression. While progress has been made in regulating disease-associated PTMs such as phosphorylation and acetylation, the approach to achieving targeted S-nitrosation for disease treatment, particularly in vivo, remains largely uncharted. This challenge arises because S-nitrosation is primarily mediated by nitric oxide (NO), a gaseous free radical that complicates efforts to confine the effects of NO to a specific protein. Herein, we designed and synthesized α-(NONOate- O 2 -yl) methyl acrylamides as in situ NO-releasing warheads linked to a Bruton’s tyrosine kinase (BTK)-specific skeleton, resulting in targeted S-nitrosation agents ( TSNO1–6 ). These TSNO compounds covalently bind to BTK, releasing NO in situ, which then reacts with BTK to achieve targeted S-nitrosation. Notably, cellular and tissue proteomic studies confirmed that TSNO1 effectively accomplished targeted S-nitrosation of BTK at Cys527, demonstrating promising in vitro and in vivo antitumor activity. Mechanistic studies indicated that S-nitrosation at Cys527 enhanced phosphorylation inhibition at Tyr551 compared to ibrutinib, impeding BTK activation and providing an additional therapeutic benefit beyond covalent inhibition. In addition, we generally extended this strategy to FGFR4 and HER2. Collectively, utilizing the warhead strategy enables us to implement targeted modulation of S-nitrosation.}, archive = {J_JACS}, author = {Chen Zhang and Hui Ye and Duorui Ji and Tao Xiong and Jiayue Yu and Ziyu Qian and Cunrui Li and Hongyu Li and Zhuangzhuang Liang and Yihua Zhang and Jianbing Wu and Zhangjian Huang}, doi = {10.1021/jacs.5c07409}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26726--26738}, shortjournal = {J. Am. Chem. Soc.}, title = {Warhead strategy for targeted protein S-nitrosation}, volume = {147}, year = {2025}, }
• (2025). Accessing square planar cobalt nitrenoid redox isomers across three oxidation states. JACS, 147(30), 26714--26725. (www)

  @article{ , abstract = {The bonding structures of cobalt nitrenoid complexes are fundamental to their reactivity across various transformations. However, unraveling the electronic configuration of these highly covalent Co–N interactions remains a significant challenge. In this study, we present the synthesis and electronic structure elucidation of a cobalt nitrenoid series in the underexplored square planar ligand field. Using a structurally rigid pincer-type platform and arylazides as the nitrene source, a suite of terminal metal nitrenoids featuring formal Co(III/IV/V) centers and electronically distinct aryl substituents was isolated and structurally characterized. Cyclic voltammetry analysis establishes a linear free energy relationship between their reduction potentials and the electronic properties of nitrene substituents. A combination of spectroscopic and computational methods was employed to probe the electronic structures of the cobalt nitrenoid series, including electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption spectroscopy (XAS), and density functional theory (DFT) calculations. The result suggests that on the continuum of metal nitrenoid redox isomerism─ranging from metal imide (NR 2– ) to imidyl radical ( 2 NR – ) to nitrene adduct ( 1 NR/ 3 NR) formulations─the isolated formal Co(III/IV/V) complexes feature predominantly [Co(II)– 2 NR – ], [Co(III)– 2 NR – ] + , and [Co(III)– 1 NR] 2+ characters, respectively.}, archive = {J_JACS}, author = {Yongxian Li and Gregory M. George and Alireza Seyed Hajiseyedjavadi and Claire E. Casaday and Samantha N. MacMillan and Dennis Nordlund and Kyle M. Lancaster and Thomas R. Cundari and Yuyang Dong}, doi = {10.1021/jacs.5c07389}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26714--26725}, shortjournal = {J. Am. Chem. Soc.}, title = {Accessing square planar cobalt nitrenoid redox isomers across three oxidation states}, volume = {147}, year = {2025}, }
• (2025). Unique conductivity behavior in water-in-salt electrolytes driven by ion clusters. JACS, 147(30), 26704--26713. (www)

  @article{ , abstract = {Understanding and predicting ion transport in aqueous electrolytes are crucial for advanced energy storage and biophysics, and many emergent technologies yet remain elusive. Herein, we introduce a unified framework to quantitatively describe and predict electrolyte conductivity that shifts from conventional molar concentration-based metrics to a volume fraction-based approach. Through analyzing a variety of electrolyte solutions via this perspective, we observe a universal conductivity peak at a 37% volume fraction. Small-angle X-ray scattering (SAXS) and molecular dynamics (MD) simulations reveal that nanometer-scale ion clusters drive this general behavior. Moreover, key geometric features of the ion transport pathways─such as pore size, tortuosity, and connectivity─follow a consistent dependence with respect to the volume fraction, reinforcing the argument for the universal conductivity trend. This paradigm shift opens new avenues for designing high-performance electrolytes and provides transformative insights for advancing studies in many fields, wherein molecular aggregates dictate transport properties.}, archive = {J_JACS}, author = {Huong T. D. Nguyen and Shao-Chun Lee and Xingyi Lyu and Lingzhe Fang and Lucas Trojanowski and Rena Gonzalez and MJ Harr and Lalita Rai and Y Z and Tao Li}, doi = {10.1021/jacs.5c07370}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26704--26713}, shortjournal = {J. Am. Chem. Soc.}, title = {Unique conductivity behavior in water-in-salt electrolytes driven by ion clusters}, volume = {147}, year = {2025}, }
• (2025). α-ketoglutarate-dependent dioxygenase-catalyzed macrocyclization in RiPPs. JACS, 147(30), 26693--26703. (www)

  @article{ , abstract = {α-Ketoglutarate-dependent dioxygenases (αKGDs) are versatile biocatalysts for oxidative reactions, yet their role in ribosomally synthesized and post-translationally modified peptide (RiPP) macrocyclization remains unexplored. In this study, we uncover the widespread co-occurrence of JmjC domain-containing αKGDs (JMJDs) with diverse RiPP subfamilies in biosynthetic gene clusters (BGCs) through bioinformatic analysis. Specifically, we identify a conserved group of class II lanthipeptide BGCs encoding a two-component JMJD pair. As a representative example, heterologous reconstitution of the cor BGC from Streptomyces corchorusii , encoding a class II lanthipeptide synthetase CorM and the αKGD pair CorB–CorD, yields the metal-binding lanthipeptide corsin, which features a methyllanthionine (MeLan) ring and a unique Cys(S)-Tyr(Cβ) cross-link. Functional studies reveal that CorM installs a MeLan ring in the precursor peptide CorA, while the CorB–CorD pair catalyzes oxidative Cys(S)-Tyr(Cβ) cross-linking. Mechanistic investigations demonstrate that CorD, a canonical JMJD, catalyzes the Tyr7 Cβ-H abstraction and generates a para -quinone methide ( p QM) intermediate, which undergoes Michael addition with Cys3. CorB, an inactive JMJD homologue, is essential for catalysis, unveiling a unique two-component αKGD system. This work expands the RiPP enzymatic toolkit by introducing αKGDs as radical catalysts for macrocyclization and advances our understanding of the diverse enzymatic strategies driving RiPP structural diversification.}, archive = {J_JACS}, author = {Yinzheng Xia and Ying Shi and Zhixi Xiao and Xiangqian Xie and Boning Wang and Hongwei Yao and Huan Wang}, doi = {10.1021/jacs.5c07332}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26693--26703}, shortjournal = {J. Am. Chem. Soc.}, title = {α-ketoglutarate-dependent dioxygenase-catalyzed macrocyclization in RiPPs}, volume = {147}, year = {2025}, }
• (2025). Catalytic reduction of dinitrogen via hydroboration. JACS, 147(30), 26684--26692. (www)

  @article{ , abstract = {The conversion of dinitrogen (N 2 ) into ammonia (NH 3 ) or other nitrogenous compounds under mild conditions remains highly desirable, given the extremely harsh conditions required by the typically employed Haber–Bosch process, which reacts N 2 with dihydrogen (H 2 ) to produce NH 3 . However, the catalytic conversion of N 2 using H 2 or related compounds containing H–E bonds (where E represents a general element) as reductants under mild conditions has remained elusive. Herein, we report the catalytic reduction of N 2 via hydroboration, wherein N 2 (1 atm) reacts with catecholborane in the presence of molybdenum–nitride complexes bearing PCP-type pincer ligands as catalysts at 60 °C, yielding up to 32 equiv of borylamines based on the molybdenum atom. The catalytic reaction proceeds through three successive 1,2-additions of hydroborane to the molybdenum–nitrogen bond, disproportionation of the molybdenum–hydride complex, and regeneration of the molybdenum–nitride complex via cleavage of the nitrogen–nitrogen triple bond. The catalytic reduction of N 2 with a “H 2 equivalent” under mild reaction conditions represents a notable advance toward the development of ideal nitrogen fixation systems.}, archive = {J_JACS}, author = {Shun Suginome and Atsushi Okochi and Taiji Nakamura and Asuka Konomi and Hiromasa Tanaka and Kazunari Yoshizawa and Yoshiaki Nishibayashi}, doi = {10.1021/jacs.5c07294}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26684--26692}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic reduction of dinitrogen via hydroboration}, volume = {147}, year = {2025}, }
• (2025). Multilevel chiral semiconductor metal-peptide framework thin film for highly circularly polarized visible photodetection. JACS, 147(30), 26674--26683. (www)

  @article{ , abstract = {The development of chiral metal–organic frameworks (MOFs) for highly circularly polarized (CP) photodetection in visible light is a challenging task. Herein, a wafer-scale multilevel chiral MOF thin film is prepared from helical secondary structural tripeptide ligand with a liquid-phase epitaxial layer-by-layer method for CP photodetector. The resulting 3D Cu-tripeptide framework CAS-4 (CAS: Chinese Academy of Sciences) thin film has multilevel chiral structure, [101] growth orientation and semiconductive feature with the mobility of 31 cm 2 V –1 s –1 , achieving a high-performance CP visible photodetector with an anisotropy factor of 0.51, a responsivity of 0.90 A/W and a high detectivity of 1.58 × 10 11 Jones at 10 V under 600 nm light irradiation. In addition, by combining image sensing with convolutional neural network technology, a simple machine vision system is simulated to achieve effective and accurate enantiomer recognition. Furthermore, the CAS-4 thin film demonstrates the achievement of chiral recognition of S- and R-naproxen enantiomers through monitoring the CP visible photodetector signal. The presented finding not only develops a new type of 3D chiral semiconductive MOF thin film for chiral photoelectric applications but also provides guidance for developing high-performance circularly polarized optoelectronic devices.}, archive = {J_JACS}, author = {Jin-Biao Zhang and Na Li and Zhi-Gang Gu and Jian Zhang}, doi = {10.1021/jacs.5c07024}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26674--26683}, shortjournal = {J. Am. Chem. Soc.}, title = {Multilevel chiral semiconductor metal-peptide framework thin film for highly circularly polarized visible photodetection}, volume = {147}, year = {2025}, }
• (2025). Reversible CO insertion into the si = si double bond enables a disila-bislactone formation via subsequent CO2 addition. JACS, 147(30), 26663--26673. (www)

  @article{ , abstract = {Carbon monoxide inserts into the Si═Si double bond of an imino(silyl)disilene and tetra(silyl)disilene affording the corresponding 1,3-disilaallene oxides, characterized by NMR spectroscopy and X-ray crystallography and supported by quantum chemical calculations. In the case of imino(silyl)disilene, the CO insertion is less exergonic than for tetrasilyldisilene and, thus, is fully reversible in the presence of a CO trapping agent. The reaction mechanisms and reversibility facilitated by the imino-substituent were supported by quantum chemical calculations. The imino-supported 1,3-disilaallene oxide can react with low-pressure CO 2 to a disila-2,4-furandione; with increased CO 2 pressure, a 6-membered ring, disila-bislactone is formed. Their formation mechanisms were investigated via DFT calculations. Reaction of CO 2 with 1,3-disilaallene oxide was compared to the imino(silyl)disilene reacting with CO 2 in a [2 + 2] cycloaddition.}, archive = {J_JACS}, author = {Fiona J. Kiefer and Arseni Kostenko and Richard Holzner and Shigeyoshi Inoue}, doi = {10.1021/jacs.5c07040}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26663--26673}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible CO insertion into the si = si double bond enables a disila-bislactone formation via subsequent CO2 addition}, volume = {147}, year = {2025}, }
• (2025). Photoswitchable fluorescence of peptide-based hemipiperazines inside of living cells. JACS, 147(30), 26652--26662. (www)

  @article{ , abstract = {Photoswitchable fluorophores that can be toggled with visible light are extremely useful for applications in super-resolution imaging. However, most small-molecule photoswitches suffer from poor aqueous solubility and limited biocompatibility and require UV-light activation. Here, we report a novel class of biocompatible, visible-light-responsive fluorophores based on hemipiperazine (HPI) scaffolds with annulated π-systems─indolo-hemipiperazines (IndHPIs) and pyrrolo-hemipiperazines (PyrHPIs). These compounds display large Stokes shifts (up to 135 nm), reversible photoisomerization with up to 620 nm wavelength of light, and, in particular examples, enhanced fluorescence quantum yields and switching thereof, augmented by internal H-bonding. Selected compounds demonstrated excellent thermal stability of their E-isomers, with half-lives of up to ∼13,000 h at 50 °C, and high fatigue resistance under repeated switching cycles. Notably, certain IndHPIs are efficiently internalized by living cells and exhibit a reversible modulation of fluorescence upon irradiation. Further mechanistic studies revealed that in vitro regeneration of the brighter isomer is mediated by glutathione (GSH) likely via a nucleophile-assisted isomerization pathway, providing a possible insight into the cellular behavior of these switches. The exceptional photophysical properties of IndHPIs position them as promising candidates for photoswitchable compounds for application in biological sciences and components of next-generation optical materials.}, archive = {J_JACS}, author = {Peter Gödtel and Anna Rösch and Susanne Kirchner and Rabia Elbuga-Ilica and Angelika Seliwjorstow and Olaf Fuhr and Ute Schepers and Zbigniew Pianowski}, doi = {10.1021/jacs.5c07013}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26652--26662}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoswitchable fluorescence of peptide-based hemipiperazines inside of living cells}, volume = {147}, year = {2025}, }
• (2025). Microenvironments as an explanation for the mismatch between photochemical absorptivity and reactivity. JACS, 147(30), 26643--26651. (www)

  @article{ , abstract = {Photochemistry is at the forefront of many modern technologies, from additive manufacturing to phototherapeutics to sun protection and organic synthesis. It is commonly believed that an absorbance spectrum, showing the likelihood of a photon to be absorbed by a chromophore at a given wavelength, is an accurate predictor of how well a photochemical process will proceed when irradiated with different colors of light. Over the past decade this paradigm has been repeatedly challenged for many photochemical systems, as a distinct mismatch between the absorption spectrum and the wavelength-resolved photochemical reactivity has been observed. Herein, we unravel the underlying mechanisms behind the mismatched reactivity and absorbance in photocycloadditions. Initially, we probe the impact that an equilibrium established between reversible photochemical processes has on the mismatch for a pyrene-chalcone molecule. Subsequently, we establish a critical link between photophysics and photochemistry with a theory based on the selective excitation of specific microenvironments, leading to molecular transitions that allow for favorable wavelength-dependent reactivity. Time-resolved and steady-state fluorescence spectroscopy measurements confirm the presence of this selectivity, with both displaying significant red-edge effects that are observed in the fluorescence spectroscopy literature, further supporting our theory. By synthetically tethering chromophores together, we evidence the importance of microenvironments and their wavelength-dependent excited-state lifetimes, presenting the missing link that explains the mismatch in many photochemical systems. The implications of the theory presented herein stretch from additive manufacturing to photodynamic therapy and beyond, meaning that researchers can leverage mismatched photochemical reactivity by simply changing the properties of the environment surrounding the chromophore.}, archive = {J_JACS}, author = {Joshua A. Carroll and Fred Pashley-Johnson and Maciej Klein and Theresa Stephan and Ajay K. Pandey and Michael Walter and Andreas-Neil Unterreiner and Christopher Barner-Kowollik}, doi = {10.1021/jacs.5c06961}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26643--26651}, shortjournal = {J. Am. Chem. Soc.}, title = {Microenvironments as an explanation for the mismatch between photochemical absorptivity and reactivity}, volume = {147}, year = {2025}, }
• (2025). Accelerated methane photo-oxidation at the Air–Water interface. JACS, 147(30), 26635--26642. (www)

  @article{ , abstract = {Methane (CH 4 ) is a potent greenhouse gas, and its atmospheric lifetime is primarily regulated by oxidative depletion. While hydroxyl radical (•OH)-initiated oxidation of CH 4 in bulk-phase systems has been thoroughly characterized, the photo-oxidation of CH 4 at the air–water interface remains poorly understood. Here, we report that photo-oxidation of CH 4 at the air–water interface of microdroplets exhibits an order of magnitude rate enhancement compared to gas-phase reactions. Quantitative analysis reveals 5.0–30.4-fold enhancements in the production rates of key oxidation products (CH 3 OOH, CH 3 OH, CH 2 O, HCOOH, and CO 2 ) in microdroplet-mediated processes relative to gas-phase counterparts under UV irradiation. We propose that this accelerated CH 4 oxidation is fueled by the reaction of interfacially accumulated •OH with CH 4 , resulting in the formation of •CH 3 through a low-barrier mechanism. Additionally, we uncover a new reaction path in which •CH 3 reacts with the interfacial superoxide radical (O 2 •– ) via a barrierless exothermic process, leading to a higher yield of CH 3 OOH than in bulk-phase reactions. This discovery provides important insights into the atmospheric CH 4 depletion process and may help resolve existing uncertainties in the estimation of atmospheric CH 4 depletion rates and the greenhouse gas budget.}, archive = {J_JACS}, author = {Xiaoshan Zheng and Ye-Guang Fang and Mengxi Tan and Baoliang Chen and Joseph S. Francisco and Chongqin Zhu and Chiheng Chu}, doi = {10.1021/jacs.5c06925}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26635--26642}, shortjournal = {J. Am. Chem. Soc.}, title = {Accelerated methane photo-oxidation at the Air–Water interface}, volume = {147}, year = {2025}, }
• (2025). Polymer-like photochromic tungsten oxide sub-1 nm nanowires. JACS, 147(30), 26626--26634. (www)

  @article{ , abstract = {Photochromic materials are promising in optical information storage, nonlinear optics, nonemissive displays, smart windows, etc. Photochromic transition metal oxides have significant advantages in stability and cost but are limited by poor processability. Herein, tungsten oxide sub-1 nm nanowires (TOSNWs) with a diameter of 0.8 nm and a length of several microns are synthesized by a solvothermal method. The extremely high aspect ratio endows them with polymer-analogous properties and good processability. The as-prepared TOSNWs exhibit a transmittance >95% in the visible light region, a rapid photochromic response within 15 s, and show broad near-infrared absorption after photochromic transformation, which are potential candidates as light-triggered transparent heat ray shielding materials.}, archive = {J_JACS}, author = {Biao Yu and Yueyue Xiu and Simin Zhang and Xun Wang}, doi = {10.1021/jacs.5c06958}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26626--26634}, shortjournal = {J. Am. Chem. Soc.}, title = {Polymer-like photochromic tungsten oxide sub-1 nm nanowires}, volume = {147}, year = {2025}, }
• (2025). Thermal crystal-to-crystal transformation unlocks Ti8O10(OOC)12-cluster-based Metal–Organic frameworks. JACS, 147(30), 26616--26625. (www)

  @article{ , abstract = {Titanium-based metal–organic frameworks (Ti-MOFs) are promising photocatalysts, yet their development has been constrained by the limited diversity of Ti-oxo clusters successfully incorporated into MOFs under solvothermal conditions. Herein, we demonstrate a thermal solid-state synthetic strategy to access new Ti-MOFs (MIL-125-HT series) featuring Ti 8 O 10 (OOC) 12 clusters via the crystal-to-crystal transformation of MIL-125 and its functionalized derivatives. Controlled thermal treatment of MIL-125 induces dehydration and rearrangement of the original Ti 8 O 8 (OH) 4 (OOC) 12 clusters while preserving crystallinity and the framework topology. The atomic-resolution structure of MIL-125-HT was determined through three-dimensional electron diffraction and synchrotron powder X-ray diffraction. The phase transition temperature and crystallinity of the resulting MIL-125-HT are governed by the functional groups on the linkers, which affect both the rotational flexibility required for cluster rearrangement and the thermal stability necessary to avoid framework collapse. Naphthalene-based linkers provide an optimal combination of flexibility and robustness, yielding highly crystalline high-temperature phases. Compared to MIL-125, MIL-125-HT exhibits a reduced band gap and enhanced photocatalytic activity in hydrogen peroxide production. This work establishes a solid-state approach for uncovering previously inaccessible Ti-MOFs, broadening their synthetic landscape and enabling new opportunities in photocatalysis.}, archive = {J_JACS}, author = {Lei Gao and Zhenghan Zhang and Jian Li and Shuai Yuan}, doi = {10.1021/jacs.5c06825}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26616--26625}, shortjournal = {J. Am. Chem. Soc.}, title = {Thermal crystal-to-crystal transformation unlocks Ti8O10(OOC)12-cluster-based Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Shape-orchestrated Soft–Hard-tandem tracers: A magnetic control strategy for advanced magnetic particle imaging. JACS, 147(30), 26605--26615. (www)

  @article{ , abstract = {Magnetic particle imaging (MPI) is a promising diagnostic technology. However, its widespread adoption is hindered by suboptimal tracer performance, largely owing to limitations in nanoparticle design. To address these challenges, we developed a novel class of shape-orchestrated octahedral iron oxide nanoparticles (O-IONPs) using an innovative soft–hard-tandem (SHT) magnetic optimization strategy. This approach significantly enhances magnetic properties by suppressing surface spin disorder and fine-tuning surface magnetic anisotropy, yielding exceptional saturation magnetization ( M s = 101.06 ± 2.40 emu/g) alongside minimal coercivity ( H c < 2 Oe). As a result, our O-IONP tracer exhibited outstanding MPI performance, generating a 5.3-fold signal enhancement over the commercial tracer Vivo Trax at equivalent Fe doses while achieving submillimeter resolution (1.0 mm) and a detection limit of 24 ng Fe. Furthermore, by coating the nanoparticles with 4T1-macrophage hybrid cell membranes, we amplified in vivo MPI signals by 76.4-fold, yielding performance comparable to that of Vivo Trax with just a 60 μg intratumoral injection. This study bridges the gap between theoretical predictions and practical MPI applications by unlocking the full diagnostic potential of MPI using the SHT strategy.}, archive = {J_JACS}, author = {Peng Yang and Deshang Duan and Weijing Liu and Yuge Li and Haohao Yan and Jiamin Xu and Yizhuo Sun and Danyang Wang and Zhuang Chen and Ruili Zhang and Jie Tian and Zhongliang Wang}, doi = {10.1021/jacs.5c06844}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26605--26615}, shortjournal = {J. Am. Chem. Soc.}, title = {Shape-orchestrated Soft–Hard-tandem tracers: A magnetic control strategy for advanced magnetic particle imaging}, volume = {147}, year = {2025}, }
• (2025). Enduring CO electrolysis with ampere-level reaction rates using nickel-doped iridium catalysts. JACS, 147(30), 26595--26604. (www)

  @article{ , abstract = {CO 2 /CO electrolysis offers a scalable pathway for electrosynthesis of multicarbon fuels and chemicals. However, current systems face challenges such as low energy and carbon efficiencies when operated at industrially relevant reaction rates. Our preliminary analysis revealed that the combination of high reaction rates and product crossover-induced pH reduction accelerates anode dissolution, leading to cathode poisoning and, ultimately, performance degradation. Here, we report a strategy to mitigate these challenges by dispersing a low concentration of nickel in an iridium oxide host to promote the stability of iridium species while inhibiting the oxidation of nickel sites. We synthesize a low-valence-nickel in iridium oxide anode material that exhibits high activity and stability for oxygen evolution, while remaining inactive for the oxidation of liquid products migrating from the cathode. In situ soft X-ray photoemission spectroscopy reveals the presence of active sites comprising Ni 2+ and Ir 4+ species. By incorporating this catalyst into an membrane electrode assembly setup, we achieve CO electroreduction on copper with a full-cell energy efficiency of 32% and a carbon efficiency of 73% at 1000 mA per square centimeter, alongside sustained stability over 1000 h of continuous operation.}, archive = {J_JACS}, author = {Hanqi Liu and Adnan Ozden and Ruihu Lu and Ning Sun and Rui Kai Miao and Kaili Yao and Ruiyan Xie and Yi Xu and Hui Zhang and Yongfeng Hu and Ziyun Wang and Jun Li and David Sinton}, doi = {10.1021/jacs.5c06853}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26595--26604}, shortjournal = {J. Am. Chem. Soc.}, title = {Enduring CO electrolysis with ampere-level reaction rates using nickel-doped iridium catalysts}, volume = {147}, year = {2025}, }
• (2025). Scaffold hopping of α,β-unsaturated ketones via divergent alkyl amine insertion. JACS, 147(30), 26584--26594. (www)

  @article{ , abstract = {α,β-Unsaturated carbonyl compounds are pivotal intermediates in organic synthesis, widely utilized in nucleophilic addition reactions for constructing C–C and C–heteroatom bonds. Primary amines are essential building blocks in drug discovery, and their reactions with α,β-unsaturated carbonyl compounds yield key intermediates for pharmaceuticals, natural products, and bioactive molecules. Traditional methods often emphasize 1,2- or 1,4-additions, targeting peripheral modifications. Meanwhile, skeletal nitrogen-insertion reactions are primarily effective with electron-rich alkenes or saturated ketone sites, while the direct editing of α,β-unsaturated ketones is typically limited to problematic Schmidt reactions. In this study, we realize a divergent skeletal editing strategy for α,β-unsaturated ketones via 2,3- and 3,4-amine insertion. This approach facilitates the selective incorporation of alkyl amines between C–C bonds within the same substrate. Our reagent-controlled protocol enables tunable insertion sites through regioselective aziridine intermediate formation and targeted C–C bond cleavage, producing most amine insertion products in a one-pot process. Importantly, this strategy provides differential and complementary regioselectivity to traditional Schmidt reactions, allowing selective synthesis of various pyridyl isomers from a single substrate, including complex natural products and drug candidates.}, archive = {J_JACS}, author = {Huiguang Yu and Lili Xu and Luyao Li and Chang Min}, doi = {10.1021/jacs.5c06690}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26584--26594}, shortjournal = {J. Am. Chem. Soc.}, title = {Scaffold hopping of α,β-unsaturated ketones via divergent alkyl amine insertion}, volume = {147}, year = {2025}, }
• (2025). Low-electromotive force-driven sodium compensation for optimizing na deposition in rechargeable sodium batteries. JACS, 147(30), 26573--26583. (www)

  @article{ , abstract = {Sufficient active Na + and stable electrode–electrolyte interfaces enable anode-free sodium batteries to achieve high energy densities and long operational lifespan. Here, we establish the critical role of low electromotive force (EMF) in promoting uniform Na deposition and stable interfacial chemistry by minimizing overpotential and mitigating steep concentration gradients. We accordingly designed a versatile cathode, Na-replenished P2-type oxides (NRP2), with reversible overstoichiometric Na-ion insertion that incorporates sodium compensation and promotes Na leveling deposition. By releasing the prestored Na-ions at a low voltage, the NRP2 cathode supplements the loss of active Na + during the initial formation of the solid electrolyte interphase (SEI). Simultaneously, it creates a low EMF to facilitate uniform and dense metal deposition at the anode surface. The deposited Na metal shows a regular two-dimensional polygonal morphology, in contrast to the dendritic morphology with the high EMF condition. As a result, the rechargeable Na-metal batteries that employ the NRP2–50 demonstrate a capacity retention of 90.1% after 500 cycles and capacity retention of 97.4% over 50 cycles in an anode-free geometry.}, archive = {J_JACS}, author = {Yu-Ying Zhang and Chao-Hui Zhang and Yu-Jie Guo and Xu-Sheng Zhang and Min Fan and Xin-Hai Meng and Xing Zhang and Yao Zhao and Fuyi Wang and Sen Xin and Yu-Guo Guo and Li-Jun Wan}, doi = {10.1021/jacs.5c06704}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26573--26583}, shortjournal = {J. Am. Chem. Soc.}, title = {Low-electromotive force-driven sodium compensation for optimizing na deposition in rechargeable sodium batteries}, volume = {147}, year = {2025}, }
• (2025). An anaerobic biomimetic metal-free AIE polymersome nanozyme as NADH oxidase mimic for photocatalytic tumor suppression by impairing cancer cell energy metabolism under hypoxia. JACS, 147(30), 26557--26572. (www)

  @article{ , abstract = {The intracellular balance between nicotinamide adenine dinucleotide and its reduced form (NAD + /NADH) is essential for cell metabolism. The NAD + /NADH redox imbalance strategy using NADH-oxidase-mimic nanozymes has emerged as an attractive antitumor strategy. Here, we develop a photocatalytic metal-free nanozyme that is a polymer vesicle (polymersome) self-assembled from PEG-block-poly(amino acid) functionalized by photocatalytic moieties with aggregation-induced emission (AIE). To enhance biocompatibility and tumor-targetability, the vesicle is coated with a folate-modified red-blood-cell membrane (FA-RBC) to get biomimetic AIE polymersome nanozyme (BV). Unlike conventional photocatalysts, BV can achieve the cyclical photocatalytic process for NADH–NAD + conversion without O 2 or additional electron acceptors. A new mechanism is proposed in which adjacent excited triplet molecules in the AIE assembly play the role of electron acceptors for complete NADH–NAD + conversion and catalyst turnover. This O 2 -independent photocatalysis is appealing in anticancer treatment since the tumor has a hypoxic microenvironment. In vitro and in vivo investigations demonstrate BV induces a severe NAD + /NADH imbalance under hypoxia to lead to inhibition of oxidative phosphorylation and glycolysis, which triggers the energy crisis in 4T1 cancer cells and in the 4T1 tumor of a subcutaneous xenograft model. This work presents a novel approach of cancer therapy through the photocatalytic impairment of tumor energy metabolism by metal-free nanozyme.}, archive = {J_JACS}, author = {Yandong Ma and Yakui Deng and Wei Xue and Xin Ji and Min-Hui Li}, doi = {10.1021/jacs.5c06533}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26557--26572}, shortjournal = {J. Am. Chem. Soc.}, title = {An anaerobic biomimetic metal-free AIE polymersome nanozyme as NADH oxidase mimic for photocatalytic tumor suppression by impairing cancer cell energy metabolism under hypoxia}, volume = {147}, year = {2025}, }
• (2025). Amplifying chirality-induced spin selectivity in helical covalent organic frameworks through fullerene encapsulation. JACS, 147(30), 26546--26556. (www)

  @article{ , abstract = {The chirality-induced spin selectivity (CISS) is fundamental to spintronics and molecular electronics; however, achieving high and tunable spin polarization remains challenging due to the difficulty in precisely engineering chiral architectures and modulating spin–orbit interactions. Here, we report a host–guest strategy to amplify the CISS effect by encapsulating fullerenes (C 60 and C 70 ) within three-dimensional (3D) helical chiral covalent organic frameworks (CCOFs). Two pairs of enantiomeric CCOFs ( 37 and 38 ) are synthesized from chiral binaphthalene dialdehydes and a tetraamine, forming right- and left-handed helical structures. The resulting fullerene@CCOF adducts, prepared via in situ self-assembly, exhibited clear chirality transfer, as evidenced by strong Cotton effects in circular dichroism spectra. Magnetic conductive atomic force microscopy (mc-AFM) revealed pronounced spin-selective charge transport in the pristine CCOFs, which was significantly enhanced upon fullerene encapsulation─boosting spin polarization from 46–50 to 77% with C 60 , and up to 90% with C 70 . The superior enhancement observed with C 70 is likely due to its ellipsoidal geometry, which facilitates stronger π–π interactions and more effective spin–orbit coupling within the chiral environment. This study represents the first demonstration of CISS modulation through guest encapsulation in chiral materials, underscoring the promise of host–guest interactions as a robust platform for developing advanced spintronic materials and devices.}, archive = {J_JACS}, author = {Xiaofeng Zhang and Shiguo Fu and Lei Jia and Bang Hou and Yong Cui and Yan Liu}, doi = {10.1021/jacs.5c06460}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26546--26556}, shortjournal = {J. Am. Chem. Soc.}, title = {Amplifying chirality-induced spin selectivity in helical covalent organic frameworks through fullerene encapsulation}, volume = {147}, year = {2025}, }
• (2025). Assignment-free determination of ligand binding sites in proteins by solid-state NMR. JACS, 147(30), 26534--26545. (www)

  @article{ , abstract = {Solid-state NMR studies of ligand binding sites in proteins traditionally require assignment of the observed resonances to the amino acid sequence. This sequential assignment is time-consuming and constitutes a major bottleneck in protein solid-state NMR. To determine ligand binding sites in proteins whose structures are already known, experimentally measured protein–ligand distances can be analyzed much more rapidly if sequential assignment can be bypassed. Here we present an assignment-free NMR approach for determining ligand binding sites in proteins. We measure 2D 13 C– 13 C resolved 13 C– 19 F rotational-echo double-resonance (REDOR) spectra that probe protein–ligand proximities and assign the peaks in the 2D spectra to residue types based on the well-known characteristic chemical shifts of amino acids. We simulate the measured REDOR dephasing using a second-moment approximation with an empirically calibrated scaling factor that accounts for experimental imperfections. This efficient REDOR simulation is combined with simulated annealing to rapidly search for ligand positions that agree with the type-assigned REDOR dephasing. We demonstrate this approach on the model protein GB1 and show that the position of a single fluorine can be determined accurately. We then apply this technique to the bacterial transporter EmrE and show that the location of a tetra-fluorinated ligand is within the range of positions found by this assignment-free REDOR approach. This technique should accelerate studies of ligand binding sites in membrane proteins, amyloids, and large protein complexes, and should also be applicable to dynamic nuclear polarization experiments at cryogenic temperature where broad lines may prohibit sequential assignment.}, archive = {J_JACS}, author = {Noah H. Somberg and Iva Sučec and Mei Hong}, doi = {10.1021/jacs.5c06493}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26534--26545}, shortjournal = {J. Am. Chem. Soc.}, title = {Assignment-free determination of ligand binding sites in proteins by solid-state NMR}, volume = {147}, year = {2025}, }
• (2025). Cascade energy transformation in hybrid nanosensitizer enables ultrasound-activated luminescence imaging and enhanced sonodynamic therapy. JACS, 147(30), 26518--26533. (www)

  @article{ , abstract = {Optical imaging plays a pivotal role in the diagnosis and management of cancer, yet conventional techniques often suffer from limitations such as tissue autofluorescence, insufficient imaging depth, and signal persistence. Here, we introduce a hybrid nanosensitizer, SPNs(SP1)@CoOOH, that leverages cascade energy transformation (ultrasonic → chemical → photonic energy) to enable ultrasound-activated luminescence imaging concomitant with enhanced sonodynamic therapy (SDT). By integrating semiconducting polymer nanoparticles (SPNs) with cobalt oxide hydroxide (CoOOH), our platform facilitates dual-pathway reactive oxygen species (ROS) generation under acidic and ultrasound costimulation. In this system, the ultrasound enhanced the chemodynamic effect of CoOOH to catalyze water into singlet oxygen, while ultrasound improves electron–hole separation within the SPNs, leading to efficient hydroxyl radical formation. This dual mechanism results in a 3.5-fold increase in ROS production relative to SPNs alone and triggers ROS-thiophene interactions that emit luminescence. Notably, the emitted luminescence correlates linearly with ROS levels and tumor inhibition rates, offering a robust method for a real-time monitoring therapeutic process. Furthermore, our modular design extends to other organic systems, including cyanine and porphyrin-based nanostructures, achieving up to 14.2-fold enhancements in ROS generation and 6.3-fold increases in luminescence intensity. By addressing the dual challenges of inefficient ROS production and real-time monitoring in SDT, our study lays the foundation for next-generation ultrasound-driven theranostics, paving the way for luminescence imaging-guided, personalized cancer therapy.}, archive = {J_JACS}, author = {Xu Li and Yong Tan and Zhe Li and Youjuan Wang and Chang Lu and Shiyi Liao and Baoli Yin and Baode Chen and Huiyi Liu and Hanlin Wei and Guosheng Song}, doi = {10.1021/jacs.5c06434}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26518--26533}, shortjournal = {J. Am. Chem. Soc.}, title = {Cascade energy transformation in hybrid nanosensitizer enables ultrasound-activated luminescence imaging and enhanced sonodynamic therapy}, volume = {147}, year = {2025}, }
• (2025). Iridium-catalyzed regio- and enantioselective reverse prenylation of tryptamines and other 3-substituted indoles. JACS, 147(30), 26506--26517. (www)

  @article{ , abstract = {Prenylated indole alkaloids from bacteria, fungi, plants, and animals comprise a large structural diversity with a broad range of biological activities. A subclass of this alkaloid family are the C 3a-reverse prenylated hexahydropyrrolo[2,3- b ]indole (HPI) natural products that are in principle synthetically accessible via a metal-catalyzed allylic substitution. Here we report the first catalytic enantioselective reverse prenylation of achiral 3-substituted indoles that furnishes hexahydropyrrolo[2,3- b ]indoles in a single step. The developed catalytic system utilizes a novel iridium–NHC–phosphoramidite catalyst and provides the C 3-prenylated products with high yields and enantioselectivities as well as complete branched selectivity. This elaborate methodology closes a systematic gap in asymmetric allylic substitution chemistry and offers a convenient strategy for the synthesis of tryptamine-derived alkaloids as demonstrated in a short biomimetic total synthesis of (−)-flustramine A, a prototypical member of this class of natural products. Mechanistic investigations elucidate the catalyst’s structure and reveal a chloride-induced allyl complex isomerization, which is dependent on the hemilabile phosphoramidite-olefin Carreira-type ligand.}, archive = {J_JACS}, author = {Leon Sander and Jonas M. Müller and Christian B. W. Stark}, doi = {10.1021/jacs.5c06364}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26506--26517}, shortjournal = {J. Am. Chem. Soc.}, title = {Iridium-catalyzed regio- and enantioselective reverse prenylation of tryptamines and other 3-substituted indoles}, volume = {147}, year = {2025}, }
• (2025). Planar defect layers template a high-pressure InBi polymorph. JACS, 147(30), 26496--26505. (www)

  @article{ , abstract = {The short- and long-range order of III–V materials under high pressure has long been the subject of debate, with advancements in structural characterization leading to significant revisions to the accepted structural models. Despite these revisions, previous high-pressure structural assignments in the In–Bi system include the site-disordered β-Sn structure type, a structure type demonstrated to be nonexistent in analogous III–V systems. While X-ray diffraction is consistent withsite disordering in InBi at high pressure, cluster expansion calculations indicate that disordering requires temperatures above 3000 K. We propose InBi as a model material for studying unique high-pressure planar defects due to its highly anisotropic stress-dependent properties and structure. Specifically, we identify two sets of planar defects that mimic the diffraction pattern of a site disordered β-Sn structure type and are compatible with the calculated disorder barrier. We derive these defects by symmetry relations over crystallographic transitions. Density functional theory calculations of the proposed defects suggest that these defects are stabilized by diminishing interlayer separations with pressure. Further, we find that one of the proposed defects closely resembles a bulk high-pressure phase of InBi, InBi-ϵ, and we assert that the proposed defects order upon heating, acting as a template for InBi-ϵ growth. The proposed defects and their electronic structure provide a basis for the trend of superconducting critical temperature with increasing pressure. These methods for identifying defects are generalizable to other materials with reports of site disorder at high pressure, prompting a broader search for related high-pressure defects.}, archive = {J_JACS}, author = {Eric A. Riesel and Zhenyao Fang and Douglas H. Fabini and Alison B. Altman and Yue Meng and Sanjit K. Ghose and Matthew L. Whitaker and Changyong Park and Dmitry Y. Popov and Andrew M. Rappe and Danna E. Freedman}, doi = {10.1021/jacs.5c06253}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26496--26505}, shortjournal = {J. Am. Chem. Soc.}, title = {Planar defect layers template a high-pressure InBi polymorph}, volume = {147}, year = {2025}, }
• (2025). C(sp3)–N coupling of nonactivated alkyl boronic pinacol esters by the merger of amino radical transfer and copper catalysis. JACS, 147(30), 26486--26495. (www)

  @article{ , abstract = {Metal-catalyzed C(sp 3 )–N coupling remains a formidable synthetic challenge, especially with alkyl electrophiles, due to competing pathways such as slow oxidative addition, β-hydride elimination, and alkyl isomerization. While alkyl halides are commonly used, their limitations have spurred interest in alternative coupling partners. Alkyl boronic pinacol esters (Bpins), though stable and widely accessible, are underutilized in C–N coupling due to their poor transmetalation reactivity and susceptibility to protodeborylation and isomerization. Here, we report a dual catalytic strategy that merges copper catalysis with photocatalytically enabled amino radical transfer (ART) to achieve C(sp 3 )–N coupling of nonactivated alkyl Bpins under mild, redox-neutral conditions. Readily available morpholino benzoate acts both as an aminyl radical precursor and as an internal oxidant, circumventing the need for external oxidants and enabling efficient coupling between two nucleophiles. This strategy delivers a general and regioselective platform for C(sp 3 )–N bond formation, accommodating a broad array of amines (12 classes), including indoles, indazoles, pyrazoles, anilines, and sulfonamides. The synthetic utility is further exemplified through the late-stage functionalization of complex drug molecules and a one-pot hydroamination of alkenes.}, archive = {J_JACS}, author = {Swapan Shil and Bishnu Pada Patra and Tania Begam and Srikrishna Bera}, doi = {10.1021/jacs.5c06042}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26486--26495}, shortjournal = {J. Am. Chem. Soc.}, title = {C(sp3)–N coupling of nonactivated alkyl boronic pinacol esters by the merger of amino radical transfer and copper catalysis}, volume = {147}, year = {2025}, }
• (2025). Breaking kasha’s rule to enable higher reactivity in photoredox catalysis. JACS, 147(30), 26477--26485. (www)

  @article{ , abstract = {Nearly all photochemical transformations known to date follow Kasha’s rule, implying that reactions occur only from the lowest electronically excited state of a given spin multiplicity due to the fast relaxation of higher-energy states. We challenge this foundational principle by demonstrating with time-resolved laser spectroscopy that the 4,4″-dicyano- p -terphenyl radical anion can undergo photoinduced electron transfer directly from a higher-energy excited state, enabling reactivity inaccessible to the lowest excited state with the same spin multiplicity. Preassociation with the substrate and driving-force optimization are critical for overcoming the kinetic barrier to subnanosecond electron transfer, enabling bimolecular anti-Kasha reactivity. This advance establishes a general and broadly applicable framework for bypassing one of the most fundamental principles of photophysics and photochemistry, Kasha’s rule, and opens new possibilities in photoredox catalysis and solar energy conversion by rethinking the energetic and kinetic landscape.}, archive = {J_JACS}, author = {Björn Pfund and Oliver S. Wenger}, doi = {10.1021/jacs.5c06115}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26477--26485}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking kasha’s rule to enable higher reactivity in photoredox catalysis}, volume = {147}, year = {2025}, }
• (2025). Terminal carboxyl editing drives divergence in fasamycin and anthrabenzoxocinone biosynthesis. JACS, 147(30), 26468--26476. (www)

  @article{ , abstract = {Aromatic polyketides are a vast category of natural products known for their wide-ranging biological activities, with their structural variety stemming from modifications to their core frameworks. This study reveals two distinct processes that shape the frameworks of (+)/(−)-anthrabenzoxocinone (ABX) and fasamycin (FAS) from a common biosynthetic precursor, compound 1 . FasS protects the carboxyl group of this molecule without altering it, preparing it for FasU, which then crafts FAS’s unique, nonplanar axial chiral aromatic framework. In contrast, Abx (+) O and Abx (−) O remove the carboxyl group from compound 1 , producing phenyldimethylanthrone (PDA), a key intermediate for (+)/(−)-ABX formation. Structural analysis of AccS (1.65 Å, FasS homologue) and Abx (+) O (1.99 Å), combined with mutagenesis studies, identifies key residues of AccS and Abx (+) O, providing insights into the carboxyl-protecting mechanism and decarboxylation mechanism. Evolutionary and functional studies further connect AccS and AbxO to the N- and C-termini of the long-studied, functionally enigmatic protein family, WhiE-ORFI (resolved in 2.3 Å). This study unveils hidden strategies for terminal carboxyl group editing, providing new insights into the origins of aromatic polyketide diversity.}, archive = {J_JACS}, author = {Kai Jiang and Cheng Zhu and Yan Gao and Yuhan Dai and Xiaoli Yan and Lu Yang and Ming Jiang and Zhi Lin and Zixin Deng and Shukun Luo and Xudong Qu}, doi = {10.1021/jacs.5c06089}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26468--26476}, shortjournal = {J. Am. Chem. Soc.}, title = {Terminal carboxyl editing drives divergence in fasamycin and anthrabenzoxocinone biosynthesis}, volume = {147}, year = {2025}, }
• (2025). The dynamical role of optical phonons and sublattice screening in a solid-state ion conductor. JACS, 147(30), 26456--26467. (www)

  @article{ , abstract = {Solid-state electrolytes (SSEs) require ionic conductivities that are competitive with liquid electrolytes to realize applications in all-solid-state batteries. Although candidate SSEs have been discovered, the underlying mechanisms enabling superionic conduction (>1 mS cm –1 ) remain elusive. In particular, the role of ultrafast lattice dynamics in mediating ion migration, which involves couplings between ions, phonons, and electrons, is rarely explored experimentally at their corresponding time scales. To investigate the complex contributions of coupled lattice dynamics on ion migration, we modulate the charge density occupations within the crystal framework and then measure the time-resolved change in impedance on picosecond time scales for a candidate SSE, Li 0.5 La 0.5 TiO 3 (LLTO). Upon perturbation, we observe enhanced ion migration at ultrafast time scales. The respective transients match the time scales of optical and acoustic phonon vibrations, suggesting their involvement in ion migration. We further computationally evaluate the effect of a charge transfer from the O 2p to the Ti 3d band on the electronic and physical structure of LLTO. We hypothesize that the charge-transfer excitation distorts the TiO 6 polyhedra by altering the local charge density occupancy of the hopping site at the migration pathway saddle point, thereby causing a reduction in the migration barrier for the Li + hop. We rule out the contribution of photogenerated electron carriers and laser heating. Overall, our investigation introduces a new spectroscopic tool to probe fundamental ion hopping mechanisms transiently at ultrafast time scales, which has previously only been achieved in a time-averaged manner or solely via computational methods.}, archive = {J_JACS}, author = {Kim H. Pham and Vijaya Begum-Hudde and Amy K. Lin and Natan A. Spear and Jackson McClellan and Michael W. Zuerch and Andre Schleife and Kimberly A. See and Scott K. Cushing}, doi = {10.1021/jacs.5c06064}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26456--26467}, shortjournal = {J. Am. Chem. Soc.}, title = {The dynamical role of optical phonons and sublattice screening in a solid-state ion conductor}, volume = {147}, year = {2025}, }
• (2025). Dynamic excited-state localization induced by Jahn–Teller distortion observed by coherent vibrational spectroscopy. JACS, 147(30), 26446--26455. (www)

  @article{ , abstract = {Molecular symmetry is a central design element in functional materials, yet its dynamic modulation in the excited state and its consequences for optoelectronic properties remain largely unexplored, particularly in main-group p-block element complexes. We address this knowledge gap by investigating unique Al(III) dinuclear triple-helical complexes that combine high symmetry with twisted π-conjugated systems and achieve exceptional optical properties of unusually large Stokes shifts and high photoluminescence quantum yields. Using transient absorption spectroscopy with a 10 fs pump pulse, we detected coherent vibrational oscillations overlapped with transient absorption/stimulated emission signals. Analysis of the dephasing times of oscillatory signals revealed photoexcitation-triggered Jahn–Teller distortions in these high-symmetry p-block complexes, evidenced by a specifically short dephasing time constant of 410 fs associated with intraligand twisting vibrations. Our findings demonstrate that excited-state symmetry breaking, strongly coupled with intraligand twisting vibrations, is crucial in determining the remarkable photofunctional properties of large Stokes shifts and high photoluminescence quantum yields. This work elucidates the fundamental mechanisms underlying the performance of these Al(III) complexes and provides a conceptual framework for designing next-generation photofunctional materials by harnessing dynamic symmetry changes.}, archive = {J_JACS}, author = {Takumi Ehara and Yusuke Yoneda and Tatsuya Yoshida and Tomohiro Ogawa and Yuto Konishi and Toshikazu Ono and Atsuya Muranaka and Hikaru Kuramochi and Kiyoshi Miyata and Ken Onda}, doi = {10.1021/jacs.5c06020}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26446--26455}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic excited-state localization induced by Jahn–Teller distortion observed by coherent vibrational spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Alkene Borylation–Hydrogenation enables highly active, site-selective cobalt-catalyzed borylation. JACS, 147(30), 26437--26445. (www)

  @article{ , abstract = {A method for promoting highly active and site-selective cobalt-catalyzed C(sp 2 )–H arene borylation is described. Addition of tert -butyl ethylene (TBE) increased the activity of the cobalt-catalyzed borylation of electron-rich arenes. With monosubstituted anisoles and anilines, synthetically useful site-selectivities favoring the meta -position of the ring were observed. Monitoring the catalytic reaction in situ by 1 H NMR spectroscopy established a borylation–hydrogenation sequence of tert -butyl ethylene as being responsible for the increased catalytic activity where borylation of the alkene preceded functionalization of the arene. Added or in situ generated trans - t BuCH═CHBPin served as the active H 2 acceptor to overcome the inhibitory effect of HBPin and enabled both HBPin and B 2 Pin 2 to be effective reagents for generating the active cobalt catalyst. Normal primary deuterium isotope effects of 5.0(1.2) and 6.0(2.0) in parallel and 3.1(1) and 3.7(3) in competition for meta and para borylation, respectively, were measured at 23 °C for the catalytic borylation of N -phenylmorpholine, supporting irreversible and rate-determining oxidative addition of the C(sp 2 )–H bond during the catalytic reaction. The combination of the kinetic isotope effects, in situ reaction monitoring, DFT studies, and stoichiometric experiments support the origin of meta selectivity as arising from irreversible oxidative addition of the meta -C(sp 2 )–H bond to cobalt(I).}, archive = {J_JACS}, author = {Alex M. Shimozono and Jose B. Roque and Haozheng Li and Tianyi Zhang and Ronghui Lin and Paul J. Chirik}, doi = {10.1021/jacs.5c05965}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26437--26445}, shortjournal = {J. Am. Chem. Soc.}, title = {Alkene Borylation–Hydrogenation enables highly active, site-selective cobalt-catalyzed borylation}, volume = {147}, year = {2025}, }
• (2025). Local coordination environment-driven structural dynamics of single-atom copper and the CO2 electroreduction pathway. JACS, 147(30), 26425--26436. (www)

  @article{ , abstract = {Structural stability is a critical factor in realizing the potential of single-atom catalysts (SACs), yet remaining a major challenge hindering their large-scale application. Understanding the operando structural dynamics of SACs is essential for elucidating the structure–activity relationship and guiding the design of high-performance SACs. In this study, we selected five well-defined mononuclear copper (Cu) complexes with varying ligand structures to explore the coordination-driven structural dynamics of Cu single atoms and their interaction with the electrochemical CO 2 reduction (CO 2 R) pathway. Coordination environments strongly influence the reconfiguration behaviors of Cu SACs by affecting the binding energy and charge distribution between Cu and the ligands. The in situ reconstructed Cu(0) and Cu(I) sites act as active centers for carbon product formation. Specifically, Cu(0) is closely associated with CH 4 generation, while a unique Cu(I)N 3 H–*CO intermediate promotes multicarbon production by acting as a bridge, transferring *CO to neighboring Cu(0) with abundant unsaturated sites. This work highlights the impact of coordination environments on product distribution by influencing the reconfiguration behaviors of SACs and provides theoretical insights for designing Cu SACs with enhanced stability and tailored CO 2 R product selectivity.}, archive = {J_JACS}, author = {Tingyu Lu and Guoshuai Shi and Yufei Liu and Xuan Luo and Yuluo Shen and Mingwei Chang and Yijie Wu and Xinyang Gao and Jing Wu and Yefei Li and Yucheng Wang and Liming Zhang}, doi = {10.1021/jacs.5c05984}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26425--26436}, shortjournal = {J. Am. Chem. Soc.}, title = {Local coordination environment-driven structural dynamics of single-atom copper and the CO2 electroreduction pathway}, volume = {147}, year = {2025}, }
• (2025). Locally confined polysulfide-reactive electrolytes for shuttle-free Sodium–Sulfur batteries. JACS, 147(30), 26414--26424. (www)

  @article{ , abstract = {Sodium–sulfur batteries promise high-energy-density and sustainable electrochemical energy storage but suffer from uncontrolled polysulfide dissolution and high sodium reactivity. These challenges fundamentally originate from poor electrolyte–electrode compatibility. Current electrolyte research inadequately addresses the trade-off between minimal polysulfide solvation and stabilizing sodium interfaces. Here, we present a locally confined polysulfide-reactive electrolyte strategy that mediates the polysulfide dissolution dynamics and sodium stability by leveraging an electrophilic solvating species with a localized high-concentration electrolyte. This design enables shuttle-free cell operation by synergistically restricting the global solvating power of the electrolyte through intermolecular interactions and locally scavenging sparingly dissolved polysulfides via electrolyte electrophilicity. The precisely confined surface reaction facilitates a protective cathode–electrolyte interface, realizing a quasi-solid-state sulfur conversion in our liquid ether-based electrolyte, which crucially avoids crossover-induced catastrophic sodium–metal degradation. The proposed electrolyte demonstrates long-term cycling of high-mass-loading sulfur cathodes (>3 mg S cm –2 with commercial carbon host and 70 wt % sulfur content), which afford 710 mA h g –1 over 400 cycles in coin cells and steady pouch cell operation over 180 cycles. This work establishes a scalable electrolyte design protocol that regulates the reaction chemistry of highly reactive electrodes, offering a pathway toward sustainable renewable energy storage.}, archive = {J_JACS}, author = {Biyu Jin and Tianxing Lai and Arumugam Manthiram}, doi = {10.1021/jacs.5c05389}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26414--26424}, shortjournal = {J. Am. Chem. Soc.}, title = {Locally confined polysulfide-reactive electrolytes for shuttle-free Sodium–Sulfur batteries}, volume = {147}, year = {2025}, }
• (2025). Stability and exsolution of Sr0.98Ti0.7Fe0.25Ni0.05O3 for the oxygen evolution reaction in an alkaline environment. JACS, 147(30), 26402--26413. (www)

  @article{ , abstract = {Developing stable, critical raw material lean catalysts for the OER is essential for low-cost green hydrogen production. In this study, dense, polished pellets of Sr 0.98 Ti 0.7 Fe 0.25 Ni 0.05 O 3 (STFNO) were employed as a model system to investigate intrinsic OER activity and stability under industrially relevant conditions. The well-defined surface and controlled interface between the sample and electrolyte represent a more fundamental approach to studying catalytic performance. Testing was conducted at elevated temperatures up to 150 °C and at a pressure of 50 bar, offering unique insights into catalytic activity and stability under harsh conditions. STFNO demonstrated excellent stability during prolonged testing and high catalytic activity. This study also explored the role of exsolution in enhancing OER performance under industrially relevant conditions. Homogeneous (Ni,Fe)O x nanoparticles, exsolved at 600 °C, yielded a notably low overpotential of 199 mV at 75 °C. These findings provide valuable insights into the activity and stability of STFNO as an industrially viable catalyst.}, archive = {J_JACS}, author = {Fabian Luca Buchauer and SangWoo Kim and So̷ren Bredmose Simonsen and Roxy Lee and WooChul Jung and Christodoulos Chatzichristodoulou}, doi = {10.1021/jacs.5c05748}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26402--26413}, shortjournal = {J. Am. Chem. Soc.}, title = {Stability and exsolution of Sr0.98Ti0.7Fe0.25Ni0.05O3 for the oxygen evolution reaction in an alkaline environment}, volume = {147}, year = {2025}, }
• (2025). Inhibitor-dependent tolerance of new delhi metallo-β-lactamase driven by single mutation-induced conformational changes. JACS, 147(30), 26389--26401. (www)

  @article{ , abstract = {The emergence of metallo-β-lactamases as formidable adversaries in the antimicrobial resistance crisis stems from their unparalleled capacity to hydrolyze β-lactam antibiotics. This study deciphers the evolutionary strategy of New Delhi metallo-β-lactamase (NDM) variants through studies of conformational dynamics. We employ hydrogen/deuterium exchange mass spectrometry (HDX-MS) to map conformational landscapes of NDM in the ligand-free state and in the bound states with inhibitors l -captopril, d -captopril, ebselen, and aspergillomarasmine A (AMA), respectively. Crucially, our findings reveal similar allosteric fingerprints corresponding to different inhibition mechanisms; that is, inhibition induces pronounced dynamic perturbations in the α3–L8–β8 region─a previously under-characterized region. Strikingly, the clinically prevalent M154L mutation in this region reshapes conformational flexibility, amplifying inhibitor-specific conformational responses without altering the l / d -captopril binding dynamics. This study demonstrates how a single mutation can be critical for antibiotic resistance evolution where zinc is scarce in the presence of AMA and ebselen, as indicated by more protected HDX patterns of the α3–L8 region and several active-site loop (ASL) regions. Our results establish three key advances: (1) identification of α3–L8 as a cryptic allosteric region governing conformational adaptability, (2) demonstration of a single mutation M154L rewiring long-range dynamic communication, and (3) proposal of conformation-guided inhibitor design as a viable strategy against NDM. Overall, this work unveils a novel perspective─resistance mutations function not merely as chemical optimizers but as allosteric modulators that exploit inherent protein plasticity. These insights position the α3–L8 region as a compelling target for developing novel inhibitors, providing a blueprint for combating the next frontier of antimicrobial resistance.}, archive = {J_JACS}, author = {Liwen Huang and Tsz-Fung Wong and Qipeng Cheng and Pui-Kin So and Ming Liu and Xuechen Li and Sheng Chen and Zhong-Ping Yao}, doi = {10.1021/jacs.5c05669}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26389--26401}, shortjournal = {J. Am. Chem. Soc.}, title = {Inhibitor-dependent tolerance of new delhi metallo-β-lactamase driven by single mutation-induced conformational changes}, volume = {147}, year = {2025}, }
• (2025). NMR assessment of the high order structure of biological therapeutics in erythrocytes provides a tool for drug delivery design. JACS, 147(30), 26379--26388. (www)

  @article{ , abstract = {An effective delivery system is crucial for ensuring the therapeutic efficacy of a drug. This is especially true for biological drugs, which possess unique physicochemical properties and complex pharmacokinetic profiles, and thus require a dedicated design. Whole erythrocytes, and more recently, nanoparticles derived from red blood cells (RBCs), have been used in preclinical studies to deliver biological therapeutics: their biocompatibility and extended circulation time help prevent immunogenicity and reduce clearance and toxicity. However, characterizing such complex systems poses challenges that complicate their development and optimization. We argue that NMR spectroscopy enables the monitoring of the preservation of the high order structure of the encapsulated proteins, as well as their concentration, thereby assisting in formulation design, development, and manufacturing.}, archive = {J_JACS}, author = {Luis Padilla-Cortés and Giulia Roxana Gheorghita and Francesco Currò and Rebecca Calamandrei and Bianca Susini and Sara Callozzo and Giulia Crivello and Pasquale Russomanno and Enrico Ravera and Linda Cerofolini and Marco Fragai}, doi = {10.1021/jacs.5c05617}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26379--26388}, shortjournal = {J. Am. Chem. Soc.}, title = {NMR assessment of the high order structure of biological therapeutics in erythrocytes provides a tool for drug delivery design}, volume = {147}, year = {2025}, }
• (2025). Complete structure of delftibactin a and its function in reductive formation of gold nanoparticles. JACS, 147(30), 26370--26378. (www)

  @article{ , abstract = {Delftia acidovorans is a rare bacterium that colonizes the surface of gold nuggets and secretes a peptidic natural product, delftibactin A ( 1 ). Compound 1 strongly chelates and readily transforms soluble and toxic Au(III) ions into inert and nontoxic gold nanoparticles, allowing the bacteria to survive metal stress from Au(III) ions. This reductive function of 1 is not shared by any other known natural products, while its stereochemistry and mode of action have remained unclear. Here, we report the first total synthesis, structural elucidation, and functional analysis of 1 . First, we enabled the collective solid-phase total synthesis of 16 possible diastereomers of 1 . Second, the complete structure of 1 was determined by a detailed NMR analysis of these diastereomers. Third, we uncovered the evolutionarily optimized nature of the stereochemistry of 1 for facile Au(III) reduction and elucidated the novel reaction mechanism of 1 . As a result, we identified the precise roles of key structural elements involved in the unprecedented activity of 1 , providing a valuable foundation for designing new molecules aimed at generating customized gold nanoparticles and mitigating toxic Au(III) ions from the environment.}, archive = {J_JACS}, author = {Aoi Takeuchi and Hiromu Kakizawa and Mizuki Sawada and Kosuke Morita and Keiichi Noguchi and Hiroaki Itoh and Masayuki Inoue}, doi = {10.1021/jacs.5c05308}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26370--26378}, shortjournal = {J. Am. Chem. Soc.}, title = {Complete structure of delftibactin a and its function in reductive formation of gold nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of (+)-herpotrichones A–C. JACS, 147(30), 26361--26369. (www)

  @article{ , abstract = {Epoxyquinoids herpotrichones A–C exhibit unique 6/6/6/6/3 pentacyclic frameworks and potent neuroprotective effects. Inspired by their proposed biosynthetic origins, we completed a total synthesis of herpotrichones A–C by devising a de novo synthesis of epoxyquinol monomer and leveraging a key Diels–Alder (DA) reaction between epoxyquinol monomer-based dienophiles and delitpyrone C-derived dienes. DFT calculations anticipated competing pathways, including homodimerization and regio- and stereoisomers formation, necessitating precise control over reaction selectivity during the key DA reaction. We discovered that the C2′ hydroxyl configuration of delitpyrone C is critical in directing the desired DA reaction, with hydrogen bonding playing a decisive role in product formation. This strategy enabled synthetic access to the herpotrichone core and facilitated the first total synthesis of all known herpotrichones.}, archive = {J_JACS}, author = {Yoojin Lee and Taewan Kim and Geon Kim and Dongwook Kim and Sunkyu Han}, doi = {10.1021/jacs.5c05061}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26361--26369}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of (+)-herpotrichones A–C}, volume = {147}, year = {2025}, }
• (2025). Breathing colloidal monolayers. JACS, 147(30), 26352--26360. (www)

  @article{ , abstract = {Reversible polymorphic transitions are common in molecular crystals and have been utilized to design reconfigurable materials. However, translating this concept to colloidal superlattices, where microscale particles are the building blocks and distinct interactions are at play, remains a challenge. Herein, we report on 2D colloidal superlattices (or monolayers) that can anisotropically expand and contract, or “breathe”, reversibly transforming between polymorphs with open and closed mesopores. The superlattices are assembled from polyhedral particles with a truncated hexagonal bipyramidal shape and through the combined use of depletion and AC electric field-induced interactions. Facet overlapping and dipolar alignment can be leveraged in the particle assembly, with their interplay enabling the formation of diverse rhombic superlattices with tunable axial angles and porosity. The assembly features various structural reconfiguration kinetics that promote crystal annealing. The fast and reversible switch between two porous superlattices manifests the stimuli-responsive breathing behavior. Our work offers a strategy toward responsive biomimetic colloidal materials.}, archive = {J_JACS}, author = {Barry Chi Hong Lai and Dengping Lyu and Matthew Chan and Zhisheng Wang and Tianran Zhang and Wei Li and Yijiang Mu and Yufeng Wang}, doi = {10.1021/jacs.5c05105}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26352--26360}, shortjournal = {J. Am. Chem. Soc.}, title = {Breathing colloidal monolayers}, volume = {147}, year = {2025}, }
• (2025). Structure and catalytic properties of homo- and heterometallic Iron(II)-based di(2-pyridyl)ketone oxoclusters. JACS, 147(30), 26338--26351. (www)

  @article{ , abstract = {Electrochemical water splitting is essential for reducing our dependence on fossil fuels through green hydrogen production and requires the design of new, low-cost, 3d transition-metal-based catalysts for the sluggish oxygen evolution reaction (OER). We report on the synthesis, characterization, and OER performance of new types of homo- and heterometallic iron(II)-based di(2-pyridyl)ketone cubanes, 1-[Fe 4 (dpy-C{OH}O) 4 (OAc) 3 (H 2 O)]ClO 4 and 2-[Fe 2 Ni 2 (dpy-C{OH}O) 4 (OAc) 3 ]ClO 4 (dpy = di(2-pyridyl)diol), referred to as 1-{Fe 4 O 4 } and 2-{Fe 2 Ni 2 O 4 }. The heterometallic oxocluster is the first sought-after molecular cutout of the key active {H 2 O–Fe 2 Ni 2 (OR) 2 –OH 2 } motif, bridging molecular and heterogeneous OER catalysts as a model to understand the key catalytic synergisms in powerful NiFe oxide-based materials. The precise positions of Fe(II) and Ni(II) cations within the 2-{Fe 2 Ni 2 O 4 } oxocluster, along with the detailed structural and electronic features, were elucidated with a variety of methods, including extended advanced X-ray absorption spectroscopy and total neutron scattering techniques, accompanied by time-dependent density functional theory (TDDFT) calculations. (Spectro)electrochemical analyses showed that 2-{Fe 2 Ni 2 O 4 } exhibits synergisms between Fe(II) and Ni(II) centers, tuning both metals’ redox potentials and the molecular stability of the mixed-valent {(Fe III ) 2 Ni 2 O 4 } precatalyst species. 2-{Fe 2 Ni 2 O 4 } displays a maximum j cat of 1.75 mA/cm 2 for the OER and a Faradaic efficiency of 84.8% under turnover conditions. Although the oxocluster experienced notable degradation during the OER, significant metal (oxy)hydroxide formation could be excluded. 2-{Fe 2 Ni 2 O 4 } is introduced as a new molecular platform for in-depth studies of NiFe synergisms, along with ligand engineering or polymer matrix strategies.}, archive = {J_JACS}, author = {Daniel R. Civettini and Carlos A. Triana and Tjeerd F. De Jong and Daniel F. Abbott and Robin N. Dürr and Sandra Luber and Victor Mougel and Greta R. Patzke}, doi = {10.1021/jacs.5c04262}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26338--26351}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure and catalytic properties of homo- and heterometallic Iron(II)-based di(2-pyridyl)ketone oxoclusters}, volume = {147}, year = {2025}, }
• (2025). Stereocomplexation-promoted alternating supramolecular copolymerization of peptide-Oligo(Lactic acid) conjugates. JACS, 147(30), 26329--26337. (www)

  @article{ , abstract = {Spontaneous association of multiple components into coassemblies significantly amplifies the complexity of supramolecular systems. Owing to varied noncovalent interactions, the precise regulation of the copolymerization pathway, molecular arrangement, and assembled morphology remains a huge challenge. Here, we report an intriguing system as the first example of using complementary stereocomplexation between enantiomeric oligo (lactic acid)s ( o LAs) to govern the supramolecular copolymerization behavior of a series of amphiphilic peptide conjugates. Specifically, the hydrophobic chiral o LAs were conjugated to various peptides, which can self-assemble on their own in an aqueous environment into straight nanofibers with bilayer molecular packing. Upon copolymerization between two monomers with enantiomeric o LAs, helical filamentous nanostructures with an interdigitated bilayer molecular arrangement were observed. A combination of TEM imaging and spectroscopic analysis further revealed the formation of alternating microstructures in the supramolecular copolymers under thermodynamic equilibrium, promoted via stereospecific interactions between enantiomeric hydrophobic chains. In addition, the copolymerization can shift from a stereocomplexation-driven to a hydrogen-bonding-dominated process with the increase in β-sheet-forming propensity in peptides, exhibiting similar self-assembly behaviors to their homopolymer counterparts. We believe that these findings provide a new perspective on the formation of alternating supramolecular copolymers and modulation between multiple intermolecular interactions.}, archive = {J_JACS}, author = {Jianqiang Wang and Wenting Li and Minghua Zhang and Zhuoqi Xu and Xiangyu Wang and Dongdong Zhou and Hao Su}, doi = {10.1021/jacs.5c04680}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26329--26337}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereocomplexation-promoted alternating supramolecular copolymerization of peptide-Oligo(Lactic acid) conjugates}, volume = {147}, year = {2025}, }
• (2025). Achieving “True” selective hydrogenation by CO treatment of the Pt/TiO2 catalyst. JACS, 147(30), 26319--26328. (www)

  @article{ , abstract = {Selective hydrogenation represents a fundamental chemical transformation in industrial catalysis, yet achieving high selectivity remains a formidable challenge, particularly toward the conversion of less reactive functional groups over more reactive ones. Current approaches often rely on a preferential manner, requiring precise reaction control to prevent complete substrate conversion, which limits the operational flexibility and complicates product separation. Here, we demonstrate that a Pt/TiO 2 catalyst, when subjected to a simple CO gas thermal treatment, can enable the true selective hydrogenation of the thermally less reactive −NO 2 group while preserving the more reactive −C═C bond. Mechanistic studies reveal that the treated catalyst features two distinct active sites: single-atom Pt sites that facilitate −C═C bond hydrogenation through rapid, reversible hydrogen insertion and elimination, giving rise to an apparent nonactivity, and TiO x and C-encapsulated Pt nanoparticles that provide selective permeability for the −NO 2 group. The discovery offers a robust solution to the challenges of selective hydrogenation, presenting a versatile strategy for the design and preparation of highly selective catalytic systems with significant implications for industrial applications.}, archive = {J_JACS}, author = {Fengwei Zhang and Feng Hong and Xuetao Qin and Xiaoqiang Du and Xunzhu Jiang and Yawei Li and Hefang Guo and Peihao Liu and Wenhao Cui and Xiangting Min and Wenting Zhang and Botao Qiao and Ding Ma}, doi = {10.1021/jacs.5c04699}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26319--26328}, shortjournal = {J. Am. Chem. Soc.}, title = {Achieving “True” selective hydrogenation by CO treatment of the Pt/TiO2 catalyst}, volume = {147}, year = {2025}, }
• (2025). Macrocyclic phage display for identification of selective protease substrates. JACS, 147(30), 26307--26318. (www)

  @article{ , abstract = {Traditional methods for identifying selective protease substrates have primarily relied on synthetic libraries of linear peptides, which offer limited sequence and structural diversity. Here, we present an approach that leverages phage display technology to screen large libraries of chemically modified cyclic peptides, enabling the identification of highly selective substrates for a protease of interest. Our method uses a reactive chemical linker to cyclize peptides on the phage surface, while simultaneously incorporating an affinity tag and a fluorescent reporter. The affinity tag enables capture of the phage library and subsequent release of phages expressing optimal substrates upon incubation with a protease of interest. The addition of a turn-on fluorescent reporter allows direct quantification of cleavage efficiency throughout each selection round. The resulting identified substrates can then be chemically synthesized, optimized and validated using recombinant enzymes and cells. We demonstrate the utility of this approach using Fibroblast Activation Protein α (FAPα) and the related proline-specific protease, dipeptidyl peptidase-4 (DPP4), as targets. Phage selection and subsequent optimization identified substrates with selectivity for each target that have the potential to serve as valuable tools for applications in basic biology and fluorescence image-guided surgery (FIGS). Overall, our strategy provides a rapid and unbiased platform for effectively discovering highly selective, non-natural protease substrates, overcoming key limitations of existing methods.}, archive = {J_JACS}, author = {Franco F. Faucher and Kristýna Blažková and Scott Lovell and Matilde Bertolini and Juan Herrero-Bourdieu and Emily D. Cosco and Matthew Bogyo and Marta Barniol-Xicota}, doi = {10.1021/jacs.5c04424}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26307--26318}, shortjournal = {J. Am. Chem. Soc.}, title = {Macrocyclic phage display for identification of selective protease substrates}, volume = {147}, year = {2025}, }
• (2025). Nucleophilic α- and β-additions enable redox-neutral aziridination of conjugated hydroxamates. JACS, 147(30), 26298--26306. (www)

  @article{ , abstract = {Aziridination of olefins using nonprotected primary amines as nitrogen donors under oxidative conditions is highly desirable but poses challenges due to the incompatibility of nonprotected amines with oxidants. To address this issue, a strategy to leverage an internal oxidant is proposed. This method enables nucleophilic α- and β-additions of amines to conjugated hydroxamates, allowing for the assembly of complex aziridines from simple and safe building blocks. Benefiting from this internal oxidant concept, electron-rich anilines are directly employed to access N -aryl aziridines. Beyond aziridination, olefin 1,2-diamination can also be achieved when secondary amines are used. Mechanistic studies suggest that an α-lactam intermediate is involved in this aziridination to enable the redox-transposition. In a broader context, this transformation represents a novel type of nucleophilic α-addition, which is rare compared to the more common β-addition (the Michael addition).}, archive = {J_JACS}, author = {Rui Wang and Quanbin Jiang and Long Jiang and Wenbo H. Liu}, doi = {10.1021/jacs.5c04286}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26298--26306}, shortjournal = {J. Am. Chem. Soc.}, title = {Nucleophilic α- and β-additions enable redox-neutral aziridination of conjugated hydroxamates}, volume = {147}, year = {2025}, }
• (2025). Structurally dynamic polyplexes enhance sentinel lymph node delivery of antisense oligonucleotides to inhibit breast cancer recurrence and metastasis. JACS, 147(30), 26286--26297. (www)

  @article{ , abstract = {Sentinel lymph nodes (SLNs), the first tumor-draining lymph nodes, play a prominent role in tumor progression. Cytotoxic CD8 + T cells in the SLN are typically suppressed in advanced cancer but, when rejuvenated, can slow cancer progression. Here, we demonstrated a molecular approach to engineering a dynamic polyplex, predominantly comprising two poly(ethylene glycol)-(glycine–lysine)10 [PEG-(GK)10] per antisense oligonucleotide (ASO) based on charge neutralization at a minimum molecular ratio, that can enhance SLN functional delivery of ASOs for replenishing immunity against breast cancer recurrence and metastasis. Using a murine breast cancer model, we successfully enriched the ASO distribution in the SLN while limiting off-target organ distribution by tuning the size of the PEG (3–80 kDa). Moreover, we obtained a less compact polyplex using conserved glycine–lysine repeats as cationic segments instead of conventional lysine repeats, resulting in improved structural dynamics and better target gene silencing efficiency in SLN. Polyplex with the optimized PEG size and dynamics was subsequently utilized to develop a regimen to deplete the transforming growth factor-β1 (TGF-β1) level in the SLN. Consequently, we successfully rejuvenated the depleted CD8 + T cells in the SLNs, corresponding to reduced postoperative tumor relapse and lung metastasis. Our findings provide a molecular rationale to enable a simple but robust TGF-β1 ASO therapeutic regimen for managing advanced breast cancer.}, archive = {J_JACS}, author = {Chun Yin Jerry Lau and Hiroaki Kinoh and Xueying Liu and Jiayuan Feng and Fadlina Aulia and Kaori Taniwaki and Nan Qiao and Satomi Ogura and Mitsuru Naito and Kanjiro Miyata}, doi = {10.1021/jacs.5c04234}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26286--26297}, shortjournal = {J. Am. Chem. Soc.}, title = {Structurally dynamic polyplexes enhance sentinel lymph node delivery of antisense oligonucleotides to inhibit breast cancer recurrence and metastasis}, volume = {147}, year = {2025}, }
• (2025). Pressure-assisted fast synthesis of zeolitic materials. JACS, 147(30), 26277--26285. (www)

  @article{ , abstract = {Zeolites are widely utilized in various industrial applications, such as ion exchangers, catalysts, and adsorbents. However, traditional zeolite crystallization is time-intensive, requiring hours to weeks under autogenous pressure in autoclaves. In this study, we developed a novel and universal pressure-assisted method for the rapid synthesis of diverse zeolites, including MFI, CHA, FAU, MOR, *BEA, LTA, and AFI, as well as zeolite-encaged ultrasmall metal clusters and atoms, using batch reactors supercharged with controlled amounts of gases. Compared to traditional hydrothermal synthesis, this method significantly accelerates the crystallization rate of zeolites by 2–18 times. Experimental and theoretical analyses reveal that an elevated synthesis pressure and increased oxygen content in the system promote the formation of singlet oxygen species, thereby facilitating T–O–T (T═Si, Al, and P) bond restructuring and accelerating zeolite nucleation. This work offers a practical and efficient pathway for rapidly synthesizing zeolites to meet industrial demands while shedding light on the underlying mechanisms of zeolite crystallization.}, archive = {J_JACS}, author = {Kai Zhang and Guangyuan He and Ning Wang and Zhuoya Dong and Yanhang Ma and Jun Xu and Donghai Mei and Qiming Sun and Jihong Yu}, doi = {10.1021/jacs.5c04247}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26277--26285}, shortjournal = {J. Am. Chem. Soc.}, title = {Pressure-assisted fast synthesis of zeolitic materials}, volume = {147}, year = {2025}, }
• (2025). Synthesis and properties of poly(vinyl chloride)-b-polyethylene multiblock copolymers through the hydrodechlorination of PVC with silylium ions. JACS, 147(30), 26267--26276. (www)

  @article{ , abstract = {Block copolymers of polyethylene (PE) and polyvinyl chloride (PVC) have remained elusive materials despite PE and PVC being the first and third most produced polymers globally, respectfully. The closest material is chlorinated polyethylene (CPE), which is commonly used as a compatibilizer and is synthesized by functionalizing PE. However, there does not exist a synthetic pathway either from monomers or via the functionalization of PE to yield a polymer that has a controlled chlorine amount and primary structure along the polymer chain. Herein, we report a series of novel block copolymers of PVC and PE, synthesized through selective hydrodechlorination of PVC. Contrary to CPE, the full range of chlorination can be obtained, and the block number can be altered. Interfacial adhesion studies reveal samples with competitive compatibilization of PVC/polyolefin elastomer (POE) blends. This method shows that postpolymerization modification can be a strategic top-down synthesis to achieve high-performance polymers that cannot be synthesized via conventional polymerization pathways.}, archive = {J_JACS}, author = {Zachary A. Wood and Tyeshia Sapp and Bailey Eberle and Xuchun Wang and Samuel B. Hunt and Sarah J. Barber and Mary Dana Czarinah L. Cheng-Tan and Tommy Yunpu Zhao and Frédéric A. Perras and Massimiliano Delferro and Byeongdu Lee and Mark D. Dadmun and Megan E. Fieser}, doi = {10.1021/jacs.5c04188}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26267--26276}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis and properties of poly(vinyl chloride)-b-polyethylene multiblock copolymers through the hydrodechlorination of PVC with silylium ions}, volume = {147}, year = {2025}, }
• (2025). Disordered Ru–O6 octahedrons for efficient and selective electro-oxidation of sulfide to sulfoxide via boosted surface oxygen kinetics. JACS, 147(30), 26254--26266. (www)

  @article{ , abstract = {Sulfoxides are essential intermediates for the production of various chemicals and pharmaceuticals, typically synthesized via direct sulfide oxidation. While current methods generally require harsh conditions and/or hazardous oxidants, electrochemical conversion from sulfide to sulfoxide promises ideal selectivity, sustainability, and energy efficiency while uniquely utilizing water as the green oxygen source. However, achieving efficient electro-organic conversion has been challenging due to sluggish surface oxygenating kinetics under nonaqueous conditions. Here we report the development of a novel amorphous ruthenium oxide catalyst characterized by disorderly connected regular/irregular Ru–O 6 octahedra. This unique surface structure significantly boosts the surface water oxidation kinetics in nonaqueous media, enabling a universal electro-oxidation approach for efficient sulfide-to-sulfoxide conversion. Superior performance was achieved under mild conditions (e.g., 99% selectivity, 98% yield, and 95% Faradaic efficiency for methyl phenyl sulfide to methyl phenyl sulfoxide), and this approach applies to a broad scope of sulfide substrates and pharmaceuticals. Scalable productions (12.95 g, 88% FE) under high current densities (>100 mA/cm 2 ) further demonstrate the practical values of this electrocatalytic synthetic methodology. Mechanistic and theoretical investigations elucidate the critical role of disorderly arranged Ru–O octahedral units in enhancing the distributions of bonding orbitals and electronic coupling near the Fermi level, leading to boosted kinetics of surface water oxidation (*OH → *O) and subsequent sulfide oxidation (*O + MPS → *MPSO), which follow an adsorbate evolution mechanism-mediated Eley–Rideal reaction (AEM-ER) pathway. Our results highlight the unique and effective role of atomic disorder in overcoming common kinetic limitations during catalyst optimization, which enables ideal direct selective electro-oxidation of organics in nonaqueous media.}, archive = {J_JACS}, author = {Pan Ran and Mingzi Sun and Aoqian Qiu and Xiao Han and Bailin Tian and Beiyao Xiang and Fangyuan Wang and Xinrui Xu and Luhan Dai and Haowen Zhang and Yang Lv and Yue Lin and Bolong Huang and Mengning Ding}, doi = {10.1021/jacs.5c04028}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26254--26266}, shortjournal = {J. Am. Chem. Soc.}, title = {Disordered Ru–O6 octahedrons for efficient and selective electro-oxidation of sulfide to sulfoxide via boosted surface oxygen kinetics}, volume = {147}, year = {2025}, }
• (2025). Activation of anionic redox for stoichiometric and li-excess metal sulfides through structural disordering: Joint experimental and theoretical study. JACS, 147(30), 26238--26253. (www)

  @article{ , abstract = {Extensive research efforts have been dedicated to Li-excess compounds with anionic redox reaction as potential high-capacity positive electrode materials for Li-ion battery applications. The origin of activation on anionic redox is still under debate, and a unified understanding is necessary, especially for sulfide-based compounds without conductive d electrons. Herein, joint experimental and theoretical study is conducted for Li-excess and stoichiometric compounds with different crystal structures, cation-disordered rocksalt, and cation-ordered layered structures. In contrast to the understanding of Li-excess oxides, sulfide-based compounds with ordered layered structures are electrochemically less active compared with the materials with disordered structure. Theoretical study reveals that a unique local structure for a sulfide ion coordinated by 6 Li ions, SLi 6 configuration, is formed, which can be found only for the disordered structure and not for the layered structure. The unique local structure triggers electron delocalization for sulfide 3p orbitals, leading to superior electronic conductivity, as experimentally evidenced, and thus anionic redox is successfully activated. Furthermore, such nonuniform local structures lead to easier structural distortion and efficient S–S dimerization, and even trimerization (S 3 2– ), upon delithiation. Although sulfide-based compounds as battery electrode materials suffer from dissolution after oxidation, this practical problem is effectively mitigated by the use of highly concentrated electrolyte solutions with fewer free solvent molecules, leading to superior reversibility for anionic redox. The insights derived can guide the development of high-energy electrode materials with anionic redox with or without transition metal ions possessing conductive d electrons.}, archive = {J_JACS}, author = {Miyuki Shinoda and Koki Matsunoshita and Masanobu Nakayama and Satoshi Hiroi and Koji Ohara and Masaki Abe and Nozomu Ishiguro and Yukio Takahashi and Gen Hasegawa and Naoaki Kuwata and Tsukasa Iwama and Takuya Masuda and Kosuke Suzuki and Hirofumi Ishii and Yu-Cheng Shao and Daisuke Shibata and Akinori Irizawa and Toshiaki Ohta and Itsuki Konuma and Teppei Ohno and Yosuke Ugata and Naoaki Yabuuchi}, doi = {10.1021/jacs.5c04018}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26238--26253}, shortjournal = {J. Am. Chem. Soc.}, title = {Activation of anionic redox for stoichiometric and li-excess metal sulfides through structural disordering: Joint experimental and theoretical study}, volume = {147}, year = {2025}, }
• (2025). Cobalt-catalyzed enantioselective and diastereodivergent construction of C–N atropisomers. JACS, 147(30), 26226--26237. (www)

  @article{ , abstract = {Herein, we report an efficient method for the synthesis of atropisomers with distal 1,3-C–N diaxes using the cobalt/Salox system via C–H and N–H annulation with benzamide and sterically hindered alkynes. This one-step, step-economical process operates at room temperature with oxygen from air as the sole oxidant, removing the need for metal oxidants, photocatalysts, or electricity. The reaction is compatible with a broad range of arylamides and alkynes, providing high yields and excellent enantioselectivity (up to >99% ee). Experimental and DFT studies indicate that the migratory insertion is the rate-determining step, while C–H activation is the enantio-determining step. Additionally, we showcase a traceless bidentate directing group strategy for the synthesis of C–N atropisomers with high enantioselectivity, where the directing group is cleaved in situ and does not remain in the final product.}, archive = {J_JACS}, author = {Abir Das and Subramani Kumaran and Pritam Maity and J. Richard Premkumar and Basker Sundararaju}, doi = {10.1021/jacs.5c03776}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26226--26237}, shortjournal = {J. Am. Chem. Soc.}, title = {Cobalt-catalyzed enantioselective and diastereodivergent construction of C–N atropisomers}, volume = {147}, year = {2025}, }
• (2025). A quasi-ordered mn-rich cathode with highly reversible oxygen anion redox chemistry. JACS, 147(30), 26218--26225. (www)

  @article{ , abstract = {Anionic oxygen redox chemistry in Li-rich Mn-based layer oxide cathodes represents a transformative approach for boosting the energy density of next-generation lithium-ion batteries. However, conventional oxygen redox reactions often induce oxygen dimerization at high voltages, leading to irreversible lattice oxygen loss and a rapid voltage fade. Herein, we achieve highly reversible oxygen redox chemistry through a new quasi-ordered structural design that incorporates both intra- and interlayer cation disorder configurations. This unique structure significantly enhances lattice oxygen stability, effectively stabilizes oxidized oxygen, and inhibits the formation of peroxo- or superoxol-like species, thereby enabling anionic redox reactions to proceed reversibly even at deep delithiation states. The quasi-ordered design mitigates irreversible phase transitions and preserves the structural integrity throughout extended cycling. Consequently, the proposed cathode demonstrates exceptional cyclability with negligible capacity and voltage fade, retaining 99% capacity and 98% average voltage after long-term cycling. This work provides fresh insights into addressing issues related to lattice oxygen instabilities and reforming strategies for developing long-life, high-energy-density anionic redox cathode materials for advanced batteries.}, archive = {J_JACS}, author = {Weiyuan Huang and Jimin Qiu and Zengqing Zhuo and Jianguo Wen and Yaqing Guo and Yifei Yuan and Zhefeng Chen and Jiangtao Hu and Tianyi Li and Lirong Zheng and Lunhua He and Jinghua Guo and Mingjian Zhang and Feng Pan and Khalil Amine and Tongchao Liu}, doi = {10.1021/jacs.5c03271}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26218--26225}, shortjournal = {J. Am. Chem. Soc.}, title = {A quasi-ordered mn-rich cathode with highly reversible oxygen anion redox chemistry}, volume = {147}, year = {2025}, }
• (2025). Frustration-induced many-body degeneracy in spin −1/2 molecular quantum rings. JACS, 147(30), 26208--26217. (www)

  @article{ , abstract = {Frustrated spin systems, where competing interactions prevent conventional magnetic ordering, provide a platform for uncovering emergent quantum phases and exotic many-body phenomena. Particularly, low-dimensional and symmetric geometries without boundary conditions allow us to study unconventional spin states. Here, we present S = 1/2 antiferromagnetic Heisenberg cyclic pentamer and hexamer via homocoupling of air-stable phenalenyl derivatives on Au(111). With a combination of scanning tunneling microscopy (STM)/scanning tunneling spectroscopy (STS) at 4.3 K and comprehensive theoretical simulations, we found that while large magnetic exchange interactions exist in both rings, the pentamer features an increased geometric frustration of the system. This frustration induces rotational symmetry in the spin wave function, leading to a 4-fold degenerate ground states of the pentamer. The interplay between molecular geometry and magnetic interactions creates a unique quantum spin environment. Our findings offer a powerful approach for constructing spin-frustrated molecular architectures, allowing precise control over quantum magnetic interactions.}, archive = {J_JACS}, author = {Donglin Li and Nan Cao and Marvin Metzelaars and Orlando J. Silveira and Joakim Jestilä and Adolfo Fumega and Tomohiko Nishiuchi and Jose Lado and Adam S. Foster and Takashi Kubo and Shigeki Kawai}, doi = {10.1021/jacs.5c03112}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26208--26217}, shortjournal = {J. Am. Chem. Soc.}, title = {Frustration-induced many-body degeneracy in spin −1/2 molecular quantum rings}, volume = {147}, year = {2025}, }
• (2025). Metal-phenolic outer membrane vesicles for cancer radioimmunotherapy. JACS, 147(30), 26195--26207. (www)

  @article{ , abstract = {Bacterial outer membrane vesicles (OMVs) with catalase deposition have significant potential for cancer immunotherapy, yet their therapeutic efficiency is limited by insufficient immune activation. Metal ions with a high atomic number could act as radiosensitizers to increase radiation-dose deposition at tumor sites and boost the immunogenic effects of radiotherapy (RT). Herein, we report metal-phenolic OMVs by cloaking OMVs with hafnium (Hf)-phenolic networks (Hf-OMVs) for enhanced cancer radioimmunotherapy. In tumor microenvironment, catalase deposited in the envelope of OMVs initiated the decomposition of hydrogen peroxide to produce oxygen, resulting in hypoxia relief. Meanwhile, the Hf reinforced the accumulation of ionizing radiation at the tumor site, thereby inducing tumor cell death and releasing tumor antigens. In addition, the OMVs with immunomodulatory performance combined with released tumor antigens to promote dendritic cell maturation, thus enhancing T cell activation and eliciting potent antitumor immunity. In breast cancer mouse models, the Hf-OMVs effectively accumulated at the tumor site following intravenous injection and significantly delayed the growth of primary and distant tumors when combined with RT. Our work provides an organic/inorganic hybrid platform bridging the superiority of natural OMVs and synthetic Hf-phenolic networks for enhanced cancer radioimmunotherapy.}, archive = {J_JACS}, author = {Chenchen Zhao and Yuanwei Pan and Lei Cao and Yuji Tang and Xiaoyuan Chen and Xingzhong Zhao and Lang Rao}, doi = {10.1021/jacs.5c02774}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26195--26207}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal-phenolic outer membrane vesicles for cancer radioimmunotherapy}, volume = {147}, year = {2025}, }
• (2025). Engineering the coordination environment of metal centers for selective and high-current CO2 electromethanation. JACS, 147(30), 26185--26194. (www)

  @article{ , abstract = {Renewable energy-driven CO 2 to CH 4 conversion represents a pivotal strategy for achieving carbon neutrality, with the primary scientific challenge residing in controllably accelerating protonation kinetics. Atomically precise engineering of metal coordination catalysts offers a promising route to tailor reaction pathways. Herein, we construct a dual-active-site catalyst featuring Cu–S and Eu–N coordination centers. Through atomic-level engineering of active site microenvironments, the optimized catalyst demonstrates performance comparable to state-of-the-art systems, achieving a remarkable CH 4 Faradaic efficiency of 75.8% alongside CH 4 partial current density of 303.3 mA cm –2 . Mechanistic studies reveal that isolated Cu sites hinder C–C coupling, while the strategically dispersed Eu sites facilitate efficient water activation, which is a critical process that generates abundant protons to accelerate the rate-limiting *CO hydrogenation step. This study establishes fundamental design principles for steering selective reaction pathways through atomic-scale modulation of active site architectures and their catalytic microenvironments.}, archive = {J_JACS}, author = {Chang Zhu and Dashuai Wang and Libin Zeng and Guanghui Feng and Yi Liang and Wanzhen Zheng and Weixiao Lin and Xianyun Peng and Zhibin Liu and Xiahan Sang and Bin Yang and Zhongjian Li and Qinghua Zhang and Lecheng Lei and Yang Hou}, doi = {10.1021/jacs.5c02458}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26185--26194}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering the coordination environment of metal centers for selective and high-current CO2 electromethanation}, volume = {147}, year = {2025}, }
• (2025). Fabrication of MOF particle assemblies for structural transformation engineering. JACS, 147(30), 26177--26184. (www)

  @article{ , abstract = {The structural flexibility of metal–organic frameworks (MOFs), which undergo structural changes upon gas adsorption, has been reported to depend on factors such as crystal structure, defects, and crystal size. On the other hand, MOFs are used as assemblies of crystals, such as pellets or membranes, but few studies have reported the effect on the flexibility in the assembly structure. In this study, we prepared assemblies of [Cu(NMe 2 -ipa)] (NMe 2 -KGM, NMe 2 -ipa = 5-dimethylamino isophthalate). NMe 2 -KGM with different packing densities and arrangements was used to compare the magnitude of structural changes during gas adsorption. It was found that structural changes of the MOFs in the regular assembly are suppressed compared to random assembly. The results of this study are expected to lead to new strategies for controlling flexibility through the design of crystal array structures.}, archive = {J_JACS}, author = {Kohei Negita and Shinpei Kusaka and Hiroaki Iguchi and Koji Yano and Seiichi Shin and Ryotaro Matsuda}, doi = {10.1021/jacs.5c02479}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26177--26184}, shortjournal = {J. Am. Chem. Soc.}, title = {Fabrication of MOF particle assemblies for structural transformation engineering}, volume = {147}, year = {2025}, }
• (2025). Chiral phosphoric acid-catalyzed enantioselective higher-order cycloadditions: Temperature-dependent periselectivity. JACS, 147(30), 26165--26176. (www)

  @article{ , abstract = {Higher-order cycloadditions (HOCs) are powerful tools for constructing complex cyclic structures, but their synthetic utility is often limited by poor periselectivity and challenges in achieving high diastereo- and enantioselectivity. Herein, we report a chiral phosphoric acid-catalyzed reaction between tropones and trifluoroacetamido-1,3-dienes that proceeds efficiently at room temperature, delivering bicyclo[4.4.1]undecatrienones in high yields with excellent peri-, diastereo-, and enantioselectivities. Without isolation, these (6 + 4) cycloadducts undergo a regioselective Cope rearrangement at 100 °C, yielding bicyclo[3.2.2]nonadienones─products of formal (4 + 2) cycloaddition. Remarkably, 7-alkyl-substituted analogues undergo a distinct transformation at 150 °C, producing tetracyclic products featuring a unique decahydro-1,5-methanoazulene motif. The presence of multiple functional groups in these adducts provides versatile synthetic handles for the further derivatization of these structurally intricate bridged polycyclic molecules.}, archive = {J_JACS}, author = {Xin-Qi Zhu and Qian Wang and Matthew D. Wodrich and Jieping Zhu}, doi = {10.1021/jacs.5c01808}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26165--26176}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral phosphoric acid-catalyzed enantioselective higher-order cycloadditions: Temperature-dependent periselectivity}, volume = {147}, year = {2025}, }
• (2025). Microcrystal electron diffraction-guided discovery of fungal metabolites. JACS, 147(30), 26158--26164. (www)

  @article{ , abstract = {Nature remains a vast repository of complex and functional metabolites whose structural characterization continues to drive innovations in pharmaceuticals, agrochemicals, and materials science. The cryogenic electron microscopy (cryoEM) method, microcrystal electron diffraction (microED, a 3D ED technique), has emerged as a powerful tool to structurally characterize small molecules. Despite this emerging role in structural chemistry, the cost and throughput of microED have limited its application in the discovery of natural products (NPs). While recent advances in sample preparation (e.g., arrayED) have provided a conceptual framework to address these challenges, they have remained unproven. Herein, we report the arrayED-driven discovery of a structurally unprecedented family of NPs (zopalides A–E), a muurolane-type sesquiterpene glycoside (rhytidoside A), aspergillicin analogs (aspergillicins H and I), and four crystal structures of previously reported fungal metabolites. Lastly, this the first time that the absolute stereo configuration of newly discovered NPs has been determined directly by microED alone without other methods using a small amount of sample}, archive = {J_JACS}, author = {David A. Delgadillo and Lin Wu and Caroline Wang and Yalong Zhang and Kunal K. Jha and Jessica E. Burch and Lygia Silva de Moraes and Isabel Hernandez Rodriguez and Melody J. Tang and Gerald F. Bills and Benjamin P. Tu and Yi Tang and Hosea M. Nelson}, doi = {10.1021/jacs.5c01466}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26158--26164}, shortjournal = {J. Am. Chem. Soc.}, title = {Microcrystal electron diffraction-guided discovery of fungal metabolites}, volume = {147}, year = {2025}, }
• (2025). Discovery of Ni(I) complexes for CO2 insertion enabled by a machine learning-computational-selection sequence. JACS, 147(30), 26149--26157. (www)

  @article{ , abstract = {The fate of a catalyst or catalytic intermediate, i.e., its speciation, in situ is a critical aspect of the efficiency of a catalyst as well as the overall reactivity and selectivity of the catalyzed transformation. However, the precise factors that dictate catalyst speciation are rarely understood and trial-and-error approaches frequently prevail. To address this challenge and develop predictive tools to guide ligand selection for a desired metal speciation in a catalytically relevant context, we evaluated the feasibility of machine learning combined with computational activation barrier predictions to achieve CO 2 insertion at room temperature for the sterically least hindered (and most vulnerable) Ni (I) –Ph complexes, which constitute key catalytic intermediates. Following an in depth computational rationalization on the origin of reactivity difference of Ni (I) versus Ni (II) toward CO 2 insertion, we subsequently pursued machine learning to identify ligands that favor the critical Ni (I) oxidation state. To this end, a descriptor database was constructed in silico . Subsequent application of machine learning led to the prediction of numerous ligands that favor the more reactive Ni (I) –Ph intermediate and oxidation state, which were subsequently filtered for candidates that also show desired room temperature reactivity through the calculation of activation barriers. Ultimately, a set of representative candidates was synthesized and experimentally tested for CO 2 insertion, confirming their reactivity and alignment with computational predictions. This work offers a blueprint for creating and analyzing virtual databases to predict ligands–including never synthesized ones–that control metal complex oxidation state, nuclearity, and reactivity.}, archive = {J_JACS}, author = {Julian A. Hueffel and Mathilde Rigoulet and Sebastian Wellig and Theresa Sperger and Jas S. Ward and Kari Rissanen and Franziska Schoenebeck}, doi = {10.1021/jacs.5c00441}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26149--26157}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of Ni(I) complexes for CO2 insertion enabled by a machine learning-computational-selection sequence}, volume = {147}, year = {2025}, }
• (2025). Structural basis for oxidized glutathione recognition by yeast cadmium factor 1. JACS, 147(30), 26139--26148. (www)

  @article{ , abstract = {Transporters from the ABCC family have an essential role in detoxifying electrophilic compounds, including heavy metals and drugs, often after conjugation with glutathione. The Yeast Cadmium Factor 1 (Ycf1) transports glutathione conjugated to toxic heavy metals including Cd 2+ , Hg 2+ , and the metalloid As 3+ into the vacuole to safely sequester them in the cell. It also has a major role in transporting oxidized glutathione to help maintain redox balance and recycle glutathione. To understand the complicated selectivity and promiscuity of binding, we determined the cryo-EM structure of Ycf1 bound to the substrate, oxidized diglutathione. We identify a glutathione binding mode with different binding characteristics to each half of the glutathione. One half of glutathione binds tightly to the substrate pocket, and the other half bound in a loose pocket. We systematically measured binding determinants with cellular survival assays under high cadmium concentrations along with molecular dynamics simulations to show how each half of the site works together to drive substrate selectivity.}, archive = {J_JACS}, author = {Tik Hang Soong and Clare F. Hotze and Darpan Raghav and Nitesh Kumar Khandelwal and Thomas M. Tomasiak}, doi = {10.1021/jacs.4c16335}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26139--26148}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural basis for oxidized glutathione recognition by yeast cadmium factor 1}, volume = {147}, year = {2025}, }
• (2025). CsICl2: A record-birefringent inorganic crystal with ultrawide infrared transparency enabled by linear interhalogen ICl2– units. JACS, 147(30), 26133--26138. (www)

  @article{ , abstract = {Birefringent crystals are essential optical materials for polarized light modulation, yet few exhibit both large birefringence and broad transparency in the mid- to far-infrared (MIR–FIR) regions. Here, we report the successful synthesis of an inorganic birefringent crystal, CsICl 2 ( CIC ), by incorporating the highly anisotropic linear ICl 2 – birefringence-active group (BAG) with a heavy Cs + cation under hydrothermal conditions. The large polarization anisotropy, perfect alignment, and dense packing of ICl 2 – endow CIC with record-high birefringence values in both the visible (Δ n exp = 0.994 at 546 nm) and infrared (Δ n cal = 0.719 at 1064 nm) regions among all known inorganic crystals with E g > 2.0 eV. CIC also exhibits an ultrawide optical transparency window from 0.367 to at least 25 μm and can be grown into centimeter-scale single crystals. This study introduces CIC as a promising IR birefringent material and highlights the potential of linear interhalogen BAGs for the design of next-generation IR optical crystals.}, archive = {J_JACS}, author = {Chong-An Chen and Yang Li and Congcong Jin and Kang Min Ok}, doi = {10.1021/jacs.5c10200}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26133--26138}, shortjournal = {J. Am. Chem. Soc.}, title = {CsICl2: A record-birefringent inorganic crystal with ultrawide infrared transparency enabled by linear interhalogen ICl2– units}, volume = {147}, year = {2025}, }
• (2025). Radical 1,3-difunctionalization of β,γ-unsaturated ketones via concomitant 1,2-carbonyl migration: An entrance to β-SF5-/β-CF3SF4 ketones. JACS, 147(30), 26124--26132. (www)

  @article{ , abstract = {The radical migration (RaM) mechanism via photoinduced transformation is a powerful tool in organic synthesis to construct new molecular scaffolds. Herein we disclose a metal-free, photoinduced 1,2-carbonyl migration of β,γ-unsaturated ketones to afford a wide range of valuable β-SF 5 /β-CF 3 SF 4 ketones. This transformation exhibits broad functional group tolerance and is suitable for the late-stage modification of complex molecules in up to 93% yield with excellent chemoselectivity and regioselectivity. Furthermore, mechanistic studies reveal that the selective synthesis of 1,3-chloropentafluorosulfanylation can be accomplished via a carbonyl migration followed by a radical chain propagation pathway. Finally, SF 5 -containing compound 5 exhibits potential anticancer activity, underscoring the utility of this approach.}, archive = {J_JACS}, author = {Jia-Yu Li and Ying Liu and Donglei Sun and Gang Wu and Shuai-Shuai Yue and Hui-Yi Yang and Hao Zhang and Wei Zhang and Meng-Meng Zheng and Xiao-Song Xue and Shuo Guo}, doi = {10.1021/jacs.5c09085}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26124--26132}, shortjournal = {J. Am. Chem. Soc.}, title = {Radical 1,3-difunctionalization of β,γ-unsaturated ketones via concomitant 1,2-carbonyl migration: An entrance to β-SF5-/β-CF3SF4 ketones}, volume = {147}, year = {2025}, }
• (2025). Diastereo- and enantioselective synthesis of polycyclic amines by cascade cyclization of aromatic aldimines with tethered alkenes via scandium-catalyzed C–H activation. JACS, 147(30), 26116--26123. (www)

  @article{ , abstract = {The development of stereoselective and atom-efficient methods for constructing densely functionalized polycyclic amines bearing multiple stereocenters is of great interest and importance, but remains a significant challenge. Herein, we report an unprecedented regioselective and stereoselective cascade cyclization of aromatic aldimines with tethered alkenes via C–H activation by half-sandwich scandium catalysts. The reaction proceeds through ortho -C–H activation of an alkene-tethered aromatic aldimine by a scandium alkyl (or amido) species in the catalyst followed by intramolecular alkene insertion ( exo -selective cyclization) into the resulting scandium–aryl bond and the subsequent intramolecular nucleophilic addition (cyclization) to the imine unit. The use of a chiral half-sandwich scandium catalyst enabled the asymmetric cascade cyclization with a high level of enantioselectivity (up to 98:2 e.r.) and diastereoselectivity (>19:1 d.r.). This protocol offers a straightforward route for the efficient and selective synthesis of a unique family of multisubstituted benzo-fused polycyclic amines, featuring 100% atom-efficiency, broad substrate scope, and excellent diastereo- and enantioselectivity.}, archive = {J_JACS}, author = {Aniket Mishra and Xiaobin Lin and Kakoli Maji and Masayoshi Nishiura and Xuefeng Cong and Zhaomin Hou}, doi = {10.1021/jacs.5c08707}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26116--26123}, shortjournal = {J. Am. Chem. Soc.}, title = {Diastereo- and enantioselective synthesis of polycyclic amines by cascade cyclization of aromatic aldimines with tethered alkenes via scandium-catalyzed C–H activation}, volume = {147}, year = {2025}, }
• (2025). Formyl radical generation from methane oxidation promoted by the superoxide radical in tungsten oxide cations WO4+. JACS, 147(30), 26109--26115. (www)

  @article{ , abstract = {The formyl radical (HCO • ) is a critical intermediate species involved in atmospheric, combustion, interstellar, and catalysis chemistry. The complicated reaction networks of HCO • formation from a variety of substrates such as CO x molecules as well as unsaturated hydrocarbons and their derivatives have been widely proposed. By contrast, the contribution of saturated hydrocarbons (e.g., methane) to HCO • generation remains largely elusive. Herein, we successfully identify that the metal oxide cluster cation, WO 4 + , that features a superoxide radical (O 2 –• ) can activate three C–H bonds of methane and then directly oxidize methane to the HCO • radical at room temperature. This finding represents a sharp improvement in the field of direct methane oxidation to oxygenated compounds by metal oxide systems wherein selective activation of one, two, or four C–H bonds was generally involved. We propose that the presence of a superoxide radical is very effective to prevent the high-valent metal center from being reduced, which is thermodynamically and kinetically advantageous for direct oxidation of methane to a free HCO • radical. This work not only reports an unprecedented route for production of the HCO • radical but also provides convincing evidence to consider methane as an important source in constructing the reaction networks relevant with HCO • generation.}, archive = {J_JACS}, author = {Yu-Ting Xiao and Yan-Xia Zhao and Yu-Zhe Hu and An Zhao and Qing-Yu Liu and Sheng-Gui He}, doi = {10.1021/jacs.5c08637}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26109--26115}, shortjournal = {J. Am. Chem. Soc.}, title = {Formyl radical generation from methane oxidation promoted by the superoxide radical in tungsten oxide cations WO4+}, volume = {147}, year = {2025}, }
• (2025). Asymmetric access to δ-hydroxy α-amino acids bearing two adjacent stereocenters from inert allylic alcohols via Cu/Ru relay catalysis. JACS, 147(30), 26102--26108. (www)

  @article{ , abstract = {Herein, we developed an efficient Cu/Ru relay catalytic system to achieve an asymmetric cascade reaction through merging hydrogen-borrowing and asymmetric Michael addition between inert allylic alcohols and ketoimine ester, enabling the efficient synthesis of biologically relevant chiral α-amino δ-hydroxy acid derivatives bearing two vicinal tertiary stereocenters in good yields with high diastereoselectivity and excellent enantioselectivity. This operationally simple and scalable protocol features excellent atom- and step-economy, broad substrate tolerance, and redox-neutral conditions. The synthetic utility was further exemplified through gram-scale synthesis, diverse downstream derivatizations, and a streamlined formal synthesis of l -pyrrolysine. Mechanistic investigations identified the Michael addition as both the stereodetermining and rate-limiting step in the cascade sequence.}, archive = {J_JACS}, author = {Qi Xiong and Bo-Bin Chen and Xiu-Qin Dong and Chun-Jiang Wang}, doi = {10.1021/jacs.5c07896}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26102--26108}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric access to δ-hydroxy α-amino acids bearing two adjacent stereocenters from inert allylic alcohols via Cu/Ru relay catalysis}, volume = {147}, year = {2025}, }
• (2025). Methylation of cytidine 1407 increases the lifetimes of the A-site ground and excited states of e. coli 16S ribosomal RNA. JACS, 147(30), 26097--26101. (www)

  @article{ , abstract = {The C5 methylation of cytidine 1407 (C1407) in the E. coli 16S rRNA is a permanent modification. The methylation occurs directly at the A-site internal loop, a known dynamic hotspot in helix 44 (H44) that undergoes conformational exchange between a functional ground and an excited state. Here, we show by relaxation dispersion NMR spectroscopy that methylation of C1407 reshapes the folding kinetics of the A-site RNA and prolongs the lifetimes of its ground and excited states. Carr–Purcell–Meiboom–Gill relaxation dispersion experiments of unmodified and m 5 C1407-modified A-site RNA reveal that C5 methylation slows down the transition rate between the ground and excited states by 1.6-fold. This kinetic effect increases the lifetimes of the excited and ground states, with the latter playing a critical role in the correct codon anti-codon recognition during the elongation phase of translation. Thus, C5 methylation of C1407 functions as a kinetic regulator in the E. coli rRNA to properly adjust the time frame for the selection of the correct tRNA–mRNA interaction.}, archive = {J_JACS}, author = {Stefan Hilber and Alessandro Marotto and Christoph Mitteregger and Martin Tollinger and Christoph Kreutz}, doi = {10.1021/jacs.5c06523}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26097--26101}, shortjournal = {J. Am. Chem. Soc.}, title = {Methylation of cytidine 1407 increases the lifetimes of the A-site ground and excited states of e. coli 16S ribosomal RNA}, volume = {147}, year = {2025}, }
• (2025). Divergent Kinetic/Thermodynamic selectivity in Palladium(II)-mediated C–H activation to form 5- and 6-membered palladacycles. JACS, 147(30), 26091--26096. (www)

  @article{ , abstract = {Palladium-catalyzed C–H functionalization proceeds via metallacycle formation and often favors 6-membered palladacycles, contrasting the typical preference for 5-membered chelates in transition-metal complexes. The present study probes the origin of this behavior by comparing the reactivity of benzoate and phenylacetate substrates in stoichiometric and catalytic reactions with MPAA-ligated Pd(OAc) 2 (MPAA = mono- N -protected amino acid). Stoichiometric competition studies show that 6-membered palladacycle formation is kinetically favored, while the 5-membered palladacycle is thermodynamically favored. Density functional theory (DFT) calculations reveal that the transition state for 5-membered palladacycle formation is inhibited by a higher distortion energy. Replacement of the α-MPAA ligand with a more flexible β-MPAA derivative lowers the transition state energy of benzoate C–H activation and improves the catalytic performance.}, archive = {J_JACS}, author = {Philip S. Zhou and Kyana M. Sanders and Ilia A. Guzei and Djamaladdin G. Musaev and Shannon S. Stahl}, doi = {10.1021/jacs.5c02735}, journal = {Journal of the American Chemical Society}, month = {7}, number = {30}, pages = {26091--26096}, shortjournal = {J. Am. Chem. Soc.}, title = {Divergent Kinetic/Thermodynamic selectivity in Palladium(II)-mediated C–H activation to form 5- and 6-membered palladacycles}, volume = {147}, year = {2025}, }
• (2025). Correction to “DNA nanopatch-specific modification of probiotics for ultrasound-triggered inflammatory bowel disease therapy”. JACS, 147(29), 26089--26090. (www)

  @article{ , archive = {J_JACS}, author = {Xiangbowen Jin and Hongyang Li and Sheng Pan and Bin Song and Yanping Jiang and Haoliang Shi and Jiawei Zhang and Binbin Chu and Houyu Wang and Yao He}, doi = {10.1021/jacs.5c09813}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {26089--26090}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “DNA nanopatch-specific modification of probiotics for ultrasound-triggered inflammatory bowel disease therapy”}, volume = {147}, year = {2025}, }
• (2025). Triplet energy transfer-based deracemization of axially chiral alkenes enabled by a dual catalyst system. JACS, 147(29), 26079--26088. (www)

  @article{ , abstract = {Photochemical deracemization has been recognized as a highly efficient strategy in asymmetric synthesis. Consequently, several pivotal chiral photosensitizers have been developed to participate in energy transfer (EnT)-based mechanisms. Nevertheless, the limited diversity of catalyst types and the pronounced spatial effects of photosensitizer moieties on enantioselectivity present an inherent challenge, thereby significantly restricting the substrate scope. In this context, exploring the feasibility of dual-catalyst systems becomes a critical task due to the flexibility of independently selecting two catalysts. Notably, the intrinsic racemization of enantioenriched products, even in the absence of chiral catalysts, represents a substantial obstacle that considerably impacts the efficiency of enantiomer enrichment. Despite these challenges, we have successfully achieved this objective, providing robust proof-of-concept validation. As a result, under a dual-catalyst system comprising a chiral phosphoric acid (CPA) and 4CzIPN mediated by visible light, a broad range of valuable axially chiral azaarylidene cycloalkanes can be synthesized with exceptional yields and enantioselectivities. The scope of the substrates is remarkably extensive, including a wide range of cyclohexanes, cyclopentanes, and cyclobutanes substituted with various azaarenes and featuring diverse stereocenter configurations. Notably, this encompasses spiro- and all-carbon quaternary stereogenic centers, all of which exhibit exceptional compatibility. More importantly, numerous bioactive molecules, such as a key mGlu5 antagonist, can be directly synthesized with high precision, further highlighting the significance of this work.}, archive = {J_JACS}, author = {Guangkuo Zeng and Wenshuo Shi and Zhuoxi Wang and Xiaowei Zhao and Yanli Yin and Zhiyong Jiang}, doi = {10.1021/jacs.5c10123}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {26079--26088}, shortjournal = {J. Am. Chem. Soc.}, title = {Triplet energy transfer-based deracemization of axially chiral alkenes enabled by a dual catalyst system}, volume = {147}, year = {2025}, }
• (2025). Poly(p-benzoquinono)diimidazole-linked covalent organic framework as an efficient anode endues sodium-ion batteries with high performance and wide temperature adaptability. JACS, 147(29), 26069--26078. (www)

  @article{ , abstract = {Sodium-ion batteries (SIBs) are potential alternatives in the postlithium electrification era. However, developing practical Na + storage devices that offer temperature resilience, high capacity, superior rate performance, and durability remains a significant challenge. Herein, a poly( p -benzoquinono)diimidazole-linked covalent organic framework (COF; named CityU-36), prepared through polycondensation between 2,3,5,6-tetraaminobenzoquinone (TABQ) and 4,4′,4″-(1,3,5-triazine-2,4,6-triyl)tribenzaldehyde (TFPT), showcases significant advantages in pushing up the ability of Na + storage and wide-temperature operability in SIBs. Thanks to its dense redox-active centers, structural robustness, uniformed porosities, and large surface area, CityU-36 exhibits an ultrahigh reversible capacity of 552 mAh g –1 at 0.1 A g –1 , outstanding rate performance of 369 mAh g –1 at 8.0 A g –1 , and exceptional long-term cyclability with 546 mAh g –1 at 5 A g –1 over 2900 cycles when used as an anode in SIBs. More importantly, the Na//CityU-36 device demonstrates all-weather working potential and exhibits wide temperature adaptability from −40 °C (321 mAh g –1 @0.03 A g –1 ) to 60 °C (357 mAh g –1 @10 A g –1 ). These attributes position CityU-36 as a superior candidate among advanced forthcoming practical SIBs.}, archive = {J_JACS}, author = {Fangyuan Kang and Lei Yan and Yongjie Cao and Zihao Chen and Yanwei Zhao and Xiyang Wang and Yuchan Zhang and Lukuan Cheng and Qianfeng Gu and Jinglun Yang and Fu-Rong Chen and Chun-Sing Lee and Yonggang Wang and Qichun Zhang}, doi = {10.1021/jacs.5c10166}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {26069--26078}, shortjournal = {J. Am. Chem. Soc.}, title = {Poly(p-benzoquinono)diimidazole-linked covalent organic framework as an efficient anode endues sodium-ion batteries with high performance and wide temperature adaptability}, volume = {147}, year = {2025}, }
• (2025). Amorphization-induced electronic modulation of Gd(OH)3 nanocages with enhanced enzymatic activities for antitumor therapy. JACS, 147(29), 26060--26068. (www)

  @article{ , abstract = {In nanotechnology-based cancer therapy, modulating electronic states of nanomaterials is crucial for influencing spatiotemporal dynamic behaviors of intracellular reduction–oxidation and redox homeostasis. Although rare-earth transition metals with 4f electrons present electronic energy levels suitable for electronic modulation, its practical realization is challenging due to strong 4f electron localization. Theoretical studies indicate that amorphization can significantly alter the electronic states of the 4f-dominated nanomaterials. However, the isotropic nature of disordered structures poses challenges for morphology and dimensional regulation of amorphous nanomaterials, which is important in tumor therapy. In this study, we designed and synthesized amorphous Gd(OH) 3 nanocages with regulated electronic states for antitumor therapy. The reduction of the Gd–O coordination number in the amorphous structure significantly diversifies the spatial occupancy, alters the electronic states, and enhances hole delocalization, thereby boosting the redox capability of the originally inert Gd 3+ compound (half-filled 4f 7 orbit). This results in unexpected peroxidase (POD)-like catalytic activity, with a K cat of 3.49 × 10 4 s –1 , which is an order of magnitude higher than that of the natural HRP enzyme. The amorphous Gd(OH) 3 nanocages also show impressive antitumor effects both in vitro and in vivo, demonstrating that amorphization is an effective strategy for modulating the electronic states of rare earth elements and unlocking new catalytic and biomedical potential for advanced synthetic nanozymes.}, archive = {J_JACS}, author = {Zezhou Wang and Qi Hu and Mengmeng Zhang and Chen Li and Shu Wang and Yanhong Li and Fengshi Li and Tianqi Guo and Pengfei Hu and Kewei Jiang and Gilberto Teobaldi and Li-Min Liu and Lin Guo}, doi = {10.1021/jacs.5c09591}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {26060--26068}, shortjournal = {J. Am. Chem. Soc.}, title = {Amorphization-induced electronic modulation of Gd(OH)3 nanocages with enhanced enzymatic activities for antitumor therapy}, volume = {147}, year = {2025}, }
• (2025). Interactions of polar and nonpolar groups of alcohols in zeolite pores. JACS, 147(29), 26049--26059. (www)

  @article{ , abstract = {Understanding the quantitative interactions among zeolite pore walls, Bro̷nsted acid sites, and molecules with both polar and nonpolar regions is essential for scoping out the potential of zeolites as sorbents and catalysts. Purely siliceous zeolites ( MFI and Beta in the present study) are hydrophobic, whereas those containing aluminum are considered hydrophilic, preferentially adsorbing organic molecules even in aqueous environments. To characterize these interactions, we use primary alcohols of increasing molecular weight, quantifying their specific interactions in the confined pore space of the alkyl (CH x ) and OH groups. Three types of interactions were identified: (i) alkyl CH x groups interacting with the zeolite pore walls (approximately 10 kJ mol –1 per carbon), (ii) alcohol OH groups interacting with the pore walls (30–35 kJ mol –1 ), and (iii) alcohol OH groups interacting with Bro̷nsted acid sites (37 kJ mol –1 ). All three interactions were well mirrored by computational simulations. The contribution of the alkyl CH x groups was inferred from the incremental increase in sorption enthalpy with increasing molecular weight; the interaction strength of the OH groups was determined by extrapolating the global adsorption enthalpy of the alcohols to a hypothetical OH group without an alkyl group. This value was identical to the adsorption enthalpy of water. The experiments demonstrated that only water has an adsorption enthalpy on zeolite pore walls lower than its condensation enthalpy (30–35 kJ mol –1 vs 45 kJ mol –1 ), limiting the concentration of water that can be adsorbed.}, archive = {J_JACS}, author = {Ruixue Zhao and Sungmin Kim and Mal-Soon Lee and Benjamin A. Jackson and Fuli Deng and Xiaomai Chen and Cong Zhou and Konstantin Khivantsev and Yue Liu and Vassiliki-Alexandra Glezakou and Roger Rousseau and Johannes A. Lercher}, doi = {10.1021/jacs.5c09340}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {26049--26059}, shortjournal = {J. Am. Chem. Soc.}, title = {Interactions of polar and nonpolar groups of alcohols in zeolite pores}, volume = {147}, year = {2025}, }
• (2025). Elucidating the electrochemical hydrogenation route by spatially isolating competing pathways. JACS, 147(29), 26040--26048. (www)

  @article{ , abstract = {Electrochemical hydrogenation can, in principle, occur through two different possible pathways. One is through the Eley–Rideal mechanism, which involves proton-coupled electron transfer directly from solvent water. Alternatively, hydrogenation can also occur through the Langmuir–Hinshelwood mechanism using surface adsorbed *H. Presumably, the competition between these pathways could exert a considerable influence on product selectivity and reaction rates, however much remains unknown regarding the nature of these processes. Here by employing a Pd membrane reactor to spatially isolate the Langmuir–Hinshelwood pathway, we demonstrate that this has a larger kinetic isotope effect (KIE) as compared to the Eley–Rideal pathway. Hence, we find that hydrogenation through the Eley–Rideal pathway results in a relatively higher incorporation of D when a H 2 O/D 2 O mixture is used as the electrolyte. Finally, we show that increased steric hindrance in the reactant molecule favors the Langmuir–Hinshelwood pathway, which was supported by our theoretical simulations. Our results have important implications on computational modeling of mechanistic pathways and catalyst design for electrochemical hydrogenation reactions.}, archive = {J_JACS}, author = {Jiguang Zhang and Chengyi Zhang and Sibo Wang and Yu Mao and Meng Wang and Qin Yang and Ruoou Yang and Yan Zhang and Shuo Chen and Jinfeng Jia and Ziyun Wang and Yanwei Lum}, doi = {10.1021/jacs.5c09295}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {26040--26048}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating the electrochemical hydrogenation route by spatially isolating competing pathways}, volume = {147}, year = {2025}, }
• (2025). The key steps and distinct performance trends of pyrrolic vs pyridinic M–N–C catalysts in electrocatalytic nitrate reduction. JACS, 147(29), 26029--26039. (www)

  @article{ , abstract = {The electrochemical nitrate reduction reaction (NO 3 RR) offers a sustainable route for ambient ammonia synthesis. While metal–nitrogen–carbon (M–N–C) single-atom catalysts have emerged as promising candidates for the NO 3 RR, the structure–activity relations underlying their catalytic behavior remain to be elucidated. Through systematic analysis of reported experimental data and pH-field coupled microkinetic modeling on a reversible hydrogen electrode (RHE) scale, we reveal that the coordination-dependent activity originates from distinct scaling relations governed by metal-intermediate interactions. M-N-Pyrrolic catalysts generally demonstrate higher turnover frequencies for ammonia production than M-N-Pyridinic catalysts. Meanwhile, the adsorption and protonation of nitrate, which is a step often dismissed and/or assumed to be simultaneous in many previous reports, are identified to be the rate-determining step (RDS) in the NO 3 RR. Remarkably, our subsequent experimental validation confirms the theoretical predictions under both neutral and alkaline conditions. This study offers a comprehensive mechanistic framework for interpreting the electrocatalytic activity of M–N–C catalysts in the NO 3 RR, showing that a classical thermodynamic “limiting-potential model” is not sufficiently accurate to capture the RDS and the catalytic performance trends of different materials (even on M-N-Pyrrolic and M-N-Pyridinic catalysts). These findings provide brand new insights into the reaction mechanism of the NO 3 RR and establish fundamental design principles for electrocatalytic ammonia synthesis.}, archive = {J_JACS}, author = {Qiuling Jiang and Mingyao Gu and Shen Pei and Tianyi Wang and Fangzhou Liu and Xin Yang and Di Zhang and Zhijian Wu and Ying Wang and Li Wei and Hao Li}, doi = {10.1021/jacs.5c09199}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {26029--26039}, shortjournal = {J. Am. Chem. Soc.}, title = {The key steps and distinct performance trends of pyrrolic vs pyridinic M–N–C catalysts in electrocatalytic nitrate reduction}, volume = {147}, year = {2025}, }
• (2025). Versatile butenolide syntheses via a structure-oriented C–H activation reaction. JACS, 147(29), 26019--26028. (www)

  @article{ , abstract = {Despite significant advances in forging a single bond via C–H activation in the past decade, one-step construction of biologically or chemically important scaffolds from abundant feedstock chemicals, namely, structure-oriented C–H activation, remains a significant challenge. Since feedstocks often contain a single functional group, multiple C(sp 3 )–H bond functionalizations are often necessary toward the assembly of densely functionalized scaffolds. As classic pharmacophores and versatile synthetic intermediates, butenolides have received extensive attention from the pharmaceutical industry and synthetic chemists. Here, we report the development of a palladium catalyst that enables the one-step conversion of aliphatic acids into ubiquitous butenolides involving triple functionalizations of methylene and methine C–H bonds with tert -butyl hydroperoxide (TBHP) as the sole oxidant. The unprecedented triazole–pyridone ligand is essential for realizing this “butenolide-oriented” C–H activation reaction. The availability of diverse aliphatic acids allows rapid access to unexplored but medicinally interesting chemical space of butenolides. Improved syntheses of a wide range of bioactive natural products and drug molecules were achieved using this reaction, including anticancer and anti-HIV compounds. As low as 1 mol % catalyst loading, ready scalability, and product purification through a simple aqueous washing represent rare practical advantages for C–H activation reactions.}, archive = {J_JACS}, author = {Yu-Kun Lin and Donghyeon Kim and Yuxin Ouyang and Jin-Quan Yu}, doi = {10.1021/jacs.5c09040}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {26019--26028}, shortjournal = {J. Am. Chem. Soc.}, title = {Versatile butenolide syntheses via a structure-oriented C–H activation reaction}, volume = {147}, year = {2025}, }
• (2025). Cu/Ir relay catalysis for regio- and enantioselective alkene Borylation/Allylic alkylation. JACS, 147(29), 26009--26018. (www)

  @article{ , abstract = {Construction of consecutive stereogenic centers with high diastereo- and enantioselectivities is a challenging task in organic synthesis. Ir-catalyzed asymmetric allylic substitution reactions with prochiral nucleophiles have evolved as an important method toward this goal. Herein, we report a Cu/Ir relay catalysis allowing for the utilization of alkylcopper reagents, in situ generated from Cu-mediated borylative difunctionalization of styrenes with B 2 pin 2 , as nucleophiles compatible with π-allyl-Ir electrophiles derived from linear allyl carbonates. High yields (up to 90%), excellent regio-, diastereo-, and enantioselectivities are achieved (up to >20:1 b/l, > 20:1 dr, and >99% ee) when appropriate chiral bisphosphine and phosphoramidite ligands are employed. Selective access to all four possible stereoisomers of the target molecule is realized by switching the absolute configurations of the ligands for Cu- and Ir-catalysts. DFT calculations shed light on the stereochemical models in this relay catalysis. An array of product transformations demonstrates the synthetic potential of this reaction.}, archive = {J_JACS}, author = {Wen-Bin Cao and Hui Xu and Yi-Zhe Lou and Yi-Ming Hou and Wen-Yun Zhang and Chao Zheng and Shu-Li You}, doi = {10.1021/jacs.5c08848}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {26009--26018}, shortjournal = {J. Am. Chem. Soc.}, title = {Cu/Ir relay catalysis for regio- and enantioselective alkene Borylation/Allylic alkylation}, volume = {147}, year = {2025}, }
• (2025). Unveiling migration dynamics of acid molecules in microenvironments via fluorescence signal: A case study in polymer emulsion film formation. JACS, 147(29), 25998--26008. (www)

  @article{ , abstract = {Ionic dynamics in microenvironments profoundly impact entire systems; however, their complexity and subtlety hinder real-time monitoring and correlation with macroscopic behaviors. Herein, with polymer emulsions as a case study, we demonstrate the feasibility of fluorescence-based techniques for tracking intricate migration dynamics of acid molecules in microenvironments. Specifically, an acid-sensitive fluorescent probe with a strong donor–acceptor effect, namely, TPE-DMA-MN, is developed. Protonation and deprotonation by hydrochloric acid molecules tune the charge transfer extent in probe molecules, resulting in a distinct fluorescence shift from near-infrared to visible yellow light. By integrating this acid-sensitive chromophore into a cationic polyurethane dispersion, we achieve real-time observation of acid migration caused by electric double-layer disruption and acid evaporation with a fluorescence wavelength shift exceeding 200 nm, visible to the naked eye. By correlating dynamic ionic processes in microenvironments with the macroscopic film formation process, we develop a simple yet efficient platform for digitally monitoring the drying and postcuring processes of polymer emulsions with high contrast and precision. This work provides a novel and versatile approach for real-time tracking of intricate ionic dynamics with broad potential applications in life and material sciences.}, archive = {J_JACS}, author = {Jin Wang and Xinwen Ou and Zihao Deng and Yanzi Xu and Wei He and Ryan T. K. Kwok and Jianwei Sun and Jacky W. Y. Lam and Ben Zhong Tang}, doi = {10.1021/jacs.5c08796}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25998--26008}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling migration dynamics of acid molecules in microenvironments via fluorescence signal: A case study in polymer emulsion film formation}, volume = {147}, year = {2025}, }
• (2025). Giant five-shell polyoxometalate cages and the single-cluster-based nanowire superstructures. JACS, 147(29), 25990--25997. (www)

  @article{ , abstract = {The preparation of polyoxometalate molecular cages has always been a long-term and challenging pursuit. In this work, we have successfully prepared two unprecedented giant heterogeneous POM-based purely inorganic molecular cages with O h symmetry, which contain the aggregation of M 6 (M = Ni, Co)-substituted trilacunary {PW 9 } and Mn-bridged {W 4 }. Sodium ions are used as templates to fill the cages. The polyanions of cages can be represented as {Na 6 (MnO 6 ) 12 (W 4 O 4 ) 12 [MnO 4 (OH 2 )] 6 (PW 9 Ni 6 O 49 H 15 ) 8 } and {Na 6 (MnO 6 ) 12 (W 4 O 4 ) 12 [MnO 4 (OH 2 )] 6 (PW 9 Co 6 O 49 H 15 ) 8 }. The entire structure can also be considered as a five-shell Na 6 @Mn 12 @{W 4 } 12 @Mn 6 @{PW 9 M 6 } 8 arrangement. The electrostatic effects of sodium ions within the cages enhance the stability of the structures, allowing them to maintain a monodisperse and stable state in aqueous solutions. Interestingly, the cages assemble into nanowires through electrostatic contact with the cationic CTA + ligand, demonstrating its flexible assembly capability at the single-cluster level. This giant POM inorganic molecular cage holds significant potential for application in the preparation of functional nanomaterials.}, archive = {J_JACS}, author = {Wen-Zhu Yang and Ya-Jie Liu and Ming-Yue Wang and Xiaoya Wang and Qingda Liu and Linjie Lan and Panchao Yin and Cai-Hong Zhan and Zhan-Guo Jiang and Xun Wang}, doi = {10.1021/jacs.5c08771}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25990--25997}, shortjournal = {J. Am. Chem. Soc.}, title = {Giant five-shell polyoxometalate cages and the single-cluster-based nanowire superstructures}, volume = {147}, year = {2025}, }
• (2025). Face-to-face helical columns with permanent polarity consisting of homochiral end-functionalized helicenes. JACS, 147(29), 25978--25989. (www)

  @article{ , abstract = {Chiral π-conjugated molecules hold great potential for applications in spin-selective organic semiconductors and chiroptical electronic devices that respond to circularly polarized light. Their performance is anticipated to be strongly influenced by how they assemble in the solid state. However, strategies for controlling the packing structure─particularly in helically twisted π-conjugated molecules─remain limited. In this work, we achieved a homochiral face-to-face columnar packing arrangement for helicene derivatives by modifying their helical ends with 2,1,3-thiadiazole and phenanthrene-fused ring structures. Theoretical calculations suggested significantly strong intermolecular interactions in the face-to-face columnar arrangement (e.g., E total = −113.9 kJ·mol –1 ), comparable to those observed in planar π-conjugated molecules, likely due to the large overlap area between adjacent helical molecules. Thiadiazole-fused derivative ( P )- TD[7]H and phenanthrene-fused derivative ( M )- 1 , with face-to-face columnar arrangements in the solid state, exhibited a photoconductivity maximum of ΦΣμ max = 1 × 10 –5 cm 2 ·V –1 ·s –1 as determined by the flash-photolysis time-resolved microwave conductivity method, confirming its potential as an organic semiconductor.}, archive = {J_JACS}, author = {Zheng Zhang and Weizhe Hu and Zhibo Liu and Yusuke Tsutsui and Yasujiro Murata and Shu Seki and Takashi Hirose}, doi = {10.1021/jacs.5c08688}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25978--25989}, shortjournal = {J. Am. Chem. Soc.}, title = {Face-to-face helical columns with permanent polarity consisting of homochiral end-functionalized helicenes}, volume = {147}, year = {2025}, }
• (2025). Automated glycan assembly of porphyromonas gingivalis lipopolysaccharide epitopes for vaccine design. JACS, 147(29), 25969--25977. (www)

  @article{ , abstract = {Porphyromonas gingivalis ( P. gingivalis ) is the major cause of chronic periodontitis and is associated with systemic diseases, such as rheumatoid arthritis. A better understanding of the interplay of the human immune system and P. gingivalis lipopolysaccharide (LPS) may result in novel treatment and prevention strategies. Twelve LPS fragments of P. gingivalis were synthesized using automated glycan assembly, with the help of remote benzoyl ester participation to introduce 1,2- cis -glycosidic linkages. Saliva and sera derived from periodontitis patients, treated periodontitis patients, and healthy patients were screened for IgG and IgA antibodies using glycan microarrays. A tetrasaccharide antigen, α- d -Galp-(1→6)-α- d -Glcp-(1→4)-α- l -Rhap-(1→3)-2-β- d -GalNAc was identified as a glycoconjugate vaccine lead against P. gingivalis and elicited strong glycan-specific IgG responses in mice, showing binding to P. gingivalis W50 and suggesting potential for both targeted protection and broader prevention of systemic diseases linked to periodontitis.}, archive = {J_JACS}, author = {Sabrina Omoregbee-Leichnitz and Emelie E. Reuber and Fabienne Weber and Kim N. Stolte and José Danglad-Flores and Henrik Dommisch and Peter H. Seeberger}, doi = {10.1021/jacs.5c08663}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25969--25977}, shortjournal = {J. Am. Chem. Soc.}, title = {Automated glycan assembly of porphyromonas gingivalis lipopolysaccharide epitopes for vaccine design}, volume = {147}, year = {2025}, }
• (2025). Passivation of hydrogen interstitials in metal halide perovskites: A time-domain ab initio study. JACS, 147(29), 25960--25968. (www)

  @article{ , abstract = {Hydrogen interstitials have been recognized recently as significant nonradiative recombination centers in hybrid lead halide perovskites. By utilizing time-domain density functional theory and nonadiabatic (NA) molecular dynamics, we investigate the nonradiative recombination mechanism and systematic passivation strategies for the H i defect in FAPbI 3 , where FA = CH(NH 2 ) 2 . We show that H i forms a Pb–H i –I trimer that introduces shallow and deep-level traps within the bandgap, leading to severe nonradiative charge losses. We demonstrate that both iodine interstitial (I i ) and alkali metals can effectively passivate the H i defect but by different mechanisms. I i disrupts the Pb–H i –I trimer interaction by breaking the H i –Pb bond, accepting an electron from H i and shifting the defect levels up into a conduction band. This results in mutual passivation of the nonmetal I i and H i defects. Alternatively, alkali metals disrupt the Pb–H i –I trimer by breaking the H i –I bond. They donate an electron to H i and shift the defect states down to the valence band. The introduction of I i and Na enhances structural disorder and shifts electron–vibrational interactions toward low-frequency modes. This, in turn, weakens the NA coupling and extends the charge carrier lifetime even relative to the pristine system. The study shows that disrupting interactions between nonmetal interstitial defects and the inorganic lattice is crucial for their passivation and that self-passivation of nonmetal interstitial defects exists in hybrid lead halide perovskites. The demonstrated systematic strategies of the H i defect passivation advance understanding of the uncommon defect properties and provide guidelines for further improvement of optoelectronic performance of hybrid lead halide perovskites.}, archive = {J_JACS}, author = {Xinbo Ma and Zihang Liu and Wei-Hai Fang and Run Long and Oleg V. Prezhdo}, doi = {10.1021/jacs.5c08630}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25960--25968}, shortjournal = {J. Am. Chem. Soc.}, title = {Passivation of hydrogen interstitials in metal halide perovskites: A time-domain ab initio study}, volume = {147}, year = {2025}, }
• (2025). Monofluoromethyl radical mediated halogen-atom transfer. JACS, 147(29), 25950--25959. (www)

  @article{ , abstract = {Halogen-atom transfer (XAT) is an effective method for generating carbon radicals from alkyl halides. While stannanes and silanes have shown potential, their toxicity and secondary reactivity necessitate the search for better alternatives. Recently, carbon-based α-amino alkyl radicals have emerged as possible substitutes; however, their generation under photochemical conditions requires the use of photocatalysts. In this work, we present a novel XAT method that eliminates the need for photocatalysts by utilizing the direct excitation of a monofluoroacetoxy ligand-containing hypervalent iodine(III) reagent. This approach allows nucleophilic monofluoromethyl radicals to efficiently form carbon radicals from activated alkyl halides. These radicals can subsequently functionalize unactivated alkenes through atom transfer radical addition (ATRA). Our mechanistic studies provide insights into the generation of monofluoromethyl radical and its unique reactivity. This work highlights the untapped potential of simple, single carbon atom-containing radicals for effective alkyl radical generation.}, archive = {J_JACS}, author = {Nagarajan Ramkumar and Anete Patricija Raiskuma and Larisa Baumane and Sergey Belyakov and Kaspars Traskovskis and Janis Veliks}, doi = {10.1021/jacs.5c08589}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25950--25959}, shortjournal = {J. Am. Chem. Soc.}, title = {Monofluoromethyl radical mediated halogen-atom transfer}, volume = {147}, year = {2025}, }
• (2025). Breaking voltage limitations: Triethyl phosphate-engineered PVDF-based electrolytes with dual-interphase stabilization for 4.7 V-class quasi-solid-state lithium metal batteries. JACS, 147(29), 25940--25949. (www)

  @article{ , abstract = {The advancement of high-voltage solid-state electrolytes constitutes a pivotal challenge for realizing practical solid-state lithium metal batteries (SSLMBs). This work overcomes intrinsic voltage constraints in conventional dimethylformamide-processed poly(vinylidene fluoride) quasi-solid-state polymer electrolytes (SPEs) through molecular engineering of triethyl phosphate (TEP) as a high-band-gap solvent. First-principles calculations demonstrate TEP’s exceptional frontier orbital configuration, featuring a 9.4 eV HOMO–LUMO gap, thus expanding the electrochemical window to 4.8 V, an enhancement of 0.5 V compared to DMF-based systems (4.3 V). Leveraging this design, the optimized SPEs enable the stable operation of Li||NCM811 cells at ultrahigh voltages up to 4.7 V. Remarkably, these cells exhibit excellent long-term cycling stability, capacity retentions of 88.2% (1800 cycles at 4.2 V) and 86.8% (900 cycles at 4.5 V) are achieved. Even under the ultrahigh voltage of 4.7 V, the batteries maintain remarkable cycling stability, successfully completing 500 cycles and showcasing exceptional performance. Multiscale analysis reveals dual interfacial stabilization mechanisms: a TEP-derived Li 3 PO 4 -rich cathode interphase suppressing structural degradation coupled with a 25 nm crystalline Li 2 O-dominated anode interphase inhibiting dendrites. This molecular design paradigm establishes a pathway toward 4.7 V-class SSLMBs through interfacial architecture stabilization.}, archive = {J_JACS}, author = {Lin Yang and Youqi Chu and Yitian Feng and Yongbiao Mu and Lingfeng Zou and Chao Li and Chaozhu Huang and Huicun Gu and Chi Li and Qing Zhang and Lin Zeng}, doi = {10.1021/jacs.5c08493}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25940--25949}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking voltage limitations: Triethyl phosphate-engineered PVDF-based electrolytes with dual-interphase stabilization for 4.7 V-class quasi-solid-state lithium metal batteries}, volume = {147}, year = {2025}, }
• (2025). Negative compressibility transitions in hybrid metal oxides. JACS, 147(29), 25931--25939. (www)

  @article{ , abstract = {Materials with negative compressibility can enable transformational technological advances spanning sensing, shielding, and optoelectronics. Virtually all materials exhibiting such expansion under pressure do so in one or two spatial directions, yet thermodynamics only forbid three-dimensional compression-induced expansion within the elastic regime absent of phase transitions. We show that a class of layered hybrid organic–inorganic metal oxides isolable through mild self-assembly reactions exhibits multiphase behavior under pressure, producing microscopic negative volume compressibility of their crystallographic unit cells. This phenomenon is only observed when molecular species bridge two-dimensional metal oxide layers. Chemical reduction─yielding mixed-valence hybrid bronzes─diminishes the effect. Evidence suggests that compression surmounts the boundary of elasticity via intermolecular carbon–carbon bond formation and structural distortion, driving interlayer expansion while liberating proton and electron equivalents.}, archive = {J_JACS}, author = {Raúl Torres-Cadena and W. Lakna N. Dayaratne and Hsing-Ta Chen and Evgenii L. Kovrigin and Matthew G. Tucker and Bianca Haberl and Adam Jaffe}, doi = {10.1021/jacs.5c08464}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25931--25939}, shortjournal = {J. Am. Chem. Soc.}, title = {Negative compressibility transitions in hybrid metal oxides}, volume = {147}, year = {2025}, }
• (2025). Preorganized internal electric field enables nucleophilic attack of a nonactivated water molecule in thymine DNA glycosylase. JACS, 147(29), 25919--25930. (www)

  @article{ , abstract = {Thymine DNA glycosylase (TDG) is a monofunctional glycosylase, playing an essential role in genome maintenance and in the DNA demethylation pathway. TDG differs from other DNA glycosylases in that it lacks a general base catalyst to activate water nucleophiles, making it appealing to understand its special catalytic mechanism. Through a combination of molecular dynamics (MD) simulations and quantum-mechanical/molecular-mechanical (QM/MM) calculations, we decipher a detailed mechanism of the TDG-catalyzed thymine excision reaction from the G:T mispair, arising mainly from deamination of the 5-methylcytosine (mC), an important epigenetic regulator of gene expression. The catalytic mechanism is shown to be devoid of leaving group protonation and nucleophile deprotonation activations, two common strategies used by other monofunctional DNA glycosylases. Instead, a rearrangement of the flipped nucleotide sugar–phosphate backbone is required before the N-glycosidic bond cleavage, which proceeds via an oxocarbenium-like transition state. Nucleophilic attack on the anomeric carbon by a nonactivated water molecule from the 3′ side stabilizes the oxocarbenium ion, which is essentially facilitated by a strong internal electric field (IEF) that points toward the same direction. The IEF mainly comes from the distorted negatively charged DNA backbone phosphodiester groups, an apparent “autocatalysis” character first found in uracil DNA glycosylase (UDG). Finally, the roles of key protein residues, including Asn140, His151, Asn191, Thr197, Asp202, and Arg275, and the substrate itself, are further discussed. These results advance our understanding of the strategy used by TDG to catalyze distinct substrates and inspire further investigation of the effect of IEF on other biological enzymes, especially DNA glycosylases.}, archive = {J_JACS}, author = {Wenwen Diao and Jing Peng and Xiaodi Fu and Fangfu Ye and Zhanfeng Wang}, doi = {10.1021/jacs.5c08420}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25919--25930}, shortjournal = {J. Am. Chem. Soc.}, title = {Preorganized internal electric field enables nucleophilic attack of a nonactivated water molecule in thymine DNA glycosylase}, volume = {147}, year = {2025}, }
• (2025). [1,3]-hydride shift in α-boryl cations: Strategic design of fluorine-triggered cyclopropanation. JACS, 147(29), 25910--25918. (www)

  @article{ , abstract = {Hydride shift represents an important process in carbocation chemistry, yet controlled access to the [1,3]-hydride shift has remained elusive despite its potential synthetic utility. Here, we report direct observation and synthetic demonstration of the [1,3]-hydride shift using α-fluoro-diborylalkanes. Initial [1,2]-fluoride migration generates an α-boryl cation that selectively undergoes a [1,3]-hydride shift via a three-center two-electron interaction, enabling efficient synthesis of cyclopropyl boronic esters. Deuterium labeling experiments and computational studies reveal the key electronic factors governing this unusual selectivity. The methodology provides both mechanistic insights into longer-range hydride shifts and a practical platform for accessing diverse molecular architectures through versatile transformations of the resulting cyclopropyl boronic esters.}, archive = {J_JACS}, author = {Seungcheol Han and Yeosan Lee and Jaeyoon Seo and Junseok Lee and Seung Hwan Cho}, doi = {10.1021/jacs.5c08276}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25910--25918}, shortjournal = {J. Am. Chem. Soc.}, title = {[1,3]-hydride shift in α-boryl cations: Strategic design of fluorine-triggered cyclopropanation}, volume = {147}, year = {2025}, }
• (2025). Upgrading ion migration and interface chemistry via a cyano-containing COF in a single-ion conductive polymer toward high-voltage Lithium–Metal batteries. JACS, 147(29), 25896--25909. (www)

  @article{ , abstract = {Concentration polarization-triggered dendrite growth hinders the practical application of solid-state polymer lithium batteries, which is caused by the uncontrolled anion migration in conventional dual-ion electrolytes. Single-ion conductive polymer electrolytes (SICPEs) offer a promise to mitigate dendrite growth via reducing concentration polarization and prohibiting salt depletion, yet they are highly challenging for successful implementation due to their narrow electrochemical window and poor ionic conductivity, which result from the deficient dissociation of Li + polyanions and sluggish chain relaxation. Here, a cyano-containing covalent organic framework (COF) is designed to fuse with SICPEs, promising fast Li + transport and remarkable interfacial stability toward high-voltage lithium–metal batteries. The electron-withdrawing cyano group on the COF facilitates the dissociation of the polyanions via ion–dipole interactions, resulting in more free-moving Li + . Rapid ion migration then occurs along the long-range cooperative ion transport pathways between the COF and SICPE. Additionally, the cyano group robustly bonds with transition metal ions of NCM cathodes to inhibit the catalytic decomposition of SICPE and guarantee the structural integrity of NCM. Hence, the as-prepared SICPE exhibits a significantly enhanced ionic conductivity of 9.2 × 10 –4 S cm –1 and an improved Li + transference number of 0.94 at room temperature. Accordingly, the NCM622||Li quasi-solid-state cell achieves an exceptional capacity retention of 92.0% over 1000 cycles at 0.5 C, while the cell pairing with the 4.8 V NCM622 cathode delivers a remarkable capacity of 149.5 mAh g –1 after 200 cycles at 0.5 C. This study provides a new perspective for facilitating ionic conductivity and interface chemistry toward the practical feasibility of single-ion conductive polymer electrolytes.}, archive = {J_JACS}, author = {Xiaosa Xu and Junjie Chen and Jin Li and Jiadong Shen and Pengzhu Lin and Zhenyu Wang and Zixiao Guo and Jing Sun and Baoling Huang and Tianshou Zhao}, doi = {10.1021/jacs.5c08267}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25896--25909}, shortjournal = {J. Am. Chem. Soc.}, title = {Upgrading ion migration and interface chemistry via a cyano-containing COF in a single-ion conductive polymer toward high-voltage Lithium–Metal batteries}, volume = {147}, year = {2025}, }
• (2025). Biomimetic sandwich-structured tubular ion pump arrays for lithium metal batteries. JACS, 147(29), 25883--25895. (www)

  @article{ , abstract = {Controlling the rapid, uniform deposition and efficient, stable stripping of Li is crucial for achieving durable high-energy-density Li-metal batteries. Herein, unique biomimetic sandwich-structured tubular ion pump arrays achieved by sandwiching ZnSe nanoparticle tubes between ultrathin N-doped graphene-like layers and vertically aligning on N-doped graphene-Ni foam (NG@ZnSe@NG) are reported, working as a highly efficient and robust Li host for homogeneous and stable Li plating/stripping. After complete lithiation, such a biomimetic tubular ion pump featuring symmetric inner and outer layers with high ion-electron transport rates and a key self-accelerating middle layer is generated, accelerating uniform Li deposition into the interior and efficient stripping of Li from the cavity. Furthermore, the formation process and unique operating mechanism of the ion pump are elucidated in detail across multiple scales using in situ X-ray diffraction (XRD) analyses, in situ transmission electron microscopy (TEM) observations, and theoretical calculations. An ultrahigh Coulombic efficiency of 99.2% over 1100 cycles in asymmetric cells and an ultralong lifespan of 4970 h in symmetric cells are achieved. When assembled with LiFePO 4 and O 2 cathodes into coin cells, exceptional electrochemical performance is exhibited. Remarkably, under harsh conditions, the NG@ZnSe@NG@Li||NCM83 pouch cell maintains 85.4% capacity retention after 130 cycles at 0.5 C (2.5 mA cm –2 ), demonstrating excellent stability and reliability in industrial applications.}, archive = {J_JACS}, author = {Shang-Qi Li and Zhenzhen Wang and Xiaoyang Zheng and Mao-Lin Guo and Jia-Ning Yang and Yong Li and Zhefei Sun and Xue-Yan Wu and Chaofei Guo and Han Tian and Hui Zong and Liang Gao and Yao-Wen Zhang and Jing-Zhe Wan and Jia-Xi Xu and Qiaobao Zhang and Kai-Xue Wang and Jie-Sheng Chen}, doi = {10.1021/jacs.5c08237}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25883--25895}, shortjournal = {J. Am. Chem. Soc.}, title = {Biomimetic sandwich-structured tubular ion pump arrays for lithium metal batteries}, volume = {147}, year = {2025}, }
• (2025). Continuous encodable reshaping of gold nanocrystals through facet modulation. JACS, 147(29), 25871--25882. (www)

  @article{ , abstract = {Shape control of nanocrystals (NCs) is crucial for tuning their assembly behavior and functional properties, yet the precise manipulation of facet composition remains challenging. Here, we present a nanocrystal reshaping strategy to control and modulate the facets of gold (Au) NCs. Our one-pot approach, conducted at room temperature, requires only initial Au NCs, Au 3+ ions, and surfactants, distinguishing it from conventional reduction-mediated “etching-and-regrowth” methods. Detailed structural studies using electron microscopy, small-angle X-ray scattering (SAXS), and UV–vis spectroscopy reveal the surfactant-encoded pathway for NC transformation from shaped particles to spheres and then into various polyhedral shapes while preserving the individual particles' volume. The proposed reshaping mechanism involves the dissolution of surface Au atoms into Au + complexes in the presence of Au 3+ and surfactant, followed by surfactant-guided redeposition and formation of facets with different atomic planes. Using the ethanol oxidation reaction (EOR) as a probe, we observe a quasi-linear decrease in onset potential and an increase in activity with increasing {100} facet exposure. This work broadens synthetic strategies by offering precise NC reshaping and facet control.}, archive = {J_JACS}, author = {Fang Lu and Yugang Zhang and Lihua Zhang and Dong Su and Zechao Zhuang and Mingzhao Liu and Jingguang G. Chen and Oleg Gang}, doi = {10.1021/jacs.5c08014}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25871--25882}, shortjournal = {J. Am. Chem. Soc.}, title = {Continuous encodable reshaping of gold nanocrystals through facet modulation}, volume = {147}, year = {2025}, }
• (2025). Unraveling the crystal structures of Ag2Ch (Ch = s, se, te) via simultaneous X-ray diffraction and total scattering. JACS, 147(29), 25858--25870. (www)

  @article{ , abstract = {Despite great interest in the properties of the Ag 2 Ch (Ch = S, Se, Te) compounds, their complex crystal structures, envisioned as a disordered liquid-like Ag substructure, are poorly understood. This limits our understanding of the structural origin of their attractive properties. From combined powder X-ray diffraction (PXRD) and X-ray total scattering (TS) in the temperature range of 300–800 K, the average and local structures for all three Ag 2 Ch compounds have been probed simultaneously for both the room-temperature (RT) and first high-temperature (HT) polymorphs. From Rietveld refinement of the PXRD data, large and highly anisotropic atomic displacement parameters were identified for Ag in all RT polymorphs, which cannot be attributed solely to thermal displacement. Furthermore, the Rietveld models struggle with describing the highly diffuse distribution of Ag in the HT polymorphs, especially for Ag 2 S and Ag 2 Se, for which the maximum entropy method (MEM) is better suited. By comparing pair distribution functions (PDFs), it is found that the local structure cannot be described by the periodic Rietveld model alone at any temperature. New structural descriptions are proposed to account for these observations, in which Ag is displacively disordered in the RT polymorphs, and the lattice is locally distorted in the HT polymorphs to resemble the RT structure due to strong Ag–Ch interactions. Thus, the chalcogenide framework is far from being rigid, the Ag substructure is far from being liquid, and both are governed by specific local chemical interactions.}, archive = {J_JACS}, author = {Marius V. B. Brix and Magnus N. Kløve and Rasmus B. Stubkjær and Kenichi Kato and Bo B. Iversen}, doi = {10.1021/jacs.5c07875}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25858--25870}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the crystal structures of Ag2Ch (Ch = s, se, te) via simultaneous X-ray diffraction and total scattering}, volume = {147}, year = {2025}, }
• (2025). Light-driven crystallization-induced dynamic resolution of amines. JACS, 147(29), 25851--25857. (www)

  @article{ , abstract = {We report a method for the dynamic resolution of racemic amines enabled by catalytic photoredox-mediated racemization coupled to in situ diastereomeric crystallization. In this design, an excited-state iridium chromophore and an achiral thiol cocatalyst mediate the racemization of α-chiral amines under mild, redox-neutral conditions. In the presence of commercially available chiral resolving acids, the desired amine enantiomer is continually precipitated from solution as an insoluble diastereomeric salt. We demonstrate the utility of this method across several structurally distinct families of secondary and tertiary amines with high yields and high levels of enantioselectivity. Given the widespread importance of α-stereogenic amines in the synthesis of fine chemicals, we anticipate that this approach may find further applications that streamline the preparation of these valuable chiral compounds.}, archive = {J_JACS}, author = {Jonathan M. Meinhardt and Diane D. Kim and Emily J. Wu and Philip R. D. Murray and Daniel P. Walker and Robert R. Knowles}, doi = {10.1021/jacs.5c07676}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25851--25857}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-driven crystallization-induced dynamic resolution of amines}, volume = {147}, year = {2025}, }
• (2025). Ni-catalyzed reductive ring contraction via desulfurative cross-coupling. JACS, 147(29), 25841--25850. (www)

  @article{ , abstract = {The construction of C–C bonds by contractive “deletion” of the sulfur atom from a C–S–C motif is a useful transformation for the synthesis of complex heterocycles. The transformation allows a user to take advantage of the nucleophilic reactivity of sulfur (e.g., for S N Ar reactions) and remove that temporary atom at a late stage. A few homogeneous metal systems have been reported to mediate such desulfurizations, but under harsh conditions and, due to the formation of stable oligomeric sulfido complexes, without catalytic turnover. Here, we report a catalytic solution using an accessible Ni precatalyst, inexpensive additives, and mild conditions. The method provides rapid access to a broad scope of fused heterocycles. Preliminary mechanistic studies provide insight into key aspects of the transformation, including the order of C–S bond activations, the synergistic effects of the unusual combination of additives, and the fate of the excised sulfur atom.}, archive = {J_JACS}, author = {Jianhan Zhou and Richard Y. Liu}, doi = {10.1021/jacs.5c07642}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25841--25850}, shortjournal = {J. Am. Chem. Soc.}, title = {Ni-catalyzed reductive ring contraction via desulfurative cross-coupling}, volume = {147}, year = {2025}, }
• (2025). Direct formation of c3 oxygenates through photocatalytic CH4–CO coupling. JACS, 147(29), 25834--25840. (www)

  @article{ , abstract = {Multicarbon (C n , where n ≥ 2) oxygenates are important industrial precursors that can be synthesized from the coupling of simple and abundant C 1 feedstock such as CH 4 . While C 2 products from this route have been reported, those involving the direct coupling of more than two C 1 precursors are rare. As a proof of concept, here we report the synthesis of acetone (CH 3 COCH 3 ) through the direct coupling of two CH 4 and one CO using a combined photothermocatalytic approach. With TiO 2 as a light absorber and Pd nanoparticle as a cocatalyst, CH 4 activation and subsequent coupling with CO were achieved at 10 bar and 150 °C. A high selectivity of acetone formation among all liquid products (>80%) was measured. Experiments with isotope-labeled precursors confirmed that the product was a result of the direct coupling of CH 4 and CO. The other major liquid product was acetic acid (CH 3 COOH), which was a result of a single coupling between CH 4 and CO. The suitable binding strength between Pd and the reactive intermediates was proposed as a key reason for the high selectivity toward C 3 products.}, archive = {J_JACS}, author = {Muchun Fei and Boqiang Chen and Yasuhiro Sakamoto and Lizhuo Wang and Yu Mu and Jiwei Zhang and James R. Wilkes and Raven Gallenstein and Jun Huang and Junwei Lucas Bao and Wei Li and Dunwei Wang}, doi = {10.1021/jacs.5c07634}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25834--25840}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct formation of c3 oxygenates through photocatalytic CH4–CO coupling}, volume = {147}, year = {2025}, }
• (2025). Discretizing cobalt Spin–Orbitals through tuning the crystal symmetry for Zinc–Air batteries. JACS, 147(29), 25825--25833. (www)

  @article{ , abstract = {Regulating the electron-spin state of metal active sites is a rarely cultivated topic for oxygen electrocatalysis. Here, a dual-ligand metal–organic framework (DM) is developed to endow Co sites with D 4 h crystal symmetry, reconfiguring their orbital degeneracy and electron spin state. The discretized spin–orbital configuration offers the accelerated transformation of the O-related intermediate by accepting electrons via partial d-orbital occupation and mediation of the hydroxyl adsorption strength through electron donation to O p-orbitals. With this orbital flexibility, Co sites serve as “Lewis acid–base” pairs that hasten O redox of oxygen during Zn–air battery cycling, which is validated by operando X-ray absorption spectroscopy and theoretical modeling. Compared to counterparts with different crystal symmetries, Zn–air batteries using the DM electrocatalyst showcase reduced charge–discharge voltage gap and high round-trip energy efficiency at high areal capacity.}, archive = {J_JACS}, author = {Yi Jiang and Ruilin Liang and Changshun Wang and Yeze Liu and Chuangwei Liu and Mohsen Shakouri and Graham King and Tom Regier and Ya-Ping Deng and Zhongwei Chen}, doi = {10.1021/jacs.5c07623}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25825--25833}, shortjournal = {J. Am. Chem. Soc.}, title = {Discretizing cobalt Spin–Orbitals through tuning the crystal symmetry for Zinc–Air batteries}, volume = {147}, year = {2025}, }
• (2025). Data science-guided development of deoxyfluorination reagents with enhanced reactivity, practicality, and safety. JACS, 147(29), 25815--25824. (www)

  @article{ , abstract = {We report the discovery and development of several new (hetero)aryl sulfonyl fluoride reagents that have enhanced deoxyfluorination reactivity, improved physical properties, and excellent safety profiles compared to those of PyFluor and other fluorination reagents such as PBSF and DAST. To select structurally diverse reagents, we computed a virtual library of (hetero)aryl sulfonyl fluorides and leveraged training set design principles to broadly survey structure–activity relationships in a model deoxyfluorination reaction. We developed predictive models to optimize sulfonyl fluoride reagents for the deoxyfluorination of a key intermediate used in the synthesis of RIPK1 inhibitor GDC-8264. The top-performing reagents demonstrated broad applicability across diverse alcohol substrate classes, including complex natural products and active pharmaceutical ingredients, highlighting the power of data science-enabled approaches in reagent development.}, archive = {J_JACS}, author = {Madeline E. Ruos and Natalie P. Romer and Julie A. Deichert and Lady Mae Alabanza and Shivaani S. Gandhi and Giselle Z. Brown and Richard C. Walroth and Karissa Cruz and Francis Gosselin and Allen Y. Hong and Matthew S. Sigman and Abigail G. Doyle}, doi = {10.1021/jacs.5c07548}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25815--25824}, shortjournal = {J. Am. Chem. Soc.}, title = {Data science-guided development of deoxyfluorination reagents with enhanced reactivity, practicality, and safety}, volume = {147}, year = {2025}, }
• (2025). Interplay between lone pair stereochemical activity and structural anisotropy drives ultralow thermal conductivity in layered AGeS3 (A = pb, sn) metal sulfides. JACS, 147(29), 25806--25814. (www)

  @article{ , abstract = {Metal sulfides have recently drawn significant interest from the scientific community due to their nontoxicity and abundance, making them suitable for a wide range of applications, including thermoelectric and optoelectronic technologies. Although numerous ternary metal sulfides have been reported in the literature, their crystal structures and physical properties remain largely unexplored. In the present work, we have synthesized bulk polycrystalline samples of AGeS 3 (A = Pb/Sn) using mechanical alloying followed by spark plasma sintering and studied their crystal structures, microstructures, and thermal and vibrational properties in relation to computational modeling. The low lattice thermal conductivity in this class of compounds is mainly attributed to the weak interlayer bonding (2D character) due to the stereochemical activity of the lone pairs of Sn 2+ in SnGeS 3 and Pb 2+ in PbGeS 3 . Importantly, we examine the nature of the chemical bonds in AGeS 3 and elucidate the origin of distinct thermal conductivities in these two compounds despite having similar crystal structures. We show that the enhanced stereochemical activity of Sn 2+ in SnGeS 3 , compared to Pb 2+ in PbGeS 3 , leads to a more distinct two-dimensional character. This is demonstrated by stronger intralayer bonding, weaker interlayer interactions, and more prominent interlayer Sn–S antibonding states near the Fermi level. Anisotropic grain growth, observed in our TEM data, further supports this interpretation. Consequently, glass-like lattice thermal conductivity is observed in SnGeS 3 while PbGeS 3 exhibits crystalline-like thermal conductivity. These findings enrich the fundamental knowledge of crystal chemistry and thermal conduction relationships in metal sulfides and encourage further investigations into the design of materials for thermal management applications.}, archive = {J_JACS}, author = {Paribesh Acharyya and Koushik Pal and Xingchen Shen and Bin Zhang and Bernard Raveau and Sara Passuti and Philippe Boullay and Pierric Lemoine and Bernard Malaman and Christophe Candolfi and Adèle Renaud and Xiaoyuan Zhou and Tristan Barbier and Emmanuel Guilmeau}, doi = {10.1021/jacs.5c07547}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25806--25814}, shortjournal = {J. Am. Chem. Soc.}, title = {Interplay between lone pair stereochemical activity and structural anisotropy drives ultralow thermal conductivity in layered AGeS3 (A = pb, sn) metal sulfides}, volume = {147}, year = {2025}, }
• (2025). Activity-based tracking of glycan turnover in microbiomes. JACS, 147(29), 25799--25805. (www)

  @article{ , abstract = {Glycans shape microbiomes in the ocean and the gut, driving key steps in the global carbon cycle and human health. Yet, our ability to track microbial glycan turnover across microbiomes is limited, as identifying active degraders without prior genomic knowledge remains a key challenge. Here, we introduce an activity-based fluorescence resonance energy transfer (FRET) probe that enables direct visualization and quantification of glycan metabolism in complex microbial communities. As a proof of concept, we investigated α-mannan degradation, a prominent polysaccharide in algal blooms. Using automated glycan assembly, we synthesized a mannan hexasaccharide bearing a fluorescein–rhodamine FRET pair. The probe was validated using a recombinantly expressed endo -α-mannanase (GH76) from Salegentibacter sp. Hel_I_6. It was shown to function in cell lysates, pure cultures, and complex microbiomes (via plate assays and microscopy). This probe enabled spatiotemporal visualization of in situ α-mannan turnover in a marine microbiome. Glycan FRET probes are versatile tools for tracking glycan degradation across biological scales from single enzymes to microbiomes.}, archive = {J_JACS}, author = {Conor J. Crawford and Greta Reintjes and Vipul Solanki and Manuel G. Ricardo and Jens Harder and Rudolf Amann and Jan-Hendrik Hehemann and Peter H. Seeberger}, doi = {10.1021/jacs.5c07546}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25799--25805}, shortjournal = {J. Am. Chem. Soc.}, title = {Activity-based tracking of glycan turnover in microbiomes}, volume = {147}, year = {2025}, }
• (2025). Gadolinium-mediated oxygen affinity induced efficient covalorization of CH4 and N2O in an Ir–Gd2O3 single-atom catalyst. JACS, 147(29), 25787--25798. (www)

  @article{ , abstract = {Valorization of nitrous oxide (N 2 O) and methane (CH 4 ) for chemicals has garnered growing interest for mitigating their climate impact. Dry reforming of methane (DRM) with industrial N 2 O exhaust offers a promising route. However, the DRM reaction often requires rigorous temperatures (>650 °C) accompanied by overoxidation, hindering CO and H 2 formation due to weak oxygen binding on catalysts. Here, we report a Gd 2 O 3 -supported iridium single-atom catalyst (SAC), with an effective Ir 1 –Gd 2 O 3 synergy. At only 450 °C, it exhibits high N 2 O (99.3%) and CH 4 (48.2%) conversion and syngas yields (138.3 mol of CO kg cat –1 h –1 and 184.9 mol of H 2 kg cat –1 h –1 ) and a H 2 /CO ratio of 1.34, over 100 h. Mechanism studies revealed that Gd 2 O 3 enabled controlled oxygen release for CO production, while Ir single atoms facilitated CH 4 activation and H 2 formation. This work presents a low-temperature, sustainable strategy for greenhouse gas utilization and highlights the potential of Gd 2 O 3 -based single-atom catalysts in heterogeneous catalysis.}, archive = {J_JACS}, author = {Yunshuo Wu and Haiqiang Wang and Feng-Shou Xiao and Zhongbiao Wu}, doi = {10.1021/jacs.5c07233}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25787--25798}, shortjournal = {J. Am. Chem. Soc.}, title = {Gadolinium-mediated oxygen affinity induced efficient covalorization of CH4 and N2O in an Ir–Gd2O3 single-atom catalyst}, volume = {147}, year = {2025}, }
• (2025). Cross-coupling between arylboronic acids and terminal alkynes in water microdroplets. JACS, 147(29), 25779--25786. (www)

  @article{ , abstract = {We report a cross-coupling reaction between terminal alkyne and arylboronic acid to form the C–C bond in water microdroplets under mild, catalyst-free conditions. A solution containing phenylacetylene (50 μM) and 4-methoxyphenylboronic acid (50 μM) in a 4:1 (H 2 O: ACN) mixture was electrosprayed at +1.5 kV, and the reaction products were analyzed using a mass spectrometer (MS). We observed C(sp 2 )-C(sp) coupling reaction products within milliseconds, which were characterized by tandem mass spectrometry (MS 2 ). Based on in situ reaction studies and radical experiments, we determined the reaction mechanism for the coupling reaction. Our approach offers a sustainable and environmentally benign pathway for the synthesis of internal aryl alkynes, making it a suitable building block for the preparation of various pharmaceutical drugs.}, archive = {J_JACS}, author = {Sandeep Bose and Mohammad Mofidfar and Richard N. Zare and Elumalai Gnanamani}, doi = {10.1021/jacs.5c07509}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25779--25786}, shortjournal = {J. Am. Chem. Soc.}, title = {Cross-coupling between arylboronic acids and terminal alkynes in water microdroplets}, volume = {147}, year = {2025}, }
• (2025). Mechanistic studies of oxidative degradation in diamine-appended Metal–Organic frameworks exhibiting cooperative CO2 capture. JACS, 147(29), 25761--25778. (www)

  @article{ , abstract = {Understanding the impact of O 2 during a carbon capture process is vital for designing robust, cost-effective materials for carrying it out. However, mechanistic studies of the O 2 -induced degradation of materials are not easily undertaken owing to the complex sequential reaction pathways that arise. Here, we report comprehensive mechanistic investigations of the O 2 -induced degradation of diamine-appended metal–organic frameworks (MOFs) exhibiting cooperative CO 2 adsorption. Oxygen exposure experiments were performed on seven different diamine-appended MOFs, including e-2–Mg 2 (dobpdc) (e-2 = N -ethylethylenediamine, dobpdc 4– = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate), under various temperatures and O 2 pressures. These experiments show that diamine degradation inhibits CO 2 chemisorption and that the degradation rate is significantly influenced by the diamine structure. In contrast, the parent frameworks remain essentially intact upon O 2 exposure. Detailed characterization of O 2 -exposed e-2–Mg 2 (dobpdc) revealed the formation of various degradation products, including acetaldehyde, carbon dioxide, water, ethylamine, and other aldehyde- and imine-containing species. Together, these observations suggest that diamine degradation occurs via C–N bond cleavage through pathways involving C-centered radicals. Furthermore, computational evaluation of the initiation and propagation pathways for amine degradation in diamine-appended MOFs indicates that (i) degradation is likely initiated by OH • , (ii) carbon-centered radicals generated via radical transfer reactions react with O 2 , leading to amine degradation, and (iii) the rate-limiting step of the degradation reactions likely involves O–O bond cleavage. Overall, these mechanistic insights could inform strategies for mitigating O 2 -induced amine degradation in next-generation carbon capture technologies.}, archive = {J_JACS}, author = {Shuoyan Xiong and Alistair J. Sterling and Nikolay V. Tkachenko and Rhea-Donna Reyes and Hsinhan Tsai and Jaeheon Lee and Yu Chen and Yang Wang and Matthew N. Dods and David Lu and Ziting Zhu and Jonas Börgel and Jeong Won Kim and Abigail J. Schmeiser and Junyang Meng and Hiroyasu Furukawa and Aaron W. Peters and Bryan D. McCloskey and Jeffrey A. Reimer and Simon C. Weston and Martin Head-Gordon and Jeffrey R. Long}, doi = {10.1021/jacs.5c07551}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25761--25778}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic studies of oxidative degradation in diamine-appended Metal–Organic frameworks exhibiting cooperative CO2 capture}, volume = {147}, year = {2025}, }
• (2025). Enhanced photothermal conversion through 2D/0D nano-heterojunction engineering for highly efficient solar desalination. JACS, 147(29), 25750--25760. (www)

  @article{ , abstract = {Two-dimensional (2D) materials are promising candidates for solar-driven desalination. However, conventional photothermal 2D materials like transition metal carbides and nitrides (MXenes) as well as transition metal dichalcogenides (TMDs) suffer from major limitations such as their complex synthesis and low photothermal conversion efficiency. In contrast, metal phosphorus trichalcogenides (MPCh 3 ) do not display the same drawbacks and possess widely tunable bandgaps (1.2–3.5 eV), making them ideal candidates for solar desalination. Moreover, their properties and applications related to light–matter interactions can be further enhanced by coupling with other low-dimensional nanostructures, tailoring hybrid van der Waals heterostructures of mixed dimensionality. Herein, we report the synthesis of FePS 3 nanosheets/carbon nanodots (CNDs) 2D/0D nanoheterojunctions and their photothermal response when integrated into a 3D photothermal evaporator. These nanoheterojunctions exhibited high photothermal conversion performance, with an average absorbance of 90.6% from the UV to the NIR and a temperature increase of 42 °C over the blank control under 1 sun illumination for 300 s. A high water evaporation rate of 1.68 kg m –2 h –1 was observed under the same condition. Photothermal conversion and water evaporation experiments, along with femtosecond transient absorption spectroscopy (fs-TAS), photoluminescence (PL) analysis, and finite-difference time-domain (FDTD) simulations, revealed that the incorporation of CNDs and formation of the nanoheterojunction synergistically enhance localized heating and light absorption, improve trapping efficiency, and optimize nonradiative transition pathways. This study demonstrates the disruptive potential of the rational design of high-performance 2D material hybrids through MPCh 3 -based nanoheterojunction engineering, unveiling its transformative capability for use in solar desalination and photothermal technologies.}, archive = {J_JACS}, author = {Honglei Wang and Yifan Bo and Hongguang Wang and Malte Klingenhof and Zhehao Tao and Dong Wang and Bing Wu and Adrián Tamayo and Bin Han and Pengfei Cheng and Peter A. van Aken and Zdenek Sofer and Runfeng Chen and Peter Strasser and Peter Schaaf and Dirk M. Guldi and Paolo Samorì}, doi = {10.1021/jacs.5c07491}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25750--25760}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced photothermal conversion through 2D/0D nano-heterojunction engineering for highly efficient solar desalination}, volume = {147}, year = {2025}, }
• (2025). Synergistic electron-deficient surface engineering: A key factor in dictating electron carrier extraction for perovskite photovoltaics. JACS, 147(29), 25738--25749. (www)

  @article{ , abstract = {Work function modulation of transparent conductive oxides via self-assembled monolayers (SAMs) facilitates efficient hole or electron extraction in optoelectronic devices. However, recent SAMs for perovskite solar cells (PSCs) diverge from traditional interfacial dipole orientation design principles, instead leveraging electron-rich and electron-deficient surface modifications. In light of these discrepancies, this study systematically analyses electron-deficient materials of varying strength, revealing the dominance of surface modifications over interfacial dipole orientation. Specifically, modulating the electron-withdrawing strength by replacing the carboxylic acid group (Bpy-COOH) with a cyanoacrylic acid moiety (Bpy-CAA) in dual-functional bipyridine-based electron-selective molecular layers (ESMLs) enhances adsorption, electron extraction, and passivation in n-i-p PSCs. Consequently, Bpy-CAA devices achieve 23.98% efficiency, surpassing Bpy–COOH–based devices (23.20%), and maintain an impressive 21.63% efficiency in 1 cm 2 cells, the highest reported for 1 cm 2 n-i-p PSCs utilizing organic ESMLs. A remarkable efficiency of 26.00% is achieved by integrating Bpy-CAA as an interfacial layer into SnO 2 /ESML/perovskite contacts while adapting this architecture into four-terminal perovskite/silicon tandem solar cells (4T-P/STSCs) yields an impressive efficiency of 30.83%, ranking among the highest reported efficiencies for 4T-P/STSCs. Overall, this work demonstrates that the electronic nature of the molecule is more decisive than dipole orientation for efficient electron extraction, and tailoring the dual-functional ESMLs effectively facilitated the development of efficient single-junction PSCs and 4T-P/STSCs.}, archive = {J_JACS}, author = {Chi Li and Paramaguru Ganesan and Yuheng Li and Shicheng Tang and Yao Wang and Chunming Liu and Lusheng Liang and Yaming Yu and Abd Rashid bin Mohd Yusoff and Michael Grätzel and Peng Gao}, doi = {10.1021/jacs.5c07357}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25738--25749}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic electron-deficient surface engineering: A key factor in dictating electron carrier extraction for perovskite photovoltaics}, volume = {147}, year = {2025}, }
• (2025). Bandgap engineering of halide perovskite nanocrystals for maximizing hole transfer: Accessing the marcus inverted region. JACS, 147(29), 25727--25737. (www)

  @article{ , abstract = {Controlling charge transfer at the semiconductor-acceptor molecule interface is important for improving the performance of semiconductor assisted photocatalytic processes. The difference between the band energies of the semiconductor and the redox potential of the acceptor is known to control the kinetics of charge transfer. By employing p -phenylenediamine (PPD) and m -phenylenediamine (MPD) as probe molecules, we have systematically probed the hole transfer from excited perovskite nanocrystals of different bandgaps. The valence band energy of the donor mixed halide perovskite nanocrystal, which varied from 1.74 to 0.94 V vs NHE through halide composition, viz., varying Cl:Br and Br:I ratio, allowed us to change the driving force (−ΔG) of hole transfer. The rate constant of hole transfer as determined from the transient absorption and photoluminescence decay measurements showed a nonlinear dependence on −ΔG. Analysis of this dependence followed Marcus-electron transfer theory with a reorganization energy of ∼1 eV. Relatively higher reorganization energy as compared to pure solvent showed the ligand shell (oleylamine) and charged nanocrystal lattice playing a major role in the interfacial charge transfer processes. The energy dependence of the charge transfer rate constant provides new insights into the photocatalytic properties of perovskite nanocrystals and ways to maximize the charge transfer yield through bandgap engineering of the semiconductor.}, archive = {J_JACS}, author = {Akshaya Chemmangat and Hsing-Ta Chen and Prashant V. Kamat}, doi = {10.1021/jacs.5c07384}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25727--25737}, shortjournal = {J. Am. Chem. Soc.}, title = {Bandgap engineering of halide perovskite nanocrystals for maximizing hole transfer: Accessing the marcus inverted region}, volume = {147}, year = {2025}, }
• (2025). Carbon capture from natural gas flue emissions and air via (Bi)Carbonate formation in a cyclodextrin-based Metal–Organic framework. JACS, 147(29), 25715--25726. (www)

  @article{ , abstract = {Carbon capture and utilization or sequestration (CCUS) from industrial point sources and direct air capture (DAC) are both necessary to curb the rising atmospheric levels of CO 2 . Amine scrubbers, the current leading carbon capture technology, suffer from poor oxidative and thermal stability, limiting their long-term cycling stability under oxygen-rich streams such as air and the emissions from natural gas combined cycle (NGCC) power plants. Herein, we demonstrate that the hydroxide-based cyclodextrin metal–organic framework (CD-MOF) Rb 2 CO 3 CD-MOF ST possesses high CO 2 capacities from dry dilute streams at low temperatures and humid streams at elevated temperatures. Additionally, it displays good thermal, oxidative, and cycling stabilities and selective CO 2 capture under mixed gas conditions in dynamic breakthrough experiments. Unexpectedly, under dry, hot conditions, a shift in the CO 2 adsorption mechanism─from reversibly formed bicarbonate to irreversibly formed carbonate─is observed, as supported by gas sorption and spectroscopic studies coupled with density functional theory (DFT) calculations. This mechanistic switch, akin to urea formation in amine-functionalized sorbents, has not been previously reported in a hydroxide-based material and sheds new light on the interplay between bicarbonate and carbonate species during CO 2 capture. Our findings provide valuable insight for the design of next-generation materials containing oxygen-based nucleophiles for carbon capture applications.}, archive = {J_JACS}, author = {S. Alexandra Lim and Mary E. Zick and Jaehwan Kim and Benjamin J. Rhodes and Joharimanitra Randrianandraina and Tristan A. Pitt and Ronald T. Jerozal and Jung-Hoon Lee and Alexander C. Forse and Phillip J. Milner}, doi = {10.1021/jacs.5c07336}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25715--25726}, shortjournal = {J. Am. Chem. Soc.}, title = {Carbon capture from natural gas flue emissions and air via (Bi)Carbonate formation in a cyclodextrin-based Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Compartmentalized suspension array for the isothermal, digital, and multiplex detection of microRNAs. JACS, 147(29), 25705--25714. (www)

  @article{ , abstract = {The sensitive and accurate detection of panels of microRNA molecules is critical to enable their use as disease biomarkers. While microarrays and next-generation sequencing allow comprehensive miRNA profiling, they generally suffer from low accuracy and sensitivity. Conversely, digital bioassays such as digital PCR provide an absolute quantification with unrivaled sensitivity, although with limited multiplexing capabilities. In this work, we describe a novel microRNA profiling procedure, termed Digiplex, that combines the multiplexing power of a DNA-grafted suspension array with the accuracy of a digital flow cytometry readout. microRNAs are first captured on fluorescently encoded DNA-grafted particle populations following a Poisson distribution. The particles are subsequently isolated in microfluidic droplets, where single captured miRNA molecules trigger an isothermal exponential amplification that ultimately activates a fluorescent probe on the particle surface. Flow cytometry analysis yields the ratio of positive to negative particles for each targeted microRNA, allowing the reconstruction of the multiplex concentration profile in one go. After optimizing the workflow on a single microRNA model, we successfully developed a 10-plex assay with femtomolar sensitivity. The Digiplex method was finally validated on total RNA samples and benchmarked against droplet digital PCR.}, archive = {J_JACS}, author = {Thomas Jet and Coline Kieffer and Yannick Rondelez and Valérie Taly and Guillaume Gines}, doi = {10.1021/jacs.5c07214}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25705--25714}, shortjournal = {J. Am. Chem. Soc.}, title = {Compartmentalized suspension array for the isothermal, digital, and multiplex detection of microRNAs}, volume = {147}, year = {2025}, }
• (2025). Selective ion binding and uptake shape the microenvironment of biomolecular condensates. JACS, 147(29), 25692--25704. (www)

  @article{ , abstract = {Biomolecular condensates modulate various ion-dependent cellular processes and can regulate subcellular ion distributions by selective uptake of ions. To understand these processes, it is essential to uncover the molecular grammar governing condensate-ion interactions. Here, we use nuclear magnetic resonance (NMR) spectroscopy of ions and model condensate components to quantify and spatially resolve selective ion binding to condensates and show that these interactions follow the “law of matching water affinities”, resulting in strong binding between proteins and chaotropic anions and between nucleic acids and kosmotropic cations. Ion uptake into condensates directly follows binding affinities, resulting in selective uptake of strong-binding ions but exclusion of weak-binding ions. Ion binding further shapes the condensate microenvironment by altering the composition, viscosity, and interface potential. Such changes can have profound effects on biochemical processes taking place inside condensates, as we show for RNA duplex formation. Our findings provide a new perspective on the role of condensate-ion interactions in cellular bio- and electrochemistry and may aid the design of condensate-targeting therapeutics.}, archive = {J_JACS}, author = {Iris B. A. Smokers and Enrico Lavagna and Rafael V. M. Freire and Matteo Paloni and Ilja K. Voets and Alessandro Barducci and Paul B. White and Mazdak Khajehpour and Evan Spruijt}, doi = {10.1021/jacs.5c07295}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25692--25704}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective ion binding and uptake shape the microenvironment of biomolecular condensates}, volume = {147}, year = {2025}, }
• (2025). Small molecule catalyst for peptide synthesis. JACS, 147(29), 25682--25691. (www)

  @article{ , abstract = {Peptide synthesis is a highly optimized process that has led to the production of new classes of therapeutics and materials. The process of peptide synthesis is straightforward: commercially available, orthogonally protected amino acids can be linked on the solid phase using highly efficient coupling agents. However, the simplicity of peptide synthesis masks a significant drawback of the current method: it is highly wasteful and utilizes a solvent that is facing restrictions on its use. A catalyst that allows solid phase synthesis of peptides in benign solvents without requirement for excess reagents and protected amino acids would have a significant impact. Here, we describe the development of a small molecule catalyst for peptide synthesis. The catalyst design incorporates redox recycling of diselenide and phosphine with air as the ultimate oxidant and phenylsilane as the ultimate reductant. The catalyst affords efficient coupling of amino acids in the solution and solid phase. Significantly, the catalyst functions with acetonitrile, bypassing the need for DMF. The current effort builds on mechanistic analysis of reaction rates and intermediates in our prior work which led to a hydrogen bonding catalyst: [ Handoko ; Panigrahi, N. R. ; Arora, P. S. J. Am. Chem. Soc. 2022 , 144 , 3637–3643]. Here, we significantly simplified earlier designs to afford an easily accessible small molecule catalyst.}, archive = {J_JACS}, author = {Nihar R. Panigrahi and Shahrukh M. Khan and Handoko and Paramjit S. Arora}, doi = {10.1021/jacs.5c07242}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25682--25691}, shortjournal = {J. Am. Chem. Soc.}, title = {Small molecule catalyst for peptide synthesis}, volume = {147}, year = {2025}, }
• (2025). Elucidating quintet-state dynamics in singlet fission oligomers and polymers with tetracene pendants. JACS, 147(29), 25672--25681. (www)

  @article{ , abstract = {To unlock the potential of molecular engineering for practical quantum sensing and computing, it is essential to create and control pure magnetic states in molecular systems. Singlet fission (SF) in organic materials offers a promising approach by generating pairs of triplet excited states from photoexcited singlets. In this work, we investigate SF in a polymer with strategically positioned tetracene pendant groups along a polynorbornene backbone and its oligomeric counterparts, facilitating intrapolymer through-space coupling. Using continuous-wave and pulsed time-resolved electron paramagnetic resonance (EPR) spectroscopy, we elucidate the spin dynamics and identify key intermediates, including the quintet state, that emerge during SF. Our findings reveal that exciton translational motion along the pendant groups enhances the dissociation of triplet pairs, with oligomer length playing a critical role in modulating spin state interconversion and exciton transport. Our results provide key insights into the SF mechanism in polymeric materials and highlight the role of oligomer length in modulating spin state interconversion and exciton transport. This work advances our understanding of SF in polymers, paving the way for their application in quantum information science and energy conversion technologies.}, archive = {J_JACS}, author = {Jasleen K. Bindra and Daniel Malinowski and Bernardo Salcido-Santacruz and Guiying He and Matthew Y. Sfeir and Luis M. Campos and Jens Niklas and Oleg G. Poluektov}, doi = {10.1021/jacs.5c07136}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25672--25681}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating quintet-state dynamics in singlet fission oligomers and polymers with tetracene pendants}, volume = {147}, year = {2025}, }
• (2025). CO2 and H2O sorption induced bulk-phase changes of CALF-20 captured using in situ laboratory X-ray powder diffraction. JACS, 147(29), 25662--25671. (www)

  @article{ , abstract = {The zinc oxalate (ox) triazolate (trz)-based MOF, Calgary Framework 20 (CALF-20), exhibits remarkable cycling stability for carbon dioxide and water adsorption and desorption and is therefore a promising candidate material for CO 2 sequestration on an industrial scale. Upon gas and vapor loading and unloading, the MOF shows pronounced structural dynamics leading to a variety of potential CALF-20 polymorphs. A systematic in situ study on CO 2 and H 2 O ad- and desorption using high-resolution, laboratory X-ray powder diffraction (XRPD) shows that the CO 2 -breathing behavior changes upon gas loading. A CO 2 uptake initially distorts the rectangular pore into a diamond shape. Upon further CO 2 incorporation, the breathing behavior changes, and the pore becomes more rectangular, again. At low temperatures (−70 °C), the uptake of CO 2 occurs in a core–shell mechanism, and the gas is bound strongly to the framework and cannot be removed by dynamic vacuum. During water uptake of CALF-20, two distinct hydrated phases can be identified. The overall water loading capacity is independent of temperature between 25 and 60 °C. In this paper, we demonstrate that recent advances in X-ray powder diffraction hard- and software enable a detailed investigation of the loading and breathing behavior of a crystalline MOF using laboratory equipment, turning this into easily accessible investigations.}, archive = {J_JACS}, author = {Sebastian Bette and Anastasia Sleptsova and Bettina V. Lotsch and Robert E. Dinnebier and Stefan Marx and Mahsa Loloei and Adebayo A. Adeleke and Nima Masoumifard and Ramanathan Vaidhyanathan}, doi = {10.1021/jacs.5c06866}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25662--25671}, shortjournal = {J. Am. Chem. Soc.}, title = {CO2 and H2O sorption induced bulk-phase changes of CALF-20 captured using in situ laboratory X-ray powder diffraction}, volume = {147}, year = {2025}, }
• (2025). Melt rheology of dendritic hyperbranched polyacrylates synthesized by controlled radical polymerization: Evidence of self-similar branch structure formation. JACS, 147(29), 25652--25661. (www)

  @article{ , abstract = {Dendritic hyperbranched poly(methyl acrylate)s (HBPMAs) with controlled molecular weight and low dispersity ( Đ ≤ 2) were synthesized by radical copolymerization of MA and a branch-inducing monomer, evolmer 2b , in the presence of organotellurium chain transfer agent (CTA) 1 , by targeting theoretical generation ( G n ) of 3–5 and branch molecular weight ( M BL ) of 0.25 M e –2.0 M e , with M e (= 11,000) being the entanglement molecular weight of PMA. The control of the self-similar branch layer structure in HBPMAs thus synthesized was examined by measuring their linear viscoelastic moduli ( G * = G ′ + iG ″). For all G n s having M BL = 0.25 M e , the storage modulus G′ was lower than the loss modulus G″ at all ω examined. This unentangled feature was observed even when the portion of the chain spanning the two outmost ends of the branches had a molecular weight of 2.0 M e , possibly because of a lack of deep penetration among those G n chains. In contrast, for M BL ≥ M e , G′ was higher than G″ in a given range of ω, and this range became wider and the relaxation mode distribution therein became broader on an increase of M BL , which is characteristic of entangled branch polymers. For the entangled HBPMA chains having the same M BL but different G n , hierarchically self-similar relaxation based on the branch retraction mechanism was confirmed for the G′ and G″ data: The data for higher G n agreed with the data for lower G n after a shift along the ω axis according to this self-similarity. For the unentangled BPMA chains of different G n , the G′ and G″ data obeyed the Rouse-type relationship based on the self-similarity but without the hierarchy. These results support good control of the dendritic branch structures of the HBPMAs synthesized with the current method.}, archive = {J_JACS}, author = {Tianxiang Tong and Masato Kibune and Masatoshi Tosaka and Yumi Matsumiya and Hiroshi Watanabe and Shigeru Yamago}, doi = {10.1021/jacs.5c06746}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25652--25661}, shortjournal = {J. Am. Chem. Soc.}, title = {Melt rheology of dendritic hyperbranched polyacrylates synthesized by controlled radical polymerization: Evidence of self-similar branch structure formation}, volume = {147}, year = {2025}, }
• (2025). Expanding the chemical space of antimicrobial peptides via enzymatic prenylation. JACS, 147(29), 25642--25651. (www)

  @article{ , abstract = {Antimicrobial peptides act primarily at the bacterial membrane interface. We report a biocatalytic strategy that enhances their potency by up to 18-fold. The improvement results from the enzymatic installation of bulky isoprenoid chains, which strengthens peptide–membrane interactions and promotes membrane destabilization. We characterize PalQ, an isoprenoid synthase-related prenyltransferase that is uniquely amenable to enzyme engineering. PalQ catalyzes prenylation at both N- and C-terminal tryptophan residues via positionally distinct C δ2 and C γ alkylation, respectively. Structure-guided mutagenesis of the prenyl donor pocket, combined with glycine substitutions near the acceptor tryptophan, expanded PalQ’s substrate scope to include diverse antimicrobial peptides and long-chain donors such as geranylgeranyl diphosphate. A computationally optimized PalQ variant further improved performance under high-salt and organic solvent conditions, enabling late-stage modification of poorly soluble peptides. These results establish PalQ as a versatile platform for site-selective lipidation and expand the accessible chemical space for peptide and protein engineering.}, archive = {J_JACS}, author = {Hikari Ozawa and Azusa Miyata and Seiichiro Hayashi and Noriyuki Miyoshi and Koichi Kato and Sohei Ito and Daisuke Fujinami}, doi = {10.1021/jacs.5c06850}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25642--25651}, shortjournal = {J. Am. Chem. Soc.}, title = {Expanding the chemical space of antimicrobial peptides via enzymatic prenylation}, volume = {147}, year = {2025}, }
• (2025). Electrochemical single-carbon insertion via distonic radical cation intermediates. JACS, 147(29), 25635--25641. (www)

  @article{ , abstract = {The synthesis of polysubstituted (hetero)aromatic compounds is essential in various fields, including pharmaceuticals, where such compounds are fundamental to many approved drugs. In this study, we present a novel electrochemical method for single-carbon insertion targeting various (hetero)aromatic compounds, with a particular focus on pyridines. In this process, the electrochemical oxidation of pyrrole derivatives produces a radical cation intermediate, which then undergoes nucleophilic attack by diazo compounds to yield polysubstituted pyridine derivatives. Notably, the insertion position is influenced by the electronic properties of N -protecting groups, allowing for unprecedented para -selective insertion through the introduction of electron-withdrawing groups. Insights from in situ spectroscopy and theoretical calculations suggest the involvement of distonic radical cation intermediates, facilitating carbon-atom migration on the aromatic ring and enabling insertion at different positions. This study expands the chemical toolkit for synthesizing polysubstituted (hetero)aromatic compounds and introduces a new concept for single-carbon insertion chemistry.}, archive = {J_JACS}, author = {Tatsuya Morimoto and Yoshio Nishimoto and Taku Suzuki-Osborne and Su-Gi Chong and Kazuhiro Okamoto and Tomoki Yoneda and Azusa Kikuchi and Daisuke Yokogawa and Mahito Atobe and Naoki Shida}, doi = {10.1021/jacs.5c06798}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25635--25641}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical single-carbon insertion via distonic radical cation intermediates}, volume = {147}, year = {2025}, }
• (2025). Nanoscale Donor–Acceptor covalent organic frameworks for mitochondria-targeted sonodynamic therapy and antitumor immunity. JACS, 147(29), 25622--25634. (www)

  @article{ , abstract = {Sonodynamic therapy (SDT) based on O 2 -dependent type II sonosensitizers (SSs) is limited by the hypoxic tumor microenvironment and aggregation-induced quenching (AIQ) of SSs. Type I SSs can generate reactive oxygen species (ROS) with reduced O 2 dependence, but their efficacy is still constrained by the high electron–hole recombination rates and low ROS yields. Here, we report the synthesis of a novel two-dimensional nanoscale covalent organic framework (nCOF), Td-Pc, for mitochondria-targeted type I/II SDT. Td-Pc is constructed from staggered zinc-phthalocyanine tetra-anhydride (Pc) units and 4,4′-(thiazolo[5,4- d ]thiazole-2,5-diyl)dianiline linkers, forming a donor–acceptor nCOF structure. This structural arrangement significantly alleviates the AIQ of Pc, enhances acoustic electron dissociation and transport, and promotes tumor accumulation. Consequently, Td-Pc enables efficient ROS generation throughout tumor tissues via both type I and II SDT mechanisms. The resulting mitochondrial oxidative stress induces immunogenic cancer cell pyroptosis and upregulates PD-L1 expression. When combined with an anti-PD-L1 monoclonal antibody, Td-Pc-mediated SDT elicits a robust antitumor immune response, leading to effective regression of orthotopic pancreatic ductal adenocarcinoma and bilateral triple-negative breast cancer without causing side effects.}, archive = {J_JACS}, author = {Jing Liu and Zhihao Zhao and Chenghua Deng and Richard Zanni and Ralph R. Weichselbaum and Wenbin Lin}, doi = {10.1021/jacs.5c06488}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25622--25634}, shortjournal = {J. Am. Chem. Soc.}, title = {Nanoscale Donor–Acceptor covalent organic frameworks for mitochondria-targeted sonodynamic therapy and antitumor immunity}, volume = {147}, year = {2025}, }
• (2025). Resin-to-resin circularity in chemical recycling of dicyclopentadiene-based cycloolefin resins. JACS, 147(29), 25613--25621. (www)

  @article{ , abstract = {Cycloolefin resins (CORs) comprising dicyclopentadiene (DCPD) cross-linkers are high performance thermosets for diverse single-use applications. If it were possible to carry out deconstruction of DCPD thermosets through exclusive reformation of the cyclopentene ring in DCPD, then linear polyDCPD chains could re-enter subsequent manufacturing cycles and enable resin-to-resin circularity. Here, we develop a chemical recycling process whereby linear polyDCPD recyclates are generated from end-of-life commercial and model CORs, including copolymers, using a second-generation Hoveyda–Grubbs ruthenium(II) alkylidene catalyst for deconstruction via ring-closing metathesis. The properties of first-generation DCPD thermosets were reproduced across subsequent generations of recycling and reuse, where up to 84% of linear DCPD was retrievable from end-of-life thermosets after deconstruction. We further quantify how comonomer incorporation, the curing process, and aging affect round-trip material efficiency and the quality of regenerated thermosets.}, archive = {J_JACS}, author = {Zhen Xu and Mason L. Witko and Hongqian Zheng and Julia Im and Shira Haber and Ankita Ghosh and Maxwell C. Venetos and Jeffrey A. Reimer and Kristin A. Persson and Brett A. Helms}, doi = {10.1021/jacs.5c06626}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25613--25621}, shortjournal = {J. Am. Chem. Soc.}, title = {Resin-to-resin circularity in chemical recycling of dicyclopentadiene-based cycloolefin resins}, volume = {147}, year = {2025}, }
• (2025). End-group engineering in amphiphilic segmented polyurethanes: Strong impact on hierarchical self-assembled structure and antibacterial activity. JACS, 147(29), 25603--25612. (www)

  @article{ , abstract = {A series of amphiphilic polyurethanes were synthesized by condensation polymerization between hexyl-diisocyanate and Boc-protected serinol in the presence of a chain-stopper R–OH ( R = short hydrocarbon chain). Deprotection of the Boc group produced amphiphilic polymers with pendant amine groups, which, at pH ∼5, adopted an intrachain H-bonding-stabilized pleated structure. Hierarchical assembly of such folded chains produced unilamellar vesicles with excellent surface display of the amine groups. During this hierarchical assembly, presumably through hydrogen bonding between the terminal urethanes, terminal hydrocarbon chains remained secluded and were compelled to be exposed at the polymersome surface. This resulted in an unexpectedly strong impact of hydrophobicity on antibacterial activity, as the surface-protruded hydrocarbons could very effectively engage in bacterial membrane disruption. Consequently, an increase in the hydrocarbon chain length from C5 to C8 caused a significant change in the minimum inhibitory concentration (MIC) from 7.8 to 3.9 μg/mL and 500 to 31.2 μg/mL, respectively, for E. coli and S. aureus . In contrast, these polymers showed negligible toxicity toward mammalian cells (HC 50 in the range of 300 μg/mL). Instead of a hydrocarbon, when a hydrophilic pyridine-containing chain-stopper was used, the resulting polymer, despite having an otherwise identical structure, showed drastically lower antibacterial activity, and the HC 50 /MIC ( E. coli ) ratio reduced by about 70 times compared to the most optimized polymer having a 2-ethyl-hexyl chain-stopper. On the other hand, a longer (C16) hydrophobic chain-stopper blocked the hierarchical assembly pathway and produced micelle-like spherical aggregates, which, upon aging, formed elongated structures with significantly reduced antibacterial activity. The lead candidate revealed highly effective biofilm eradication.}, archive = {J_JACS}, author = {Ranajit Barman and Rajesh Khamrui and Sugam Kumar and Vinod K. Aswal and Suhrit Ghosh}, doi = {10.1021/jacs.5c06603}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25603--25612}, shortjournal = {J. Am. Chem. Soc.}, title = {End-group engineering in amphiphilic segmented polyurethanes: Strong impact on hierarchical self-assembled structure and antibacterial activity}, volume = {147}, year = {2025}, }
• (2025). Stereoconvergent aminoboration of (Z/E)-mixed alkenes via bimetallic asymmetric relay catalysis. JACS, 147(29), 25592--25602. (www)

  @article{ , abstract = {Methods for the enantioselective transformations of alkenes constitute one of the most frequently used strategies in synthetic chemistry. Despite tremendous advancements in this domain, achieving the asymmetric difunctionalization of ( Z / E )-mixed alkenes in a stereoconvergent manner poses a formidable challenge. Here, we present a bimetallic relay-catalyzed asymmetric aminoboration of ( Z / E )-isomer mixtures with an engineered ferrocene–oxazoline (FcPHOX) ligand. The reactions proceed efficiently and exhibit a broad substrate scope with excellent enantio- and diastereoselectivity (generally >90% e.e. and up to 99:1 d.r.), affording chiral β-aminoalkylboronates as the key synthons for important bioactive molecules. The synthetic potential of this method is highlighted by the late-stage modification of complex molecules, versatile utility of these products, stereodivergent synthesis of four stereomers, and a sequence stereoconvergent aminoboration direct from propylbenzene. Experimental studies and density functional theory (DFT) calculations were conducted to elucidate the roles of two metal catalysts and crucial effect of the engineered ligand in origins of excellent enantio- and diastereoselectivities.}, archive = {J_JACS}, author = {Jianjun Yin and Xiuping Yuan and Simin Wang and Dazhen Shi and Shucheng Ma and Lihan Zhu and Xiaoyu Li and Qian Zhang and Tao Xiong}, doi = {10.1021/jacs.5c06354}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25592--25602}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereoconvergent aminoboration of (Z/E)-mixed alkenes via bimetallic asymmetric relay catalysis}, volume = {147}, year = {2025}, }
• (2025). Enhancing CO2 electroreduction to ethylene in acidic solution by optimizing cation configuration on the cu surface. JACS, 147(29), 25584--25591. (www)

  @article{ , abstract = {The electroreduction of CO 2 to C 2 H 4 offers a promising avenue for advancing carbon neutrality and promoting sustainable chemical manufacturing. In acidic environments, while long-term operational stability and CO 2 utilization efficiency are enhanced, the formation of C–C bonds is hindered due to the weak adsorption of *CO intermediates and the competing hydrogen evolution reaction (HER). Theoretical studies suggest that K + cations with reduced bound water content can strengthen the adsorption of the critical *CO intermediate, and that elevated K + concentrations on the Cu electrode surface significantly facilitate CO 2 electroreduction to C 2 H 4 . In this work, a catalyst termed Cu TEA was developed by strategically modifying the Nafion ionomer distribution within the catalyst layer. This structural adjustment effectively lowers the bound water associated with K + cations and concurrently elevates the surface concentration of K + on the Cu electrode, thereby promoting C–C coupling for C 2 H 4 formation while suppressing HER. Consequently, Cu TEA achieves a Faradaic efficiency of 70.2% for C 2 H 4 production, accompanied by a high partial current density of 561.6 mA cm –2 in an acidic electrolyte (pH = 1).}, archive = {J_JACS}, author = {Yaoyu Yin and Zhongnan Ling and Shiqiang Liu and Jiapeng Jiao and Yiyong Wang and Yaguang Peng and Xing Tong and Meng Zhou and Rongjuan Feng and Xueqing Xing and Yi Xu and Qinggong Zhu and Xiaofu Sun and Mingchuan Luo and Xinchen Kang and Buxing Han}, doi = {10.1021/jacs.5c06402}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25584--25591}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing CO2 electroreduction to ethylene in acidic solution by optimizing cation configuration on the cu surface}, volume = {147}, year = {2025}, }
• (2025). Multistep 11-cis to all-trans retinal photoisomerization in bestrhodopsin, an unusual microbial rhodopsin. JACS, 147(29), 25571--25583. (www)

  @article{ , abstract = {Rhodopsins constitute a broad class of retinal-binding photoreceptors. Microbial rhodopsins are canonically activated through an all- trans to 13- cis photoisomerization, whereas animal rhodopsins are mostly activated through an 11- cis to all- trans isomerization. Bestrhodopsins constitute a special microbial rhodopsin subfamily, with bistable rhodopsin domains that can be photoswitched between a far red-absorbing state D661 and a green-absorbing state P540. Its photochemistry involves a peculiar all -trans to 11- cis isomerization for the D661 to P540 photoreaction and vice versa. Here, we present the P. antarctica bestrhodopsin 11- cis to all- trans photoreaction as determined by femtosecond-to-submillisecond transient absorption, femtosecond stimulated Raman and flash-photolysis spectroscopy. The primary photoreaction involves ultrafast isomerizations in 240 fs from the 11- cis reactant to a mixture of highly distorted all- trans and 13- cis photoproducts. The 13- cis fraction then thermally isomerizes to a distorted all- trans RSB in 120 ps. We propose bicycle pedal models for the branched photoisomerizations with corotation of the C11═C12 and C13═C14 double bonds. One reactant fraction undergoes bicycle pedal motion aborted at the C13═C14 double bond, resulting in all- trans retinal. The other fraction undergoes a full bicycle pedal motion of both C11═C12 and C13═C14, resulting in 13- cis retinal. The primary products are trapped high up the ground-state potential energy surface with a low energetic barrier that facilitates thermal isomerization from 13- cis to all- trans retinal in 120 ps. All- trans retinal then structurally and energetically relaxes with subsequent time constants of 0.7 and 62 μs and 4.4 ms, along with counterion protonation, completing the P540 to D661 photoreaction.}, archive = {J_JACS}, author = {Matthias Broser and Spyridon Kaziannis and Ivo H.M. van Stokkum and Atripan Mukherjee and Jakub Dostal and Wayne Busse and Arno Munhoven and Cesar Bernardo and Peter Hegemann and Miroslav Kloz and John T.M. Kennis}, doi = {10.1021/jacs.5c06216}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25571--25583}, shortjournal = {J. Am. Chem. Soc.}, title = {Multistep 11-cis to all-trans retinal photoisomerization in bestrhodopsin, an unusual microbial rhodopsin}, volume = {147}, year = {2025}, }
• (2025). Sono-destructive polymeric nanocapsules enable spatiotemporal orchestration of DC-T cell crosstalk in combined in situ vaccination and cytokine therapy. JACS, 147(29), 25553--25570. (www)

  @article{ , abstract = {Antigen-directed T cell cancer immunotherapy is increasingly shifting toward combination regimens with complementary mechanisms to enhance efficacy without exacerbated toxicity. However, rationally designing efficient combination strategies in this realm remains a challenge. Herein, we engineered a sono-destructive and clinically approved β-amino ester random copolymer (PBAE) nanoplatform that integrates sonosensitizers and interleukin-12 (IL-12) to spatially and temporally regulate antitumor immunity. The PBAE polymer features a thioacetal backbone that enables ultrasound (US)-triggered complete fragmentation, allowing for precise and rapid spread of tumor antigens, immunogenic molecules, and a single low dose of IL-12 (one-tenth of the high doses typically used for therapeutic benefit). In a preclinical human papillomavirus (HPV) 16 oncoproteins E6/E7-expressing tumor model, this combination therapy demonstrates superior antitumor efficacy alongside a robust safety profile. Mechanistically, US-mediated in situ vaccination activates multiple subsets of dendritic cells (DCs), including conventional type I DC (cDC1), cDC2, monocyte-derived DCs, and plasmacytoid DCs, enhancing the presentation of released E7 antigens to prime T cells. IL-12 further amplifies the cytotoxic activity of E7-specific CD8 + T cells and drives the differentiation of T helper 1 cells, complementing therapeutic effect through increased production of cytotoxic enzymes, and cytokines. This work presents an advanced combination regimen for streamlined cancer immunotherapy.}, archive = {J_JACS}, author = {Wencong Jia and Wei Yang and Ye Wu and Hongze Ren and Yiwen Jia and Weifan Ye and Yujie Xie and Yu Chen and Meihua Yu}, doi = {10.1021/jacs.5c06120}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25553--25570}, shortjournal = {J. Am. Chem. Soc.}, title = {Sono-destructive polymeric nanocapsules enable spatiotemporal orchestration of DC-T cell crosstalk in combined in situ vaccination and cytokine therapy}, volume = {147}, year = {2025}, }
• (2025). Engineered nano-micro pyroptosis generators: A magnetic-metallo-immunotherapeutic strategy to reinforce transarterial embolization. JACS, 147(29), 25536--25552. (www)

  @article{ , abstract = {Gasdermin-mediated pyroptosis represents a promising immunotherapeutic strategy, yet requires precise tumor-specific activation. Magnetic hyperthermia therapy (MHT) has the potential to induce pyroptosis in hepatocellular carcinoma (HCC), while its efficacy is limited by suboptimal heating efficiency and tumor resistance. Herein, we developed an innovative magnetic-metallo-immunotherapeutic platform by engineering nanomicro pyroptosis generators, thereby enhancing transarterial embolization (TAE). Through compositional and structural optimization, Zn–Fe 3 O 4 @Co–Fe 3 O 4 core–shell nanocubes (ZnCo–Fe 3 O 4 CSNCs) with enhanced magnetothermal properties were obtained, which exhibited significantly improved saturation magnetization (Ms) and coercivity (Hc). These nanocubes were further assembled via microfluidic technology into magnetic microspheres (MSs) with tunable sizes, integrating the therapeutic functions of TAE and MHT. Under an alternating magnetic field (AMF), the ZnCo–Fe 3 O 4 MSs demonstrated temperature-dependent ion release and localized hyperthermia while simultaneously inhibiting heat shock protein (HSP) upregulation through metabolic interference. This orchestrated therapeutic cascade effectively triggered pyroptosis in cancer cells, subsequently activating the immune response and thereby enhancing the efficacy of magnetic-metallo-immunotherapy. The strategic combination of this platform with immune checkpoint blockade (ICB) therapy provoked comprehensive systemic immune activation, markedly enhancing treatment efficacy and suppressing the progression of both primary tumors and distant tumors. Notably, ZnCo–Fe 3 O 4 MSs demonstrated an exceptional capacity to modulate the immunosuppressive tumor niche while substantially improving TAE performance through their unique embolization-immunomodulation functionality. Overall, this study highlights new avenues for exploring pyroptosis-mediated magnetic-metallo-immunotherapy for effective cancer therapy.}, archive = {J_JACS}, author = {Di Wang and Linzhu Zhang and Jihu Nie and Nailin Yang and Shumin Sun and Chunjie Wang and Zifan Pei and Fei Gong and Xingwei Sun and Yong Jin and Liang Cheng}, doi = {10.1021/jacs.5c06039}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25536--25552}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineered nano-micro pyroptosis generators: A magnetic-metallo-immunotherapeutic strategy to reinforce transarterial embolization}, volume = {147}, year = {2025}, }
• (2025). Enantioconvergent Chan–Lam coupling: Synthesis of chiral benzylic amides via cu-catalyzed deborylative amidation. JACS, 147(29), 25527--25535. (www)

  @article{ , abstract = {The Chan–Lam coupling represents one of the most effective methods for constructing C–N bonds due to its mild reaction conditions and broad functional group compatibility. However, asymmetric versions of this transformation to forge C(sp 3 )–N bonds have remained elusive due to the need for a general mechanistic framework to engage alkylboron reagents. Herein, we demonstrate the first enantioconvergent Chan–Lam C(sp 3 )–N coupling using synthetically modular alkylboronic pinacol esters. The reported transformation imparts a high degree of enantioselectivity and tolerates a wide range of functional groups, heterocycles, and pharmaceutically relevant frameworks. The reaction mechanism was investigated through Hammett analysis, radical clock tests, and radical trapping experiments. Density functional theory (DFT) calculations support a radical relay pathway: oxidative homolysis of the C–B bond generates prochiral alkyl radicals, which are functionalized by in situ generated Cu(II) intermediate through an inner-sphere mechanism.}, archive = {J_JACS}, author = {Jonathan Vu and Graham C. Haug and Tanner J. Schubert and Joshua F. Head and Robert S. Paton and Yuyang Dong}, doi = {10.1021/jacs.5c05884}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25527--25535}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioconvergent Chan–Lam coupling: Synthesis of chiral benzylic amides via cu-catalyzed deborylative amidation}, volume = {147}, year = {2025}, }
• (2025). Active sites under electronic effect are more sensitive to microenvironment in CO2 electroreduction. JACS, 147(29), 25517--25526. (www)

  @article{ , abstract = {Tailoring the structure of the active sites and engineering the microenvironment to tune catalytic performance are both at the forefront of catalysis. Yet, design principles bridging the two remain missing. Here, we synthesize a platform consisting of well-defined cubic Cu nanocrystals with an oxide coating of tunable porosity, here alumina. We indicate that varying the porosity modulates the relative importance of the native geometric effect and the introduced interfacial electronic effect. We link the change in porosity to the catalytic behavior in the electrochemical CO 2 reduction reaction. In particular, we use the shift in selectivity as a key descriptor to show that the electronic effect overrules the geometric effect with increasing porosity. We find that a balance between geometric and electronic effects optimizes the intrinsic catalytic reactivity. Importantly, we use this platform to propose that active sites under electronic effect are more sensitive to the change in microenvironment, here exemplified by alkali cations in the electrolyte. The fundamental insights gathered through the proposed catalytic platform stimulate future discussion on linking the nature of the active sites and the microenvironment engineering.}, archive = {J_JACS}, author = {Petru P. Albertini and Jennifer Calderon Mora and Margarita Guskova and Pattaraphon Rodlamul and Noah Hicks and Jari Leemans and Anna Loiudice and Raffaella Buonsanti}, doi = {10.1021/jacs.5c05697}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25517--25526}, shortjournal = {J. Am. Chem. Soc.}, title = {Active sites under electronic effect are more sensitive to microenvironment in CO2 electroreduction}, volume = {147}, year = {2025}, }
• (2025). Cooperative photoenzymatic catalysis for enantioselective Fluoroalkylation/Cyclization cascade. JACS, 147(29), 25508--25516. (www)

  @article{ , abstract = {Due to the invaluable properties of organofluorine compounds, incorporating a fluorinated unit has become necessary in pharmaceuticals, agrochemicals, and materials. However, achieving asymmetric fluorination such as trifluoromethylation through chemo- or biocatalysis has been a synthetic challenge. Here, we introduce a unique cooperative photoenzymatic catalysis for the enantioselective fluoroalkylation/cyclization cascade. This method, utilizing the engineered flavin-dependent “ene”-reductases (EREDs) and an exogenous photocatalyst (PC), produces a variety of fluorinated cyclic ketones with high yield and enantioselectivity. The discovery of stereocomplementary enzymes that provide access to both enantiomers of the cyclized products further enhances the synthetic applications of our method. The radical-trapping, spectroscopic, and kinetic studies have substantiated the interaction mode between the PC and the enzyme and demonstrated a cascade reaction mechanism involving a unique intermolecular addition of fluorinated radicals and a stereocontrolled intramolecular cyclization. Isotopic labeling experiments support flavin as the source of the hydrogen atom. Molecular dynamics simulations reveal that the binding interaction of the enzyme and the intermediate triggers the photoinduced enantioselective cyclization. This work underscores the potential of enzymes for the asymmetric synthesis of fluorinated compounds.}, archive = {J_JACS}, author = {Dongshan Wu and Sanshan Wang and Haowen Zhang and Han Ke and Zeying Sun and Shuhan Xie and Yihui Gao and Jun Yang and Bingwu Wang and Xiaoguang Lei}, doi = {10.1021/jacs.5c05656}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25508--25516}, shortjournal = {J. Am. Chem. Soc.}, title = {Cooperative photoenzymatic catalysis for enantioselective Fluoroalkylation/Cyclization cascade}, volume = {147}, year = {2025}, }
• (2025). Harnessing the piezo-phototronic effect in flexible chiral organic single crystals for light-responsive tactile sensing. JACS, 147(29), 25498--25507. (www)

  @article{ , abstract = {The piezo-phototronic effect arises from the interaction between mechanical stress, driven by the piezoelectric effect, and light, which induces the phototronic effect, ultimately influencing the electronic properties of a material. When the piezoelectric and phototronic effects combine, the resulting piezo-phototronic effect imparts enhanced or tunable properties to optoelectronic devices that respond to both light and mechanical strain. While inorganic materials are widely studied for piezo-phototronic properties, organic materials present more attractive alternatives due to their modular properties, and cost-effectiveness. Flexible organic single crystals are well-suited for optoelectronic device fabrication due to their defect-free structure and well-ordered packing, which enhances device performance. Despite these advantages, the simultaneous integration of photoexcitation, semiconductor functionality, and piezoelectricity, the foundation of the piezo-phototronic effect, remains unexplored in flexible organic single crystals. Here, we report the discovery of a mechanically flexible single crystal exhibiting the piezo-phototronic effect. The molecular design strategy played a crucial role, wherein the incorporation of chiral and light-absorbing moieties imparts piezo- and phototronic properties, respectively. The flexible crystals are further used to fabricate a piezo-phototronic device, which demonstrates exceptional strain-dependent photocurrent modulation and a high detection sensitivity of ∼158%. Furthermore, the piezo-phototronic device could distinguish between light and dark conditions and respond to mechanical stress, thereby highlighting its multipurpose sensing capabilities. The enhanced response under light exposure also suggests promising applications in wearable technology for human-machine interfaces and health monitoring, where the simultaneous sensing of light and mechanical deformation is crucial for improved functionality and performance.}, archive = {J_JACS}, author = {Kiran Arora and Dalip Saini and Sudip Naskar and Subash Chandra Sahoo and Dipankar Mandal and Prakash P. Neelakandan}, doi = {10.1021/jacs.5c05701}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25498--25507}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing the piezo-phototronic effect in flexible chiral organic single crystals for light-responsive tactile sensing}, volume = {147}, year = {2025}, }
• (2025). Pericyclic umpolung in a catalytic asymmetric Diels–Alder reaction of tropone with enol ethers. JACS, 147(29), 25489--25497. (www)

  @article{ , abstract = {One remarkable feature of catalysis in chemical synthesis is its capacity to override substrate-imposed reactivity and selectivity. The inversion of normal reaction patterns, commonly known as Umpolung, can be divided into (1) functional group Umpolung, where electrophilic groups are rendered nucleophilic (or vice versa), and (2) pericyclic Umpolung, in which the regioselectivity of pericyclic reactions is reversed relative to the predictions of frontier molecular orbital (FMO) theory. Although catalytic functional group Umpolung has been extensively investigated, the highly organized, concerted nature of pericyclic reactions makes inverting their conventional regioselectivity particularly challenging. To date, such inversion has been achieved only using engineered substrates or near-stoichiometric amounts of molecular cages. Here, we report an example of a chiral confined acid-catalyzed, asymmetric Umpolung of the Diels–Alder reaction. In our system, tropone reacts with enol ethers to deliver “contra-FMO” products with high yield, stereoselectivity, and regioselectivity. Mechanistic and computational studies indicate that a network of attractive noncovalent interactions, including π–π-interactions, nonclassical hydrogen bonding, and dispersion, governs the inverted regioselectivity. We anticipate that confined acid catalysis will open new avenues for addressing challenges in pericyclic Umpolung and regioselectivity control.}, archive = {J_JACS}, author = {Tianyu Zheng and Zikuan Wang and Benjamin Mitschke and Nils Nöthling and Markus Leutzsch and Frank Neese and Benjamin List}, doi = {10.1021/jacs.5c05709}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25489--25497}, shortjournal = {J. Am. Chem. Soc.}, title = {Pericyclic umpolung in a catalytic asymmetric Diels–Alder reaction of tropone with enol ethers}, volume = {147}, year = {2025}, }
• (2025). Carboranes without cage carbons: Closo-dodecaborate mimics of neutral closo-carboranes. JACS, 147(29), 25478--25488. (www)

  @article{ , abstract = {Substituted two-dimensional aromatic systems, such as arenes, exhibit well-established reactivity patterns at specific sites, largely due to the pronounced electronic directing effects of attached substituents. In contrast, the regioselectivity of three-dimensional aromatic molecules as a function of substituents remains less understood and documented. In this work, we demonstrate that a series of closo -dodecaborate ([B 12 H 12 ] 2– ) cluster isomers containing two -NMe 3 + moieties exhibit unprecedented regioselective reactivity at boron vertices farthest from the charged substituents. Through a combination of theoretical and experimental studies, we reveal that these boron clusters display near-perfect regioselectivity with multiple electrophiles, ultimately enabling vertex differentiation chemistry within these systems. This observed phenomenon closely parallels the reactivity patterns typically associated with icosahedral closo -carboranes, where a carbon-based vertex induces a strong electronic dipole, leading to pronounced vertex-specific reactivity differences at boron sites. Our findings suggest that these modified closo -dodecaborates serve as electronic analogs of neutral closo -carboranes, achieving similar electronic directing effects without the need for cage-based carbon atoms. Instead, exopolyhedral substituents alone govern the regioselective behavior, expanding the potential for tailored functionalization in boron cluster chemistry.}, archive = {J_JACS}, author = {Austin D. Ready and Varun Tej Raviprolu and Tyler A. Kerr and Joseph W. Treacy and Mei L. Matsumoto and Prairie E. Hammer and Ellen M. Sletten and K. N. Houk and Alexander M. Spokoyny}, doi = {10.1021/jacs.5c05637}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25478--25488}, shortjournal = {J. Am. Chem. Soc.}, title = {Carboranes without cage carbons: Closo-dodecaborate mimics of neutral closo-carboranes}, volume = {147}, year = {2025}, }
• (2025). Interactional fingerprints offer accessible, rapid, and qualitative characterization of graphene oxide. JACS, 147(29), 25471--25477. (www)

  @article{ , abstract = {Graphene-based materials (GBMs), including graphene oxide and graphene, are atomically thin materials with great promise, but efforts to realize their potential have been hampered by inconsistent material supply and the lack of rapid, accessible characterization methods. Here we present a new approach to characterization, based on surface interactions with a series of probe molecules. We demonstrate that our method facilitates qualitative comparisons of graphene oxide materials─for example, if batches of material differ─an accessible quality control method for materials producers and users alike, using widely available instruments. Furthermore, we show that in some circumstances, we may quantify systematic differences, such as surface modifications. Since many applications of materials depend on surface interactions, we suggest that this approach is applicable beyond quality control as a more direct approach to probe material surfaces and a valuable alternative to instrumental methods in GBMs and beyond.}, archive = {J_JACS}, author = {Blanca Ivonne Vergara-Arenas and Esmé Shepherd and Ivan Alfaro and Edward Cross and Huong Le and Andrew J. Surman}, doi = {10.1021/jacs.5c05355}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25471--25477}, shortjournal = {J. Am. Chem. Soc.}, title = {Interactional fingerprints offer accessible, rapid, and qualitative characterization of graphene oxide}, volume = {147}, year = {2025}, }
• (2025). Proton-catalyzed interconversion of Tungsten(VI) imido isopropylidene and propylene complexes. JACS, 147(29), 25462--25470. (www)

  @article{ , abstract = {Additions of two equivalents of (CF 3 ) 3 COH (R F9 OH) or (CF 3 ) 2 MeCOH (R F6 OH) to W(NAr) 2 R 2 complexes (Ar = 2,6-diisopropylphenyl, R = n -propyl or i -propyl) offer the opportunity to synthesize propylene or isopropylidene olefin metathesis-active complexes in the absence of free propylene. Propylene and isopropylidene complexes (W(NAr)(ArNH 2 )(OR F9 ) 2 (propylene) and W(NAr)(ArNH 2 )(OR F9 ) 2 (CMe 2 )) are formed at room temperature from both W(NAr) 2 ( i -propyl) 2 and W(NAr) 2 ( n -propyl) 2 complexes upon addition of two equivalents of R F9 OH; no W = CHCH 2 Me complexes are observed. Similar results are found for W(NAd) 2 (propyl) 2 complexes (Ad = 1-adamantyl). Both RNH 2 and RNH 2 B(C 6 F 5 ) 3 (R = Ar or Ad) catalyze the interconversion of propylene and isopropylidene complexes. Addition of R F6 OH to W(NAr) 2 R 2 or W(NAd) 2 R 2 complexes leads to mixtures that contain largely propylene complexes. Addition of (CF 3 )Me 2 COH (R F3 OH) to W(NAr) 2 ( i -Pr) 2 yields only propylene complexes. One propylene complex, W(NAd)(OR F9 ) 2 (CH 2 ═CHMe)(dme), was isolated, structurally characterized, and found to react with AdNH 2 to reform W(NAd)(OR F9 ) 2 (CMe 2 )(AdNH 2 ). It is proposed that propylene and isopropylidene complexes interconvert through the formation of an intermediate isopropyl complex.}, archive = {J_JACS}, author = {Milan Maji and Logan Trowbridge and Maxime Boudjelel and Richard R. Schrock and Matthew P. Conley and Veronica Carta}, doi = {10.1021/jacs.5c05262}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25462--25470}, shortjournal = {J. Am. Chem. Soc.}, title = {Proton-catalyzed interconversion of Tungsten(VI) imido isopropylidene and propylene complexes}, volume = {147}, year = {2025}, }
• (2025). Concise synthesis of fostriecin and analogs through late-stage chemoenzymatic installation of their key pharmacophores. JACS, 147(29), 25454--25461. (www)

  @article{ , abstract = {As one of the most potent and selective protein phosphatase inhibitors, fostriecin shows a broad range of anticancer activities. In light of this property, a phase I clinical trial was conducted on fostriecin but was soon halted due to issues with compound stability and purity. Numerous efforts in the past two decades have yielded 17 successful syntheses that proceed in 17–34 steps. Herein, we develop a modular chemoenzymatic approach that provides fostriecin and its analogs in a collective manner in 9 steps (longest linear sequence) from readily available ( R )-1,2,4-butanetriol. The synthesis features a convergent assembly of three key fragments and a late-stage chemoenzymatic derivatization of an advanced intermediate that (i) installs two of the key pharmacophores and (ii) allows ready diversification of the hydrophobic tail. A key feature in this derivatization is the optimization of an enzymatic C–H oxidation step through the concurrent use of rational enzyme engineering and small molecule additives for activity improvement. Cumulatively, our strategy capitalizes on the exquisite chemoselectivity of enzymatic transformations while ensuring synthetic modularity and versatility for analog generation. This work will facilitate future investigations into the biological activities and medicinal chemistry of the natural product family.}, archive = {J_JACS}, author = {Yanlong Jiang and Xuerong Yu and Hans Renata}, doi = {10.1021/jacs.5c05269}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25454--25461}, shortjournal = {J. Am. Chem. Soc.}, title = {Concise synthesis of fostriecin and analogs through late-stage chemoenzymatic installation of their key pharmacophores}, volume = {147}, year = {2025}, }
• (2025). Dissimilar diffusion mechanisms of li+, na+, and k+ ions in anhydrous fe-based prussian blue cathode. JACS, 147(29), 25441--25453. (www)

  @article{ , abstract = {Prussian Blue (PB, AFe[Fe(CN) 6 ], where A = Li, Na, K, etc. ), a three-dimensional (3D) metal–organic framework (MOF), emerges as a promising cathode material, particularly for next-generation Na- and K-ion batteries. However, the microscopic occupation positions and diffusion behaviors of A + ions in the unit cell have been inadequately elucidated. This study systematically compares the diffusion mechanisms of multiple Li + , Na + , and K + ions using density functional theory calculations. We clarified the new stable occupation sites for Li + and Na + ions: the face-centered (FC) 24d and off-FC 48g sites, respectively. The smaller ionic radii of Li + and Na + ions contribute to their enhanced Coulombic attractions from CN – anions. Li + ions are more self-diffusive than Na + at high temperatures; however, at room temperature, Na + ions have comparable self-diffusivities and lower activation energies than Li + ions. This is attributed to the smaller tilting of [Fe(CN) 6 ]-octahedra induced by Na + ions’ transfers, resulting in a shallower potential energy landscape than for Li + ions. These results demonstrated that the anhydrous Fe-based pristine PB crystal is an excellent Na + -ion conductor. Meanwhile, K + ions prefer the conventional body center (8c site) and exhibit negligible self-diffusivities without anionic defects. Surprisingly, they show anisotropic diffusion along anion vacancy channels in the defective crystal, in contrast with the isotropic pathways for Li + and Na + ions. These findings update the fundamental chemistry of the diffusivity correlation with the electronic orbital interactions and framework distortion within general MOF materials.}, archive = {J_JACS}, author = {Dan Ito and Seong-Hoon Jang and Hideo Ando and Toshiyuki Momma and Yoshitaka Tateyama}, doi = {10.1021/jacs.5c05274}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25441--25453}, shortjournal = {J. Am. Chem. Soc.}, title = {Dissimilar diffusion mechanisms of li+, na+, and k+ ions in anhydrous fe-based prussian blue cathode}, volume = {147}, year = {2025}, }
• (2025). Structural mechanism of insect cuticular protein binding to chitin revealed by solid-state NMR. JACS, 147(29), 25429--25440. (www)

  @article{ , abstract = {The exoskeleton of an insect is a fascinating example of how nature employs organic substances to craft high-performance materials, characterized by their hardness, tensile strength, and lightweight. Dissecting the atomic-level arrangement of these multifunctional organics, primarily proteins and chitin, within insect cuticles will aid in deciphering this enigma. Despite its importance, revealing the mechanism of interaction between cuticular proteins and chitin polysaccharides in heterogeneous systems remains a challenge. Nuclear magnetic resonance (NMR) spectroscopy, renowned for its ability to provide atomic-resolution insights, is adept at obtaining distance information and local structure without the need for long-range order. Here, cuticular proteins and chitin polysaccharides, which are prominent components of the insect cuticle, were studied using combining solution and solid-state NMR methods. Our results indicate that the larval cuticle proteins of Ostrinia furnacalis ( Of LCP30-C) are intrinsically disordered in aqueous solution but undergo a conformational transition from unfolded to folded upon binding to chitin polysaccharides. High-resolution 1 H-detected solid-state NMR spectra enable us to obtain the atomic-resolution structure of Of LCP30-C in its chitin-binding state. Aromatic amino acids located on the same side of the planar-shaped structure act as adhesive patches, adhering to the chitin surface and exerting a critical influence during the chitin-protein binding process. Our results provide a feasible basis for studying the ubiquitous interactions between cuticular proteins and polysaccharides.}, archive = {J_JACS}, author = {Shuaifei Hu and Juan Li and Fenghou Yuan and Jin Zhang and Xinyue Cheng and Shengqi Xiang and Changlin Tian and Weimin Gong and Tian Liu and Chaowei Shi}, doi = {10.1021/jacs.5c05099}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25429--25440}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural mechanism of insect cuticular protein binding to chitin revealed by solid-state NMR}, volume = {147}, year = {2025}, }
• (2025). Probing strain in individual palladium nanocrystals during electrochemically induced phase transitions. JACS, 147(29), 25417--25428. (www)

  @article{ , abstract = {The palladium–hydrogen system plays a crucial role in catalysis, hydrogen production and storage, hydrogen embrittlement, and sensing technologies. Understanding the transition of palladium nanocrystals (NCs) from the hydrogen-poor (α) phase to the hydrogen-rich (β) phase is crucial for elucidating hydrogen absorption/desorption mechanisms as well as related phenomena such as hydrogen trapping. In this study, we carefully minimized undesired X-ray beam effects and used in situ Bragg coherent diffraction imaging under electrochemical control to map the strain and lattice parameter distribution within individual palladium NCs across electrochemical potentials relevant to hydrogen absorption and desorption. Lattice parameter changes in both α and β phases are tracked, and reversible strain inversion during the α-to-β phase transition is observed. Through strain and reciprocal space analysis and molecular simulations, a model for the α-to-β phase transition is proposed, which includes a hydrogen-saturated subsurface shell, hydrogen depletion from the α phase during β phase nucleation, and propagation of the β phase in a spherical-cap fashion.}, archive = {J_JACS}, author = {Clément Atlan and Corentin Chatelier and Apinya Ngoipala and Kyle Olson and Arnaud Viola and Ewen Bellec and Michael Grimes and Bruno Gilles and Minaam Qamar and Matous Mrovec and Steven J. Leake and Joël Eymery and Tobias U. Schülli and Matthias Vandichel and Marie-Ingrid Richard and Frédéric Maillard}, doi = {10.1021/jacs.5c05102}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25417--25428}, shortjournal = {J. Am. Chem. Soc.}, title = {Probing strain in individual palladium nanocrystals during electrochemically induced phase transitions}, volume = {147}, year = {2025}, }
• (2025). Unveiling janus chemical processes in contact-electro-chemistry through oxygen reduction reactions. JACS, 147(29), 25407--25416. (www)

  @article{ , abstract = {Oxygen reduction reaction (ORR), operating via four-electron (H 2 O) or two-electron (H 2 O 2 ) pathways, underpins critical processes in energy conversion and biological metabolism. Solid–liquid contact electrification enables 2e – ORR for both pollutant oxidation degradation and metal reduction without external metal catalysts. However, the criteria dictating oxidation versus reduction in such Janus contact-electro-chemistry (CE-Chemistry) systems remain unclear. This study systematically demonstrates that the redox selectivity in CE-Chemistry is controlled by the standard electrode potential (SEP) of the reactants, with a clear threshold distinguishing the oxidation and reduction pathways. Reduction of metal ions (e.g., [AuCl 4 ] − , Pd 2+ , [PtCl 4 ] 2– Ag + , Rh 3+ , and Ir 3+ ) was achieved when their SEPs lie between the 2e – ORR ( E 0 = 0.695 V vs NHE) and the 4e – ORR ( E 0 = 1.229 V vs NHE). Conversely, SEPs below the 2e – ORR threshold favored oxidation (e.g., ferrocyanide). For the first time, methanol-to-formaldehyde oxidation was achieved in both aqueous and nonaqueous CE-Chemistry. Remarkably, the formaldehyde production rate in dimethyl sulfoxide was 25 times higher than in aqueous systems, which has already surpassed some photocatalytic processes. This study provides a comprehensive mechanistic framework for CE-Chemistry, highlighting the pivotal role of SEPs in regulating its Janus redox properties and the tunable radical reactivity in nonaqueous environments.}, archive = {J_JACS}, author = {Ting Gan and Zhe Yang and Shaoxin Li and Han Qian and Zhijian Li and Jiajin Liu and Puguang Peng and Jinbo Bai and Hanbin Liu and Zhonglin Wang and Di Wei}, doi = {10.1021/jacs.5c05124}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25407--25416}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling janus chemical processes in contact-electro-chemistry through oxygen reduction reactions}, volume = {147}, year = {2025}, }
• (2025). Spin delocalization of nitrile-ligated diarylboryl radicals enables photochemical boracycle synthesis via N-borylimidoyl radicals. JACS, 147(29), 25397--25406. (www)

  @article{ , abstract = {Tetracoordinate boracycles are important motifs in organic synthesis and materials science, yet their synthesis remains constrained by two-electron processes requiring directing groups or highly reactive boron reagents. Herein, we report a photochemical strategy enabling the modular, single-step assembly of tetracoordinate boron–nitrogen heterocycles from olefins, nitriles, and tetraarylborates. This method bypasses traditional directing groups and strong boron electrophiles, providing access to previously inaccessible boracyclic architectures. More importantly, mechanistic experiments and DFT calculations reveal a distinct radical-mediated cyclization mechanism involving a novel class of N -borylimidoyl radicals, which are generated from nitrile-ligated diarylboryl radicals via spin delocalization. Preliminary studies demonstrate that these imidoyl radicals could also be leveraged to access tri- and tetrasubstituted 2-fluoropyrroles and bridged boracycles.}, archive = {J_JACS}, author = {Yubing Pang and Xiaoyu Yan and Hasil Aman and Meichen Xu and Juntao Ye}, doi = {10.1021/jacs.5c09280}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25397--25406}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin delocalization of nitrile-ligated diarylboryl radicals enables photochemical boracycle synthesis via N-borylimidoyl radicals}, volume = {147}, year = {2025}, }
• (2025). Strain-engineered rh single atoms on curved WS2 for hydrogen production and coupled photochemical water splitting. JACS, 147(29), 25385--25396. (www)

  @article{ , abstract = {Hydrogen is a promising clean energy carrier, yet the high energy demand of water electrolysis limits its widespread adoption. Catalysis is crucial to enhance the efficiency of hydrogen production and lower energy costs. However, conventional catalyst design guided by the d-band theory faces inconsistencies in predicting adsorption behavior, and the oxygen evolution reaction (OER) remains a major efficiency bottleneck. To address these challenges, we developed a strain-engineered Rh single-atom catalyst anchored on curved WS 2 supported by carbon nanotubes (Rh SA /WS 2 @CNT) to modulate the electronic structure. The resultant catalyst achieves an ultralow overpotential of 17.4 mV at 10 mA cm –2 for the hydrogen evolution reaction (HER) and a mass activity ∼65 times higher than that of commercial Pt/C. Mechanistic analysis reveals that the H* adsorption trend contradicts d-band theory predictions but is explained by orbital symmetry adaptation, where the strain-modulated d xz orbital plays a major role in governing adsorption energetics. Beyond catalyst design, the HER catalyst was coupled with a photocatalytic iodide oxidation reaction (IOR) to replace the OER and reduce the water-splitting voltage to 0.7 V. This study not only introduces a strain-engineering strategy to optimize single-atom catalysts but also demonstrates a coupled electro-photo system that enhances energy efficiency, offering an alternative approach for sustainable hydrogen production.}, archive = {J_JACS}, author = {Ting Gao and Jie Gu and Changheng Yang and Rui Wang and Chan Wang and Pengfei Zhang and Jiatong Li and Xiaoyan Zheng and Yunmiao Fan and Puheng Yang and Xiufu Hua and Junfeng Hui and Huigang Zhang}, doi = {10.1021/jacs.5c04928}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25385--25396}, shortjournal = {J. Am. Chem. Soc.}, title = {Strain-engineered rh single atoms on curved WS2 for hydrogen production and coupled photochemical water splitting}, volume = {147}, year = {2025}, }
• (2025). Engineering mono- vs dinuclear Iron(II)-active sites to steer liquid oxygenate selectivity in methane oxidation pathways using o2. JACS, 147(29), 25372--25384. (www)

  @article{ , abstract = {The selective oxidation of methane to liquid oxygenates using O 2 under mild conditions remains a grand challenge due to the chemical inertness of methane and the competing thermodynamically favored overoxidation. We report the development of well-defined mono- and dinuclear bipyridyl Fe(II) hydroxyl species within a porous metal–organic framework [MOF-253(Al)], which enable methane oxidation by O 2 via distinct oxidation pathways with exceptionally high product selectivity. The MOF-supported dinuclear Fe(II) catalyst (MOF-253-Fe 2 ) having a [(bpy)Fe II (μ 2 –OH)(OH)] 2 active site achieves 100% liquid selectivity toward acetic acid with a productivity of 2757 mmol CH3CO2H mol Fe –1 h –1 at 160 °C. In comparison, the MOF-supported mononuclear (bpy)Fe II (OH) 2 catalyst (MOF-253-Fe) exhibits a remarkably high methanol productivity of 6060 mmol CH3OH mol Fe –1 h –1 with 96% selectivity in the aqueous phase at 95 °C. Spectroscopic and mechanistic studies suggested that the confinement and stabilization of [(bpy)Fe II (μ 2 –OH)(OH)] 2 active site in the MOF-253-Fe 2 framework facilitate redox cooperativity and multielectron transfer, enabling sequential O 2 activation, methane C–H bond activation, followed by C–C bond coupling with in situ -generated CO to yield acetic acid through the formation of [(bpy)Fe III (μ 2 –OH)(OH) 2 ] 2 catalytic intermediate. In contrast, the MOF-253-Fe catalyst lacks such synergy but efficiently promotes methane C–H hydroxylation to yield methanol. This work underscores the importance of active site engineering in governing product selectivity and provides valuable insights into the design of advanced catalysts for selective methane functionalization.}, archive = {J_JACS}, author = {Poorvi Gupta and Manav Chauhan and Bharti Rana and Rahul Kalita and Rishabh Maurya and Kuntal Manna}, doi = {10.1021/jacs.5c04682}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25372--25384}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering mono- vs dinuclear Iron(II)-active sites to steer liquid oxygenate selectivity in methane oxidation pathways using o2}, volume = {147}, year = {2025}, }
• (2025). Competitive carbonate binding hinders electrochemical CO2 reduction to CO on cu surfaces at low overpotentials. JACS, 147(29), 25361--25371. (www)

  @article{ , abstract = {The electrochemical reduction of CO 2 to useful chemicals holds promise for a sustainable carbon cycle. However, the key factors that control the pathways to various desired products remain unresolved, partially due to the limited knowledge of reaction intermediates on the electrode surface. To address this, we utilize in situ electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy in combination with density functional theory calculation to examine the potential-dependent composition of adsorbed species during CO 2 reduction on polycrystalline copper. The results reveal that carbonate anion adsorption outcompetes other carbon-containing species, including adsorbed CO 2 activation intermediate *COO – and *CO, which has the effect of anodically shifting the onset potential of *CO formation in electrolyte solutions with a lower carbonate concentration. These results suggest that the competitive binding of carbonate impedes the reduction of CO 2 on the Cu surface. Monte Carlo simulations show that both potential dependent electrode surface change and electrode-carbonate Coulomb interaction are key to understanding the competitive binding process. Our findings suggest that reducing the competitive binding of carbonate may be a promising route to improve the CO 2 reduction on Cu electrodes at low overpotentials.}, archive = {J_JACS}, author = {Jinhui Meng and Jessica Freeze and Linsey Nowack and Chaoyu Li and Hongsen Wang and Héctor D. Abruña and Adam P. Willard and Victor S. Batista and Tianquan Lian}, doi = {10.1021/jacs.5c04518}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25361--25371}, shortjournal = {J. Am. Chem. Soc.}, title = {Competitive carbonate binding hinders electrochemical CO2 reduction to CO on cu surfaces at low overpotentials}, volume = {147}, year = {2025}, }
• (2025). Compositional design guides property control in A2M2+xTi1–(x/4)Q4 semiconductors. JACS, 147(29), 25350--25360. (www)

  @article{ , abstract = {We introduce 15 new members to the A 2 M 2+ x Ti 1–( x /4) Q 4 family (A = K, Rb, Cs; M = Cu, Ag; Q = S, Se, Te; x = 0 – 1 1 3 ) of semiconductors, for which all compositions afford the ThCr 2 Si 2 structure-type with two-dimensional (2D) [M 2+ x Ti 1–( x /4) Q 4 ] 2– layers. We unveil how A, M, Q, and the vacancies inherent to the [M 2+ x Ti 1–( x /4) Q 4 ] 2– layers serve as four tunable compositional variables that influence both the local atomic and electronic structures with systematic impacts on the optoelectronic and thermal properties in a predictable manner. Namely, increased distortion within the [M 2+ x Ti 1–( x /4) Q 4 ] 2– layers occurs when M = Ag, lowering the melting temperatures of all Ag compounds relative to their Cu counterparts for a given Q. The electronic structures are primarily influenced by Q, with a substitution of S → Se → Te narrowing the average band gaps from 2.30 → 1.49 → 0.74 eV. For a given Q, however, Ag lowers the energy of the valence band maximum (VBM) compared to Cu, and relative to vacuum. Increasing the Ag/Ti ratio inserts additional Ag into the inherent vacancies within the [Ag 2+ x Ti 1–( x /4) S 4 ] 2– layers of Cs 2 Ag 3.3 Ti 0.675 S 4 compared to Cs 2 Ag 2 TiS 4 , raising the valence band maximum from −5.26 → −4.83 eV, which in turn narrows the band gap from 2.48 → 1.85 eV. Such broad ranges in thermal and optoelectronic properties within this family provide interest for diverse applications. Moreover, because this work establishes the independent influences of A, M, Q, and the inherent vacancies on properties for a constant structure-type, all composition-property relationships should apply to other structure-types containing any of these elements or inherent vacancies.}, archive = {J_JACS}, author = {Michael A. Viti and Zhi Li and Craig C. Laing and Christopher Wolverton and Mercouri G. Kanatzidis}, doi = {10.1021/jacs.5c04520}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25350--25360}, shortjournal = {J. Am. Chem. Soc.}, title = {Compositional design guides property control in A2M2+xTi1–(x/4)Q4 semiconductors}, volume = {147}, year = {2025}, }
• (2025). Intramolecular oxo atom migration to the cis thiolate sulfur of an fe-oxo intermediate. JACS, 147(29), 25337--25349. (www)

  @article{ , abstract = {Herein, we show for the first time that thiolate ligands can play an important role in promoting 2e- oxo atom transfer with nonheme iron. We examine the mechanism of oxo atom transfer to a cis thiolate sulfur for two structurally related iron complexes using low-temperature kinetics, spectroscopic, and computational methods. Intermediate oxo atom donor adducts, FeOIAr, are spectroscopically characterized and shown to have electronic spectral, EPR, and Mössbauer parameters, and kinetic barriers dependent on the nature of the oxo atom donor. More stable adducts containing pyridine N-oxide (PNO) were crystallographically characterized and computationally optimized to establish optimum functionals and basis sets. Oxo atom transfer is shown both experimentally and computationally to involve a stepwise, as opposed to a concerted, mechanism. A new metastable intermediate is observed by low-temperature Mössbauer and ⊥-mode EPR after the Fe–O x IPh intermediate and prior to the final sulfenate Fe-OSR product. The DFT calculated minimum energy pathway is shown to contain a local minimum between the Fe–O 2 IPh adduct and Fe–S(R)O product. The DFT optimized geometric and electronic structure of this intermediate is shown to be consistent with an S = 1 Fe(IV)═O that is antiferromagnetically coupled to an S = 1/2 radical delocalized over the two cis thiolate-sulfurs, analogous to the electronic configuration of P450 Cmpd I. Radical character on the thiolate sulfur adjacent to the oxo is shown to facilitate trapping of the high-valent Fe-oxo as a η 2 -SO-Fe sulfenate complex.}, archive = {J_JACS}, author = {Deesha D. Malik and Shilpa Bhatia and Maike N. Lundahl and Haley N. Bautel and Dylan M. Rogers and Werner Kaminsky and Julie A. Kovacs}, doi = {10.1021/jacs.5c04340}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25337--25349}, shortjournal = {J. Am. Chem. Soc.}, title = {Intramolecular oxo atom migration to the cis thiolate sulfur of an fe-oxo intermediate}, volume = {147}, year = {2025}, }
• (2025). Ferrous iron metabolism modulator for immune stress regulation and its application in skin allograft models. JACS, 147(29), 25325--25336. (www)

  @article{ , abstract = {The dysregulation of ferrous iron (Fe 2+ ) metabolism, which is closely linked to immune stress, plays a pivotal role in driving pathological processes such as ferroptosis and hyperinflammation. Therefore, it is crucial to modulate Fe 2+ metabolism to alleviate iron overload and immune stress. However, current iron chelators, which are commonly used as iron metabolism modulators, primarily target ferric ions (Fe 3+ ), the downstream oxidation product of Fe 2+ . This approach not only limits their modulation efficacy but also poses a risk of disrupting Fe 3+ homeostasis in healthy tissues. Herein, a novel Fe 2+ metabolism modulator, DHU-Feex1, was developed by optimizing the electronic structure of iron chelators through theoretical calculations. DHU-Feex1 preferentially recognized Fe 2+ and effectively inhibited the iron-mediated Fenton reaction. Additionally, by responding to hydroxyl radicals and sequentially scavenging Fe 3+ , DHU-Feex1 mitigated the harmful effects of ferroptosis. In vivo validation using a mouse skin allograft model demonstrated the therapeutic potential of DHU-Feex1. The modulator remarkably prolonged graft survival and reduced immune rejection by precisely regulating immune responses. Gene and protein expression analyses further revealed that DHU-Feex1 effectively regulated ferroptosis-related pathways and suppressed inflammation, confirming its role as an immunomodulatory agent. In summary, this study presents DHU-Feex1 as a promising strategy for modulating immune responses, particularly in diseases associated with Fe 2+ metabolism disorders.}, archive = {J_JACS}, author = {Zhiting Wu and Liyi Zhang and Xinrui Mao and Jingjing Zhu and Jiaoduan Li and Chengcheng Wang and Weiwei Jiang and Yun Zhang and Xuexue Huang and Hongjun Zhuang and Peng Wei and Tao Yi}, doi = {10.1021/jacs.5c04246}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25325--25336}, shortjournal = {J. Am. Chem. Soc.}, title = {Ferrous iron metabolism modulator for immune stress regulation and its application in skin allograft models}, volume = {147}, year = {2025}, }
• (2025). Phosphorylation-inducing molecules for regulating dynamic cellular processes. JACS, 147(29), 25316--25324. (www)

  @article{ , abstract = {Dynamic cellular processes often employ protein phosphorylation for rapid information transfer within and between cells. Phosphorylation-inducing chimeric small molecules (PHICS) have been developed for targeted protein phosphorylation by on-demand inducing a kinase–protein pairing. However, widespread application of PHICS has been limited as previously reported PHICS that recruited AMP-activated protein kinase (AMPK) required serum starvation and target protein overexpression, recruited only a few of the potential AMPK complexes, and exhibited poor dose and temporal control. Herein, we report an AMPK PHICS platform that operates under physiological conditions (i.e., no serum starvation), recruits multiple AMPK complexes, and can induce target protein phosphorylation with dose and temporal control. We demonstrated the utility of this platform for controlling phosphorylations that underlie two dynamic cellular processes, namely, oncogenic signaling and phase separation. An AMPK PHICS directed against Bruton’s tyrosine kinase (BTK), which is a driver of several B cell malignancies, was effective at inducing the death of drug-resistant cancer cells. Here, PHICS induced inhibitory phosphorylations on BTK and attenuated its oncogenic pathway. Phosphorylation of Liprin-α3 induces phase separation in neurons and is critical for neurotransmitter release. Using AMPK PHICS that phosphorylated Liprin-α3, we induced Liprin-α3 phase separation with dose and temporal control. We envision that this PHICS platform will find utility in inducing and controlling protein phosphorylations for basic research and biomedicine.}, archive = {J_JACS}, author = {Rajaiah Pergu and Vedagopuram Sreekanth and Praveen Kokkonda and Sophia Lai and Praveen K. Tiwari and Sameek Singh and Junya Kawai and Santanu Singha and Wenzhi Tian and Vikram Thimaradka and Surached Siriwongsup and Kien Tran and Amit Choudhary}, doi = {10.1021/jacs.5c04275}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25316--25324}, shortjournal = {J. Am. Chem. Soc.}, title = {Phosphorylation-inducing molecules for regulating dynamic cellular processes}, volume = {147}, year = {2025}, }
• (2025). Chemoenzymatic synthesis of glycosphingolipids having an HNK-1 epitope for erythrocyte cell surface remodeling. JACS, 147(29), 25306--25315. (www)

  @article{ , abstract = {Several neuropathies, such as Guillain–Barré syndrome and myelin-associated glycoprotein neuropathy (MAG), are caused by antibodies targeting glycosphingolipids. Several studies have indicated that MAG arises from pathogenic IgM autoantibodies targeting sulfoglucuronyl (HNK-1)-containing glycosphingolipids. The exact mechanism by which IgM neuropathy occurs has not been fully elucidated. Furthermore, no appropriate diagnostic tools are available for MAG using sulfoglucuronyl-containing glycosphingolipids. To address these limitations, we describe here a synthetic strategy that makes it possible to prepare sulfoglucuronyl paraglobosides using a neo chemoenzymatic approach. It is based on the enzymatic assembly of N -acetyllactosamine (LacNAc) backbones as thioglycosides that were subjected to protecting group manipulations to give glycosyl acceptors for the chemical installation of a sulfated glucuronic acid moiety. A late-stage conversion of the thioglycosides into anomeric fluorides made it possible to enzymatically introduce sphingosine. The resulting compounds were acylated to provide 3-sulfo-glucuronyl- and glucuronyl-containing glycosphingolipids, respectively. The glycosphingolipids were employed to remodel the surface of erythrocytes to examine complement-mediated toxicity by an anti-HNK-1 antibody. It was found that erythrocytes remodeled with exogenously administered HNK-1 containing glycosphingolipid undergo complement-dependent lysis when incubated with an anti-CD57 IgM antibody, whereas a compound lacking a sulfate was not able to induce this effect. The approach could be extended to the gangliosides GM1a and GD1a, which have been implicated in Guillain–Barré syndrome. The results highlight that cell surface remodeling will be attractive for diagnosis, disease monitoring, and immunological research of diseases associated with pathogenic antibodies targeting glycosphingolipids.}, archive = {J_JACS}, author = {Mehman I. Bunyatov and Geert-Jan Boons}, doi = {10.1021/jacs.5c04179}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25306--25315}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemoenzymatic synthesis of glycosphingolipids having an HNK-1 epitope for erythrocyte cell surface remodeling}, volume = {147}, year = {2025}, }
• (2025). Hydroxylated boron crystal domain-modulated heterostructure carbon catalysts for efficient hydrogen peroxide generation. JACS, 147(29), 25295--25305. (www)

  @article{ , abstract = {Metal-free heterostructure carbon catalysts are promising alternatives to metal-based catalysts for electrochemical hydrogen peroxide (H 2 O 2 ) synthesis via the two-electron oxygen reduction reaction (2e – ORR). However, one appropriate nanocrystal type is being sought to resolve a concern at industrial-level current densities. Herein, nano boron crystal domains (B n ) overcame the stability limitations of traditional carbon-based electrocatalysts for sustainable H 2 O 2 production and industrial application. A B n –C catalyst offered multiple active sites, while the nano B n imparted an O 2 enrichment effect enhancing mass transfer during ORR electrocatalysis. The B n –C exhibited a very high mass activity (11.6/10.7 mol g cat –1 h –1 ) in alkaline/neutral electrolytes and showed negligible loss in activity and Faradaic efficiency (over 90%) during 100 h continuous electrolysis at high current density (>300 mA cm –2 ). Density functional theory and in situ Raman experiments demonstrated that the –OH groups connecting nano B n provided an inductive effect on B atoms in the carbon matrix, alleviating a binding strength that is too strong with *OOH intermediate.}, archive = {J_JACS}, author = {Yuhan Wu and Qixin Yuan and Yuying Zhao and Kang Sun and Hao Sun and Kui Wang and Shengchun Hu and Geoffrey I. N. Waterhouse and Jingjie Wu and Ziyun Wang and Jianchun Jiang and Mengmeng Fan}, doi = {10.1021/jacs.5c03955}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25295--25305}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydroxylated boron crystal domain-modulated heterostructure carbon catalysts for efficient hydrogen peroxide generation}, volume = {147}, year = {2025}, }
• (2025). Silica-driven CO2 reduction in water microdroplets. JACS, 147(29), 25287--25294. (www)

  @article{ , abstract = {Carbon dioxide (CO 2 ), the most notorious greenhouse gas responsible for global warming and ocean acidification, could persist in the atmosphere for 50 to 200 years, posing substantial long-term environmental challenges. However, its environmental fate remains not fully clear. This study reveals a previously unrecognized silica-driven CO 2 reduction pathway in ubiquitous water microdroplets, enabling the efficient conversion of CO 2 primarily into formic acid, along with other C 1 and C 2 products such as methanol, acetic acid, and ethanol, under ambient conditions. Notably, the reaction proceeds at a rate of 3.24 mmol g –1 h –1 , exceeding those reported for microdroplet systems utilizing amine absorbents or metal catalysts. Bonn–Oppenheimer molecular dynamics simulations further reveal that at the gas–water interface, a hydrated electron (H 2 O ·– ) reduces CO 2 to a CO 2 ·– radical anion, which subsequently abstracts a hydrogen atom from Si–OH sites on SiO 2 nanoparticles, yielding HCOO – as the primary product. Simultaneously, SiO 2 nanoparticles undergo partial disintegration, exposing fresh surfaces and generating additional Si–OH sites, thereby continuously promoting CO 2 conversion. These findings provide critical insights into climate evolution mechanisms, the chemical processes underlying acid rain and aerosol formation, and the advancement of efficient CO 2 utilization strategies.}, archive = {J_JACS}, author = {Wanting Chen and Jia Liu and Qi Jiang and Ning Wang and Xuemei Wu and Deming Xia and Gaohong He and Joseph S. Francisco}, doi = {10.1021/jacs.5c03921}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25287--25294}, shortjournal = {J. Am. Chem. Soc.}, title = {Silica-driven CO2 reduction in water microdroplets}, volume = {147}, year = {2025}, }
• (2025). What makes au nanospheres superior to octahedral and cubic counterparts for the deposition of a pt monolayer shell?. JACS, 147(29), 25273--25286. (www)

  @article{ , abstract = {This study demonstrates that Au nanospheres are advantageous over their octahedral and cubic counterparts as seeds in the synthesis of Au@Pt core–shell nanocrystals with a monolayer shell. In combination with experimental characterization, we show through training a machine-learned interatomic potential that the Au nanospheres exhibit a large fraction of low-coordination atoms which are uniformly distributed over the surface. The corresponding high-index facets, including {211}, {311}, {331}, {210}, and {310}, on a spherical seed promote nucleation while greatly shortening the diffusion distance for adatoms. In addition, the high-index facets are instrumental in retaining the deposited Pt atoms on the outermost surface by retarding their inter-diffusional exchange with the underlying Au atoms. By switching from a monolayer made of pure Pt to those made of Pt–Au alloys, we can optimize both the activity and selectivity of the nanocrystals toward the two-electron oxygen reduction reaction for the electrochemical synthesis of H 2 O 2 . This method should be extendible to the fabrication of other core–shell nanocatalysts with desired monolayer shells for various catalytic reactions.}, archive = {J_JACS}, author = {Kei Kwan Li and Lance Kavalsky and Marc Figueras-Valls and Yong Ding and Manos Mavrikakis and Younan Xia}, doi = {10.1021/jacs.5c03700}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25273--25286}, shortjournal = {J. Am. Chem. Soc.}, title = {What makes au nanospheres superior to octahedral and cubic counterparts for the deposition of a pt monolayer shell?}, volume = {147}, year = {2025}, }
• (2025). Enantioconvergent Radical–Radical cross-coupling via magnesium-mediated charge-transfer photocatalysis. JACS, 147(29), 25264--25272. (www)

  @article{ , abstract = {Radical asymmetric reactions represent a crucial strategy in asymmetric synthesis, which is characterized by their high reaction efficiency and unique reactivity profiles. Despite significant progress in radical-based asymmetric transformations, the formation of C–N bonds using nonredox metal complexes via the inner-sphere stereocontrol mechanism remains a formidable challenge in the development of novel asymmetric catalytic strategies. This study introduces an innovative and highly efficient asymmetric photochemical bifunctional catalysis that utilizes a combination of magnesium salts and chiral PyBOX-type (pyridine-bisoxazoline) C 2 -symmetric ligands under visible light irradiation. This approach enables the selective α-amidation of β-keto esters via an N -centered radical mechanism, facilitating the synthesis of substituted β-keto amino acid derivatives with a fully substituted stereocenter. The reaction proceeds in good yields (up to 79%) and excellent enantioselectivity (up to 94%). The catalysis proceeds through the in situ formation of prochiral quaternary charge-transfer complexes, which promote the Lewis acid-supported generation of radicals, thereby mediating the subsequent enantioconvergent radical–radical cross-coupling. Notably, the β-keto ester serves a trifunctional role as a sensitizer, reductant, and radical precursor, while the N -protected iminopyridinium ylide functions as both the oxidant and N -centered radical precursor. Experimental and computational mechanistic studies corroborate the enantioconvergent radical–radical cross-coupling process.}, archive = {J_JACS}, author = {Lei Yan and Hui-Qing Yang and Wan-Lei Yu and Xu-Gang Zhang and Peng-Fei Xu}, doi = {10.1021/jacs.5c03154}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25264--25272}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioconvergent Radical–Radical cross-coupling via magnesium-mediated charge-transfer photocatalysis}, volume = {147}, year = {2025}, }
• (2025). Unlocking a biological interface of chiral supramolecular helical polymers. JACS, 147(29), 25254--25263. (www)

  @article{ , abstract = {Here we report a C 3 -symmetric metal-binding tripeptide, BTMA-1 , that self-assembles in water into either a chiral supramolecular helical polymer or a discrete Co II peptide helicate, depending on metal coordination. The Co II peptide helicate exhibits high affinity and selectivity toward DNA three-way junctions (3WJ), a class of noncanonical DNA structures with emerging biological relevance. Importantly, we demonstrate that the recognition process can be triggered dynamically by adding Co II ions to a dispersion of the supramolecular polymer, which acts as an inert precursor reservoir in physiological media. In this way, our strategy shows that chiral supramolecular helical polymers can form temporarily inactive aggregates that release discrete helicates for biomolecular recognition, such as 3WJ binding, upon metal ion coordination. Overall, this mechanism reveals a previously unexplored capability of this class of materials and offers a new approach for the design of responsive supramolecular systems for nucleic acid recognition and anticancer therapy.}, archive = {J_JACS}, author = {Ana Alcalde-Ordóñez and Axel Sarmiento and Jacobo Gómez-González and David Bouzada and Manuel Núñez-Martínez and Manuel Fernández-Míguez and Rafael Rodríguez and Félix Freire and M. Eugenio Vázquez and Miguel Vázquez López}, doi = {10.1021/jacs.5c02902}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25254--25263}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking a biological interface of chiral supramolecular helical polymers}, volume = {147}, year = {2025}, }
• (2025). Multivalency controls the growth and dynamics of a biomolecular condensate. JACS, 147(29), 25242--25253. (www)

  @article{ , abstract = {Biomolecular condensates are essential for cellular organization and function, yet understanding how chemical and physical factors govern their formation and dynamics has been limited by a lack of noninvasive measurement techniques. Conventional microscopy methods often rely on fluorescent labeling and substrate immobilization, which can perturb the intrinsic properties of condensates. To overcome these challenges, we apply label-free, contact-free holographic video microscopy to study the behavior of a condensate-forming protein in vitro. This technique enables rapid, high-throughput, and precise measurements of individual condensate diameters and refractive indexes, providing unprecedented insight into size distributions and dense-phase macromolecular concentrations over time. Using this method, we investigate the kinetics of droplet growth, aging, and equilibrium dynamics in the model condensate-forming protein PopZ. By systematically varying the concentration and valence of cations, we uncover how multivalent ions influence condensate organization and dynamics, a hypothesis we further test using super-resolution microscopy. Our findings reveal that PopZ droplet growth deviates from classical models such as Smoluchowski coalescence and Ostwald ripening. Instead, we show that condensate growth is consistent with gelation at the critical overlap concentration. Holographic microscopy offers significant advantages over traditional techniques, such as differential interference contrast microscopy, delivering reproducible measurements and capturing condensate dynamics with unparalleled precision. This work highlights the power of holographic microscopy to probe the material properties and mechanistic underpinnings of biomolecular condensates, paving the way for deeper insights into their roles in synthetic systems.}, archive = {J_JACS}, author = {Julian von Hofe and Jatin Abacousnac and Mechi Chen and Moeka Sasazawa and Ida Javér Kristiansen and Soren Westrey and David G. Grier and Saumya Saurabh}, doi = {10.1021/jacs.5c02947}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25242--25253}, shortjournal = {J. Am. Chem. Soc.}, title = {Multivalency controls the growth and dynamics of a biomolecular condensate}, volume = {147}, year = {2025}, }
• (2025). Enzymatic basis of stereochemical control in reserpine biosynthesis. JACS, 147(29), 25233--25241. (www)

  @article{ , abstract = {Reserpine is a landmark natural product that has profoundly influenced our understanding of neurotransmitter biology and cardiovascular medicine. Its complex structure, featuring a unique C3 β-configuration and five consecutive chiral centers, has inspired generations of synthetic chemists to develop innovative strategies for its construction. However, the biosynthetic logic underlying nature’s stereochemical control in the assembly of this intricate molecule has remained elusive. Here, we investigate the biosynthetic pathway of reserpine in Rauvolfia verticillata , revealing that α-configured strictosidine serves as the biosynthetic precursor. The crucial C3 β-configuration is established through a two-step enzymatic epimerization, orchestrated by a flavin-dependent oxidase and a NADPH-dependent reductase. The consecutive chiral centers are constructed through coordinated action of distinct enzyme families. Through the identification of eight biosynthetic enzymes, including those catalyzing late-stage methoxylation, we successfully reconstituted the biosynthesis of rauvomitorine G, which contains all the stereochemical features present in reserpine. This work unveils nature’s elegant approach to stereoselective synthesis of complex alkaloids and provides valuable biocatalytic tools for molecular functionalization.}, archive = {J_JACS}, author = {Jiaqing Cao and Jingxiao Zhong and Feng Li and Yindi Jiang}, doi = {10.1021/jacs.5c02863}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25233--25241}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzymatic basis of stereochemical control in reserpine biosynthesis}, volume = {147}, year = {2025}, }
• (2025). A [2.1.0]-fused bicyclic intermediate is produced during the biosynthesis of oxetane nucleosides. JACS, 147(29), 25224--25232. (www)

  @article{ , abstract = {AlsB and OxsB are homologous B 12 -dependent radical S -adenosyl- l -methionine enzymes involved in the biosynthesis of the oxetane nucleosides albucidin and oxetanocin A. Both pathways also require a second enzyme (AlsA and OxsA, respectively) to complete the biosynthesis of the oxetane ring. Herein, OxsB and AlsB are both shown to catalyze an intramolecular C–C bond formation between two sp 3 -hybridized carbons in 5 ′ -phosphates of 2 ′ -deoxyadenosine to yield corresponding phosphates of the same highly strained [2.1.0]-bicyclic species. This compound undergoes nonenzymatic decomposition; however, in the presence of OxsA or AlsA, it is instead converted to oxetanocin A aldehyde phosphate or albucidin phosphate, respectively. This completes the description of oxetanocin A and albucidin biosynthetic pathways. Formation of the bicyclic intermediate involves hydrogen atom abstraction from both C2 ′ and C4 ′ in the substrate, which suggests an unprecedented catalytic role for cobalamin in stabilizing a carbon radical intermediate, thereby facilitating an intramolecular radical recombination reaction.}, archive = {J_JACS}, author = {Yu-Hsuan Lee and Po-Hsun Fan and Yu-Cheng Yeh and Mark W. Ruszczycky and Yujie Geng and Aoshu Zhong and Hung-wen Liu}, doi = {10.1021/jacs.5c01831}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25224--25232}, shortjournal = {J. Am. Chem. Soc.}, title = {A [2.1.0]-fused bicyclic intermediate is produced during the biosynthesis of oxetane nucleosides}, volume = {147}, year = {2025}, }
• (2025). Ligand design enables the palladium-catalyzed intermolecular carbochlorocarbonylation of alkynes and cyclopentenone formation. JACS, 147(29), 25215--25223. (www)

  @article{ , abstract = {Herein, we demonstrate that ligand design enables the direct addition of acid chlorides across alkynes in a single step with complete atom economy to afford α,β-unsaturated acid chloride products. This carbochlorocarbonylation reaction, which proceeds through the formal cleavage and reassembly of C–COCl bonds, was developed and explored for a range of acid chlorides and alkynes. During the course of this work, the formation of synthetically useful cyclopentenones through a formal C–H functionalization step was serendipitously observed at elevated temperatures. After optimizing for this divergent reactivity, we explored the substrate scope and undertook experiments to investigate the underlying mechanistic pathway for the formation of this product. Overall, this work expands the carbochlorocarbonylation reaction from activated substrates to alkynes. Further, it provides insight into ligand design for the exploration of fundamental reactivity.}, archive = {J_JACS}, author = {Elliott H. Denton and Hendrik L. Schmitt and Olivera Stepanović and Patrick Müller and Alexander F. Müller and Daniel Svoboda and Bill Morandi}, doi = {10.1021/jacs.5c01707}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25215--25223}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand design enables the palladium-catalyzed intermolecular carbochlorocarbonylation of alkynes and cyclopentenone formation}, volume = {147}, year = {2025}, }
• (2025). Photo-controlled conductance and thermopower switching in a soft photochromic metallo-supramolecular polymer via EGaIn junctions. JACS, 147(29), 25201--25214. (www)

  @article{ , abstract = {Photochromic soft metallo-supramolecular materials undergo precise, reversible transformations in structure and electronic properties under light irradiation, offering potential applications in optoelectronics, sensing, and molecular switches. Herein, we report the synthesis, characterization, and investigation of light-induced reversible morphological transformations in a Zn(II)-based photochromic coordination polymer gel (Zn-pcCPG), integrated with a dithienylethene (DTE) unit. Upon UV irradiation (λ = 365 nm), Zn-pcCPG undergoes morphological transformation from nanofibers in the gel state to spherical nanoparticles in the sol state, involving reversible photoswitching with distinct color change. To explore the charge transport properties of these metallo-supramolecular polymers, we created a EGaIn/GaO X //Zn-pcCPG//Au TS junction using the nanostructures of Zn-pcCPG on a template-stripped gold substrate (Au TS ) and a soft conformal EGaIn as the top electrode. These measurements show a reversible conductance photoswitching between the “open” and “closed” states of the coordination polymer gel containing a DTE core with an on/off ratio of ≈58 at −1 V. Additionally, we have also demonstrated the on-surface photoswitching of morphology and conductance properties. Interestingly, thermoelectric property measurements reveal a HOMO-dominated charge transport for both “open” and “closed” forms of Zn-pcCPG, with a reversible thermopower switching from +163 μV/K (open form) to +21 μV/K (closed form) and vice versa. By employing UV–Vis and ultraviolet photoelectron spectroscopy measurements, we have explained the experimental conductance and thermopower trends. This is the first study to demonstrate reversible conductance and thermopower switching with morphological transitions in a photochromic coordination polymer gel (pcCPG), paving the way for advancements in CPG-based supramolecular electronics.}, archive = {J_JACS}, author = {Souvik Mondal and Arpita Panda and Tarak Nath Das and Faruk Ahamed Rahimi and Sunil Kumar and Pooja Singh and Veerabhadrarao Kaliginedi and Tapas Kumar Maji}, doi = {10.1021/jacs.5c00670}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25201--25214}, shortjournal = {J. Am. Chem. Soc.}, title = {Photo-controlled conductance and thermopower switching in a soft photochromic metallo-supramolecular polymer via EGaIn junctions}, volume = {147}, year = {2025}, }
• (2025). Profiling of diverse pyridoxal-5′-phosphate dependent enzymes reveals promiscuous aldolase activity with (2-azaaryl)methanamines. JACS, 147(29), 25191--25200. (www)

  @article{ , abstract = {The elaboration of amine substrates through C–C bond-forming reactions is important in the synthesis of bioactive small molecules. Pyridoxal-5′-phosphate (PLP)-dependent enzymes have emerged as valuable biocatalysts for this class of reactions, due to their high stereoselectivity and ability to forge new C–C bonds on unprotected α-amino acid substrates. However, the use of abiological primary amines as pronucleophiles with enzymes such as threonine aldolase has been unexplored, moderating the utility of a biocatalytic approach in the synthesis of diverse 1,2-amino alcohols. In this report, we disclose the discovery and engineering of a PLP-dependent aldolase that accepts (2-azaaryl)methanamines in an aldol-type transformation. The 1,2-amino alcohol products generated, which contain representative heteroaromatic pharmacophores, are delivered with control over both the diastereoselectivity and enantioselectivity in the C–C bond-forming event. Protein engineering provided variants with improved binding affinity for the abiological substrate and decreased affinity for the native α-amino acid, overcoming inhibition of the abiotic reaction by components of lysate, a major challenge in reaction discovery with PLP-dependent enzymes such as threonine aldolases. This work represents the first known example of C–C bond formation on nonamino acid substrates with threonine aldolase and provides a platform for further development of complexity-building biocatalytic reactions with abiotic amine substrates.}, archive = {J_JACS}, author = {Kendrick L. Smith and Madeline A. Arbuckle and Alexander T. Kim and Chun-Yi Tsai and John A. McIntosh and Deeptak Verma and Eunjae Shim and Alison R. H. Narayan}, doi = {10.1021/jacs.5c04098}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25191--25200}, shortjournal = {J. Am. Chem. Soc.}, title = {Profiling of diverse pyridoxal-5′-phosphate dependent enzymes reveals promiscuous aldolase activity with (2-azaaryl)methanamines}, volume = {147}, year = {2025}, }
• (2025). Nucleophilic α-functionalization of benzyl amines using an engineered threonine aldolase. JACS, 147(29), 25184--25190. (www)

  @article{ , abstract = {Chiral amines are ubiquitous in pharmaceuticals and agrochemicals, making their efficient and selective synthesis a significant synthetic challenge. Threonine aldolases synthesize chiral amines via stereoselective C–C bond formation; however, they are restricted to small amino acids as pro-nucleophiles, limiting their utility in chemical synthesis. Here, we report an engineered threonine aldolase capable of α-functionalizing benzylamines. The evolved enzyme has excellent catalytic efficiency and accepts a broad range of (heterocyclic)benzyl amines and structurally diverse aldehydes to yield single-enantiomers of 1,2-amino alcohols in high-yield and diastereoselectivity. Mechanistic and crystallographic studies provide a rationale for how these mutations enable this previously unknown function. Moreover, beneficial mutations can be transferred to a related pyridoxal-dependent protein, highlighting the generality of these insights.}, archive = {J_JACS}, author = {Yao Ouyang and Suhao Wang and Damien Sorigue and Todd K. Hyster}, doi = {10.1021/jacs.5c04097}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25184--25190}, shortjournal = {J. Am. Chem. Soc.}, title = {Nucleophilic α-functionalization of benzyl amines using an engineered threonine aldolase}, volume = {147}, year = {2025}, }
• (2025). Eggerthella lenta produces a cryptic pro-inflammatory lipid. JACS, 147(29), 25180--25183. (www)

  @article{ , abstract = {Eggerthella lenta is both one of the most studied and least understood members of the human gut microbiome. Most of the interest in this Gram-positive anaerobe originates from multiple robust associations of its population with a variety of autoimmune diseases, perhaps most notably inflammatory bowel disease (IBD). The links between bacteria and inflammation are only partially known. Inflammation is driven by Th17 cells and their inflammatory cytokine IL-17, and the population of these cells is promoted by a transcription factor, RORγt. Bacterial metabolites appear to activate RORγt in a cell- and antigen-independent fashion, but the metabolites and their activating mechanism are unknown. This report describes an assay-driven search for pro-inflammatory metabolites from E. lenta that revealed a plasmalogen-triggered plasmalogen pair that forms a single molecule signal transduction device. Small electrophiles characteristic of inflammatory environments react with the plasmalogen’s sensitive vinyl ether moiety to create a lipid signal, a lysoglycoglycerolipid that upregulates the inflammatory cytokines TNF-α and IL-6 through a TLR receptor. This provides a molecular mechanism that allows E. lenta to upregulate inflammatory responses in a cell- and antigen-independent fashion. This molecular mechanism is similar to an endogenous signaling system that upregulates RORγt through a triggered mammalian plasmalogen signal, 1–18:0-lysophosphatidylethanolamine.}, archive = {J_JACS}, author = {Yern-Hyerk Shin and Sunghee Bang and Ramnik Xavier and Jon Clardy}, doi = {10.1021/jacs.5c08613}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25180--25183}, shortjournal = {J. Am. Chem. Soc.}, title = {Eggerthella lenta produces a cryptic pro-inflammatory lipid}, volume = {147}, year = {2025}, }
• (2025). Steric control in low-valent mn diamide complexes: Contrasting magnesium and manganese in n2 and benzene activation. JACS, 147(29), 25174--25179. (www)

  @article{ , abstract = {Reduction of Mn II precursors with bulky diamide ligands provided access to a complex with the longest known Mn–Mn bond and to a rare example of N 2 activation at high-spin Mn I centers. While some instructive parallels can thus be drawn to observations made for Mg analogues, the accessibility of filled d orbitals in the respective Mn I intermediates leads to a distinct behavior toward benzene that undergoes an oxidative addition.}, archive = {J_JACS}, author = {Siad Wolff and Matthew J. Evans and Thayalan Rajeshkumar and Dat T. Nguyen and Konstantin B. Krause and Amanda Opis-Basilio and Christian Herwig and Laurent Maron and Cameron Jones and Christian Limberg}, doi = {10.1021/jacs.5c08422}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25174--25179}, shortjournal = {J. Am. Chem. Soc.}, title = {Steric control in low-valent mn diamide complexes: Contrasting magnesium and manganese in n2 and benzene activation}, volume = {147}, year = {2025}, }
• (2025). Sub-nanometer confinement suppresses autoionization of water. JACS, 147(29), 25167--25173. (www)

  @article{ , abstract = {Water confined within nanometer-scale environments plays a central role in functional materials for nanofluidic and membrane-based applications, where acid–base equilibria and proton transport govern essential processes such as ion conduction, energy conversion, and chemical separations. Similar mechanisms are also fundamental to biological systems, including enzyme catalysis and cellular signaling. At sub-nanometer scales, confinement and interfacial interactions dramatically reshape the molecular landscape, challenging conventional assumptions about pH and chemical reactivity. Here, we combine density-corrected density functional theory with machine-learned interatomic potentials to investigate the autoionization of water confined to quasi-two-dimensional monolayers within sub-nanometer slit pores. We find that extreme confinement markedly suppresses water autoionization, raising the effective p K w by more than two units. This suppression originates from hydroxide ion destabilization at interfaces, driven by restricted hydrogen bonding, hindered molecular reorientation, and a breakdown of Grotthuss proton transport caused by topological frustration in the hydrogen-bond network. These findings offer a molecular-level understanding of how confinement modulates fundamental aqueous chemistry and establish guiding principles for tuning aqueous phase reactivity in nanoscale environments.}, archive = {J_JACS}, author = {Saswata Dasgupta and Suman Saha and Francesco Paesani}, doi = {10.1021/jacs.5c08273}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25167--25173}, shortjournal = {J. Am. Chem. Soc.}, title = {Sub-nanometer confinement suppresses autoionization of water}, volume = {147}, year = {2025}, }
• (2025). Multiple Host–Guest interactions in Metal–Organic frameworks constructed by inverted calix[4]arenes. JACS, 147(29), 25162--25166. (www)

  @article{ , abstract = {Calixarenes are versatile macrocyclic compounds featuring unique basket-like cavities that are capable of encapsulating guest molecules selectively. Yet, their application potentials as the building blocks for supramolecular assemblies have not been thoroughly explored. In this work, a carboxyl-modified azocalix[4]arene (CAC4A) is selected as the organic ligand to construct metal–organic frameworks (MOFs), an emerging class of porous materials based on coordination units. Herein, three calixarene-based MOFs are developed based on varied metals, including La 3+ , Ca 2+ , and Mn 2+ . Benefiting from the low symmetry of the calixarene ligands, the three MOFs feature abundant structural diversity, wherein two inverted calixarenes are bridged by metal nodes to produce nanocavities. These cavities, or pores, are interconnected to generate one-dimensional (1D) chains or two-dimensional (2D) sheets that are further assembled into porous frameworks. Such a bottom-up assembly not only presents an approach to constructing hierarchical porous structures, but also gives rise to enhanced adsorption abilities based on host–guest interactions. Single crystal X-ray diffraction can also be employed to determine the interactions between the guest molecule, like iodine, and the frameworks directly.}, archive = {J_JACS}, author = {Zongsu Han and Kun-Yu Wang and Yifan Guo and Ze-Han Wang and Rong-Ran Liang and Yihao Yang and Jiatong Huo and Dong-Sheng Guo and Hong-Cai Zhou}, doi = {10.1021/jacs.5c08164}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25162--25166}, shortjournal = {J. Am. Chem. Soc.}, title = {Multiple Host–Guest interactions in Metal–Organic frameworks constructed by inverted calix[4]arenes}, volume = {147}, year = {2025}, }
• (2025). Taming enolate regioselectivity: Catalyst-guided divergent synthesis of atropisomeric pyridones via switchable C- and O-acylation. JACS, 147(29), 25153--25161. (www)

  @article{ , abstract = {Catalyst-guided divergent synthesis marks a paradigm shift in organic synthesis, offering transformative potential to access structurally diverse molecules. By leveraging symmetric enolates as programmable synthons, we established a catalyst-guided atroposelective C - and O -acylation for the switchable divergent synthesis of N–C and N–N axially chiral pyridones. The outstanding enantio- and regiocontrol ( C - vs O -acylation) originated from the development of new chiral 4-pyrrolidinopyridine (PPY) derivatives and PPY- N -oxides as orthogonal acyl-transfer catalysts. These catalysts exhibited complementary reactivity and selectively delivered C - or O -acylated products. Notably, their exceptional atroposelective control capabilities enabled access to both C–N and N–N atropisomers, expanding the scope of accessible chiral architectures of conventional catalysts in this class. The synthetic applications were further displayed by the postfunctionalization, underscoring the methodology’s potential in accessing structurally complex chiral frameworks.}, archive = {J_JACS}, author = {Jun Qin and Jimeng Ge and Hongyu Qu and Xiaoping Xue and Zhenhua Gu and Ruixian Deng}, doi = {10.1021/jacs.5c07688}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25153--25161}, shortjournal = {J. Am. Chem. Soc.}, title = {Taming enolate regioselectivity: Catalyst-guided divergent synthesis of atropisomeric pyridones via switchable C- and O-acylation}, volume = {147}, year = {2025}, }
• (2025). Kinetic resolution of heterocyclic lactams by a photocatalytic cobalt-catalyzed dehydrogenation. JACS, 147(29), 25148--25152. (www)

  @article{ , abstract = {Chiral heterocyclic lactams have been kinetically resolved in a photochemical process that involves selective hydrogen abstraction by a chiral benzophenone catalyst. Recognition of one enantiomer is achieved by a two-point hydrogen bonding interaction that directs the reactive carbonyl group of the photocatalyst to the C–H bond at the stereogenic center within the lactam. The generated radical is converted to an oxidized product in a cobaloxime-catalyzed dehydrogenation reaction. The unreactive enantiomer is retained and isolated in enantiomerically enriched form (21 examples, 31–56% yield, 90–99% ee).}, archive = {J_JACS}, author = {Chao Zhou and Thorsten Bach}, doi = {10.1021/jacs.5c07524}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25148--25152}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetic resolution of heterocyclic lactams by a photocatalytic cobalt-catalyzed dehydrogenation}, volume = {147}, year = {2025}, }
• (2025). A visible-light-responsive octahedral cage for efficient and selective cross-[2 + 2] cycloadditions. JACS, 147(29), 25142--25147. (www)

  @article{ , abstract = {Host–guest complexation enhances or even alters photoreaction selectivity by preorganizing substrates within the host’s confined cavities. Since most previous hosts exhibited no visible-light absorption, at least one of the reactants needed to be an aromatic compound with UV-light absorption. Here, we developed a visible-light-responsive M 6 L 4 octahedral cage that retains the encapsulation ability of standard M 6 L 4 cages by simply replacing the photoinert metal unit at every vertex with a photoactive cyclometalated Pt(II) unit. This design enabled efficient visible-light-induced cross-[2 + 2] cycloadditions of inert substrates, demonstrating perfect stereo- and site-selectivity via confinement. The selective cross-[2 + 2] cycloaddition was achieved even catalytically, which was impossible with previous M 6 L 4 cages.}, archive = {J_JACS}, author = {Rikuya Tanaka and Hiroki Takezawa and Makoto Fujita}, doi = {10.1021/jacs.5c07355}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25142--25147}, shortjournal = {J. Am. Chem. Soc.}, title = {A visible-light-responsive octahedral cage for efficient and selective cross-[2 + 2] cycloadditions}, volume = {147}, year = {2025}, }
• (2025). Ketosynthase domain catalyzes β-lactonization in the biosynthesis of the HMG-CoA synthase inhibitor hymeglusin. JACS, 147(29), 25136--25141. (www)

  @article{ , abstract = {Hymeglusin ( 1 ) is a fungal polyketide consisting of a β-lactone ring with a unique (3 R ,4 R ) configuration. 1 is a potent 3-hydroxy-3-methylglutaryl-CoA (HMG-CoA) synthase inhibitor. Because it circumvents drug resistance in methicillin-resistant Staphylococcus aureus (MRSA), combination therapy using 1 would be a promising strategy for the treatment of infectious diseases caused by MRSA. Despite its pharmaceutical importance, the biosynthesis of 1 , with respect to the formation of the characteristic β-lactone ring that is essential for its activity, had not been elucidated to date. During our genome mining of fungal highly reducing polyketide synthases (HR-PKSs), we identified a biosynthetic gene cluster for 1 in Nigrospora fungi. Heterologous expression and biochemical analysis of recombinant HR-PKS revealed that the ketosynthase (KS) domain of HR-PKS catalyzes the β-lactonization of the mature polyketide chain in the termination step. This study unveiled the previously unknown programming of HR-PKS catalysis and added one unique example to the noncanonical function of KS domains in type I PKS systems.}, archive = {J_JACS}, author = {Mizuki Hirokawa and Taro Ozaki and Kento Tsukada and Akihiro Sugawara and Yohei Morishita and Teigo Asai}, doi = {10.1021/jacs.5c07060}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25136--25141}, shortjournal = {J. Am. Chem. Soc.}, title = {Ketosynthase domain catalyzes β-lactonization in the biosynthesis of the HMG-CoA synthase inhibitor hymeglusin}, volume = {147}, year = {2025}, }
• (2025). MnBi2 is a permanent magnet. JACS, 147(29), 25129--25135. (www)

  @article{ , abstract = {Creating and understanding new permanent magnets requires an understanding of the impact of orbital angular momentum on coercivity. A simple approach to interrogating this relationship is by incorporating high Z (where Z is the atomic number) elements into binary compounds to maximize spin–orbit coupling. The Mn–Bi system is an appealing platform for these studies since it contains MnBi, a permanent magnet with a large coercive field. We previously identified a new compound in the Mn–Bi system, MnBi 2 , but could not elucidate its magnetic properties ex situ due to its decomposition upon decompression. Here, we harnessed synchrotron X-ray magnetic circular dichroism to probe the magnetism of MnBi 2 at high pressure within a diamond anvil cell. Our results indicate that MnBi 2 exhibits ferromagnetic hysteresis at both 10 K and room temperature. Through calculations and experiments, we show that orbital angular momentum and spin–orbit coupling from Bi impart magnetic anisotropy in MnBi 2 . Comparing the Mn–Bi family of compounds, we consider the Bi p and d orbitals to explain the differences in magnetic behavior within the system. Collectively, these results validate leveraging high- Z elements in the synthesis of new hard permanent magnets.}, archive = {J_JACS}, author = {Catherine K. Badding and Eric A. Riesel and Ryan A. Murphy and Danilo Puggioni and Dmitry Popov and Gilberto Fabbris and Daniel Haskel and James M. Rondinelli and Alison B. Altman and Danna E. Freedman}, doi = {10.1021/jacs.5c06874}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25129--25135}, shortjournal = {J. Am. Chem. Soc.}, title = {MnBi2 is a permanent magnet}, volume = {147}, year = {2025}, }
• (2025). (Hetero)anilines from dinitrogen via nucleophilic aromatic substitution at tungsten nitrido complexes. JACS, 147(29), 25123--25128. (www)

  @article{ , abstract = {A protocol for the arylation of both N atoms in dinitrogen is presented. This protocol relies on the use of tungsten pincer complexes to split N 2 and generate tungsten nitrides, which were shown to undergo nucleophilic aromatic substitution (S N Ar) reactions with electron-deficient aryl chlorides. Starting from ( 15 N) 2 , this two-step process was exploited for the preparation of different 15 N-labeled aryl amines.}, archive = {J_JACS}, author = {Lukas Eberle and Joachim Ballmann}, doi = {10.1021/jacs.5c06407}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25123--25128}, shortjournal = {J. Am. Chem. Soc.}, title = {(Hetero)anilines from dinitrogen via nucleophilic aromatic substitution at tungsten nitrido complexes}, volume = {147}, year = {2025}, }
• (2025). Structure and mechanism of the azomycin biosynthetic enzyme RohQ that catalyzes a spontaneous cyclodehydration. JACS, 147(29), 25117--25122. (www)

  @article{ , abstract = {RohQ from the azomycin biosynthetic pathway catalyzes a spontaneous cyclodehydration to form 2-aminoimidazole. Here we report the structure and mechanism of RohQ and use a serendipitously bound imidazole to pinpoint active site residues. We propose that catalysis occurs at the dimeric interface using two key aspartic acid residues for proton transfer steps to accelerate 3 × 10 4 -fold intramolecular cyclization of a guanidino group and aldehyde, releasing water. Our work expands our understanding of de novo emerged enzymes and provides the first structural and mechanistic view of a yet-unexplored protein family.}, archive = {J_JACS}, author = {Zi-Wang Wei and Phillip Daniel-Ivad and Li Zhang and Katherine S. Ryan}, doi = {10.1021/jacs.5c04341}, journal = {Journal of the American Chemical Society}, month = {7}, number = {29}, pages = {25117--25122}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure and mechanism of the azomycin biosynthetic enzyme RohQ that catalyzes a spontaneous cyclodehydration}, volume = {147}, year = {2025}, }
• (2025). Correction to “Trilocked photodynamic senolytic inducer potentiating immunogenic senescent cell removal for liver fibrosis resolution”. JACS, 147(28), 25115--25116. (www)

  @article{ , archive = {J_JACS}, author = {Pei Lu and Huihui Zhou and Xiaoxiao Xu and Ying Long and Jian-Hui Jiang and Fenglin Wang}, doi = {10.1021/jacs.5c08349}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25115--25116}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Trilocked photodynamic senolytic inducer potentiating immunogenic senescent cell removal for liver fibrosis resolution”}, volume = {147}, year = {2025}, }
• (2025). A superatomic {Ag8}6+ cluster induced by asymmetric mixed-addendum polyoxometalate. JACS, 147(28), 25107--25114. (www)

  @article{ , abstract = {Polyoxometalate (POM)-encapsulated Ag nanoclusters have attracted increasing research interest due to their intriguing structural diversities and synergistic catalytic properties; however, the types of POM ligands are limited to the multidentate lacunary or ring-shaped POMs. Herein, we develop an asymmetric POM-induced synthetic strategy to synthesize a superatomic {Ag 8 } 6+ cluster encapsulated by six redox-active mixed-addendum P 2 W 15 Nb 3 ligands, (C 16 H 36 N) 6 Na 4 H 24 [Na 2 Ag 8 (P 2 W 15 Nb 3 O 61 ) 6 ]·36CH 3 CN ( {Ag 8 @(P 2 W 15 Nb 3 ) 6 } ). The oriented aggregation of Ag + ions is attributed to the unevenly distributed electron density over the asymmetric mixed-addendum P 2 W 15 Nb 3 ligands. The resulting {Ag 8 @(P 2 W 15 Nb 3 ) 6 } cluster exhibits interesting photothermal and photocatalytic performance due to the redox activity of P 2 W 15 Nb 3 ligands. This work presents a new research avenue for the construction of Ag nanoclusters induced by asymmetric all-inorganic POM ligands and will stimulate the structural exploration and catalytic applications of atomically precise metal nanoclusters.}, archive = {J_JACS}, author = {Zichen Zhao and Jianyu Wei and Zhong-Ling Lang and Manzhou Chi and Xiaoyi Liu and Jiaxin Yang and Guo-Yu Yang and Hongjin Lv}, doi = {10.1021/jacs.5c09440}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25107--25114}, shortjournal = {J. Am. Chem. Soc.}, title = {A superatomic {Ag8}6+ cluster induced by asymmetric mixed-addendum polyoxometalate}, volume = {147}, year = {2025}, }
• (2025). Binding-enhanced organic semiconductor-bacteria hybrids for efficient visible light-driven CO2 conversion to bioplastics. JACS, 147(28), 25097--25106. (www)

  @article{ , abstract = {Photosynthetic semiconductor–biohybrids, which integrate excellent light-harvesting capabilities of semiconductors and high activity and selectivity of biocatalysts, have proven a promising strategy to enable solar–driven CO 2 conversion to chemicals. However, broadening the light–harvesting scope and strengthening interfacial contact, which facilitates enhancing solar–to–chemical conversion efficiencies, remain challenging. Herein, we report a series of organic semiconductors (OSCs) to hybridize with nonphotosynthetic bacteria, Ralstonia eutropha , realizing efficient CO 2 photoreduction to poly−β–hydroxybutyrate (PHB). The OSCs with extended conjugated backbones absorb light from the entire visible region, while their side chains containing zwitterionic choline phosphate form quadrupoles with phosphatidyl choline on the cell membrane, fortifying interfacial interactions between OSCs and bacteria. Both aspects facilitate the utilization of more photon energy and improve the transmembrane transfer of photogenerated electrons into the cells, strengthening the metabolic pathways in bacteria. Accordingly, an optimal OSC–biohybrid driven by visible light offers continuous production of PHB from CO 2 for several days, with a maximum yield of 107.3 mg L –1 OD 600 –1 and a CO 2 –to–PHB quantum efficiency of 1.14%. Our strategy not only endows nonphotosynthetic bacteria with photosynthetic capacity but also achieves matchable photoautotrophic PHB output with that from heterotrophic fermentation.}, archive = {J_JACS}, author = {Yulong Zhang and Xuan Liu and Yu Zhang and Yajing Zhang and Wenhui Sun and Wangyin Wang and Xupeng Cao and Xin Guo and Can Li}, doi = {10.1021/jacs.5c09410}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25097--25106}, shortjournal = {J. Am. Chem. Soc.}, title = {Binding-enhanced organic semiconductor-bacteria hybrids for efficient visible light-driven CO2 conversion to bioplastics}, volume = {147}, year = {2025}, }
• (2025). Conformational selection mechanism of rhomboid-catalyzed intramembrane proteolysis revealed by solid-state NMR. JACS, 147(28), 25088--25096. (www)

  @article{ , abstract = {Intramembrane rhomboid proteases catalyze the hydrolysis of peptide bonds within membrane-embedded substrates, and play a pivotal role in the physiological processes of both prokaryotic and eukaryotic cells. Although multiple structures of rhomboid proteases have been solved, a comprehensive understanding of their catalytic mechanism remains elusive due to the absence of native transmembrane substrates. Here, we investigate the conformational characteristics and dynamic behavior of Ps TatA, a native rhomboid protease substrate from Providencia stuartii , in lipid bilayers by solid-state nuclear magnetic resonance (ssNMR). Secondary chemical shifts indicate an extended N-terminus of Ps TatA within the lipid bilayer, contradicting the prior assumption of an α-helical conformation. Moreover, we observed multiple N-terminus conformations that are susceptible to modulation by lipid components and the dynamics of the substrate are influenced by the thickness of the membrane. The introduction of rhomboid protease did not induce a direct alteration in the structural configuration of the substrate but instead selectively stabilized a particular conformation by modulating the local membrane environment. This insight sheds new light on the intricate interplay between rhomboid proteases and their substrates within the lipid environment.}, archive = {J_JACS}, author = {Shuaifei Hu and Juan Li and Jin Zhang and Chaowei Shi}, doi = {10.1021/jacs.5c09134}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25088--25096}, shortjournal = {J. Am. Chem. Soc.}, title = {Conformational selection mechanism of rhomboid-catalyzed intramembrane proteolysis revealed by solid-state NMR}, volume = {147}, year = {2025}, }
• (2025). Self-propulsion of biomimetic nanomotors promotes diffusion and convection transport for enhanced radiotherapy in solid glioblastoma. JACS, 147(28), 25072--25087. (www)

  @article{ , abstract = {As a principal adjuvant therapy for glioblastoma (GBM), radiotherapy (RT) is instrumental in extending patient survival. Radiosensitizers could enhance the cytotoxic effects of radiation on tumor cells. However, their accumulation and penetration are significantly hindered by the blood–brain barrier (BBB) and weak convection and diffusion due to elevated interstitial pressure and the dense extracellular matrix within GBM, which reduces the effectiveness of RT. To maximize the radiosensitizing efficiency, it is imperative to develop a delivery system capable of crossing the BBB, specifically targeting GBM, and penetrating the center of the GBM. We propose utilizing cell membrane camouflage to achieve BBB crossing and tumor targeting and the self-propulsion ability of nanomotors to promote diffusion and overcome convection within GBM, thereby facilitating deep tumor penetration. We first clarify that the hollow structure with an opening exhibits a stronger propulsive force than the Janus structure under identical conditions. Subsequently, we developed a facile method to prepare nanomotors featuring a hollow structure with an opening. By camouflaging the nanomotors with hybrid cell membranes with BBB-crossing and tumor-targeting capabilities, we create biomimetic nanomotors (Bio-motors). Results show our Bio-motors possess enhanced diffusion capacity and achieve deep penetration under reverse pressure gradients, which also effectively traverse the BBB, target GBM, and penetrate deeply within the tumor. Notably, the Bio-motors enhance radiosensitivity and inhibit GBM growth, thereby prolonging the median survival of GBM-bearing mice. Our Bio-motors will significantly boost RT efficacy for GBM patients and could be readily adapted into versatile carriers for tumor therapy due to the modular design.}, archive = {J_JACS}, author = {Heping Wang and Dingxuan Lan and Hongmei Cao and Weitao Zhao and Han Gui and Ziwei Han and Yumin Zhang and Xue Xue and Jianfeng Liu}, doi = {10.1021/jacs.5c09121}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25072--25087}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-propulsion of biomimetic nanomotors promotes diffusion and convection transport for enhanced radiotherapy in solid glioblastoma}, volume = {147}, year = {2025}, }
• (2025). Platinum-catalyzed C–F bond reconstruction via the multi-unit insertion for remote fluorine migration. JACS, 147(28), 25061--25071. (www)

  @article{ , abstract = {Precise control over fluorine positioning in organic molecules remains a long-standing challenge in synthetic chemistry. Here, we report a conceptually distinct strategy for remote C–F bond reconstruction via platinum-catalyzed multiunit insertion. This transformation exploits allylic gem -difluorides as modular fluorinated synthons and strained N-heterocycles as directional coupling partners, enabling the intramolecular delivery of fluorine over distances spanning up to 19 bonds. Central to this process is a Pt–F shuttle mechanism, wherein successive nucleophilic insertions and ligand exchanges guide fluoride relocation with high regioselectivity and atom economy. Systematic studies reveal that the extent of fluorine migration is governed by substrate stoichiometry, while mechanistic investigations confirm that selective C–F bond formation is mediated by coordinated Pt–F species, rather than by free fluoride anions. This work establishes a programmable platform for long-range fluorine transfer in catalysis, offering a blueprint for remote editing of C–F bonds with broad implications in molecular design, drug discovery, and fluorine-based materials.}, archive = {J_JACS}, author = {Yi-Bin Wang and Ming Chen}, doi = {10.1021/jacs.5c08669}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25061--25071}, shortjournal = {J. Am. Chem. Soc.}, title = {Platinum-catalyzed C–F bond reconstruction via the multi-unit insertion for remote fluorine migration}, volume = {147}, year = {2025}, }
• (2025). Homolytic H2O dissociation into hydroxyl and hydrogen radicals on sulfur-deficient greigite for efficient hydration reactions. JACS, 147(28), 25052--25060. (www)

  @article{ , abstract = {Homolytic dissociation of ubiquitous water (H 2 O) into radical species is pivotal in driving reactions across chemical, biological, geoscientific, and environmental domains; yet, it faces substantial challenges in cleaving the robust O–H bond and preventing radical recombination. Herein, we demonstrate that greigite with sulfur vacancies (SVs) can ambiently dissociate H 2 O into reactive hydroxyl (•OH) and hydrogen (•H) radicals in a stoichiometric manner. This process is facilitated by the inverse-spinel structure of Fe 3 S 4 , where the antiparallel arrangement of high-spin Fe atoms localizes electrons at SVs, enabling barrierless cleavage of the O–H bond to yield •OH and •H. Concurrently, adjacent S atoms with pronounced Lewis basicity effectively stabilize the generated •H, promoting its spatial separation from the •OH confined on SVs. This interesting water homolysis scheme, characterized by synchronous •OH and •H generation, triggers efficient and selective hydrations of styrene and its derivatives to high-value-added aldehydes and energy-rich methane via a radical pathway.}, archive = {J_JACS}, author = {Cancan Ling and Hao Li and Yaling Li and Long Zhao and Sicong Ma and Yi Liu and Meiqi Li and Jincai Zhao and Lizhi Zhang}, doi = {10.1021/jacs.5c08801}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25052--25060}, shortjournal = {J. Am. Chem. Soc.}, title = {Homolytic H2O dissociation into hydroxyl and hydrogen radicals on sulfur-deficient greigite for efficient hydration reactions}, volume = {147}, year = {2025}, }
• (2025). Too fast for spin flipping: Absence of chirality-induced spin selectivity in coherent electron transport through single-molecule junctions. JACS, 147(28), 25043--25051. (www)

  @article{ , abstract = {Chirality-induced spin selectivity (CISS), which refers to the ability of chiral molecules to preferentially select spins during electron transfer, has attracted great attention during the past two decades. However, the theoretical and experimental understanding of the CISS effect remains preliminary. In this study, we demonstrate that there is no distinguishable CISS effect in the case of coherent electron transport through single chiral molecular junctions for a set of four molecule studied here. Our conclusion is based on statistical evaluations of thousands of single-molecule junctions across four different molecules with different origins of chirality measured by the scanning tunneling microscope-based break-junction technique. The experimental results for all molecules show no dependence on external magnetic field or chirality in both conductance and current–voltage measurements. In addition, ab initio Hartree-Fork calculations combined with the nonequilibrium Green’s function method reveal that the spin–orbit coupling within chiral junctions bound to a few gold atoms is generally too weak to induce detectable spin polarizations from spin flipping or spin filtering during the ultrafast electron-transport time scale. The absence of an observable CISS effect in the coherent electron-transport regime suggests that the effect may only be found in other electron-transfer regimes and requires further experimental and theoretical efforts to achieve a comprehensive understanding.}, archive = {J_JACS}, author = {Liang Li and Wanzhuo Shi and Ankit Mahajan and Junxiang Zhang and Marta Gómez-Gómez and Jorge Labella and Shayan Louie and Tomás Torres and Stephen Barlow and Seth R. Marder and David R. Reichman and Latha Venkataraman}, doi = {10.1021/jacs.5c08517}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25043--25051}, shortjournal = {J. Am. Chem. Soc.}, title = {Too fast for spin flipping: Absence of chirality-induced spin selectivity in coherent electron transport through single-molecule junctions}, volume = {147}, year = {2025}, }
• (2025). Reversible thermosalience as a result of cooperative bond and molecular rotations in a multicomponent hydrogen-bonded solid. JACS, 147(28), 25035--25042. (www)

  @article{ , abstract = {Thermosalient materials, which are organic or metal–organic analogs of martensitic solids, exhibit rapid mechanical responses triggered by a change in temperature. Although methods have been developed to classify thermosalient solids based on their molecular and supramolecular structures, characterizing structural changes before and after salient events is challenging due to the violent response of the crystalline material. Here, we describe a multicomponent organic solid, wherein the components self-assemble into a one-dimensional hydrogen-bonded polymer, and reversible thermosalient behavior was discovered. Thermosalient solids typically undergo overall small structural changes; surprisingly, detailed structural analysis before and after the transition demonstrates cooperative bond and molecular rotations lead to significant sliding between layers, which is preceded by anisotropic expansion of the cell. Layer sliding affords the formation of significant π-stacking interactions, and calculations show the two phases are similar in energy. This work provides direct insight into structural changes during salient events, aids in understanding stimuli-responsive molecular solids, and discusses supramolecular interactions as stabilizing yet flexible motifs that can enable dynamic structural properties.}, archive = {J_JACS}, author = {Gary C. George, III and Jesus Daniel Loya and Delbert S. Botes and Kristin M. Hutchins}, doi = {10.1021/jacs.5c08534}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25035--25042}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible thermosalience as a result of cooperative bond and molecular rotations in a multicomponent hydrogen-bonded solid}, volume = {147}, year = {2025}, }
• (2025). Unraveling pathway complexity in the supramolecular polymerization of Z-shaped perylenediimides: From kinetic H-aggregates to thermodynamic null supramolecular polymers. JACS, 147(28), 25024--25034. (www)

  @article{ , abstract = {This work reports the synthesis of Z-shaped PDI (Z-PDI) 1 and explores its self-assembly behavior. The lateral trialkoxybenzamide moieties in compound 1 promote the formation of metastable monomeric units ( M *) through intramolecular hydrogen bonds, which undergo kinetically controlled supramolecular polymerization. This process exhibits pathway complexity, yielding H -type aggregates ( AggI H ) under kinetic control and, remarkably, null aggregates ( AggII n ) under thermodynamic control. The conversion follows a competitive pathway, in which both aggregated states compete for the free monomeric species. A combination of experimental data and theoretical calculations reveals that the formation of AggI H is governed by the intermolecular hydrogen bonding between amide groups and the π-stacking of the aromatic cores. The thermodynamically favored null aggregate AggII n also arises from the same noncovalent interactions but its unique nature stems from a balance between Coulombic and charge-transfer interactions─similar in magnitude yet opposite in sign, resulting in an optical absorption profile nearly identical to that of the monomer. The living supramolecular polymerization of Z-shaped PDI 1 enables the transition from kinetically trapped to thermodynamically stable aggregates. These findings highlight the critical role of the molecular design in achieving null aggregation and pathway complexity, while emphasizing the importance of π-overlap, intermolecular distance, and chromophore orientation in determining the nature of the resulting supramolecular assemblies.}, archive = {J_JACS}, author = {Alfonso J. Schwalb and Cristina Naranjo and Alberto Fernández-Alarcón and Fátima García and Enrique Ortí and Juan Aragó and Luis Sánchez}, doi = {10.1021/jacs.5c08436}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25024--25034}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling pathway complexity in the supramolecular polymerization of Z-shaped perylenediimides: From kinetic H-aggregates to thermodynamic null supramolecular polymers}, volume = {147}, year = {2025}, }
• (2025). Room temperature ring opening of benzene by four-electron reduction and carbonylation. JACS, 147(28), 25017--25023. (www)

  @article{ , abstract = {Cleaving a benzene ring under mild conditions requires disrupting its aromaticity, which is a significant challenge in modern chemistry. Although the generation of cyclic products from cleaving benzene has been reported in a few cases, the formation of acyclic products remains exceedingly rare. Inspired by the transition metal-mediated cleavage of inert bonds through multielectron reduction and functionalization, we have discovered an unprecedented ring-opening protocol for benzene and toluene. This is achieved by the reactions of their four-electron-reduced scandium arene complexes with metal hexacarbonyls M(CO) 6 (M = Cr, Mo, and W), resulting in the formation of linear hexadiene products. Further mechanistic studies indicate that the transformation involves the dearomatization of benzene into a dianionic 1,3-cyclohexadiene moiety, followed by the cleavage of the carbon–carbon bond to form the linear hexadiene unit. This work demonstrates a new strategy for the ring opening of benzene through a multielectron-reduction/functionalization approach.}, archive = {J_JACS}, author = {Leiyang Zhang and Ziang Jiang and Cuijuan Zhang and Kehang Cheng and Songyang Li and Yueze Gao and Xiaotai Wang and Jiaxiang Chu}, doi = {10.1021/jacs.5c08414}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25017--25023}, shortjournal = {J. Am. Chem. Soc.}, title = {Room temperature ring opening of benzene by four-electron reduction and carbonylation}, volume = {147}, year = {2025}, }
• (2025). Delivery of peptide-LYTAC via polyporus polysaccharide microneedles for targeted CD47 degradation and enhanced tumor immunotherapy. JACS, 147(28), 25004--25016. (www)

  @article{ , abstract = {Targeting immune checkpoints, such as CD47, holds promise for overcoming immune evasion in cancer, but current therapies face challenges related to toxicity and limited efficacy. Here, we develop a novel dissolvable microneedle (MN) platform that integrates a CD47-targeting peptide-based LYTAC (RS17-M6P 3 ) and polyporus polysaccharide (PPS) to simultaneously induce immune checkpoint degradation and reprogram the immunosuppressive tumor-associated macrophage microenvironment. The RS17-M6P 3 peptide is designed for efficient CD47 degradation in vitro and in vivo via the lysosomal pathway without significant toxic effects on red blood cells. PPS, a natural immunomodulator, enhances macrophage polarization from an M2 (immunosuppressive) to an M1 (pro-inflammatory) phenotype, further boosting macrophage-mediated phagocytosis of tumor cells. When incorporated into a dissolvable MN platform, RS17-M6P 3 and PPS work synergistically to augment antitumor immunity. In both melanoma and breast cancer mouse models, PPS/RS17-M6P 3 -loaded microneedles effectively suppressed tumor growth, accompanied by enhanced immune activation and improved antitumor efficacy. This innovative MN-based delivery system provides a safer and noninvasive strategy for cancer immunotherapy by combining immune checkpoint degradation with immune modulation, laying the groundwork for the development of peptide-based LYTACs and natural polysaccharides as potent cancer therapies.}, archive = {J_JACS}, author = {Jiayi Lin and Xiaokun Zhang and Aoyu Cheng and Maomao Ren and Xiaopan Yao and Xin Sun and Rui Liang and Shengxin Lu and Long Gao and Yajie Kan and Bei Wang and Ye Wu and Hongzhuan Chen and Weidong Zhang and Xin Luan}, doi = {10.1021/jacs.5c08368}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {25004--25016}, shortjournal = {J. Am. Chem. Soc.}, title = {Delivery of peptide-LYTAC via polyporus polysaccharide microneedles for targeted CD47 degradation and enhanced tumor immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Multireference theory of scanning tunneling spectroscopy beyond one-electron molecular orbitals: Can we image molecular orbitals?. JACS, 147(28), 24993--25003. (www)

  @article{ , abstract = {Recent progress in on-surface chemistry has enabled the synthesis of novel polyradical molecules with interesting electronic structure, which are hardly available in solution chemistry. Moreover, the possibility to characterize their electronic structure with scanning tunneling spectroscopy (STS) with the unprecedented spatial resolution opens new possibilities to understand their nontrivial electronic structure. However, experimental STS maps of molecules on surfaces are interpreted using one-electron STM theory within the framework of one-electron molecular orbitals nowadays. Although this standard practice often gives relatively good agreement with experimental data for closed-shell molecules, it fails to address multireference polyradical molecules. In this manuscript, we provide multireference STM theory including out-of-equilibrium processes of removing/adding an electron within the formalism of many-electron wave functions for the neutral and charged states. This can be accomplished by the concept of so-called Dyson orbitals. We will discuss the examples where the concept of Dyson orbitals is mandatory to reproduce experimental STS maps of polyradical molecules. Finally, we critically review the possibility of the experimental verification of the so-called SOMO/HOMO inversion effect using STS maps in polyradical molecules. Namely, we will demonstrate that experimental STS measurements cannot provide any information in case of strongly correlated molecules about the ordering of one-electron molecular orbitals and, therefore neither about the SOMO/HOMO inversion effect.}, archive = {J_JACS}, author = {Manish Kumar and Diego Soler-Polo and Marco Lozano and Enzo Monino and Libor Veis and Pavel Jelinek}, doi = {10.1021/jacs.5c08166}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24993--25003}, shortjournal = {J. Am. Chem. Soc.}, title = {Multireference theory of scanning tunneling spectroscopy beyond one-electron molecular orbitals: Can we image molecular orbitals?}, volume = {147}, year = {2025}, }
• (2025). In situ probing and phosphate-assisted recovery of proton transfer to eliminate H2O2 formation in the oxygen reduction reaction. JACS, 147(28), 24984--24992. (www)

  @article{ , abstract = {Single-atom Fe–N–C is a promising candidate for the oxygen reduction reaction (ORR) at the cathode of proton-exchange membrane fuel cells (PEMFCs). However, under strongly acidic conditions, Fe–N–C suffers from severe oxidation from Fenton reactions caused by trace amounts of dissolved Fe and a 2-electron (2e) ORR product of H 2 O 2 . Herein, we demonstrate a facile and general strategy to nearly eliminate the 2e path of the ORR by introducing phosphates. We discover that bubbling O 2 into water introduces an inherent problem in breaking the hydrogen-bond network and thus hindering proton transfer, resulting in a decreased 4e ORR selectivity. Introducing phosphates is found to recover the hydrogen-bond network to eliminate the 2e path. This strategy works well for Fe–N–C, commercial Pt/C, and even carbon catalysts with a dominant 2e selectivity, resulting in negligible H 2 O 2 production and better stability in both the rotating ring-disk electrode system and flow cell. Our work provides deep insight into the ORR mechanism and a useful strategy to lower the cost and lengthen the lifetime of PEMFCs by using nonnoble metal electrocatalysts as cathodes.}, archive = {J_JACS}, author = {Xiang Li and Chuanqi Cheng and Qingqing Ruan and Ying Gao and Lingjun Kong and Yanmei Shi and Bin Zhang}, doi = {10.1021/jacs.5c07815}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24984--24992}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ probing and phosphate-assisted recovery of proton transfer to eliminate H2O2 formation in the oxygen reduction reaction}, volume = {147}, year = {2025}, }
• (2025). Intrareticular energy transfer in dual-photosensitized Metal–Organic frameworks to enhance photoelectrochemical performance. JACS, 147(28), 24976--24983. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) have garnered significant interest in photoelectrochemistry (PEC). To overcome the intrinsic drawbacks of narrow-wavelength absorption and limited photon utilization, this study used two photosensitizers as hybrid ligands to realize intrareticular energy transfer (IRET) and multiple wavelength light absorption for enhancing photoelectrochemical performance. The dual-photosensitized MOF (dpMOF) contained a [Cd 2 (COO) 4 ] paddlewheel unit as the metal node along with meso-tetra(4-carboxyphenyl)porphine and pyridine-functionalized boron dipyrromethene ligands serving as the energy acceptor and donor units, respectively. Both experimental data and theoretical calculations confirmed the energy transfer. The IRET process possessed an energy transfer efficiency of up to 88.3%, significantly promoting photon utilization and charge separation. Compared with single photosensitized MOFs with similar topologies, IRET in dpMOF resulted in 2.6–6.5 times enhanced photocurrent under multiple wavelength irradiation. Therefore, an advanced PEC biosensing strategy was proposed to demonstrate the PEC application of dpMOF. This work offers new insights into the design of enhanced MOFs and photoconversion applications.}, archive = {J_JACS}, author = {Weisu Kong and Tianrui Liu and Xiaoxiao Meng and Pengfei Dong and Jianping Lei and Huangxian Ju}, doi = {10.1021/jacs.5c07699}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24976--24983}, shortjournal = {J. Am. Chem. Soc.}, title = {Intrareticular energy transfer in dual-photosensitized Metal–Organic frameworks to enhance photoelectrochemical performance}, volume = {147}, year = {2025}, }
• (2025). DNA aptamer-guided glycomimetics for developmental stage-specific glycocalyx engineering to control stem cell differentiation. JACS, 147(28), 24969--24975. (www)

  @article{ , abstract = {Heparan sulfate glycosaminoglycans in the stem cell glycocalyx are crucial in controlling growth factor activity during development. Augmenting the surface of stem cells with synthetic heparan sulfate mimetics with defined compositions and growth factor binding profiles has emerged as a promising strategy to fine-tune cellular signaling responses and differentiation. However, current glycocalyx engineering methods lack specificity for stem cells or require prior genetic manipulation, limiting their applicability in a therapeutic context. Here, we report a heparan sulfate mimetic containing a DNA aptamer with affinity for the membrane-associated pluripotency marker, alkaline phosphatase, that can be selectively targeted to the surface of embryonic stem cells. The glycomimetic-enhanced fibroblast growth factor 2 recruitment to the stem cell surface activated signaling through the mitogen-activated protein kinase pathway and promoted neural differentiation. While the present work targets pluripotent cells specifically, it can be more broadly applicable to progenitor cells at other developmental stages to better control their differentiation and enhance their therapeutic potential.}, archive = {J_JACS}, author = {Sean C. Purcell and Matthew R. Naticchia and Julianna L. Follmar and Nathaniel Marroquin and Hans Jefferson C. Ng and Kamil Godula}, doi = {10.1021/jacs.5c07724}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24969--24975}, shortjournal = {J. Am. Chem. Soc.}, title = {DNA aptamer-guided glycomimetics for developmental stage-specific glycocalyx engineering to control stem cell differentiation}, volume = {147}, year = {2025}, }
• (2025). DACH-ZYC-Phos/Pd-catalyzed enantioselective allenylation of secondary phosphine oxides via ligand relay. JACS, 147(28), 24958--24968. (www)

  @article{ , abstract = {Chiral allenyl phosphine oxides hold significant application value in organic synthesis, serving as efficient catalysts, ligands, and versatile synthons. However, the development of transition metal-catalyzed asymmetric synthesis for these compounds remains unexplored, primarily due to the facile tautomerization of phosphine oxides into trivalent R 1 R 2 P–OH species, which may severely deactivate transition metal catalysts through strong coordination interactions. Herein, a ligand relay strategy has been applied to address this challenge in the Pd-catalyzed enantioselective coupling reactions of propargylic benzoates and secondary phosphine oxides (SPOs) to afford chiral trisubstituted allenyl phosphine oxides with high ee. The ligand relay protocol involves the initial coordination of a palladium catalyst with readily available triphenylphosphine, followed by dynamic ligand exchange with the stretchable chiral ligand DACH-ZYC-Phos-C1 ( L26 ), while PPh 3 does not work as a nonchiral ligand for palladium catalysts in this transformation. Chiral trivalent organophosphines with high ee have been obtained upon the reduction of allenyl phosphine oxides. Mechanistic studies revealed the nature of the kinetic resolution. DFT calculations provide a mechanistic rationale for the observed high enantioselectivity and superior catalytic efficiency, which is governed by the ligand L26 through steric repulsions that selectively destabilize the disfavored oxidative addition transition states.}, archive = {J_JACS}, author = {Zhaoqiang Chen and Huanan Wang and Ping Du and Jiaao Zhao and Xue Zhang and Hui Qian and Junliang Zhang and Shengming Ma}, doi = {10.1021/jacs.5c07465}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24958--24968}, shortjournal = {J. Am. Chem. Soc.}, title = {DACH-ZYC-Phos/Pd-catalyzed enantioselective allenylation of secondary phosphine oxides via ligand relay}, volume = {147}, year = {2025}, }
• (2025). Speed matters: Directed assembly of icosahedral HPV virus-like particles. JACS, 147(28), 24950--24957. (www)

  @article{ , abstract = {Virus-like particles (VLPs) are an important vaccine modality. They self-assemble from virus capsid proteins, and the optimum immunogenic response is expected from VLPs with the same structure as the native virion. However, without the guardrails that guide the assembly of native viruses, off-target structures often result. Here, we show that assembly of HPV (human papillomavirus) VLPs can be redirected to form almost exclusively the native structure, a 21 MDa pseudo- T = 7 icosahedron consisting of 72 pentamers of the L1 capsid protein. HPV VLP assembly products were interrogated using charge detection mass spectrometry and resistive pulse sensing. Under standard conditions, the measured size distributions show that the assembly reaction stalls before most of the particles reach the T = 7 icosahedron, leading to a broad distribution of VLP sizes with some much more abundant than others. The preferred sizes correlate with particularly stable structures found in simulations. These results point to an assembly mechanism where spherical morphology is retained, and error-correction allows particles to fall into kinetic traps provided by particularly stable arrangements of pentamers. By accelerating the assembly reaction, conditions can be found where the 21 MDa T = 7 particles form almost exclusively. We hypothesize that accelerating assembly thwarts error-correction, so that the assembling particles skip over the kinetic traps. The T = 7 particles formed by accelerated assembly are more resistant to dissociation than the heterogeneous particles generated by slower assembly. The generation of high-stability particles that are uniform in size and shape and resemble the morphology of the naturally occurring virion has important benefits.}, archive = {J_JACS}, author = {Shelby M. Klein and Angela Patterson and Kim Young and MacRyan P. Biever and Lohra M. Miller and Adam Zlotnick and Stephen C. Jacobson and Martin F. Jarrold}, doi = {10.1021/jacs.5c07472}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24950--24957}, shortjournal = {J. Am. Chem. Soc.}, title = {Speed matters: Directed assembly of icosahedral HPV virus-like particles}, volume = {147}, year = {2025}, }
• (2025). Thermoresponsive Platinum(II) 2,6-di(pyrid-2-yl)pyrazine complexes with unusual aggregation behavior upon heating. JACS, 147(28), 24941--24949. (www)

  @article{ , abstract = {A series of alkynylplatinum(II) complexes with 2,6-di(pyrid-2-yl)pyrazine ligand has been synthesized and characterized. Interestingly, the complexes have been found to exhibit unprecedented thermochromic behavior with absorption maxima shifting to the longer-wavelength region upon increasing temperature. This phenomenon is significantly different from that in conventional platinum(II) systems, where an elevated temperature typically promotes the dissociation of aggregates and diminishes MMLCT absorptions. Transmission electron microscopy (TEM) and variable-temperature 1 H NMR spectroscopy suggest a thermoresponsive morphological transformation behavior from rods to circular morphologies, driven by the preferential formation of π–π and Pt···Pt interactions over hydrogen bonding interactions upon the disruption of hydrogen bonding at high temperature, as supported by solution-state Fourier transform infrared (FT-IR) spectroscopy together with computational studies. This unusual optical and morphological transformation is rarely observed, as it represents a stark contrast to the deaggregation behavior upon increasing temperature typical of the control and commonly found platinum(II) complexes and organic compounds.}, archive = {J_JACS}, author = {Tracy Ho-Ying Chan and Ziyong Chen and Ming-Yi Leung and Michael Ho-Yeung Chan and Eric Ka-Ho Wong and Wai Kit Tang and Vivian Wing-Wah Yam}, doi = {10.1021/jacs.5c07413}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24941--24949}, shortjournal = {J. Am. Chem. Soc.}, title = {Thermoresponsive Platinum(II) 2,6-di(pyrid-2-yl)pyrazine complexes with unusual aggregation behavior upon heating}, volume = {147}, year = {2025}, }
• (2025). Asymmetric C–C coupling to drive CO conversion to acetate. JACS, 147(28), 24932--24940. (www)

  @article{ , abstract = {Electrochemical reduction of carbon monoxide (CORR) provides pathways for decarbonizing chemical manufacturing by producing high-value multicarbon (C 2+ ) products, though achieving high activity and selectivity toward a single principal C 2+ product remains challenging. Acetate, a critical liquid product, can be metabolized by bacteria to synthesize long-chain carbon compounds. Here, we design a core–shell Cu 2 O/Cu-2-methylimidazole (CuIM) catalyst with dual Cu sites (Cu + and Cu 0 ) during the CORR, which shifts the reaction pathway from symmetric *CO–*CO coupling to asymmetric *CH 2 –*CO coupling, thereby enhancing acetate formation. Ex situ X-ray diffraction spectroscopy (XRD) and in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) analyses reveal that Cu + remains stable and acts as an active site for generating *CH 2 intermediates on the CuIM catalyst. The CuIM electrocatalyst achieves a Faradaic efficiency (FE) of 77.8% for acetate production from CO and a partial current density of 541.3 mA cm –2 . These advancements enable high energy efficiency in membrane electrode assemblies and reduced downstream separation costs for liquid products in solid-state electrolyte systems.}, archive = {J_JACS}, author = {Jia Liu and Ouwen Peng and Derong Chen and Xiaocang Han and Shibo Xi and Qikun Hu and Zixuan Gao and Yijia Yuan and Kun Zhang and Kian Ping Loh}, doi = {10.1021/jacs.5c07400}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24932--24940}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric C–C coupling to drive CO conversion to acetate}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of chartelline c. JACS, 147(28), 24921--24931. (www)

  @article{ , abstract = {Chartellines are cytotoxic marine alkaloids that were isolated in the late 1980s. Their unique, heavily oxidized structures, comprising a spirocyclic β-lactam, a halogenated indolenine, a chloroenamide, and a 2-haloimidazole, have motivated extensive efforts toward their synthesis. However, only a single synthesis of any chartelline has been reported in the nearly 40 years since their isolation. Here, we describe a route to chartelline C ( 3 ) from the macrolactam 21 , an intermediate we employed en route to the related securine and securamine alkaloids. The key challenges in converting macrolactam 21 to chartelline C ( 3 ) involve stereocontrolled construction of the C2–C3 enamide, isomerization of the trans- C10–C11 alkene, formation of the strained spirocyclic β-lactam, and chlorination of the enamide. Each of these challenges was addressed by an unconventional approach. The macrolactam 21 was converted to cis- enamide (2 Z ,10 E )-24 by in situ masking of the C12 ketone, followed by stereoselective acid-catalyzed elimination of the C2 carbinolamide. The C10–C11 trans -alkene was isomerized by a photolytic process; control experiments suggest that this isomerization occurs by energy transfer. The β-lactam was constructed by a solid-state reaction involving the adsorption of the bromoindolenine 26 onto activated basic alumina. Late-stage enamide chlorination, which had been an obstacle in prior approaches, was accomplished by a novel photoredox-mediated halogenation. These latter studies suggest that N -haloanomeric amides and N -haloguanidines may act as halogen atom transfer agents under thermal or photolytic conditions. Finally, we show that chartelline C ( 3 ) reacts with sulfur-based nucleophiles, suggesting that further studies of their biological activity may be warranted.}, archive = {J_JACS}, author = {Noah M. Bartfield and Brandon W. Alexander and Seth B. Herzon}, doi = {10.1021/jacs.5c07148}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24921--24931}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of chartelline c}, volume = {147}, year = {2025}, }
• (2025). Determination of intermolecular distances in dilute solutions of macroions and their direct correlations with self-assembly and macrophase transitions. JACS, 147(28), 24913--24920. (www)

  @article{ , abstract = {This work demonstrates new attempts to determine the intermolecular distances between charged macroionic solutes in their dilute solutions, which regulate the solute’s microphase (self-assembly) and macrophase transitions. Small-angle X-ray scattering (SAXS) and analytical ultracentrifuge (AUC) techniques were applied to determine the intermolecular distances for the 2.42 nm-sized, spherical uranyl peroxide molecular cluster {U 60 } in their self-assembled states in dilute aqueous solution and concentrated phases, respectively. The counterion-mediated attraction among {U 60 } leads to characteristic, inter-{U 60 } distances in solutions, which increase gradually with decreasing the strength of introduced counterions (e.g., lower valency). The gradual increment of inter-{U 60 } distance demonstrates a nice correlation with the macroscopic phase transitions of {U 60 }, from single crystals to concentrated fluids containing rigid 2-D sheets, then to dilute solutions containing a small amount of standalone, floating 2-D sheets of {U 60 }, and finally to dilute solutions containing a limited amount of self-assembled single-layered, spherical blackberry structures of different sizes from the bending of more flexible 2-D sheets.}, archive = {J_JACS}, author = {Kexing Xiao and Yifan Zhou and Jennifer E.S. Szymanowski and Xiaohan Xu and Shirish Chodankar and Peter C. Burns and Tianbo Liu}, doi = {10.1021/jacs.5c07326}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24913--24920}, shortjournal = {J. Am. Chem. Soc.}, title = {Determination of intermolecular distances in dilute solutions of macroions and their direct correlations with self-assembly and macrophase transitions}, volume = {147}, year = {2025}, }
• (2025). Unraveling the potential-dependent selectivity of propylene electrooxidation: The role of electrochemistry-induced reconstruction. JACS, 147(28), 24900--24912. (www)

  @article{ , abstract = {Using Pd or Pt to achieve propylene electrooxidation is a sustainable electrosynthesis technique to produce oxy-organics. However, the origin behind their potential-dependent product selectivity still remains unclear. Herein, we integrate advanced theoretical methods across grand-canonical ensemble density functional theory (DFT) calculations, Pourbaix analyses, and microkinetic modeling to uncover the completed reaction network of propylene electrooxidation for the first time and found that the electrochemistry-induced reconstructed active center under working potentials, including phase conversion and surface coverage, dominates the potential-dependent selectivity of propylene electrooxidation over Pd and Pt catalysts. With increasing working potential (0.7–1.4 V vs reversible hydrogen electrode, RHE), the active center of the Pd electrode gradually reconstructs from partially O-covered (1/3 ML O*) metallic Pd surface to PdO with partial surface hydroxylation (1/2 ML OH*), and the main product is acrolein at first, then changes to acetone and propylene glycol (PG). On the contrary, the electrochemically reconstructed PtO 2 with partial surface hydroxylation (1/2 ML OH*) is the active center of the Pt electrode under the whole operating conditions (1.2–1.6 V RHE ), and the main products are propylene oxide (PO) and acetone. Our results reproduce the potential-dependent performance of Pd and Pt electrodes from available experiments. In short, this work has clarified the long-standing controversies over the key factors determining propylene electrooxidation products on Pd and Pt, and it reveals the key role of surface reconstruction and active site switching under working potential.}, archive = {J_JACS}, author = {Danyang Li and Panpan Sun and Di Zhang and Hao Li and Haoxiang Xu and Dapeng Cao}, doi = {10.1021/jacs.5c07246}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24900--24912}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the potential-dependent selectivity of propylene electrooxidation: The role of electrochemistry-induced reconstruction}, volume = {147}, year = {2025}, }
• (2025). Cathepsin B-ignited nanorocket to blast tumor lysosomes for TLR-fortified lysosomal immunotherapy with dual-switchable Fluorescence/Magnetic resonance imaging. JACS, 147(28), 24884--24899. (www)

  @article{ , abstract = {Immunotherapy based on immunogenic cell death (ICD) holds great promise for cancer treatment, but conventional ICD inducers often suffer from low specificity and limited tumor permeability, restricting their therapeutic effectiveness. Herein, a dual-switchable fluorescence (FL)/magnetic resonance imaging (MRI)-guided nanorocket (UIOQM-IQ) is meticulously designed to blast lysosomes through lysosomal cathepsin B (CTSB)-responsive nanoparticles aggregation, which can trigger lysosomal membrane permeabilization (LMP) to precisely induce ICD. This nanorocket consists of an ultrasmall iron oxide (UIO) nanoparticle conjugated with a CTSB-cleavable peptide, an aggregation-induced emission fluorophore QMTPA, and a Toll-like receptor 7/8 agonist imidazoquinoline (IQ). Upon arrival in the acidic tumor microenvironment, UIOQM-IQ initiates IQ release in a pH-dependent manner. Subsequently, CTSB in tumor lysosomes specifically cleaves the peptide within UIOQM to induce the concurrent release and aggregation of QMTPA and UIO nanoparticles. The aggregation of QMTPA activates a FL “off-on” switch to significantly improve tumor visualization, while UIO aggregates induce a distinct MRI contrast shift from T 1 to T 2 , enabling deep-tissue imaging and real-time monitoring of nanoparticles aggregation. Notably, bulky UIO aggregates within lysosomes lead to elevated osmotic pressure, disrupting lysosomal integrity and eliciting LMP-induced ICD (LICD) through activating the ferroptosis pathway. This LICD strategy markedly enhances tumor immunogenicity and potentiates antigen presentation to realize lysosomal immunotherapy. Meanwhile, IQ synergistically augments immune activation through effective stimulation of antigen-presenting cells. Overall, this CTSB-ignited nanorocket addresses critical limitations of traditional ICD inducers and integrates dual-switchable FL/MR imaging with targeted immune activation, thereby offering a clinically promising strategy for advanced imaging-guided cancer immunotherapy.}, archive = {J_JACS}, author = {Yue Chen and Qinyi Chen and Yuanyuan Ma and Xinge Su and Cheng Zhang and Kejing Li and Meiyi Liang and Minghao Sun and Liyuan Zhang and Xihe Kuang and Teng Zhang and Junjie Zhang and Ran Yan and Shenghong Ju and Wenpei Fan}, doi = {10.1021/jacs.5c07105}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24884--24899}, shortjournal = {J. Am. Chem. Soc.}, title = {Cathepsin B-ignited nanorocket to blast tumor lysosomes for TLR-fortified lysosomal immunotherapy with dual-switchable Fluorescence/Magnetic resonance imaging}, volume = {147}, year = {2025}, }
• (2025). Proline-mediated enhancement in evolvability of disulfide-rich peptides for discovering protein binders. JACS, 147(28), 24870--24883. (www)

  @article{ , abstract = {Disulfide-rich peptides (DRPs), particularly those featuring the inhibitor cystine knot (ICK) motif, represent promising scaffolds for developing next-generation protein modulators and therapeutic agents due to their remarkable stability and specificity. However, their inherent structural integrity and lack of structural plasticity significantly limit their evolvability, creating a fundamental bottleneck in engineering novel functionalities. To address this challenge, we developed a novel proline scanning strategy aimed at enhancing the evolvability of the ICK scaffolds. This strategy leverages the proline-mediated structural decoupling between scaffold and nonscaffold residues in DRPs to promote their evolvability. By strategically incorporating prolines as pre-encoded scaffold residues, we engineered ICK variants with significantly improved foldability and tolerance to sequence variations. This advancement enabled the construction of diverse peptide libraries suitable for screening platforms, including mRNA and phage display. Utilizing this approach, we successfully identified DRPs exhibiting low-nanomolar affinity to clinically important targets, such as TROP2 and 4-1BB. Structural characterization revealed that these evolved DRPs adopted unique three-dimensional structures stabilized by up to four disulfide bonds, demonstrating both high oxidative folding efficiency and enhanced evolvability due to proline incorporation. To evaluate their therapeutic potential, we developed a DRP-based chimeric antigen receptor (CAR) targeting TROP2. The DRP-based CAR T cells exhibited potency comparable to conventional single-chain variable fragment (scFv)-based CAR T cells but with a notably improved safety profile. Overall, our work establishes a robust framework for expanding the functional versatility of DRP scaffolds, facilitating the discovery and development of structurally diverse and functional DRPs for broad applications in therapeutics and drug development.}, archive = {J_JACS}, author = {Hongtan Liu and Lulu Song and Xiaoting Meng and Jinjing Li and Shihui Fan and Huilei Dong and Xiaoran Wang and Maolin Li and Haipeng Yu and Yu-Hsuan Tsai and Yizhen Yin and Chuanliu Wu}, doi = {10.1021/jacs.5c07075}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24870--24883}, shortjournal = {J. Am. Chem. Soc.}, title = {Proline-mediated enhancement in evolvability of disulfide-rich peptides for discovering protein binders}, volume = {147}, year = {2025}, }
• (2025). Formation of sandwich complexes between lanthanides and chlorophylls recovers photosynthetic activity and imparts crop resistance to UV stress via single-nanodose seed treatment. JACS, 147(28), 24857--24869. (www)

  @article{ , abstract = {Lanthanides (Lns) have been used as fertilizers in several countries over the past 50 years, yet their interaction with plant metabolism remains largely unknown, with only a few confirmed biological roles, such as cofactors in specific dehydrogenases found in methylotrophic organisms. This study investigates the interplay between Ln ions and chlorophylls (Chls), showing that throughout the Ln series, Ln-Chls replace Mg 2+ at the center of the pigment structures through the formation of sandwich-like Ln-porphyrin complexes. When applied as seed treatment to four staple crops (i.e., barley, chickpea, corn, and soybean), Lns enhance seedlings’ growth. Mobility of lanthanum from the rhizosphere to plants is favored when the metal is in neutral or weakly charged forms, as studied by changing the salt used (i.e., LaCl 3 , La(NO 3 ) 3 , LaPO 4 , La 2 (CO 3 ) 3 , [LaEDTA(H 2 O) 3 ]K, or [LaDOTA(H 2 O)]K). These results highlight the role of the Casparian strip in modulating the apoplastic movement of Lns in the stele and suggest that plants possess an uptake system with binding strengths comparable to or stronger than La-DOTA complexes. Additionally, when complexed with trehalose in seed treatments, Ln 3+ protected pigments from UV stress, enhancing the resilience of the four staple crops to abiotic stressors.}, archive = {J_JACS}, author = {Giorgio Rizzo and Benedetto Marelli}, doi = {10.1021/jacs.5c07071}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24857--24869}, shortjournal = {J. Am. Chem. Soc.}, title = {Formation of sandwich complexes between lanthanides and chlorophylls recovers photosynthetic activity and imparts crop resistance to UV stress via single-nanodose seed treatment}, volume = {147}, year = {2025}, }
• (2025). Stereodivergent synthesis of perhydrobenz[e]indene terpenoids. JACS, 147(28), 24847--24856. (www)

  @article{ , abstract = {The development of stereodivergent synthetic methods has enormous potential in total synthesis owing to their ability to unify and streamline strategies toward a large collection of natural products. In this article, we describe a stereodivergent Rautenstrauch rearrangement in which a choice of Au- or Pd-based catalyst provided a uniform entry toward all four possible stereoisomers of the 6/6/5 tricyclic core of perhydrobenz[ e ]indene terpenoids. Alongside the development of a general strategy to access the core scaffolds of these unique families of metabolites, computational studies rationalized the observed diastereoselectivity during key cyclizations. Ultimately, these studies led to the total syntheses of several distinctive perhydrobenz[ e ]indene natural products, including N -acetyl-polyveoline, dasyscyphin B, and rhabdastin B.}, archive = {J_JACS}, author = {Cheng Yang and Christopher J. Huck and Yaroslav D. Boyko and Shang Ning and Uroš Vezonik and Alexander S. Shved and Scott E. Denmark and Binh Khanh Mai and David Sarlah}, doi = {10.1021/jacs.5c07068}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24847--24856}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereodivergent synthesis of perhydrobenz[e]indene terpenoids}, volume = {147}, year = {2025}, }
• (2025). Covalent organic framework membranes for enhanced gas dissolution in oxygenation. JACS, 147(28), 24838--24846. (www)

  @article{ , abstract = {Membrane-mediated gas-to-liquid mass transfer is crucial for chemical reactions and biological processes, yet low gas solubility in water limits exchange efficiency. To address this challenge, we leverage periodic, hydrophilic gradient nanochannels in highly oriented covalent organic framework (COF) membranes. These membranes exhibit a significantly higher oxygen dissolution rate than macroporous membranes with greater gas permeability, driven by nanoconfinement effects and increased liquid meniscus curvature, which reduce the hydrogen bond density and lower the oxygen–water binding energy. The engineered COF membrane achieves an unprecedented O 2 transfer rate of 2838 mL m –2 min –1 to blood, 11 times higher than that of the conventional oxygenation membrane, poly(4-methyl-1-pentene), while offering comparable blood compatibility and anticoagulant properties, along with a reduced risk of gas embolism.}, archive = {J_JACS}, author = {Dafei Sheng and Xinlin Li and Shuang Zhao and Chao Sun and Qianli Ma and Xiao Feng and Bo Wang}, doi = {10.1021/jacs.5c06822}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24838--24846}, shortjournal = {J. Am. Chem. Soc.}, title = {Covalent organic framework membranes for enhanced gas dissolution in oxygenation}, volume = {147}, year = {2025}, }
• (2025). Beyond blue: Systematic modulation of electronic structure and redox properties of type 1 copper in azurin. JACS, 147(28), 24825--24837. (www)

  @article{ , abstract = {The reduction potentials of metal ions ( E °′), crucial for optimizing biological processes like electron transfer and catalysis, are finely tuned by interactions between the primary and secondary coordination spheres (PCS, SCS). While previous successes in tuning E °′ in azurin have provided deeper insights into how the SCS influences electronic structure and associated redox properties of “classic” blue copper proteins, our understanding of E °′ tuning in other subclasses of type 1 Cu (T1Cu) proteins, such as green and red copper proteins, remains rudimentary. To address this issue, we report the design of a green copper center in azurin where an equatorial-to-axial shift in a histidine binding interaction leads to reorientation of the Cu-centered redox active molecular orbital and a +100 mV shift in E °′. In contrast to a 22 mV decrease in E °′ when a hydrophobic interaction is introduced in wild-type azurin through the Met13Phe mutation, this same mutation leads to a 65 mV increase in our designed green Cu azurin. More importantly, using a combination of EPR spectroscopy, protein crystallography, and quantum mechanical calculations, we uncover correlations between E °′, d–s orbital mixing, and the angle between S Cys –Cu and N δH46 –Cu bonds, ∠(S Cys –Cu–N δH46 ), allowing rationalization of increases in E °′ of green Cu proteins through an entropically driven T-shape distortion. By providing direct connections between geometry, electronic structure, and functional properties such as E °′, this work opens previously unexplored routes to systematically modulating E °′ through the combination of spatial reorientation of the redox active molecular orbital and varying geometric distortion in the primary coordination sphere.}, archive = {J_JACS}, author = {Casey Van Stappen and Jiaqing Xu and Yiwei Liu and Jacqueline Van Stappen and Wantae Kim and Y. Jessie Zhang and Yi Lu}, doi = {10.1021/jacs.5c07009}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24825--24837}, shortjournal = {J. Am. Chem. Soc.}, title = {Beyond blue: Systematic modulation of electronic structure and redox properties of type 1 copper in azurin}, volume = {147}, year = {2025}, }
• (2025). Versatile cell design for molten fluoride salt spectroscopy: Investigating metal-ion speciation in molten fluoride salts. JACS, 147(28), 24814--24824. (www)

  @article{ , abstract = {Fluoride-based molten salts are widely used in industrial applications including aluminum production, thermal energy storage, optical crystal growth, and advanced nuclear reactor designs. Despite the wide range of uses, fundamental understandings of coordination chemistry and methods for probing molten fluorides are scarce, likely due to the difficulty of probing fluoride melts with spectroscopic techniques. Performing spectroscopic measurements of fluoride-based salts is challenging due to the highly corrosive nature of these salts, which can degrade many common optical materials. In this work, we present a versatile optical cell design that enables spectroscopic measurements of corrosive melts. This innovative cell design overcomes the challenges posed by the corrosive nature of the salts, allowing for an accurate and consistent spectroscopic analysis. This work reports temperature-dependent absorption measurements for Co 2+ , Ni 2+ , and Cr 3+ analytes in LiF-NaF-KF eutectic salt (i.e., FLiNaK), which are common corrosion products originating from structural alloys in molten-fluoride handling. Absorption spectra were used to understand interactions of these analytes with FLiNaK, particularly ligand field coordination. The analysis of absorption spectra was complemented by structural analyses using ab initio molecular dynamics (AIMD) simulations, providing deeper insights into the behavior of the analytes in FLiNaK. Our findings indicate that the analytes studied in this work exist in octahedral or near-octahedral coordination states that remain stable across the temperature range of 500–600 °C. This work not only highlights an applied solution to performing optical spectroscopy in corrosive, high-temperature melts but also provides important fundamental insight on coordination behavior of transition-metal species in molten fluorides.}, archive = {J_JACS}, author = {Garrett S. LeCroy and Linu Malakkal and Michael E. Woods and Qiufeng Yang and Benjamin Beeler and Ruchi Gakhar}, doi = {10.1021/jacs.5c07007}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24814--24824}, shortjournal = {J. Am. Chem. Soc.}, title = {Versatile cell design for molten fluoride salt spectroscopy: Investigating metal-ion speciation in molten fluoride salts}, volume = {147}, year = {2025}, }
• (2025). Structure and biosynthesis of aridomycins reveal a glycosylated prodrug strategy for self-resistance. JACS, 147(28), 24801--24813. (www)

  @article{ , abstract = {Polyketides, nonribosomal peptides, and their hybrids constitute a major class of clinically important antibiotics. To avoid self-toxicity, producing organisms must employ mechanisms of self-resistance. Here, we describe the structures, biosynthesis, and self-resistance strategy of the aridomycins, new linear polyketide antibiotics. Using NMR spectroscopy, whole genome sequencing, and bioinformatics, we determined the absolute configurations of all 28 stereocenters and identified a previously unrecognized acyltransferase specificity motif (GHSQ···FVAH) associated with hydroxymalonyl-ACP incorporation. We also assigned the biosynthetic gene cluster (BGC) for aridomycin, as well as for blasticidin A, a polyketide structurally related to the well-characterized aflastatin A, both of which support the new AT motif assignment. Interestingly, aridomycin A, the glycosylated congener, lacked antimicrobial activity against multidrug-resistant pathogens and the producing Amycolatopsis strains. Its temporal production preceding the aglycone aridomycin B, together with substrate specificity studies of the glycosyltransferase AriGT, indicate that reversible glucosylation acts as a self-resistance mechanism. To our knowledge, this represents the first example of such a strategy outside the macrolide class.}, archive = {J_JACS}, author = {Hong-Bing Liu and Shannon I. Ohlemacher and Robert D. O’Connor and Rahim Rajwani and Jared S. Wood and Gengxiang Zhao and R. Thomas Williamson and Carole A. Bewley}, doi = {10.1021/jacs.5c06894}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24801--24813}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure and biosynthesis of aridomycins reveal a glycosylated prodrug strategy for self-resistance}, volume = {147}, year = {2025}, }
• (2025). Sulfur[n]arenes: Synthesis and solid-state supramolecular dimerization via multiple Sulfur···Sulfur interactions. JACS, 147(28), 24793--24800. (www)

  @article{ , abstract = {Controlling structural dimensionality is key to designing supramolecular assemblies with tunable properties. Herein, we report synthesis of a series of new macrocycles, termed ″sulfur[ n ]arenes″, containing multiple sulfur atoms. They show discrete self-assembly structures by cooperative σ-hole interactions between chemically identical sulfur atoms. Single-crystal X-ray diffraction analysis revealed that sulfur[5]arenes form discrete dimer structures stabilized by multiple S···S interactions. Computational studies suggested that inclusion of alkyl chains stabilizes unidirectional orientation of monomer units, maximizing these interactions. Additionally, macrocyclization significantly enhanced fluorescence quantum yield from corresponding monomer (up to Φ FL = 0.88) by suppressing singlet-to-triplet intersystem crossing and nonradiative decay from the excited state.}, archive = {J_JACS}, author = {Shunsuke Ohtani and Keiichiro Murakami and Kazeto Nakaguchi and Kenichi Kato and Yun Hee Koo and Shu Seki and Tomoki Ogoshi}, doi = {10.1021/jacs.5c06891}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24793--24800}, shortjournal = {J. Am. Chem. Soc.}, title = {Sulfur[n]arenes: Synthesis and solid-state supramolecular dimerization via multiple Sulfur···Sulfur interactions}, volume = {147}, year = {2025}, }
• (2025). Denitrogenative alkylation of K-Ras(G12D) inhibits oncogenic signaling in cancer cells. JACS, 147(28), 24785--24792. (www)

  @article{ , abstract = {Pancreatic ductal adenocarcinoma (PDAC) is the most lethal common cancer. More than 90% of PDAC tumors are caused by KRAS mutations, with the majority expressing the K-Ras(G12D) oncoprotein. Despite extensive drug discovery efforts across academia and industry, there are no approved drugs directly targeting K-Ras(G12D) in a mutant-selective manner. We report a series of α-diazoacetamide compounds that form covalent bonds via denitrogenative alkylation of acquired aspartic acid at the mutation site. The lead molecule allosterically inhibits the mitogen-activated protein kinase pathway downstream of K-Ras and therefore inhibits the growth of KRAS G12D -driven cancer cell lines but not non-G12D mutation cancer cell lines. Our results show that the diazo-carboxy ligation spares not only the unreactive Gly12 residue in the K-Ras wild-type protein but also strong nucleophiles such as the Cys12 residue in K-Ras(G12C). The preference for a weak nucleophile carboxylic acid over canonically stronger nucleophiles provides the basis to expand the covalently targetable proteome to aspartic and glutamic acids.}, archive = {J_JACS}, author = {Qinheng Zheng and Kevan M. Shokat}, doi = {10.1021/jacs.5c06745}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24785--24792}, shortjournal = {J. Am. Chem. Soc.}, title = {Denitrogenative alkylation of K-Ras(G12D) inhibits oncogenic signaling in cancer cells}, volume = {147}, year = {2025}, }
• (2025). Ba7Nb4MoO20: A proton or oxide ion conductor?. JACS, 147(28), 24774--24784. (www)

  @article{ , abstract = {Ba 7 Nb 4 MoO 20 is a recently emerging fast oxide ion conductor, attracting increasing attention. It was reported to also show proton conduction in a humid atmosphere, which is, however, opposite to the results in this work. Theoretical calculations indicate that protons can hardly move, being stabilized in the perovskite blocks or trapped in the palmierite layers, which is in line with the experimental evidence of almost no H 2 O/D 2 O isotope effect and a negligibly small transport number of protons by EMF measurements up to 800 °C. It is thereby clear that Ba 7 Nb 4 MoO 20 is almost a pure oxide ion conductor even though it can be hydrated upon exposure to moisture. The hydration in fact stabilizes interstitial oxide ions (O5 site) in the palmierite layers by forming Nb 2 O 9 H units, leading to reduced bulk conductivity in the pristine and slightly Nb-rich compositions at <400 °C. However, by heating up over 400 °C, the bulk conductivity in the wet atmosphere surpasses that in the dry one, benefitting from an injection of protons into the perovskite blocks to release free O5 ions for oxide ion conduction, indicating that hydration may provide extra oxide ions to enhance the oxide ion conduction.}, archive = {J_JACS}, author = {Sara Adeeba Ismail and Kazuaki Toyoura and Lulu Jiang and Amir Masoud Dayaghi and Hui Guo and Maxim Avdeev and Huaican Chen and Wen Yin and Wang Hay Kan and Truls Norby and Donglin Han}, doi = {10.1021/jacs.5c06467}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24774--24784}, shortjournal = {J. Am. Chem. Soc.}, title = {Ba7Nb4MoO20: A proton or oxide ion conductor?}, volume = {147}, year = {2025}, }
• (2025). Arginine-N,N′-bisprenyltransferases: Switchable catalysis in consecutive guanidine-N-prenylation. JACS, 147(28), 24766--24773. (www)

  @article{ , abstract = {Lipidation is a promising strategy to enhance the membrane affinity and the serum stability of peptide drugs. Cyanobactin prenyltransferases catalyze the prenylation of peptides with diverse chemoselectivity. Among these enzymes, AutF and AgcF catalyze the mono- and bisprenylations of Arg- N ω , respectively, although the structural basis for these distinct prenylation modes remained unknown. Through genome mining, we herein identified a new Arg- N ω -bisprenyltransferase, DciF, from Dolichospermum circinale AWQC310F. Crystallographic analysis and subsequent mutagenesis studies identified key active site residues that play pivotal roles in Arg- N ω -bisprenylation. Manipulations of the active site pocket successfully converted an Arg- N ω -bisprenyltransferase into an Arg- N ω -monoprenyltransferase, and vice versa , elucidating its role as a determinant factor for prenylation rounds. DciF efficiently catalyzed Arg- N ω -bisprenylation on various cyclic and linear peptides, demonstrating its remarkable potential as a biocatalytic tool for site-selective peptide modification. This study broadens the scope of biocatalytic peptide modifications and establishes a new framework for engineering cyanobactin prenyltransferases to control their prenylation rounds.}, archive = {J_JACS}, author = {Kei Fujita and Yuito Yamada and Tomo Taniguchi and Daisuke Fujinami and Takahiro Mori and Kenichi Matsuda and Ikuro Abe and Toshiyuki Wakimoto}, doi = {10.1021/jacs.5c06501}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24766--24773}, shortjournal = {J. Am. Chem. Soc.}, title = {Arginine-N,N′-bisprenyltransferases: Switchable catalysis in consecutive guanidine-N-prenylation}, volume = {147}, year = {2025}, }
• (2025). Decompression-induced chemical reaction in CL-20. JACS, 147(28), 24759--24765. (www)

  @article{ , abstract = {Energetic materials have closely correlated safety and high-pressure chemical reaction kinetics. While extensive research has typically focused on structural evolution and reversible phase transitions at high pressures, chemical decomposition pathways remain underexplored. Here, we report a novel pressure-induced chemical reaction in CL-20 during decompression from a peak pressure of 26.2 GPa under nonhydrostatic compression. Infrared spectroscopy confirmed chemical bond cleavage, yielding gaseous decomposition products primarily composed of N 2 O and CO 2 . Molecular dynamics simulations revealed that the initial decomposition steps involved H migration, OH transfer, β-scission of the C–C bridge, and cleavage of C–N bonds. Notably, under improved hydrostatic conditions (using KBr as the pressure-transmitting medium), the reaction threshold pressure increased to 30.1 GPa, highlighting the critical roles of shear stress in the diamond anvil cell environment. This study represents the first clear demonstration of decompression-induced chemical reactions in condensed explosives, providing fundamental insights into their intrinsic safety mechanisms as well as their initiation and detonation behaviors.}, archive = {J_JACS}, author = {Xin Zhang and Kaiyuan Shi and Jian Xu and Fengyuan Shi and Jian Wang and Jiaqing Zhang and Xingbang Dong and Jun Kong and Zhaoxu Du and Haotian Yang and Xiao Dong and Jun Chen and Wanghua Chen and Lei Su}, doi = {10.1021/jacs.5c06401}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24759--24765}, shortjournal = {J. Am. Chem. Soc.}, title = {Decompression-induced chemical reaction in CL-20}, volume = {147}, year = {2025}, }
• (2025). Mechanical recycling of mixed plastics by supramolecular dynamic cross-linking strategy. JACS, 147(28), 24747--24758. (www)

  @article{ , abstract = {Mechanical recycling of waste plastics is one of the main strategies for addressing plastic pollution, but most waste plastics exist as incompatible mixed plastics that undergo phase separation, making their direct mechanical recycling challenging. Here, a supramolecular dynamic cross-linking strategy using only a small amount of supramolecular dynamic small-molecule cross-linkers was designed to compatibilize and directly mechanically recycle a variety of nonpolar/nonpolar, nonpolar/polar, and polar/polar polymer blends. These difunctional small-molecule cross-linkers contain functional groups with supramolecular dynamic cross-linking capability and functional groups that can be easily grafted to various polymers. Under industrial processing conditions (reactive extrusion using a twin-screw extruder), these small-molecule cross-linkers can be grafted to both components of the mixed plastics. This leads to the in situ formation of a dynamic-cross-linked network that significantly improves the mechanical properties of the blends. More importantly, this strategy achieved the large-scale and multiple recycling/reuse of postconsumer mixed plastics using commercially available small-molecule cross-linkers.}, archive = {J_JACS}, author = {Jiawei Chen and Wenbing Wang and Chen Zou and Changle Chen}, doi = {10.1021/jacs.5c06330}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24747--24758}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanical recycling of mixed plastics by supramolecular dynamic cross-linking strategy}, volume = {147}, year = {2025}, }
• (2025). Distal c(sp3)-H amidation via Ind*RhIII catalyzed nitrene transfer. JACS, 147(28), 24734--24746. (www)

  @article{ , abstract = {The Ind*Rh III catalyzed distal amidation of C(sp 3 )–H sites was explored, harnessing amides as weakly coordinating directing groups. The combined use of an Ind*Rh III complex and 2-pyridone ligand delivered the enhanced catalytic activity required to functionalize both primary and secondary β-C(sp 3 )–H sites. The accelerated nitrene transfer catalysis facilitated the late-stage functionalization of pharmaceutical derivatives and the synthesis of drug conjugates bearing peptides, biotin, or E3-ligase binders. The post-polymerization modification of poly(2-alkyl-2-oxazoline)s and poly(2-alkyl-2-oxazine)s using Ind*Rh III nitrene transfer catalysis involving the site-selective C–H amidation of polymer side chains was also achieved.}, archive = {J_JACS}, author = {Hannah J. Ross and Yihui Yu and Liselle Atkin and Milad Ghorbani and Kelly Mint and Nicole Warne and Kristian Kempe and Daniel L. Priebbenow}, doi = {10.1021/jacs.5c06232}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24734--24746}, shortjournal = {J. Am. Chem. Soc.}, title = {Distal c(sp3)-H amidation via Ind*RhIII catalyzed nitrene transfer}, volume = {147}, year = {2025}, }
• (2025). Formaldehyde-mediated initial Carbon–Carbon bond formation in zeolite-catalyzed methanol-to-hydrocarbon conversion. JACS, 147(28), 24719--24733. (www)

  @article{ , abstract = {Zeolite-catalyzed methanol-to-hydrocarbon conversion is a promising technology for the sustainable production of valuable hydrocarbon products. However, the mechanism behind the formation of the first carbon–carbon bond has been a subject of controversy for several decades. By comprehensive consideration of previous experimental phenomena and theoretical studies, a formaldehyde (HCHO)-based first carbon–carbon formation mechanism is proposed. Within the new mechanism, hydrated or methylated products of HCHO (methanediol, methyloxymethanol, and dimethyloxymethane) with much weaker C–H bond strengths replace methane in the traditional methane-HCHO mechanism, allowing energetically and kinetically favorable pathways to form the first C–C bond. The formed C–C bond products are further converted to ketene and olefins via the methylation-decarbonylation route. The plausibility of the newly proposed mechanism is confirmed by both theoretical calculations and experiments in various MTH zeolite catalysts. A key intermediate in this mechanism is glycolaldehyde, which was captured in situ by both mass spectrometry and Fourier transform infrared spectroscopy. The viability of the mechanism in different zeolites, as predicted theoretically, was also confirmed by gas chromatography. Not only does this new mechanism introduce an innovative pathway for the first C–C bond formation, but it also provides a comprehensive explanation of the specific role of HCHO in the early stage of the MTH process and associated reactions.}, archive = {J_JACS}, author = {Wei Chen and Julia Sobalska and Wenqian Fu and Karolina A. Tarach and Massimo Bocus and Tiandi Tang and Kinga Góra-Marek and Veronique Van Speybroeck}, doi = {10.1021/jacs.5c06141}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24719--24733}, shortjournal = {J. Am. Chem. Soc.}, title = {Formaldehyde-mediated initial Carbon–Carbon bond formation in zeolite-catalyzed methanol-to-hydrocarbon conversion}, volume = {147}, year = {2025}, }
• (2025). Engineering low-resistance heterogeneous nanofluidics for ultrahigh osmotic energy conversion. JACS, 147(28), 24708--24718. (www)

  @article{ , abstract = {Emerging heterogeneous nanofluidics are promising alternatives for harvesting sustainable and clean osmotic energy, primarily due to their capability to reduce Gibbs free energy dissipation. However, the misalignment of nanochannels across different layers in heterogeneous nanofluidics results in low ion flux and high transport resistance, thereby limiting their practical applications. Here, we develop a continuous in situ growth strategy to construct heterogeneous metal–organic framework nanofluidics (H-CuMOF-NMs) that contribute to an enhanced ion flux of 1.13 × 10 14 ions s –1 . The channel-structure-matched nanochannels substantially reduce the transport resistance for Na + ions to selectively pass through heterogeneous interfaces, as corroborated by theoretical simulations. Consequently, an impressive output power density of 12.1 W m –2 is achieved by mixing natural seawater and river water. Large-scale H-CuMOF-NMs measuring 20 × 40 cm 2 are successfully manufactured as commercial membrane stacks capable of continuously powering electrical devices. The proposed nanofluidics show significant potential in separation processes and energy conversion.}, archive = {J_JACS}, author = {Ke Li and Zidi Yan and Shuo Yang and Weiwen Xin and Xuanze Li and Yuge Wu and Kehan Zou and Dehua Huang and Haoyang Ling and Tianchi Liu and Zhehua Zhang and Xiang-Yu Kong and Lei Jiang and Liping Wen}, doi = {10.1021/jacs.5c06122}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24708--24718}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering low-resistance heterogeneous nanofluidics for ultrahigh osmotic energy conversion}, volume = {147}, year = {2025}, }
• (2025). Sequence programmable Order–Disorder transitions in supramolecular assembly of peptide nanofibers. JACS, 147(28), 24699--24707. (www)

  @article{ , abstract = {Protein–protein interactions determine the assembly of complexes that are responsible for numerous key biological processes. The assembly of many natural protein complexes is mediated by post-translational structural changes and environmental stimuli. In this study, we show that incorporation of adjacent lysine residues results in the pH-tunable stability of peptide secondary structure and assembly, allowing for the incorporation of complementary order-inducing motifs. The strategic placement of cysteine pairs in the same peptide sequence results in redox-dependent disulfide staple formation, inducing a transition from random coil to β-sheet conformation and subsequent supramolecular nanofiber assembly from otherwise disordered peptide monomers. Spectroscopic, imaging, molecular dynamics, and kinetic studies highlight the critical role of sequence motif location, oligomerization, and the competitive interplay between intra- and interpeptide disulfide bonding in determining assembly outcomes. We extend this approach to demonstrate phosphorylation-dependent assembly from the design of the same parent peptide sequence, suggesting a general approach to the design of diverse stimulus-responsive peptide sequences for supramolecular assembly. These findings also provide a framework for investigating sequence-dependent pathways in amyloid fiber formation with potential implications for neurodegenerative disease research.}, archive = {J_JACS}, author = {Zachary J. Urbach and Naomy Marrufo and Quynh Theresa H. Do and Jully Nguyen Le and Michał Wierzbicki and Yuanming Song and Khawla Mustafa and Fengbin Wang and Edward H. Egelman and Zhibin Guan and Douglas J. Tobias and Allon I. Hochbaum}, doi = {10.1021/jacs.5c05344}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24699--24707}, shortjournal = {J. Am. Chem. Soc.}, title = {Sequence programmable Order–Disorder transitions in supramolecular assembly of peptide nanofibers}, volume = {147}, year = {2025}, }
• (2025). Organic carbon monoxide prodrugs activated by endogenous reactive oxygen species for targeted delivery. JACS, 147(28), 24691--24698. (www)

  @article{ , abstract = {Carbon monoxide (CO) has demonstrated therapeutic benefits in reactive oxygen species (ROS)-rich environments, such as inflammation and cancer. However, the targeted delivery of CO remains challenging, limiting its clinical application and necessitating the development of improved CO-prodrugs. Herein, we report a radical-activated, metal-free, CO-prodrug designed to address delivery limitations and avoid metal-associated toxicity. This tertiary aldehyde-based prodrug is stable under physiological conditions and, upon activation by a radical trigger, releases CO, 2-ethyl-1-butene, and a nontoxic thiol carrier. The stability of the CO-prodrug building block allows for its incorporation into synthetic peptides via solid-phase peptide synthesis and site-specific bioconjugation to therapeutic antibodies. We synthesized trastuzumab conjugates with a CO-prodrug-to-antibody ratio of 23 and demonstrated efficient, tumor-specific CO release in HER2-high-expressing cells. These findings open new avenues for investigating the therapeutic effects of CO. We anticipate that our metal-free CO-prodrug strategy will be broadly applicable to a wide range of synthetic peptide- and protein-based therapeutics.}, archive = {J_JACS}, author = {Inga Cernauskiene and Claudio D. Navo and Carlos Labão-Almeida and Rupert S. J. Proctor and Bengt H. Gless and Wei Ting Khaw and Cong Tang and M. Milagros Muriel-Olaya and Gonzalo Jiménez-Osés and Gonçalo J. L. Bernardes}, doi = {10.1021/jacs.5c05952}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24691--24698}, shortjournal = {J. Am. Chem. Soc.}, title = {Organic carbon monoxide prodrugs activated by endogenous reactive oxygen species for targeted delivery}, volume = {147}, year = {2025}, }
• (2025). Synthesis of 1,n-diamines via selective catalytic C–H diamination. JACS, 147(28), 24684--24690. (www)

  @article{ , abstract = {A new practical strategy for the conversion of alkanes to diamines is reported. It relies on a one-pot dirhodium(II)-catalyzed amination of two C(sp 3 )–H bonds with sulfamates in the presence of a potent iodine(III) oxidant. This approach gives access to diamines with various substitution patterns depending on the C–H bonds that are cleaved. Thus, it gives access to 1, n -diamines (2 < n < 7) isolated with very high levels of regioselectivity, yields of up to 86%, and enantiomeric ratios of up to 94.5:5.5. The reaction can be performed with two different sulfamates, a process that offers the opportunity to differentiate both nitrogen atoms. The key role of the iodine(III) oxidant for the in situ formation of iminoiodinane is revealed by mass spectrometry experiments.}, archive = {J_JACS}, author = {Théo Bissonnier and Erwan Brunard and Michael Andresini and Salomé Poyer and Tanguy Saget and Philippe Dauban}, doi = {10.1021/jacs.5c05969}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24684--24690}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of 1,n-diamines via selective catalytic C–H diamination}, volume = {147}, year = {2025}, }
• (2025). Orthogonally functionalizable redox-responsive polymer brushes: Catch and release platform for proteins and cells. JACS, 147(28), 24672--24683. (www)

  @article{ , abstract = {Polymer brushes engineered to “specifically capture” and “release on demand” analytes such as dyes, proteins, and cells find biomedical applications ranging from protein immobilization to cell death. Utilizing a disulfide-linker-containing monomer as a building block enables the fabrication of a redox-responsive polymer brush platform with the “catch and release” attribute. Herein, thiol-reactive redox-responsive polymer brushes are fabricated using a pyridyl disulfide-based monomer, and their postpolymerization functionalization is demonstrated via thiol–disulfide exchange reaction with thiol-containing dyes, (bio)molecules, and cell adhesive ligands. After establishing reversible conjugation using a fluorescent dye and other model compounds, copolymer brushes postmodified with thiol-containing mannose demonstrated selective immobilization of concanavalin A in the presence of peanut agglutinin. In addition, a thiolated RGD peptide was conjugated to the side chain of polymer brushes to facilitate cell adhesion, followed by on-demand harvesting. To enable localized drug delivery to surface-adhered cells, orthogonal chain end and side chain functionalization using the thiol-Michael addition and thiol–disulfide exchange reaction, respectively, was used to conjugate the cell adhesive RGD peptide and the anticancer drug doxorubicin (DOX). On-demand DOX release and internalization by surface-bound cancer cells were demonstrated via cleavage of disulfide linkages in the presence of a reducing agent. This approach may provide an attractive methodology to deliver therapeutic agents precisely to specific cells.}, archive = {J_JACS}, author = {Aysun Degirmenci and Rana Sanyal and Harm-Anton Klok and Amitav Sanyal}, doi = {10.1021/jacs.5c05856}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24672--24683}, shortjournal = {J. Am. Chem. Soc.}, title = {Orthogonally functionalizable redox-responsive polymer brushes: Catch and release platform for proteins and cells}, volume = {147}, year = {2025}, }
• (2025). Conjugated bisphosphonic acid self-assembled monolayers for efficient and stable inverted perovskite solar cells. JACS, 147(28), 24662--24671. (www)

  @article{ , abstract = {Chemically modifiable self-assembled monolayer (SAM)-based hole transport layers are crucial for achieving high-efficiency inverted perovskite solar cells (PSCs). However, designing molecular structures that simultaneously ensure strong binding affinity, interfacial stability, and optimized energy level alignment remains challenging. Here, we introduce TPA2P ((2-(4-(diphenylamino)phenyl)-1-phosphonovinyl)phosphonic acid), a novel SAM material featuring a conjugated bisphosphonic acid anchoring group. This dual phosphonic acid configuration enhances substrate binding on indium tin oxide (ITO), improves SAM uniformity, and increases interfacial stability. Furthermore, the ethylene bridge facilitates efficient intramolecular charge transfer (ICT) from the electron-donating triphenylamine unit to the electron-accepting bisphosphonic acid group. This ICT induces significant charge redistribution in TPA2P, resulting in a deep HOMO level at −5.47 eV. This optimized energy alignment reduces interfacial energy losses and significantly enhances hole extraction efficiency. As a result, TPA2P-based inverted PSCs achieve a high power conversion efficiency of 26.11%, an exceptional fill factor of 85.03%, and outstanding operational stability under continuous illumination. These findings provide an effective molecular design strategy for advancing high-performance and stable perovskite photovoltaics.}, archive = {J_JACS}, author = {Songyang Yuan and Chengda Ge and Tianyi Zhang and Gengyang Su and Quanrun Qiu and Guanhua Ren and Lingyi Ke and Gengxin Du and Guangruixing Zou and Nan Zhang and Hui Liu and Qingduan Li and Tao Jia and Yue-Peng Cai and Shengjian Liu and Hin-Lap Yip}, doi = {10.1021/jacs.5c05801}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24662--24671}, shortjournal = {J. Am. Chem. Soc.}, title = {Conjugated bisphosphonic acid self-assembled monolayers for efficient and stable inverted perovskite solar cells}, volume = {147}, year = {2025}, }
• (2025). Ligand-mediated proton-coupled electron injection into reactive cores of soluble macroanion-like complexes of titanium dioxide. JACS, 147(28), 24653--24661. (www)

  @article{ , abstract = {Although widely utilized as reactive components of devices and functional materials, the harnessing of metal-oxide nanocrystals (NCs) as ligand-tunable reaction centers of soluble catalysts remains an ongoing challenge. We now report that readily modifiable, oxidatively inert polyoxometalate (POM) ligands amplify and rationally control rates of photocatalytic H 2 evolution by anatase-TiO 2 NCs. This was achieved using a series of four POM-derived oxo-donor ligands, [(X n+ W 11 O 39 )Ti IV –O – ] (10-n)– , X n+ = Al 3+ , Si 4+ , P 5+ , and [(P 2 W 17 O 61 )Ti IV –O – ] 8– (written here as oxo-anion donors) coordinated via bridging-oxo linkages to Ti atoms at the surfaces of 7 ± 1.6 nm anatase-TiO 2 NCs, wherein the four respective macroanion-like complexes are each ligated, on average, by 90 ± 15 POM anions. Under UV–vis light irradiation in water (10% MeOH), rates of H 2 evolution are a linear function of the quantum yield for photocatalytic oxidation of MeOH by the Ti-substituted POM ligands. This rate-limiting ligand reduction is followed by rapid visible-light driven proton-coupled electron injection into TiO 2 , which proceeds until rates of H 2 evolution achieve parity with those of POM reduction, resulting finally in a dynamic steady state. Here, the NC core of the most reactive, [(P 5+ W 11 O 39 )Ti IV –O−] 5– −ligated complex, 3 , is populated by 440 electrons and 440 protons, representing an effective H + concentration of 10 M (per nm 3 of TiO 2 ). The findings show that metal-oxide NCs can function as the reactive centers of ligand-tunable catalysts and, more generally, provide fundamental mechanistic understanding that establishes new structure–reactivity relationships for the design of rationally tunable modular components of functional materials.}, archive = {J_JACS}, author = {Manoj Raula and Sapir Dabush Avnaim and Aranya Kar and Meital Samin and Shubasis Roy and Mark Baranov and Nitai Leffler and Zhong-Ling Lang and Josep M. Poblet and Ira A. Weinstock}, doi = {10.1021/jacs.5c05809}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24653--24661}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand-mediated proton-coupled electron injection into reactive cores of soluble macroanion-like complexes of titanium dioxide}, volume = {147}, year = {2025}, }
• (2025). Spatial-interactive synergistic confinement in isoreticular Metal–Organic frameworks for facilitating C2H2 separation from CO2 with record packing density. JACS, 147(28), 24643--24652. (www)

  @article{ , abstract = {The synchronous implementation of precise molecule recognition and efficient gas accumulation in porous materials is highly desirable but challenging for physisorptive separation/storage applications. Here, we demonstrate the feasibility of achieving effective acetylene (C 2 H 2 ) purification from a C 2 H 2 /CO 2 mixture with record-high gas packing density by modulating the pore size and interpenetrating symmetry in three isomorphic pillar-layered MOFs (CTGU-41/42/43). The 1D rectangular narrow channels and regularly arranged paired binding sites trigger spatial-interactive synergistic confinement (SISC), enabling suitable molecular orientation and spacing distances during C 2 H 2 adsorption within these MOFs. In particular, CTGU-41 exhibits exceptional adsorption selectivity (41.4) toward the C 2 H 2 /CO 2 mixture (v/v, 50/50) with a record-high C 2 H 2 storage density of 0.91 g mL –1 at 298 K and 100 kPa, which, to the best of our knowledge, surpasses the density of solid-C 2 H 2 (4.2 K) for the first time. The practical C 2 H 2 /CO 2 separation ability of CTGU-41/42/43 is further validated by column breakthrough experiments with high purity of C 2 H 2 (>99.0%) and good separation factors (6.7–11.3). The SISC mechanism clarified in this work deepens the fundamental understanding of dense gas arrangement in specific adsorption space, which can be generalized to other challenging gas separation and storage applications.}, archive = {J_JACS}, author = {Xue-Qian Wu and Cai-Lian Liao and Jun-Jie Wu and Peng-Dan Zhang and Guangtong Hai and Meidi Wang and Ya-Pan Wu and Jian-Rong Li and Dong-Sheng Li}, doi = {10.1021/jacs.5c05650}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24643--24652}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatial-interactive synergistic confinement in isoreticular Metal–Organic frameworks for facilitating C2H2 separation from CO2 with record packing density}, volume = {147}, year = {2025}, }
• (2025). Mixed-chirality prohibitin peptide: D-(RLARLAR)2 enhances stability and in vivo effects on obesity. JACS, 147(28), 24628--24642. (www)

  @article{ , abstract = {Obesity stands as a global epidemic and is the primary risk factor for type 2 diabetes, ranking as the fifth leading cause of death worldwide. While lifestyle changes can address body fat accumulation, pharmacotherapies can also assist in sustained weight loss. Here, we report the design of a new generation of prohibitin peptide-based therapeutics engineered to target white adipose tissues. These peptides demonstrate significant reduction of body weight in a high-fat diet-induced obesity mouse model and represent a paradigm shift in approaches to the treatment of obesity by inducing mitochondrial uncoupling. The most potent compound, PTP-r, was prohibitin-TP01 substituted with d- arginine. Overall, the study reveals the promising development of next-generation adipose-targeting prohibitin peptides, capable of curbing adipocyte expansion and body weight, with favorable preclinical safety profiles. These peptides hold immense potential for developing new treatments to address obesity and metabolic syndrome.}, archive = {J_JACS}, author = {Lai Yue Chan and Benjamin D. Weger and Meltem Weger and Junqiao Du and Nicole Lawrence and Marlon H. Cardoso and Samilla B. de Rezende and Jéssica A.I. Muller and Kuok Yap and Brian W−C Tse and Kamil A. Sokolowski and Robert K.P. Sullivan and Jennifer Gunter and Octávio L. Franco and Frédéric Gachon and David J. Craik}, doi = {10.1021/jacs.5c05536}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24628--24642}, shortjournal = {J. Am. Chem. Soc.}, title = {Mixed-chirality prohibitin peptide: D-(RLARLAR)2 enhances stability and in vivo effects on obesity}, volume = {147}, year = {2025}, }
• (2025). Mixed amide paracyclophane assemblies emulating supramolecular copolymers. JACS, 147(28), 24615--24627. (www)

  @article{ , abstract = {[2.2]Paracyclophanes ( [2 . 2]pCps ), with their intimately spaced arene decks, have been used to study intermolecular charge-transfer effects in chromophores and for applications in photoredox chemistry and organic electronics. In 2016, we reported the synthesis and characterization of the first [2.2]pCp -tetracarboxamide ( [2.2]pCpTA ), envisaged as a covalently fixed supramolecular dimer of 2,5-dimethylterephthalamides. Demonstrated here is the idea that mixed-amide [ n . n ]pCpMTA s can be used to emulate stereoelectronic effects in alternating supramolecular copolymers. As exemplars, we report mixed-deck pseudo - ortho and pseudo - meta [2.2]pCpMTA monomers, each furnished with pairs of C - and N -centered amides arrayed in distinct substitution patterns. Programmable transannular H-bonding pairs dictate both small-molecule conformations and specific amide sequencing in emergent supramolecular assemblies. Variable-concentration and variable-temperature spectroscopy, X-ray crystallography, and density functional theory (DFT) data have been obtained that relate H-bonding geometry, elongation constant ( K e ), assembly mechanism, and dipolar effects to the realization of unique structural control in amide-based supramolecular polymers. Characterization of the [2.2]pCpMTA monomers and their self-assembly behavior more broadly shows how stereoelectronic engineering either encourages or dissuades supramolecular polymerization, insight that can be applied beyond cyclophane-based architectures.}, archive = {J_JACS}, author = {Cole D. Stearns and Ajeet Kumar and Ion Ghiviriga and Lukasz M. Dobrzycki and Khalil A. Abboud and Ronald K. Castellano}, doi = {10.1021/jacs.5c05543}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24615--24627}, shortjournal = {J. Am. Chem. Soc.}, title = {Mixed amide paracyclophane assemblies emulating supramolecular copolymers}, volume = {147}, year = {2025}, }
• (2025). Direct natural seawater electrolysis through a photoinduced asymmetric electric field. JACS, 147(28), 24604--24614. (www)

  @article{ , abstract = {Direct natural seawater electrolysis offers a pathway for green hydrogen production, yet its industrialization is hindered by precipitation formation and sluggish water dissociation kinetics on the cathode. Herein, we propose a photoinduced asymmetric electric field (PAEF) that dynamically affects the interfacial H-bond network under illumination, forming OH – diffusion channels and reorienting water configurations. The transient absorption spectroscopy indicates carrier dynamics for PAEF in a designed photoresponsive catalytic system. The regulated interfacial water structure by PAEF avoids the formation of precipitate and lowers the water dissociation kinetic barrier on the cathode. Such a PAEF-enabled catalytic system shows a low overpotential of 299 mV at 100 mA cm –2 in natural seawater, with <5% activity decay after 100 h continuous operation. A light-assisted asymmetric electrolyzer (natural seawater in the cathode chamber) delivers 0.5 A cm –2 at 2.35 V (60 °C), while integration with the solar panel module maintains compatibility and a high solar-to-hydrogen efficiency (>10%) under fluctuating sunlight energy. By introducing an external light field, this work provides a scalable pathway for durable natural seawater electrolysis.}, archive = {J_JACS}, author = {Zhan Zhao and Yuanyuan Liu and Yiming Chen and Guangmin Ren and Zizhen Li and Zisheng Zhang and Chunhu Li and Xiangchao Meng}, doi = {10.1021/jacs.5c05372}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24604--24614}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct natural seawater electrolysis through a photoinduced asymmetric electric field}, volume = {147}, year = {2025}, }
• (2025). Water-in-salt solution for direct regeneration of degraded lithium iron phosphate. JACS, 147(28), 24594--24603. (www)

  @article{ , abstract = {Direct regeneration has emerged as a pioneering paradigm in green recycling of lithium-ion battery (LIBs) cathode materials, leveraging the inherent atomic and structural advantages of degraded materials. The solution-based regeneration strategy offers significant advantages, particularly in promoting homogeneous lithiation and mitigating the thermal instability of lithium iron phosphate (LFP) materials. However, lithium supplementation for degraded LFP (DLFP) in aqueous solutions is significantly constrained by the narrow electrochemical stability window (ESW) and the limited selection of redox agents. Herein, we propose a promising water-in-salt solution system that enables the spontaneous lithiation of DLFP. This approach not only expands the ESW of the solution but also modifies the lithium solvation structure, facilitating more efficient lithium supplementation. Using the lithium chloride–gallic acid solution as a demonstration, the regenerated cathode materials exhibit excellent electrochemical performance, achieving a specific capacity of 146 mAh g –1 at 1 C with 83% capacity retention after 500 cycles. This research offers critical insights into solution-based lithium supplementation and paves the way for the more efficient recycling of degraded LIBs.}, archive = {J_JACS}, author = {Jie Tang and Bosi Huang and Xiao Xiao and Haotian Qu and Ya Song and Junfeng Li and Yanze Song and Haocheng Ji and Junxiong Wang and Yanfei Zhu and Guangmin Zhou}, doi = {10.1021/jacs.5c05384}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24594--24603}, shortjournal = {J. Am. Chem. Soc.}, title = {Water-in-salt solution for direct regeneration of degraded lithium iron phosphate}, volume = {147}, year = {2025}, }
• (2025). Design principles for narrow-gap hybrid semiconductors: Insights from viologen-tin and viologen-lead iodides. JACS, 147(28), 24573--24593. (www)

  @article{ , abstract = {Hybrid metal halide semiconductors containing “electronically active” organics are an arising subclass of materials that derive remarkable emergent optical properties from blending organic orbitals with the photophysics of metal halide semiconductors. Although this subclass has been known for some time, the majority of reported compounds are lead halides, and there is a paucity of systematic studies investigating the influence of structure and composition on organic energy levels in these materials. Herein we report the first viologen tin hybrids to be published in the form of: HVSnI 4 (HV = hydroviologen), MeVSn 2 I 6 (MeV = methylviologen), and EtVSn 2 I 6 (EtV = ethylviologen). These materials exhibit emergent electronic structures where charge-transfer from the inorganic lattice to viologen LUMO states results in optical gaps as narrow as 1.10 eV. Through comparison of these compounds with their lead analogs and viologen iodide salts, we develop a systematic understanding of energy levels and lead/tin systems, which allows us to identify key chemical principles for future narrow-gap hybrid materials. We find that organic LUMO states in these materials are relatively immobile under the exchange of lead with tin but are strongly influenced by substituent choice, conformation, π–π stacking, and the polarizability of the inorganic lattice. We further study the energetic landscape of these materials in a set of lead/tin alloys (EtVPb 2– x Sn x I 6 ) that do not exhibit the anomalous band-bowing typically associated with lead/tin alloys, providing a new point of evidence that this phenomenon generally relies on concomitant motions of the inorganic conduction and valence band. Photoresponse of HVSnI 4 pressed pellet devices to 1064 nm light establishes the potential of these materials for NIR optoelectronic applications.}, archive = {J_JACS}, author = {Robert P. Reynolds and Jessica H. Persaud and George Volonakis and Andrew J. Torma and Patricia E. Meza and Zek E. Kelly and Constantinos C. Stoumpos and Vinayak P. Dravid and Claudine Katan and Aditya D. Mohite and Mercouri G. Kanatzidis}, doi = {10.1021/jacs.5c05202}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24573--24593}, shortjournal = {J. Am. Chem. Soc.}, title = {Design principles for narrow-gap hybrid semiconductors: Insights from viologen-tin and viologen-lead iodides}, volume = {147}, year = {2025}, }
• (2025). Biomineralized engineered bacterial outer membrane vesicles as cGAS-STING nanoagonists synergize with lactate metabolism modulation to potentiate immunotherapy. JACS, 147(28), 24555--24572. (www)

  @article{ , abstract = {The immunosuppressive tumor microenvironment (TME) significantly limits the efficacy of cancer immunotherapy. Activation of the cyclic guanosine monophosphate-adenosine monophosphate synthase (cGAS) stimulator of interferon genes (STING) pathway and depletion of the tumor metabolic byproduct lactate (LA) represent promising strategies to reverse the immunosuppressive TME and enhance antitumor therapeutic outcomes. Herein, biomineralized engineered bacterial outer membrane vesicles (OMVs@MnCaP-FA) are developed to synergistically activate the cGAS-STING pathway and modulate LA metabolism for antitumor immunotherapy. Upon internalization by 4T1 tumor cells, OMVs@MnCaP-FA undergo acid-responsive degradation, releasing Ca 2+ , Mn 2+ , and lactate oxidase (LOX)-expressing OMVs (OMVs-EcL). These components collectively promote mitochondrial DNA (mtDNA) generation, enhance cGAS-mediated mtDNA recognition and cyclic GMP-AMP (cGAMP) production, and potentiate the binding of cGAMP to STING, leading to robust activation of the cGAS-STING signaling pathway. More importantly, OMVs-EcL-mediated LA depletion reprograms the immunosuppressive TME into an immunoresponsive state, revitalizing antitumor immunity. In vivo studies demonstrate that the combined activation of the cGAS-STING pathway and regulation of LA metabolism effectively inhibit primary tumor growth and metastatic progression, highlighting the potential of this synergistic strategy for advancing antitumor immunotherapy.}, archive = {J_JACS}, author = {Qian-Ru Li and Xiaoyang Zhang and Cheng Zhang and Yun Zhang and Mei-Ting Niu and Zhu Chen and Shi-Man Zhang and Jinlian He and Wei-Hai Chen and Xian-Zheng Zhang}, doi = {10.1021/jacs.5c05148}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24555--24572}, shortjournal = {J. Am. Chem. Soc.}, title = {Biomineralized engineered bacterial outer membrane vesicles as cGAS-STING nanoagonists synergize with lactate metabolism modulation to potentiate immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Programmable liposome organization via DNA origami templates. JACS, 147(28), 24548--24554. (www)

  @article{ , abstract = {Liposomes are essential vehicles for membrane protein reconstitution and drug delivery, making them vital tools in both in vivo and in vitro studies. However, the lack of robust techniques for the precise arrangement of these synthetic vesicles limits their potential applications. Here, we present a modular polymerization platform based on square DNA origami to template the formation and organization of liposomes. By programming the sequence, number, position, chirality, and flexibility of sticky ends on each square, we assemble uniformly sized liposomes into diverse two-dimensional (2D) arrays, as well as finite lattices and rings. Additionally, we demonstrate stepwise assembly and targeted disassembly, enabling dynamic structural control. These complex liposome architectures represent a significant advancement in the fields of biotechnology, nanotechnology, and bottom-up biology.}, archive = {J_JACS}, author = {Zhao Zhang and Zhaomeng Feng and Xiaowei Zhao and Zhiheng Yu and Edwin R. Chapman}, doi = {10.1021/jacs.5c05196}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24548--24554}, shortjournal = {J. Am. Chem. Soc.}, title = {Programmable liposome organization via DNA origami templates}, volume = {147}, year = {2025}, }
• (2025). Ammonia synthesis under ambient conditions: Insights into Water–Nitrogen–Magnetite interfaces. JACS, 147(28), 24538--24547. (www)

  @article{ , abstract = {New routes for transforming nitrogen into ammonia at ambient conditions would be a milestone toward an energy efficient and economically attractive production route in comparison to the traditional Haber–Bosch process. Recently, the synthesis of ammonia from water and nitrogen at room temperature and atmospheric pressure has been reported to be catalyzed by Fe 3 O 4 at the air–water interface. By integrating ambient pressure X-ray photoelectron spectroscopy and ab initio molecular dynamics and free energy calculations, we investigate the underlying thermodynamic mechanisms governing ammonia and hydrazine formation at the water–Fe 3 O 4 –nanoparticle interface. We find that, unlike pure Fe 3 O 4 where N 2 can only interact with a limited number of Fe sites, hydroxylated species introduce large and diverse adsorption geometries where N 2 can bind through either Fe sites or Fe-OH groups, each of which are capable of independently facilitating proton-coupled electron transfer.}, archive = {J_JACS}, author = {Sruthy K. Chandy and Mauricio Lopez Luna and Nykita Z. Rustad and Isaac N. Zakaria and Andreas Siebert and Shane Devlin and Wan-Lu Li and Monika Blum and Teresa Head-Gordon}, doi = {10.1021/jacs.5c04852}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24538--24547}, shortjournal = {J. Am. Chem. Soc.}, title = {Ammonia synthesis under ambient conditions: Insights into Water–Nitrogen–Magnetite interfaces}, volume = {147}, year = {2025}, }
• (2025). Design and application of cereblon-recruiting prodegraders. JACS, 147(28), 24527--24537. (www)

  @article{ , abstract = {Cereblon (CRBN) is one of the most widely co-opted E3 ligase substrate receptor proteins in targeted protein degradation (TPD), and several CRBN-recruiting degraders are currently in late-stage preclinical evaluation. While the diversity of CRBN-recruiting moieties has rapidly expanded, the glutarimide ring has remained largely conserved in these ligands. Glutarimides can form during protein cleavage events via the intramolecular cyclization of glutamine within the protein backbone. Inspired by this biological mechanism, we developed CRBN-recruiting prodegraders by replacing the glutarimide in parent degraders with uncyclized glutamine analogs. Prodegraders derived from a potent, cytotoxic GSPT1 degrader exhibited in cellulo cyclization, resulting in GSPT1 degradation. Optimization of the prodegrader scaffold revealed that glutarimide cyclization rates─and consequently, degradation kinetics─were tunable, with the most optimized prodegrader displaying degradation efficacy and cytotoxicity comparable to the parent, glutarimide-containing GSPT1 degrader. Furthermore, this prodegrader strategy can be readily applied to other known CRBN-based molecular glues and PROTACs. In contrast to conventional glutarimide-containing degraders, the amide of the prodegrader scaffold provides an accessible conjugation handle for stimulus-sensitive groups. We show that prodegraders can be conjugated to and released in vitro from a photolabile protecting group and a commonly used cathepsin-cleavable degrader–antibody conjugate (DAC) linker. Therefore, these prodegrader scaffolds introduce a generalizable conjugation strategy for CRBN-recruiting degraders to DAC linkers, eliminating the need for extensive degrader modifications to incorporate a conjugation handle. Overall, these findings establish the feasibility of utilizing glutamine analogs as a CRBN-recruiting prodegrader strategy and highlight their potential application in targeted drug delivery systems.}, archive = {J_JACS}, author = {Davis H. Chase and Alicia Stein and Daniel E. Grinshpun and Mackenzie W. Krone and Craig M. Crews}, doi = {10.1021/jacs.5c05036}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24527--24537}, shortjournal = {J. Am. Chem. Soc.}, title = {Design and application of cereblon-recruiting prodegraders}, volume = {147}, year = {2025}, }
• (2025). Mechanochemical formation mechanism of alloyed AgBi-elpasolites. JACS, 147(28), 24519--24526. (www)

  @article{ , abstract = {Mechanochemical ball mill synthesis is an emerging method for producing complex materials, including alloyed halide elpasolite semiconductors. This solvent-free method offers precise control over chemical composition, enabling fine-tuning of the optical and mechanical properties. However, the formation mechanism of alloyed elpasolites remains unclear. In this work, we elucidate the crystallization kinetics of mechanochemical formation of Cs 2 AgBi 0.5 M 0.5 Br 6 [M = Sb 3+ , In 3+ , or Fe 3+ ] using in situ synchrotron X-ray diffraction experiments. We identify the reaction intermediates for the parent composition Cs 2 AgBiBr 6 , and we find that −Bi 0.5 Sb 0.5 – forms via a similar reaction pathway. Alloying with In 3+ or Fe 3+ , on the other hand, occurs via an additional cation-exchange step. These insights into the mechanochemical formation mechanisms of alloyed AgBi-elpasolites provide guidelines toward rational compositional engineering of complex materials.}, archive = {J_JACS}, author = {Huygen J. Jöbsis and Loreta A. Muscarella and Michał Andrzejewski and Nicola P.M. Casati and Eline M. Hutter}, doi = {10.1021/jacs.5c05045}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24519--24526}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanochemical formation mechanism of alloyed AgBi-elpasolites}, volume = {147}, year = {2025}, }
• (2025). Shaping peptide assemblies using multifaceted cyclic tectons. JACS, 147(28), 24510--24518. (www)

  @article{ , abstract = {Constructing distinct biomacromolecular assemblies typically necessitates target-specific selection and engineering of building blocks alongside optimization of assembly conditions. The challenge lies in achieving diverse morphological outcomes using simple, shared modules under identical conditions, a hallmark of natural systems that remains elusive in synthetic approaches. Here, we present a molecular scaffold-based strategy to instruct the coassembly of the same set of peptides into a variety of nanostructures across multiple dimensions. We create trifaceted cyclic scaffolds to manipulate two pairs of dimeric coiled-coil peptides prior to coassembly. These scaffolds, with addressable and orthogonal modules, allow controlled exposure of their cohesive faces, directing the formation of nanotriangles and fibrillar and lamellar assemblies. By tuning interpeptide arrangements that dictate scaffold geometry, we construct nonstraight fibrils with tunable curvature, which are rarely observed before. Notably, these scaffolds exhibit plasticity in adapting the sizes and orientations of cohesive faces to different assembly morphologies. The resultant nanostructures are consistent with the design and simulation results, demonstrating the reliability and predictability of this approach. Multifaceted cyclic scaffolds bridge the intellectual and physical gaps between building peptides and assemblies, holding promise for endowing various existing assembly systems with high tunability and versatility.}, archive = {J_JACS}, author = {Chenru Wang and Dexin Lu and Jiakang Li and Linyuan Chen and Xiaobing Zuo and Chuanliu Wu and Xian-Kui Wei and Binju Wang and Yun-Bao Jiang and Tao Jiang}, doi = {10.1021/jacs.5c04788}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24510--24518}, shortjournal = {J. Am. Chem. Soc.}, title = {Shaping peptide assemblies using multifaceted cyclic tectons}, volume = {147}, year = {2025}, }
• (2025). Oxidized overlayers of ruthenium and iridium as electrocatalysts for anodic reactions. JACS, 147(28), 24502--24509. (www)

  @article{ , abstract = {Renewable energy technologies often rely on rutile tetravalent oxides, such as ruthenium(IV) oxide and iridium(IV) oxide, to catalyze anodic reactions that are paired with fuel formation. Herein, we report the synthesis of angstrom-scale and nanoscale oxidized overlayers of ruthenium (o-RuO x ) and iridium (o-IrO x ) from simple aqueous precursors grown on earth-abundant supports and state-of-the-art oxide electrocatalysts. The resulting overlayers exhibit distinct redox features and chemical states as indicated by cyclic voltammetry, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. The electrocatalysts exhibit increased activity towards anodic reactions. In particular, annealed o-RuO x grown on TiO 2 (a-TiO 2 /o-RuO x ) results in an electrocatalyst with an overpotential of 213, 206, and 14 mV at 10 mA cm –2 for the oxygen evolution reaction (OER) in acid, the OER in base, and the chlorine evolution reaction, respectively. The activity of a-TiO 2 /o-RuO x corresponds to a 47.7×, 117.4×, and 1.3× increase in ruthenium mass activity compared to RuO 2 towards the OER in acid, the OER in base, and the chlorine evolution reaction, respectively. These findings highlight the unique chemistry of oxidized overlayers and their potential to meet operational demands for renewable energy technologies.}, archive = {J_JACS}, author = {Conner J. Soderstedt and Yong Yuan and S. Avery Vigil and Heber H. Ford and Matteo Fratarcangeli and Ziqing Lin and Jingguang G. Chen and Ivan A. Moreno-Hernandez}, doi = {10.1021/jacs.5c04767}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24502--24509}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxidized overlayers of ruthenium and iridium as electrocatalysts for anodic reactions}, volume = {147}, year = {2025}, }
• (2025). A refined bulk P–I–N structure in all-polymer solar cells to achieve 20.1% efficiency and improved stability. JACS, 147(28), 24491--24501. (www)

  @article{ , abstract = {All-polymer solar cells (all-PSCs) have shown good potential for achieving balanced power conversion efficiency (PCE) and operational stability. However, precise control of the morphology remains challenging. Here, we constructed a bulk p–i–n structure with a regulated i-region by incorporating a shamrock-shaped nonfullerene acceptor, AQI4. This ternary formulation resulted in optimized energy-level stairing, enhanced exciton dissociation, and reduced energy loss. In blended thin film fabrication, a binary solvent of chlorobenzene (CB):o-xylene (OXY) was used, which enhanced the crystallization of the polymers and formed a high-density fibril network. The i-region width was reduced to less than 2 nm. This structural refinement enabled efficient charge transport through tie-chains between polymer crystallizations, thereby suppressing charge recombination. As a result, the organic solar cell (OSC) devices achieved a PCE of 20.1% (certified as 19.5%) and retained good stability. The T 80 lifetime of over 1800 h in the OSC structure was recorded. Notably, the binary solvent CB:OXY also contributed to a feasible printing fabrication; the 18.4 cm 2 OSC mini-modules achieved a PCE of 16.5%. Our results suggest that the shape of the guest molecule may be a key point to modulate the bulk p–i–n structure and improve the performance of all-PSCs.}, archive = {J_JACS}, author = {Jinge Zhu and Rui Zeng and Erjun Zhou and Chao Li and Jiawei Deng and Mengzhen Du and Qing Guo and Mengwei Ji and Zongtao Wang and Yi Lin and Fei Han and Jiaxin Zhuang and Senke Tan and Lixuan Kan and Lei Zhu and Ming Zhang and Feng Liu}, doi = {10.1021/jacs.5c04656}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24491--24501}, shortjournal = {J. Am. Chem. Soc.}, title = {A refined bulk P–I–N structure in all-polymer solar cells to achieve 20.1% efficiency and improved stability}, volume = {147}, year = {2025}, }
• (2025). Mechanochemical synthesis of h– materials: Hydrogen-rich perovskite oxyhydrides with lattice strain as an ammonia synthesis catalyst. JACS, 147(28), 24482--24490. (www)

  @article{ , abstract = {Mixed-anion perovskite compounds containing hydride ions (H – ) are promising catalysts for ammonia synthesis under mild reaction conditions. Oxyhydride BaTiO 3– x H x is a typical example, with a positive correlation between H – concentration x and catalytic activity; however, the previously reported topochemical synthesis achieved a maximum x value of ∼0.6. Herein, we significantly expand the H – solubility limit to ∼1 by using mechanochemical synthesis, wherein its nonthermal reaction condition enables oxyhydride formation rather than undesired metal-hydride formation and/or hydrogen desorption. The prepared Ru/BaTiO 2 H catalyst showed notable activity for ammonia synthesis (34 mmol g –1 h –1 at 400 °C and 0.9 MPa), which is much higher than that of the reported Ru/BaTiO 2.5 H 0.5 catalyst. More surprisingly, when compared at the same H – concentration of x = 0.5, the mechanochemically prepared sample was approximately three times more active than the topochemically prepared sample. The Bragg coherent X-ray diffraction imaging (Bragg-CDI) technique revealed a non-negligible lattice strain in the mechanochemical product, not only at the surface but also inside the crystal, which is approximately ten times larger than that of the topochemical product, likely contributing to the enhanced catalytic activity. These findings indicate that mechanochemical synthesis enables the design of functional H – -based materials in terms of both the H – concentration and the lattice strain.}, archive = {J_JACS}, author = {Fumitaka Takeiri and Norihiro Oshime and Shibghatullah Muhammady and Tasuku Uchimura and Hiroshi Yaguchi and Jun Haruyama and Akihiko Machida and Tetsu Watanuki and Takashi Saito and Kazuhiro Mori and Kenji Ohwada and Masaaki Kitano and Genki Kobayashi}, doi = {10.1021/jacs.5c04467}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24482--24490}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanochemical synthesis of h– materials: Hydrogen-rich perovskite oxyhydrides with lattice strain as an ammonia synthesis catalyst}, volume = {147}, year = {2025}, }
• (2025). Covalent template-guided synthesis of endo-functionalized oligophenylene cages. JACS, 147(28), 24473--24481. (www)

  @article{ , abstract = {Herein, we demonstrate the efficient covalent template-guided synthesis of lantern-shaped endo -functionalized oligophenylene cages 1 . The synthetic route proceeds by virtue of cooperative bond formations via Suzuki–Miyaura cross-coupling and the use of covalent templates through intermolecular 6-fold coupling among three molecules. Using templates 4a and 4b , template-containing cages 6a and 6b were constructed in 68 and 36% yield, respectively, and the subsequent quantitative removal of the templates led to the corresponding OH- and NH 2 -functionalized cages 1a and 1b . In the absence of templates, intermolecular 4-fold coupling among three molecules afforded cages 1a and 1b in only 7 and 1% yield, respectively. The proposed mechanism for the efficient intermolecular 6-fold coupling was corroborated by electrospray ionization mass spectrometry (ESI-MS) monitoring experiments. Moreover, OH- and NH 2 -functionalized cages were found to encapsulate l -TrpOMe ( G1 ) and diphenyl phosphate ( G2 ), respectively, within their cavities through interactions between polar functional groups.}, archive = {J_JACS}, author = {Kosuke Ono and Fumito Sasamori and Hatsune Izawa and Hiroki Baba and Shion Masano and Ryutaro Shirataki and Hidetoshi Kawai and Kei Goto}, doi = {10.1021/jacs.5c04400}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24473--24481}, shortjournal = {J. Am. Chem. Soc.}, title = {Covalent template-guided synthesis of endo-functionalized oligophenylene cages}, volume = {147}, year = {2025}, }
• (2025). Corrosion-resistant MoO3/Fe2O3/MoS2 heterojunctions stabilize OH– adsorption for efficient light-assisted seawater electrooxidation. JACS, 147(28), 24461--24472. (www)

  @article{ , abstract = {Direct seawater electrolysis holds promise for sustainable hydrogen production, yet challenges such as severe chlorine corrosion on the anode and high energy barriers for oxygen evolution reaction (OER) limit its operational time and efficiency. Herein, we present MoO 3 /Fe 2 O 3 /MoS 2 heterojunctions to mitigate chlorine-induced corrosion and achieve effective photoelectric synergy. The in situ leached MoO 4 2– and SO 4 2– inhibitors reduce Cl – adsorption, thereby ensuring high OER selectivity, while the MoO 3 /Fe 2 O 3 /MoS 2 balances the repelling effects of these inhibitors, facilitating OH – adsorption and widening the overpotential gap between water oxidation and chlorine oxidation. The MoO 3 /Fe 2 O 3 /MoS 2 catalyst outperforms its Fe 2 O 3 counterpart in terms of lifespan, maintaining stability at 100 and 300 mA cm –2 for 100 and 500 h, respectively. Additionally, built-in electric fields formed at the interfaces lower interfacial resistance and extend the lifetime of photogenerated carriers by 1.47-fold, allowing for a 20.4% increase in seawater OER current density under light irradiation. Our findings offer a viable strategy for designing high-performance electrocatalysts for light-assisted seawater electrolysis.}, archive = {J_JACS}, author = {Zhen Li and Wei Tao and Ying Wang and Xucun Ye and Yiqun Chen and Byungchan Han and Lawrence Yoon Suk Lee}, doi = {10.1021/jacs.5c04085}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24461--24472}, shortjournal = {J. Am. Chem. Soc.}, title = {Corrosion-resistant MoO3/Fe2O3/MoS2 heterojunctions stabilize OH– adsorption for efficient light-assisted seawater electrooxidation}, volume = {147}, year = {2025}, }
• (2025). Optimizing surface electronic structure by ba dispersion for enhanced high-temperature oxygen evolution reaction activity. JACS, 147(28), 24451--24460. (www)

  @article{ , abstract = {Surface modification is an advanced strategy to engineer and optimize the work function of the perovskite oxides, which can influence the surface electron and ion transfer processes and tune the surface adsorption of the reaction intermediates, thus enhancing the catalytic activity by creating more active sites. Herein, we modify the surface electronic structure of the Pr 0.9 CoO 3−δ anode of the solid oxide electrolysis cells (SOECs) by the high-temperature dispersion of Ba species. Comprehensive structural and electrochemical characterizations, along with in situ characterizations and density functional theory calculations, reveal that Ba dispersion significantly enhances the surface d–p orbital hybridization between Co and O atoms and thus weakens Co–O bond covalency, facilitating oxygen vacancy formation and oxygen ion mobility. Electrochemical testing demonstrates that the Ba-dispersed anode exhibits significantly reduced polarization resistance and superior high-temperature oxygen evolution reaction activity with a current density of 3.36 A·cm –2 at 1.6 V and 800 °C. These findings provide a novel strategy for engineering surface electronic structures to enhance SOEC performance, offering insights into rational catalyst design for efficient energy conversion applications.}, archive = {J_JACS}, author = {Hewei Liu and Mengna Wang and Tianfu Liu and Geng Zou and Yige Guo and Shaowei Zhang and Jingcheng Yu and Lina Yu and Qingda An and Yuefeng Song and Guoxiong Wang}, doi = {10.1021/jacs.5c03987}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24451--24460}, shortjournal = {J. Am. Chem. Soc.}, title = {Optimizing surface electronic structure by ba dispersion for enhanced high-temperature oxygen evolution reaction activity}, volume = {147}, year = {2025}, }
• (2025). Direct synthesis of para-xylene from CO2 hydrogenation with a record-high space-time yield. JACS, 147(28), 24442--24450. (www)

  @article{ , abstract = {The direct synthesis of para -xylene ( p -X) from CO 2 hydrogenation with high space-time yield (STY) remains a significant challenge due to two primary limitations: the Anderson–Schulz–Flory distribution, which restricts the C 8 selectivity to ∼6.8 C%, and the thermodynamic equilibrium, which confines the p -X content among xylene isomers to 15–25%. Herein, we report a composite catalyst, K-FeMn/Hollow ZSM-5, that enables the efficient hydrogenation of CO 2 to p -X by integrating two synergistic catalytic functions. The K-FeMn component facilitates the reverse water-gas shift reaction and Fischer–Tropsch synthesis to olefin processes, generating light olefin intermediates. These intermediates are subsequently transformed to p -X within the hollow ZSM-5 zeolite through oligomerization, cyclization, and aromatization. The hollow ZSM-5 features a suitable pore size to facilitate p -X diffusion only, while its passivated external acid sites effectively suppress isomerization and alkylation of p -X outside the zeolite. As a result, the K-FeMn/Hollow ZSM-5 catalyst achieves a p -X STY of 41.7 g kg cat –1 h –1 at a CO 2 conversion of 46.1%, surpassing all previously reported values. This work demonstrates a novel approach to overcome the local thermodynamic equilibria by specific catalyst design and the spatial separation of processes toward CO 2 hydrogenation into p -X.}, archive = {J_JACS}, author = {Lijun Zhang and Teng Li and Wenjie Xiang and Zhiwei Ye and Luyao Wu and Wei Xia and Hao Huang and Zhihao Liu and Xiuyun Jiang and Guangbo Liu and Zhiliang Jin and Weizhe Gao and Hongliang Li and Jie Zeng and Noritatsu Tsubaki}, doi = {10.1021/jacs.5c03380}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24442--24450}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct synthesis of para-xylene from CO2 hydrogenation with a record-high space-time yield}, volume = {147}, year = {2025}, }
• (2025). Chirality-contiguous bridged carboranes: Synergistic scalable synthesis and amplification of circularly polarized luminescence. JACS, 147(28), 24430--24441. (www)

  @article{ , abstract = {Icosahedral carboranes are promising structural motifs for optoelectronic functional materials owing to their unique three-dimensional aromatic architectures and distinctive electronic properties. However, their applications remain restricted by the absence of efficient and scalable asymmetric synthesis and limited circularly polarized luminescence (CPL) studies. Herein, we developed a highly stereoselective and straightforward asymmetric synthesis for chiral carborane molecules. This method employs readily available starting materials and enables the precise construction of optically pure chirality-contiguous bridged carborane derivatives via a two-step, one-pot protocol, achieving scalable synthesis on a 10 g-scale without chiral HPLC resolution. After chiral carborane substituents were introduced onto the organic conjugated chromophores, a series of CPL-active molecules with excellent performance were obtained. Their luminescence dissymmetry factors ( g lum ) reached up to 10 –3 level, and the quantum yields ( Φ PL ) achieved up to 0.70. Furthermore, it has been observed that the introduction of carborane into the chiral bridging structure significantly enhances the Φ PL and g lum values of the luminescent compounds. Such concurrent enhancement of both parameters is scarcely documented. Applying one of the chiral emissive compounds, a good enantioselective discrimination of several free amino acids in the aqueous phase has been achieved. This study provides an effective and feasible synthetic route for the stereoselective large-scale synthesis of diverse chiral carborane derivatives. The demonstrated enhancements in both photophysical metrics and chiral recognition applications highlight the dual functionality of these hybrid systems, providing strategic insights for developing chiral materials in polymer science, pharmaceutical chemistry, and optoelectronics.}, archive = {J_JACS}, author = {Longfei Nan and Pei He and Tingwei Zhang and Yiran Dong and Chao Feng and Tong He and Pengfei Li and Yanfeng Zhang and Yong Nie and Jiao Jiao}, doi = {10.1021/jacs.5c03381}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24430--24441}, shortjournal = {J. Am. Chem. Soc.}, title = {Chirality-contiguous bridged carboranes: Synergistic scalable synthesis and amplification of circularly polarized luminescence}, volume = {147}, year = {2025}, }
• (2025). Self-stabilized charge states in a double-decker molecular magnet on pb(111). JACS, 147(28), 24422--24429. (www)

  @article{ , abstract = {Electron charging plays a key role in physicochemical processes, whose intrinsic stabilization in single molecules is desirable for tailoring molecular functionality and developing molecular devices, but remains elusive on surfaces. Here, we show that molecular charge states can be self-stabilized via intramolecular distortion in single bis(phthalocyaninato)terbium(III) (TbPc 2 ) double-decker molecules, which were grown on the Pb(111) substrate. Using scanning tunneling microscopy and spectroscopy, we identify fractions of TbPc 2 molecules that reduce to 2-fold symmetry, exhibiting energy-split molecular orbitals and two types of different spin states. Our first-principles calculations unveil that the symmetry reduction is induced by charging-triggered Jahn–Teller distortions, which lift the degenerate orbitals into two 2-fold symmetric orbitals. Single or double occupancy of the lower-energy orbital results in different molecular spin states. Such intramolecular distortion traps the excess electrons stably without explicit involvement of the substrate, in contrast to previously observed molecular charge states. These charged single molecules can be manipulated with the tip individually. This study offers a new avenue for tailoring the charge and spin states of molecules.}, archive = {J_JACS}, author = {Xin Liao and Rui-Jing Sun and Emi Minamitani and Lian-Zhi Yang and Tao Xie and Wen-Hao Zhang and Chaofei Liu and Svetlana Klyatskaya and Mario Ruben and Ying-Shuang Fu}, doi = {10.1021/jacs.5c03347}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24422--24429}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-stabilized charge states in a double-decker molecular magnet on pb(111)}, volume = {147}, year = {2025}, }
• (2025). Conversion of soluble polyimines to covalent organic framework films and composites. JACS, 147(28), 24413--24421. (www)

  @article{ , abstract = {Covalent organic frameworks (COFs) have been demonstrated for promising applications across research areas and industries. As research in the field advances, there is an increasing need for processing techniques for printing and fabricating COFs, as well as for synthesizing COF composites for advanced materials. To achieve this goal, a versatile approach allowing the synthesis of COFs through polyimines has been developed. Specifically, linear polyimines derived from an aliphatic diamine and aryl dialdehydes were synthesized and subjected to exchange reactions with various vertex amines to generate high-crystallinity imine-based COFs. These polyimines, also referred to as Schiff base polymers, are soluble in organic solvents, enabling solution-based processing and printing with vertex amines to create films of the desired shapes. Highly crystalline COF films were then fabricated by converting precursor films through vapor annealing. This process enables the fabrication of COFs on both microscopic and macroscopic scales. Furthermore, this method provides a straightforward approach to creating advanced functional materials, such as COF/CNT nanocomposites.}, archive = {J_JACS}, author = {Ly D. Tran and Sachin Babu and Morgan E. Loveday and Vincent W. Chen and Dayanni D. Bhagwandin and John H. Dunlap and Kirt A. Page and Hilmar Koerner and Abigail T. Juhl and Christopher A. Crouse and Nicholas R. Glavin and Luke A. Baldwin}, doi = {10.1021/jacs.5c03079}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24413--24421}, shortjournal = {J. Am. Chem. Soc.}, title = {Conversion of soluble polyimines to covalent organic framework films and composites}, volume = {147}, year = {2025}, }
• (2025). A microporous hydrogen-bonded organic framework with alkynyl sites for highly efficient Propane/Propylene separation. JACS, 147(28), 24403--24412. (www)

  @article{ , abstract = {Developing propane-selective adsorbents for propane/propene (C 3 H 8 /C 3 H 6 ) separation can energy-efficiently produce high-purity C 3 H 6 , but it remains unexploited in porous hydrogen-bonded organic frameworks (HOFs) because of lacking effective C 3 H 8 binding sites. Reticular chemistry provides a powerful strategy for fine-tuning of pore size and functionality; however, this strategy is extremely challenging to be implemented in HOFs owing to the weak H-bonds with poor directionality. Herein, we report, for the first time, the implementation of a reticular chemistry strategy to design and synthesize a series of isoreticular HOFs (ZJU-HOF-59–ZJU-HOF-62) for achieving highly efficient C 3 H 8 /C 3 H 6 separation. Four isoreticular HOFs were constructed by four tetracarboxylic ligands, in which their pore sizes and functional sites are systematically engineered. These HOFs exhibit a tunable and gradually improved binding preference of C 3 H 8 over C 3 H 6 . Among them, ZJU-HOF-62 with abundant dialkynyl sites and suitable pore sizes demonstrates the fully inverse C 3 H 8 /C 3 H 6 separation, exhibiting the highest C 3 H 8 uptake (146.8 cm 3 g –1 ) and C 3 H 8 /C 3 H 6 selectivity (1.53) at 298 K and 1 bar. Theoretical calculations reveal that multiple dialkynyl and carboxylic sites provide stronger multipoint H-bonding and van der Waals interactions with C 3 H 8 than C 3 H 6 . The excellent separation capacity of ZJU-HOF-62 for actual C 3 H 8 /C 3 H 6 mixtures was proved by dynamic breakthrough experiments, providing a maximum C 3 H 6 productivity of 12.1 L kg –1 . This work opens the design of porous HOFs for challenging C 3 H 8 /C 3 H 6 separation.}, archive = {J_JACS}, author = {Yu-Bo Wang and Yu-Xin Lin and Jia-Xin Wang and Xu Zhang and Hui Wu and Wei Zhou and Banglin Chen and Guodong Qian and Bin Li}, doi = {10.1021/jacs.5c02924}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24403--24412}, shortjournal = {J. Am. Chem. Soc.}, title = {A microporous hydrogen-bonded organic framework with alkynyl sites for highly efficient Propane/Propylene separation}, volume = {147}, year = {2025}, }
• (2025). Optimizing the ru Catalyst–Support interaction via tunnel size of MnO2 support for enhanced acidic water oxidation. JACS, 147(28), 24392--24402. (www)

  @article{ , abstract = {Metal–support interaction (MSI) has profound impacts on the catalytic performance of heterogeneous catalysts. Rational modulation of MSI will give rise to unusually high activity and stability. Here, we demonstrate that the MSI strength can be effectively tuned by the tunnel size of MnO 2 supports to help address the two fundamental challenges in Ru-based acidic oxygen evolution reaction (OER): the sluggish kinetics and the instability of Ru sites. Through crystallographic engineering from α-MnO 2 to β-MnO 2 polymorphs, we found that the reduced tunnel size of MnO 2 increases planar oxygen (O pla ) concentration and promotes the formation of strong Ru–O pla –Mn bonds, thereby enhancing the Ru/MnO 2 interactions. However, an excessively small tunnel size in β-MnO 2 leads to surface amorphization and elongated Ru–O pla –Mn bonds after Ru incorporation, thus reversely weakening the Ru/MnO 2 interactions. Our work manifests distinct volcano-shaped dependencies for both MSI strength and OER activity as a function of the tunnel size of MnO 2 supports. The optimized Ru-γ-MnO 2 catalyst, featuring an intermediate tunnel size and the strongest MSI, achieves an exceptional mass activity (1743 A g –1 at 1.5 V) while maintaining a high stability. Our results suggest that strong Ru–O pla –Mn interactions promote the formation of the OOH* intermediate through high Ru–O covalency and stabilize reactive Ru species against dissolution through double-exchange charge transfer from low-valence Mn sites. These findings offer valuable insights into the modulation of MSI via structural design of support for the optimization of other supported catalysts.}, archive = {J_JACS}, author = {Sixuan She and Changsheng Chen and Ke Fan and Gao Chen and Yanping Zhu and Daqin Guan and Yu-Cheng Huang and Hsiao-Chien Chen and Zezhou Lin and Hon Fai Wong and Liuqing Li and Ye Zhu and Chi Wah Leung and Yuen Hong Tsang and Haitao Huang}, doi = {10.1021/jacs.5c02857}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24392--24402}, shortjournal = {J. Am. Chem. Soc.}, title = {Optimizing the ru Catalyst–Support interaction via tunnel size of MnO2 support for enhanced acidic water oxidation}, volume = {147}, year = {2025}, }
• (2025). Colossal room-temperature magnetoelectric coupling in anion-deficient layered perovskite films with ordered cation distribution. JACS, 147(28), 24382--24391. (www)

  @article{ , abstract = {The anion-deficient layered perovskite Pb 2 Fe 2 O 5 , featuring a polarizable active Pb cation with lone pair electrons and a magnetically active transition metal Fe cation, presents a promising candidate for multiferroic applications. Nonetheless, the exploration of multiferroic properties and magnetoelectric coupling in Pb 2 Fe 2 O 5 is extremely rare due to its complex structure. Herein, a colossal magnetoelectric coupling coefficient (5.19 × 10 5 mV cm –1 Oe –1 ), high ferroelectric polarization (2 μC/cm 2 ), and magnetic moment (25 emu/cc) at room temperature have been discovered in an epitaxial Pb 2+0.48 Fe 2 O 5 film. The findings of this study demonstrate that the introduction of excessive Pb ions can disrupt the disordered arrangement of the mixed layer and convert it to an ordered distribution to improve ferroelectric properties. This research not only enriches the magnetoelectric coupling material system but also offers a viable strategy for achieving strong room-temperature magnetoelectric coupling and multiferroicity in layered oxide materials.}, archive = {J_JACS}, author = {Hongwei Wang and Xiangfei Li and Jun Miao and Kun Lin and Qiang Li and Xin Chen and Yili Cao and Xi Shen and Youwen Long and Yu Chen and Jiaou Wang and Jing Zhou and Yi Wang and Qiliang Li and Richeng Yu and Xianran Xing}, doi = {10.1021/jacs.5c01840}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24382--24391}, shortjournal = {J. Am. Chem. Soc.}, title = {Colossal room-temperature magnetoelectric coupling in anion-deficient layered perovskite films with ordered cation distribution}, volume = {147}, year = {2025}, }
• (2025). Ionic hydrophobic gates on Metal–Organic frameworks enable high-purity CO2 separation from humid flue gas. JACS, 147(28), 24370--24381. (www)

  @article{ , abstract = {Efficient extraction of high-purity CO 2 from humid flue gas via adsorptive separation offers a promising and sustainable solution for carbon reduction and downstream applications. However, the coadsorption of H 2 O vapor and N 2 from humid flue gas remains a persistent challenge that limits separation efficiency. To overcome this issue, this work introduces a novel concept of ionic hydrophobic gates on porous adsorbents, which enables one-step separation of high-purity CO 2 directly from humid flue gas. By assembling hydrophobic ionic liquids and fluorine-rich terephthalaldehyde onto the surface of a metal–organic framework (MOF), this design establishes H 2 O barriers and CO 2 channels on the outer shell while maintaining pore integrity in the core. The resulting core–shell material demonstrates exceptional CO 2 adsorption capacity and an extraordinary CO 2 /N 2 selectivity of 1780 (15/85, v/v), surpassing conventional adsorbents. Notably, dry CO 2 with 99.999% purity is successfully extracted from humid flue gas (relative humidity, RH = 100%) in a single breakthrough experiment. In situ diffuse reflectance Fourier transform infrared spectroscopy (in situ DRIFTS) and density functional theory calculations reveal that fluorine-rich hydrophobic sites act as effective H 2 O barriers, while ionic liquid segments facilitate the transport of CO 2 through hydrogen bonding and electrostatic interactions. Owing to its excellent scalability and broad compatibility with diverse MOF platforms, this ionic hydrophobic gating strategy offers a robust and versatile approach for constructing advanced gas separation materials, holding great promise for industrial applications in carbon capture, clean energy, and sustainable chemical processes.}, archive = {J_JACS}, author = {Deyun Sun and Shangqing Chen and Miao He and Hongxue Xu and Yongxiang Sun and Lijuan Shi and Hongbo Zeng and Qun Yi}, doi = {10.1021/jacs.5c02093}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24370--24381}, shortjournal = {J. Am. Chem. Soc.}, title = {Ionic hydrophobic gates on Metal–Organic frameworks enable high-purity CO2 separation from humid flue gas}, volume = {147}, year = {2025}, }
• (2025). Impact of temperature on zeolitization elucidated by in situ high-energy X-ray total scattering measurement. JACS, 147(28), 24360--24369. (www)

  @article{ , abstract = {Zeolites are generally synthesized by the hydrothermal method, where temperature is an important parameter. Previous studies have shown that aging can accelerate the synthesis of zeolites; however, while the phenomena have been well investigated, the medium-range structural evolution of the aluminosilicate species during zeolite synthesis has not yet been fully understood, leaving the underlying mechanism unclear. Herein, zeolite X (FAU-type framework) is selected as an example to reveal the role of temperature in zeolitization, and the structural evolutions during the induction and crystallization processes of zeolite X under different temperatures are comparatively investigated by the advanced in situ high-energy X-ray total scattering (HEXTS) technique, combined with UV-Raman spectroscopy and ex situ HEXTS. Zeolite X is synthesized in a homemade reactor, by aging the reactants at 70 °C prior to the hydrothermal treatment at 90 °C. At an aging temperature of 70 °C, 4-rings (4Rs) and double 6-ring ( d6r ) units are formed in the amorphous matrix, which are subsequently assembled to form ordered large structures (12Rs and sod -cages) at 90 °C, triggering the formation of a crystalline framework. In comparison, when the reactant is only treated at 90 °C without aging, an SOD-type framework is formed instead of the targeted FAU-type due to the lack of d6r units. Our findings demonstrate that a suitable aging temperature is crucial for zeolite synthesis, and temperature significantly influences the local structural evolutions during the formation of zeolites.}, archive = {J_JACS}, author = {Zimu Zhou and Peidong Hu and Hiroki Yamada and Jo-Chi Tseng and Koji Ohara and Yasuo Yonezawa and Tatsuya Okubo and Toru Wakihara}, doi = {10.1021/jacs.5c02078}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24360--24369}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of temperature on zeolitization elucidated by in situ high-energy X-ray total scattering measurement}, volume = {147}, year = {2025}, }
• (2025). Spike signals and MD simulations reveal the significance of peptide stretching in nanopore protein sequencing. JACS, 147(28), 24347--24359. (www)

  @article{ , abstract = {Current nanopore protein sequencing methods lack detailed insights into the translocation dynamics of peptides within nanopores, impeding further advancements and optimizations. In this study, we have identified a unique set of spike signals that characterize the translocation process of a single-stranded DNA (ssDNA)-peptide conjugate through nanopores. We propose a spring oscillation model (which only exhibits contraction and stretch, not classic harmonic oscillation or vibration) to explain the generation of these spike signals and validate it through experiments involving base loss, the introduction of the C6 spacer in ssDNA, and molecular dynamics (MD) simulations. Additionally, the introduction of negatively charged amino acids to induce a stretching force stabilizes the peptide conformation, halting spring oscillations and restoring distinct step-like signals for amino acid identification. Our findings revealed the central difficulty to achieve single amino acid resolution in universal peptide sequencing, which can be fixed by stretching the peptides during translocation using additional field force, paving the way for enhancing high-resolution nanopore-based protein sequencing technologies.}, archive = {J_JACS}, author = {Zhijie Chen and Jiaqi Wang and Xiaoran Meng and Fengcan Ye and Lue Wang and Yang Xu and Xinyan Wang and Qinrui Wang and Han Wen and Jingwei Bai}, doi = {10.1021/jacs.5c00827}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24347--24359}, shortjournal = {J. Am. Chem. Soc.}, title = {Spike signals and MD simulations reveal the significance of peptide stretching in nanopore protein sequencing}, volume = {147}, year = {2025}, }
• (2025). Exploration of lithium-ion conductors based on local coordination environments using crystallographic site fingerprints. JACS, 147(28), 24336--24346. (www)

  @article{ , abstract = {The development of high-performance solid-state electrolytes for Li-ion batteries represents a critical challenge because many potential Li-containing compounds remain unexplored. In order to overcome this challenge, in this study, we utilized a semisupervised learning approach to streamline the discovery of novel Li-ion conductors by focusing on local coordination environments. Herein, we introduced four structure-representation descriptors to represent local coordination and applied agglomerative clustering to a data set of 3,835 Li-containing structures. The clusters were subsequently labeled with available experimentally determined ionic conductivity values to assess the efficacy of these descriptors in identifying promising conductors. After screening the obtained high-conductivity clusters and their neighboring structures, we shortlisted 147 compounds, which were further evaluated by molecular dynamics simulations to identify Li 3 LaP 2 S 8 as a potential candidate. Li 3 LaP 2 S 8 experimentally displayed low conductivity; however, optimizing the lithium content yielded Li 3.1 La 0.9 Sr 0.1 P 2 S 8 , which showed a conductivity of 2.1 × 10 –6 S cm –1 at 298 K. To the best of our knowledge, this is the first reported investigation of Li 3 LaP 2 S 8 as a solid-state electrolyte and highlights the power of semisupervised learning in accelerating the discovery of advanced materials. Our findings provide a valuable methodology for developing next-generation solid-state battery technologies.}, archive = {J_JACS}, author = {Songjia Kong and Naoki Matsui and Satoshi Hori and Masaaki Hirayama and Kazuhiro Mori and Takashi Saito and Ryoji Kanno and Kota Suzuki}, doi = {10.1021/jacs.5c00856}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24336--24346}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploration of lithium-ion conductors based on local coordination environments using crystallographic site fingerprints}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic synthesis of hydrogen peroxide by rhenium modified Metal–Organic frameworks incorporating bianthracene ligands. JACS, 147(28), 24326--24335. (www)

  @article{ , abstract = {Photocatalytic synthesis of hydrogen peroxide (H 2 O 2 ) from oxygen (O 2 ) is a challenging process. Metal–organic framework (MOF) materials are emerging photocatalysts with potential tunable light absorption properties. Herein, we report a rhenium (Re) modified Zr-based MOF, Re10-MFM-67, in which active Re sites are incorporated into MFM-67 by partial replacement of 9,9′-bianthracene-10,10′-dicarboxylic acid (H 2 L 1 ) with a [(H 2 L 2 )Re I (CO) 3 Cl] (H 2 L 2 = 2,2′-bipyridine-5,5′-dicarboxylic acid) moiety. Re10-MFM-67 (10 refers to the molar percentage content of Re complex within the material) exhibits broadband light absorption with an exceptional rate of formation of H 2 O 2 from O 2 of 8.50 mmol g cat –1 h –1 and a record turnover frequency (TOF) of 28.7 h –1 under visible light irradiation (λ > 400 nm). Synchrotron powder X-ray diffraction (SPXRD) and neutron powder diffraction (NPD) confirm the structure of Re10-MFM-67, and together with extended X-ray absorption fine structure (EXAFS) analysis establish the coordination environment and binding of the [Re I (CO) 3 Cl] moiety within the framework structure. In situ electron paramagnetic resonance (EPR) spectroscopy suggests that photocatalytic H 2 O 2 generation on Re10-MFM-67 occurs via a two-step oxygen reduction reaction (ORR) pathway with the superoxide anion formed as an intermediate. This study promotes the design of MOF-based photocatalysts with conjugated ligands for efficient photosynthesis.}, archive = {J_JACS}, author = {Boya Tang and David Brooks and Meng He and Yinlin Chen and Zhaozhao Hu and Xue Han and Jiangnan Li and Siyu Zhou and Jiarui Fan and Yukun Ye and Ivan da Silva and Cheng Li and Zi Wang and Lutong Shan and Bing Han and Weiyao Li and Daniil Polyukhov and Bing An and Catherine Dejoie and Martin Wilding and Shaojun Xu and Meredydd Kippax-Jones and Zhaodong Zhu and Yujie Ma and Floriana Tuna and Eric J. L. McInnes and Sarah J. Day and Stephen P. Thompson and Mark D. Frogley and Louise S. Natrajan and Martin Schröder and Sihai Yang}, doi = {10.1021/jacs.5c00603}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24326--24335}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic synthesis of hydrogen peroxide by rhenium modified Metal–Organic frameworks incorporating bianthracene ligands}, volume = {147}, year = {2025}, }
• (2025). Lithium-mediated ammonia electrosynthesis over orderly arranged dipoles regulated solid-electrolyte interphase. JACS, 147(28), 24317--24325. (www)

  @article{ , abstract = {The electrocatalytic lithium-mediated nitrogen reduction reaction (Li-NRR) is considered as a promising alternative to the energy-intensive Haber-Bosch route. However, the solid electrolyte interphase that is derived from the electrolyte easily hinders the diffusion and nucleation of Li + , which ultimately suppresses N 2 activation and the subsequent protonation process. Herein, we successfully construct surface oxygen vacancies (O v ) on commercial BaTiO 3 (BTO) nanoparticles and further drive the phase transition from cubic/tetragonal to rhombohedral, which enhances the ferroelectricity of O v -enriched BaTiO 3 (BTOV) and produces orderly arranged dipoles. Systematic experimental and computational results validate that O v -induced orderly arranged dipoles readily bind anions in the electrolyte and promote their reduction to form a LiF-rich SEI. The optimized anion-derived SEI enhances the Li + transfer kinetics and effectively facilitates the uniform nucleation of Li + , which enables lower energy of Li + desolvation and the reactant crossing the SEI. Thus, the as-prepared BTOV delivers a faradaic efficiency of 93.01% and an NH 3 yield rate of 6.94 nmol s –1 cm –2 at −0.5 V which achieves more than a 45-fold performance improvement compared to the BTO counterpart. This work opens new horizons for the introduction of orderly arranged dipoles to modulate SEI chemistry and further enhance the intrinsic activity of the Li-NRR.}, archive = {J_JACS}, author = {Fangying Duan and Junwu Chen and Mengfei Zhang and Yiming Liu and Hao Xue and Yu Sun and Qiongguang Li and Xuehua Zhang and Zijian Gao and Zongjing Lu and Philippe Schwaller and Guangjin Zhang and Jian Zhang and Menglei Yuan}, doi = {10.1021/jacs.5c00551}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24317--24325}, shortjournal = {J. Am. Chem. Soc.}, title = {Lithium-mediated ammonia electrosynthesis over orderly arranged dipoles regulated solid-electrolyte interphase}, volume = {147}, year = {2025}, }
• (2025). Synthesis, structure, and electronic properties of [Cr6@Sn8Sb8(en)2]3–: A cr6 octahedron encapsulated in a zintl-ion ligand. JACS, 147(28), 24309--24316. (www)

  @article{ , abstract = {The reaction of CrCp 2 with K 2 SnSb yields a Zintl-ion cluster containing an octahedral Cr 6 core, surrounded by an Sn 8 Sb 8 ring and two further ethylenediamine ligands that cap two mutually trans Cr centers. The Cr–Cr bond lengths of 2.453(2) to 2.482(2) Å are remarkably short, much shorter than those in any of the 20-electron chalcogenide-capped analogues, Cr 6 E 8 (PR 3 ) 6 , indicating unusually strong Cr–Cr bonding. An isotropic signal in the electron paramagnetic resonance (EPR) spectrum with g = 2.21 is consistent with a 23-electron Cr 6 13+ core, three electrons more reduced than the Cr 6 16+ units present in Cr 6 E 8 (PR 3 ) 6 . An analysis of the electronic structure using density functional theory (DFT) indicates that the additional three electrons enter Cr–Cr bonding orbitals, which are stabilized as a result of the weak π-donor properties of the Sn 8 Sb 8 16– Zintl ligand.}, archive = {J_JACS}, author = {Wei-Xing Chen and Aidan Manley and Zi-Sheng Li and John E. McGrady and Zhong-Ming Sun}, doi = {10.1021/jacs.5c00515}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24309--24316}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis, structure, and electronic properties of [Cr6@Sn8Sb8(en)2]3–: A cr6 octahedron encapsulated in a zintl-ion ligand}, volume = {147}, year = {2025}, }
• (2025). Structural insights into the force-transducing mechanism of a Motor–Stator complex important for bacterial outer membrane lipid homeostasis. JACS, 147(28), 24299--24308. (www)

  @article{ , abstract = {Gram-negative bacteria assemble an asymmetric outer membrane (OM) that functions as an effective barrier against antibiotics. Building a stable and functional OM requires the assembly and maintenance of balanced levels of proteins, lipopolysaccharides, and phospholipids into the bilayer. In Escherichia coli , the trans-envelope Tol–Pal complex has recently been established to play a primary role in maintaining OM lipid homeostasis. It is believed that the motor–stator complex TolQR exploits the proton motive force in the inner membrane to induce conformational changes in the TolA effector, ultimately generating a force across the cell envelope to activate processes at the OM. Molecular details of how such force transduction occurs via the TolQRA complex are unknown. Here, we solve structures of the E. coli TolQRA complex using single-particle cryo-EM, capturing the transmembrane (TM) regions of the purified complex in two distinct states at ∼3.6 and ∼4.2 Å nominal resolutions. We define how the TolA N-terminal TM helix interacts with an asymmetric TolQ 5 R 2 subcomplex in two different positions, revealing how the two TolQRA states are related by rotation of the TolQ pentamer. By considering structural prediction and biochemical evidence for the periplasmic domains of the complex, we propose a working model for how proton passage through the complex induces rotary movement that can be coupled to TolA for force transduction across the cell envelope.}, archive = {J_JACS}, author = {Jiang Yeow and Chee Geng Chia and Nadege Zi-Lin Lim and Xiaodan Zhao and Jie Yan and Shu-Sin Chng}, doi = {10.1021/jacs.4c18050}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24299--24308}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural insights into the force-transducing mechanism of a Motor–Stator complex important for bacterial outer membrane lipid homeostasis}, volume = {147}, year = {2025}, }
• (2025). Spectroscopic characterization of radical pair photochemistry in nonmigratory avian cryptochromes: Magnetic field effects in GgCry4a. JACS, 147(28), 24286--24298. (www)

  @article{ , abstract = {The magnetic compass sensor in night-migratory songbirds is thought to be a flavin-tryptophan radical pair formed by blue-light excitation of the protein cryptochrome-4a (Cry4a) localized in photoreceptor cells in the birds’ retinas. The effects of applied magnetic fields on the photochemistry of purified Cry4a from the migratory European robin are well characterized, but it is less clear what, if anything, distinguishes the magnetic responses of the Cry4a proteins from migratory and nonmigratory species. We present here a detailed study of the magnetic sensitivity of Cry4a from the nonmigratory chicken. The wild-type protein is compared with two mutants in which either Arg317 or Glu320, both close to the tryptophan radical, were replaced by the amino acids Cys and Lys, respectively, found in Cry4a from robins and other night-migratory passerines. These sites had previously been identified as probably facilitating the evolution of an optimized magnetic sensor for nocturnal orientation in songbirds. Neither of these mutations was found to affect the reaction kinetics or magnetic sensitivity of the radical pairs, suggesting that any differences in Cry4a between robin and chicken must stem from their ability to transmit magnetic information, for example via protein–protein interactions. In contrast, a Trp → Phe mutation at the end of the tryptophan-tetrad electron transfer chain in both cryptochromes led to a large increase in magnetic sensitivity, suggesting different sensing and signaling roles for the third and fourth tryptophans.}, archive = {J_JACS}, author = {Jamie Gravell and Patrick D. F. Murton and Tommy L. Pitcher and Kevin B. Henbest and Jessica Schmidt and Madeline M. Buffett and Gabriel Moise and Angela S. Gehrckens and Daniel R. Cubbin and Ana Štuhec and Lewis M. Antill and Olivier Paré-Labrosse and Marco Bassetto and Ghazaleh Saberamoli and Jingjing Xu and Corinna Langebrake and Miriam Liedvogel and Erik Schleicher and Stefan Weber and Rabea Bartölke and Henrik Mouritsen and P. J. Hore and Stuart R. Mackenzie and Christiane R. Timmel}, doi = {10.1021/jacs.4c14037}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24286--24298}, shortjournal = {J. Am. Chem. Soc.}, title = {Spectroscopic characterization of radical pair photochemistry in nonmigratory avian cryptochromes: Magnetic field effects in GgCry4a}, volume = {147}, year = {2025}, }
• (2025). Probing the oxidative addition transition state in nickel metallaphotoredox catalysis using intramolecular 13C kinetic isotope effects. JACS, 147(28), 24275--24285. (www)

  @article{ , abstract = {The merger of nickel and photoredox catalysis has enabled a wide range of C–C and C–X bond formations under mild conditions. Central to the mechanistic understanding of these catalytic reactions is the identification of the nickel species involved in the key oxidative addition step. Intramolecular 13 C kinetic isotope effects (KIEs) in conjunction with DFT analysis are a reliable, quantitative approach to identify the oxidation state and ligand environment at the metal center during oxidative addition. This methodology is applied to evaluate the mechanism of two distinct nickel metallaphotoredox-catalyzed reactions. Specifically, we probe the oxidative addition step of nickel metallaphotoredox catalyzed C(sp 2 )–C(sp 3 ) cross-coupling reactions that utilize either neutral bipyridyl ligands (NiCl 2 (dtbbpy)(H 2 O) 4 ) or anionic diketonate ligands (Ni(THMD) 2 ) and utilize this information to elucidate the operational catalytic cycles in these reactions. In the N- methyl selective arylation of trialkyl amines catalyzed by NiCl 2 (dtbbpy)(H 2 O) 4 , a Ni(I)(dtbbpy)(α-aminoalkyl) complex is invoked as the most likely species involved in the oxidative addition step. An alternative mechanism is also identified that is consistent with the experimental KIEs, involving oxidative addition to a Ni(0)(dtbbpy)(methyleneiminium) bromide complex. In the deaminative arylation of sterically hindered primary amines catalyzed by Ni(THMD) 2 , our results indicate that an anionic Ni(I)(THMD)(Cl) complex is likely involved in the oxidative addition step, a finding that accounts for the rate acceleration observed in the presence of tetrabutyl ammonium chloride as an additive. These results illustrate that intramolecular 13 C KIEs are an effective experimental probe to address challenging mechanistic questions in nickel metallaphotoredox catalysis.}, archive = {J_JACS}, author = {Chetan Joshi and Julia R. Dorsheimer and Victor O. Nyagilo and Mariah Carol Ramos and Subhrashis Banerjee and Bangaru Bhaskararao and Yangyang Shen and Tomislav Rovis and Mathew J. Vetticatt}, doi = {10.1021/jacs.4c10182}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24275--24285}, shortjournal = {J. Am. Chem. Soc.}, title = {Probing the oxidative addition transition state in nickel metallaphotoredox catalysis using intramolecular 13C kinetic isotope effects}, volume = {147}, year = {2025}, }
• (2025). Dynamin-like proteins combine mechano-constriction and membrane remodeling to enable two-step mitochondrial fission via a “Snap-through” instability. JACS, 147(28), 24258--24274. (www)

  @article{ , abstract = {Mitochondrial fission is controlled by dynamin-like proteins, the dysregulation of which is correlated with diverse diseases. Fission dynamin-like proteins are GTP hydrolysis-driven mechanoenzymes that self-oligomerize into helical structures that constrict membranes to achieve fission while also remodeling membranes by inducing negative Gaussian curvature, which is essential for the completion of fission. Despite advances in optical and electron imaging technologies, the underlying mechanics of mitochondrial fission remain unclear due to the multiple times involved in the dynamics of mechanoenzyme activity, oligomer disassembly, and membrane remodeling. Here, we examine how multiscale phenomena in dynamin Drp1 synergistically influence membrane fission using a mechanical model calibrated with small-angle X-ray scattering structural data and informed by a machine learning analysis of the Drp1 sequence, and tested the concept using optogenetic mechanostimulation of mitochondria in live cells. We find that free dynamin-like proteins can trigger a “snap-through instability” that enforces a shape transition from an oligomer-confined cylindrical membrane to a drastically narrower catenoid-shaped neck within the spontaneous hemi-fission regime, in a manner that depends critically on the length of the confined tube. These results indicate how the combination of assembly and paradoxically disassembly of dynamin-like proteins can lead to diverse pathways to scission.}, archive = {J_JACS}, author = {Haleh Alimohamadi and Elizabeth Wei-Chia Luo and Xiaoying Liu and Wasi Iqbal and Rena Yang and Shivam Gupta and Kelsey A Nolden and Taraknath Mandal and R. Blake Hill and Liting Duan and Gerard C. L. Wong}, doi = {10.1021/jacs.5c06352}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24258--24274}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamin-like proteins combine mechano-constriction and membrane remodeling to enable two-step mitochondrial fission via a “Snap-through” instability}, volume = {147}, year = {2025}, }
• (2025). Drp1 proteins released from hydrolysis-driven scaffold disassembly trigger nucleotide-dependent membrane remodeling to promote scission. JACS, 147(28), 24248--24257. (www)

  @article{ , abstract = {Dynamin-related protein (Drp1) drives mitochondrial fission, dysregulation of which leads to neurodegenerative, metabolic, and apoptotic disorders. The precise mechanism of fission completion is unclear. One prevailing model is based on GTP-driven assembly of Drp1 helices that increase confinement via force generation. However, constriction to nanoscopic tubule radii appears necessary but not sufficient for scission. The other is based on GTP-driven disassembly of a constricting Drp1 scaffold that drives a membrane disturbance, but the relation of disassembly to scission and GTP hydrolysis remain uncertain. Elucidation of mitochondrial fission is complicated by the multiple time-involved in the dynamics of mechanoenzyme activity, oligomer disassembly, and membrane remodeling. Using machine learning, synchrotron X-ray scattering, and a theoretical model, our data support a model where progressive GTP hydrolysis enables free Drp1s to increase their capacity for inducing membrane negative Gaussian curvature (NGC). Furthermore, we identify Drp1 variants that diminish this progressive capacity. Machine learning reveals that predicted NGC-generating sequences of the Drp1 oligomer are not in contact with the confined lipid tube and that scission-enhancing membrane remodeling is triggered by free Drp1 released upon disassembly.}, archive = {J_JACS}, author = {Elizabeth Wei-Chia Luo and Kelsey A Nolden and Haleh Alimohamadi and Michelle W. Lee and Liting Duan and R. Blake Hill and Gerard C. L. Wong}, doi = {10.1021/jacs.4c15836}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24248--24257}, shortjournal = {J. Am. Chem. Soc.}, title = {Drp1 proteins released from hydrolysis-driven scaffold disassembly trigger nucleotide-dependent membrane remodeling to promote scission}, volume = {147}, year = {2025}, }
• (2025). Monolayered Metal–Organic framework unlocks integration of shaped nanoparticles for synergistic photocatalysis. JACS, 147(28), 24241--24247. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) with ordered structures and high surface areas are promising supports for metal nanoparticles (MNPs) in synergistic catalysis. However, their limited pore sizes restrict integration to small spherical MNPs, excluding shaped MNPs that are critical for exposing specific lattice surfaces and achieving a superior catalytic performance. In this work, we address this limitation by reducing MOFs to monolayers, enabling the integration of shaped MNPs onto their surfaces to significantly enhance the catalytic efficiency. The monolayered MOF (monoMOF), Hf 12 -Ir, with a thickness of ∼1.8 nm, was synthesized using photosensitizing DBB-Ir-F linkers. Freshly synthesized cubic Cu nanoparticles (Cu-NPs, ∼35 nm) were functionalized with thioctic acid (TA) via Cu–S coordination and integrated onto the surface of Hf 12 -Ir through carboxylate-Hf 12 coordination, forming the Cu/Hf 12 -Ir composite. Upon light irradiation, Cu/Hf 12 -Ir achieved exceptional CO 2 -to-CO conversion with a turnover frequency of 82.9 mmol g Cu –1 h –1 and a CO selectivity of 98.3%. This catalytic performance was over an order of magnitude higher than that of the homogeneous system (Cu-NPs and H 2 DBB-Ir-F) and the small spherical MNPs-based composite (S-Cu/Hf 12 -Ir). Mechanistic studies revealed a synergistic effect between the Cu-NPs and Hf 12 -Ir, where their proximity enhanced electron transfer from the photoexcited DBB-Ir-F centers to the Cu-NPs. This work demonstrates a straightforward strategy for constructing MNP-monoMOF composites and highlights the critical charge transfer pathway between the photosensitizing monoMOF and catalytic MNPs.}, archive = {J_JACS}, author = {Kun Wang and Yufeng Zhang and Zizhuo Gong and An Li and Yiyang Ma and Jun-Hao Wang and Zhaozhao Hu and Ruizhi Huang and Zi Yang and Zixuan Yu and Senhai Zeng and Jiangnan Li and Sihai Yang and Ya-Wen Zhang and Guangxu Lan}, doi = {10.1021/jacs.5c09403}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24241--24247}, shortjournal = {J. Am. Chem. Soc.}, title = {Monolayered Metal–Organic framework unlocks integration of shaped nanoparticles for synergistic photocatalysis}, volume = {147}, year = {2025}, }
• (2025). Collapse of lipid membranes into distended lipidic cubic phases at high solvent levels, membrane remodelling, and self-repair. JACS, 147(28), 24235--24240. (www)

  @article{ , abstract = {Performance plastics, such as poly(methyl methacrylate), underpin the modern economy. Global manufacturing of plastic precursors relies on fossil carbon sources, and the urgently needed shift toward renewable carbon use through biofermentation is hindered by the low tolerance of producer strains to methacrylate esters. The principal mode of butyl methacrylate cellular toxicity is membrane disruption. To understand this process, the conditions for membrane stability, and recovery after solvent shock, we investigate the phase stability of hydrated lipid membranes at high levels of a key intermediate, butyl methacrylate. We assess the role of cis - vs trans -unsaturation in 18-carbon chain phospholipids on butyl methacrylate-induced phase conversion and polymorphism. Using ssNMR, SAXS and cryoEM, we demonstrate the formation of stable lipidic cubic phases in hydrated lipid/solvent ( cis -chain phospholipid lipid/butyl methacrylate) systems at a 1:6 molar ratio entirely lacking monoolein. Transient lipidic cubic phases form in trans -chain phospholipid/butyl methacrylate systems, which slowly convert to bilayers through a spontaneous “membrane healing” process during recovery after solvent shock. The observed bicontinuous nanostructures with a cubic phase architecture coexist with a stable, monocontinuous hydrated phase of the same morphology but with simpler topological connectivity, which demonstrates that phase stability in cubic phases does not require topological complementarity. We propose trans -lipid substitutions in membranes of fermentative strains as a key step toward sustainable production of methacrylate esters.}, archive = {J_JACS}, author = {Vivien Yeh and Alice Goode and Nikul Khunti and Julie Watts and Christopher Parmenter and Michael Fay and David Johnson and Nathan Cowieson and Boyan Bonev}, doi = {10.1021/jacs.5c07146}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24235--24240}, shortjournal = {J. Am. Chem. Soc.}, title = {Collapse of lipid membranes into distended lipidic cubic phases at high solvent levels, membrane remodelling, and self-repair}, volume = {147}, year = {2025}, }
• (2025). Structural, compositional, and morphological interrelationships in rocksalt (FeCoMnMgZn)O high entropy oxide nanocrystals for oxygen evolution electrocatalysis. JACS, 147(28), 24230--24234. (www)

  @article{ , abstract = {The colloidal synthesis of high entropy oxide (HEO) nanocrystals requires navigating and balancing competing reaction pathways, which are often unknown. There is also a limited understanding of HEO nanocrystal formation and growth pathways, which hinders morphological control. Here, we report on the colloidal synthesis of rocksalt-type (FeCoMnMgZn)O nanocrystals with different morphologies. Reaction pathway studies show a Fe-rich spinel-type intermediate and indicate that competing chemical reactivities dictate the final compositions and morphologies. Atomic resolution imaging analysis of concave cubic and dendritic (FeCoMnMgZn)O nanocrystals indicate a 1.73% lattice expansion relative to bulk FeO. The (FeCoMnMgZn)O nanocrystals are active electrocatalysts for the oxygen evolution reaction in alkaline media.}, archive = {J_JACS}, author = {Gaurav R. Dey and Simeon Teklu and Zixiao Shi and Meixue Hu and Katherine L. Thompson and Samuel S. Soliman and Robert W. Lord and Héctor D. Abruña and David A. Muller and Raymond E. Schaak}, doi = {10.1021/jacs.5c06732}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24230--24234}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural, compositional, and morphological interrelationships in rocksalt (FeCoMnMgZn)O high entropy oxide nanocrystals for oxygen evolution electrocatalysis}, volume = {147}, year = {2025}, }
• (2025). Elementary steps in olefin metathesis: Nickelacyclobutanes via cycloaddition to nickel carbenes. JACS, 147(28), 24225--24229. (www)

  @article{ , abstract = {Olefin metathesis and cyclopropanation, major reactions in the synthetic toolbox, are predominantly catalyzed by platinum-group metals. First-row transition metal alternatives are desirable from the perspective of supply-chain sustainability. Although cyclopropanation by nickel catalysts is well established, limited evidence exists for the chemical feasibility of the cycloaddition step essential for inner-sphere cyclopropanation or olefin metathesis. We describe Ni(PP)(=CPh 2 ) complexes that provide this missing evidence. These complexes react with styrene and phenyl vinyl sulfone (PVS) to form β-H elimination products that imply nickelacyclobutane (NiCB) intermediates. For the PVS system, the NiCB could be observed directly by NMR analysis and X-ray crystallography. This is the sole example to date of an obervable NiCB generated via cycloaddition, beyond the fluorinated examples. Computations pinpoint a decreased energy barrier to cycloreversion, relative to reductive elimination or β-H elimination, as the core requirement to achieve metathesis. This work thus demonstrates that nickel complexes can engage in cycloaddition, the missing elementary step essential for olefin metathesis, and establishes the design parameters essential to close the catalytic cycle.}, archive = {J_JACS}, author = {Samantha K. Cormier and Marco Foscato and Michael J. Ferguson and Vidar R. Jensen and R. Tom Baker and Deryn E. Fogg}, doi = {10.1021/jacs.5c06505}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24225--24229}, shortjournal = {J. Am. Chem. Soc.}, title = {Elementary steps in olefin metathesis: Nickelacyclobutanes via cycloaddition to nickel carbenes}, volume = {147}, year = {2025}, }
• (2025). Deoxygenative [3 + 2] annulation of α,β-unsaturated carbonyl compounds and electron-rich olefins via photocatalytic umpolung of triarylphosphine. JACS, 147(28), 24220--24224. (www)

  @article{ , abstract = {A visible-light-driven deoxygenative [3 + 2] annulation between α,β-unsaturated carbonyl compounds and electron-rich olefins was developed, which proceeded under mild conditions with a broad substrate scope and functional group tolerance, enabling straightforward access to diverse substituted cyclopentenes. This cascade annulation strategy exploited the reactivity of phosphine radical cations, generated from triarylphosphines by the oxidation with the excited-state iridium-based photocatalysts, toward olefins to form the corresponding distonic radical cations with a chain length pertinent to constructing cyclopentene scaffolds via sequential radical addition and intramolecular Wittig reaction.}, archive = {J_JACS}, author = {Taiga Ando and Daisuke Yokogawa and Kohsuke Ohmatsu and Takashi Ooi}, doi = {10.1021/jacs.5c06114}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24220--24224}, shortjournal = {J. Am. Chem. Soc.}, title = {Deoxygenative [3 + 2] annulation of α,β-unsaturated carbonyl compounds and electron-rich olefins via photocatalytic umpolung of triarylphosphine}, volume = {147}, year = {2025}, }
• (2025). Membrane-anchored polyproline provides controlled microdomain formation and permeability in lipid vesicles. JACS, 147(28), 24213--24219. (www)

  @article{ , abstract = {This study introduces the synthesis of a new class of lipopolymers composed of l -proline monomer units and a phospholipid initiator. By anchoring polyproline chains to the membrane, reversible phase separation was achieved, with clusters forming at high temperature and dispersing upon cooling. Confocal microscopy and FRAP analyses confirmed microdomain formation after heating and restored diffusion properties after cooling, demonstrating dynamic control over local membrane composition. Importantly, the microdomains enhanced membrane permeability, enabling size-controlled release of encapsulated molecules, including synthetic polymers and enzymes. The system showed adaptability across various membrane compositions, suggesting its potential for applications in drug delivery or synthetic biology, especially for mimicking protein-like behavior in lipid vesicles.}, archive = {J_JACS}, author = {Rosanna Le Scouarnec and Emmanuel Ibarboure and Léna Alembik and Sebastien Lecommandoux and Jeanne Leblond Chain and Colin Bonduelle}, doi = {10.1021/jacs.5c06134}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24213--24219}, shortjournal = {J. Am. Chem. Soc.}, title = {Membrane-anchored polyproline provides controlled microdomain formation and permeability in lipid vesicles}, volume = {147}, year = {2025}, }
• (2025). Rh-catalyzed atroposelective single-carbon insertion. JACS, 147(28), 24206--24212. (www)

  @article{ , abstract = {Single-carbon insertion processes have gained considerable momentum over the past few years. Although innovative methods have emerged for converting indole or indene into quinoline or naphthalene cores, the enantioselective version of such ring-expansions to create (hetero)biaryl atropisomers has not been developed. Herein, we report the first enantioselective single-carbon insertion that converts 3-aryl indoles to atropochiral quinolines. Key in the process was the generation of a chiral Rh-carbynoid that mediated in the creation of the stereogenic C( sp 2 )–C( sp 2 ) axis.}, archive = {J_JACS}, author = {Bowen Li and Valero G. Alfonso and Alessio Puggioli and Albert Solé-Daura and Feliu Maseras and Marcos G. Suero}, doi = {10.1021/jacs.5c06139}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24206--24212}, shortjournal = {J. Am. Chem. Soc.}, title = {Rh-catalyzed atroposelective single-carbon insertion}, volume = {147}, year = {2025}, }
• (2025). Gene-inherited [Se2] dimers in a reactive salt flux: Synthesis of a quasi-one-dimensional NbSe2 superconductor. JACS, 147(28), 24201--24205. (www)

  @article{ , abstract = {Transition metal dichalcogenides (TMDs) have attracted much attention due to their excellent properties in many fields. The existing thermodynamically stable TMDs are almost two-dimensional or three-dimensional in structure; therefore, the synthesis of new kinetic stable TMDs with lower dimensions is of great significance in materials science and chemistry. Here, we demonstrated the synthesis of a new type of NbSe 2 with one-dimensional (1D) Nb[Se 2 ] chains by using K 2 Se 2 with low melting points as the reactive salt fluxes. In this reaction, the [Se 2 ] dimers in K 2 Se 2 , acting like “genes”, are “inherited” by the 1D-NbSe 2 , reducing the dimension of the material to 1D and generating a new metastable phase. Several measurements confirmed the existence of a 1D chain structure from the aspects of morphology, structure, oxidation valence state, and phonon vibration. Magnetic and electrical property measurements show that the samples behave as paramagnetic metals in the normal state and exhibit superconductivity below 9.5 K. In this work, we highlight the opportunity to gain a series of low-dimensional new type MQ2 (M = metal, Q = S, Se, Te) that will inspire future efforts in material science.}, archive = {J_JACS}, author = {Ruijin Sun and Haodong Li and Duo Zhang and Dezhong Meng and Changchun Zhao and Shifeng Jin}, doi = {10.1021/jacs.5c05796}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24201--24205}, shortjournal = {J. Am. Chem. Soc.}, title = {Gene-inherited [Se2] dimers in a reactive salt flux: Synthesis of a quasi-one-dimensional NbSe2 superconductor}, volume = {147}, year = {2025}, }
• (2025). Synthesis of borylated orphaned cyclopropanes through a boron-enabled cycloisomerization reaction. JACS, 147(28), 24193--24200. (www)

  @article{ , abstract = {Cyclopropanes are important building blocks that are used widely in the pharmaceutical and agrochemical industries. However, synthesizing highly substituted cyclopropanes has proven to be challenging. Herein, we disclose a new strategy to prepare borylated cyclopropanes through the use of a boron-enabled cycloisomerization reaction. The method relies on the generation of a triplet biradical through an energy transfer process. Subsequent 1,2-boron shift leads to the formation of a triplet 1,3-biradical, which is poised to undergo radical recombination in concert with intersystem crossing. The generated borylated cyclopropanes are useful intermediates, as a variety of highly substituted cyclopropanes can be easily prepared.}, archive = {J_JACS}, author = {Jarett M. Posz and Anagha Veluthanath Nair and Ryan Van Hoveln and M. Kevin Brown}, doi = {10.1021/jacs.5c05763}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24193--24200}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of borylated orphaned cyclopropanes through a boron-enabled cycloisomerization reaction}, volume = {147}, year = {2025}, }
• (2025). A carbamoyl N-methyltransferase catalyzes N-methylation of the primary amide in ansacarbamitocin biosynthesis. JACS, 147(28), 24186--24192. (www)

  @article{ , abstract = {Primary amide-specific N -methyltransferases are extremely scarce in microbial secondary metabolism. Here, Asc-Orf2, an N -methyltransferase involved in the biosynthesis of ansacarbamitocins, was identified to catalyze the methylation of the 3- O -carbamoyl moiety. Structural analysis identified an unprecedented NPPH catalytic motif, offering a mechanistic basis to overcome the chemical inertness of primary amides. The 3- O -( N -methyl)-carbamoyl maytansinoid derivatives, modified via Asc-Orf2-catalyzed methylation, exhibited markedly enhanced antitumor activity, highlighting the magic methylation effect in bioactivity modulation. Furthermore, structure-targeted engineering expanded the catalytic scope of Asc-Orf2, enabling the directed synthesis of an N -allylated carbamoyl maytansinoid derivative optimized for antibody-drug conjugate payload.}, archive = {J_JACS}, author = {Zhongyue Li and Wanting Yang and Zhonglin Sun and Haoxin Wang and Chunhua Lu and Deyu Zhu and Yuemao Shen}, doi = {10.1021/jacs.5c05398}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24186--24192}, shortjournal = {J. Am. Chem. Soc.}, title = {A carbamoyl N-methyltransferase catalyzes N-methylation of the primary amide in ansacarbamitocin biosynthesis}, volume = {147}, year = {2025}, }
• (2025). Direct evidence of bimolecular proton-coupled energy transfer at room temperature. JACS, 147(28), 24181--24185. (www)

  @article{ , abstract = {A new elementary reaction, denoted proton-coupled energy transfer (PCEnT), has been recently reported in a series of donor–acceptor molecules. In this reaction, excited state energy transfer is made possible by a simultaneous transfer of a proton on the energy acceptor. This type of elementary reaction could have, by analogy to proton-coupled electron transfer, an important role in photochemistry and energy transportation of biological systems. In the previously reported case, the reaction is shown to occur intramolecularly in a covalently linked system in a 77 K glass. In this work, we identify a suitable bimolecular system for PCEnT and provide direct evidence for PCEnT in a room temperature solution using fluorescence spectroscopy. Based on these results, we discuss some simple design principles for PCEnT, including some of the current obstacles in designing a successful system.}, archive = {J_JACS}, author = {Andrea Rosichini and Giorgio Scattolini and Leif Hammarström}, doi = {10.1021/jacs.5c05126}, journal = {Journal of the American Chemical Society}, month = {7}, number = {28}, pages = {24181--24185}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct evidence of bimolecular proton-coupled energy transfer at room temperature}, volume = {147}, year = {2025}, }
• (2025). Correction to “Exploring the structural origins of optically efficient one-dimensional lead halide perovskite nanostructures”. JACS, 147(27), 24179--24180. (www)

  @article{ , archive = {J_JACS}, author = {Alexander M. Oddo and Daniel Chabeda and Jaydeep Basu and Marcel Arnold and Chengyu Song and Eran Rabani and Peidong Yang}, doi = {10.1021/jacs.5c09524}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24179--24180}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Exploring the structural origins of optically efficient one-dimensional lead halide perovskite nanostructures”}, volume = {147}, year = {2025}, }
• (2025). Self-protection mechanism and mass transport governing o2 tolerance in an iron porphyrin homogeneous catalyst for CO2 electroreduction. JACS, 147(27), 24171--24178. (www)

  @article{ , abstract = {The electrochemical reduction of CO 2 , coupled with renewable energy, offers a promising approach to convert CO 2 to valuable products. However, the presence of O 2 in operating environments presents challenges such as catalyst degradation. Transition metal complexes, such as iron tetraphenylporphyrin (TPPFe), are molecular electrocatalysts with tunable structures and redox properties that make them attractive for CO 2 reduction. A critical challenge for practical application is achieving O 2 tolerance─the ability of the catalyst to sustain CO 2 reduction without degradation in the presence of O 2 . This study highlights the self-protection mechanism of TPPFe in homogeneous electrocatalysis against O 2 and reactive oxygen species (ROS). Using rotating disk voltammetry, constant potential electrolysis, and spectro-electrochemistry, we demonstrate that lesser reduced TPPFe states selectively reduce O 2 , form a protective layer that shields the active catalyst for CO 2 reduction. Furthermore, we reveal that mass transport significantly influences the efficiency of CO 2 -to-CO conversion in O 2 -containing environments, with stirring rates during electrolysis directly affecting CO faradaic yields. This self-protection mechanism, applicable to other catalysts with multiple redox states and adaptable to molecular catalysts immobilized in thick films, underscores the importance of optimizing mass transport conditions and catalyst design to achieve an O 2 -tolerant CO 2 reduction.}, archive = {J_JACS}, author = {Catherine M. Harvey and Sylvie Chardon-Noblat and Cyrille Costentin}, doi = {10.1021/jacs.5c09840}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24171--24178}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-protection mechanism and mass transport governing o2 tolerance in an iron porphyrin homogeneous catalyst for CO2 electroreduction}, volume = {147}, year = {2025}, }
• (2025). Welding 2D semiconducting crystals by covalent stitching of grain boundaries in WS2. JACS, 147(27), 24162--24170. (www)

  @article{ , abstract = {The advent of transition metal dichalcogenides (TMDCs) has revolutionized the field of optoelectronics. In this context, recent advances in the large-area synthesis of monolayer WS 2 opened the door to potential optoelectronic applications because of its inherently high photoluminescence (PL) yield and superior electron mobility. However, randomly distributed point and line defects are key bottlenecks for efficient charge transport, hindering further development of system-on-chip (SoC) technologies. Herein, we report a molecular welding strategy using benzene-1,4-dithiol (BDT) to simultaneously passivate sulfur vacancies and bridge grain boundary (GB) fissures in monolayer WS 2 . The GB welding was monitored on the atomic scale by high-angle annular dark-field scanning transmission electron microscopy. This treatment yields uniform PL emission, ∼200-fold enhancement in electron mobility, and a three-order-of-magnitude increase in both on-state current and I on / I off ratio for transistors across GBs, comparable to intragrain characteristics. Additionally, temperature-dependent PL spectroscopy was employed to identify the defect types and the activation energy of GBs. Our approach, utilizing the facile vapor deposition of ad-hoc molecules to repair line defects in 2D crystals, offers a scalable and effective solution to repair extended line defects in two-dimensional (2D) semiconductors, advancing the development of high-performance, uniform 2D optoelectronic systems.}, archive = {J_JACS}, author = {Bin Han and Chun Ma and Ke Jiang and Maria Batuk and Ahin Roy and Lucia Hughes and Hanlin Wang and Verónica Montes-García and Can Wang and Fanny Richard and Devu Prasad and Antonio Gaetano Ricciardulli and Sara Bals and Valeria Nicolosi and Yumeng Shi and Paolo Samorì}, doi = {10.1021/jacs.5c08763}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24162--24170}, shortjournal = {J. Am. Chem. Soc.}, title = {Welding 2D semiconducting crystals by covalent stitching of grain boundaries in WS2}, volume = {147}, year = {2025}, }
• (2025). Enhanced electrical conductivity by the heavy chalcogen effect in Metal–Organic frameworks. JACS, 147(27), 24152--24161. (www)

  @article{ , abstract = {Establishing effective strategies to impart electrical conductivity to metal–organic frameworks (MOFs) provides new opportunities for advancing research in electronic materials. In this study, we develop a heavy chalcogen incorporation strategy by constructing a new family of isoreticular two-dimensional conductive MOFs, Cu-X-HHS, through the interconnection of Cu ions with three hexahydroxysumanene (HHS) ligands which are embedded chalcogen (X) atoms, including sulfur (S), selenium (Se), and tellurium (Te). Cu-X-HHS MOFs have an infinitely extended wavy and honeycomb network structure. A substantial enhancement in electrical conductivity is observed with increasing atomic number of the incorporated chalcogenides, among which Cu-Te-HHS exhibits an impressive room temperature conductivity of 3.21 S cm –1 , 10,000 times higher than the S-containing analog. Mechanism study reveals that the chalcogen atoms with gradually decreased electronegativity and increased atomic radii affect the frontier orbital matching between the ligand and the Cu ions, as well as the interlayer interaction in the Cu-X-HHS MOFs.}, archive = {J_JACS}, author = {Mingyu Yang and Junjun Tan and Ziping Wang and Dehu Li and Wu Xu and Hong Wang and Long Yuan and Chao Yang and Zheng Meng}, doi = {10.1021/jacs.5c08594}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24152--24161}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced electrical conductivity by the heavy chalcogen effect in Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Overcoming the hydrolytic susceptibility of thiol-reactive reversible warheads through the development of substituted phenyl cyanoacrylamides. JACS, 147(27), 24140--24151. (www)

  @article{ , abstract = {The ascent of α-cyanoacrylamide covalent warheads for the reversible engagement of cysteine thiols has led to the development of a novel class of selective inhibitors. As part of our efforts to develop peptide-based hydrogel materials that incorporate these warheads, we observed that α-cyanoacrylamides undergo undesired retro-Knoevenagel hydrolysis under physiological conditions. This instability extends to small molecule kinase inhibitors as well, possibly affecting their pharmacokinetics. To gain an understanding of this hydrolytic activity, we performed a series of reactivity studies employing BTK and sickle cell inhibitors as well as model peptides. During these studies, we unexpectedly discovered that an α-cyanoacrylamide-functionalized derivative of the sickle cell inhibitor, voxelotor, was exceptionally stable toward hydrolysis. Subsequent structure–activity studies coupled with molecular truncation afforded a small, hydrolytically stable dimethoxyphenyl cyanoacrylamide (DiMe) warhead. This compact unit demonstrates negligible hydrolysis for over a week under physiological conditions while still being prone to reversible thiol addition. Extensive quantum chemistry calculations provide an electronic and structural understanding of this selective reactivity. The utility of the DiMe warhead was demonstrated in the context of small molecule BTK inhibition and should find broad use as a hydrolytically stable yet thiol-reactive reversible warhead in other applications.}, archive = {J_JACS}, author = {Monessha Nambiar and Yixin Xie and Joseph Ivanic and Joel P. Schneider}, doi = {10.1021/jacs.5c08170}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24140--24151}, shortjournal = {J. Am. Chem. Soc.}, title = {Overcoming the hydrolytic susceptibility of thiol-reactive reversible warheads through the development of substituted phenyl cyanoacrylamides}, volume = {147}, year = {2025}, }
• (2025). A chemoproteomic approach for system-wide and site-specific uncovering of functional protein N-glycosylation. JACS, 147(27), 24127--24139. (www)

  @article{ , abstract = {Technological advances in proteomics, including sample separation, mass spectrometry, and searching algorithms, have empowered in-depth discovery of protein post-translational modifications from biological samples. However, there is still a considerable delay in systematic research on the functional significance of these modifications. Herein, we develop a new thermal proteomic strategy, Refined-TPP, enabling the efficient study of protein thermostability with improved sensitivity and increased throughput by 5-fold. Its robust performance in target identification was demonstrated by the metabolite NADPH as well as the drug panobinostat. We further propose glyco-dependent thermal shift profiling (GTSP), a novel chemical proteomic methodology, to systematically examine the effects of site-specific modifications on the thermal stability of native proteins. Finally, we probed 208 functionally important N-glycosites mapping 113 proteins and elucidated their pivotal roles in protein functions, including protein stability, subcellular localization, and enzyme activity. This globally biophysical assay bridges the gap between structural modifications and their functional impacts on proteins and provides here a robust platform for the first time to effectively interrogate functional implications of N-glycosylation. It is also readily applicable in a high-throughput and unbiased manner to further investigations into diverse objects, including drug-target screening, protein interactions, and other functional PTM exploration.}, archive = {J_JACS}, author = {Guoli Wang and Shiyun Ma and Haoru Song and Yuying Liang and Xinze Li and Lei Zhang and Haojie Lu and Ying Zhang}, doi = {10.1021/jacs.5c08065}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24127--24139}, shortjournal = {J. Am. Chem. Soc.}, title = {A chemoproteomic approach for system-wide and site-specific uncovering of functional protein N-glycosylation}, volume = {147}, year = {2025}, }
• (2025). De novo peptides that induce the Liquid–Liquid phase separation of α-synuclein. JACS, 147(27), 24113--24126. (www)

  @article{ , abstract = {Liquid–liquid phase separation (LLPS) of proteins can form membraneless organelles in the cell and can lead to pathological aggregation associated with neurodegenerative diseases. However, progress in controlling LLPS has been limited, and there has been no emergence of engineered de novo molecules to induce and modulate LLPS of targeted proteins. Here, we report de novo peptides that efficiently induce the LLPS of α-synuclein (αSyn), a protein involved in Parkinson’s disease, discovered by the RaPID (random nonstandard peptides integrated discovery) system. These peptides primarily interact with the C-terminal region of αSyn, leading to the formation of an interaction network with αSyn and resulting in efficient droplet formation. Our study demonstrates the capacity of target-specific peptides to control LLPS and the subsequent liquid–solid phase transition (LSPT). Our novel LLPS-inducing and LSPT-modulating peptides may serve as a promising tool for fundamental investigations of LLPS and potentially for therapeutic intervention in amyloid diseases.}, archive = {J_JACS}, author = {Tatsuya Ikenoue and Masatomo So and Naohiro Terasaka and Wei-En Huang and Yasushi Kawata and Yohei Miyanoiri and Kiyoto Kamagata and Hiroaki Suga}, doi = {10.1021/jacs.5c08019}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24113--24126}, shortjournal = {J. Am. Chem. Soc.}, title = {De novo peptides that induce the Liquid–Liquid phase separation of α-synuclein}, volume = {147}, year = {2025}, }
• (2025). Dynamic relocation of copper catalysts in gas diffusion electrodes during CO2 electroreduction. JACS, 147(27), 24103--24112. (www)

  @article{ , abstract = {Developing technologies that convert CO 2 into valuable carbon products using renewable energy is of growing significance. Copper (Cu) is a unique electrocatalyst capable of reducing CO 2 to value-added multicarbon (C 2+ ) compounds. While recent in situ studies have elucidated the dynamic evolution of Cu catalysts during electrochemical CO 2 reduction reactions (CO 2 RR), the relationship between catalyst behavior in gas diffusion electrodes (GDEs) and C 2+ product selectivity at industrially relevant current densities remains insufficiently understood. In this study, we examined the correlation between the structure, chemical state, and C 2+ selectivity of Cu catalysts in Cu-GDEs during CO 2 RR operation at current densities exceeding 200 mA/cm 2 . Ex situ and in situ scanning X-ray fluorescence microscopy revealed significant relocation of Cu within the GDE after CO 2 RR. In situ X-ray absorption spectroscopy identified the presence of Cu 1+ species during operation, indicating that Cu relocation proceeds via a dissolution-redeposition. The dissolution-redeposition behavior was found to be pH-dependent and more pronounced at high pH. Online gas chromatography demonstrated that the decrease in C 2+ selectivity over time was primarily due to flooding, overshadowing the impact of Cu relocation on C 2+ selectivity. These findings provide important insights for designing stable and highly selective Cu-based GDEs for practical CO 2 electrolyzers.}, archive = {J_JACS}, author = {Daiko Takamatsu and Naoto Fukatani and Akio Yoneyama and Tatsumi Hirano and Kakuro Hirai and Shin Yabuuchi and Koichi Watanabe and Kazuhide Kamiya and Shuji Nakanishi}, doi = {10.1021/jacs.5c07944}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24103--24112}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic relocation of copper catalysts in gas diffusion electrodes during CO2 electroreduction}, volume = {147}, year = {2025}, }
• (2025). Unraveling ground-state electron transfer in photoredox n-doping of conjugated polymers through real-time quantum dynamics. JACS, 147(27), 24095--24102. (www)

  @article{ , abstract = {We recently demonstrated that photoredox catalysts can enable n-type doping of conjugated polymers under light at room temperature. While experimental data confirm that the key electron transfer step can proceed from the photoredox catalyst to the conjugated polymer without the involvement of a second photon, a pathway typically invoked to access highly polarized excited states, the underlying mechanism remains elusive. In this work, we employ real-time quantum electron dynamics to investigate the fundamental mechanisms governing this specific charge transfer process and its dependence on the geometric orientation. Our energetic analysis reveals that while this charge transfer process from the photoredox catalyst to the conjugated polymer is thermodynamically favorable, it is only kinetically accessible via through-space charge transfer in a limited set of orientations between the photoredox catalyst and the conjugated polymer. To further enhance the doping efficiency, we propose applying an external static field along the electron transfer direction. Quantum dynamic simulations demonstrate that such an external bias suppresses the tunneling barrier, leading to a faster and more efficient charge transfer. These findings provide valuable design principles for optimizing molecular doping strategies, highlighting the role of structural packing and external field modulation in improving the charge injection and transport in organic electronic materials.}, archive = {J_JACS}, author = {Mengqi Yang and Xinzheng Yang and Eleftherios Lambros and Shiv Upadhyay and Liang Yan and Wei You and Xiaosong Li}, doi = {10.1021/jacs.5c07990}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24095--24102}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling ground-state electron transfer in photoredox n-doping of conjugated polymers through real-time quantum dynamics}, volume = {147}, year = {2025}, }
• (2025). Enantioselective synthesis of 2,3-disubstituted azetidines via copper-catalyzed boryl allylation of azetines. JACS, 147(27), 24085--24094. (www)

  @article{ , abstract = {Disclosed here is a highly enantioselective difunctionalization of azetines for convenient access to chiral 2,3-disubstituted azetidines, a family of important scaffolds previously lacking general access. With Cu/bisphosphine as a catalyst, two versatile functionalities (boryl and allyl) were installed on azetine with concomitant construction of two new stereogenic centers. This represents a rare demonstration of Cu-catalyzed asymmetric boryl alkylation of electron-rich olefins and C═C bonds in strained heterocycles. The use of allyl phosphates proved critical not only to overcome the low reactivity of the borylated alkylcuprate intermediate toward alkylation but also to avoid competing side reactions. Remarkably, in almost all cases, single isomers were obtained with complete regio-, enantio-, and diastereoselectivies on the azetidine motif as well as excellent control on the double bond configuration. The mild conditions exhibited outstanding functional group compatibility and chemoselectivity. The versatile boryl and allyl functionalities allowed for easy transformations of the products to other useful chiral azetidines previously lacking straightforward access. Control experiments and kinetic studies indicated that the reaction proceeds by a fast boryl cupration of azetine followed by rate-determining allylation via an intrinsically controlled S N 2′ pathway.}, archive = {J_JACS}, author = {Minghui Zhu and Jianwei Sun}, doi = {10.1021/jacs.5c07821}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24085--24094}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective synthesis of 2,3-disubstituted azetidines via copper-catalyzed boryl allylation of azetines}, volume = {147}, year = {2025}, }
• (2025). Enzymatic stereoselective nucleophilic cyclization governs atypical spirotetronate assembly in lucensimycin a biosynthesis. JACS, 147(27), 24077--24084. (www)

  @article{ , abstract = {Lucensimycin A is a structurally unique spirotetronate polyketide featuring a rare spiro[tetronate-hydrophenanthrene] tetracyclic core, distinct from the classical spiro[tetronate-cyclohexene] scaffolds formed via intramolecular Diels–Alder (IMDA) cyclizations. Here, we identified and characterized the luc biosynthetic gene cluster from Streptomyces fagopyri NAX0062, revealing a divergent biosynthetic logic. The pathway begins with type I PKS assembly of a linear polyketide, followed by tetronate ring formation by a canonical tetronate cassette. A flavin-dependent Diels–Alderase (LucM) then catalyzes an IMDA reaction to form a decalin intermediate. Unusually, the Diels–Alderase homologue LucK catalyzes a stereoselective intramolecular nucleophilic cyclization─rather than a pericyclic reaction─to generate the spiro[tetronate-hydrophenanthrene] core, following acetylation by LucN. Oxidative cleavage of a terminal alkene (by LucO3) completes the pathway. Structural and mutational analysis of LucK revealed that Glu16 and Glu85 function as general acid/base catalysts to drive the nucleophilic cyclization reaction, highlighting LucK as a mechanistically distinct cyclase. This work uncovers a previously unrecognized enzymatic strategy for spirocyclic construction and expands the catalytic repertoire of β-barrel enzymes in polyketide biosynthesis.}, archive = {J_JACS}, author = {Meng Yu Xi and Bo Zhang and Ting Peng and Xiu Xiu Ma and Ao Zhu and Zi Jie Wang and Yucheng Gu and Ren Xiang Tan and Hui Ming Ge}, doi = {10.1021/jacs.5c07754}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24077--24084}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzymatic stereoselective nucleophilic cyclization governs atypical spirotetronate assembly in lucensimycin a biosynthesis}, volume = {147}, year = {2025}, }
• (2025). A 54.6 GHz clock transition in ho3+ electron spin qubits assembled into a Metal–Organic framework. JACS, 147(27), 24068--24076. (www)

  @article{ , abstract = {A high-symmetry assembly of molecular spin qubits has been achieved in the metal–organic framework (MOF) [Ho(pzdo) 4 ](ClO 4 ) 3 ( 1 ), where the eight-coordinate Ho 3+ nodes are bridged by pyrazine-1,4-dioxide (pzdo) ligands. The approximate square-antiprismatic ( D 4 d ) coordination of the Ho 3+ ion leads to the stabilization of the m J = ±4 ground-state doublet due to crystal-field splitting of the J = 8 total angular momentum state. Mixing of the m J = +4 and m J = –4 projection states opens a zero-field energy gap (Δ) resulting in the spin clock transition (SCT) evident in the EPR spectra of 1 . The SCTs are known to protect qubits from the surrounding magnetic noise to first order, thus enhancing the coherence time of the superposition states crucial for quantum information processing. Frequency-dependent EPR studies reveal that the Ho 3+ centers in 1 exhibit a high-frequency SCT with Δ SCT = 54.6 GHz, which can be beneficial to minimizing second-order decoherence effects. The angular dependence of the resonance fields maps well onto the lattice symmetry, with two distinct orientations of the molecular anisotropy axes related to the tetragonal space group symmetry. All salient aspects of the magnetic and EPR measurements have been captured by a model that uses a new theoretical technique based on a constrained DFT derivation of the effective spin Hamiltonian. This work demonstrates the possibility of engineering SCTs in ordered arrays of molecular spin qubits, thus paving the way to scaling up molecular systems that are promising for applications in emerging quantum technologies.}, archive = {J_JACS}, author = {Miguel Gakiya-Teruya and Robert Stewart and Linqing Peng and Shuanglong Liu and Chenghan Li and Hai-Ping Cheng and Garnet Kin-Lic Chan and Stephen Hill and Michael Shatruk}, doi = {10.1021/jacs.5c07796}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24068--24076}, shortjournal = {J. Am. Chem. Soc.}, title = {A 54.6 GHz clock transition in ho3+ electron spin qubits assembled into a Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Electroreductive borylation of chloroalkanes and polyvinyl chloride plastics. JACS, 147(27), 24060--24067. (www)

  @article{ , abstract = {Covalent modification of poly(vinyl chloride) (PVC) with additives that are typically mixed into PVC plastics would eliminate migration and leaching of these essential plasticizers and stabilizers. This report details an electroreductive methodology for the borylation of PVC, as well as of simple chloroalkanes, using inexpensive boron sources. Mechanistic studies implicate C–B bond formation from the reaction of a boron electrophile and an organomagnesium intermediate. While conventional Grignard formation from employing Mg 0 metals failed, Grignard intermediates were rapidly generated from chloroalkanes and highly reactive Mg deposits generated at the cathode during electrolysis. Translation of this methodology from small- to macromolecular chloroalkanes, like PVC, required the addition of surfactants that disrupt the micellar conformation of PVC in THF. This approach exposes the C–Cl bonds for activation at the cathodic surface. These operationally simple conditions enabled borylation of PVC on a multigram scale without chain scission. Finally, the borylated PVCs were further elaborated into PVCs with various functional groups using robust synthetic methods to create materials with distinct bulk properties, including improved thermal stability and increased plasticity.}, archive = {J_JACS}, author = {Immaculata O. Onuigbo and Jordan L. Zackasee and Valmuri Srivardhan and Jennifer Alina Spejcher and Christo S. Sevov}, doi = {10.1021/jacs.5c07692}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24060--24067}, shortjournal = {J. Am. Chem. Soc.}, title = {Electroreductive borylation of chloroalkanes and polyvinyl chloride plastics}, volume = {147}, year = {2025}, }
• (2025). Unprecedented flux-mediated synthesis of crystalline polyimide covalent organic frameworks using the 4-dimethylaminopyridine (DMAP)-type nucleophilic catalyst for use in efficient photosynthesis of H2O2. JACS, 147(27), 24050--24059. (www)

  @article{ , abstract = {Photocatalytic H 2 O 2 production from water and O 2 represents a sustainable approach for clean chemical synthesis, but developing efficient and stable photocatalysts remains challenging. Herein, we report a novel 4-dimethylaminopyridine (DMAP)-type nucleophilic catalyst-mediated flux synthesis strategy to prepare crystalline polyimide covalent organic frameworks (PI-COFs) as efficient photocatalysts for H 2 O 2 generation. Interestingly, by introducing molten DMAP as the reaction medium, we achieved three PI-COFs (DMAP-BNCOFs, DMAP-BBCOFs, and DMAP-NNCOFs) with significantly enhanced crystallinity and porosity compared to those obtained in conventional solvothermal synthesis. The optimized PI-COFs showed excellent photocatalytic activity, among which DMAP-BNCOFs could achieve a H 2 O 2 production rate of 8051.4 μmol h –1 g –1 without the presence of any sacrificial agents under visible-light irradiation, representing the most efficient polymeric/framework photocatalysts ever reported. The photocatalyst demonstrated remarkable stability over 90 h of continuous operation with no activity loss. DMAP-BNCOFs exhibited a lower exciton binding energy and longer excited-state lifetime compared with those of DMAP-BBCOFs and DMAP-NNCOFs. Experimental and theoretical studies revealed that enhanced performance stems from the optimal electronic structure, efficient charge separation, and accelerated O 2 activation. This work provides new insights into the flux synthesis approach and rational design of PI-COF photocatalysts and establishes an effective strategy for sustainable H 2 O 2 production.}, archive = {J_JACS}, author = {Minghui Chen and Junchen Wang and Tao Wei and Boxin Zhang and Kai Guo and Yaqing Feng and Bao Zhang}, doi = {10.1021/jacs.5c07684}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24050--24059}, shortjournal = {J. Am. Chem. Soc.}, title = {Unprecedented flux-mediated synthesis of crystalline polyimide covalent organic frameworks using the 4-dimethylaminopyridine (DMAP)-type nucleophilic catalyst for use in efficient photosynthesis of H2O2}, volume = {147}, year = {2025}, }
• (2025). Nature of the active sites and reaction mechanism during methanol steam reforming over Cu/ZnO: An isotopic modulated excitation diffuse reflectance infrared fourier transform spectroscopy study. JACS, 147(27), 24040--24049. (www)

  @article{ , abstract = {Hydrogen production with high efficiency and low CO selectivity is the objective of developing methanol steam reforming (MSR) catalysts. The nature of the active sites and reaction mechanisms, however, has not been fully resolved, hampering the rational design of improved catalysts. Herein, we apply the isotope modulation excitation-phase sensitive detection-diffuse reflectance infrared Fourier transform spectroscopy (ME-PSD-DRIFTS) method to identify active surface species and determine the reaction pathway of the dynamic processes. The findings show that methoxy, hydroxyl, and formate species are the key reactive intermediates on the Cu/ZnO catalyst, while carbonate species formed at higher temperatures are spectators that do not participate in the reaction. In addition, the MSR reaction on Cu/ZnO undergoes a “formate” route. Typically, methanol absorbs and dissociates to surface methoxy, which then reacts with hydroxyl from the dissociation of water to form surface formate species and finally decomposes to form CO 2 and H 2 . The interfacial sites play key roles in methoxy dehydrogenation and water dissociation. The results highlight the potential of ME-PSD-DRIFTS to provide a detailed molecular level understanding of the reaction mechanism(s) in the MSR reaction and the dynamics of surface catalytic processes for heterogeneous catalysts in general.}, archive = {J_JACS}, author = {Didi Li and Runfa Qiu and Benjamin M. Moskowitz and Zhaocong Jiang and Haoyuan Gu and Qihang Wen and Israel E. Wachs and Minghui Zhu}, doi = {10.1021/jacs.5c07628}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24040--24049}, shortjournal = {J. Am. Chem. Soc.}, title = {Nature of the active sites and reaction mechanism during methanol steam reforming over Cu/ZnO: An isotopic modulated excitation diffuse reflectance infrared fourier transform spectroscopy study}, volume = {147}, year = {2025}, }
• (2025). Self-resistance guided discovery of a hybrid polyketide-peptide antibiotic from vibrio ruber. JACS, 147(27), 24032--24039. (www)

  @article{ , abstract = {A biosynthetic gene cluster that produces a putative antibacterial natural product was identified from the genome of Vibrio ruber DSM 16370 based on its colocalization with a gene encoding an aminoacyl-tRNA synthetase homologue. Biological assays confirmed that the biosynthetic pathway produced an antibacterial metabolite while also verifying assignment of the aminoacyl-tRNA synthetase as a self-resistance mechanism. The structures of five closely related compounds of mixed polyketide─nonribosomal peptide origin were elucidated. Sequence analysis, mutagenesis and stable isotope feeding studies led to decoding of a plausible biosynthetic pathway for these natural products. The primary products, a trio of interconverting isomers designated vibriomycins A, B, and B′, were found to be unusual allosteric inhibitors of bacterial threonyl-tRNA synthetases. Our study highlights the feasibility of discovering new anti-infective chemotypes via genome mining.}, archive = {J_JACS}, author = {Shreya Kishore and Thomas M. Privalsky and Antonio Del Rio Flores and Stephen R. Lynch and Chaitan Khosla}, doi = {10.1021/jacs.5c07625}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24032--24039}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-resistance guided discovery of a hybrid polyketide-peptide antibiotic from vibrio ruber}, volume = {147}, year = {2025}, }
• (2025). Nitrogen-rich porous-conjugated framework for efficient capture and electroreduction of simulated flue gas in acidic electrolyte. JACS, 147(27), 24023--24031. (www)

  @article{ , abstract = {Achieving the integration of simulated flue gas catalysis with acidic eCO 2 RR represents a highly promising and economically viable strategy for industrialization, yet remains unexplored. Here, with the design of a nitrogen-rich conjugated framework (CAU-35), we first report the successful demonstration of highly efficient conversion of simulated flue gas to formic acid in an acidic environment, while further unveiling a novel mechanism of protonation-enhanced adsorption. Through the integrated construction of capture and catalysis, the system can achieve an unprecedented Faradaic efficiency of 96.6% for formic acid production and a remarkable single-pass conversion efficiency up to 71.4% in a flow cell, surpassing the performance of conventional alkaline systems and those utilizing pure CO 2 as a feedstock. Moreover, comparative studies with the nitrogen-free analogue (CAU-7) unequivocally demonstrate that the anomalous enhancement in acidic acid stems from material protonation. Further complemented by molecular dynamics simulations, the novel mechanism is uncovered by which material protonation can enhance CO 2 adsorption and catalytic performance via optimization of interfacial interaction. These fundamental insights provide critical principles for system optimization and microenvironmental design, paving the way for the practical implementation of eCO 2 RR technologies.}, archive = {J_JACS}, author = {Weiyi Liu and Zunhang Lv and Xin Li and Changli Wang and Chongao Tian and Xiao Feng and Bo Wang and Wenxiu Yang}, doi = {10.1021/jacs.5c07519}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24023--24031}, shortjournal = {J. Am. Chem. Soc.}, title = {Nitrogen-rich porous-conjugated framework for efficient capture and electroreduction of simulated flue gas in acidic electrolyte}, volume = {147}, year = {2025}, }
• (2025). Synergistic Iron–Molybdenum effects for selective electrocatalytic reduction of nitrite to nitric oxide. JACS, 147(27), 24014--24022. (www)

  @article{ , abstract = {We report an efficient bimetallic Mo(IV)Fe(II) electrocatalyst that achieves highly selective nitrite-to-NO reduction. This catalyst demonstrates exceptional performance, with a record turnover frequency (TOF) of ∼10 3 s –1 and a Faradaic efficiency of 93.8%. Mechanistic studies integrating experimental and DFT analyses reveal that the Mo(IV) center preferentially binds NO over the Fe(II) site, preventing the catalytic cycle from terminating at a stable ferrous nitrosyl species. The synergistic interplay between the Fe and Mo centers enhances nitrite dynamic coordination and facilitates reductive N–O bond cleavage, highlighting the critical role of bimetallic synergism in lowering energy barriers and driving demanding exergonic reaction steps involving electron and proton transfer.}, archive = {J_JACS}, author = {Zhiqiang Peng and Jianglan Liu and Xiao-Yi Yang and Shengfa Ye and Xuebin Jiang and Bin Chen and Rong-Zhen Liao and Chen-Ho Tung and Wenguang Wang and Li-Zhu Wu}, doi = {10.1021/jacs.5c07512}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24014--24022}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic Iron–Molybdenum effects for selective electrocatalytic reduction of nitrite to nitric oxide}, volume = {147}, year = {2025}, }
• (2025). Asymmetric C–H amination via Fe(III)-metalloradical catalysis featuring α-Fe(IV)-aminyl radicals as key intermediates. JACS, 147(27), 24001--24013. (www)

  @article{ , abstract = {Metalloradical catalysis (MRC) offers a general mechanistic platform for controlling the reactivity and selectivity of homolytic radical reactions. While Co(II)-based d 7 -metalloradical catalysts have dominated the field, we introduce here an Fe(III)-based d 5 -metalloradical system that is highly effective for asymmetric C–H amination. In particular, we reveal that five-coordinate Fe(III) complexes of porphyrins with an axial ligand, a family of stable 15e-metalloradicals, are potent metalloradical catalysts for 1,5-C(sp 3 )–H amination of aryl azides. Leveraging a specially designed D 2 -symmetric chiral amidoporphyrin ligand, this Fe(III)-based metalloradical system enables the homolytic activation of various aryl azides for the intramolecular amination of diverse C(sp 3 )–H bonds, allowing for the high-yielding construction of chiral indolines with excellent enantioselective control. Notably, this process operates without light or additional additives and generates N 2 as the sole byproduct. Through comprehensive experimental investigations and detailed computational studies, we provide compelling evidence in support of the underlying stepwise radical mechanism. The catalytic pathway involves key steps of hydrogen atom abstraction (HAA) and radical substitution (RS), mediated by the initially generated α-Fe(IV)-aminyl radicals and the subsequently formed ε-Fe(IV)-alkyl radicals, respectively.}, archive = {J_JACS}, author = {Wan-Chen Cindy Lee and Duo-Sheng Wang and Arghya Deb and Yiling Zhu and X. Peter Zhang}, doi = {10.1021/jacs.5c07473}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {24001--24013}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric C–H amination via Fe(III)-metalloradical catalysis featuring α-Fe(IV)-aminyl radicals as key intermediates}, volume = {147}, year = {2025}, }
• (2025). A radiolabeled photoswitchable g protein-coupled receptor antagonist enlightens ligand binding kinetics associated with photoswitching. JACS, 147(27), 23991--24000. (www)

  @article{ , abstract = {Photopharmacology offers powerful opportunities to control protein signaling using photoresponsive ligands. Despite the vast potential of photoswitchable ligands for spatiotemporal target protein control, research on ligand-protein binding kinetics of these ligands remains limited. Herein, we describe the discovery of the first radiolabeled photoswitchable ligand, [ 3 H]VUF26063 ([ 3 H] 3f ), to assess light-dependent ligand-protein binding kinetics in real time. The key compound ( 3f ) is an arylazopyrazole-based antagonist targeting a prototypic family A G protein-coupled receptor (GPCR), the histamine H 3 receptor (H 3 R), and enabled convenient radiolabeling via a growth vector on the pyrazole. Its photochemical properties, subnanomolar affinity of the trans isomer and a 50-fold decrease in affinity upon switching, allowed for reversible photochemical control of H 3 R binding kinetics in real time. The kinetic binding data obtained with this radiolabeled ligand indicate that 3f isomerizes in the H 3 R extended binding pocket upon illumination. Our results shed light on the binding kinetics of photoswitchable ligands and will have relevance beyond GPCRs as targets.}, archive = {J_JACS}, author = {Lars C. P. Binkhorst and Ivana Josimovic and Bas De Boer and Icaro A. Simon and Frank Van Der Aa and Barbara A. Zarzycka and Iwan J. P. De Esch and Henry F. Vischer and Albert D. Windhorst and Maikel Wijtmans and Rob Leurs}, doi = {10.1021/jacs.5c07349}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23991--24000}, shortjournal = {J. Am. Chem. Soc.}, title = {A radiolabeled photoswitchable g protein-coupled receptor antagonist enlightens ligand binding kinetics associated with photoswitching}, volume = {147}, year = {2025}, }
• (2025). Near-infrared light-accelerated bioorthogonal drug uncaging and photothermal ablation by anisotropic Pd@Au plasmonic nanorods. JACS, 147(27), 23980--23990. (www)

  @article{ , abstract = {Selective activation of chemotherapeutics at the tumor site via bioorthogonal catalysis is a promising strategy to reduce collateral damage to healthy tissues and organs. Despite significant advances in this field, targeted drug activation by transition-metal catalysts is still limited by insufficient spatiotemporal control over the metal-mediated uncaging process. Herein, we report the development of anisotropic Pd@Au plasmonic nanorods with the capacity to accelerate dealkylation reactions under near-infrared (NIR) irradiation, thereby enabling precise control over when and where these catalytic devices are switched on. We also show that the stability and in cellulo chemical properties of Pd@Au nanorods are enhanced by Au–S functionalization with PEGylated phospholipids and report the development of a novel masking group for prodyes and prodrugs: the POxOC group, designed to improve physicochemical properties and the rate of the Pd-triggered dye/drug release process. NIR-photoactivation of lipo-Pd@Au nanorods is able to catalyze the uncaging of inactive drug precursors and release heat to the environment, killing cancer cells in culture and xenografted in zebrafish. This work provides a novel targeted strategy for photothermal chemotherapy by NIR-laser focalization.}, archive = {J_JACS}, author = {M. Carmen Ortega-Liebana and Jana Travnickova and Catherine Adam and Davir González-Calderón and Álvaro Lorente-Macías and Charles Lochenie and Raul Arenal and E. Elizabeth Patton and Asier Unciti-Broceta}, doi = {10.1021/jacs.5c07261}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23980--23990}, shortjournal = {J. Am. Chem. Soc.}, title = {Near-infrared light-accelerated bioorthogonal drug uncaging and photothermal ablation by anisotropic Pd@Au plasmonic nanorods}, volume = {147}, year = {2025}, }
• (2025). Quantum spin dynamics of one-dimensional magnetic van der waals heterostructures. JACS, 147(27), 23972--23979. (www)

  @article{ , abstract = {The discovery of intrinsic magnetism within a single molecule has attracted significant interest. However, progress in the applications of nanospintronics using molecular magnets has been sluggish due to stability issues with both the devices and their performance. In this study, we propose a promising approach to protect magnetic molecules from the environment by encapsulating them in nanoscale tubular holes of carbon tubes. An atomic-resolution scanning transmission electron microscopy (STEM) image revealed that dysprosium chloride encapsulated in CNT forms a one-dimensional chain with a compressed layer gap compared to the bulk sample. Charge transfer between the SWCNT and dysprosium chloride chains has been confirmed through optical characteristics, X-ray photoelectron spectroscopy measurements, and DFT calculations. The magnetic chain exhibits distinct quantum spin dynamics compared to those of the bulk sample. This distinction is primarily due to the modulation of magnetic anisotropy in Dy(III) ions, which is facilitated by charge transfer and structural alterations. Our work provides insights into the interaction between inner encapsulated spins and CNT, establishing the groundwork for electrical spin manipulation in new “spintronics double quantum dot” CNT nanodevices.}, archive = {J_JACS}, author = {Jing Li and Zhen Zhang and Yunfei Li and Hui Zhang and Yunlei Zhong and Alei Li and Yu Teng and Jian Yao and Chao Zhou and Zhaochuan Fan and Lin Geng and Lixing Kang}, doi = {10.1021/jacs.5c07286}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23972--23979}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantum spin dynamics of one-dimensional magnetic van der waals heterostructures}, volume = {147}, year = {2025}, }
• (2025). A Heteroleptic/Trimetallic OsII–RuII–ZnII sierpiński triangle for efficient photodynamic therapy of hypoxic tumors mainly through type i mechanism. JACS, 147(27), 23957--23971. (www)

  @article{ , abstract = {Owing to its less oxygen-dependent mechanism, type I photodynamic therapy (PDT) has exhibited significant superiority over the more common type II PDT in the treatment of hypoxic tumors. Supramolecular coordination complexes (SCCs) have shown great potential in photodynamic cancer therapy; however, SCC-based photosensitizers which can achieve type I PDT have rarely been reported. Herein, we present the design and synthesis of a novel heteroleptic/trimetallic Os II –Ru II –Zn II Sierpiński triangle ST-2 via coordination-driven self-assembly. The distinctive SCC ST-2 displayed high generation ability of reactive oxygen species (ROS) and boosted the production of O 2 –• involved in the type I mechanism. Detailed in vitro investigations demonstrated ST-2 exhibited excellent PDT efficacy against all tested cancer cell lines with low IC 50 values in the subnanomolar range and high phototoxicity indexes (PI) up to 750 even under hypoxic conditions and induced cancer cell death mainly through type I PDT. The anticancer mechanism could be ascribed to the mitochondrial and lysosomal damages as well as cell apoptosis and cell cycle arrest. Further studies confirmed that ST-2 disintegrated 3D multicellular tumor spheroids and effectively inhibited the growth of solid hypoxic tumors in mice with minimal side effects. This work not only provides an alternative strategy for the development of highly efficient type I photosensitizers but also opens new possibilities for Sierpiński triangles in biomedicine.}, archive = {J_JACS}, author = {Huan Qin and Qiaolin Chen and Bangtang Chen and Jun Wang and Huilin Su and Xiaojie Huang and Qiangqiang Dong and Mingzhao Chen and Zhimin Jiang and Yingying Li and Pingshan Wang and Zhilong Jiang}, doi = {10.1021/jacs.5c07313}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23957--23971}, shortjournal = {J. Am. Chem. Soc.}, title = {A Heteroleptic/Trimetallic OsII–RuII–ZnII sierpiński triangle for efficient photodynamic therapy of hypoxic tumors mainly through type i mechanism}, volume = {147}, year = {2025}, }
• (2025). Diastereo- and enantioselective pd-catalyzed C–P coupling for axially and P-chiral phosphine oxides via simultaneous dynamic kinetic asymmetric transformation and kinetic resolution. JACS, 147(27), 23946--23956. (www)

  @article{ , abstract = {The catalytic asymmetric synthesis of atropisomers bearing axial and P -chirality is highly appealing yet remains a significant synthetic challenge. Herein, we report a Pd-catalyzed diastereo- and enantioselective C–P coupling reaction that enables the atroposelective construction of P -stereogenic heterobiaryls via the combination of dynamic kinetic asymmetric transformation of heterobiaryls and kinetic resolution of nonsymmetric secondary phosphine oxides. This protocol exhibits a broad substrate scope with excellent functional group tolerance, delivering a diverse array of axial and P -chiral phosphine oxides in high yields and excellent diastereoselectivities with near-perfect enantioselectivities. The synthetic utility of this method is further demonstrated by the facile preparation of multichiral Lewis base catalysts and the asymmetric synthesis of chiral P , N -ligands such as QUINAP.}, archive = {J_JACS}, author = {Shen Gao and Lei Su and Jiawang Liu}, doi = {10.1021/jacs.5c07049}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23946--23956}, shortjournal = {J. Am. Chem. Soc.}, title = {Diastereo- and enantioselective pd-catalyzed C–P coupling for axially and P-chiral phosphine oxides via simultaneous dynamic kinetic asymmetric transformation and kinetic resolution}, volume = {147}, year = {2025}, }
• (2025). Designing high-temperature stable electrolytes: Insights from the degradation mechanisms of boron-containing additives. JACS, 147(27), 23931--23945. (www)

  @article{ , abstract = {With the increasing energy density and expanding applications of lithium-ion batteries, the demand for enhanced high-temperature performance has grown significantly. Although previous studies have attempted to improve the high-temperature stability through electrolyte modifications, the underlying failure mechanisms and the rational design principles for suitable electrolyte systems remain insufficiently understood. This study focuses on electrolytes containing boron-based additives, particularly lithium tetraborate, which exhibits excellent rate capability and impressive low-temperature performance but suffers from instability at elevated temperatures. Our investigation reveals that high-temperature battery failure is not solely attributed to aluminum current collector corrosion and the thermal instability of the bulk electrolyte but also to interphasial instability. These include detrimental side reactions catalyzed by Ni-rich cathodes and compromised electron-blocking capabilities of interphasial films. Based on these findings, we propose a new design guideline for high-temperature-stable electrolyte solutions, which is validated by the successful application of tris(2,2,2-trifluoroethyl) borate and 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl) cyclotrisiloxane as functional additives. These additives effectively address the identified degradation pathways, resulting in significantly enhanced high-temperature performance. This comprehensive framework provides valuable insights into the rational design of advanced electrolyte systems for lithium-ion batteries that can be operated across a broad temperature range.}, archive = {J_JACS}, author = {Zhangyating Xie and Zhiyong Xia and Jie Cai and Ruoyu Guo and Yili Chen and Wentao Liang and Ziyuan Tang and Qinqin Cai and Zekai Ma and Jiarong He and Ronghua Zeng and Boris Markovsky and Doron Aurbach and Lidan Xing and Weishan Li}, doi = {10.1021/jacs.5c06741}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23931--23945}, shortjournal = {J. Am. Chem. Soc.}, title = {Designing high-temperature stable electrolytes: Insights from the degradation mechanisms of boron-containing additives}, volume = {147}, year = {2025}, }
• (2025). Displaying in vivo “Assembly–Disassembly” cascade with “Off–On–Off” magnetic resonance imaging signals in tumor. JACS, 147(27), 23923--23930. (www)

  @article{ , abstract = {“Assembly–Disassembly” cascade has been utilized as a highly effective approach for tumor theranostics, but its real-time in vivo monitoring remains challenging. Current strategies face a fundamental trade-off between penetration depth and real-time nature, while there is still no report on integrating both features to display this dynamic cascade in a living organism. In this work, we develop a gadolinium (Gd) probe Cys(StBu)-Asp-Asp-Asp-Asp-Lys-Lys(DOTA(Gd))-CBT ( Gd-AD ) to display an in vivo “Assembly–Disassembly” cascade via T 1 -weighted “Off–On–Off” 1 H magnetic resonance imaging (MRI) signals. Under reduction conditions, Gd-AD undergoes a CBT-Cys click reaction to assemble into a Gd nanoparticle, with enhanced 1 H MRI signals of 59.3% and 25.4% in cells and in tumors, respectively (“Off–On”). Upon enterokinase (ENTK) cleavage, the nanoparticle disassembles, rendering decreased 1 H MRI signals of 23.4% and 15.2% in cells and in tumors, respectively (“On–Off”). A scrambled control probe Asp-Asp-Asp-Asp-Lys-Cys(StBu)-Lys(DOTA(Gd))-CBT ( Gd-A ), which responds to reduction and ENTK to assemble into a Gd nanoparticle with “Off–On” 1 H MRI signals, is designed and studied in parallel. During 1 h tumor imaging, while Gd-A only displays “Off–On” 1 H MRI signals, Gd-AD clearly shows “Off–On–Off” signals to reflect the “Assembly–Disassembly” cascade of Gd nanoparticles in tumor. We expect that our strategy of real-time display of in vivo “Assembly–Disassembly” cascade could help people to optimize their nanodrug-based tumor theranostics in the near future.}, archive = {J_JACS}, author = {Hai-Dong Xu and Xianbao Sun and Zheng Huang and Xiaotong Cheng and Xiancheng Fu and Jiayu Li and Ziwen Wei and Junchao Qian and Gaolin Liang}, doi = {10.1021/jacs.5c06634}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23923--23930}, shortjournal = {J. Am. Chem. Soc.}, title = {Displaying in vivo “Assembly–Disassembly” cascade with “Off–On–Off” magnetic resonance imaging signals in tumor}, volume = {147}, year = {2025}, }
• (2025). Micro crystalline sponge method combined with small-wedge synchrotron crystallography for nanogram scale molecular structure elucidation. JACS, 147(27), 23917--23922. (www)

  @article{ , abstract = {The crystalline sponge (CS) method enables X-ray structural analysis without the requirement of crystallization of the target compound. However, several technical and crystallographic challenges, such as low guest occupancy, static disorder, and crystal degradation, continue to limit both the accuracy and the success rate of the method. In this study, we explored the downsizing of CS crystals to the range of 1–10 μm to improve data quality and reduce the amount of sample required. By employing the small-wedge synchrotron crystallography method, which utilizes synchrotron X-ray sources and data merging techniques, we achieved significant improvements in structural accuracy and broadened the method’s applicability, even to trace samples at the nanogram level (∼3 ng).}, archive = {J_JACS}, author = {Satoshi Yoshida and Seiki Baba and Nobuhiro Mizuno and Yuki Nakamura and Sota Sato and Makoto Fujita}, doi = {10.1021/jacs.5c06360}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23917--23922}, shortjournal = {J. Am. Chem. Soc.}, title = {Micro crystalline sponge method combined with small-wedge synchrotron crystallography for nanogram scale molecular structure elucidation}, volume = {147}, year = {2025}, }
• (2025). Single-molecule reactor based on the excluded volume effect of bottlebrush polymers. JACS, 147(27), 23910--23916. (www)

  @article{ , abstract = {Precise spatiotemporal control of chemical reactions, as in living organisms, is a longstanding challenge in chemistry. Herein, we develop a bottlebrush polymer reactor (BBPR), which is a simple yet versatile single-molecule reactor consisting of a bottlebrush polymer that can spatially confine various polymerization reactions. The dense side chains of bottlebrush polymers generate a strong excluded volume effect (EVE) that effectively prevents reactions between the backbone chains of individual BBPRs. However, BBPRs allow the intrusion of small molecules and linear polymer chains. BBPRs can confine two distinct polymerization reactions, namely, ring-opening metathesis polymerization and Suzuki–Miyaura polymerization, without significant inter-reactor coupling reactions. The BBPR concept offers flexibly adjustable confinement spaces, selective permeability, and facile product release, providing a new paradigm for precision control of chemical reactions.}, archive = {J_JACS}, author = {Xiangyuan Guo and Dian Zhang and Naoko Yoshie and Shintaro Nakagawa}, doi = {10.1021/jacs.5c06532}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23910--23916}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-molecule reactor based on the excluded volume effect of bottlebrush polymers}, volume = {147}, year = {2025}, }
• (2025). Going to extreme lengths: Bicyclic diborane(6) anions and the limits of Boron–Boron σ bonding. JACS, 147(27), 23900--23909. (www)

  @article{ , abstract = {The reaction of (naphthalen-1,8-diyl)dilithium (NapLi 2 ) with difluoro(mesityl)borane (MesBF 2 ) in Et 2 O yielded a new 1,5-diborocine, 1 , representing a straightforward route to this rare class of eight-membered boracycle. The reduction of 1 with excess Li yielded Li + salts of [ 1 ] 2– , whose THF and pyridine solvates possess among the longest crystallographic B–B bonds currently known (1.9909(17) and 2.017(2) Å), and the latter is the first instance of an organoboron compound with an electron-precise B–B bond length beyond 2 Å. The THF solvate comproportionates with 1 to form [Li(THF) 4 ][ 1 ] containing a long (2.3–2.4 Å), covalent one-electron σ bond, and both [ 1 ] ·– and [ 1 ] 2– demonstrate incredible stability despite geometric strain on the central bond. These experimental findings, combined with theoretical bonding analyses of various one- and two-electron boron–boron bonds using DFT, give valuable insight into the limits of covalent boron–boron bonding and the diversity in bonding observed near these limits.}, archive = {J_JACS}, author = {Douglas Turnbull and Elaina Bourque and Nathan D. D. Hill and Marc-André Légaré}, doi = {10.1021/jacs.5c06498}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23900--23909}, shortjournal = {J. Am. Chem. Soc.}, title = {Going to extreme lengths: Bicyclic diborane(6) anions and the limits of Boron–Boron σ bonding}, volume = {147}, year = {2025}, }
• (2025). Impact of induced fitting and secondary noncovalent interactions on site-selective and enantioselective C–H functionalization of arylcyclohexanes. JACS, 147(27), 23891--23899. (www)

  @article{ , abstract = {A major challenge in organic synthesis is the selective functionalization of C–H bonds. As most organic compounds contain multiple C–H bonds with similar properties, distinguishing between them requires precise control. In this study, we show how transition metal catalysts can adopt many of the characteristics associated with enzymes, leading to unprecedented site-selectivity in the C–H functionalization step. The catalysts are dirhodium complexes that adopt a bowl-shaped shape on formation. The flexible microenvironment within the bowl causes an induced fitting to occur as the reagent and substrate approach the catalyst. The key factors controlling the selectivity are noncovalent interactions between the approaching substrate and the catalyst wall, which cause a specific C–H bond in the substrate to be placed close to the metal-bound reagent.}, archive = {J_JACS}, author = {Duc Ly and Yannick T. Boni and Korkit Korvorapun and Volker Derdau and John Bacsa and Djamaladdin G. Musaev and Huw M. L. Davies}, doi = {10.1021/jacs.5c06398}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23891--23899}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of induced fitting and secondary noncovalent interactions on site-selective and enantioselective C–H functionalization of arylcyclohexanes}, volume = {147}, year = {2025}, }
• (2025). Design and semisynthesis of ubiquitin extension probes for structural analysis of cullin1-mediated substrate polyubiquitination. JACS, 147(27), 23878--23890. (www)

  @article{ , abstract = {Chemical trapping strategies have recently emerged as powerful approaches for investigating the structural dynamics of E3 ligase-catalyzed substrate ubiquitination. However, current ubiquitination-derived probes are limited to studying substrate mono- or diubiquitination events. Probes capable of investigating how E3 ligases accommodate E2–Ub conjugates and ubiquitinated substrates to generate longer ubiquitin chains remain unexplored. In this work, we report the development of two Cullin1 E3 ligase (CRL1)-dependent probes, Extension Probe Ub2 and Extension Probe Ub4 , which mimic transient intermediates formed during CRL1-catalyzed K48-linked diubiquitin and tetraubiquitin chain formation on substrate p27. Notably, a chemoenzymatic semisynthetic strategy was devised to generate Extension Probe Ub4 , involving the enzymatic conjugation of a preformed K48-linked diubiquitin to a synthetic Ub-p27-degron construct using the E2 conjugating enzyme UBE2K. Both Extension Probe Ub2 and Extension Probe Ub4 formed stable complexes with N8-CRL1 Skp1/Skp2/Cks1 (comprising neddylated Cullin1–Rbx1 and the substrate receptor complex Skp1–Skp2–Cks1), facilitating structural analysis by chemical cross-linking mass spectrometry (CX-MS) and cryo-electron microscopy (cryo-EM). Our results indicate the presence of multiple distinct conformations of the catalytic module (comprising the RING domain of Rbx1, CDC34–Ub, and the acceptor ubiquitin) within the di- and tetraubiquitination complexes, while the conformation of the Cullin1–Skp1–Skp2–Cks1 subunit remains unchanged. In conclusion, this work expands the toolkit available for chemical trapping strategies and provides advanced insights into CRL-catalyzed substrate polyubiquitination.}, archive = {J_JACS}, author = {Chuntong Li and Fangyu Zhao and Chong Zuo and Liying Zhang and Yangwode Jing and Xu Li and Guo-Chao Chu and Luyu Shi and Yingyue Zhang and Han Wang and Shuzhe Sun and Maoshen Sun and Huasong Ai and Lu-Jun Liang and Jinghong Li}, doi = {10.1021/jacs.5c06399}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23878--23890}, shortjournal = {J. Am. Chem. Soc.}, title = {Design and semisynthesis of ubiquitin extension probes for structural analysis of cullin1-mediated substrate polyubiquitination}, volume = {147}, year = {2025}, }
• (2025). Single-component high-performance adhesives enabled by synergistic supramolecular and covalent polymerization. JACS, 147(27), 23868--23877. (www)

  @article{ , abstract = {The development of high-strength supramolecular adhesives from a single small molecule is a highly compelling research goal, as it offers the potential for lightweight, reversible, and stimuli-responsive bonding systems. However, achieving such adhesives presents significant challenges. Herein, we present a novel tripodal multifunctional molecule, BTA-C7 , designed to exploit a synergistic supramolecular and covalent polymerization strategy to achieve a remarkable adhesive performance. BTA-C7 features a central benzene-1,3,5-tricarboxamide (BTA) core from which cyanostilbene moieties extend, each terminating in a benzo-crown-ether macrocycle. Under ambient conditions, while the highly directional hydrogen bonding between tripodal amide groups induces one-dimensional (1D) stacked arrays, the terminal benzo-crown-ether macrocycles facilitate the assemblies of the 1D chains, thereby promoting the formation of supramolecular networks exhibiting a baseline adhesion of 2.28 MPa as measured by lap-shear tests. Notably, under ultraviolet (UV) irradiation, the supramolecular networks undergo additional covalent photo-cross-linking through a [2 + 2] cycloaddition reaction, facilitated by the supramolecular confinement of cyanostilbene moieties. This process significantly enhances the adhesion strength to 5.18 MPa. Comparative studies with model compounds BTA-O7 (devoid of crown ether moieties, replaced by acyclic glycol chains) and BTE-C7 (with amide units replaced by ester groups) reveal that amide and crown ether units are indispensable for both supramolecular networks and covalent cross-linking.}, archive = {J_JACS}, author = {Yan Shao and Wen Li and Massimo Cametti and Zoran Džolić and Zeyang Ding and Zairan Yang and Ying Xie and Shimei Jiang}, doi = {10.1021/jacs.5c06302}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23868--23877}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-component high-performance adhesives enabled by synergistic supramolecular and covalent polymerization}, volume = {147}, year = {2025}, }
• (2025). Scaling the altermagnet GdAlSi beyond the monolayer limit. JACS, 147(27), 23857--23867. (www)

  @article{ , abstract = {Altermagnets, an emerging class of magnetic materials, combine zero net magnetization with strong spin-based phenomena that makes them highly attractive for spintronics. Practical applications require altermagnets to be brought to the nanoscale; however, this area is scarcely explored experimentally. Recently, films of the Weyl altermagnet GdAlSi have been studied down to a single monolayer to reveal symmetry breaking and thickness-dependent evolution of its properties. Here, we show that the structure of GdAlSi allows for further miniaturization, making 1/2 monolayer a basic building block for construction of 2D spintronic materials. Epitaxy of 1/2 monolayer of GdAlSi results in a film with nearly compensated magnetic moments; it exhibits a semiconducting behavior, in contrast to the metallic monolayer and the bulk. The semiconductor demonstrates colossal negative magnetoresistance, exceeding that in a monolayer by more than an order of magnitude. The anomalous Hall effect in 1/2 monolayer of GdAlSi follows the universal scaling relation for magnetic semiconductors. The fabricated material is seamlessly integrated with Si, thus holding high promise for ultracompact spintronics.}, archive = {J_JACS}, author = {Oleg E. Parfenov and Dmitry V. Averyanov and Ivan S. Sokolov and Alexey N. Mihalyuk and Oleg A. Kondratev and Alexander N. Taldenkov and Andrey M. Tokmachev and Vyacheslav G. Storchak}, doi = {10.1021/jacs.5c06305}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23857--23867}, shortjournal = {J. Am. Chem. Soc.}, title = {Scaling the altermagnet GdAlSi beyond the monolayer limit}, volume = {147}, year = {2025}, }
• (2025). A molecular glue approach to control the half-life of CRISPR-based technologies. JACS, 147(27), 23844--23856. (www)

  @article{ , abstract = {Cas9 is a programmable nuclease that has furnished transformative technologies, including base editors and transcription modulators (e.g., CRISPRi/a), but several applications of these technologies, including therapeutics, mandatorily require precision control of their half-life. For example, such control can help avert any potential immunological and adverse events in clinical trials. Current genome editing technologies to control the half-life of Cas9 are slow, have lower activity, involve fusion of large response elements (>230 amino acids), utilize expensive controllers with poor pharmacological attributes, and cannot be implemented in vivo on several CRISPR-based technologies. We report a general platform for half-life control using the molecular glue, pomalidomide, that binds to a ubiquitin ligase complex and a response-element bearing CRISPR-based technology, thereby causing the latter’s rapid ubiquitination and degradation. Using pomalidomide, we were able to control the half-life of large CRISPR-based technologies (e.g., base editors and CRISPRi) and small anti-CRISPRs that inhibit such technologies, allowing us to build the first examples of on-switch for base editors. The ability to switch on, fine-tune, and switch-off CRISPR-based technologies with pomalidomide allowed complete control over their activity, specificity, and genome editing outcome. Importantly, the miniature size of the response element and favorable pharmacological attributes of the drug pomalidomide allowed control of activity of base editor in vivo using AAV as the delivery vehicle. These studies provide methods and reagents to precisely control the dosage and half-life of CRISPR-based technologies, propelling their therapeutic development.}, archive = {J_JACS}, author = {Vedagopuram Sreekanth and Max Jan and Kevin T. Zhao and Donghyun Lim and Surached Siriwongsup and Jessie R. Davis and Marie McConkey and Veronica Kovalcik and Sam Barkal and Benjamin K. Law and James Fife and Ruilin Tian and Michael E. Vinyard and Basheer Becerra and Martin Kampmann and Richard I. Sherwood and Luca Pinello and David R. Liu and Benjamin L. Ebert and Amit Choudhary}, doi = {10.1021/jacs.5c06230}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23844--23856}, shortjournal = {J. Am. Chem. Soc.}, title = {A molecular glue approach to control the half-life of CRISPR-based technologies}, volume = {147}, year = {2025}, }
• (2025). Introduction of reactive thiol handles into tyrosine-tagged proteins through enzymatic oxidative coupling. JACS, 147(27), 23834--23843. (www)

  @article{ , abstract = {Site-specific protein bioconjugation methods have enabled the development of new therapeutics and materials, and further development of existing techniques has expanded the compatible library of protein substrates for bioconjugation. Among these techniques, the enzyme tyrosinase has demonstrated a promising ability to form protein–protein conjugates between exposed tyrosine and cysteine residues. In this work, we observed that the tyrosinase variant from Bacillus megaterium , termed megaTYR, has an increased tolerance for small-molecule thiol substrates, which can inhibit the activity of other tyrosinases. Among the breadth of thiol substrates that could be reliably coupled to tyrosine-tagged proteins was dithiothreitol (DTT), which effectively introduces a free thiol handle and provides a convenient method to bypass the genetic incorporation of cysteine residues for bioconjugation. Accordingly, these thiolated proteins could undergo additional coupling to commercially available maleimide probes as well as other tyrosine-tagged proteins. This was demonstrated by the conjugation of targeting proteins to drugs, fluorescent probes, and therapeutic enzymes. Of particular note and building on a previous report of a tyrosinase-sensitive tyrosine residue on the Fc region of antibodies, commercially available monoclonal antibodies (mAbs) treated with PNGase F were conjugated to DTT to produce THIOMAB equivalents. These intermediates were subsequently used to make functional antibody–drug and antibody–toxin protein conjugates. This facile method to convert accessible tyrosine residues on proteins to thiol tags extends the use of tyrosinase-mediated oxidative coupling to a broader range of protein substrates.}, archive = {J_JACS}, author = {Paul Huang and Wendy Cao and Jennifer L. Fetzer and Nicholas S. Dolan and Matthew B. Francis}, doi = {10.1021/jacs.5c06195}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23834--23843}, shortjournal = {J. Am. Chem. Soc.}, title = {Introduction of reactive thiol handles into tyrosine-tagged proteins through enzymatic oxidative coupling}, volume = {147}, year = {2025}, }
• (2025). Exploring the role of the nephelauxetic effect in circularly polarized luminescence of chiral Chromium(III) complexes. JACS, 147(27), 23827--23833. (www)

  @article{ , abstract = {A novel chiral chromium(III) molecular ruby [Cr(qpp) 2 ] 3+ (qpp = N -methyl- N -(pyridin-2-yl)-6-(quinolin-8-yl)pyridin-2-amine) has been synthesized, enantiomerically resolved, and fully characterized. The circularly polarized luminescence (CPL) spectra revealed two emission bands of opposite polarization in the near-infrared region (700–800 nm), corresponding to the metal-centered transitions Cr( 2 T(1) → 4 A 2 ) and Cr( 2 E(1) → 4 A 2 ). Notably, the dissymmetry factor g lum reached 0.11 for the former transition, which is among the highest reported for chromium(III) systems. Comparison with structurally related homo- and heteroleptic chromium(III) complexes underscores the important role of the nephelauxetic effect in tuning CPL properties. Increased metal–ligand covalency, indicative of a stronger nephelauxetic effect, enhances orbital mixing and modifies the electronic character of the emissive states. These changes influence both electric and magnetic transition dipole moments, leading to noticeable variations in dissymmetry factor g lum . Altogether, these observations highlight the potential of fine-tuning metal–ligand covalency as a rational strategy for optimizing the chiroptical properties of chromium(III) complexes, with promising implications for bioimaging, molecular probes, and circularly polarized optoelectronic devices.}, archive = {J_JACS}, author = {Maxime Poncet and Laura Cuevas-Contreras and Yating Ye and Laure Guénée and Carlos M. Cruz and Claude Piguet and Juan-Ramón Jiménez}, doi = {10.1021/jacs.5c06196}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23827--23833}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploring the role of the nephelauxetic effect in circularly polarized luminescence of chiral Chromium(III) complexes}, volume = {147}, year = {2025}, }
• (2025). Rational design of a foldon-derived heterotrimer guided by quantitative native mass spectrometry. JACS, 147(27), 23819--23826. (www)

  @article{ , abstract = {Designing stable hetero-oligomeric protein complexes with defined intersubunit stoichiometry remains a significant challenge. In this study, we report the design of a highly selective heterotrimeric assembly derived from the well-known foldon homotrimer. We generated an aab heterotrimer by replacing glutamine 11 with glutamic acid, to destabilize the homotrimer, and replacing valine 14 with either alanine or leucine, to stabilize the hydrophobic core of the heterotrimer. Native mass spectrometry (MS) was essential for guiding the design process, enabling precise characterization of oligomeric states and their equilibrium distributions. The heterotrimer structure was validated by X-ray crystallography. Our findings highlight the effectiveness of combining rational design with native MS to develop specific hetero-oligomeric assemblies.}, archive = {J_JACS}, author = {Xinyu Liu and David S. Roberts and Craig A. Bingman and Ying Ge and Samuel H. Gellman}, doi = {10.1021/jacs.5c06094}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23819--23826}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design of a foldon-derived heterotrimer guided by quantitative native mass spectrometry}, volume = {147}, year = {2025}, }
• (2025). High-throughput electrochemical delamination of two-dimensional covalent organic frameworks. JACS, 147(27), 23809--23818. (www)

  @article{ , abstract = {Porous crystalline nanosheets of two-dimensional covalent organic frameworks (2D COFs) possess intriguing structural features and extensive application potential. However, the scalable and efficient synthesis of well-crystallized COF nanosheets remains challenging despite recent advances in exfoliation and in situ growth techniques. Here we report a high-throughput electrochemical strategy that nondestructively delaminates polycrystalline 2D COF films into large nanosheets with long-range crystallographic order. This method achieves a remarkable delamination productivity of 100 mg h –1 , yielding crystalline nanosheets that are readily dispersible across various solvents including water. Principal component analysis reveals solvent permittivity and polarity, along with film wettability, as critical factors governing the delamination efficiency. Complementary diffraction, spectroscopy, and electron microscopy studies elucidate a synergistic delamination mechanism involving molecular preintercalation, framework protonation, and electrolysis-driven gas evolution. Leveraging the intrinsic microporosity and excellent solution processability of these nanosheets, we demonstrate their utility in producing membranes for efficient antibiotic desalination. This work advances the scalable synthesis of crystalline COF nanosheets, broadening the application toolkit of COFs.}, archive = {J_JACS}, author = {Tong Ju and Xiansong Shi and Zhenshu Si and Tianci Feng and Jianghai Long and Congcong Yin and Zhe Zhang and Yong Wang}, doi = {10.1021/jacs.5c06026}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23809--23818}, shortjournal = {J. Am. Chem. Soc.}, title = {High-throughput electrochemical delamination of two-dimensional covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Unlocking a nano-aluminum oxide lewis acid layer as the electrocatalyst for hydrogenation of thiophene and other arenes. JACS, 147(27), 23797--23808. (www)

  @article{ , abstract = {Owing to the ready formation of an insulating oxide layer, there is an intrinsic obstacle to the use of aluminum material as the cathode in the electrocatalytic reaction. In this report, a new Al-based material with a surface aluminum oxide/chloride nanolayer (nAlClO@Al) is prepared. Via the quantum tunneling effect, this material realizes conductivity through the nano-Al–O layer. This material exhibits unusual inertness toward the hydrogen evolution reaction, leaving a wide reduction window for the substrate. Primed with the native Lewis acidity of the Al–Cl structure, this material achieves the electrocatalytic hydrogenation of thiophenes with up to >95% conversion, >95% selectivity, and 90% Faraday efficiency. This catalysis is applicable to heteroarene and benzene rings. In particular, the chemoselectivity is controlled by the nAlClO@Al catalyst instead of the substrate, which is complementary to electrochemical Birch chemistry.}, archive = {J_JACS}, author = {Xiaofeng Zhang and Aoqian Qiu and Pan Ran and Mengning Ding and Xu Cheng}, doi = {10.1021/jacs.5c06034}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23797--23808}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking a nano-aluminum oxide lewis acid layer as the electrocatalyst for hydrogenation of thiophene and other arenes}, volume = {147}, year = {2025}, }
• (2025). Biosynthesis of biphenomycin-like macrocyclic peptides by formation and cross-linking of ortho-tyrosines. JACS, 147(27), 23781--23796. (www)

  @article{ , abstract = {Ribosomally synthesized and posttranslationally modified peptides (RiPPs) are a growing class of natural products. Multinuclear nonheme iron-dependent oxidative enzymes (MNIOs, previously DUF692) are involved in a range of unprecedented biochemical reactions. Over 13,500 putative MNIO-encoding biosynthetic gene clusters (BGCs) have been identified by sequence similarity networks. In this study, we investigated a set of precursor peptides containing a conserved FHAFRF motif in MNIO-encoding BGCs. These BGCs contain genes encoding an MNIO, a RiPP recognition element-containing protein, an arginase, a hydroxylase, and a vitamin B12-dependent radical SAM enzyme (B12-rSAM). Using heterologous reconstitution of a representative BGC from Peribacillus simplex ( pbs cluster) in E. coli , we demonstrated that the MNIO in conjunction with the partner protein catalyzes ortho -hydroxylation of each of the phenylalanine residues in the conserved FRF motif, the arginase forms an ornithine from the arginine, the ornithine residue is hydroxylated, and the B12-rSAM cross-links the ortho -Tyr side chains by a C–C linkage forming a macrocycle. A protease matures the RiPP to its final form. The elucidated structure shares close similarity to biphenomycins, a class of peptide antibiotics for which the biosynthetic pathway has not been characterized. Substrate scope studies suggest some tolerance of the MNIO and the B12-rSAM enzymes. This study expands the diverse array of posttranslational modifications catalyzed by MNIOs and B12-rSAM enzymes, deorphanizes biphenomycin biosynthesis, and provides a platform for the production of analogs from orthologous BGCs.}, archive = {J_JACS}, author = {Chandrashekhar Padhi and Lingyang Zhu and Jeff Y. Chen and Chuan Huang and Ryan Moreira and Gregory L. Challis and Max J. Cryle and Wilfred A. van der Donk}, doi = {10.1021/jacs.5c06044}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23781--23796}, shortjournal = {J. Am. Chem. Soc.}, title = {Biosynthesis of biphenomycin-like macrocyclic peptides by formation and cross-linking of ortho-tyrosines}, volume = {147}, year = {2025}, }
• (2025). Dimensional evolution guides property control in the AnCu4–nTiS4 semiconductor series. JACS, 147(27), 23766--23780. (www)

  @article{ , abstract = {Through progressive reduction of the three-dimensional (3D) covalent network of Cu 4 TiS 4 , we isolate seven new members of the A n Cu 4– n TiS 4 family (A = alkali metal; n = 0–4), spanning 3D, 2D, 1D, and 0D structural fragments. The dimensional reduction is rational, as it preserves the edge-sharing connectivity between [CuS 4 ] 7– and [TiS 4 ] 4– tetrahedra across the series. This structural evolution is driven by the stepwise substitution of Cu with alkali metals, guiding the formation of fragments with reduced dimensionality. The effects of “ n ” and “A” on the crystal structures, stabilities, electronic structures, and optoelectronic properties are profound, demonstrating that the manipulation of alkali metal size and A n Cu 4– n TiS 4 stoichiometry enables predictable variations in structure and properties. For example, the n = 0 and n = 4 end members of the A n Cu 4– n TiS 4 family set the range of achievable band gaps with 2.00 eV for Cu 4 TiS 4 , 2.60 eV for Na 4 TiS 4 , and intermediate values for the n = 1–3 members. Notably, CsCu 3 TiS 4 exhibits exceptional air stability and congruent melting, with density functional theory (DFT) calculating moderate hole and electron effective masses in specific crystallographic directions ( m h = 1.24 m 0 , m e = 0.87 m 0 ). Additionally, A 3 CuTiS 4 (A = Na, K, Rb) displays direct band gap behavior and long photoluminescence lifetimes of 2.3–8.6 μs, and K 3 CuTiS 4 has a PLQY of 5.19%. These findings underscore the potential of the A n Cu 4– n TiS 4 family for applications in optoelectronics and demonstrate widely applicable design concepts that unveil rational stoichiometries within a given composition space to generate a series of crystal structures related through an evolving covalent dimensionality that corresponds to a predictable electronic structure and property progression.}, archive = {J_JACS}, author = {Michael A. Viti and Zhi Li and Zhifu Liu and Christopher Wolverton and Mercouri G. Kanatzidis}, doi = {10.1021/jacs.5c05985}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23766--23780}, shortjournal = {J. Am. Chem. Soc.}, title = {Dimensional evolution guides property control in the AnCu4–nTiS4 semiconductor series}, volume = {147}, year = {2025}, }
• (2025). Reconstitution of [Fe]-hydrogenase with model complexes reveals functional roles of methyl groups in the metallocofactor. JACS, 147(27), 23758--23765. (www)

  @article{ , abstract = {While [Fe]-hydrogenase represents a promising biological alternative to noble-metal hydrogenation catalysts, difficulties in its production and genetic manipulation significantly hinder both mechanistic investigations and practical applications. Semisynthetic [Fe]-hydrogenases, assembled from recombinant apoenzymes and synthetic FeGP cofactor mimics, address these limitations, yet early-generation semisynthetic [Fe]-hydrogenases suffer from low activity due to incomplete pyridinol ligand features on the FeGP cofactor mimics. Here, we investigate the roles of 3- and 5-methyl substituents on the FeGP cofactor’s pyridinol ligand by designing and characterizing model complexes 2–4 . Reconstitution studies demonstrate that the 3-methyl group boosts catalytic activity (a 35-fold increase over nonmethylated analogs) and reconstitution kinetics, while the 5-methyl group enhances oxidative stability. The optimized variant, jHmd-4 , achieves specific activities of 38.5 (forward) and 33.5 U·mg –1 (reverse), reaching 8% of native enzyme activity─the highest reported for semisynthetic systems to date. This breakthrough establishes a tunable platform for developing efficient biohydrogenation catalysts, while providing key insights into metalloenzyme engineering.}, archive = {J_JACS}, author = {Chao Wang and Haoyu Li and Jinsi Li and Chang Wang and Jinmeng Yu and Seigo Shima and Gangfeng Huang and Hui-Jie Pan}, doi = {10.1021/jacs.5c05803}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23758--23765}, shortjournal = {J. Am. Chem. Soc.}, title = {Reconstitution of [Fe]-hydrogenase with model complexes reveals functional roles of methyl groups in the metallocofactor}, volume = {147}, year = {2025}, }
• (2025). MXenoids: Generalization of MXene-inspired covalent surface modifications across two-dimensional materials. JACS, 147(27), 23743--23757. (www)

  @article{ , abstract = {The ability to perform versatile covalent surface modifications in two-dimensional (2D) inorganic materials marks a significant advance in the functionalization of this broad family of materials. One particularly successful example of 2D materials with chemically modifiable surfaces are 2D transition metal carbides and nitrides (MXenes). MXenes’ strong in-plane metal–carbon bonds and labile surface metal–halide bonds create altogether unprecedented opportunities for versatile postsynthetic modifications and assembling complex materials, including various organic–inorganic hybrids. We demonstrate the general applicability of this surface modification strategy to non-MXene halide-terminated 2D materials, termed MXenoids. These surface modifications enable compositional and electronic structure engineering, introduce chiral hybrid organic–inorganic structures, and photoluminescence ranging from near-IR to blue. This study highlights the avenue of surface chemistry-driven materials design, enhancing the functional capabilities of 2D materials.}, archive = {J_JACS}, author = {Chenkun Zhou and Young-Hwan Kim and Benjamin Atterberry and Vikash Khokhar and Arashdeep S. Thind and Francisco Lagunas and Ruiming Lin and Di Wang and Wooje Cho and Zirui Zhou and Maia E. Czaikowski and Alexander S. Filatov and John S. Anderson and Robert F. Klie and Richard D. Schaller and De-en Jiang and Aaron J. Rossini and Dmitri V. Talapin}, doi = {10.1021/jacs.5c05771}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23743--23757}, shortjournal = {J. Am. Chem. Soc.}, title = {MXenoids: Generalization of MXene-inspired covalent surface modifications across two-dimensional materials}, volume = {147}, year = {2025}, }
• (2025). Atomically precise [Cu23H4(SC7H7)18(PPh3)6] nanocluster: Structural integration of johnson solids through a cu(0) center and electrocatalytic functionality. JACS, 147(27), 23733--23742. (www)

  @article{ , abstract = {In recent years, copper (Cu) nanoclusters (NCs) have attracted significant attention for their potential in catalytic applications. However, the inherent high reactivity of Cu(0) often leads to instability, making it challenging to synthesize stable Cu(0)-based NCs. As a result, most reported systems are limited to Cu(I)-based NCs, which in turn constrains their effectiveness and broader applicability in catalysis. Here, we present a synthetic strategy to fabricate a stable Cu(0)-containing, [Cu 23 H 4 (SC 7 H 7 ) 18 (PPh 3 ) 6 ] NC, where the Cu(0) center is atomically protected by two Cu(I)-based Johnson solids and stabilized by the additional Cu(I) units, thiolate ligands and interstitial hydrides. Although neutral PPh 3 ligands are also present, their attachment is positioned away from the Cu(0) center, primarily serving to stabilize the overall geometry and prevent further structural distortions. This robust architectural framework enables the NC to maintain exceptional structural stability and catalytic performance in electrochemical CO 2 reduction reactions, facilitating a consistent selectivity for the end product over time. Density functional theory calculations validate the experimental findings, confirming HCOOH as the preferred product. This preference arises from the lower limiting potential for *HCOO formation, attributed to its enhanced stabilization through a favorable combination of electronic and geometric structure─features that clearly distinguish it from Cu(I) NCs.}, archive = {J_JACS}, author = {Sourav Biswas and Yamato Shingyouchi and Maho Kamiyama and Masaki Ogami and Haohong Song and Bo Li and Song Wang and Tokuhisa Kawawaki and De-en Jiang and Yuichi Negishi}, doi = {10.1021/jacs.5c05665}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23733--23742}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomically precise [Cu23H4(SC7H7)18(PPh3)6] nanocluster: Structural integration of johnson solids through a cu(0) center and electrocatalytic functionality}, volume = {147}, year = {2025}, }
• (2025). Coprecipitated enzyme-encapsulated covalent organic frameworks for biocatalysis. JACS, 147(27), 23724--23732. (www)

  @article{ , abstract = {Enzymes are powerful biocatalysts but suffer from a loss of activity under harsh conditions. In this study, we developed a one-pot aqueous synthesis of enzyme-encapsulated covalent organic frameworks (COFs) to enhance both the stability and reusability of enzymes and provided a detailed analysis of enzyme-COF interactions. We successfully encapsulated β-glucosidase (BGL), alkaline phosphatase (ALP), and eight other enzymes and proteins within the TpAzo COF. Solid-state 2D NMR correlation spectroscopy provided direct molecular-level evidence of interactions between the enzyme and COF backbone, confirming structural integrity and encapsulation efficiency. Scattering-type scanning near-field optical microscopy (s-SNOM) and nanoscale Fourier-transform infrared spectroscopy (nanoFTIR) further validated the presence of BGL within the COF. The encapsulated BGL and ALP retained their catalytic activity with recyclability for up to ten cycles. Notably, the COF enhanced BGL’s stability against denaturation in aqueous sodium dodecyl sulfate (SDS) solutions across a concentration range of 1–15% (w/v). This work establishes a strategy for enzyme encapsulation, leveraging enzyme-COF interactions to improve stability under extreme conditions.}, archive = {J_JACS}, author = {Satyadip Paul and Mani Gupta and Shayan Karak and Yogeshwar D. More and Soumyadeep Saha and Ashok Kumar Mahato and Ekta Nehra and Yusuke Nishiyama and Jin-Chong Tan and Supratim Datta and Rahul Banerjee}, doi = {10.1021/jacs.5c05496}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23724--23732}, shortjournal = {J. Am. Chem. Soc.}, title = {Coprecipitated enzyme-encapsulated covalent organic frameworks for biocatalysis}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic 1,2-dicarboxylation of unactivated alkynes with CO2. JACS, 147(27), 23715--23723. (www)

  @article{ , abstract = {The carboxylation of widely available raw materials with CO 2 represents a highly desirable transformation in synthetic chemistry, enabling the streamlined synthesis of valuable carboxylic acids. While the photocatalytic carboxylation of activated unsaturated compounds with CO 2 has emerged as a powerful strategy for accessing diverse carboxylated products, the direct carboxylation of unactivated alkynes with CO 2 remains a formidable challenge due to the intrinsic inertness of both aliphatic alkynes and CO 2 . Herein, we report the first visible-light photocatalytic 1,2-dicarboxylation of unactivated alkynes with CO 2 , providing a versatile platform for synthesizing structurally diverse succinic acid derivatives. This method exhibits good functional group tolerance and high chemoselectivity under mild reaction conditions. Mechanistic investigations indicated that the in situ generated carbon dioxide radical anion (CO 2 •– ) might initiate the first hydrocarboxylation of unactivated alkynes to deliver a key acrylate intermediate, which could undergo a second hydrocarboxylation process to selectively yield succinic acid derivatives. The synthetic utility of this protocol is further demonstrated by constructing bioactive molecules and CO 2 -based polyesters.}, archive = {J_JACS}, author = {Wei Wang and Si-Shun Yan and Yi Liu and Jia-Shun Zhu and Jing-Wei Yang and Jin-Cheng Xu and Yang-Yi Tao and Jin-Chan Li and Lei Song and Jian-Heng Ye and Da-Gang Yu}, doi = {10.1021/jacs.5c05537}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23715--23723}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic 1,2-dicarboxylation of unactivated alkynes with CO2}, volume = {147}, year = {2025}, }
• (2025). Identifying driving and spectator phonon modes in pentacene exciton transport. JACS, 147(27), 23705--23714. (www)

  @article{ , abstract = {In organic semiconductors, the crystal packing motif is known to modify electronic properties, such as exciton transport dynamics. Phonon vibrations can drive or hinder exciton transport, and understanding the role of these intermolecular vibrations can aid in the rational design of materials for improved solar cell efficiency. In this article, we use double pulse spatially offset femtosecond stimulated Raman spectroscopy (SOFSRS) to identify the functional role of phonon modes in pentacene exciton transport. In SOFSRS, we photoexcite our sample at a spatially offset position relative to the Raman pump and probe, which allows us to track changes in the excited state structure over micrometer length scales and femtosecond time scales during exciton transport. We first measure the phonon modes in a single crystal and then use optical pulse shaping to selectively amplify each mode and measure the resulting exciton transport dynamics along the fast and slow transport axes using SOFSRS. We compare the resulting dynamics with a single pulse excitation SOFSRS to assign driving and spectator phonon modes. We find that a 91 cm –1 phonon mode drives exciton transport preferentially along the slow transport axis. We also find two modes at 161 and 176 cm –1 that drive an increase in the overall excited state population. By comparing these to first-principles density functional theory calculations, we assign a plausible mechanism for exciton–phonon coupling. This study presents a new experimental method that can determine the functional role of phonon vibrations in mediating exciton transport.}, archive = {J_JACS}, author = {Pauline G. Lynch and Samson Baughman and Tina N. Mihm and Sahar Sharifzadeh and Renee R. Frontiera}, doi = {10.1021/jacs.5c05271}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23705--23714}, shortjournal = {J. Am. Chem. Soc.}, title = {Identifying driving and spectator phonon modes in pentacene exciton transport}, volume = {147}, year = {2025}, }
• (2025). Macroscopic homochiral twist enables continuous in situ rotational movement in photomechanical assemblies. JACS, 147(27), 23696--23704. (www)

  @article{ , abstract = {Various light-driven motions have been reported with molecular assemblies, yet continuous in situ rotational movement is rare, which is essential to simulate biological rotary motors and achieve efficient energy transduction. Inspired by natural helical systems, here, we introduce the chirality into the assembly and construct a macroscopic homochiral twisted assembly at the microscale. This assembly (BNP twist) rotated continuously under UV light (365 nm) irradiation. The speed of BNP twist rotation is regulated by controlling both light intensity and assembly size, and the rotation direction is affected by the geometrically unequal light exposure due to the twisted structure. This light-driven continuous mechanical rotation is due to the high distortion caused by the effective transfer and amplification of molecular isomerization by supramolecular self-assembly, as well as the kinematic advantages and geometric properties conferred by the macroscopic chiral twisted structure. Our research results provide a possible method for the design of continuous photomechanical assemblies, which are in sight to be used in light-driven mechanical systems, micro/nanorobots, and photoelectric devices.}, archive = {J_JACS}, author = {Yixuan Jiang and Jingsong Feng and Ji Zhang and Xiaoqi Yu and Shanshan Yu}, doi = {10.1021/jacs.5c05364}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23696--23704}, shortjournal = {J. Am. Chem. Soc.}, title = {Macroscopic homochiral twist enables continuous in situ rotational movement in photomechanical assemblies}, volume = {147}, year = {2025}, }
• (2025). Interspersed assembled monolayers enhance hole transport in high-efficiency organic and perovskite solar cells. JACS, 147(27), 23683--23695. (www)

  @article{ , abstract = {We propose a novel concept called interspersed assembled monolayers (IAMs), which leverage a dispersant molecule sharing a similar backbone with the host self-assembled monolayer (SAM) but possessing a distinct donor–acceptor (D–A) strength, aimed to suppress micelle formation. We designed two dispersant backbones, NNN (triazolo) and NSN (thiadiazolo), both featuring electron-withdrawing backbones, but NSN exhibits a substantially larger dipole moment, which in the current study seems to reduce interfacial energy barriers. Compared to SAMs, employing an IAM strategy with a long side chain (BO) raises power conversion efficiencies (PCE) across various organic solar cell (OSC) architectures. In the PM6:Y6 system, the original PCE of 16.46% improves to 16.72% when using NNN-BO, and further increases to 18.04% with NSN-BO, which has a stronger dipole moment. Perovskite solar cells (PSCs) also benefit, with PCE rising from 23.84 to 24.17% (NNN-BO) and 25.01% (NSN-BO). Moreover, short-side-chain variants NSN-C4 and NSN-IB in PM6:L8-BO-based OSCs yield PCE of 19.01 and 18.94%, respectively, while in PSCs, these dispersants achieve 24.95 and 24.94%, which all closely approximate the performance of long-side-chain NSN-BO (19.23 and 25.01%). Systematic investigation thus demonstrates that, in the design of IAM molecules, both the conjugated backbone and appended side chains must be taken into account. The underlying mechanisms have been revealed through comprehensive femtosecond transient absorption and time-resolved photoluminescence, showing the key to dispersants in promoting charge extraction, mitigating recombination and film morphology. These IAM-integrated components also exhibit environmental and thermal stability, paving a practical way to high-performance IAM-based PSCs and OSCs.}, archive = {J_JACS}, author = {Chieh-Ming Hung and Jing-Han Shi and Hsiao-Chun Tsai and Chi-Ping Lin and Bo-Han Chen and Shang-Da Yang and Pi-Tai Chou}, doi = {10.1021/jacs.5c05341}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23683--23695}, shortjournal = {J. Am. Chem. Soc.}, title = {Interspersed assembled monolayers enhance hole transport in high-efficiency organic and perovskite solar cells}, volume = {147}, year = {2025}, }
• (2025). Adaptive zincophilic-hydrophobic interfaces via additive engineering for robust zinc-based flow batteries. JACS, 147(27), 23672--23682. (www)

  @article{ , abstract = {Zinc-based flow batteries (Zn-FBs) have emerged as promising candidates for large-scale energy storage (ES) systems due to their inherent safety and high energy density. However, dendrite formation and water-induced parasitic reactions at the Zn anode critically compromise long-term operational stability. While aqueous Zn battery additives have been extensively explored, systematic selection criteria for high-areal-capacity Zn-FBs remain absent. Here, we establish zincophilicity and interfacial hydrophobicity as dual descriptors for additive screening. A dimensionless parameter η, defined as the ratio of the adsorption energy on Zn to the binding energy of free water molecules, identifies 1-ethylpyridinium bromide (EPD) as the most optimal pyridinium additive with the highest η value. Mechanistic studies reveal that EPD spontaneously assembles into a dynamic electric-field-responsive interface, which self-adapts to morphological perturbations during electrodeposition and guides Zn 2+ flux along equipotential contours, preventing surface roughening. The in situ formed zincophilic-hydrophobic interphase alters interfacial chemistry by displacing reactive water molecules, achieving dual suppression of hydrogen evolution and dendrite propagation. Implementation of this strategy in Zn–Br 2 flow batteries enables ultrastable cycling over 4000 cycles (166 days) at 40 mA cm –2 , delivering a cumulative plating capacity of 80 Ah cm –2 ─about 11.4-fold improvement over the baseline system (7.0 Ah cm –2 ). This work demonstrates an adaptive interface engineering strategy that directs ion redistribution, advancing the development of reliable electrolytes for sustainable metal-based flow batteries.}, archive = {J_JACS}, author = {Shengnan Wang and Ninggui Ma and Pu Zhang and Hu Hong and Qing Li and Qingshun Nian and Yiqiao Wang and Zhuoxi Wu and Jiaxiong Zhu and Shixun Wang and Jun Fan and Chunyi Zhi}, doi = {10.1021/jacs.5c05027}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23672--23682}, shortjournal = {J. Am. Chem. Soc.}, title = {Adaptive zincophilic-hydrophobic interfaces via additive engineering for robust zinc-based flow batteries}, volume = {147}, year = {2025}, }
• (2025). Operando heating and cooling electrochemical 4D-STEM probing nanoscale dynamics at Solid–Liquid interfaces. JACS, 147(27), 23654--23671. (www)

  @article{ , abstract = {Operando / in situ methods have revolutionized our fundamental understanding of molecular and structural changes at solid–liquid interfaces and enabled the vision of “watching chemistry in action”. Operando transmission electron microscopy (TEM) emerges as a powerful tool to interrogate time-resolved nanoscale dynamics, which involve local electrical fields and charge transfer kinetics distinctly different from those of their bulk counterparts. Despite early reports on electrochemical or heating liquid-cell TEM, developing operando TEM with simultaneous electrochemical and thermal control remains a formidable challenge. Here, we developed operando heating and cooling electrochemical liquid-cell scanning TEM (EC-STEM). By integrating a three-electrode electrochemical circuit and an additional two-electrode thermal circuit, we can investigate heterogeneous electrochemical kinetics across a wide temperature range of −50 to 300 °C. We used Cu electrodeposition/stripping processes as a model system to demonstrate quantitative electrochemistry from −40 to 95 °C in both transient and steady states in aqueous and organic solutions, which paves the way for investigating energy materials operating in extreme climates. Machine learning-assisted quantitative 4D-STEM structural analysis in cold liquids (−40 °C) reveals a distinct two-stage growth of nanometer-scale mossy Cu nanoislands with random orientations followed by μm-scale Cu dendrites with preferential orientations. This work benchmarked electrochemistry in the three-electrode EC-STEM and systematically investigated the temperature and pH dependence of the Pt pseudoreference electrode (RE). At room temperature, the Pt pseudo-RE shows a reliable potential of 0.8 ± 0.1 V vs the standard hydrogen electrode and remains pH-independent on the reversible hydrogen electrode scale. We anticipate that operando heating/cooling EC-STEM will become invaluable for understanding fundamental temperature-controlled nanoscale electrochemistry and advancing renewable energy technologies (e.g., catalysts and batteries) in realistic climates.}, archive = {J_JACS}, author = {Sungin Kim and Valentin Briega-Martos and Shikai Liu and Kwanghwi Je and Chuqiao Shi and Katherine Marusak Stephens and Steven E. Zeltmann and Zhijing Zhang and Rafael Guzman-Soriano and Wenqi Li and Jiahong Jiang and Juhyung Choi and Yafet J. Negash and Franklin S. Walden, II and Nelson L. Marthe, Jr. and Patrick S. Wellborn and Yaofeng Guo and John Damiano and Yimo Han and Erik H. Thiede and Yao Yang}, doi = {10.1021/jacs.5c05005}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23654--23671}, shortjournal = {J. Am. Chem. Soc.}, title = {Operando heating and cooling electrochemical 4D-STEM probing nanoscale dynamics at Solid–Liquid interfaces}, volume = {147}, year = {2025}, }
• (2025). Circularly polarized luminescence and photoinduced spin polarization in helicene-bis-TEMPO diradicals. JACS, 147(27), 23643--23653. (www)

  @article{ , abstract = {Readily accessible high spin excited states are highly coveted due to their potential use in spintronic and quantum sensing applications. Adding a chiral twist to this problem potentially allows for control of the emergent spin polarization through the helicity of the system. Herein we report the realization of a novel, chiral, diradical system, H6-bis-TEMPO , consisting of two TEMPO radicals bridged by a chiral carbo[6]helicene, which after photoexcitation of the helicene core generates a weakly coupled three-spin system comprising the helicene triplet ( S = 1) and the two TEMPO radicals ( S = 1/2). Time-resolved absorption and theoretical calculations help explain the specific photophysics of this system, while time-resolved EPR shows that the TEMPO radicals become spin polarized once the photoexcited spin intermediate has decayed. Comparison with a nonradical bis-dibenzoate capped helicene H6-bis-BENZ experimentally validates the results. This work constitutes a first step toward the realization of molecular systems able to generate spin polarization through helical chirality at the single-molecule level. Moreover, the helically chiral TEMPO persistent radical showscircularly polarized luminescence.}, archive = {J_JACS}, author = {Stefano Cadeddu and Rituparno Chowdhury and Chiara Delpiano Cordeiro and Saurav Parmar and Augusta Kramer and Marie Cordier and Anne Pensel and Nicolas Vanthuyne and Roberta Sessoli and Mario Chiesa and Yu-Kai Liao and Richard H. Friend and Enrico Salvadori and Jochen Autschbach and Jeanne Crassous}, doi = {10.1021/jacs.5c04887}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23643--23653}, shortjournal = {J. Am. Chem. Soc.}, title = {Circularly polarized luminescence and photoinduced spin polarization in helicene-bis-TEMPO diradicals}, volume = {147}, year = {2025}, }
• (2025). Dual active sites on Cu/Cu2O heterostructures for the cascade electrocatalytic synthesis of amino acids. JACS, 147(27), 23635--23642. (www)

  @article{ , abstract = {Electrocatalytic C–N coupling enables the efficient and sustainable production of amino acids. However, it suffers from complex reaction pathways and intense adsorption competition between the reactants and intermediates on a single site. Herein, we report a cascade catalytic strategy on Cu/Cu 2 O heterostructures for the electrosynthesis of amino acids from nitrate and keto acids. The catalysts are capable of producing a wide range of amino acids (including alanine, glycine, leucine, and glutamic acid), achieving an impressively high Faradaic efficiency of up to 75.78% and a yield of as high as 478.89 mmol h –1 g cat –1 for alanine. Mechanism explorations disclose the reconstruction of CuO/C electrocatalysts into Cu/Cu 2 O heterostructures and a cascade catalytic pathway on Cu 0 /Cu + dual sites. The reduction of NO 3 – and the protonation of C═N intermediates are successively realized on the Cu 0 and Cu + sites, respectively. Meanwhile, abundant Cu/Cu 2 O interfaces facilitate the transfer of intermediates. This work provides new insights into the design of bimetallic active sites for the electrosynthesis of amino acids and is conducive to the highly efficient and sustainable production of highly value-added organonitrogen compounds.}, archive = {J_JACS}, author = {Jing Tan and Qiuyan Shen and Xixiong Jin and Min Wang and Bohan A and Weiren Chen and Zixuan Wei and Lingxia Zhang and Jianlin Shi}, doi = {10.1021/jacs.5c04649}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23635--23642}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual active sites on Cu/Cu2O heterostructures for the cascade electrocatalytic synthesis of amino acids}, volume = {147}, year = {2025}, }
• (2025). Quantitative protein labeling in live cells by controlling the redox state of encoded tetrazines. JACS, 147(27), 23625--23634. (www)

  @article{ , abstract = {The site-specific attachment of fluorophores, probes, or drugs to proteins in living systems is critical for advancing our understanding of biology and drug development. The site-specific encoding of 1,2,4,5-tetrazine (Tet) residues into target proteins provides the rapid kinetics and stability required for quantitative labeling in living cells, a property that is increasingly desirable as the resolution and specificity of imaging increases. Here, we adapt a common gel-shift assay to create a “PEG Chaser assay” for evaluating labeling completeness in living cells by “chasing” in-cell Tet reactions with an in vitro reaction with a TCO-PEG 5000 polymer; then, a gel shift distinguishes proteins that did not react in cells from those that did. We apply this to observe that encoded Tets exist in an equilibrium between oxidized (Tz) and reduced (DHTz) forms in living cells. We further show how a recently developed photooxidation treatment can convert the nonreactive DHTz Tet-protein to the reactive Tz form and enables its rapid, quantitative in-cell labeling. We then develop genetic code expansion machinery for encoding two new Tet ncAAs with different redox potentials and show how the tuning of the Tet redox is a useful variable for controlling the reactivity of Tet ncAAs. Specifically, the new Tet3H ncAA enables photoactivatable labeling and complete protein labeling in living cells in 5 min. This in-depth evaluation of the impact of the intracellular reducing environment on Tet reactivity and the demonstration of controlling Tet redox in living cells expands the utility of encodable Tet in living cells.}, archive = {J_JACS}, author = {Alex J. Eddins and Yogesh M. Gangarde and Anamika Singh and Subhashis Jana and Yunan Zheng and Nathan D. Alexander and Justin M. Reitsma and Richard B. Cooley and P. Andrew Karplus and Ryan A. Mehl}, doi = {10.1021/jacs.5c04605}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23625--23634}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantitative protein labeling in live cells by controlling the redox state of encoded tetrazines}, volume = {147}, year = {2025}, }
• (2025). Imaging and tailoring chemical evolution kinetics of (0001) facet on single β-Co(OH)2 nanoplates for the electrocatalytic oxygen evolution reaction. JACS, 147(27), 23617--23624. (www)

  @article{ , abstract = {The (0001) crystal facet of β-Co(OH) 2 has been widely accepted as an inert facet for the oxygen evolution reaction (OER), while the (101̅0) facet is considered more active. However, mechanistic details regarding the origin of the differences at the coordination environment and the electronic state level remain unexplored to date. Herein, we used a multimode optical imaging method to track the evolving heterogeneous dynamics of cobalt species during the OER process and correlate it with the OER performance. Cobalt underwent the oxidation to Co Oh 3+ , distorted to Co Td 3+ , and subsequently oxidized to Co Td 4+ , in which the distribution was mapped by vis-absorption imaging. It indicates that cobalt was negligibly oxidized to Co Td 4+ on the (0001) facet, because of the coordination-saturated environment, while it was relatively facile on the (101̅0) facet. The adsorbate evolution mechanism (AEM) process and lattice-oxygen-mediated mechanism (LOM) process during OER were spatiotemporally decoupled by electrochemiluminescence (ECL) imaging. Furthermore, the cobalt oxidation kinetics was tailored by the atom topping (Fe/Ni) strategy, which was accelerated by iron doping and retarded by nickel doping. On this basis, we propose a lattice O v -involved mechanism for transforming Co Oh 3+ to Co Td 3+ , which is a crucial step to Co Td 4+ . The accelerated oxidation kinetics is from the enrichment of O v , which induces abundant coordination-unsaturated cobalt, facilitating the transformation to Co Td 3+/4+ . This study examined the oxidation kinetics of cobalt with high spatiotemporal resolution and further tailors the distribution of Co Td 4+ , which is expected to promote future research on the kinetic tuning of crystal facets.}, archive = {J_JACS}, author = {Zhe Zhang and Fan Zhang and Yu Cui and Wen Luo and Miao Shu and Shuren Wang and Zhouguang Lu and Yanglong Hou and Rui Hao}, doi = {10.1021/jacs.5c04465}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23617--23624}, shortjournal = {J. Am. Chem. Soc.}, title = {Imaging and tailoring chemical evolution kinetics of (0001) facet on single β-Co(OH)2 nanoplates for the electrocatalytic oxygen evolution reaction}, volume = {147}, year = {2025}, }
• (2025). Mesoporous Metal–Organic framework from templated synthesis as mechanical metamaterials. JACS, 147(27), 23608--23616. (www)

  @article{ , abstract = {This work aims to demonstrate the fabrication of a mesoporous metal–organic framework (MOF) via templated synthesis using a self-assembled block copolymer as a template, giving a nanonetwork MOF with enhanced toughness due to the effect of deliberate structuring on mechanical performance (the character of mechanical metamaterials). Polystyrene- b -polydimethylsiloxane (PS- b -PDMS) can self-assemble as a diamond phase, followed by hydrofluoric acid etching of PDMS, giving mesoporous PS as a template for the coordination-driven self-assembly reaction of ZIF-67. After the templated synthesis of ZIF-67, followed by removal of the PS template, diamond-structured mesoporous ZIF-67 with faceted texture can be obtained due to the confined growth of ZIF-67 as a single crystal. The deliberate structuring with the nanonetwork struts of the mesoporous ZIF-67 single crystal gives a significant improvement in energy dissipation capability with a brittle-to-ductile transition, as evidenced by nanoindentation tests, offering promising catalytic applications by improving the accessible active sites in mesoporous MOF and material toughness due to the nanonetwork structure.}, archive = {J_JACS}, author = {Ting-Wei Liang and Chien Chen and Shinpei Kusaka and Suhail K. Siddique and Cheng-Yen Chang and Ryotaro Matsuda and Rong-Ming Ho}, doi = {10.1021/jacs.5c04214}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23608--23616}, shortjournal = {J. Am. Chem. Soc.}, title = {Mesoporous Metal–Organic framework from templated synthesis as mechanical metamaterials}, volume = {147}, year = {2025}, }
• (2025). The swiss army knife of alginate metabolism: Mechanistic analysis of a mixed-function polysaccharide Lyase/Epimerase of the human gut microbiota. JACS, 147(27), 23594--23607. (www)

  @article{ , abstract = {The alginate-degrading enzyme Bo PL38 of the human gut bacterium Bacteroides ovatus CP926 degrades all three polysaccharide structures found in alginate, a major constituent of brown macroalgae, making it a valuable tool for the selective production of alginate oligosaccharides with industrial and biotechnological potential. Despite its abundance, alginate’s heterogeneous composition limits its full utilization. Modification by epimerases and lyases can help to overcome this limitation, but typically requires distinct enzymes for each polysaccharide structure. Here, we combined experimental and computational approaches to elucidate the catalytic machinery that enables Bo PL38 to act across all alginate structures. We resolved in crystallo complexes of Bo PL38 with alginate oligosaccharides, providing key insights into substrate binding. These structures informed QM/MM MD simulations, which uncovered distinct conformational and reaction pathways for mannuronate and guluronate conversion. The simulations identified different transition states, showing how a single active site architecture facilitates C5 proton abstraction at subsite +1 by Y298 and H243, enabling syn - and anti -β-elimination, respectively. A well-defined residue network mediates substrate recognition, and site-directed mutagenesis revealed that disruption of this network destabilizes the active site architecture. Notably, R292 plays a critical role in distorting the sugar at subsite +1 into a preactivated conformation while also stabilizing the active site tunnel through a salt bridge. Finally, NMR spectroscopy revealed that Bo PL38 also catalyzes mannuronate-to-guluronate epimerization, highlighting its multifunctionality. These findings provide molecular insight into how a single enzyme accommodates alginate’s structural diversity and offer new opportunities for enzymatic polysaccharide engineering.}, archive = {J_JACS}, author = {Tobias Tandrup and José Pablo Rivas-Fernández and Mikkel Madsen and Mette E. Rønne and Agnes B. Petersen and Leesa J. Klau and Anne Tøndervik and Casper Wilkens and Finn L. Aachmann and Carme Rovira and Birte Svensson}, doi = {10.1021/jacs.5c03557}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23594--23607}, shortjournal = {J. Am. Chem. Soc.}, title = {The swiss army knife of alginate metabolism: Mechanistic analysis of a mixed-function polysaccharide Lyase/Epimerase of the human gut microbiota}, volume = {147}, year = {2025}, }
• (2025). Precursors of carboximidates deriving from thioamide-trimethyl-lock system: A general method for designing stable cascade acid-sensitive prodrugs. JACS, 147(27), 23583--23593. (www)

  @article{ , abstract = {We report a cascade acid-sensitive prodrug design strategy utilizing a thioamide-trimethyl-lock system. This approach successfully balances prodrug stability and high acid sensitivity, enabling precise drug release in acidic microenvironments. The thioamide system further acts as a hydrogen sulfide (H 2 S) donor, providing organ-protective effects. In vivo studies in a mouse MCAO stroke model and a 4T1 breast tumor model confirmed significant therapeutic efficacy, including reduced toxicity, enhanced tumor inhibition, and improved safety. Histological analysis revealed minimized systemic toxicity, particularly cardiotoxicity, compared to conventional treatments. This robust and versatile cascade acid-sensitive design has broad applications in chemical biology and drug delivery.}, archive = {J_JACS}, author = {Jianru Liu and Yuanan Wang and Qiwei Zhou and Wen Peng and Peiyuan Li and Chao Ban and Yangyin Xue and Yan Liang and Zhongbo Wang and Hao Hao and Yanzhao Chen and Weiwei Guo and Yueqin Zheng}, doi = {10.1021/jacs.5c03565}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23583--23593}, shortjournal = {J. Am. Chem. Soc.}, title = {Precursors of carboximidates deriving from thioamide-trimethyl-lock system: A general method for designing stable cascade acid-sensitive prodrugs}, volume = {147}, year = {2025}, }
• (2025). Long-lived immunogenic cell death induced by a water-soluble redox active Au(I) bis-N-heterocyclic carbene. JACS, 147(27), 23574--23582. (www)

  @article{ , abstract = {Immunogenic cell death (ICD) is a form of regulated cell death that engages the immune system by releasing damage-associated molecular patterns, making it a promising target for cancer immunotherapy. Presented here is the synthesis and evaluation of a series of asymmetric redox-active water-soluble Au(I) bis-N-heterocyclic carbenes (Au(I) bis-NHCs). We explore the structure–activity relationships between redox activity, water solubility and ICD induction, building on our previous work with a redox-active Au(I) bis-NHC ( 1 ) that effectively induced ICD but suffered from poor water solubility. To overcome this limitation, we synthesized several water-soluble redox-active Au(I) bis-NHCs, derivatives 2–4 , by modifying the imidazole moiety. Compound 2 was identified as the lead, balancing water solubility and ICD induction efficacy. This compound, featuring a naphthoquinone moiety, and was found to generate reactive oxygen species (ROS) and trigger key ICD biomarkers, including calreticulin (CRT) translocation, ATP release, and high mobility group box 1 (HMGB1) secretion. A control compound lacking the redox active naphthoquinone failed to elicit these ICD markers or promote ROS production. Across the series 1–4 a correlation was observed between ROS generation and ICD biomarker expression. In vivo studies in syngeneic immunocompetent mice demonstrated that compound 2 not only prevents CT26 colorectal cancer tumor growth upon challenge with live cancer cells but also elicits a long-lived immune response upon rechallenge 12 months later.}, archive = {J_JACS}, author = {Matthew S. Levine and Sajal Sen and Esther Y. Maier and Mireya Mota and Miae Won and Jiexi Li and Jonathan F. Arambula and Vincent M. Lynch and Jong Seung Kim and Ronald A. DePinho and Brent Iverson and Jonathan L. Sessler}, doi = {10.1021/jacs.5c03455}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23574--23582}, shortjournal = {J. Am. Chem. Soc.}, title = {Long-lived immunogenic cell death induced by a water-soluble redox active Au(I) bis-N-heterocyclic carbene}, volume = {147}, year = {2025}, }
• (2025). Experimental quantum simulation of chemical dynamics. JACS, 147(27), 23566--23573. (www)

  @article{ , abstract = {Accurate simulation of dynamic processes in molecules and reactions is among the most challenging problems in quantum chemistry. Quantum computers promise efficient chemical simulation, but the existing quantum algorithms require many logical qubits and gates, placing practical applications beyond existing technology. Here, we carry out the first quantum simulations of chemical dynamics by employing a more hardware-efficient encoding scheme that uses both qubits and bosonic degrees of freedom. Our trapped-ion device accurately simulates the dynamics of nonadiabatic chemical processes, which are among the most difficult problems in computational chemistry because they involve strong coupling between electronic and nuclear motions. We demonstrate the programmability and versatility of our approach by simulating the dynamics of three different molecules, as well as open-system dynamics in the condensed phase, all with the same quantum resources. Our approach requires orders of magnitude fewer resources than equivalent qubit-only quantum simulations, demonstrating the potential of using hybrid encoding schemes to accelerate quantum simulations of complex chemical processes, which could have applications in fields ranging from energy conversion and storage to biology and drug design.}, archive = {J_JACS}, author = {Tomas Navickas and Ryan J. MacDonell and Christophe H. Valahu and Vanessa C. Olaya-Agudelo and Frank Scuccimarra and Maverick J. Millican and Vassili G. Matsos and Henry L. Nourse and Arjun D. Rao and Michael J. Biercuk and Cornelius Hempel and Ivan Kassal and Ting Rei Tan}, doi = {10.1021/jacs.5c03336}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23566--23573}, shortjournal = {J. Am. Chem. Soc.}, title = {Experimental quantum simulation of chemical dynamics}, volume = {147}, year = {2025}, }
• (2025). Luminescent liquid-crystalline J-aggregate based on a columnar axial coassembly. JACS, 147(27), 23556--23565. (www)

  @article{ , abstract = {Controlling the self-assembly of dyes is essential for designing functional materials with tailored optical, electronic, and mechanical properties. However, achieving precise structures from two distinct chromophores remains a major challenge in the field, requiring sophisticated strategies to direct their organization at the molecular level. In the present work, we report a novel approach to engineer complex liquid-crystalline (LC) columnar nanostructures through the precise coassembly of two bis-dendronized chromophores: a tris( p -phenyleneethynylene) (TPE) dicarboxylic acid ( 1 ) and a tris( p -phenylenevinylene) (TPV) bis(pyridine) ( 2 ). TPE 1 forms an unconventional four-stranded orthogonal columnar LC phase via hydrogen bonding between carboxylic acid groups, while TPV 2 adopts a lamellar soft-crystalline phase. Remarkably, their equimolar mixture ( 1·2 ) gives rise to an unprecedented two-component columnar liquid crystal. This coassembly is grounded on the complementary hydrogen bonding between pyridine and carboxylic acid groups that leads to the formation of 1D strands composed of alternating molecules of 1 and 2 . These strands hierarchically organize by π–π interactions into eight-stranded columnar structures in which the 1 / 2 molecules are oriented with the transition dipole moments parallel to the columnar axis. This configuration promotes slipped π–π interactions and J-type coupling of the TPE and TPV components, resulting in a fluorescent LC material. This work paves the way for the design of precision multicomponent assemblies, opening exciting avenues for advanced optoelectronic and photonic materials.}, archive = {J_JACS}, author = {Llorenç Rubert and Clémence Marre and Pedro Ximenis and Rosa M. Gomila and Antonio Frontera and Bartolome Soberats}, doi = {10.1021/jacs.5c03166}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23556--23565}, shortjournal = {J. Am. Chem. Soc.}, title = {Luminescent liquid-crystalline J-aggregate based on a columnar axial coassembly}, volume = {147}, year = {2025}, }
• (2025). General modular and convergent approach to diversely functionalized allylic systems. JACS, 147(27), 23545--23555. (www)

  @article{ , abstract = {Synthesis of allylic functionalized motifs forging C–O, C–C, and C–S bonds has been achieved via visible-light-induced palladium catalysis. Simple alkenes, readily available 1,1-dielectrophiles, and commercially available nucleophiles are directly coupled in a sequential manner to construct a diverse array of medicinally relevant complex molecules. Unlike the classical Tsuji-Trost reaction, this protocol eliminates the need for prefunctionalized starting materials, offering a much more general and modular approach with options for stereoselective reactions. Additionally, inherent synthetic challenges associated with oxygen-, carbon-, and sulfur-based nucleophiles are addressed, thus establishing a versatile toolkit for accessing allylic ethers, esters, sulfones, and alkylated motifs.}, archive = {J_JACS}, author = {Sachin Giri and Nikita Kvasovs and Vladimir Gevorgyan}, doi = {10.1021/jacs.5c02866}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23545--23555}, shortjournal = {J. Am. Chem. Soc.}, title = {General modular and convergent approach to diversely functionalized allylic systems}, volume = {147}, year = {2025}, }
• (2025). Interplay between mixed and pure exciton states controls singlet fission in rubrene single crystals. JACS, 147(27), 23536--23544. (www)

  @article{ , abstract = {Singlet fission (SF) is a multielectron process in which one singlet exciton S converts into a pair of separated triplet excitons T . SF is widely studied as it may help overcome the Shockley–Queisser efficiency limit for semiconductor photovoltaic cells. To elucidate and control the SF mechanism, great attention has been given to the identification of intermediate states in SF materials, which often appear elusive due to the complexity and fast time scales of the SF process. Here, we apply 14 fs-1 ms transient absorption techniques to high-purity rubrene single crystals to disentangle the intrinsic fission dynamics from the effects of defects and grain boundaries and to identify reliably the fission intermediates. Our data demonstrates that above-gap excitation directly generates a hybrid vibronically assisted mixture of singlet state and triplet-pair multiexciton [S/TT] , which rapidly (<100 fs) and coherently branches into pure singlet or triplet excitations. The relaxation of [S/TT] to S is followed by a relatively slow and temperature-activated (48 meV activation energy) incoherent fission process. The SF competing pathways and intermediates revealed here unify the observations and models presented in previous studies of SF in rubrene and offer alternative strategies for the development of SF-enhanced photovoltaic materials.}, archive = {J_JACS}, author = {Dmitry R. Maslennikov and Marios Maimaris and Haoqing Ning and Xijia Zheng and Navendu Mondal and Vladimir V. Bruevich and Saied Md Pratik and Yifan Dong and John W. G. Tisch and Andrew J. Musser and Vitaly Podzorov and Jean-Luc Bredas and Veaceslav Coropceanu and Artem A. Bakulin}, doi = {10.1021/jacs.5c02993}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23536--23544}, shortjournal = {J. Am. Chem. Soc.}, title = {Interplay between mixed and pure exciton states controls singlet fission in rubrene single crystals}, volume = {147}, year = {2025}, }
• (2025). Accessing a hidden pathway to supramolecular toroid through vibrational strong coupling. JACS, 147(27), 23528--23535. (www)

  @article{ , abstract = {Control over specific intermolecular interactions is crucial to the formation of unique supramolecular assemblies. Recently, vibrational strong coupling (VSC) has emerged as a new tool for manipulating these interactions. Although VSC shows promise for controlling molecular assembly, it has not yet demonstrated the capability to open a pathway for creating structures that are inaccessible by conventional assembly methods. Here, we used VSC to control the transformation process of a naphthalenediimide supramolecular polymer induced by a click reaction. The supramolecular polymers with reactive ethynyl groups undergo a transformation from long fibers to thick fibers upon induction by an amino-yne click reaction in the absence of VSC. Under VSC of the C–H stretch, the click reaction within supramolecular polymers is accelerated; no such acceleration occurs in the reaction of individual monomers, suggesting that the acceleration is due to changes in the assembled structures. Indeed, applying the VSC to the C–H stretch uniquely altered the morphological transformation process, leading to the formation of metastable toroids instead of thick fibers. Notably, the molecular assembly cannot be directed toward a toroidal structure without a VSC. Theoretical simulations suggested that slipped packing configurations in the supramolecular polymers form the curvature necessary for toroidal structures. The experimental results, supported by theoretical simulations, suggest that intermolecular interactions among naphthalenediimide molecules are modified under VSC, leading to a slipped packing configuration of the toroidal assembly. These findings link the VSC-induced modulation of intermolecular interactions to structural outcomes, establishing VSC as a tool for manipulating molecular assembly beyond traditional assembly methods.}, archive = {J_JACS}, author = {Shunsuke Imai and Takumi Hamada and Misa Nozaki and Takatoshi Fujita and Mariko Takahashi and Yasuhiko Fujita and Koji Harano and Hiroshi Uji-i and Atsuro Takai and Kenji Hirai}, doi = {10.1021/jacs.5c02960}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23528--23535}, shortjournal = {J. Am. Chem. Soc.}, title = {Accessing a hidden pathway to supramolecular toroid through vibrational strong coupling}, volume = {147}, year = {2025}, }
• (2025). Direct ice splitting into h2 and o2 enabled by high ionic conductivity. JACS, 147(27), 23519--23527. (www)

  @article{ , abstract = {The molecular splitting of H 2 O is fundamentally significant in energy conversion and storage. While liquid water splitting has achieved scientific and engineering success, the decomposition of solid-state ice has yet to be realized. Here we demonstrate that ice can be directly split at temperatures as low as −40 °C. We show that ice can serve as a high-performance solid electrolyte for proton and hydroxide conduction, with proton mobility estimated to be 1–2 orders of magnitude higher than in liquid water. As a result, ice splitting is achieved at a voltage of 2.18 V at 10 mA cm –2 , with an energy efficiency of approximately 70% at −10 °C. By using ice as a solid electrolyte, ice splitting circumvents the issue of hydrogen crossover, which is inherent in water splitting. These findings introduce new pathways for energy conversion and storage through ice at sub-0 °C temperatures and further provide new insights for the understanding of the electrochemical process in ice.}, archive = {J_JACS}, author = {Bohan Deng and Guangqiang Yu and Wei Zhao and Zhuting Zhang and Xiaoyan Li and Kai Huang and Lifen Wang and Hailin Peng and Huajian Gao and Xibo Li and Hui Wu}, doi = {10.1021/jacs.5c01779}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23519--23527}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct ice splitting into h2 and o2 enabled by high ionic conductivity}, volume = {147}, year = {2025}, }
• (2025). Chaperone-mediated regulation of tau phase separation, fibrillation, and toxicity. JACS, 147(27), 23504--23518. (www)

  @article{ , abstract = {Biological condensates are involved in several essential processes but may also be tangled into disease progression in protein misfolding diseases such as Alzheimer’s disease and tauopathies. One hallmark of these disorders is the appearance of fibrillar aggregates formed by microtubule-stabilizing Tau protein. Notably, Tau can also assemble into biological condensates and droplets via liquid–liquid phase separation (LLPS). The molecular mechanisms of the conversion of functional Tau toward insoluble fibrils, potentially via LLPS processes, remain largely unknown, and efficient treatment approaches to target toxic pathways and species are still missing. Here, we show that the molecular chaperone-like Bri2 BRICHOS domain efficiently inhibits full-length Tau fibril formation and subsequent neurotoxicity by specifically suppressing secondary nucleation processes. Further, at substoichiometric ratios, Bri2 BRICHOS modulates the potency of Tau to form droplets, incorporates into Tau droplets, and alters the dynamic behavior of Tau. In contrast, at superstoichiometric Bri2 BRICHOS ratios, Tau droplet formation is abolished. Finally, Bri2 BRICHOS reduces Tau fibril toxicity in electrophysiological experiments on hippocampal slice preparations. Taken together, Bri2 BRICHOS targets molecular processes related to protein misfolding, where our study provides molecular insights into how the inhibition of secondary nucleation pathways and modulated droplet formation are eventually linked to attenuated neurotoxicity.}, archive = {J_JACS}, author = {Cecilia Mörman and Axel Leppert and Giusy Pizzirusso and Zihan Zheng and Xun Sun and Rakesh Kumar and Henrik Biverstål and Michael Landreh and Jan Johansson and Luis Enrique Arroyo-Garcia and Jinghui Luo and Gefei Chen and Axel Abelein}, doi = {10.1021/jacs.5c01369}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23504--23518}, shortjournal = {J. Am. Chem. Soc.}, title = {Chaperone-mediated regulation of tau phase separation, fibrillation, and toxicity}, volume = {147}, year = {2025}, }
• (2025). Revealing the hidden polysulfides in solid-state Na–S batteries: How pressure and electrical transport control kinetic pathways. JACS, 147(27), 23492--23503. (www)

  @article{ , abstract = {Room temperature operation of Na–S batteries with liquid electrolytes is plagued by fundamental challenges stemming from polysulfide solubility and their shuttle effects. Inorganic solid electrolytes offer a promising solution by acting as barriers to polysulfide migration, mitigating capacity loss. While the sequential formation of cycling products in molten-electrode and liquid electrolytes-based Na–S batteries generally aligns with the expectations from the Na–S phase diagram, their presence, stability, and transitory behavior in systems with inorganic solid electrolytes at room temperature, remain poorly understood. To address this, we employed operando scanning microbeam X-ray diffraction, operando X-ray photoelectron spectroscopy and ex-situ X-ray absorption spectroscopy to investigate the sulfur conversion mechanisms in Na–S cells with Na 3 PS 4 and Na 4 (B 10 H 10 )(B 12 H 12 ) electrolytes. Our findings reveal the formation of crystalline and amorphous polysulfides, including those predicted by the Na–S phase diagram (e.g., Na 2 S 5 , Na 2 S 4 , Na 2 S 2 , Na 2 S), high-order polysulfides observed in liquid-electrolyte systems (e.g., Na 2 S x , where x = 6–8), and phases like Na 2 S 3 typically stable only under high-temperature or high-pressure conditions. We demonstrate that these transitions are governed by diffusion-limited kinetics and localized stress concentrations, emphasizing the critical role of pressure, which serves as both a thermodynamic variable, as well as a design parameter, for optimizing solid-state Na–S battery performance necessary for pushing these cells closer to the commercial frontier.}, archive = {J_JACS}, author = {Hung Quoc Nguyen and Mikael Dahl Kanedal and Juraj Todt and Feng Jin and Quyen Do and Dora Zalka and Alexey Maximenko and Dragos Stoian and Norbert Schell and Wouter van Beek and Harald Fitzek and Johannes Rattenberger and Valerie Siller and Steven T. Boles and Mario El Kazzi and Jozef Keckes and Daniel Rettenwander}, doi = {10.1021/jacs.5c00465}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23492--23503}, shortjournal = {J. Am. Chem. Soc.}, title = {Revealing the hidden polysulfides in solid-state Na–S batteries: How pressure and electrical transport control kinetic pathways}, volume = {147}, year = {2025}, }
• (2025). Real-time optical control of CB1 receptor signaling in vitro with tethered photoswitchable (−)-trans-Δ9-tetrahydrocannabinol derivatives. JACS, 147(27), 23482--23491. (www)

  @article{ , abstract = {Understanding the intricacies of the endocannabinoid system is hindered by the lack of tools to target specific pools of CB1 receptors (CB1Rs) across diverse neural circuits associated with mood, motor function, cognition, and other physiological processes. Herein, we introduce the first photoswitchable, orthogonal remotely tethered cannabinoid ligand, PORTL-THC 24 , designed to achieve cell-specific and reversible control of CB1R signaling with high spatial and temporal resolution, thereby overcoming the limitations of conventional freely diffusible ligands. PORTL-THC 24 was selectively tethered to membrane-anchored SNAP-tags expressed in live cells, and provided reversible optical control of CB1R signaling when photoswitched by UV-A irradiation. We validated the functionality of PORTL-THC 24 in live Neuro2a cells using a novel real-time cAMP imaging assay, demonstrating light-dependent and reversible modulation of endogenously expressed CB1R activity. Additionally, we demonstrated that SNAP-tethered PORTL-THC 24 does not induce CB1R internalization, distinguishing it from conventional, freely diffusible agonists. Our results establish PORTL-THC 24 as a powerful tool for optical control of CB1R in a spatially restricted manner, setting the stage for dissecting CB1R function in complex settings and advancing the study of cannabinoid signaling across various physiological and pathological contexts.}, archive = {J_JACS}, author = {Sarahi J. Garza and Bilal Kicin and Roman C. Sarott and Patrick Pfaff and Miroslav Kosar and Tatum Weishaar and Paul Schnacke and Braden T. Lobingier and Erick M. Carreira and James A. Frank}, doi = {10.1021/jacs.4c18379}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23482--23491}, shortjournal = {J. Am. Chem. Soc.}, title = {Real-time optical control of CB1 receptor signaling in vitro with tethered photoswitchable (−)-trans-Δ9-tetrahydrocannabinol derivatives}, volume = {147}, year = {2025}, }
• (2025). Unraveling the formation kinetics of the first intermediate in the oxygen evolution reaction on MnOx with different electron configurations. JACS, 147(27), 23473--23481. (www)

  @article{ , abstract = {In the electrocatalytic oxygen evolution reaction (OER), it has been a long-standing issue to establish the relationship between intermediate kinetics, catalyst structures, and OER activity, which is challenging due to the difficulty in following the intermediate kinetics and charge dynamics simultaneously. Here, using home-built operando electrochemical transient absorption (EC-TA) spectroscopy, we succeeded in resolving the kinetics of the first intermediate (*OH species) in the OER catalytic cycle on MnO x -based electrocatalysts, which is consistent with microkinetics simulation. In the formation process of *OH species, proton transfer is slower than electron transfer, resulting in the continuous formation of *OH species after the interruption of the potential pulse. Based on a comparison of *OH formation rates in four MnO x -based catalysts with different electron configurations, the formation rates of *OH species are highly dependent on the coordination symmetry of the corner-shared Mn 3+ O 6 octahedron in the catalyst. The formation rate of *OH species in a catalyst with a corner-shared Mn 3+ O 6 octahedron of D 3d symmetry exhibits a ∼100-fold (2.33 × 10 3 s –1 ) increase compared with that in a catalyst with a corner-shared Mn 3+ O 6 octahedron of D 4h symmetry (2.45 × 10 1 s –1 ). More importantly, the formation rates of *OH species show a positive correlation with the reaction rates of the rate-determining step (RDS) in the OER catalytic cycle. The insight into the formation kinetics of the first OER intermediate in the OER processes indicates the crucial role of the initial rate in the OER catalytic cycle and sheds light on the OER kinetic mechanism on electrocatalysts.}, archive = {J_JACS}, author = {Ruifang Wei and Dongfeng Li and Panwang Zhou and Runze Liu and Chenwei Ni and Zeyu Cheng and Xiuli Wang and Can Li}, doi = {10.1021/jacs.4c18273}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23473--23481}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the formation kinetics of the first intermediate in the oxygen evolution reaction on MnOx with different electron configurations}, volume = {147}, year = {2025}, }
• (2025). Quantum hydrogen tunneling in an iridium dihydride complex. JACS, 147(27), 23458--23472. (www)

  @article{ , abstract = {Quantum mechanical tunneling (QMT) is the mechanism by which a particle can pass through a high potential energy barrier. Although rooted in quantum physics, QMT influences key chemical reactions in a number of ways. Here, we show that a new iridium dihydride complex IrH2 bearing a N , B -bidentate pyridine carboranyl ligand [(C 5 H 4 N)CB 11 H 10 ] undergoes H···H exchange coupling via QMT, as supported by variable temperature NMR studies showing large temperature-dependent exchange coupling constants J H–H (99–162 Hz), nonlinear Arrhenius behavior of the exchanging hydrogens, and the absence of detectable J H–D coupling in the deuterium-enriched complex IrHD . These observations agree with the predicted existence of quantum exchange coupling in metal dihydrides reported by Zilm and Heinekey [ J. Am. Chem. Soc. 1990 , 112, 3, 920–929]. The observed high relaxation rates T 1,min (0.250–0.262 s) support the assignment for IrH2 as being a metal dihydride rather than a nonclassical dihydrogen complex, thus ruling out any major involvement from a classical scalar coupling to the observed large J H–H coupling constants. The reactivity of complex IrH2 against various bases, nucleophiles, and electrophiles was investigated, and X-ray photoelectron spectroscopy as well as computational studies were conducted, all of which support an Ir in the formal + III oxidation state for IrH2 .}, archive = {J_JACS}, author = {Mustapha Hamdaoui and Yann Cornaton and Xingyu Lu and Xiaohuo Shi and Huan Zhang and Jiyong Liu and Bernhard Spingler and Jizeng Sun and Jean-Pierre Djukic and Simon Duttwyler}, doi = {10.1021/jacs.4c17482}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23458--23472}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantum hydrogen tunneling in an iridium dihydride complex}, volume = {147}, year = {2025}, }
• (2025). Orbital hybridization of π-conjugated ligands with atomically precise metal clusters for enhanced two-photon absorption. JACS, 147(27), 23451--23457. (www)

  @article{ , abstract = {The nonlinear optical phenomenon of two-photon absorption (TPA) has numerous applications in scientific fields. However, designing materials with efficient TPA that meet the technical requirements is challenging. The fundamental optical properties of a material depend on its density of states (DOS). In this study, we achieved efficient TPA by controlling the DOS via tuning the orbital energy levels of gold clusters and molecular ligands. We synthesized Au 36 (NP) 24 with an atomically precise Au 36 core and 24 naphthalenethiol (NP) ligands and evaluated the orbital hybridization effect on the TPA cross-section, σ (2) , of 6000 GM under 800 nm excitation. The synthesized Au 36 (NP) 24 exhibited a considerably high σ (2) , originating from the DOS, suitable for near-double resonance enhancement because of the hybridization between the Au 36 and (NP) 24 orbitals. This orbital hybridization approach between functional molecules and a metal kernel provides a versatile design strategy for tuning the DOS of materials for various purposes including nonlinear optics.}, archive = {J_JACS}, author = {Masanori Sakamoto and Yoshiyuki Mizuhata and Wataru Ota and Tatsuki Konishi and Hirokazu Tahara and Kenji Kamada and Tohru Sato}, doi = {10.1021/jacs.4c16216}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23451--23457}, shortjournal = {J. Am. Chem. Soc.}, title = {Orbital hybridization of π-conjugated ligands with atomically precise metal clusters for enhanced two-photon absorption}, volume = {147}, year = {2025}, }
• (2025). Reversible multielectron transfer chemistry of I-activated voltage-enhanced ferrocene-based organic cathodes. JACS, 147(27), 23441--23450. (www)

  @article{ , abstract = {Organic molecule engineering has the potential to design materials with multiple electroactive centers, affording high energy storage capabilities and low-cost chemistry. The discovery of ferrocenes contributes significantly to the broad applications of organometallic compounds. Even though their reversible redox reactions can be used in batteries, their low potential and limited electron density per unit mass pose some challenges. Here, we report an I-activated voltage-enhanced ferrocene-based molecule, (ferrocenylmethyl) trimethylammonium iodide (FcNI), featuring a dual redox center by decorating the ferrocene backbone with designed functional groups to regulate the electron energy of Fe 3+/2+ redox couples. It enables multielectron transfer of I 0/– and Fe 3+/2+ , a sharply increased potential of Fe 3+/2+ redox couples, and high-power energy storage with cycling stability. An organic cathode based on FcNI molecules displays a discharge capacity of over 400 mAh g –1 at 2 A g –1 with high-voltage plateaus up to 1.7 and 3.5 V when coupled with a zinc or lithium anode, respectively, and an excellent rate capability. Our results show that organic molecules can be programmed with multiple redox sites to develop high-voltage, fast-charging, and high-capacity organic rechargeable batteries.}, archive = {J_JACS}, author = {Pei Li and Yichao Yan and Jiaxiong Zhu and Yiqiao Wang and Leyu Bi and Hu Hong and Xinru Yang and Yuwei Zhao and Qing Li and Shengnan Wang and Yue Hou and Alex K.-Y. Jen and Chunyi Zhi}, doi = {10.1021/jacs.4c12173}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23441--23450}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible multielectron transfer chemistry of I-activated voltage-enhanced ferrocene-based organic cathodes}, volume = {147}, year = {2025}, }
• (2025). Toward iridium-catalyzed asymmetric branched-selective α-alkylation of aldehydes with unactivated alkenes enabled by a pyrazole mediator. JACS, 147(27), 23434--23440. (www)

  @article{ , abstract = {Aldehyde α-alkylation remains a challenging transformation. On the other hand, given the wide availability of alkenes, it has been an attractive objective to use unactivated alkenes as alkylating agents. Here, as an initial model study, we report a stepwise asymmetric α-alkylation of aldehydes with simple alkenes as the coupling partner. The reaction is enabled by a distinct pyrazole mediator and catalyzed by a chiral cationic Ir complex. The C–H alkylation of the N -alkenyl pyrazole intermediates proceeded with excellent enantioselectivity and high branched selectivity. Preliminary mechanistic studies indicate that the branched selectivity is consistent with the involvement of an Ir–carbon migratory insertion pathway. This asymmetric alkylation method shows promise to simplify syntheses of chiral fragments of bioactive compounds.}, archive = {J_JACS}, author = {Kezhi Chen and Brianna Lopez and Justin Bilenker and Guangbin Dong}, doi = {10.1021/jacs.5c08385}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23434--23440}, shortjournal = {J. Am. Chem. Soc.}, title = {Toward iridium-catalyzed asymmetric branched-selective α-alkylation of aldehydes with unactivated alkenes enabled by a pyrazole mediator}, volume = {147}, year = {2025}, }
• (2025). 2D covalent organic frameworks with cpt-defect topology enabled by a node-splitting strategy. JACS, 147(27), 23429--23433. (www)

  @article{ , abstract = {Reticular chemistry provides a robust platform for the construction of two-dimensional covalent organic frameworks (2D COFs) with tailored architectures and functionalities. A key synthetic challenge lies in the integration of densely arranged functional moieties without compromising long-range structural order. Herein, we report a node-splitting strategy in which half of the 6-connected C 3 -symmetric nodes in the cpt topology are replaced by trios of 2-connected C 2 v -symmetric nodes, generating a new cpt-defect topology. Directional hydrogen bonding among the C 2 v nodes drives the formation of well-defined hydrogen-bonded nanotraps while preserving crystalline periodicity. The resulting COFs exhibit remarkable performance in gold ion (Au 3+ ) recovery, with COF-36 achieving a maximum adsorption capacity of 1725 mg g –1 and over 99% removal efficiency under strongly acidic conditions. Density functional theory (DFT) calculations attribute this high affinity to the geometric complementarity between the nanotrap cavity and the [AuCl 4 ] − anion, enabling the formation of multiple stabilizing hydrogen bonds. This work establishes node splitting as a versatile approach for topological and functional engineering in COFs, broadening their potential for advanced applications.}, archive = {J_JACS}, author = {Jialiang Liu and Guangshan Zhou and Jingming Yang and Chengtao Gong and Hao Wang and Wenmei Jiao and Yongwu Peng}, doi = {10.1021/jacs.5c08143}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23429--23433}, shortjournal = {J. Am. Chem. Soc.}, title = {2D covalent organic frameworks with cpt-defect topology enabled by a node-splitting strategy}, volume = {147}, year = {2025}, }
• (2025). A molecular tricopper phosphide: Synthesis, functionalization, and hydrogen atom abstraction. JACS, 147(27), 23422--23428. (www)

  @article{ , abstract = {Despite relevance as molecular analogs of binary metal/pnictogen heterogeneous catalysts, late-metal molecular phosphido clusters are scarce. Herein, we describe an entry into copper phosphido and phosphinidiide chemistry leveraging the reducing nature of a prearranged Cu 0 2 Cu I core. Pnictogen atom capture from Na[PCO] affords the first molecular copper phosphide ( 2 ), which is a potent nucleophile. Electrophilic functionalization yields a series of phosphinidiide complexes, including the parent P–H compound ( 3 H ). Electrochemical measurements suggest that 2 participates in hydrogen atom transfer chemistry; thermochemical benchmarking and reactivity studies support a moderate P–H bond strength of 69.1 kcal/mol for 3 H . These findings provide insights into structural characteristics and proton coupled electron transfer reactivity of Cu 3 P units, conspicuous structures in copper phosphide heterogeneous catalysis.}, archive = {J_JACS}, author = {Andrew W. Beamer and Kareem Aboulhosn and Joshua A. Buss}, doi = {10.1021/jacs.5c07984}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23422--23428}, shortjournal = {J. Am. Chem. Soc.}, title = {A molecular tricopper phosphide: Synthesis, functionalization, and hydrogen atom abstraction}, volume = {147}, year = {2025}, }
• (2025). Gram-scale total synthesis of illisimonin a. JACS, 147(27), 23417--23421. (www)

  @article{ , abstract = {Illisimonin A, a structurally complex sesquiterpenoid isolated from the Illicium genus, possesses a 5/5/5/5/5 pentacyclic scaffold featuring seven contiguous, fully substituted chiral quaternary carbon centers. Herein, we report a gram-scale total synthesis of (±)-Illisimonin A achieved in 14 steps. The strategic approach features several key transformations: (1) a pentafulvene-involved intramolecular [6 + 2] cycloaddition that rapidly assembles the linear 5/5/5 tricyclic core, (2) a pentafulvene-involved intramolecular alkylation enabling polycyclic framework construction, (3) a nitroso-Diels–Alder reaction for precise oxidation state installation, and (4) a late-stage Ru-catalyzed oxidative lactonization.}, archive = {J_JACS}, author = {Liangchao Zhu and Jinrui Li and Zhaohong Lu}, doi = {10.1021/jacs.5c07921}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23417--23421}, shortjournal = {J. Am. Chem. Soc.}, title = {Gram-scale total synthesis of illisimonin a}, volume = {147}, year = {2025}, }
• (2025). A concise total synthesis of glycinoeclepin a. JACS, 147(27), 23411--23416. (www)

  @article{ , abstract = {Here we report a concise and modular synthesis of the complex triterpenoid glycinoeclepin A, a picomolar hatching stimulus for the notorious pest soybean cyst nematode. The synthesis features the strategic use of a polyfunctional platform intermediate bearing an aldehyde, a vinyl triflate, and an exo -cyclic alkene─three functional groups with orthogonal reactivity. From here, a programmable Cr-mediated diastereoselective homoallenylation of aldehyde, followed by a Pd-catalyzed intramolecular oxygenative cyclization, efficiently forged the densely functionalized 5,6-fused core system. The oxa -bicyclic appendage was installed via an allyl phosphonate enabled coupling. The remaining alkene was selectively homologated via a hydroboration, Wittig reaction. Final oxidations completed the total synthesis of glycinoeclepin A. This concise route not only provides access to glycinoeclepin A and analogs for potential biological studies but also establishes a general platform for synthesizing architecturally complex polycyclic natural products.}, archive = {J_JACS}, author = {Kang Shen and Qiyang Wang and Tao Zhu and Yiyang Qiao and Pengfei Hu}, doi = {10.1021/jacs.5c07696}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23411--23416}, shortjournal = {J. Am. Chem. Soc.}, title = {A concise total synthesis of glycinoeclepin a}, volume = {147}, year = {2025}, }
• (2025). Post-synthetic transformation of high entropy alloy nanoparticles into high-entropy intermetallics for selective acetylene semi-hydrogenation catalysis. JACS, 147(27), 23405--23410. (www)

  @article{ , abstract = {Nanoparticles of intermetallic compounds can function as high surface area catalysts with unique activity and selectivity that emerge from their atomically ordered crystal structures. High-entropy intermetallic nanoparticles are especially interesting catalytic targets, as their complex compositions are anticipated to further modify and tune catalytic properties. However, the synthesis of high-entropy intermetallic nanoparticles has been challenging, since simultaneous control of crystal structure and multimetal mixing is often favored at high temperatures while nanoscopic particle sizes are favored at lower temperatures. Here, we demonstrate a solution-based postsynthetic transformation strategy that converts high-entropy alloy nanoparticles into high-entropy intermetallics. Colloidal high-entropy alloy nanoparticles with predefined homogeneous metal mixing, including NiPdPtRhIr, NiFeCoPdPt, and NiFePdPtIr, convert to γ-brass, CsCl, and NiAs-type high-entropy intermetallics of Zn, In, and Sn, respectively, which span a range of compositions and crystal structures. The γ-brass (NiPdPtRhIr) 10 Zn 42 nanoparticles are active catalysts for acetylene semi-hydrogenation, exhibiting better selectivity than isostructural Pd 10 Zn 42 and pointing to the role of high-entropy mixing in improving catalytic performance.}, archive = {J_JACS}, author = {Samuel S. Soliman and Mustafa Eid and Zachary Mitarotonda and Kathryn MacIntosh and Gaurav R. Dey and Robert M. Rioux and Raymond E. Schaak}, doi = {10.1021/jacs.5c07553}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23405--23410}, shortjournal = {J. Am. Chem. Soc.}, title = {Post-synthetic transformation of high entropy alloy nanoparticles into high-entropy intermetallics for selective acetylene semi-hydrogenation catalysis}, volume = {147}, year = {2025}, }
• (2025). Water droplet microlightning sparks alkyne ozonolysis. JACS, 147(27), 23399--23404. (www)

  @article{ , abstract = {We report that microlightning during the spraying of pure water microdroplets can cleave alkyne triple bonds via the in situ formation of ozone. When alkyne vapors are introduced into a spray of water microdroplets under ambient conditions, carboxylic acids are detected by high-resolution mass spectrometry (MS). Control experiments confirmed that both water and molecular oxygen in the gas surrounding the droplets are essential in this transformation. Intermediates of ozonolysis were captured by MS and tandem mass spectrometry (MS 2 ), which further verified the proposed mechanism through ozone generation from water droplet microlightning. Our findings demonstrate a green, catalyst-free method for breaking the C≡C bond of alkynes and forming the corresponding carboxylic acids.}, archive = {J_JACS}, author = {Yifan Meng and Elumalai Gnanamani and Richard N. Zare}, doi = {10.1021/jacs.5c07564}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23399--23404}, shortjournal = {J. Am. Chem. Soc.}, title = {Water droplet microlightning sparks alkyne ozonolysis}, volume = {147}, year = {2025}, }
• (2025). Electrons and their multiple kinetic fates in an ionic liquid. JACS, 147(27), 23395--23398. (www)

  @article{ , abstract = {Ionic liquids (ILs) for electrochemical, nuclear, and solar energy applications operate under harsh conditions, where electrons and transient radical species can form. This communication discusses why anions such as bis(trifluoromethylsulfonyl)imide (Tf 2 N – ) are reduced at the electron-rich electrode whereas in laser photoionization or pulse radiolysis studies, where electrons are ejected from species in the bulk, we often detect long-lived electrons in cavities that interact with IL cations instead. This work argues that bulk excess electrons generated photolytically or radiolytically follow kinetically favored pathways. As such, cavity electrons may not be the most energetically favorable states, but when they form, and they do form, they are kinetically stable. Reduction reactions of anions or electron localization in cavities and subsequent reactions are all expected outcomes. Here we focus on a pyrrolidinium-based IL of the dicyanamide (N(CN) 2 – ) anion because of its large electrochemical window and very low viscosity, which are ideal for energy applications.}, archive = {J_JACS}, author = {Hung H. Nguyen and Katie Huber and Dishan Das and Bichitra Borah and Matthew S. Emerson and Meghan Knudtzon and James F. Wishart and David A. Blank and Claudio J. Margulis}, doi = {10.1021/jacs.5c07005}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23395--23398}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrons and their multiple kinetic fates in an ionic liquid}, volume = {147}, year = {2025}, }
• (2025). μMap-FFPE: A high-resolution protein proximity labeling platform for formalin-fixed paraffin-embedded tissue samples. JACS, 147(27), 23387--23394. (www)

  @article{ , abstract = {Many disease states can be understood by elucidating small-scale biomolecular protein interaction networks, or microenvironments. Photoproximity labeling methods, like μMap, have recently emerged as high-resolution techniques for mapping spatial relationships within subcellular architectures. However, in vitro models typically utilized lack the cell-type heterogeneity and three-dimensional structure essential for translating findings to clinical settings. To this end, formalin-fixed paraffin-embedded (FFPE) tissues are invaluable model systems for biomedical research, as they preserve complex multicellular interaction networks in their natural environment. While identifying microscale interactions in these samples could provide critical clinical insights, chemical modifications introduced during formalin-fixation and de-cross-linking are incompatible with standard photoproximity labeling techniques. Herein, we introduce μMap-FFPE, a new labeling system that enables comparison of the CD20 interactome across healthy cells, cancerous cells, and preserved patient tissues.}, archive = {J_JACS}, author = {Noah B. Bissonnette and Marie E. Zamanis and Steve D. Knutson and Zane Boyer and Angelo Harris and Daniel Martin and Jacob B. Geri and Suzana Couto and Tahamtan Ahmadi and Anantharaman Muthuswamy and Mark Fereshteh and David W. C. MacMillan}, doi = {10.1021/jacs.5c06489}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23387--23394}, shortjournal = {J. Am. Chem. Soc.}, title = {μMap-FFPE: A high-resolution protein proximity labeling platform for formalin-fixed paraffin-embedded tissue samples}, volume = {147}, year = {2025}, }
• (2025). Regiodivergent α- and β-functionalization of saturated N-heterocycles by photocatalytic oxidation. JACS, 147(27), 23381--23386. (www)

  @article{ , abstract = {Synthetic methods that provide access to two different types of products via a central intermediate are highly valuable but difficult to establish. Here, we present a photocatalytic, regiodivergent method for the functionalization of saturated N -heterocycles at either the α- or the β-position. A t -butyl carbamate (Boc)-stabilized iminium ion serves as the key intermediate en route to either α-hydroxylation or β-elimination, depending on the choice of base. The operationally simple procedures use a readily available flavin-based catalyst and reagents, aqueous media and do not require metals. Combined with facile downstream derivatization, the regiodivergent reaction gives rapid access to a large set of functionalized piperidines, molecules that are highly sought-after for the synthesis of pharmaceuticals and agrochemicals.}, archive = {J_JACS}, author = {Jonas W. Rackl and Alexander F. Müller and Antonia Profyllidou and Helma Wennemers}, doi = {10.1021/jacs.5c06177}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23381--23386}, shortjournal = {J. Am. Chem. Soc.}, title = {Regiodivergent α- and β-functionalization of saturated N-heterocycles by photocatalytic oxidation}, volume = {147}, year = {2025}, }
• (2025). Artificial intelligence paradigms for next-generation Metal–Organic framework research. JACS, 147(27), 23367--23380. (www)

  @article{ , abstract = {After the development of the famous “Transformer” network architecture and the meteoric rise of artificial intelligence (AI)-powered chatbots, large language models (LLMs) have become an indispensable part of our daily activities. In this rapidly evolving era, “all we need is attention” as Google’s famous transformer paper’s title [Vaswani et al., Adv. Neural Inf. Process. Syst. 2017 , 30] implies: We need to focus on and give “attention” to what we have at hand, then consider what we can do further. What can LLMs offer for immediate short-term adaptation? Currently, the most common applications in metal–organic framework (MOF) research include automating literature reviews and data extraction to accelerate the material discovery process. In this perspective, we discuss the latest developments in machine-learning and deep-learning research on MOF materials and reflect on how their utilization has evolved within the LLM domain from this standpoint. We finally explore future benefits to accelerate and automate materials development research.}, archive = {J_JACS}, author = {Aydin Ozcan and François-Xavier Coudert and Sven M. J. Rogge and Greta Heydenrych and Dong Fan and Antonios P. Sarikas and Seda Keskin and Guillaume Maurin and George E. Froudakis and Stefan Wuttke and Ilknur Erucar}, doi = {10.1021/jacs.5c08214}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23367--23380}, shortjournal = {J. Am. Chem. Soc.}, title = {Artificial intelligence paradigms for next-generation Metal–Organic framework research}, volume = {147}, year = {2025}, }
• (2025). Radical sorting catalysis via bimolecular homolytic substitution (SH2): Opportunities for C(sp3)–C(sp3) cross-coupling reactions. JACS, 147(27), 23351--23366. (www)

  @article{ , abstract = {The development of efficient C(sp 3 )–C(sp 3 ) cross-coupling methods that expand access to a pharmaceutically relevant three-dimensional chemical space represents a key frontier in organic synthesis. Traditional cross-coupling strategies readily achieve C(sp 2 )–C(sp 2 ) and C(sp 2 )–C(sp 3 ) bond formation but face significant challenges in C(sp 3 )–C(sp 3 ) coupling due to issues of sluggish inner sphere reductive elimination, β-hydride elimination, and limited cross-selectivity. Recent advances in C(sp 3 )–C(sp 3 ) cross-coupling have highlighted the potential of an alternative bond-forming mechanism, bimolecular homolytic substitution (S H 2), as an outer sphere pathway to overcome these limitations. This strategy leverages a “radical sorting effect”, in which sterically distinct alkyl radicals are partitioned based on their substitution patterns. This perspective provides a comprehensive analysis of S H 2-mediated C(sp 3 )–C(sp 3 ) cross-coupling reactions from 2021 to 2024, focusing on iron, nickel, and cobalt catalysis and their powerful applications in quaternary carbon center (QCC) formation. We also highlight emerging opportunities in single functional group cross-coupling and alkene functionalization, demonstrating the versatility of S H 2 in accessing complex molecular architectures from abundant feedstock chemicals. By addressing key challenges in C(sp 3 )–C(sp 3 ) cross-coupling, S H 2 radical sorting catalysis holds significant promise for expanding the C(sp 3 )-rich chemical space and enabling transformative advances in organic synthesis.}, archive = {J_JACS}, author = {Iona M. McWhinnie and Robert T. Martin and Jiaxin Xie and Ruizhe Chen and Cesar N. Prieto Kullmer and David W. C. MacMillan}, doi = {10.1021/jacs.5c07367}, journal = {Journal of the American Chemical Society}, month = {7}, number = {27}, pages = {23351--23366}, shortjournal = {J. Am. Chem. Soc.}, title = {Radical sorting catalysis via bimolecular homolytic substitution (SH2): Opportunities for C(sp3)–C(sp3) cross-coupling reactions}, volume = {147}, year = {2025}, }
• (2025). Correction to “Ab initio design of molecular qubits with electric field control”. JACS, 147(26), 23349--23350. (www)

  @article{ , archive = {J_JACS}, author = {William T. Morrillo and Herbert I. J. Cumming and Andrea Mattioni and Jakob K. Staab and Nicholas F. Chilton}, doi = {10.1021/jacs.5c08471}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23349--23350}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Ab initio design of molecular qubits with electric field control”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Electrochemical reduction of n2 to ammonia promoted by hydrated cation ions: Mechanistic insights from a combined computational and experimental study”. JACS, 147(26), 23348. (www)

  @article{ , archive = {J_JACS}, author = {Xin Mao and Xiaowan Bai and Guanzheng Wu and Qing Qin and Anthony P. O’Mullane and Yan Jiao and Aijun Du}, doi = {10.1021/jacs.5c08467}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23348}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Electrochemical reduction of n2 to ammonia promoted by hydrated cation ions: Mechanistic insights from a combined computational and experimental study”}, volume = {147}, year = {2025}, }
• (2025). In situ synthesis of multifunctional 3D polymeric artificial organelles in living cells. JACS, 147(26), 23339--23347. (www)

  @article{ , abstract = {Artificial organelles have been developed to restore dysfunction or to introduce new-to-nature functions to the host cells, although limitations, such as instability, still exist. Here, we develop a new strategy to fabricate structurally stable polymeric “artificial organelles” by in situ crosslinking of multibranched monomers intracellularly using bioorthogonal click chemistry. The fabricated artificial organelles bearing bioorthogonal reactive centers allow for functional molecule conjugation and cargo release, enabling effective cell modification and manipulation. This demonstration opens up a multitude of new possibilities for empowering cells with new functions that surpass or complement their intrinsic capabilities.}, archive = {J_JACS}, author = {Lulu Zhang and Hao Liu and Hebin Xu and Min Wang and Huanfang Liu and Wenjing Li and Cuiqi Zhang and Wenyu Han and Jie Chen and Yichuan Zhang}, doi = {10.1021/jacs.5c08624}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23339--23347}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ synthesis of multifunctional 3D polymeric artificial organelles in living cells}, volume = {147}, year = {2025}, }
• (2025). Anionic Metal–Organic framework as an ultrafast single-ion conductor for exceptional performance rechargeable zinc batteries. JACS, 147(26), 23331--23338. (www)

  @article{ , abstract = {Anionic metal–organic frameworks (MOFs) are promising single-ion conductive electrolytes in quasi-solid-state batteries. Herein, we propose an anionic MOF as a promising single Zn 2+ conductor for high-performance quasi-solid-state zinc-ion battery (ZIB). The anionic MOF is synthesized by reacting carboxylic acid functionalized tetraphenylborate with a Zr 6 -oxo cluster, which displays outstanding ionic conductivity (0.83 mS cm –1 at −40 °C, 2.75 mS cm –1 at 25 °C, and 7.9 mS cm –1 at 120 °C), an impressive Zn 2+ transference number ( t Zn 2+ = 0.90), low activation energy (0.19 eV), good interfacial compatibility, and excellent rate performance. The fabricated quasi-solid-state ZIB using NH 4 V 4 O 10 cathode delivers a remarkable capacity of 497 mAh g –1 at 0.3 A g –1 under ambient conditions and can maintain capacities of 420, 350, and 270 mAh g –1 at elevated current densities of 1, 5, and 10 A g –1 with both capacities and Coulombic efficiency retention at 100% after 2500 cycles. Even at a low temperature of −40 °C or with a high current density of 100 A g –1 , excellent reversible capacities and rate performance can still be achieved. This work set up a new direction for designing and developing anionic porous materials as advanced solid electrolytes for zinc and/or other secondary batteries.}, archive = {J_JACS}, author = {Qingchun Xia and Xuxiao Ma and Pengtao Qiu and Guozan Yuan and Xuenian Chen}, doi = {10.1021/jacs.5c08566}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23331--23338}, shortjournal = {J. Am. Chem. Soc.}, title = {Anionic Metal–Organic framework as an ultrafast single-ion conductor for exceptional performance rechargeable zinc batteries}, volume = {147}, year = {2025}, }
• (2025). Selective iridium-catalyzed reductive amination inside living cells. JACS, 147(26), 23318--23330. (www)

  @article{ , abstract = {Given that amino groups are ubiquitous in bioactive molecules, abiotic routes to incorporate them into cellular species offer new opportunities to study and manipulate living systems. In the present work, we report the first biocompatible method to prepare 1°, 2°, or 3° amines selectively starting from an aldehyde and nitrogen precursor through iridium-catalyzed reductive amination. To prevent overalkylation, we developed a nontoxic self-immolative agent comprising 4-(1-aminoethyl)phenol that can condense with carbonyl groups and undergo 1,6-elimination upon reduction to the desired 1° amines. The use of an electron-poor half-sandwich Ir catalyst favored the formation of amine over alcohol products. To synthesize 2° or 3° amines, the aldehydes were combined with the appropriate 1° or 2° amine, respectively, under our standard reaction conditions. Our method is sufficiently mild to perform on proteins, as demonstrated by the conversion of aldehyde-containing allysine residues in bovine serum albumin to lysine. Importantly, we showed that Ir-catalyzed reductive amination could be applied inside living cells, such as by generating the alkaloid phenethylamine or calcium-reducing drug cinacalcet to elicit different biological responses. The amines formed via intracellular reductive amination were quantified by high performance liquid chromatography, revealing that turnover numbers of up to ∼20 were achieved. This work is expected to enable greater versatility and precision in transforming a wide range of aldehyde-containing entities within living environments, further expanding our biosynthetic chemistry toolbox.}, archive = {J_JACS}, author = {Rahul D. Jana and Hieu D. Nguyen and Loi H. Do}, doi = {10.1021/jacs.5c08536}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23318--23330}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective iridium-catalyzed reductive amination inside living cells}, volume = {147}, year = {2025}, }
• (2025). Revealing effect of surface hydroxyl variation on charge spatiotemporal dynamics in photocatalysis. JACS, 147(26), 23308--23317. (www)

  @article{ , abstract = {Oxide semiconductor photocatalysts are widely used for solar energy conversion, and the abundant intrinsic hydroxyl groups as defect sites on their surfaces play a key role in photocatalytic performance. However, the nature of surface hydroxyl-related defect states and their effect on the behavior of photogenerated charges, especially if targeted for charge separation, and whether the electrons and holes facing these hydroxyl sites in the same temporal and spatial ranges compete and conflict are unknown. Understanding these may help us to reasonably control defect-induced charge separation. Here, we perform an energy-, time-, and space-resolved study to reveal the effect of surface hydroxyl variation of BiOCl photocatalyst particles on photogenerated charge dynamics. We reveal that picosecond-level trapping and millisecond-level stability of holes initiated in electron-occupied states induced by hydroxyl sites are the greatest contributor to hole separation but the culprits that hinder electron utilization. Eliminating them can reduce unnecessary recombination and introduce unoccupied states, resulting in electron trapping and stabilization on the surface. Guided by these findings, selectively removing and holding hydroxyl sites on specific crystal planes can achieve the effective spatial separation of electrons and holes and show the associated enhanced reaction performance, especially in photocatalytic reduction. Operando imaging indicates that the surface hydroxyl-related charge-transfer sites align with reaction sites. This study reveals the critical role of surface defect states related to surface hydroxyl variation on charge separation and transport, which helps to understand the pivotal role of surface states in the entire photocatalytic process, also providing a valuable reference for most oxide semiconductor photocatalysts with intrinsic surface hydroxyl groups.}, archive = {J_JACS}, author = {Hanyu Yao and Qian Li and Yuying Gao and Han Feng and Panwang Zhou and Zhongrui Min and Thomas Dittrich and Prajakta Kokate and Keshav M. Dani and Ruotian Chen and Can Li and Fengtao Fan}, doi = {10.1021/jacs.5c08206}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23308--23317}, shortjournal = {J. Am. Chem. Soc.}, title = {Revealing effect of surface hydroxyl variation on charge spatiotemporal dynamics in photocatalysis}, volume = {147}, year = {2025}, }
• (2025). Electrochemical direct hydroxylation of benzylic C–H bonds assisted by HFIP. JACS, 147(26), 23297--23307. (www)

  @article{ , abstract = {Benzylic alcohols represent a privileged structural motif that is ubiquitous in bioactive natural products and pharmaceutical agents. Selective oxidative hydroxylation of benzylic C–H bonds is an efficient, atom-economical, and environmentally friendly methodology. However, the inherent obstacle of alcohol overoxidation still poses a significant challenge. Herein, we report an HFIP-assisted electrochemical oxidative hydroxylation of benzylic C–H bonds, utilizing green, benign H 2 O as the hydroxyl source. This method exhibits remarkable compatibility with a broad range of substrates, including electron-rich, electron-neutral, and electron-deficient alkylarenes, alkylarenes bearing primary, secondary, and tertiary benzylic C–H bonds, and even pharmaceutical molecules. Notably, the method enables efficient synthesis of 18 O-labeled biorelevant derivatives, highlighting its utility for isotopic-labeling studies. Furthermore, this electrochemical protocol has been shown to be readily scalable (up to 10 g under 200 mA/cm 2 ), thus demonstrating its promising potential for industrial application. Mechanistic studies have revealed that benzylic alcohols can be stabilized by HFIP via hydrogen-bonding interactions, thereby reducing the electron density of the aromatic rings, subsequently deactivating its further oxidation and improving the selectivity of the reaction.}, archive = {J_JACS}, author = {Cui Zhang and Haobo Tang and Xilin Zhao and Xianglin Shen and Youai Qiu}, doi = {10.1021/jacs.5c08109}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23297--23307}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical direct hydroxylation of benzylic C–H bonds assisted by HFIP}, volume = {147}, year = {2025}, }
• (2025). Ultrafast coherent electron transfer through intermolecular quantum well states. JACS, 147(26), 23286--23296. (www)

  @article{ , abstract = {Molecular materials offer a boundless design palette for light absorption and charge transport in both natural photosynthesis and engineered photovoltaics. They function in combination as chromophores, donors, conductors, and acceptors, enabling the excitation and charge carrier transport through space and wire-like intramolecular pathways. Although quantum coherence is believed to enhance photoexcitation and photoinduced charge transfer, fluctuating and inhomogeneous environments accelerate decoherence. Here, we assemble a nanoporous medium consisting of a templated bipyridyl ethylene (BPE) molecule array on a Ag(111) surface that functions as an exceptional intermolecular nonnuclear quantum well conductor of coherent electron waves spanning over 20 Å length. Time-periodic driving of the Ag/BPE interface by femtosecond pulses promotes electrons into a ladder of Floquet quasi-energy donor states, where intermolecular quantum well states act as a resonant doorway for coherent electron transport into BPE/vacuum image potential acceptor states. The bifurcation of electron passage between the Floquet donor ladder and the charge transfer acceptor channel is recorded by projecting the active electrons into the photoemission continuum in an interferometric time- and angle-resolved multiphoton photoemission experiment. We find that exceptional decoupling of electrons from the metal substrate by the molecule-dressed vacuum preserves the coherence on the ∼150 fs time scale. This offers a new paradigm for quantum state design where a molecule-dressed vacuum mediates coherent electron transport in nanoporous molecular architectures.}, archive = {J_JACS}, author = {Xintong Li and Linjie Chen and Zehua Wang and Andi Li and Huimin Xu and Guangzhen Shen and Jianyi Liu and Xuefeng Cui and Shijing Tan and Jin Zhao and V. Ara Apkarian and Bing Wang and Hrvoje Petek}, doi = {10.1021/jacs.5c08068}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23286--23296}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrafast coherent electron transfer through intermolecular quantum well states}, volume = {147}, year = {2025}, }
• (2025). Ammonium cation-promoted CO2 electroreduction on au in acidic media. JACS, 147(26), 23277--23285. (www)

  @article{ , abstract = {The electrochemical reduction of CO 2 in acidic media has received considerable attention, as it can mitigate the carbonate formation issue. However, the available protons in acidic media can boost the hydrogen evolution reaction (HER), so alkali metal cations are generally employed to promote the CO 2 reduction reaction (CO 2 RR) while suppressing the HER. Here we report that NH 4 + cations are more effective promoters of CO 2 electrolysis on Au in acidic media than Na + and K + , achieving a 3-fold improvement in the CO 2 RR activity. The promotional effect of NH 4 + cations is mainly attributed to their enhanced electrostatic stabilization of the CO 2 adsorption, which is the rate-limiting step for the CO 2 RR on Au. An estimation of the local pH under relevant conditions indicates that NH 4 + can mitigate the interfacial pH swing during the CO 2 RR compared to Na + and K + . Further studies on Au nanocatalysts of varying sizes indicate that the cation effect is independent of the catalytic sites. Our work advances the understanding of the cation effect on CO 2 RR using nonmetal cations and demonstrates a viable cation strategy to enhance CO 2 electrolysis.}, archive = {J_JACS}, author = {Kaige Shi and John Janisch and Zhuanghe Ren and Zhen Meng and Deborah Israel and Duy Le and William E. Kaden and Talat S. Rahman and Xiaofeng Feng}, doi = {10.1021/jacs.5c08017}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23277--23285}, shortjournal = {J. Am. Chem. Soc.}, title = {Ammonium cation-promoted CO2 electroreduction on au in acidic media}, volume = {147}, year = {2025}, }
• (2025). Catalytic asymmetric synthesis of axially chiral methylenecyclopropanes. JACS, 147(26), 23270--23276. (www)

  @article{ , abstract = {Atropisomeric compounds and 1,3-disubstituted allenes are the most common examples of axial chirality in organic chemistry. However, there are less explored classes of axially chiral molecules that may also hold significant value in asymmetric synthesis. Here, we report a catalytic asymmetric synthesis of axially chiral methylenecyclopropanes by a [2 + 1]-cycloaddition of an alkene and a vinylidene equivalent. Computational models provide a rationale for the origin of asymmetric induction and indicate that key elements of stereocontrol differ from catalytic enantioselective cyclopropanation reactions using carbenes. Methylenecyclopropanes participate in a broad range of axial-to-central chirality transfer reactions that take advantage of addition to the alkene or ring-opening of the strained three-membered ring.}, archive = {J_JACS}, author = {Jaysan Janabel and Deepesh Kumar and Vibha V. Kanale and Mingxin Liu and Christopher Uyeda}, doi = {10.1021/jacs.5c07968}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23270--23276}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic asymmetric synthesis of axially chiral methylenecyclopropanes}, volume = {147}, year = {2025}, }
• (2025). Radical strategy to the boron-to-copper transmetalation problem: N-alkylation with alkylboronic esters. JACS, 147(26), 23259--23269. (www)

  @article{ , abstract = {Organoboron compounds represent highly versatile reagents in organic synthesis, but their application to forge C(sp 3 )–heteroatom bonds, particularly C(sp 3 )–N coupling, remains underdeveloped. While the integration of alkylboron reagents with copper catalysis offers a promising approach, the inherently sluggish boron-to-copper transmetalation presents a significant challenge. Here, we develop a radical strategy to circumvent the two-electron transmetalation problem via an alkyl radical-capture mechanism, wherein the alkyl radical is generated through an aminyl radical-mediated boron abstraction. Leveraging a reductively activated boron-group transfer reagent, this mechanistically distinct approach enables a general N -alkylation using a diverse array of readily available N -nucleophiles and alkylboronic esters. This transformation differs fundamentally from previous approaches to provide a greater number of N -derivatives of complex small molecules with excellent regioselectivity. This method’s operational simplicity, broad functionality compatibility, and scalability enable streamlined access to N -alkylated architectures, addressing unmet needs in medicinal and process chemistry programs.}, archive = {J_JACS}, author = {Ruocheng Sang and Jason E. Gestwicki}, doi = {10.1021/jacs.5c07856}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23259--23269}, shortjournal = {J. Am. Chem. Soc.}, title = {Radical strategy to the boron-to-copper transmetalation problem: N-alkylation with alkylboronic esters}, volume = {147}, year = {2025}, }
• (2025). Efficient implementation of MINT-based chemiresistor arrays for artificial olfaction. JACS, 147(26), 23248--23258. (www)

  @article{ , abstract = {We demonstrate the possibility of using an array of MINT-based chemiresistors for the selective detection of VOCs at room temperature. Four new types of MINTs with different functional groups (MINT ALKENE (X:–CH = CH 2 ), MINT COOMe (X:–COOMe), MINT COOH (X:–COOH), and MINT OH (X:–CH 2 OH)) were specifically synthesized to prepare a set of six sensing layers, which included, in addition to the new MINTs, a pristine SWNTs layer and a MINT XYLENE layer. The functionalized sensing layers were tested by exposing them to NH 3 , NO 2 , EtOH, IPA, acetone, benzene, and NaClO vapors in the ppm range. We showed that MINT functionalization enhances response to analytes with respect to pristine SWNTs. When assembled into an array, our sensing layers can operate at room temperature as an electronic nose, disclosing the possibility of using these layers in low-power-consumption wearable devices. Correlation plots, PCA, and UMAP analysis show that a remarkable discrimination of ammonia with respect to interfering gases can be reached by the e-nose. Gas mixtures were also discriminated, as shown for NH 3 /ethanol, acetone/ethanol, and isopropanol/acetone mixtures, which are relevant in view of breathomics applications. The efficient preparation method of sensing layers allows for an improvement of performance, as shown for one of the best performing chemiresistors in the set, resulting in a sensitivity increase (up to 10×) and a dramatic reduction of response and recovery times.}, archive = {J_JACS}, author = {Michele Galvani and Alejandro López-Moreno and Natalia Martín Sabanés and Sylwia Parzyszek and Michele Zanotti and Sonia Freddi and Emilio M. Pérez and Luigi Sangaletti}, doi = {10.1021/jacs.5c07781}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23248--23258}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient implementation of MINT-based chemiresistor arrays for artificial olfaction}, volume = {147}, year = {2025}, }
• (2025). Dynamic evolution from propane to ethylene over mordenite zeolite for syngas conversion: Transition from hydrocarbon pool to carbonylation route. JACS, 147(26), 23239--23247. (www)

  @article{ , abstract = {Understanding the topology-dependent evolution of reaction intermediates during syngas conversion over an oxide-zeolite (OX-ZEO) bifunctional catalytic system is essential to the development of novel catalysts for regulating product distribution. In this study, we observed a dynamic shift in ethylene selectivity from 14.3% to 80% over time on stream using an unmodified commercial mordenite (MOR) zeolite combined with ZnAlO x . Concurrently, the propane selectivity gradually decreased from 46.9% to 0.3%. We confirmed that this alternative change in reaction time-dependent product distribution was closely linked to the evolution of intermediates, which relied on the accessibility of the 12-ring (R) and 8R pore channels varying with the degree of in situ coke deposition. The methanol-to-propylene (MTP) reaction route within 12R pores predominated the initial reaction phase with methanol as the intermediate, resulting in the formation of propane. Once the 12R pores were filled with MTP-formed coke, the carbonylation route within the 8R pores took over the reaction process. The coke-deposited ZnAlO x –MOR bifunctional system demonstrated stable activity, achieving a high ethylene selectivity of 80% and an ethylene/propylene ratio of 12.7. This study illustrates that in situ coke deposition into the 12R pores of MOR and molecular diffusion behavior are effective methods to enhance ethylene production during syngas conversion over the OX-ZEO catalyst, but there is no need to selectively deactivate the 12R acid sites through the introduction of pyridine.}, archive = {J_JACS}, author = {Jie Tuo and Yaqi Fan and Qi Yang and Xianchen Gong and Yan Wang and Hao Xu and Yanhang Ma and Yejun Guan and Peng Wu}, doi = {10.1021/jacs.5c07640}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23239--23247}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic evolution from propane to ethylene over mordenite zeolite for syngas conversion: Transition from hydrocarbon pool to carbonylation route}, volume = {147}, year = {2025}, }
• (2025). Modulating the nitrate reduction pathway on unconventional phase ultrathin nanoalloys for selective ammonia electrosynthesis. JACS, 147(26), 23226--23238. (www)

  @article{ , abstract = {Ammonia (NH 3 ) electrosynthesis from nitrate-polluted wastewater is a challenging but meaningful technique for the future green chemical and sewage disposal industries. The dominant difficulties lie in how to realize a highly selective, low-overpotential, and rapid electrocatalytic nitrate reduction reaction (NO 3 RR). Herein, we propose a catalyst crystal phase and electrode/electrolyte interface dual engineering strategy to enhance the neutral NO 3 RR performance of ultrathin alloy nanostructures. The obtained unconventional 2H-RhCu not only shows higher intrinsic NH 3 selectivity than its traditional face-centered cubic and amorphous/crystalline counterparts but also delivers superior Faradaic efficiency and yield rate toward NH 3 in K + -based electrolyte over those in Li + /Na + -based ones. In situ studies and theoretical calculations reveal that the faster generation/conversion kinetics of key intermediates, weaker N–N recombination, and unique *NO bri adsorption configuration at electrode/electrolyte interfaces account for this significant enhancement. In addition, rechargeable Zn-nitrate/methanol flow batteries with 2H-RhCu were constructed as a demonstration of potential applications.}, archive = {J_JACS}, author = {Jingwen Zhou and Fu Liu and Zhihang Xu and Jian-An Yin and Liang Guo and Fengkun Hao and Yunhao Wang and Yuecheng Xiong and Xichen Zhou and Cheng Wang and Yangbo Ma and Xiang Meng and Pengyi Lu and Jinwen Yin and An Zhang and Jie Wang and Chenliang Ye and Qiang Li and Chongyi Ling and Hsiao-Chien Chen and Hao Ming Chen and Ye Zhu and Jian Lu and Zhanxi Fan}, doi = {10.1021/jacs.5c07490}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23226--23238}, shortjournal = {J. Am. Chem. Soc.}, title = {Modulating the nitrate reduction pathway on unconventional phase ultrathin nanoalloys for selective ammonia electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Coordination chemistry meets boron helices: Cationic double-stranded diborahelicates and bora[7]helicenes with multicolor emission. JACS, 147(26), 23213--23225. (www)

  @article{ , abstract = {Helicates and helicenes represent two prominent classes of synthetic molecular helices, desirable for their potential in chiroptical applications. Incorporating boron into their backbone presents a promising strategy to enhance the optical properties; however, the development of boron-doped helical systems featuring tunable emission, high configurational stability, and strong chiroptical response has been limited by synthetic challenges. We report the chemistry of bora[7]helicene and its dimeric diborahelicate. While the dimeric form is thermodynamically favored in the haloborane precursor, saturation of the boron coordination sphere by exogenous carbene or carbone ligands induces monomerization, reverting the structure to the bora[7]helicene. By employing a variety of ligands, late-stage structural diversification was achieved, yielding the first examples of cationic boron helices, which show exceptional emission tunability across the entire visible spectrum, and chiroptical responses surpassing those of previously reported [7]helicenes. Theoretical studies indicate that the double-helix geometry and the intramolecular charge transfer play a significant role in achieving high dissymmetry factors.}, archive = {J_JACS}, author = {Heechan Kim and Robert J. Gilliard, Jr.}, doi = {10.1021/jacs.5c07436}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23213--23225}, shortjournal = {J. Am. Chem. Soc.}, title = {Coordination chemistry meets boron helices: Cationic double-stranded diborahelicates and bora[7]helicenes with multicolor emission}, volume = {147}, year = {2025}, }
• (2025). Catalytic asymmetric P-site dearomatization enables kinetic resolution. JACS, 147(26), 23202--23212. (www)

  @article{ , abstract = {Dearomatization of planar aromatics offers unparalleled opportunities for the construction of three-dimensional stereochemical frameworks. However, the inherent instability of dearomatized intermediates, particularly bearing labile C(sp 3 )–heteroatom bonds, has hindered progress due to competing rearomatization pathways. By capitalizing on arene dearomatization and transforming the rearomatization predicament into a new opportunity, we herein present a stability-driven catalytic asymmetric dearomatization/rearomatization (CADA/RA) cooperative strategy to resolve racemic P -stereogenic compounds. Through the systematic engineering of phenolic substrates, bench-stable P -site dearomatized products with dual C(sp 3 )–P and C(sp 3 )–Cl bonds were isolated. Chiral Lewis acid catalysis enabled kinetic resolution (KR) and parallel kinetic resolution (PKR), achieving full enantiomeric separation with exceptional stereocontrol across diverse substrates. Mechanistic analysis revealed competing substrate- and catalyst-controlled pathways for stereochemical precision. Postsynthetic chemoselective Cl - or P -liberation furnished enantioenriched P -chiral compounds. This method transforms the challenges of dearomatization and rearomatization into opportunities for stereochemical complexity generation, offering a robust platform to synthesize P -chiral building blocks and ligand precursors.}, archive = {J_JACS}, author = {Dongwei Zhao and Junjie Sun and Ning Chen and Yicong Ge and Jingjing Liu and Lu Bai and Xinjun Luan}, doi = {10.1021/jacs.5c07259}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23202--23212}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic asymmetric P-site dearomatization enables kinetic resolution}, volume = {147}, year = {2025}, }
• (2025). Core@Shell AgBr@CsPbBr3 nanocrystals as precursors to hollow lead halide perovskite nanocubes. JACS, 147(26), 23192--23201. (www)

  @article{ , abstract = {We report the synthesis of colloidal core@shell AgBr@CsPbBr 3 nanocubes by a one-pot approach, where the nucleation and growth of AgBr nanocrystals occurs rapidly after the injection of chemical precursors. This is immediately followed by the overgrowth of CsPbBr 3 , delivering AgBr@CsPbBr 3 nanocubes of several tens of nanometers in size, with the volume of the AgBr core being only a small fraction of the overall nanocrystal volume. The formation of a core@shell geometry is facilitated by the epitaxial compatibility between AgBr and CsPbBr 3 along multiple crystallographic directions. Exchange with Cl – ions leads to Ag@CsPbCl 3 nanocubes, whereas exchange with I – ions leads to hollow CsPbI 3 nanocubes, due to selective etching of the AgBr (or Ag) core region by the I – ions diffusing in the nanocubes. These hollow CsPbI 3 nanocubes can then be converted into hollow CsPbBr 3 and CsPbCl 3 nanocubes by halide exchange. The optical emission properties of the hollow CsPbX 3 (X = Cl, Br, I) nanocubes are in line with those expected from large, non-hollow halide perovskite nanocrystals, indicating that the small hollow region in the cubes has no major influence on their optical properties.}, archive = {J_JACS}, author = {Zhanzhao Li and Yurii P. Ivanov and Anna Cabona and Andrea Fratelli and Stefano Toso and Saptarshi Chakraborty and Giorgio Divitini and Ilka Kriegel and Sergio Brovelli and Liberato Manna}, doi = {10.1021/jacs.5c07200}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23192--23201}, shortjournal = {J. Am. Chem. Soc.}, title = {Core@Shell AgBr@CsPbBr3 nanocrystals as precursors to hollow lead halide perovskite nanocubes}, volume = {147}, year = {2025}, }
• (2025). Defect tolerance via external passivation in the photocatalyst SrTiO3:Al. JACS, 147(26), 23180--23191. (www)

  @article{ , abstract = {The efficiency of solar-to-energy conversion in semiconductors is limited by charge carrier recombination, often via defect-induced gap states. Although some materials exhibit an intrinsic defect tolerance that avoids fast recombination channels, there are few examples among metal oxides. We investigate the water splitting photocatalyst SrTiO 3 , where photocatalytic performance is enhanced by extrinsic Al doping. We propose that defect tolerance emerges through a passivation effect that effectively eliminates in-gap states and nonradiative recombination. First-principles defect calculations show that oxygen vacancies are the primary defect species in SrTiO 3 under oxygen-poor synthetic conditions, which provide in-gap states that are active for carrier capture. Al substitutions are preferred at Ti sites adjacent to the oxygen vacancy, forming [ V O -Al Ti ] defect complexes. As the oxygen vacancy in-gap state is derived from Ti 3d–Ti 3d interactions across the vacancy, substituting Ti with Al deactivates this interaction and eliminates the in-gap state. The absence of valence d orbitals in Al is key for in-gap state reduction, as supported by the consideration of other dopants such as Sc. Our study illustrates how an orbital-wise understanding of defect states can enable doping strategies to achieve defect tolerance in materials like SrTiO 3 , paving the way for improved solar-to-energy conversion.}, archive = {J_JACS}, author = {Kanta Ogawa and Seán R Kavanagh and Fumiyasu Oba and Aron Walsh}, doi = {10.1021/jacs.5c07104}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23180--23191}, shortjournal = {J. Am. Chem. Soc.}, title = {Defect tolerance via external passivation in the photocatalyst SrTiO3:Al}, volume = {147}, year = {2025}, }
• (2025). Near-saturated coordinated cations in oxyhalide superionic conductors boost high-rate all-solid-state batteries. JACS, 147(26), 23170--23179. (www)

  @article{ , abstract = {Amorphous oxyhalide solid electrolytes (SEs) have garnered significant attention due to their excellent cathodic stability and favorable mechanical properties. However, the correlations between the structural characteristics in the amorphous phase and Li + transport behavior remain underexplored, limiting further promotion of the ionic conductivities of these SEs. Herein, we establish a correlation between cationic coordination saturation in amorphous oxyhalide SEs and Li + transport. Based on this correlation, near-saturated coordinated cation (NSCC)-incorporated Li 1.5 Zr 0.5 M 0.5 Cl 5.0 O 0.5 SEs (M = Nb or Ta, denoted as Nb- or Ta-LZCO) are developed with abundant vacancy concentrations and weakened Li–Cl interaction, thereby significantly enhancing Li + transport. As a result, the Nb-LZCO and Ta-LZCO SEs achieve impressive ionic conductivities of 2.33 and 3.88 mS cm –1 , respectively, at 25 °C. All-solid-state lithium batteries assembled with representative Ta-LZCO and a LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode demonstrate superior rate performance and long-term cycling stability, delivering a high specific capacity of 120.0 mAh g –1 at 10.0 C (1 C = 195 mA g –1 ) and an outstanding capacity retention of 84.85% after 2000 cycles. This work establishes a generalizable strategy for designing amorphous SEs with high ionic conductivity by modulating the cationic coordination environment.}, archive = {J_JACS}, author = {Long Qian and Shuibin Tu and Yue Wang and Xiaofei Yang and Chao Ye and Shi-Zhang Qiao}, doi = {10.1021/jacs.5c07052}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23170--23179}, shortjournal = {J. Am. Chem. Soc.}, title = {Near-saturated coordinated cations in oxyhalide superionic conductors boost high-rate all-solid-state batteries}, volume = {147}, year = {2025}, }
• (2025). Selective CO2 adsorption in ultrahydrophobic molecular pyrene frameworks by computational design. JACS, 147(26), 23160--23169. (www)

  @article{ , abstract = {The separation of carbon dioxide from industrial flue gas streams using porous materials is often thwarted by humidity. Most porous sorbents adsorb water more effectively than CO 2 . Hence, water can out-compete CO 2 for adsorption sites, lowering the working CO 2 sorption capacity and increasing sorbent regeneration costs. Here, two pyrene-based hydrogen bonded organic frameworks (HOFs) are described that can separate CO 2 under humid conditions. The framework building blocks were chosen in a high-throughput density functional theory screen, followed by crystal structure prediction (CSP) to target a hydrophobic two-dimensionally porous framework. Gas sorption experiments showed selective adsorption of CO 2 and exceptionally low water adsorption in these HOFs. Dynamic column breakthrough measurements using mixed gas environments showed that the CO 2 working capacity was totally unaffected by water under simulated flue gas conditions up to 75% relative humidity. One of the CO 2 -selective HOFs, diMeTBAP-α, was shown by CSP to be the most thermodynamically stable structure on the crystal energy landscape. This stability prediction was reflected by experiments, where an isostructural, scalable analogue of diMeTBAP-α, MeTBAP-α, retained its porosity and crystallinity after boiling in aqueous acids, which is important for carbon capture from acidic, humid flue gas.}, archive = {J_JACS}, author = {Sam D. Harding and Tao Liu and Linjiang Chen and Siyuan Yang and Isaiah Borne and Thomas Fellowes and Aaron W. Peters and Simon C. Weston and John W. Ward and Andrew I. Cooper}, doi = {10.1021/jacs.5c06861}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23160--23169}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective CO2 adsorption in ultrahydrophobic molecular pyrene frameworks by computational design}, volume = {147}, year = {2025}, }
• (2025). Second-sphere interaction allows selective reduction of nitrite to NO or ammonia by synthetic iron porphyrins. JACS, 147(26), 23145--23159. (www)

  @article{ , abstract = {Heme nitrite reductases (NiRs) are key enzymes in the assimilatory and dissimilatory reduction of nitrite (NO 2 – ) by 6e – /8H + to NH 4 + and by 1e – /2H + to NO during denitrification in the global nitrogen cycle. The different heme cofactors in different NiRs are flanked by highly conserved second-sphere basic residues in their active sites, e.g., histidine, lysine, and arginine. Biochemical and computational investigations have indicated that these basic residues offer hydrogen bond stabilization and provide protons to the intermediate species formed during NO 2 – reduction. Iron porphyrins with one or two pendent pyridines, mimicking the basic residues in the active site of NiRs, are synthesized, and their electrochemical NO 2 – reduction is investigated. The second-sphere hydrogen bonding residues allow the iron porphyrin with two pendent pyridines to successfully emulate the reactivity of cytochrome c NiR, where it can generate >95% NO (1e – /2H + ) at high potentials and >75% NH 4 + (6e – /8H + ), rest being NO, at lower potentials without releasing any other partially reduced species. These pendent pyridines stabilize the NO 2 – binding and very selective reduction of NO 2 – to either NO or NH 4 + in the presence of a modest proton donor. While the reduction to NO can be satisfactorily achieved using one basic group in the second sphere, the 6e – /8H + reduction to NH 4 + can be achieved satisfactorily only when two such basic groups are present. The quantitative understanding of the roles played by these basic residues in these reactions, obtained from these functional synthetic models, highlights the importance of these basic residues in multiproton multielectron reduction reactions in nature.}, archive = {J_JACS}, author = {Sudip Barman and Paramita Saha and Abhishek Dey}, doi = {10.1021/jacs.5c06960}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23145--23159}, shortjournal = {J. Am. Chem. Soc.}, title = {Second-sphere interaction allows selective reduction of nitrite to NO or ammonia by synthetic iron porphyrins}, volume = {147}, year = {2025}, }
• (2025). C-terminal radical oxidation inhibits α-synuclein aggregation and cytotoxicity via an oxidative oligomer-disrupting pathway. JACS, 147(26), 23136--23144. (www)

  @article{ , abstract = {α-Synuclein (α-Syn) aggregation is a hallmark of Parkinson’s disease and other neurodegenerative disorders. This study investigates the impact of controlled radical oxidation on α-Syn aggregation and associated cytotoxicity. Using a microscale low-temperature plasma device for submillisecond radical oxidation, combined with native ion mobility-mass spectrometry and liquid chromatography-tandem mass spectrometry, we demonstrate radical-directed preferential oxidation of the α-Syn C-terminal region. This targeted oxidation leads to the inhibition of protein aggregation and reduced cytotoxicity in SH-SY5Y cells. Mechanistic analysis reveals that ultrafast C-terminal radical oxidation impairs α-Syn oligomerization propensity, likely by preventing conformational transitions critical for forming stable amorphous deposits and well-ordered fibers. Notably, this inhibitory effect is specific to monomer oxidation prior to aggregation rather than oxidation of preformed fibers. Our findings unveil a novel oxidative oligomerization-disrupting pathway that modulates α-Syn fibrillization behavior, offering new insights into the complex interplay between oxidative stress and protein aggregation in neurodegenerative diseases. This study challenges conventional views of the detrimental role of oxidative stress in α-Syn pathology and suggests potential neuroprotective strategies based on targeted oxidative modifications.}, archive = {J_JACS}, author = {Xiaoli Wang and Tingting Liang and Anran Jin and Chenao Zhang and Jiaxin Zhou and Mingrui Li and Ziyi Sun and Gongyu Li}, doi = {10.1021/jacs.5c06792}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23136--23144}, shortjournal = {J. Am. Chem. Soc.}, title = {C-terminal radical oxidation inhibits α-synuclein aggregation and cytotoxicity via an oxidative oligomer-disrupting pathway}, volume = {147}, year = {2025}, }
• (2025). Thioether-functionalized self-healing polyolefins for flexible conductors. JACS, 147(26), 23128--23135. (www)

  @article{ , abstract = {The growing demand for flexible conductors in wearable electronics and soft robotics drives the need for elastomeric substrates with multiple functions, including robust mechanical properties, strong interfacial adhesion, and autonomous self-healing. Herein, we report a new class of polyolefin-based elastomers that address these multifaceted requirements. These materials are synthesized via a one-pot, scandium-catalyzed copolymerization of ethylene with thiophenyl-substituted propylenes in a sequence-controlled manner. By varying the substituents on the sulfur atom and the commoner feed ratio, the mechanical properties of the resulting copolymers can be finely tuned across a wide range. Remarkably, phenylthio-substituted copolymers exhibit high toughness, excellent elasticity, and intrinsic self-healing capability. Furthermore, these copolymers exhibit strong adhesion to gold nanoparticles due to the unique affinity between sulfur and gold. This interaction significantly enhances the durability of gold-coated copolymer conductors. This work underscores the potential of catalyst-controlled copolymerization of functionalized olefins for creating multifunctional polyolefin materials for flexible electronic applications.}, archive = {J_JACS}, author = {Mingjun Chi and Lulu Sun and Masayoshi Nishiura and Lin Huang and Haoran Zhang and Yuji Higaki and Sunghoon Lee and Kenjiro Fukuda and Yanan Zhao and Takao Someya and Zhaomin Hou}, doi = {10.1021/jacs.5c06579}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23128--23135}, shortjournal = {J. Am. Chem. Soc.}, title = {Thioether-functionalized self-healing polyolefins for flexible conductors}, volume = {147}, year = {2025}, }
• (2025). Quaternary carbon as a locus for skeletal disconnection. total synthesis of (±)-tubingensin a featuring assembly of the backbone stereotriad using a halo-Prins/Halo-nazarov cascade. JACS, 147(26), 23120--23127. (www)

  @article{ , abstract = {The first successful fragment coupling/cationic cascade approach for the synthesis of a complex indoloditerpenoid tubingensin A is described. The synthesis is the first example of a novel disconnection strategy targeting a central quaternary carbon locus. A halo -Prins/ halo -Nazarov cationic cascade sequence enabled the rapid preparation of a complex intermediate as a single diastereomer, containing the vicinal quaternary centers found in the backbone stereotriad. This approach installed much of the complex carbon skeleton of tubingensin A in one step from fragment coupling of two simple reactants. To complete the synthesis, the indane ring system is converted to the target cis- decalin, preserving the integrity of the stereotriad. The isopropylidene fragment is appended in the endgame. The target is obtained in 15 fully diastereoselective steps from simple achiral materials. Investigation of the halo -Nazarov cyclization revealed fluxional behavior in the Friedel–Crafts termination step.}, archive = {J_JACS}, author = {Aleksa Milosavljevic and Georgios Alachouzos and Alison J. Frontier}, doi = {10.1021/jacs.5c06475}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23120--23127}, shortjournal = {J. Am. Chem. Soc.}, title = {Quaternary carbon as a locus for skeletal disconnection. total synthesis of (±)-tubingensin a featuring assembly of the backbone stereotriad using a halo-Prins/Halo-nazarov cascade}, volume = {147}, year = {2025}, }
• (2025). Microtesla signal amplification by reversible exchange enables simultaneous over 5% polarization of 77Se and 15N at natural abundance in a Selenium–Nitrogen heterocycle. JACS, 147(26), 23113--23119. (www)

  @article{ , abstract = {Signal amplification by reversible exchange (SABRE) increases NMR sensitivity through polarization transfer from parahydrogen, offering a cost-effective alternative to dissolution dynamic nuclear polarization ( d -DNP). For the first time, this study demonstrates nuclear spin hyperpolarization of 77 Se nuclei by SABRE, achieved for a biologically important selenium–nitrogen heterocycle, 3-methyl-[1,2,4]-selenadiazolo-[4,5- a ]-pyridine-4-ium chloride (SDAP), via polarization transfer at mictrotesla magnetic fields. Under microtesla SABRE conditions, polarization transfer on both 77 Se and 15 N nuclei is achieved simultaneously, leading to the formation of multinuclear hyperpolarization within the time scale of several seconds. The resulting NMR signal enhancements achieved are 12,000-fold and 17,000-fold at a magnetic field of 9.4 T for 77 Se and 15 N, respectively, corresponding to over 5% polarization for each nucleus. This enables fast single-scan detection at micromolar concentrations by heteronuclear NMR. Our work overcomes the sensitivity limitations of 15 N and 77 Se NMR spectroscopy and provides new opportunities for studying selenium-containing compounds in organic synthesis and biological systems.}, archive = {J_JACS}, author = {Alexey S. Kiryutin and Danil A. Markelov and Zhanna V. Matsulevich and Irina D. Kosenko and Nikolay V. Kireev and Ivan A. Godovikov and Alexandra V. Yurkovskaya}, doi = {10.1021/jacs.5c06450}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23113--23119}, shortjournal = {J. Am. Chem. Soc.}, title = {Microtesla signal amplification by reversible exchange enables simultaneous over 5% polarization of 77Se and 15N at natural abundance in a Selenium–Nitrogen heterocycle}, volume = {147}, year = {2025}, }
• (2025). Steering magnetic coupling in diradical nonbenzenoid nanographenes. JACS, 147(26), 23103--23112. (www)

  @article{ , abstract = {Magnetic properties arising from controlled spin–spin interactions hold great promise for applications in spintronics and quantum technologies. In nanographenes, pentagonal and heptagonal rings introduce geometric frustration and sublattice imbalance, fundamentally altering spin localization and facilitating the emergence of open-shell structures. The precise engineering of magnetic order and coupling strength in the resulting nonbenzenoid nanographenes, however, remains a challenging and underexplored area. Here, we demonstrate an on-surface synthesis of nanographenes incorporating five- and seven-membered rings through a sequence of intramolecular C–C bond formations between methyl and aryl units. Two products are generated: the partially cyclized intermediate MAAT and the fully cyclized end product MAZC. Due to the presence of iodo groups, the resulting monomers obtained can be covalently connected via Ullmann-like coupling in variable modes, enabling programmable spin arrangements. While MAZC exists as a nonmagnetic species, MAAT featuring one seven-membered ring holds an unpaired S = 1/2 spin and exhibits Kondo resonance on a metal surface. By change of the connectivity between two MAAT units, tunable magnetic ground states and precise control over the exchange-interaction strength can be achieved. These findings, supported by scanning probe microscopy and density functional theory, establish a novel strategy for designing defined carbon nanostructures with tailored topological defects and offer fine-tuned manipulation of molecular magnetism.}, archive = {J_JACS}, author = {Ye Liu and Svenja Weigold and Linghao Yan and Zixuan Wei and Malte Hanne and Olena Tverskoy and Sifan You and Miao Xie and Yanfang Zhang and Qiang Chen and Frank Rominger and Uwe H. F. Bunz and Jan Freudenberg and Shixuan Du and Klaus Müllen and Lifeng Chi}, doi = {10.1021/jacs.5c06416}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23103--23112}, shortjournal = {J. Am. Chem. Soc.}, title = {Steering magnetic coupling in diradical nonbenzenoid nanographenes}, volume = {147}, year = {2025}, }
• (2025). Ligand tuning of molecular ag catalysts enables efficient direct propylene electrooxidation to propylene glycol. JACS, 147(26), 23090--23102. (www)

  @article{ , abstract = {Renewable-electricity-driven direct oxidation of propylene (C 3 H 6 ) presents a sustainable route for propylene glycol (PG) production. Silver (Ag) shows a 30-fold lower price compared to other active noble metals (platinum and palladium) but suffers from low activity. Here, we report a ligand-tuning strategy in Ag-based molecular catalysts for efficient direct C 3 H 6 -to-PG conversion. By broad ligand screening, Ag chelated with phenanthroline (phen) and supported on a carbon nanotube (Ag-phen/CNT) was identified to display superior performance. Mechanistic studies revealed that the electron-donating ability of phen facilitated the formation of high-valence Ag-oxo species, which served as the rate-determining step for C 3 H 6 oxidation. Based on the promoting role of the electron-donating effect on catalytic performance, substituents with diverse electron-donating and -withdrawing properties were introduced to the phen’s scaffold. As a result, a linear correlation between the logarithm of the reaction rate and Hammett constants of the substituents was revealed. Based on this correlation, Ag chelated with dimethoxy-substituted phen (Ag-OMe-phen/CNT) was discovered as a more efficient catalyst. In a three-compartment flow cell under a current density of 50 mA cm –2 , this catalyst exhibited high PG productivity (432.8 μmol cm –2 h –1 ), FE (46.5%), selectivity (97.1%), and turnover frequency (73.0 min –1 ), outperforming previous Ag-based catalysts and is superior to state-of-the-art Pt and Pd catalysts in terms of productivity, selectivity, and TOF. This work shows the great potential of precisely tuning ligands in molecular catalysts to modulate electronic properties for efficient PG electrosynthesis and beyond.}, archive = {J_JACS}, author = {Xi Wang and Si-Min Xu and An-Zhen Li and Bo-Jun Yuan and Qiujin Shi and Xiang Liu and Ming Xu and Yuanbo Liu and Kejian Kong and Chunyu Zhang and Ruo-Pu Li and Cheng Tang and Zhuo Chen and Bi-Jie Li and Haohong Duan}, doi = {10.1021/jacs.5c06198}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23090--23102}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand tuning of molecular ag catalysts enables efficient direct propylene electrooxidation to propylene glycol}, volume = {147}, year = {2025}, }
• (2025). Multifunctional polar 2D lead iodide perovskites exhibiting persistent spin texture. JACS, 147(26), 23079--23089. (www)

  @article{ , abstract = {Ferroelectric Rashba semiconductors are a rare class of multifunctional materials promising for spin–orbitronics due to the possibility of electrically switchable spin textures. Hybrid organic–inorganic metal halide perovskites offer exceptional tunability that can be harnessed to target noncentrosymmetry; however, the complex interactions between organic and inorganic components are not rationally understood. Here, we use an asymmetric spacer cation with a strong molecular dipole moment (2-fluorobenzylammonium, 2FBZ) and increase the intrinsic quantum well thickness to n > 1 to synthesize three new polar 2D lead iodide perovskites (2FBZ) 2 (A) n -1 Pb n I 3 n +1 with A = methylammonium (MA) or formamidinium (FA) and n = 2, 3. Single-crystal structure analysis reveals the C 2v symmetry of these crystal structures and substantial structural distortions, which enable Rashba and Dresselhaus band splitting and persistent spin texture, confirmed by DFT calculations. Measurements of the resulting symmetry-dependent properties, such as second harmonic generation, switchable photovoltaic effect, ferroelectric polarization, and low temperature photoluminescence show switchable ferroelectric semiconducting properties. These results introduce a general chemical design strategy toward polar symmetry by exploiting the complex interplay between asymmetric spacer cations and A-site cations in quasi-2D ( n > 1) halide perovskites to realize new classes of multifunctional materials for future spin–orbitronic applications.}, archive = {J_JACS}, author = {Willa Mihalyi-Koch and Zhenbang Dai and Meng-Jia Sun and Jae Yong Park and David P. Lafayette, II and Kyana M. Sanders and Ilia A. Guzei and John C. Wright and Libai Huang and Andrew M. Rappe and Song Jin}, doi = {10.1021/jacs.5c06227}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23079--23089}, shortjournal = {J. Am. Chem. Soc.}, title = {Multifunctional polar 2D lead iodide perovskites exhibiting persistent spin texture}, volume = {147}, year = {2025}, }
• (2025). Revealing the impact of g-tensor anisotropy on the charge recombination in Donor–Acceptor dyads under high magnetic fields. JACS, 147(26), 23068--23078. (www)

  @article{ , abstract = {Four new donor–acceptor dyads, featuring triarylamine donors and perylene diimide acceptors, were synthesized to investigate the influence of the g -tensor on the magnetic field-dependent spin dynamics of the resulting radical pairs. These pairs are characterized by the exchange interaction 2 J being larger than the effective isotropic hyperfine coupling a eff . To control the isotropic g -factor and g -tensor anisotropy of the radical anion generated via photoinduced electron transfer, the perylene diimides were functionalized with phenyl chalcogen ethers. In dyads containing oxygen, sulfur, and selenium ether substituents, not only was the characteristic 2 J -resonance observed but also a pronounced high-field effect in the charge recombination kinetics, extending up to B = 10 T. Quantum dynamics simulations based on the stochastic Liouville equation revealed that this effect is primarily driven by g -tensor anisotropy-induced relaxation, which increases along the chalcogen ether series. Additionally, we derived an exact analytical solution describing the impact of g -factor differences and g -tensor anisotropy on spin relaxation in the high-field limit. These findings highlight the critical role of g -tensor-induced relaxation in radical pairs at high magnetic fields, offering new insights for the molecular design of materials with potential applications in quantum information science, where incoherent relaxation processes should be avoided.}, archive = {J_JACS}, author = {Paul Mentzel and Luca Gerhards and Denise Koppenhöfer and Alexander Schmiedel and Marco Holzapfel and Nikita N. Lukzen and Ilia A. Solov’yov and Ulrich E. Steiner and Christoph Lambert}, doi = {10.1021/jacs.5c06173}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23068--23078}, shortjournal = {J. Am. Chem. Soc.}, title = {Revealing the impact of g-tensor anisotropy on the charge recombination in Donor–Acceptor dyads under high magnetic fields}, volume = {147}, year = {2025}, }
• (2025). Chiral aromatic micelles as chiroptical host tools for large metallodyes in water. JACS, 147(26), 23060--23067. (www)

  @article{ , abstract = {In contrast to abundant aliphatic chiral cavities in nature, synthetic chiral cavities formed by self-assembly of aromatic subunits are quite rare, particularly providing an ability in induced chirality. Here, we report new chiral aromatic micelles capable of inducing the optical chirality of large metallodyes upon encapsulation. The aromatic micelle, with a core diameter of ∼3 nm, forms from axially chiral amphiphiles featuring a bent mesityl-substituted BINOL framework. Unlike alkyl and aromatic micelles reported previously, the obtained micelle emits strong fluorescence (Φ F > 40%) through the aggregation-induced emission effect in water. The adaptable chiral cavity of the micelle efficiently encapsulates several kinds of achiral metallodyes, such as metalated porphyrins and norcorroles, to afford aqueous host–guest composites, displaying efficient dye-based induced chirality through multiple CH-π interactions. Remarkably, the chirality induction of metallophthalocyanine, bearing a completely planar framework, and its stacked dimer can also be demonstrated (up to | g abs | = 2.4 × 10 –3 ) in the cavity under ambient aqueous conditions. To the best of our knowledge, the present aromatic micelles are the first host tools to induce the chiral properties of common to rare metallodyes, without additional covalent functionalizations . The chiroptical properties of the obtained host–guest composites are further tunable (i.e., 0.1- to 1.6-fold intensity) upon thermal stimuli in an irreversible fashion without disassembly.}, archive = {J_JACS}, author = {Yoshihisa Hashimoto and Yuya Tanaka and Si-Yu Liu and Hiroshi Shinokubo and Michito Yoshizawa}, doi = {10.1021/jacs.5c06179}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23060--23067}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral aromatic micelles as chiroptical host tools for large metallodyes in water}, volume = {147}, year = {2025}, }
• (2025). Guest-shape-directed structural switching between two isomers of a pd6 host and its structural adaptability for selective photodimerization. JACS, 147(26), 23049--23059. (www)

  @article{ , abstract = {The structure and functions of metal–organic cages are heavily dependent on the nature of the building blocks. Herein, a dimethyl-substituted propane diamine blocked cis -Pd(II) acceptor ( A ) was designed, which upon self-assembly with the tri-imidazole ligand ( L ), generated an unusual A 6 L 4 octahedral cage ( M1O ) instead of the expected isomeric double-square architecture that was obtained from the tetramethyl-substituted ethylene diamine blocked cis -Pd(II) acceptor in water. Interestingly, in the presence of planar guests ( Gn ), M1O showed a transformation to a transient double-square architecture ( M1DS ), forming host–guest complexes with two such guests, (Gn) 2 @M1DS . The transient double-square cage ( M1DS ) readily converts back to the parent octahedral structure, M1O upon the removal of the guests. On the contrary, tetrahedral guests ( G5 / G6 ) stabilized the octahedral isomer of the host ( M1O ) by acting as suitable templates. Additionally, tetrahedral guests could induce the reverse transformation of M1DS to M1O by driving out planar guests from metastable M1DS . The specific antiparallel orientation and proximity of two anthracene derivatives within M1DS enabled them to be selectively transformed to the trans isomers of their respective dimers under photoirradiation. Upon dimer formation, the nonplanar product was expelled readily from the cavity of M1DS , and the host switched back to its original octahedral form ( M1O ), which functionally and structurally imitates enzymatic activity. Thus, a multifunctional supramolecular host was obtained that showed unique guest-shape-driven reversible structural switching and acted as an adaptive host for selective photodimerization.}, archive = {J_JACS}, author = {Ranit Banerjee and Pallab Bhandari and Neal Hickey and Partha Sarathi Mukherjee}, doi = {10.1021/jacs.5c06104}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23049--23059}, shortjournal = {J. Am. Chem. Soc.}, title = {Guest-shape-directed structural switching between two isomers of a pd6 host and its structural adaptability for selective photodimerization}, volume = {147}, year = {2025}, }
• (2025). Highly antiaromatic naphtho-1,2-diboretes as precursors for tunable, unsymmetrical 1,4-diboraanthracenes. JACS, 147(26), 23034--23048. (www)

  @article{ , abstract = {The four-electron reduction of doubly IMes- and SIMes-stabilized 2,3-bis(dibromoboryl)naphthalene (IMes = 1,3-dimesitylimidazol-2-ylidene; SIMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene, mesityl = 2,4,6-trimethylphenyl) yields the first N-heterocyclic carbene (NHC)-stabilized naphtho[2,3- c ][1,2]diboretes 3a and 3b , which were isolated as dark-blue and red solids, respectively, and analyzed by nuclear magnetic resonance (NMR) and ultraviolet-visible (UV-vis) spectroscopy as well as X-ray crystallography. The synthesis of 3b is systematically accompanied by NHC ring-expanding boron insertion side reactions, absent in that of 3a . Both experimental and computational data show that unlike their biradical cyclic alkyl(amino)carbene (CAAC)-stabilized counterparts, the 1,2-diborete rings in 3a and 3b are closed-shell 4π-antiaromatic compounds. The differences between the IMes and SIMes derivatives lie in the additional delocalization of the π-electron density to one of the SIMes ligands in 3b , which results in an unsymmetrical conformation with lower B═B double bond character and a more planar C 2 B 2 ring. Reactions of 3a and 3b with terminal alkynes (HC≡CR; R = H, TMS (= SiMe 3 ), p EP (= p -(HCC)C 6 H 4 ), Fc (= ferrocenyl)) yield the first examples of aromatic 1,4-diboraanthracenes (1,4-DBAs) ( 6a/b-R ) by insertion of the alkyne CC unit into the strained diborete B═B bond. These compounds are highly colorful (green-purple), quasi-planar, and aromatic. While most internal alkynes do not react with 3a or 3b , reactions with the highly electron-deficient alkyne DMAD (= dimethyl acetylenedicarboxylate) also yield the corresponding yellow-colored 1,4-DBA. Furthermore, the parent 1,4-DBA 6a-H undergoes a Diels–Alder reaction with DMAD to yield a naphtho[2,3- c ][1,4]diborabarrelene, while 6a/b- p EP undergoes a 1,4-addition of the alkynyl C–H functionality of a second equivalent of HC≡C( p EP).}, archive = {J_JACS}, author = {Marco Neder and Merle Arrowsmith and Lukas Endres and Cornelius Mihm and Samuel Nees and Rüdiger Bertermann and Holger Braunschweig}, doi = {10.1021/jacs.5c06017}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23034--23048}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly antiaromatic naphtho-1,2-diboretes as precursors for tunable, unsymmetrical 1,4-diboraanthracenes}, volume = {147}, year = {2025}, }
• (2025). Uncovering hidden orders within deformable materials: The case of dysprosium. JACS, 147(26), 23026--23033. (www)

  @article{ , abstract = {The intrinsic orders within deformable materials can be masked by lattice defects, an issue that has been largely overlooked. Uncovering these hidden orders is likely to offer new insights into material properties. Here, we address this issue by introducing a zero-gravity synthesis method to fabricate highly crystalline and nearly stress-free microspheres from deformable materials, as demonstrated with dysprosium metal. Interestingly, we find that the intrinsic atomic order of dysprosium is an unusual low-symmetry orthorhombic Cmcm phase, which contrasts with the widely accepted hexagonal P 6 3 / mmc structure. Through first-principles crystal field theory calculations, we determine the intrinsic orbital order, showing that the Cmcm phase arises from a nonzero quadrupole operator for the Dy’s 4f-electron shell in its ferromagnetic state. This operator possesses an opposite sign compared to that of terbium, driving contrary significant magnetoelastic distortions within the basal plane. These findings aid in understanding the functions of rare-earth-related functional materials like giant magnetostriction. We expect to uncover more hidden orders in deformable materials, thereby deepening our knowledge of their performances.}, archive = {J_JACS}, author = {Zeyu Qiao and Kun Lin and Sergii Khmelevskyi and Leonid V. Pourovskii and Hankun Xu and Meng He and Chengyi Yu and Yili Cao and Qiang Li and Xianran Xing}, doi = {10.1021/jacs.5c06003}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23026--23033}, shortjournal = {J. Am. Chem. Soc.}, title = {Uncovering hidden orders within deformable materials: The case of dysprosium}, volume = {147}, year = {2025}, }
• (2025). Natural-language-interfaced robotic synthesis for AI-copilot-assisted exploration of inorganic materials. JACS, 147(26), 23014--23025. (www)

  @article{ , abstract = {The automation of chemical synthesis presents opportunities to enhance experimental reproducibility and accelerate discovery. Traditional closed-loop approaches, while effective in specific domains, are often constrained by rigid workflows and the requirement for specialized expertise. Here, we introduce a chemical robotic explorer integrated with an artificial intelligence (AI) copilot to enable a more flexible and adaptive synthesis, simplifying the process from inspiration to experimentation. This modular platform uses a large language model (LLM) to map natural language synthetic descriptions to executable unit operations, including temperature control, stirring, liquid and solid handling, filtration, etc. By integrating AI-driven literature searches, real-time experimental design, conversational human–AI interaction, and feedback-based optimization, we demonstrate the capabilities of AI in successfully synthesizing 13 compounds across four distinct classes of inorganic materials: coordination complexes, metal–organic frameworks, nanoparticles, and polyoxometalates. Notably, this approach enabled the discovery of a previously unreported family of Mn–W polyoxometalate clusters, showing the potential of AI-enhanced robotics as a generalizable and adaptable platform for material innovation.}, archive = {J_JACS}, author = {Lin Huang and Chao Zhang and Yun Fu and Yibin Jiang and Enyu He and Ming-Qiang Qi and Ming-Hao Du and Xiang-Jian Kong and Jun Cheng and Leroy Cronin and Cheng Wang}, doi = {10.1021/jacs.5c05916}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23014--23025}, shortjournal = {J. Am. Chem. Soc.}, title = {Natural-language-interfaced robotic synthesis for AI-copilot-assisted exploration of inorganic materials}, volume = {147}, year = {2025}, }
• (2025). ANHC-stabilized low-valent phosphorus compound: Exploring dual catalytic activity via nucleophilicity and P(I)/P(III) redox reactivity. JACS, 147(26), 23001--23013. (www)

  @article{ , abstract = {In this work, we present the synthesis and detailed characterization of a low-valent phosphorus compound, mesoionic N-heterocyclic phosphinidene (mNHP, 2 ), stabilized by an abnormal N-heterocyclic carbene (aNHC). Natural resonance theory analysis and the formation of a bis-borane adduct (confirmed by a single-crystal X-ray diffraction study) revealed that the phosphorus center in mNHP has access to two lone pairs of electrons, as expected for a P(I) species. Beyond its structural characterization, we also investigated both the nucleophilic and redox reactivity of mNHP. Its interactions with CO 2 and CS 2 demonstrated its nucleophilic capabilities, while its reaction with a C(Ar)-F bond highlighted its redox behavior through oxidative addition at the P(I) center, transforming it into a P(III) species. These dual reactivities were subsequently integrated into catalytic cycles, positioning mNHP as an effective low-valent, metal-free catalyst for the formylation of thiols using CO 2 via nucleophilicity and hydrodefluorination of aryl fluoride compounds via the P(I)/P(III) redox cycle. Various spectroscopic investigations, including X-ray photoelectron spectroscopy (XPS), trapping of intermediates, and detailed DFT studies, helped us to understand the dual reactivity of this low-valent phosphorus compound.}, archive = {J_JACS}, author = {Nimisha Gautam and Sreejyothi P and Kaushik Soni and Subhajit Chakraborty and Subir Maji and Kalishankar Bhattacharyya and Swadhin K. Mandal}, doi = {10.1021/jacs.5c05832}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {23001--23013}, shortjournal = {J. Am. Chem. Soc.}, title = {ANHC-stabilized low-valent phosphorus compound: Exploring dual catalytic activity via nucleophilicity and P(I)/P(III) redox reactivity}, volume = {147}, year = {2025}, }
• (2025). A photophosphorylation nanobot for restoring anabolism of myocardial injury. JACS, 147(26), 22986--23000. (www)

  @article{ , abstract = {Myocardial injury poses a significant obstacle due to the limited capacity for self-repair or dysfunction in ATP generation, leading to mortality risks worldwide. Here, we present a photophosphorylation nanobot capable of actively targeting therapeutics for myocardial injury in zebrafish larvae by accelerating the supply of ATP. Janus photophosphorylation nanobots are created through mechanical extrusion-assisted phase separation, forming asymmetric F o F 1 -ATPases embedded in a proteoliposome. Light-induced synergistic rotation of F o F 1 -ATPase significantly enhances the effective translational diffusion of nanobots by 89%, accompanying the photophosphorylation for generating ATP. The photophosphorylation nanobots display cell-like adaptive positive phototaxis motion and a phototactic swarm. These programmable phototactic nanobots can actively target the heart, improve intracellular ATP concentration to restore cellular metabolism, and finally repair myocardial injury. Such self-propelled and maneuverable nanobots that can actively modulate cellular energy metabolism in vivo hold considerable promise for advancing the targeted regulation of diseases associated with bioenergy metabolism in the future.}, archive = {J_JACS}, author = {Yue Li and Ying Chen and Yingjie Wu and Mingjun Xuan and Junbai Li and Qiang He}, doi = {10.1021/jacs.5c05904}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22986--23000}, shortjournal = {J. Am. Chem. Soc.}, title = {A photophosphorylation nanobot for restoring anabolism of myocardial injury}, volume = {147}, year = {2025}, }
• (2025). Coordinated residue motions at the Enzyme–Substrate interface promote DNA translocation in polymerases. JACS, 147(26), 22972--22985. (www)

  @article{ , abstract = {The translocation of DNA in polymerase (Pol) enzymes is a critical step for Pol-mediated nucleic acid polymerization, essential for storing and transmitting genetic information in all living organisms. During this process, the newly elongated double-stranded DNA has to shift along the Pol enzyme to recreate the initial configuration at the metal-aided reactive center, where nucleotide addition can occur recurrently at every catalytic cycle. Double-stranded DNA translocation, therefore, allows the enzyme to add one more nucleotide to the growing strand, complementary to the template strand, without the enzyme dissociating from the DNA. Yet, the dynamic mechanism by which the Pol·DNA complex accomplishes DNA translocation remains poorly understood at the atomistic level. Here, leveraging recent structural data on DNA polymerase η (Polη), we elucidate its translocation mechanism, which we show to occur via an enzyme motion where the shift of Polη is asynchronous along the two DNA strands. Through equilibrium molecular dynamics and deep-learning-guided enhanced sampling simulations, we found that such a mechanism relies precisely on a set of positively charged residues of the enzyme that operate in a coordinated way at the Polη·DNA interface. Moving like screen wipers, such a dynamic mechanism of these residues promotes DNA translocation. These findings now offer new avenues to comprehend further such a complex yet fundamental dynamic process for DNA polymerization.}, archive = {J_JACS}, author = {Alessia Visigalli and Enrico Trizio and Luigi Bonati and Pietro Vidossich and Michele Parrinello and Marco De Vivo}, doi = {10.1021/jacs.5c05888}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22972--22985}, shortjournal = {J. Am. Chem. Soc.}, title = {Coordinated residue motions at the Enzyme–Substrate interface promote DNA translocation in polymerases}, volume = {147}, year = {2025}, }
• (2025). Cryogenically flexible phosphorescent organic crystals that transmit self-sustained persistent luminescence with spatiotemporal control. JACS, 147(26), 22961--22971. (www)

  @article{ , abstract = {Concomitant long-lived phosphorescence and cryogenic elasticity in soft matter is an immensely challenging endeavor due to the contrasting effect of low temperatures on these properties. While the low temperature normally extends and enhances phosphorescence, it typically compromises mechanical elasticity by freezing the molecular motion, inevitably leading to brittleness and cracking of soft materials. In this work, we posit that the emerging class of organic crystals can overcome this intrinsic disparity and describe an organic crystalline material that meets both requirements─an exceptional elasticity of its crystals at 77 K and ultralong afterglow of up to about 30 s, the longest lifetime of a flexible organic crystal reported to date. The material, triphenylene, was prepared as elastic crystals, where the molecular rigidity and dense packing enable reversible lattice deformation and mechanical robustness on cooling, while they also result in prolonged phosphorescence at low temperatures. Crystals of this material act as dynamic phosphorescent waveguides, with their emission persisting in low temperatures and dark, demonstrating both sustained signal transmission capabilities and a unique opportunity for spatiotemporal control of the optical output. At a conceptual level, the results introduce organic crystals for time-encoded biological information transmission, providing a novel material platform for flexible, lightweight optical devices and sensors that can function in extreme environments.}, archive = {J_JACS}, author = {Xuesong Yang and Mingqi Zhang and Baolei Tang and Lijie Wang and Bing Yang and Liang Li and Panče Naumov and Hongyu Zhang}, doi = {10.1021/jacs.5c05733}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22961--22971}, shortjournal = {J. Am. Chem. Soc.}, title = {Cryogenically flexible phosphorescent organic crystals that transmit self-sustained persistent luminescence with spatiotemporal control}, volume = {147}, year = {2025}, }
• (2025). Optically detected coherent spin control of organic molecular color center qubits. JACS, 147(26), 22951--22960. (www)

  @article{ , abstract = {Molecular optical-spin interfaces are emerging as promising alternatives to solid-state defects, such as diamond nitrogen vacancy centers for quantum information science applications. In this work, we report a new organic molecular color center consisting of two luminescent tris(2,4,6-trichlorophenyl)methyl ( TTM ) radicals connected at the 2,6-positions of a toluene bridge. Optical polarization of the |T 0 ⟩ sublevel of the triplet ground state is achieved by spin-selective excited-state intersystem crossing from the |T + ⟩ and |T – ⟩ sublevels of the triplet excited state. Steric hindrance between the toluene methyl group and the phenyls of the TTM radicals results in a structure that increases the excited-state intersystem crossing spin selectivity while reducing the electronic coupling between the TTM subunits. This results in an order of magnitude increase in the optically detected magnetic resonance contrast and longer excited-state lifetimes relative to the sterically unencumbered analogue. We demonstrate coherent microwave manipulation of the spin-polarized ground-state populations and coherences using optical detection of Rabi nutations, Hahn echo formation, and echo decay measurements at 85 K in a nuclear-spin-rich solvent matrix. This marks a crucial step toward leveraging the favorable spin relaxation times of organic molecules for applications as quantum sensors at temperatures that heretofore have been difficult to achieve by molecular color centers.}, archive = {J_JACS}, author = {Sebastian M. Kopp and Shunta Nakamura and Yong Rui Poh and Kathryn R. Peinkofer and Brian T. Phelan and Joel Yuen-Zhou and Matthew D. Krzyaniak and Michael R. Wasielewski}, doi = {10.1021/jacs.5c05718}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22951--22960}, shortjournal = {J. Am. Chem. Soc.}, title = {Optically detected coherent spin control of organic molecular color center qubits}, volume = {147}, year = {2025}, }
• (2025). General model for d-center prediction in multi-principal-element alloys. JACS, 147(26), 22944--22950. (www)

  @article{ , abstract = {The center of the d-band or d-orbital of a transition metal site serves as a key electronic structure descriptor in electrocatalysis, yet its prediction across diverse material systems remains challenging, particularly for disordered multi-principal-element alloys (MPEAs). In this study, we present a general, physically interpretable model for predicting d-center values across a wide range of surfaces and compositions, including 10,680 density functional theory (DFT)-relaxed slabs and over 1.2 million d-center values. Inspired by cluster expansion theory, the model captures local coordination environments to accurately estimate d-centers, achieving a mean absolute error (MAE) of ∼0.09 eV, even when considering only the first nearest-neighbor interactions. We further demonstrate the influence of structural orientation of surface and featurization schemes for surface slabs, as well as regression methods, revealing potential for further improvements with a trade-off between model generalizability and complexity with accuracy. The resulting model offers rapid and reliable d-center estimation, enabling high-throughput screening and mechanistic interpretation in catalysis design. Additionally, the model coefficients provide a direct and accessible tool for both experimentalists and theorists to gain valuable insights into the MPEA surface electronic behavior.}, archive = {J_JACS}, author = {Lin Wang and Yizhan Zhang and Kayla James and Bin Ouyang}, doi = {10.1021/jacs.5c05649}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22944--22950}, shortjournal = {J. Am. Chem. Soc.}, title = {General model for d-center prediction in multi-principal-element alloys}, volume = {147}, year = {2025}, }
• (2025). Reengineering cyanine dyes via borondifluoro indolenine: A tunable platform for wash-free imaging and responsive biosensing. JACS, 147(26), 22932--22943. (www)

  @article{ , abstract = {Fluorescent probes are essential tools for visualizing biological processes, yet conventional cyanine dyes suffer from limited structural flexibility, poor photostability, and weak compatibility with wash-free imaging. Here, we introduce a modular, neutral BF 2 -bridged cyanine (BCy) platform by re-engineering the indolium scaffold with a borondifluoro indolenine (BFI) fragment. BCy dyes exhibit high brightness (up to 12.4 × 10 4 M –1 cm –1 ), robust photostability, and emissions spanning 588–837 nm. The tunable BFI moiety enables the construction of wash-free, far-red/NIR probes for the plasma membrane, lipid droplets, mitochondria, and lysosomes as well as pH- and H 2 O 2 -responsive sensors. These probes support high-contrast multicolor and STED imaging, as well as dynamic organelle tracking in live cells and a mouse model of liver injury. This work establishes BF 2 -cyanines as robust scaffolds for next-generation fluorophores in advanced bioimaging and biomedical diagnostics.}, archive = {J_JACS}, author = {Zixuan Zhan and Jifa Zhang and Tianruo Shen and Jie Li and Li Chai and Lili Pan and Haihui Yang and Tianyou Liu and Xiaogang Liu and Wuyu Mao}, doi = {10.1021/jacs.5c05565}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22932--22943}, shortjournal = {J. Am. Chem. Soc.}, title = {Reengineering cyanine dyes via borondifluoro indolenine: A tunable platform for wash-free imaging and responsive biosensing}, volume = {147}, year = {2025}, }
• (2025). Mechanometallaphotoredox catalysis: Utilizing increased throughput mechanochemistry to develop solvent-minimized aryl amination and c(sp2)-c(sp3) cross-coupling reactions with increased tolerance to aerobic conditions. JACS, 147(26), 22919--22931. (www)

  @article{ , abstract = {Photocatalysis as a tool used in organic synthesis has predominantly relied on the use of solvents, be it under homogeneous or heterogeneous conditions. In particular, metallaphotoredox catalysis reactions commonly use toxic organic solvents such as DMA and DMF. Herein, we demonstrate how mechanophotocatalysis, the synergistic union of mechanochemistry and photocatalysis, is compatible with this class of dual catalysis reactions involving both photocatalyst and nickel(II) cocatalysts. Using ball milling, these mechanistically complex reactions can be conducted in the absence of a bulk solvent and under air, affording high-yielding aryl aminations and C(sp2)-C(sp3) cross-couplings with alkyl carboxylic acids, alkyl trifluoroborate salts, and alkyl bromides. These advances are facilitated by the introduction of a novel reaction vessel design for conducting four mechanophotocatalysis reactions simultaneously. This work highlights the promise of solvent-minimized photocatalysis reactions, demonstrating that in these examples bulk solvent is redundant, thus significantly reducing this waste stream. Through time-resolved photoluminescence studies, we observed that the excited states of five different photocatalysts were quenched by oxygen more significantly in solution than in the solid state, providing evidence for the origin of the increased tolerance to aerobic conditions that these mechanophotocatalysis reactions experience.}, archive = {J_JACS}, author = {Francis Millward and Eli Zysman-Colman}, doi = {10.1021/jacs.5c05503}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22919--22931}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanometallaphotoredox catalysis: Utilizing increased throughput mechanochemistry to develop solvent-minimized aryl amination and c(sp2)-c(sp3) cross-coupling reactions with increased tolerance to aerobic conditions}, volume = {147}, year = {2025}, }
• (2025). Chemically tuning room temperature pulsed optically detected magnetic resonance. JACS, 147(26), 22911--22918. (www)

  @article{ , abstract = {Optical detection of magnetic resonance enables spin-based quantum sensing with high spatial resolution and sensitivity─even at room temperature─as exemplified by solid-state defects. Molecular systems provide a complementary, chemically tunable, platform for room-temperature optically detected magnetic resonance (ODMR)-based quantum sensing. A critical parameter governing sensing sensitivity is the optical contrast─i.e., the difference in emission between two spin states. In state-of-the-art solid-state defects such as the nitrogen-vacancy center in diamond, this contrast is approximately 30%. Here, capitalizing on chemical tunability, we show that room-temperature ODMR contrasts of 40% can be achieved in molecules. Using a nitrogen-substituted analogue of pentacene (6,13-diazapentacene), we enhance contrast compared to pentacene and, by determining the triplet kinetics through time-dependent pulsed ODMR, show how this arises from accelerated anisotropic intersystem crossing. Furthermore, we translate high-contrast room-temperature pulsed ODMR to self-assembled nanocrystals. Overall, our findings highlight the synthetic handles available to optically readable molecular spins and the opportunities to capitalize on chemical tunability for room-temperature quantum sensing.}, archive = {J_JACS}, author = {Sarah K. Mann and Angus Cowley-Semple and Emma Bryan and Ziqiu Huang and Sandrine Heutz and Max Attwood and Sam L. Bayliss}, doi = {10.1021/jacs.5c05505}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22911--22918}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemically tuning room temperature pulsed optically detected magnetic resonance}, volume = {147}, year = {2025}, }
• (2025). Controlled writhing of chiral matter in deformable droplet confinement. JACS, 147(26), 22901--22910. (www)

  @article{ , abstract = {Chirality─the property of being nonsuperimposable on its mirror image─plays a fundamental role in shaping how materials interact with light, molecules, and external fields. This property is key to advancements in areas such as quantum computing, flexible electronics, and smart sensors. However, controlling chirality in materials beyond the molecular scale has remained a significant challenge. In this study, we demonstrate a new approach for controlling the chirality of self-assembled materials by manipulating their behavior within deformable emulsion droplets. These droplets, ranging from nanometers to micrometers in size, guide the twisting of chiral fibrils formed through molecular self-assembly, with the droplet size determining the chirality. Our results, based on over 20 different chiral molecules, show that droplet confinement can induce chirality inversion, where nanoscale and microscale droplets exhibit opposite handedness. When the size of the droplet matches the persistence length of the chiral fibrils, the particles form superhelical structures. If mismatched, the fibrils twist in the opposite direction. In addition, we show that surfactant-coated helical fibrils can elongate into micrometer-long structures via living self-assembly, with chirality dictated by the as-formed helical fibrils and not the additional monomers. This work paves the way for new strategies to design and control chiral materials with tailored properties for a range of cutting-edge applications.}, archive = {J_JACS}, author = {Rongjuan Liu and Xiaobin Dai and Benyou Li and Qiang Li and Jingjing Wei and Li-Tang Yan and Zhijie Yang}, doi = {10.1021/jacs.5c05428}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22901--22910}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlled writhing of chiral matter in deformable droplet confinement}, volume = {147}, year = {2025}, }
• (2025). Interface engineering between photocatalyst and cocatalyst: A strategy for enhancing interfacial charge transfer and water oxidation of layered oxyhalides. JACS, 147(26), 22892--22900. (www)

  @article{ , abstract = {Loading cocatalysts on photocatalysts is essential to enhance photocatalytic activity; however, the charge transfer from the photocatalyst to cocatalyst often governs the overall efficiency of the reactions. Nevertheless, their interface remains elusive and poses challenges for proactive control. The current study addresses the interface engineering to improve the O 2 evolution activity of oxyhalide photocatalysts by leveraging the unique band structures. Utilizing an oxyhalide Bi 4 NbO 8 Cl as a model photocatalyst, in which DFT calculations showed electrons and holes tend to accumulate in the fluorite and perovskite layer, respectively, we combined the exposure of the perovskite layer via acid treatment with the loading of water oxidation cocatalyst Ir species (hereafter denoted as IrO 2 ). This approach resulted in a 17-fold enhancement in the rate of evolution of the O 2 compared to unmodified pristine Bi 4 NbO 8 Cl. The observed O 2 evolution rate was markedly higher than that of the reported oxyhalide photocatalysts, with an apparent quantum efficiency reaching 16%. Various characterizations, including transient absorption spectroscopy, demonstrated that the significantly enhanced O 2 evolution was due to the efficient hole transfer between Bi 4 NbO 8 Cl and IrO 2 , resulting from loading IrO 2 onto the perovskite layer (the hole accumulation layer) exposed through the acid treatment. By employing the surface-modified Bi 4 NbO 8 Cl as an O 2 evolution photocatalyst, we have achieved interparticle Z-scheme water splitting without any electron mediators. This research paves the way for rational control of photocatalyst-cocatalyst interface structures to improve the photocatalytic activities of various materials.}, archive = {J_JACS}, author = {Hajime Suzuki and Kengo Minamimoto and Yusuke Ishii and Osamu Tomita and Akinobu Nakada and Shunsuke Nozawa and Akira Yamakata and Ryu Abe}, doi = {10.1021/jacs.5c05452}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22892--22900}, shortjournal = {J. Am. Chem. Soc.}, title = {Interface engineering between photocatalyst and cocatalyst: A strategy for enhancing interfacial charge transfer and water oxidation of layered oxyhalides}, volume = {147}, year = {2025}, }
• (2025). Autonomous dynamic control of crown ether cargo release from [2]Rotaxane carriers in a piperidine oscillator. JACS, 147(26), 22883--22891. (www)

  @article{ , abstract = {Chemical oscillations play a fundamental role in biological systems, yet their synthetic counterparts remain challenging to implement with functional outputs. Here, we report a piperidine-based chemical oscillator that autonomously drives periodic cleavage of a [2]rotaxane carrier, leading to controlled cargo release. The system operates through self-sustained oscillations, triggering rotaxane cleavage and the release of a crown ether cargo. Crown ethers were selected for their reactivity distinct from piperidine, while Fmoc-protected benzylamine rotaxane structures allowed for straightforward carrier modification. For all tested carriers, a piperidine pulse is present and occurs simultaneously with carrier cleavage, yielding up to 95% cargo release. Under flow conditions, periodic cargo release was sustained without extensive reoptimization, demonstrating the robustness of the system. Additionally, by adjusting space velocity, trigger concentration, and inhibitor levels, the oscillation period was varied by up to 2.5 h, with cargo release amplitude changing more than 3-fold. This work demonstrates the potential of catalytic oscillators to regulate downstream processes, paving the way toward construction of complex dynamic chemical systems.}, archive = {J_JACS}, author = {Kamil D. Petryczkiewicz and Johanan Kootstra and Maëlle Le Cacheux and Aleksei Tsygankov and Jan L. Sneep and Matthijs ter Harmsel and Syuzanna R. Harutyunyan}, doi = {10.1021/jacs.5c05460}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22883--22891}, shortjournal = {J. Am. Chem. Soc.}, title = {Autonomous dynamic control of crown ether cargo release from [2]Rotaxane carriers in a piperidine oscillator}, volume = {147}, year = {2025}, }
• (2025). Copper-catalyzed highly efficient and asymmetric allylic C–H oxidation of 3-aryl-substituted terminal alkenes. JACS, 147(26), 22873--22882. (www)

  @article{ , abstract = {Asymmetric allylic C(sp 3 )–H oxidation of terminal alkenes provides a streamlined process for accessing allylic alcohols and their derivatives; however, it represents a long-standing challenge in the field for several decades. Herein, we disclosed a copper-catalyzed approach for the enantioselective allylic C(sp 3 )–H oxidation of terminal alkenes, facilitated by introducing a sterically bulky B 2 Im(C 6 F 5 ) 6 anion. Notably, a wide range of aryl-substituted terminal alkenes were used as limiting reagents, delivering various products with excellent enantioselectivity and regioselectivity (up to 99% ee, >20:1 b/l). Mechanistically, the bulky counteranion was found to be essential for achieving excellent enantioselective control and high catalytic efficiency.}, archive = {J_JACS}, author = {Yibo Zhou and Pinhong Chen and Guosheng Liu}, doi = {10.1021/jacs.5c05382}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22873--22882}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper-catalyzed highly efficient and asymmetric allylic C–H oxidation of 3-aryl-substituted terminal alkenes}, volume = {147}, year = {2025}, }
• (2025). Electrode fouling by gas bubbles enables catalyst-free hydrogen peroxide synthesis. JACS, 147(26), 22864--22872. (www)

  @article{ , abstract = {Hydrogen peroxide (H 2 O 2 ) is an essential chemical for environmental remediation, chemical synthesis, and energy storage, yet conventional synthetic methods are energy-intensive and environmentally taxing. Herein, we report a catalyst-free strategy for H 2 O 2 synthesis by exploiting the gas–liquid–solid triple phase boundary formed at bubble-pinned porous carbon electrodes. The process involves three key mechanisms: (i) hydroxide anions enrichment in the electric double layer reduces the energy barrier for their oxidation to hydroxyl radicals, (ii) the hydrophobic bubble interface suppresses overoxidation, favoring the two-electron water oxidation pathway, and (iii) oxygen molecules capture electrons from previous steps to form H 2 O 2 . Density functional theory calculations indicate a 30% reduction in work function at the bubble-pinned interface compared to bubble-free counterparts, which thermodynamically promotes the electrochemical oxidation of hydroxide anions. Experiments verify that both water and oxygen are involved in H 2 O 2 generation, and mechanistic details are confirmed by trapping different radical intermediates. This study demonstrates an efficient and sustainable alternative for H 2 O 2 production, advancing interface-driven and catalyst-free chemistry.}, archive = {J_JACS}, author = {Xiaoxue Song and Yangyang Wan and Qian Yang and Jianze Zhang and Yuqiao Zhang and Zhongti Sun and Shun Li and Jianming Zhang and Xinxing Zhang and Simone Ciampi and Long Zhang}, doi = {10.1021/jacs.5c05286}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22864--22872}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrode fouling by gas bubbles enables catalyst-free hydrogen peroxide synthesis}, volume = {147}, year = {2025}, }
• (2025). Data-driven insight into the universal Structure–Property relationship of catalysts in Lithium–Sulfur batteries. JACS, 147(26), 22851--22863. (www)

  @article{ , abstract = {Despite tremendous efforts in catalyzing the sulfur reduction reaction (SRR) in high-capacity lithium–sulfur (Li–S) batteries, understanding the universal and quantitative structure–property relationships (UQSPRs) of SRR remains elusive. Such an unclarity results from the limitations of first-principle calculations in analyzing vast, high-dimensional, and heterogeneous data. Here, we present a collaborative data-driven model for heterogeneous catalytic knowledge fusion, detecting over 2,900 articles on SRR published between 2004 and 2024. By using sure independence screening and sparsifying operator, we surprisingly identified a composite descriptor, D , dominated by the dispersion factor. In contrast to the classical electronic state analysis framework, the dispersion factor directly established UQSPRs between atom topological arrangement and catalyst-polysulfide interaction intensity, accurately predicting the catalytic activity of over 800 types of catalysts. Combined with a volcano plot linking the overpotential to the interaction intensity, we determined the D value range of high catalytic activity, facilitating the discovery of tens of novel SRR catalysts from 374,833 candidates, many of which escaped previous human chemical intuition. As a representative, CrB 2 demonstrated superior catalytic activity under high sulfur loadings of 12.0 mg cm –2 and low temperatures of −25 °C. Pouch cells with CrB 2 achieved a gravimetric specific energy of 436 Wh kg –1 under a high sulfur content of 76.1% and lean-electrolyte conditions of 2.8 μL mg –1 . Our data-driven method enables new opportunities to fundamentally identify UQSPRs using vast and heterogeneous data, suggesting the promise of revisiting under-exploited knowledge from the historical literature for novel catalyst discovery.}, archive = {J_JACS}, author = {Zhiyuan Han and Shengyu Tao and Yeyang Jia and Mengtian Zhang and Ruifei Ma and Xiao Xiao and Jiaqi Zhou and Runhua Gao and Kai Cui and Tianshuai Wang and Xuan Zhang and Guangmin Zhou}, doi = {10.1021/jacs.5c04960}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22851--22863}, shortjournal = {J. Am. Chem. Soc.}, title = {Data-driven insight into the universal Structure–Property relationship of catalysts in Lithium–Sulfur batteries}, volume = {147}, year = {2025}, }
• (2025). Achieving high-performance defect-free LiCoO2 cathode via a dopant-free approach. JACS, 147(26), 22839--22850. (www)

  @article{ , abstract = {Elevating the charging voltage of layered oxide cathodes to achieve higher capacity induces phase transitions associated with transition metal slab gliding, which significantly impacts the material’s structural stability. Doping with inert elements is commonly employed to delay such phase transitions to higher voltages. However, these electrochemically inactive elements do not participate in redox reactions, thereby compromising lithium storage capacity. This compromise raises a critical and underexplored issue regarding whether doped materials with reduced capacity still maintain an advantage in energy density. In this study, using LiCoO 2 as a model material, it was observed that an increase in the concentration of Al dopant indeed delayed the onset voltage of the H1–3 phase transition. However, the extent of delithiation associated with this phase transition remains largely unchanged. When the discharge capacity is controlled to just below the threshold for the global H1–3 phase transition, the undoped material demonstrates even superior capacity retention and rate performance compared to the doped samples, at a lower charging cutoff voltage. Comprehensive experimental characterizations and theoretical calculations reveal that the doping-induced structural defects hinder Li + conduction and promote oxygen release, consequently accelerating performance degradation. This study suggests that in the development of high-voltage layered oxide cathodes, it is crucial to prioritize enhancing material capacity. Additionally, it is imperative to meticulously assess the adverse effects of doping, as industrial preparation methods often lead to nonideal dopant incorporation, causing undesirable structural defects that are particularly harmful to the reversibility of high-voltage phase transitions.}, archive = {J_JACS}, author = {Sichen Jiao and Yu Li and Ting Lin and Shuhang Feng and Chengzhen Zhang and Hongyi Pan and Weiguang Lin and Xiqian Yu and Lin Gu and Xuejie Huang and Liquan Chen and Hong Li}, doi = {10.1021/jacs.5c05162}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22839--22850}, shortjournal = {J. Am. Chem. Soc.}, title = {Achieving high-performance defect-free LiCoO2 cathode via a dopant-free approach}, volume = {147}, year = {2025}, }
• (2025). Post-polymerization modification of polyethylene through photochemical oximation and consecutive ketonization. JACS, 147(26), 22827--22838. (www)

  @article{ , abstract = {Post-polymerization modification of polyolefins provides access to functional polymers not readily available through bottom-up synthesis, thereby expanding the range of material properties available. Here, we demonstrate the clean and efficient functionalization of polyethylene through the solvent- and catalyst-free photochemical oximation, using t -butyl nitrite as an inexpensive and easy to handle NO radical source. Using various grades of polyethylene, we successfully incorporated oxime, ketone, and nitro groups on the polymer backbone, without radical cleavage or crosslinking. The functionalization degree of the three different functional groups is tuneable depending on the reaction atmosphere and system pressure, and the total functionalization degree can reach up to 2.9%. Detailed analysis of the post-modified polyethylene using 15 N labeling revealed that the photochemical oximation preferentially functionalizes the pre-terminal carbon and that the functional groups are randomly spaced along the polymer backbone rather than adjacent. These results underscore the novelty and robustness of this methodology, enabling tailored polyolefins with properties that may expand their applications and potentially improve their recyclability.}, archive = {J_JACS}, author = {Maartje Otten and Inèz Klein Gebbink and Patrick J. Schara and Željko Tomović and Martin Lutz and Pieter C.A. Bruijnincx and Arnaud Thevenon}, doi = {10.1021/jacs.5c05212}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22827--22838}, shortjournal = {J. Am. Chem. Soc.}, title = {Post-polymerization modification of polyethylene through photochemical oximation and consecutive ketonization}, volume = {147}, year = {2025}, }
• (2025). Designing natural cell-inspired heme-spurred membrane electrode assembly for fuel cells. JACS, 147(26), 22818--22826. (www)

  @article{ , abstract = {Developing highly efficient and durable membrane electrode assemblies (MEAs) is imperative for the widespread implementation of proton exchange membrane fuel cells (PEMFCs). However, the poor mass transfer efficiency and sluggish oxygen reduction reaction (ORR) kinetics have significantly suppressed the power density and longevity of platinum (Pt)-based MEA in PEMFCs, particularly when using an ultralow Pt loading. Inspired by the functional principles of hemoglobin in red blood cells, we present a Heme-cofactor strategy to create a “respiratory proton-transfer chain” for PEMFCs. This strategy can efficiently spur the catalytic activity of Pt while enhancing the mass transfer efficiency of MEAs, in which the multifunctional Heme featuring carboxyl and Fe 2+ groups can accelerate the proton and oxygen transport as well as boost the ORR kinetics. As a result, by integrating Heme with typical Pt catalysts (i.e., commercial Pt/C, commercial Pt 3 Co/C, and homemade PtCo), the peak power density (PPD) and mass activity (MA) of Heme-spurred Pt-type MEAs can be dramatically enhanced by 50 to 109%, respectively. Particularly, with a low Pt loading of 0.1 mg Pt cm –2 , the Heme-spurred PtCo-based MEA achieves record PPDs of 3.8 W cm –2 (H 2 –O 2 ) and 1.9 W cm –2 (H 2 –air), significantly surpassing the previous PPD records set by state-of-the-art MEAs. Meanwhile, our developed Heme-spurred MEA can even be run stably at 1.5 A cm –2 for over 50 days (1250 h) with 93% MA retention. These results underscore the viability of this universal and efficient Heme-cofactor strategy for practical fuel cell applications.}, archive = {J_JACS}, author = {Zhongliang Huang and Changhong Zhan and Yujia Yuan and Bingyi Song and Junyang Pan and Li-Ming Yang and Tian-Yi Ding and Lisong Chen and Nanjun Chen and Xiaoqing Huang}, doi = {10.1021/jacs.5c05017}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22818--22826}, shortjournal = {J. Am. Chem. Soc.}, title = {Designing natural cell-inspired heme-spurred membrane electrode assembly for fuel cells}, volume = {147}, year = {2025}, }
• (2025). Enhancing water oxidation performance of transition metal oxides by atomically precise heteroatom doping. JACS, 147(26), 22806--22817. (www)

  @article{ , abstract = {Heteroatom doping is an effective strategy for tuning the electronic structure and stability of non-noble transition metal (e.g., Fe, Co, and Ni) oxides for cost-efficient oxygen evolution reactions (OERs), but conventional doping methods usually give rise to unpredictable and uneven doping sites or even phase separation. Here, we develop an interfacial diffusion strategy for atomically precise doping of less electronegative heteroatoms to the lattices of 3 d transition metal (Fe, Co, Ni) oxides, leveraging on the simple yet effective lattice-match principle. Taking Fe 2 O 3 as a model, Cr can be uniformly doped and arranged in the alternating cation layers against Fe. As-prepared FeCrO 3 lowers the overpotential from 438 mV of Fe 2 O 3 to 258 mV at 10 mA cm –2 in 1.0 M KOH and can operate for at least 1100 h with almost no performance attenuation at 250 mA cm –2 . Multiple characterizations reveal that the ordered arrangement of Cr around Fe sites induces an electron flux from Cr to Fe, stabilizing active Fe 2+ species and accelerating the Fe 2+ /Fe 3+ /Fe 4+ redox cycle, thereby promoting water activation and *OH dehydrogenation. Besides, ordered Cr doping improves the OER stability of FeCrO 3 by preserving surface basicity through Lewis acidic Cr 3+ and stabilizing the Fe–O bond to shift the reaction mechanism from lattice oxygen oxidation (LOM) to adsorbate evolution (AEM). This atomically precise doping strategy is easily scaled-up for kilogram production of FeCrO 3 , and it is readily extendable to other transition metal oxides (e.g., NiO and Co 3 O 4 ). Our work underscores the importance of atomically precise surface engineering in the manufacture of catalysts.}, archive = {J_JACS}, author = {Zhipu Zhang and Shanshan Lu and Moshuqi Zhu and Fuli Wang and Kaiwen Yang and Bin Dong and Qiaofeng Yao and Wenping Hu}, doi = {10.1021/jacs.5c04572}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22806--22817}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing water oxidation performance of transition metal oxides by atomically precise heteroatom doping}, volume = {147}, year = {2025}, }
• (2025). Reconfiguration of active species under light for enhanced photocatalysis. JACS, 147(26), 22796--22805. (www)

  @article{ , abstract = {Photocatalysis has emerged as a cornerstone of synthetic chemistry, enabling mild and selective transformations by using sustainable light sources. A common assumption persists that most photocatalysts are taken for granted to function as monomorphic species throughout the catalytic cycle. Our findings challenge this premise and discover a new mechanistic picture, demonstrating that the evolution of the catalyst under light is not a degradation artifact but a productive and exploitable transformation pathway. Using phenothiazine (PHT) as a model, we demonstrate that light triggers in situ formation of a diverse “cocktail” of catalytically active dimer, trimer, oligomers and their oxides with unique photophysical and redox properties. These reconfigured species expand the usable light spectrum, including red light, and exhibit better catalytic performance in oxidative coupling and sulfide oxidation reactions. The reconfigured catalysts unlock multiwave activation, driving oxidative coupling and sulfide oxidation reactions with remarkable efficiency (up to 99% yield) across UV to red light (λ = 650 nm), far beyond the capabilities of the parent PHT. We introduce the ReAct-Light concept (Reconfigurable Active species under Light) to capture this dynamic, wavelength-adaptive behavior. The work provides an example of key mechanistic insight into dynamic catalyst evolution, opening the way for the design of next-generation adaptive catalysts with enhanced efficiency.}, archive = {J_JACS}, author = {Julia V. Burykina and Iana I. Surzhikova and Ruslan R. Shaydullin and Andrey D. Kobelev and Artem N. Fakhrutdinov and Kirill S. Kozlov and Valentine P. Ananikov}, doi = {10.1021/jacs.5c05052}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22796--22805}, shortjournal = {J. Am. Chem. Soc.}, title = {Reconfiguration of active species under light for enhanced photocatalysis}, volume = {147}, year = {2025}, }
• (2025). Tiara ni clusters for electrocatalytic nitrate reduction to ammonia with 97% faradaic efficiency. JACS, 147(26), 22785--22795. (www)

  @article{ , abstract = {The electroreduction of nitrate (NO 3 – ) for sustainable ammonia (NH 3 ) production has recently emerged as a green process to solve water contamination and produce valuable chemicals. In this study, we developed Ni 6 @CuFe-LDH composites comprising tiara Ni 6 (SC 2 H 4 COOH) 12 (Ni 6 ) clusters anchored on the edges of 2D CuFe-LDH (LDH: layered double hydroxides) nanosheets via electrostatic interactions. The Ni 6 @CuFe-LDH catalyst exhibits high electrochemical performance in nitrate reduction reaction (NO 3 RR). Specifically, the Ni 6 @CuFe-LDH gives rise to an excellent faradaic efficiency of ∼97%, significantly surpassing the ∼73% FE of the pristine CuFe-LDH, with the NH 3 productivity (0.91 mmol mg –1 h –1 ) being similar to that of the CuFe-LDH. Mechanistic studies reveal that the superior electrocatalysis of Ni 6 -based catalysts is primarily due to the synergistic interaction between Ni 6 clusters and CuFe-LDH, which alters the rate-determining step (RDS) of the desorption of *NH 3 species (for CuFe-LDH) to the *NO 3 → *NO 2 step (for Ni 6 @CuFe-LDH); this is corroborated by the control experiments of NO 2 RR, in situ Raman and infrared spectroscopies, and computational approaches. In all, these efforts push forward the NO 3 RR research to study the structure–property relationships from the micro/nano-level to the precise atomic-level.}, archive = {J_JACS}, author = {Xinrui Gu and Jingjing Zhang and Song Guo and Yifei Zhang and Liangliang Xu and Rongchao Jin and Gao Li}, doi = {10.1021/jacs.5c04950}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22785--22795}, shortjournal = {J. Am. Chem. Soc.}, title = {Tiara ni clusters for electrocatalytic nitrate reduction to ammonia with 97% faradaic efficiency}, volume = {147}, year = {2025}, }
• (2025). Electron spillover into water layers: A quantum leap in understanding capacitance behavior. JACS, 147(26), 22778--22784. (www)

  @article{ , abstract = {We investigate the electronic and molecular properties of the electrified Pt(111)–water interface using molecular dynamics simulations, leveraging electronic-structure-aware density-functional theory (DFT) and classical force field approaches. Electrification is induced by introducing excess electrons with homogeneously distributed, nonionic counter-charges, allowing for a targeted analysis of electronic and water density responses without interference from electrolyte ions. Our results reveal that, within the DFT framework, the Pt(111)–water interface deviates from the classical picture, where excess electronic charge remains localized at the metallic surface. Instead, approximately 30–40% of the electronic excess charge density penetrates into the interfacial water region─a behavior that is absent in vacuum conditions or when using classical force fields. This redistribution of charge provides a compelling explanation for long-standing discrepancies in the modeling of this interface, including the stabilization of partially charged interfacial species such as H + and most importantly the severe underestimation─by an order of magnitude─of the interfacial capacitance in force-field-based methods. Our findings highlight the crucial role of electronic charge spillover in defining interfacial behavior which provides critical insights about the approximations in classical descriptions and for the development of more accurate computational models of electrochemical systems.}, archive = {J_JACS}, author = {Lang Li and Thorben Eggert and Karsten Reuter and Nicolas G. Hörmann}, doi = {10.1021/jacs.5c04728}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22778--22784}, shortjournal = {J. Am. Chem. Soc.}, title = {Electron spillover into water layers: A quantum leap in understanding capacitance behavior}, volume = {147}, year = {2025}, }
• (2025). Self-aggregative recognition and extraction of perfluorooctanesulfonate with flexible cationic water-soluble deep cavitands. JACS, 147(26), 22768--22777. (www)

  @article{ , abstract = {Cationic water-soluble deep cavitands enable hierarchical assembly-based recognition, optical detection, and extraction of perfluoroalkyl substances (PFAS) in aqueous solution. Recognition of PFAS occurs at the lower rim crown of the cavitand, which triggers self-aggregation of a PFAS-cavitand complex, allowing extraction from water. In addition, when paired with an indicator dye that can be bound in the cavity of the host molecule, the PFAS-cavitand association causes a significant (>20-fold at micromolar [PFAS]) enhancement of dye fluorescence due to conformational rearrangement of the fluxional cavitand AMI , allowing optical detection of PFAS. The cavitands are water-soluble, and the detection and recognition occur in purely aqueous solution. The association is most effective for long-chain sulfonate PFAS, and as such, selective optical detection of perfluorooctanesulfonate is possible, with a LOD = 130 nM in buffered water and 530 nM in real-world samples such as polluted canal water. By pairing the AMI host with multiple dyes in an array-based format, full discrimination of five other PFAS can be achieved at micromolar concentrations via differential sensing. In addition, the aggregation process allows extraction of PFAS from solution, and a 99% reduction of PFOS concentration in water is possible with a single treatment of an equimolar concentration of AMI cavitand. The hierarchical nature of the cavitand recognition system allows both selective, sensitive optical detection and extraction of PFAS from water with a single scaffold.}, archive = {J_JACS}, author = {Ria Lian and Yu-Dong Yang and Jose L. Moreno, Jr. and Becky L. Eggimann and Junyi Chen and Lucas J. Gibson-Elias and Christoper G. Williams and Peixi Jiang and Andrew J. Lee and Leonard J. Mueller and Jonathan. L. Sessler and J. Ilja Siepmann and Darren W. Johnson and Richard J. Hooley}, doi = {10.1021/jacs.5c04762}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22768--22777}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-aggregative recognition and extraction of perfluorooctanesulfonate with flexible cationic water-soluble deep cavitands}, volume = {147}, year = {2025}, }
• (2025). Unlocking chromium decarboxylative ligand-to-metal charge transfer: Efficient and redox-neutral allylation of aldehydes using carboxylic acids. JACS, 147(26), 22759--22767. (www)

  @article{ , abstract = {Here, we report the light-induced decarboxylative ligand-to-metal charge transfer (LMCT) of Cr(III) carboxylate complexes and demonstrate its applicability toward stereoselective Nozaki-Hiyama-Kishi (NHK) allylation reactions. The critical design element of our reaction was identifying a bipyridyl ligand scaffold that enables a single Cr catalyst to facilitate both photolytic dissociation and aldehyde addition. This approach allows for the direct utilization of carboxylic acids and eliminates the need for external redox reagents. The broad utility of this protocol was demonstrated by the preparation of a variety of homoallylic alcohols in good yields and diastereoselectivities as well as the identification of advantageous retrosynthetic disconnections. Extensive studies supported the LMCT mechanism of this transformation, including the characterization of the catalytically active Cr-carboxylate species.}, archive = {J_JACS}, author = {Supeng Wu and Ziqi Jiao and Alex T. Sung and Abigail B. Faulhaber and Nathan D. Schley and Alexander W. Schuppe}, doi = {10.1021/jacs.5c04691}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22759--22767}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking chromium decarboxylative ligand-to-metal charge transfer: Efficient and redox-neutral allylation of aldehydes using carboxylic acids}, volume = {147}, year = {2025}, }
• (2025). Uncovering polyoxometalate speciation in hydrothermal systems by combining computational simulation with X-ray total scattering. JACS, 147(26), 22747--22758. (www)

  @article{ , abstract = {A systematic approach for understanding the pH-dependent speciation of molecular metal-oxide nanoclusters beyond ambient conditions, which combines computational predictions with X-ray total scattering experiments, is presented. We demonstrate that temperature-dependent water properties have a significant impact on molecular energies derived from implicit solvent modeling and propose an efficient correction strategy. Based on this, we expand our methodology toward the elevated temperatures and pressures characteristic of hydrothermal synthesis. Correlating these computational results with experimental observations reveals a remarkable synergy between the two approaches, which helps to differentiate closely related polyoxometalates coexisting in solution. We find that qualitative trends are directly reproduced computationally, while the intricate nature of polyoxometalate speciation is best captured by adjusting computational predictions based on experimental insights. The derived knowledge of the clusters present under various conditions enables us to rationalize the crystallization of h-MoO 3 at high temperatures and very acidic pH. With this, our study highlights the potential of hybrid approaches for elucidating solution-based oxide formation under extreme conditions.}, archive = {J_JACS}, author = {Laura S. Junkers and Diego Garay-Ruiz and Jordi Buils and Rebecca S. Silberg and Guilherme B. Strapasson and Kirsten M. Ø. Jensen and Carles Bo}, doi = {10.1021/jacs.5c04696}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22747--22758}, shortjournal = {J. Am. Chem. Soc.}, title = {Uncovering polyoxometalate speciation in hydrothermal systems by combining computational simulation with X-ray total scattering}, volume = {147}, year = {2025}, }
• (2025). The science of polymer chemical recycling catalysis: Uncovering kinetic and thermodynamic linear free energy relationships. JACS, 147(26), 22734--22746. (www)

  @article{ , abstract = {Polymer recycling must accelerate to limit ever-growing wastes and carbon dioxide emissions. Polymer chemical recycling to monomer enables multiple closed recycling loops, tackling the material and property losses endemic to mechanical recycling. Polyesters and polycarbonates, derived from 6- and 7-membered heterocycles, are leading sustainable materials produced by equilibrium polymerizations that can be reversed for selective and efficient chemical recycling to monomer. A systematic understanding of the depolymerization kinetic and thermodynamic structure-recycling relationships is needed; in particular, studies should focus on the low-energy and minimal-chemical additive conditions required for any larger-scale processes. Here, the depolymerization kinetic parameters, including rate constants and transition state energy barriers, are measured for a systematic series of leading aliphatic polyesters and polycarbonates. These recycling experiments are conducted under common conditions using neat polymer melts, at temperatures from 90 to 190 °C and with low loadings (1:100–1000) of a fast, selective, and commercial zinc(II)bis(2-ethylhexanoate) catalyst. The systematic kinetic measurements quantify the influences of different repeat units, substituents, and end-group chemistries on the recycling process. All the polymers conform to a linear free energy relationship between the depolymerization kinetic (Δ G d ⧧ ) and thermodynamic (Δ G d ) energy differences. The discovery of recycling catalysis linear free energy relationships allows for the rational selection of the lowest temperature (and energy) recycling conditions, operable using neat polymers, to deliver both high monomer conversions and rates. The quantified structure-recycling relationships are also used to efficiently and selectively separate mixtures of structurally similar polymers by their quantitative chemical recycling into pure monomers.}, archive = {J_JACS}, author = {Thomas M. McGuire and David Ning and Antoine Buchard and Charlotte K. Williams}, doi = {10.1021/jacs.5c04603}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22734--22746}, shortjournal = {J. Am. Chem. Soc.}, title = {The science of polymer chemical recycling catalysis: Uncovering kinetic and thermodynamic linear free energy relationships}, volume = {147}, year = {2025}, }
• (2025). Photochemical ligand-based CO2 reduction mediated by ruthenium formyl species. JACS, 147(26), 22725--22733. (www)

  @article{ , abstract = {A new, ligand-based strategy for CO 2 reduction to formate has been demonstrated. This approach relies on the photochemical generation of a coordinatively saturated transient ruthenium metalloformyl species, Ru-CHO, capable of reducing CO 2 to free formate directly. Under this paradigm, a highly reactive radical cation which is capable of facile formal hydrogen atom transfer (HAT) is generated via reductive quenching of an excited-state photosensitizer. Sequential electron transfer (ET) and HAT steps to a ruthenium carbonyl complex subsequently yield the Ru-CHO species, which upon further reduction undergoes fast hydride transfer to CO 2 , producing free formate. High formate selectivity (up to 98%) and impressive catalytic performance (TON ∼ 5300; TOF ∼ 0.1 s –1 ) were observed. Detailed mechanistic studies revealed that the overall process is highly sensitive to the identity of the radical cation, with divergent reactivity observed when HAT thermodynamics are altered. These findings provide new insights into ligand-based hydride transfer mechanisms and establish a foundation for the rational design of selective CO 2 reduction catalysts.}, archive = {J_JACS}, author = {Sai Puneet Desai and Andressa V. Müller and Chiara Cappuccino and Dmitry E. Polyansky and David C. Grills and Mehmed Z. Ertem and Javier J. Concepcion}, doi = {10.1021/jacs.5c04611}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22725--22733}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemical ligand-based CO2 reduction mediated by ruthenium formyl species}, volume = {147}, year = {2025}, }
• (2025). A hexagonal bipyramidal Uranyl(V) single-ion magnet showing finger-type photoluminescence. JACS, 147(26), 22714--22724. (www)

  @article{ , abstract = {The occurrence of uranyl(V) compounds in nuclear fuel cycles and radioactive waste necessitates a deep understanding of the electronic structure of these 5f 1 species. Characteristic properties of pentavalent uranium can include single-molecule magnet (SMM) behavior and finger-like luminescence. However, both properties have not previously been observed in the same uranyl(V) complex. Here, we show that one-electron reduction of the hexagonal bipyramidal uranyl(VI) compound [UO 2 (L N6 )][BPh 4 ] 2 ( 1-U ) gives the uranyl(V) congener [UO 2 (L N6 )][BPh 4 ] ( 2-U ) (L N6 is a hexadentate N -donor with two connected bis (imino)pyridine groups). In addition to field-induced slow magnetic relaxation, 2-U displays photoluminescence upon excitation at 440 nm, the first time that both phenomena are observed in one uranyl(V) complex. The emission from 2-U is characterized by five well-resolved bands in the region 510–586 nm, in contrast to the broad emission observed for 1-U centered on 650 nm. The relationship between the electronic structure of 1-U and 2-U is emphasized by the photochromic behavior of 1-U, which, upon irradiation at 365 nm, adopts a stable photoexcited state 1-U * following a ligand-to-metal electron transfer, with the magnetic and spectroscopic properties of 1-U * being similar to those of 2-U . A computational study of 1-U and 2-U explains their contrasting emission profiles in terms of the uranyl oxo ligands participating in the key transitions for 2-U but not for 1-U , with the stretching vibrations of the L N6 ligand also contributing to the fine structure.}, archive = {J_JACS}, author = {Pei-Yu Liao and Hao-Ran Xing and Yi-Ling Zhong and Xi-Nan Xu and Peng-Xu Lu and Shang-Da Jiang and Cheng-Hui Li and Jun-Liang Liu and Richard A. Layfield and Ming-Liang Tong}, doi = {10.1021/jacs.5c04541}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22714--22724}, shortjournal = {J. Am. Chem. Soc.}, title = {A hexagonal bipyramidal Uranyl(V) single-ion magnet showing finger-type photoluminescence}, volume = {147}, year = {2025}, }
• (2025). Synergistic catalysis by cu single atoms and atomically cu-doped au nanoparticles in a Metal–Organic framework for photocatalytic CO2 reduction to C2H6. JACS, 147(26), 22705--22713. (www)

  @article{ , abstract = {Photocatalytic CO 2 reduction to C 2 hydrocarbons is considered more valuable and yet highly challenging due to the multielectron process and sluggish kinetics of C–C coupling, which requires multiple active sites to work synergistically. In this work, through a photodeposition method, Cu single-atom sites and atomically Cu-doped Au nanoparticles were simultaneously anchored on a photoactive metal–organic framework (MOF) with mesoporous channels, closely integrating distinct sites within a confined environment. Thanks to the electron accumulation of plasmonic metal nanoparticles and the synergy among different active sites, this MOF composite can achieve efficient photocatalytic reduction of CO 2 to C 2 H 6 with a production rate as high as 69.9 μmol g –1 h –1 and a selectivity as high as 71.1%. Photocatalytic experiments with control samples unveiled the critical roles of different active sites at each step, which was further confirmed by in situ characterizations and theoretical calculations. This finding highlights the potential of MOFs as an ideal platform for the integration of various active sites for synergistically catalytic applications.}, archive = {J_JACS}, author = {Di Chen and Bingxian Chu and Fayan Li and Yu-Tao Zheng and Yu Lu and Bing Shao and Lei Li and Ning-Yu Huang and Qiang Xu}, doi = {10.1021/jacs.5c04364}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22705--22713}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic catalysis by cu single atoms and atomically cu-doped au nanoparticles in a Metal–Organic framework for photocatalytic CO2 reduction to C2H6}, volume = {147}, year = {2025}, }
• (2025). Unraveling bifurcating pathways for CO and HCOOH formation: Insights from stopped-flow FTIR spectroscopy of a second-sphere modified mn catalyst. JACS, 147(26), 22697--22704. (www)

  @article{ , abstract = {Manganese bipyridine tricarbonyl complexes show high efficiency and selectivity in electrochemical CO 2 reduction (e-CO 2 RR) to CO. Efforts to shift selectivity toward HCOOH have been made by introducing second-sphere hydroxyl or amine functional groups and using amines or proton-coupled electron transfer (PCET) mediators. However, the direct spectroscopic evidence for the bifurcation pathways leading to CO and HCOOH remained elusive. Using stopped-flow mixing with decamethyl cobaltocene reductant and time-resolved infrared (TRIR) spectroscopy, we identified, for the first time, the key intermediates in this bifurcation pathway for an Mn complex with second-sphere hydroxyl groups in real time under catalytic conditions. The measured rate constants align with reported TOF values from electrochemical studies, validating the relevance of the results to e-CO 2 RR conditions. Our findings reveal that HCOOH production involves proton transfer from hydroxyl groups to the doubly reduced Mn center, forming the Mn-hydride intermediate, followed by CO 2 insertion, leading to the Mn-formate intermediate. However, the inability of the resulting phenolate to rebind protons from weak acids like water leads to rapid catalyst degradation, limiting sustained catalysis. This work provides mechanistic insights and paves the way for designing molecular catalysts with enhanced selectivity and stability for HCOOH production during e-CO 2 RR.}, archive = {J_JACS}, author = {Samir Chattopadhyay and Sudip Barman and Reiner Lomoth and Leif Hammarström}, doi = {10.1021/jacs.5c04274}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22697--22704}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling bifurcating pathways for CO and HCOOH formation: Insights from stopped-flow FTIR spectroscopy of a second-sphere modified mn catalyst}, volume = {147}, year = {2025}, }
• (2025). Small molecules influence the physical microenvironment of biomolecular condensates. JACS, 147(26), 22686--22696. (www)

  @article{ , abstract = {Biomolecular condensates exhibit distinct microenvironments that arise from interactions between proteins, RNA, and solutions. In aqueous solutions, these membraneless structures constantly encounter small molecules that could affect the structure and properties of the condensates. However, the effects of organic small molecules in water solutions on the microenvironments of condensates remain poorly understood. In this study, we used various organic solutes as an example to explore how small molecules could influence the physicochemical properties in the microenvironment of protein condensates. Particularly, we quantitatively studied micropolarity and microviscosity using a combination of techniques, including fluorescence lifetime imaging microscopy, fluorescence recovery after photobleaching, and passive rheology. Unexpectedly, our results revealed that the microenvironment was not correlated with the polarity of organic solutes; instead, the correlation was observed on the interaction strength between water and small molecules. We found that solutes with stronger interaction with water and weaker interaction with proteins increase the micropolarity and decrease the microviscosity of condensates. Furthermore, we demonstrated that the modulation of the micropolarity of condensates could impact the miscibility of multicomponent condensates. Finally, we showed that organic solutes could influence the micropolarity of condensates and the partitioning of products in condensates, thus affecting the rate and equilibrium of the chemical reactions. In summary, our work provides a quantitative analysis of how the microenvironment of biomolecular condensates is impacted by organic solutes. Since protein condensates coexist with various types of metabolites in the aqueous cellular milieu, results from this work offer insights into how organic metabolites could regulate the microenvironment and behaviors of biological condensates.}, archive = {J_JACS}, author = {Yifei Pan and Junlin Lei and Shiqi Mou and Zhili Wu and Longchen Zhu and Liyao Zeng and Feng Luo and Yaping Ding and Yu Liu and Xin Zhang}, doi = {10.1021/jacs.5c04180}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22686--22696}, shortjournal = {J. Am. Chem. Soc.}, title = {Small molecules influence the physical microenvironment of biomolecular condensates}, volume = {147}, year = {2025}, }
• (2025). Durable anion exchange membrane water electrolysis in low-alkaline concentration electrolyte. JACS, 147(26), 22677--22685. (www)

  @article{ , abstract = {Anion-exchange-membrane water electrolysis (AEMWE) is a promising technology for scalable green hydrogen production. However, the conventional use of high-alkalinity conditions accelerates membrane degradation, emphasizing the need for low-alkalinity operation to ensure long-term stability. For a low-alkalinity electrolyte with a high water-dissociation energy barrier, Ru serves as an ideal cathodic catalyst owing to its strong Ru–H bond, which provides distinguished water dissociation ability. However, the trade-off is high *H coverage, causing sluggish kinetics and limited durability during high-current operation. Herein, we developed an Ir–Ru solid solution catalyst, which enables rapid hydrogen transfer kinetics through a hydrogen spillover mechanism at high current. As a result, AEMWE with the Ir–Ru solid solution achieved a cell voltage of 1.75 V at 1 A cm –2 in 0.05 M KOH. Notably, the low-alkalinity AEMWE cell exhibited exceptional durability for over 1000 h, surpassing most of the previously reported data under similar operating conditions. Isotope labeling and in situ characterizations confirmed that dissociated *H spills from efficient water-dissociation sites on Ru to favorable hydrogen-desorption sites on Ir with lower *H coverage, significantly improving activity and stability at high current densities.}, archive = {J_JACS}, author = {Haifeng Shen and Fei-Yue Gao and Haobo Li and Jun Xu and Mietek Jaroniec and Yao Zheng and Shi-Zhang Qiao}, doi = {10.1021/jacs.5c04194}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22677--22685}, shortjournal = {J. Am. Chem. Soc.}, title = {Durable anion exchange membrane water electrolysis in low-alkaline concentration electrolyte}, volume = {147}, year = {2025}, }
• (2025). Macrocyclic chelators for aqueous lanthanide separations via precipitation: Toward sustainable recycling of rare-earths from NdFeB magnets. JACS, 147(26), 22666--22676. (www)

  @article{ , abstract = {Rare-earth elements (REEs) are critical materials in modern industry, but their production has a significant environmental footprint. Environmentally friendly separation methods would enable efficient, sustainable recycling of REEs. This work introduces a class of cyclen-based macrocyclic chelators that induce significant differences in solubility for REE chelates, enabling their selective precipitation from pH-neutral aqueous solution. The process was refined using simple coordinating additives (e.g., acetate) to form ternary coordination compounds to fine-tune these chelate solubilities. Conditions were optimized for the REEs found in NdFeB magnets, allowing separations of even adjacent lanthanides by repeated precipitations. Separation factors comparable to those of industrial solvent extraction methods were achieved without organic solvents. Analysis of NdFeB magnets from current electric car motors revealed an unexpected presence of holmium as a supplement and/or replacement for terbium and dysprosium, suggesting shifting industrial trends with implications for future recycling efforts. In a case study, one such automotive magnet was processed to obtain a 99.7% pure neodymium product. Scalable, tunable, and entirely aqueous, this approach advances the sustainable use of REEs toward a circular economy.}, archive = {J_JACS}, author = {Kelsea G. Jones and Tomáš David and Martin Loula and Stanislava Matějková and Jan Blahut and Anatolij Filimoněnko and Miroslava Litecká and Jan Rohlíček and Jiří Böserle and Miloslav Polasek}, doi = {10.1021/jacs.5c04150}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22666--22676}, shortjournal = {J. Am. Chem. Soc.}, title = {Macrocyclic chelators for aqueous lanthanide separations via precipitation: Toward sustainable recycling of rare-earths from NdFeB magnets}, volume = {147}, year = {2025}, }
• (2025). Bridge-mediated electron transfer: Bioinspired redox communication for sustained nitrite-independent anaerobic ammonium oxidation. JACS, 147(26), 22655--22665. (www)

  @article{ , abstract = {The lack of nitrite (NO 2 – ) in real wastewater severely limits the sustainable nitrogen removal of anaerobic ammonium oxidation (anammox). Although microbial extracellular electron transfer (EET) provides a new approach for NO 2 – -independent anammox, the slow electron transfer at the microbe–material interface hinders its engineering application. Herein, this study proposes a strategy to enhance the electrical contact between microorganisms and insoluble acceptors through conductive bridging materials (e.g., Fe 2 O 3 nanoparticles encapsulated by flavin-rich extracellular polymeric substances). Results showed that the interface between anammox bacteria (AMX1) and Fe 2 O 3 exhibited a high electron flux (6.86 mA·cm –2 ), considerably higher than all reports to date, achieving stable ammonium (NH 4 + ) removal of approximately 97.90% and operating continuously for over 150 days. Building on the efficient EET, Fe 2 O 3 was further triggered into Fe 2+ /Fe 3+ redox signaling for microbial metabolic coordination. Specifically, Fe 2+ signals channeled reducing power into coenzyme A/biotin synthesis in symbiotic bacteria (VER2) and fed back to the carbon fixation enzyme (FC = 1.1-fold) of AMX1 through chemotaxis migration and cross-feeding, while Fe 2+ was reconverted to Fe 3+ . The Fe 3+ signals induced gene expression (Log 2 FC > 0) of EET-associated proteins and simultaneously facilitated the conversion of electricity to critical chemical energy, accelerating the autotrophic growth of AMX1. In this way, anammox bacteria not only survived but also thrived in NO 2 – -limited environments, with relative abundance increasing by 127.22% to sustain NH 4 + removal. This study offers a novel solution to the NO 2 – supply challenge in wastewater treatment, advancing industry toward carbon neutrality goals.}, archive = {J_JACS}, author = {Quanhao Dou and Jiachun Yang and Li Zhang and Running Fan and Yongzhen Peng}, doi = {10.1021/jacs.5c04107}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22655--22665}, shortjournal = {J. Am. Chem. Soc.}, title = {Bridge-mediated electron transfer: Bioinspired redox communication for sustained nitrite-independent anaerobic ammonium oxidation}, volume = {147}, year = {2025}, }
• (2025). Closed-loop framework for discovering stable and low-cost bifunctional metal oxide catalysts for efficient electrocatalytic water splitting in acid. JACS, 147(26), 22642--22654. (www)

  @article{ , abstract = {Electrocatalytic water splitting, comprising the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), provides a sustainable route for hydrogen production. While low-cost metal oxides (MOs) are appealing as alternatives to noble metal electrocatalysts, their application in acidic media remains challenging. However, the dynamic nature of some MO surface structures under electrochemical conditions offers an opportunity for rational catalyst design to achieve bifunctionality in acidic OER and HER. Here, we present a closed-loop framework that integrates potential catalyst exploration (front-end), synthesis and electrochemical tests (mid-end), and advanced characterizations (back-end). This framework combines crucial steps in electrocatalyst exploration, including data mining, surface state analysis, microkinetic modeling, and proof-of-concept experiments to identify stable and cost-effective MO catalysts for acidic water splitting. Using this approach, RbSbWO 6 is identified as a promising bifunctional catalyst for the first time, with experimental validation demonstrating its exceptional stability and performance under acidic OER and HER. Notably, RbSbWO 6 outperforms many other reported non-noble stoichiometric MO catalysts that have not undergone major modifications for acidic water splitting. These findings, derived from our Digital Catalysis Platform (DigCat), establish RbSbWO 6 as a highly effective non-noble stoichiometric bifunctional MO catalyst and underscore the power of our closed-loop workflow for accelerating catalyst discovery. This framework begins with the DigCat platform, concludes with experimental validation, and feeds into the platform, demonstrating its potential for designing electrocatalysts in other systems such as metal nitrides or carbides. This study demonstrates the importance and high efficiency of data-driven approaches as a new scientific discovery paradigm.}, archive = {J_JACS}, author = {Xue Jia and Zihan Zhou and Fangzhou Liu and Tianyi Wang and Yuhang Wang and Di Zhang and Heng Liu and Yong Wang and Songbo Ye and Koji Amezawa and Li Wei and Hao Li}, doi = {10.1021/jacs.5c04079}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22642--22654}, shortjournal = {J. Am. Chem. Soc.}, title = {Closed-loop framework for discovering stable and low-cost bifunctional metal oxide catalysts for efficient electrocatalytic water splitting in acid}, volume = {147}, year = {2025}, }
• (2025). CO2 conversion to methanol by hydrogen species on n-type oxide semiconductors. JACS, 147(26), 22634--22641. (www)

  @article{ , abstract = {An n-type amorphous indium-based oxide semiconductor, a-InGaZnO x (a-IGZO), was found to be a promising catalyst for CO 2 hydrogenation to methanol. The oxide obtained from the mixed-hydroxide gel proved to be a unique n-type semiconductor material with a large surface area of more than 100 m 2 /g and a high carrier electron concentration of approximately 10 18 /cm 3 . Incorporating a metal/semiconductor junction with 5 wt % Pd significantly enhanced catalytic performance, achieving a reaction rate more than 20 times higher and a methanol selectivity exceeding 90 mol %. Compared to ZnO and Ga 2 O 3 in terms of electronic properties, the superior performance of the indium-based oxides was attributed to their high carrier electron concentration and a conduction band minimum (CBM) positioned near the universal hydrogen charge transition energy level [UHE: ε H (H + /H – ]. Temperature-programmed desorption mass spectrometry (TPD-MS) analyses indicated that the a-IGZO had an unusually high hydrogen adsorption capacity for an oxide material. The introduction of Pd further enhanced hydrogen adsorption in indium-based oxides; this enhancement was not observed in ZnO and Ga 2 O 3 , which have low carrier electron concentrations. In situ transmittance Fourier transform-Infrared (FT-IR) spectroscopy of Pd/a-IGZO to probe free-electron absorption revealed that hydrogen dissociating on Pd subsequently spilled over to the oxide, where it acted as a shallow donor, increasing the carrier electron concentration. Hard X-ray photoelectron spectroscopy (HAXPES), which is surface and bulk-sensitive, showed that the valence states of the In 3+ , Ga 3+ and Zn 2+ remain unchanged after H 2 annealing, even in the presence of Pd nanoparticles. We propose a mechanism in which hydrogen donors and carrier electrons near the UHE promote the formation of both negatively and positively charged hydrogen species on the oxide, enabling the selective conversion of CO 2 to methanol.}, archive = {J_JACS}, author = {Kazuki Fukumoto and Hideto Tsuji and Masatake Tsuji and Masakazu Koike and Kohei Takatani and Masahiko Shimizu and Masaaki Kitano and Hideo Hosono}, doi = {10.1021/jacs.5c03910}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22634--22641}, shortjournal = {J. Am. Chem. Soc.}, title = {CO2 conversion to methanol by hydrogen species on n-type oxide semiconductors}, volume = {147}, year = {2025}, }
• (2025). Controlling multiphase coacervate wetting and self-organization by interfacial proteins. JACS, 147(26), 22622--22633. (www)

  @article{ , abstract = {Biomolecular condensates help organize biochemical processes in cells and synthetic cell analogues. Many condensates exhibit multiphase architectures, yielding compartments with distinct functions. However, how cells regulate the transformation between different multiphase architectures remains poorly understood. Here, we use multiphase coacervates as model condensates and present a new approach to control wetting and self-organization in multiphase coacervates by introducing a surface-active protein, α-synuclein (αSyn). αSyn can localize at the interface of uridine 5′-triphosphate (UTP)/poly- l -lysine (pLL)/oligo- l -arginine (R 10 ) multiphase coacervates and induce the transformation from nested droplets into partially wetted droplets. The exposed UTP/R 10 core coacervate droplets adhered to neighboring (shell) coacervates, forming structures similar to polymers and leading to a dynamic yet stable self-organized network of connected coacervates, which we call coacervate polymers. A theoretical model demonstrates that multiphase coacervates transition to partial wetting upon increasing the interfacial protein, consistent with experimental observations. When three neighboring coacervates are not aligned, surface tension straightens their arrangement, similar to semiflexible polymers. This mechanism likely extends to larger structures, promoting chain formation while preventing fusion. Interestingly, diverse proteins were found to be surface active in multiphase coacervates: BSA, mCherry, and FtsZ all exhibited the same effect on multiphase coacervates’ partial wetting and organization. These findings suggest that interfacial proteins could be used by cells not only to stabilize condensates, but also to control multiphase organization and to regulate the interaction between condensates.}, archive = {J_JACS}, author = {Tiemei Lu and Susanne Liese and Brent S. Visser and Merlijn H. I. van Haren and Wojciech P. Lipiński and Wilhelm T. S. Huck and Christoph A. Weber and Evan Spruijt}, doi = {10.1021/jacs.5c03870}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22622--22633}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlling multiphase coacervate wetting and self-organization by interfacial proteins}, volume = {147}, year = {2025}, }
• (2025). Deep learning for fluorescence lifetime predictions enables high-throughput in vivo imaging. JACS, 147(26), 22609--22621. (www)

  @article{ , abstract = {Fluorescence lifetime imaging microscopy (FLIM) is a powerful optical tool widely used in biomedical research to study changes in a sample’s microenvironment. However, data collection and interpretation are often challenging, and traditional methods such as exponential fitting and phasor plot analysis require a high number of photons per pixel for reliably measuring the fluorescence lifetime of a fluorophore. To satisfy this requirement, prolonged data acquisition times are needed, which makes FLIM a low-throughput technique with limited capability for in vivo applications. Here, we introduce FLIMngo, a deep learning model capable of quantifying FLIM data obtained from photon-starved environments. FLIMngo outperforms other deep learning approaches and phasor plot analyses, yielding accurate fluorescence lifetime predictions from decay curves obtained with fewer than 50 photons per pixel by leveraging both time and spatial information present in raw FLIM data. Thus, FLIMngo reduces FLIM data acquisition times to a few seconds, thereby, lowering phototoxicity related to prolonged light exposure and turning FLIM into a higher throughput tool suitable for the analysis of live specimens. Following the characterization and benchmarking of FLIMngo on simulated data, we highlight its capabilities through applications in live, dynamic samples. Examples include the quantification of disease-related protein aggregates in non-anaesthetised Caenorhabditis ( C. ) elegans , which significantly improves the applicability of FLIM by opening avenues to continuously assess Caenorhabditis elegans throughout their lifespan. Finally, FLIMngo is open-sourced and can be easily implemented across systems without the need for model retraining.}, archive = {J_JACS}, author = {Sofia Kapsiani and Nino F. Läubli and Edward N. Ward and Ana Fernandez-Villegas and Bismoy Mazumder and Clemens F. Kaminski and Gabriele S. Kaminski Schierle}, doi = {10.1021/jacs.5c03749}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22609--22621}, shortjournal = {J. Am. Chem. Soc.}, title = {Deep learning for fluorescence lifetime predictions enables high-throughput in vivo imaging}, volume = {147}, year = {2025}, }
• (2025). Elucidating the Curtin–Hammett principle in glycosylation reactions: The decisive role of equatorial glycosyl triflates. JACS, 147(26), 22597--22608. (www)

  @article{ , abstract = {The glycosylation reaction represents a crucial and challenging reaction used in oligosaccharide synthesis. Specifically, attaining complete stereocontrol during glycosylation reactions remains challenging. Its complex nature is defined by the highly reactive intermediates that form upon the activation of a glycosyl donor. Low-abundant species may afford the major product via Curtin–Hammett kinetics and have long been proposed to play a major role. Therefore, characterizing these elusive stereodirecting intermediates is key to understanding glycosylation reaction mechanisms. Herein, we applied a combination of (exchange) NMR techniques to establish the equilibration rates of glycosyl triflate reaction intermediates and their ensuing glycosylation reaction kinetics. To this end, we studied the glycosylation reactions of 6,3-mannuronic acid and 6,3-glucuronic acid lactone donors. Using the complete set of reaction kinetics data, we constructed a computational kinetic model that shows that these compounds indeed react according to a Curtin–Hammett scenario. Furthermore, we were able to rationalize the observed stereochemical reaction outcomes using quantum-chemically computed potential energy surfaces for these glycosylation reactions. Hence, this workflow can now be used to obtain a complete reaction kinetics overview to retrieve the reaction pathway(s) that drive product formation.}, archive = {J_JACS}, author = {Peter H. Moons and Frank F. J. de Kleijne and Teun van Wieringen and Floor ter Braak and Hero R. Almizori and Luuk J. H. Jakobs and Willem P. M. de Kleijne and Floris P.J.T. Rutjes and Jonathan Martens and Jos Oomens and Peter A. Korevaar and Paul B. White and Thomas J. Boltje}, doi = {10.1021/jacs.5c03519}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22597--22608}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating the Curtin–Hammett principle in glycosylation reactions: The decisive role of equatorial glycosyl triflates}, volume = {147}, year = {2025}, }
• (2025). Sulfur vacancy boosts light-driven C–N coupling in upcycling of polylactic acid to alanine. JACS, 147(26), 22589--22596. (www)

  @article{ , abstract = {Photocatalytic C–N coupling of lactic acid (LA) and ammonia for alanine synthesis provides an attractive route for the upcycling of poly(lactic acid) (PLA) plastic waste. Although several advancements have been made in enhancing the photocatalytic alanine synthesis, current research lacks a clear understanding of how the photocatalyst structure influences the C–N coupling reaction. It is highly desirable to design a rational photocatalyst system to boost the C–N coupling, both for advancing mechanistic understanding and for optimizing catalysis. In this work, we have successfully developed sulfur-vacancy CdS (S v -CdS) as a photocatalyst, achieving a record-breaking alanine formation rate of 72.5 mmol g cat –1 h –1 , which surpasses the highest value reported in the literature to date. More importantly, for the first time, we have demonstrated that the photocatalytic amination of LA to alanine occurs exclusively through a radical pathway, where S vacancies weaken the adsorption of C α • and NH 2 • radicals on the S v -CdS surface, thereby promoting the C–N coupling. In contrast, Cd vacancies in cadmium-vacancy CdS are more favorable for activation of the C α –H bond in LA, but they are less effective for the C–N coupling. This work offers further insights into the mechanism of the photocatalytic C–N coupling reaction and opens a practical route for upcycling PLA plastic waste into value-added chemicals.}, archive = {J_JACS}, author = {Yuqi Zhang and Tingting Fan and Xia-Guang Zhang and Zhou Chen and Zhiwei Hu and Ting-Shan Chan and Xiaodong Yi and Xiaoqing Huang}, doi = {10.1021/jacs.5c03401}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22589--22596}, shortjournal = {J. Am. Chem. Soc.}, title = {Sulfur vacancy boosts light-driven C–N coupling in upcycling of polylactic acid to alanine}, volume = {147}, year = {2025}, }
• (2025). Copper–Carbon bond Metal–Organic frameworks for highly efficient and stable CO2 electrochemical methanation. JACS, 147(26), 22580--22588. (www)

  @article{ , abstract = {Cu-based metal–organic frameworks (Cu-MOFs) integrate the high tunability of molecular systems with the high activity of metal sites, making them promising electrocatalysts for the electrocatalytic reduction of carbon dioxide (CO 2 RR). To date, the primary challenge in the application of Cu-MOFs in electrocatalytic CO 2 RR is their poor stability during the reduction process. Herein, we pursue experimental and theoretical insights into Cu-C MOFs for the CO 2 RR for the first time. Notably, Cu-TEPT, a Cu-C MOF synthesized through the reaction of tetrakis(acetonitrile)copper(I) Trifluoromethanesulfonate with 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (TEPT) ligand, exhibited remarkable activity toward methane (CH 4 ) production. It achieved a high Faradaic efficiency (FE) of 83.6% and a CH 4 partial current density of up to 295.4 mA cm –2 , marking one of the highest performances reported to date. Experimental and theoretical studies indicated that the outstanding CO 2 RR performance and stability of Cu-TEPT result from the ligand-protected alkynyl Cu(I) sites in Cu-TEPT, which effectively stabilize the Cu + sites and accelerate the kinetics of CO 2 to CH 4 .}, archive = {J_JACS}, author = {Shuaiqiang Jia and Qinggong Zhu and Xiao Chen and Cheng Xue and Mengke Dong and Ting Deng and Hailian Cheng and Ting Yao and Jiapeng Jiao and Zhanghui Xia and Jianrong Zeng and Chunjun Chen and Haihong Wu and Mingyuan He and Buxing Han}, doi = {10.1021/jacs.5c03158}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22580--22588}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper–Carbon bond Metal–Organic frameworks for highly efficient and stable CO2 electrochemical methanation}, volume = {147}, year = {2025}, }
• (2025). Electron phase detection in single molecules by interferometry. JACS, 147(26), 22572--22579. (www)

  @article{ , abstract = {Interferometry has underpinned a century of discoveries, ranging from the disproval of the ether theory to the detection of gravitational waves, offering insights into wave dynamics with unrivaled precision through the measurement of phase relationships. In electronics, phase-sensitive measurements can probe the nature of transmissive topological and quantum states, but are only possible using complex device structures in magnetic fields. Here we demonstrate electronic interferometry in a single-molecule device through the study of nonequilibrium Fano resonances. We show the phase difference between an electronic orbital and a coupled Fabry–Perot resonance are tunable through electric fields, and consequently it is possible to read out quantum information in the smallest materials, offering new avenues for the coherent manipulation down to single molecules.}, archive = {J_JACS}, author = {Zhixin Chen and Jie-Ren Deng and Mengyun Wang and Nikolaos Farmakidis and Jonathan Baugh and Harish Bhaskaran and Jan A. Mol and Harry L. Anderson and Lapo Bogani and James O. Thomas}, doi = {10.1021/jacs.5c03056}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22572--22579}, shortjournal = {J. Am. Chem. Soc.}, title = {Electron phase detection in single molecules by interferometry}, volume = {147}, year = {2025}, }
• (2025). Unusually stable synthetic diheme bis-Fe(IV)oxo: An intermediate in diheme enzymes MauG and BthA. JACS, 147(26), 22562--22571. (www)

  @article{ , abstract = {Widespread diheme enzymes MauG and BthA of the bacterial cytochrome c peroxidase (bCCP) superfamily produce an unusually stable bis -Fe(IV) intermediate upon 2e¯-oxidation. Herein, we report, for the first time, the synthesis and characterization of the unusually stable bis -Fe(IV)═O intermediate, as a synthetic mimic of the bis -Fe(IV) species generated in the catalytic cycle of the native diheme enzymes that display similar stability at room temperature. Various spectroscopic techniques, including UV–vis, ESI-MS, EPR, resonance Raman, and Mössbauer, were utilized to thoroughly characterize this fairly stable intermediate. The reaction of a diiron(III) porphyrin dimer with soluble iodosylbenzene ( s PhIO) at −80 °C produces a red-colored solution of a hitherto unknown six-coordinate bis- Fe(III)porphyrin- s PhIO adduct which quickly undergoes O–I bond cleavage to yield the green bis -Fe(IV)═O intermediate. The reactivities of such a bis -Fe(IV)═O intermediate have also been demonstrated in the oxygen atom transfer (OAT) and C–H bond activation reactions. Computational studies revealed that the local electric field (LEF) of one heme exerted on the other heme unit is most likely the root cause of the unusual stability of the bis -Fe(IV)═O complex reported here. Indeed, the bis -Fe(IV)═O intermediate has been found to be stabilized significantly relative to its monomeric unit, and the stability of the dimeric system is maximized when the two porphyrin planes are relatively oriented by 20°, at which the LEF reaches its maximum value. The present work provides an excellent opportunity for the mechanistic investigation of the highly challenging and unexplored diheme enzymatic processes and will therefore have widespread practical applicability.}, archive = {J_JACS}, author = {Deepannita Samanta and Sabyasachi Sarkar and Dinesh Singh and Soumya Samanta and Santanu Manna and Kshatresh Dutta Dubey and Abhishek Dey and Sason Shaik and Sankar Prasad Rath}, doi = {10.1021/jacs.5c03000}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22562--22571}, shortjournal = {J. Am. Chem. Soc.}, title = {Unusually stable synthetic diheme bis-Fe(IV)oxo: An intermediate in diheme enzymes MauG and BthA}, volume = {147}, year = {2025}, }
• (2025). Rational design of electric field-responsive building blocks for all-organic 2D magnetoelectric materials. JACS, 147(26), 22550--22561. (www)

  @article{ , abstract = {Development of technologically promising magnetoelectric materials, where magnetic properties can be controlled by electric fields (E-fields), has focused on inorganic systems. Here, we propose a strategy for modulating magnetic exchange coupling ( J ) in purely organic systems through experimentally realizable E-fields. Our approach leverages two established concepts: (i) E-field-induced twisting of dipolar organic linkers and (ii) control of J via conformational changes in organic diradicals. Using density functional theory calculations, we investigated the effects of applied E-fields on diradicals with two coplanar spin-carrying trioxotriangulene (TOT) radicals connected by dipolar aryl linkers. We find that E-fields induce significant conformational changes in the linkers (twisting) that alters π-conjugation and, in turn, the magnetic J coupling between TOT radicals. In-plane E-fields twist the linkers toward the plane of the radicals, enhancing π-conjugation and increasing AFM coupling. Out-of-plane E-fields induce more orthogonal linker conformations and decrease the coupling strength. The magnetoelectric response depends on a combination of steric hindrance, π-conjugation, and polarization. Significant and measurable cumulative changes in J of up to 3.9 meV could be achieved by using in-plane and out-of-plane E-fields of up to 0.5 V/Å. In some cases, applied E-fields can also induce switching between paramagnetism and antiferromagnetism. Calculations on a 2D covalent organic framework (COF) based on a network of TOT radicals and dipolar linkers confirm that this approach is also viable for extended systems. Such COFS could also display E-field induced ferroelectric responses. Overall, our proof-of-principle study highlights the interplay between molecular structure, E-fields, and magnetism and establishes an innovative and chemically rational framework for developing all-organic magnetoelectric materials.}, archive = {J_JACS}, author = {Kílian Jutglar-Lozano and Mercè Deumal and Jordi Ribas-Arino and Stefan T. Bromley}, doi = {10.1021/jacs.5c02910}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22550--22561}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design of electric field-responsive building blocks for all-organic 2D magnetoelectric materials}, volume = {147}, year = {2025}, }
• (2025). Breaking the strongest organic bonds by water: Defluorosubstitutions at the Air–Water interface of microdroplets. JACS, 147(26), 22542--22549. (www)

  @article{ , abstract = {The C–F bond is recognized as the strongest single bond in organic chemistry. Activating such inert bonds typically demands rigorous reaction conditions, often involving expensive transition metal catalysts or harsh reagents. In stark contrast, this study demonstrates reagent-free defluorosubstitution reactions using only water. We observed the selective cleavage of Csp 2 –F and Csp 3 –F bonds, resulting in the formation of highly reactive carbocation species and fluoride anions at the air–water interface when aqueous solutions of organofluorine substrates (ArF and ArCF 3 ) were sprayed into the air. The carbocations formed at the interface subsequently reacted with various nucleophiles to yield defluorosubstitution products. A mechanistic investigation suggests that a one-electron reduction of the aromatic substrate facilitates rapid heterolytic cleavage of the C–F bond, occurring in less than a millisecond. Thus, fluorine, often described as a “small atom with a big ego”, has been effectively knocked out of organofluorine compounds by water.}, archive = {J_JACS}, author = {Abhijit Nandy and Anitesh Rana and Norio Shibata and Shibdas Banerjee}, doi = {10.1021/jacs.5c02851}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22542--22549}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking the strongest organic bonds by water: Defluorosubstitutions at the Air–Water interface of microdroplets}, volume = {147}, year = {2025}, }
• (2025). Electron sextets as optically addressable molecular qubits: Triplet carbenes. JACS, 147(26), 22529--22541. (www)

  @article{ , abstract = {There is a growing demand in quantum information science and sensing for electron spin purification and readout via a spin-optical interface. This technique, known as optically detected magnetic resonance (ODMR), has been applied to diamond-NV centers and transition-metal complexes. Metal-free counterparts of these optically addressable spin qubits promise to be cheaper, more sustainable color centers with prolonged polarization lifetimes. However, progress has been hindered by the low ODMR signals of carbon-based π-diradicals, partly due to the lack of a ground singlet-to-triplet intersystem crossing (ISC). In this work, we propose exploring organic systems that are even more electron-deficient: electron sextets. Using triplet carbenes as an example, we illustrate how the ground singlet–triplet gap can be widened beyond thermal energy with the associated singlet-to-triplet ISC made available by vibronic effects. Through careful molecular engineering, this ISC can occur at a rate similar to and with an opposite spin selectivity from the excited-state ISC well-established in π-diradicals, unlocking a new ODMR pathway with potential signal gains. Persistent triplet carbenes are a renascent field, with multiple stable molecules being isolated in the past five years. To motivate further development of its emissive properties, we illustrate our design in three realistic carbene candidates that incorporate existing strategies for carbene stabilization. Ultimately, we believe that a new realm of quantum materials can be uncovered by expanding our scope toward stable electron sextets.}, archive = {J_JACS}, author = {Yong Rui Poh and Xiao Chen and Hai-Ping Cheng and Joel Yuen-Zhou}, doi = {10.1021/jacs.5c02672}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22529--22541}, shortjournal = {J. Am. Chem. Soc.}, title = {Electron sextets as optically addressable molecular qubits: Triplet carbenes}, volume = {147}, year = {2025}, }
• (2025). Multicomponent ru-based alloys with a face-centered cubic structure achieve high activity and CO tolerance for hydrogen oxidation electrocatalysis. JACS, 147(26), 22517--22528. (www)

  @article{ , abstract = {The face-centered cubic (fcc) Ru exhibits great potential for the alkaline hydrogen oxidation reaction (HOR), while achieving high HOR activity and CO tolerance poses a formidable challenge for Ru catalysts in practical fuel cells, particularly when using CO-contaminated H 2 , such as gray and blue hydrogen. Here, we propose a compositional diversification strategy to create 14 types of fcc Ru-based alloys, in which adjustable compositions can tune the nanostructure while offsetting the limitations of single Ru. Among them, quinary RuInPtNiCu nanocrystals (NCs) exhibit an outstanding HOR activity of 5.36 A mg PGM –1 , which is 15.9 and 2.9 times higher than those of commercial Pt/C (0.338 A mg PGM –1 ) and single Ru NCs (1.88 A mg PGM –1 ), respectively. More importantly, the RuInPtNiCu-based membrane electrode assembly (MEA) achieves a high peak power density of 1.72 W cm –2 and a remarkable mass activity of 19.0 A mg PGM –1 @0.65 V in H 2 –O 2 , and the RuInPtNiCu-based MEA can be run stably at 0.6 A cm –2 for over 100 h. Moreover, the RuInPtNiCu retains 94.6% of the HOR current after exposure to H 2 containing 1000 ppm CO for 8000 s in a rotating disk electrode and retains 92.5% of cell voltage after a CO-toxicity stability test in fuel cells, underscoring its exceptional CO tolerance. Mechanism and computation studies corroborate that the optimized electronic structure and atomic configuration of RuInPtNiCu weaken the adsorption of surface species (*H, *OH, and CO) and alter the CO adsorption mode on active sites, thus leading to enhanced HOR performance and CO tolerance.}, archive = {J_JACS}, author = {Qing Yao and Renjie Ren and Yuanmin Zhu and Wei Yan and Zhiyong Yu and Zhongliang Huang and Aiying Song and Haixin Lin and Lin Zhuang and Zhe-Ning Chen and Nanjun Chen and Xiaoqing Huang}, doi = {10.1021/jacs.5c02339}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22517--22528}, shortjournal = {J. Am. Chem. Soc.}, title = {Multicomponent ru-based alloys with a face-centered cubic structure achieve high activity and CO tolerance for hydrogen oxidation electrocatalysis}, volume = {147}, year = {2025}, }
• (2025). Photocatalyst design with an electrical-polarization-ability descriptor for exclusive C–H bond activation in methanol. JACS, 147(26), 22509--22516. (www)

  @article{ , abstract = {Photocatalysis is increasingly used as an effective tool for green synthesis, where the precise activation of specific chemical bonds is crucial for achieving high selectivity. Descriptor-based scaling has emerged as an effective method for assessing structure–activity relationships in heterogeneous photocatalysis; however, selectivity-related descriptors remain scarce. Here, we introduce the “electrical-polarization-ability (δ)” as a novel descriptor that considers the polarity of the active site and its surrounding microenvironment, incorporating electrical, structural, and orbital contributions. δ allows for the quantification of surface–adsorbate interactions across various semiconductors. This descriptor is evaluated in the photocatalytic activation of C–H or O–H bonds in methanol, where preferential C–H bond activation leads to oxidative coupling to yield ethylene glycol (EG), an important bulk chemical. δ captures selectivity trends among experimentally reported semiconductors with diverse properties and aids in the rational design of carbon-doped hexagonal boron nitride (C- h -BN), achieving an exceptional EG selectivity of 98.9%. Our work underscores the promising potential to accelerate innovation in green synthesis through descriptor-guided selective photocatalyst design.}, archive = {J_JACS}, author = {Leyuan Cui and Jun Feng and Shimiao Wu and Sha Xu and Xuejiao Wu and Shuhong Zhang and Qinghong Zhang and Gang Fu and Ye Wang and Shunji Xie}, doi = {10.1021/jacs.5c02280}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22509--22516}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalyst design with an electrical-polarization-ability descriptor for exclusive C–H bond activation in methanol}, volume = {147}, year = {2025}, }
• (2025). Alloy reorganization and dynamics in group-10-Metal–Gallium nanoparticles under reactive atmospheres: Impact on local environment and reactivity. JACS, 147(26), 22498--22508. (www)

  @article{ , abstract = {Bimetallic nanoparticles are catalysts for reactions such as CO x hydrogenation or propane dehydrogenation. Recently, gallium has been identified as a promoter, which enables dispersion of transition metal sites, increasing their activity and selectivity. However, quantitative information on alloying dynamics under reaction conditions is not readily available, and a general computational method to access such information is lacking. Here, an ab initio molecular dynamics workflow with enhanced sampling methods is used to probe the alloying behavior of Ni-, Pd-, and Pt-Ga nanoparticles under operating conditions ( T = 600 °C) in the presence of H 2 or CO. The three metals display different alloying behaviors with Ga: Ni forms a core surrounded by gallium, while Pd and Pt form different alloyed structures. Both H 2 and CO shift the alloying states to different extents. A set of three descriptors is then proposed to compare and quantify the alloying behavior of these catalyst models: (i) the position α min of the most stable alloying state; (ii) the curvature η of the free energy at α min , referred to as the alloying hardness; and (iii) the skew κ of the free energy at α min , which relates to its propensity to alloy or segregate. The cost of alloy reorganization, which correlates with alloy hardness, is a major part of the free energy barriers of propane dehydrogenation. Since the alloying behavior of a catalyst is a critical parameter that is overlooked in catalyst design, quantitative descriptors are the first step in designing alloys with set catalytic properties.}, archive = {J_JACS}, author = {Quentin Pessemesse and Alexandre Perochon and Christophe Copéret and Marie-Eve L. Perrin and Pierre-Adrien Payard}, doi = {10.1021/jacs.5c01968}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22498--22508}, shortjournal = {J. Am. Chem. Soc.}, title = {Alloy reorganization and dynamics in group-10-Metal–Gallium nanoparticles under reactive atmospheres: Impact on local environment and reactivity}, volume = {147}, year = {2025}, }
• (2025). Colossal thermal expansion and continuous rolling locomotion of a robust flexible molecular single crystal. JACS, 147(26), 22488--22497. (www)

  @article{ , abstract = {Amplifying microscopic or molecular perturbations to induce macroscopic mechanical effects in well-ordered molecular crystals is the foundation of the newly recognized potential of organic crystalline smart materials for soft organic electronics, optics, actuators, switches, and robots. Diverse molecular crystal actuators that transform external energy into mechanical motions have been prepared in the past decade, yet their spatiotemporal operational capability, adaptability, reversibility, and durability have not been fully explored. In this study, we present adaptive molecular single crystals that can respond to force, heat, and light, demonstrating mechanical flexibility, reversible expansion, and complex movements, including rolling and climbing locomotion. These crystals exhibit significant anisotropic thermal expansion within the temperature range from 303 to 413 K, expanding by approximately 4.8% along their longest axis. The exceptional flexibility and thermal expandability of this material enable quick and sustained locomotion of the single crystals when exposed to ultraviolet light. Our findings highlight the considerable yet underexplored potential of adaptive organic crystals that can be used as lightweight thermomechanical and photomechanical actuators.}, archive = {J_JACS}, author = {Bo Jing and Wenjie Kuang and Jinhe Li and Yongsheng Zhang and Songgu Wu and Liang Li and Panče Naumov and Junbo Gong}, doi = {10.1021/jacs.5c02006}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22488--22497}, shortjournal = {J. Am. Chem. Soc.}, title = {Colossal thermal expansion and continuous rolling locomotion of a robust flexible molecular single crystal}, volume = {147}, year = {2025}, }
• (2025). Small protein domains as potential spin labels for in vitro, cellular, and light-induced dipolar EPR spectroscopy. JACS, 147(26), 22473--22487. (www)

  @article{ , abstract = {This study explores the potential of small light-oxygen-voltage (LOV) domains for utilization as protein spin labels in different dipolar EPR spectroscopy methods. The distinctive photochemical properties of selected LOV domain variants are exploited to generate a variety of (meta)stable flavin mononucleotide (FMN) radicals upon blue light absorption. Three different radicals, FMN ·– , FMNH · , and an FMN-methionine radical, and an excited FMN triplet species, were generated. The FMN radicals were generated in LOV single domains and two model LOV1-LOV2 fusion proteins, and the latter proteins demonstrated that simple and effective orthogonal spin labeling can be performed. Subsequently, dipolar EPR experiments were conducted in aqueous solution and in cells with and without additional light excitation, in order to measure the distances between the FMN cofactor radicals, and to infer the structure and dynamics of the LOV domain proteins. Interestingly, all LOV1-LOV2 fusion proteins exhibit defined but largely distinct distances. This can be attributed to two factors: the respective LOV domains have different interactions with each other, and the presence of neutral FMN radicals leads to dimerization of the LOV1 domains. Nevertheless, using LOV domains as genetically encoded spin labels could offer numerous advantages. As a true molecular biology concept, labeling and measurements can be performed in any accessible cell type using light as the only stimulus. Additionally, the various paramagnetic FMN states enable the measurement of distances between two radicals, as well as between a radical and a triplet state.}, archive = {J_JACS}, author = {Andreas Günter and Susanna Ciuti and Lukas Denkhaus and Anna Sappler and Laura Orian and Stefan Gerhardt and Oliver Einsle and Stefan Weber and Marilena Di Valentin and Erik Schleicher}, doi = {10.1021/jacs.5c01875}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22473--22487}, shortjournal = {J. Am. Chem. Soc.}, title = {Small protein domains as potential spin labels for in vitro, cellular, and light-induced dipolar EPR spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Regular mesoporous superparticles with a tailored opening window and tunable surface crisscrossed grooves. JACS, 147(26), 22460--22472. (www)

  @article{ , abstract = {Regular hollow mesoporous superparticles with an opening window and controllable surface grooves can significantly improve the high-loading performance of aqueous zinc ion hybrid capacitors, but their synthesis remains a great challenge. Herein, an electrostatic force-assisted monomicelle confined assembly strategy is demonstrated for synthesizing such regular mesoporous hollow superparticles. The mesoporous superparticles feature a hollow (∼250 nm) in the center and a tailored transverse window (35–50 nm) to enable the superparticles to be totally connected from the inner to external surface, and a monolayer of spherical mesopores (∼15 nm) is arrayed in an orderly fashion on the hollow shell to form the unique crisscrossed grooves. Notably, an accurate manipulation in the width (29.5–62.4 nm), depth (2.1–40.7 nm), and number in the horizontal and vertical (11 × 11–5 × 5) grooves can be realized. Finally, the mesoporous superparticles as the high-loading electrodes in aqueous zinc ion hybrid capacitors exhibit a weak polarization, a high specific capacity (205 mAh g, –1 at 0.1 A g –1 ), and an excellent rate performance (105 mAh g –1 at 10 A g –1 ). The adjustability of surface grooves enables the orthogonal control of the charge transfer rate and ion diffusion rate. The mesoporous superstructures demonstrate the potential for energy storage applications in different environments.}, archive = {J_JACS}, author = {Xiankai Fan and Jie Wang and Ziyan Han and Hao Li and Luxiao Zhang and Yujuan Zhao and Linlin Duan and Hui Shen and Jun Li and Lipeng Wang and Wanhai Zhou and Xiaojun Gu and Jiangwei Zhang and Dongliang Chao and Zaiwang Zhao and Dongyuan Zhao and Limin Wu}, doi = {10.1021/jacs.5c01622}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22460--22472}, shortjournal = {J. Am. Chem. Soc.}, title = {Regular mesoporous superparticles with a tailored opening window and tunable surface crisscrossed grooves}, volume = {147}, year = {2025}, }
• (2025). Superconductivity in metastable K1+δMo6Se8: A potassium-intercalated chevrel phase. JACS, 147(26), 22453--22459. (www)

  @article{ , abstract = {The Chevrel phase (CP), characterized by its unique Mo 6 X 8 (X = S, Se, Te) cluster structure, represents a class of promising materials demonstrating exceptional performance in various applications, including battery cathodes, electrocatalysts, and superconductors. However, the exploration of new CP derivatives remains challenging due to the inherent lattice destabilization caused by cation intercalation, particularly evident in selenide and telluride systems. This study reports the successful synthesis of thermodynamically metastable K 1+ δ Mo 6 Se 8 ( δ ∼ 0.37) and the superconducting properties therein. K 1+ δ Mo 6 Se 8 crystallizes in the triclinic space group P 1̅ (No. 2), where potassium cations occupy interstitial sites between the Mo 6 Se 8 clusters. Comprehensive characterization through electrical resistivity, magnetization, and specific heat measurements reveals bulk superconductivity at T c = 8.9 K. Notably, the upper critical field is estimated to be 26.4 T, violating the Pauli paramagnetic limit. Furthermore, low-temperature specific heat analysis indicates possible multigap superconducting behavior. Our findings not only expand the family of high-critical-field superconducting CPs but also demonstrate the potential to synthesize novel CP materials through solid-state reactions at lower temperatures.}, archive = {J_JACS}, author = {Yun-Qing Shi and Xiao-Ping Ma and Le-Wei Chen and Jun-Kun Yi and Menghu Zhou and Ya-Dong Gu and Qing-Song Yang and Jian-Qi Li and Huai-Xin Yang and Bin-Bin Ruan and Zhi-An Ren}, doi = {10.1021/jacs.5c01401}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22453--22459}, shortjournal = {J. Am. Chem. Soc.}, title = {Superconductivity in metastable K1+δMo6Se8: A potassium-intercalated chevrel phase}, volume = {147}, year = {2025}, }
• (2025). Spatial heterogenous redox couples degradation in sodium-ion battery cathode materials and the mitigation of voltage fade by blocking oxygen release. JACS, 147(26), 22444--22452. (www)

  @article{ , abstract = {The use of anionic redox has become a new paradigm for improving the energy density of rechargeable batteries, which is essential for improving the market competitiveness of sodium-ion batteries. However, issues such as voltage attenuation and cycling stability degradation persist in layered oxide anion redox cathode materials. In this study, we systematically investigate the classic Na-ion cathode material Na 0.6 Li 0.2 Mn 0.8 O 2 , and the primary causes of voltage decay are identified as the activation of cations and the reduction in anion redox activity. In addition, the activation of cations is closely associated with anion reactions. Through the application of sophisticated multiscale synchrotron absorption spectroscopy and imaging techniques, we have identified a pronounced pattern of spatially dependent degradation in the evolution of redox couples, which is more evident from the material’s surface to its core. With this understanding, we introduced a surface fluorination approach that modulates the local chemical coordination environment. This strategy increases the formation energy of surface oxygen vacancies and locks transition metals oxide state. Consequently, it enables more reversible anionic redox reactions, which block the spatial progression of degradation and mitigates voltage decay.}, archive = {J_JACS}, author = {Jiangnan Huang and Zhichen Xue and Sang-Jun Lee and Hongyi Chen and Xiaobo Ji and Ke Du}, doi = {10.1021/jacs.5c00969}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22444--22452}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatial heterogenous redox couples degradation in sodium-ion battery cathode materials and the mitigation of voltage fade by blocking oxygen release}, volume = {147}, year = {2025}, }
• (2025). Insights into the mechanisms of small molecule-induced agonism and antagonism of a quorum sensing receptor in pseudomonas aeruginosa. JACS, 147(26), 22427--22443. (www)

  @article{ , abstract = {Common bacteria use chemical signals to assess their cell density in a process called quorum sensing (QS). The pathogen Pseudomonas aeruginosa utilizes QS to control many virulence factors and traits involved in infection. Two QS signals used by P. aeruginosa are N -acyl l -homoserine lactones, which are recognized by three LuxR-type receptors, LasR, QscR, and RhlR. Modulation of LuxR-type receptor activity with non-native small molecules has been the focus of extensive efforts to attenuate virulence in P. aeruginosa . However, further development of these compounds has been slowed by the limited understanding of their mechanisms of action, either as agonists or antagonists. Specifically, how binding of ligand effectively transduces information to the DNA binding domain of LuxR-type proteins to promote or inhibit DNA binding is largely unknown. Herein, we report a suite of biochemical and biophysical experiments to characterize the interactions between the QscR receptor and a collection of compounds that alters QscR activity in cell-based reporter assays. We use the results of these investigations to propose models for a “signal transduction” mechanism between the QscR ligand binding domain and DNA binding domain upon ligand-induced agonism and antagonism. These models are tied to receptor levels and thus could have different implications for ligand behavior at nonquorate and quorate populations. Our findings also suggest limitations of cell-based reporter assays as proxies for biophysical parameters of QscR transcriptional activity, and we outline other experiments that may avoid these limitations. The methods and models presented here should be broadly applicable to the LuxR-type receptor family.}, archive = {J_JACS}, author = {Matthew J. Styles and Michelle E. Boursier and Cassandra M. Doody and Kayleigh E. Nyffeler and Helen E. Blackwell}, doi = {10.1021/jacs.5c00523}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22427--22443}, shortjournal = {J. Am. Chem. Soc.}, title = {Insights into the mechanisms of small molecule-induced agonism and antagonism of a quorum sensing receptor in pseudomonas aeruginosa}, volume = {147}, year = {2025}, }
• (2025). Engineering of sono-activatable immunogels for immunometabolism disorder normalization therapy of breast cancer. JACS, 147(26), 22412--22426. (www)

  @article{ , abstract = {Sonodynamic therapy (SDT) represents a promising approach for localized immunotherapy of solid tumors, yet its clinical translation is limited by therapy stress-induced adaptive immune resistance. Here, we demonstrate that SDT initially elicits antitumor immune response while consequently induces immunometabolic dysregulation via the interferon-gamma (IFN-γ)/indoleamine-2,3-dioxygenase-1 (IDO-1) axis to promote regulatory T cell (Treg) expansion. To counteract this negative regulation mechanism, we develop a sono-activatable prodrug (MB–MT) by conjugating the sonosensitizer methylene blue (MB) with the IDO-1 inhibitor 1-methyltryptophan (MT) via an ultrasound-labile urea bond. MB–MT is further incorporated into a thermosensitive hydrogel to yield an ultrasound-responsive immunogel that enables spatiotemporally confined SDT while locally suppressing IDO-1-mediated immune suppression. The combination of the immunogel with SDT treatment markedly normalizes the immunosuppressive tumor microenvironment to inhibit primary and metastatic tumor growth, and prevent postoperative recurrence in multiple synergistic mouse models of triple negative breast cancer (TNBC). This work presents a practical strategy for localized immunotherapy of TNBC by spatiotemporally confined normalization of immunometabolism disorder.}, archive = {J_JACS}, author = {Yu Guo and Jiaxing Pan and Junjue Wang and Huijuan Zhang and Wenfang Yang and Fangmin Chen and Bowen Yin and Xiran Cai and Wei Tao and Twan Lammers and Yi Lai and Haijun Yu and Xiuli Hu and Zhiai Xu}, doi = {10.1021/jacs.5c00124}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22412--22426}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering of sono-activatable immunogels for immunometabolism disorder normalization therapy of breast cancer}, volume = {147}, year = {2025}, }
• (2025). Elucidation of the pH-dependent electric double layer structure at the positively charged amorphous Alumina/Water interface using heterodyne-detected vibrational sum-frequency generation. JACS, 147(26), 22402--22411. (www)

  @article{ , abstract = {Alumina is one of the most abundant oxides in nature. Hence, the molecular-level elucidation of the alumina/water interface is important not only for a fundamental understanding of the oxide surface, but also for applications of oxide-related materials in extensive research fields. In the present study, the water structure in the electrical double layer (EDL) at the alumina–water interface is investigated through the interface-selective vibrational spectra (χ (2) ) in the OH stretch region, measured with heterodyne-detected vibrational sum-frequency generation spectroscopy. The imaginary part of χ (2) (Imχ (2) ) spectra is collected while salt concentrations are varied (0.01–5.0 M) in the acidic and neutral pH range (pH 2.0–8.0), where the alumina surface is positively charged. The spectral additivity of the Imχ (2) spectra enables the decomposition of the spectra into the contributions of the diffuse layer (DL) and Stern layer (SL) to discuss them separately. The surface charge density at each pH is evaluated from the salt-concentration dependence of the amplitude of the DL spectra using the modified Gouy–Chapman theory, providing a single p K a value of ∼3.7 ± 0.2 due to the Al 2 OH 2 + /Al 2 OH equilibrium at the alumina surface. Moreover, it is found that the spectra of the DL and SL are very similar to each other, indicating that the water in the SL is bulk-like water with highly concentrated salt, without specific interaction with the alumina surface. This implies that the water structure of the EDL at the alumina/water interface is much simpler than that at the silica/water interface, where the water molecule has specific interactions with the silica surface. These findings reveal that the alumina/water interface provides another distinct prototype of the EDL structure at oxide/water interfaces.}, archive = {J_JACS}, author = {Feng Wei and Satoshi Nihonyanagi and Tahei Tahara}, doi = {10.1021/jacs.4c18656}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22402--22411}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidation of the pH-dependent electric double layer structure at the positively charged amorphous Alumina/Water interface using heterodyne-detected vibrational sum-frequency generation}, volume = {147}, year = {2025}, }
• (2025). Rotation kinetics of molecular motors influence their ability to kill cancer cells and induce cellular calcium signaling. JACS, 147(26), 22387--22401. (www)

  @article{ , abstract = {Although chemical agents have long been the primary method for influencing cellular behavior, mechanical forces also play an important role in many cellular processes. Most mechanical forces are applied externally to cell membranes. However, it has recently been demonstrated that mechanical forces can be applied to cells from within using synthetic molecular motors (MMs). MMs mechanically influence their environment by undergoing rapid unidirectional rotation when irradiated with light. The activation of MMs in cell membranes can lead to various effects, ranging from cell death when activated for minutes to intracellular calcium signaling when activated for <1 s. The purpose of this study is to investigate the structure–function relationships governing the effectiveness of MMs in several different biological applications. We do this by synthesizing four nearly identical MMs, where we modify the functional group that significantly influences MM rotation to contain either a methyl, isopropyl, tert -butyl, or phenyl group. We use density functional theory (DFT) calculations to determine the relative rotation rates of the four MMs and reveal that the methylated MM is the fastest, while bulkier substituents result in slower rotation. The MM with a methyl substituent is the most effective at killing cells and inducing intracellular calcium signaling. This study reinforces the idea that MMs influence cellular environments primarily through unidirectional molecular rotation, and it further demonstrates that internal mechanical forces can controllably induce cell activity.}, archive = {J_JACS}, author = {Dallin Arnold and Bowen Li and Jacob L. Beckham and Katherine Lopez-Jaime and Ciceron Ayala-Orozco and Yuchen Rui and Gautam Chaudhry and Jorge M. Seminario and James M. Tour}, doi = {10.1021/jacs.4c17732}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22387--22401}, shortjournal = {J. Am. Chem. Soc.}, title = {Rotation kinetics of molecular motors influence their ability to kill cancer cells and induce cellular calcium signaling}, volume = {147}, year = {2025}, }
• (2025). Deciphering the thiolactonization mechanism in thiolactomycin biosynthesis. JACS, 147(26), 22368--22386. (www)

  @article{ , abstract = {Thiolactomycin ( 1 ), which features a unique γ-thiolactone ring, is a promising antibiotic candidate that specifically targets bacterial type II fatty acid synthase. Despite extensive studies on its pharmacological activities, modes of action, and chemical synthesis, the enzymatic processes responsible for forming the activity-determining γ-thiolactone ring have remained largely unknown. Here, we resolve this problem by revealing that the condensation and heterocyclization (Cy) domain of the nonribosomal peptide synthetase (NRPS) TlnC (TlnC Cy ), along with the cytochrome P450 enzyme TlnA, cooperatively enable the γ-thiolactone assembly. TlnC Cy mediates an unusual sulfurtransfer reaction to sulfurate the polyketide intermediate, generating a thiocarboxylate intermediate. Subsequently, TlnA acts as a γ-thiolactone synthase, converting the linear thiocarboxylate intermediate into 1 via a distal radical-based cyclization mechanism. These findings not only expand the functional and catalytic repertoires of NRPS Cy domains and P450 enzymes but also highlight a special enzymatic strategy for γ-thiolactone biosynthesis in nature.}, archive = {J_JACS}, author = {Jiawei Guo and Qiaoyu Zhang and Yang Shen and Fangyuan Cheng and Moli Sang and Xuan Wang and Yunjun Pan and Mingyu Liu and Hao-Bing Yu and Bo Hu and Sheng Wang and Liangzhen Zheng and Ce Geng and Chaofan Yang and Lianzhong Luo and Gang Zhang and Lei Du and Yuanning Li and Wei Zhang and Yandong Zhang and Binju Wang and Shengying Li and Xingwang Zhang}, doi = {10.1021/jacs.4c14296}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22368--22386}, shortjournal = {J. Am. Chem. Soc.}, title = {Deciphering the thiolactonization mechanism in thiolactomycin biosynthesis}, volume = {147}, year = {2025}, }
• (2025). Orthogonal thiol addition chemistry based on ether acrylates. JACS, 147(26), 22363--22367. (www)

  @article{ , abstract = {The thiol-Michael and radical thiol–ene addition chemistries are extremely powerful tools for the construction of advanced soft matter materials. However, a critical challenge of these chemistries lies in their nonideal orthogonality in which both acrylates (Michael acceptors) and electron-rich olefins are active in a radical thiol–ene reaction. Herein, we show that by employing an ether acrylate (β-alkoxyacrylate), readily accessible via the efficient hydroxyl–yne click reaction, true orthogonality between activated double bonds can be achieved. Critically, we exploit the radical inactive property of the ether acrylate for the efficient synthesis of difficult-to-prepare sequence-defined main-chain macromolecular photoswitches and brush-like polymers. The results reported open a straightforward opportunity to synthetically access advanced materials with controllable properties.}, archive = {J_JACS}, author = {Linh Duy Thai and Marco Neumaier and Christopher Barner-Kowollik}, doi = {10.1021/jacs.5c08202}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22363--22367}, shortjournal = {J. Am. Chem. Soc.}, title = {Orthogonal thiol addition chemistry based on ether acrylates}, volume = {147}, year = {2025}, }
• (2025). Asymmetric total synthesis of (−)-crotonine g and (−)-crotonolide d. JACS, 147(26), 22358--22362. (www)

  @article{ , abstract = {The first enantioselective total syntheses of crotonine G and crotonolide D are disclosed. The synthetic approach employs a SmI 2 mediated ketyl radical cyclization to form the highly congested quaternary carbon at the center of these complex molecules. Following the furan introduction, the core structure of the natural product is constructed via oxidative olefin cleavage to install the unusual C-19 and C-20 oxidation. Finally, palladium-catalyzed carbonylation, furan oxidation and acid mediated condensation/epimerization complete the synthesis.}, archive = {J_JACS}, author = {Hao Yu and Yutaro Hatano and Peng-Jui Chen and Scott C. Virgil and Brian M. Stoltz}, doi = {10.1021/jacs.5c07585}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22358--22362}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric total synthesis of (−)-crotonine g and (−)-crotonolide d}, volume = {147}, year = {2025}, }
• (2025). Net oxidative addition of h2 to {MII}2+ (M = pd, pt) by heterolysis and protic rebound. JACS, 147(26), 22351--22357. (www)

  @article{ , abstract = {Electrophilic transition metal complexes like {M II (EtXantphos) 2 } 2+ (M II = Pd II , Pt II ) heterolyze H 2 into a hydride-associated electrophile {H–M II (EtXantphos) 2 } + and a proton, which typically associates to an added base (or basic ligand). For {H–M II (EtXantphos) 2 } + , the metal can be the most basic site in the system, which results in a product that is indistinguishable from oxidative addition {(H) 2 M IV (EtXantphos) 2 } 2+ . By considering the kinetics and thermodynamics of each elementary step – initial heterolysis, followed by a subsequent return of the heterolyzed proton – we suggest that oxidative addition products may be underrepresented tautomers in heterolytic pathways. The gained understanding was used to characterize the first (di)hydride of Pd IV , generated by formal oxidative addition of H 2 to Pd II .}, archive = {J_JACS}, author = {Nisha Rao and Jonathan L. Kuo}, doi = {10.1021/jacs.5c07140}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22351--22357}, shortjournal = {J. Am. Chem. Soc.}, title = {Net oxidative addition of h2 to {MII}2+ (M = pd, pt) by heterolysis and protic rebound}, volume = {147}, year = {2025}, }
• (2025). Catalytic asymmetric reactions of alkyl alkynyl ketimines: A versatile approach to chiral α-trialkyl amines. JACS, 147(26), 22344--22350. (www)

  @article{ , abstract = {Chiral α-tertiary amine motifs exist in a variety of drugs and bioactive natural products. Therefore, considerable efforts have been devoted to the synthesis of chiral α-tertiary amines. Although chiral α-trialkyl amines are structurally most diverse and synthetically most important among α-tertiary amines, catalytic asymmetric methods toward these chiral amines remain extremely limited. Here, we report a new method for the catalytic asymmetric synthesis of chiral α-tertiary propargyl amines, which was realized by a chiral ammonium salt-catalyzed reaction of alkynyl ketimines with enals and enones. This reaction exhibited broad substrate tolerance with respect to variations on both alkynyl ketimines and enals, producing a diverse range of chiral α,α-dialkyl propargyl amines with either α- or α,β-stereocenters. Additionally, these chiral amines could be readily transformed into chiral α-trialkyl amines, which were especially challenging to synthesize by existing methods. We anticipate that this method could provide a broadly useful approach for the asymmetric synthesis of chiral α-tertiary amines.}, archive = {J_JACS}, author = {Chao Fei and Xiang-Lei Han and Yang Yu and Yongwei Wu and Zhongyue Lu and Zhe Li and Jisheng Luo and Li Deng}, doi = {10.1021/jacs.5c06976}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22344--22350}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic asymmetric reactions of alkyl alkynyl ketimines: A versatile approach to chiral α-trialkyl amines}, volume = {147}, year = {2025}, }
• (2025). Initiation-confined holographic photopolymerization under visible light. JACS, 147(26), 22335--22343. (www)

  @article{ , abstract = {Holographic photopolymerization provides a robust approach for the advanced manufacturing of structurally ordered devices. However, photogenerated radicals in bright regions are prone to cross-regional diffusion and induce unwanted polymerizations in dark regions, making efficient holographic manufacturing exceedingly challenging. Herein, we report a breakthrough by spatially confining the initiation function, enabling the unprecedentedly rapid formation of predesigned submicron-ordered grating structures within merely 0.75 s under visible light holographic exposure. Theoretical computations attribute the success of this initiation-confined approach to orders of magnitude larger reaction rate constants of initiation than propagation. This approach is highly versatile, facilitating the fabrication of both transmission- and reflection-type volume holographic grating structures starting from various reaction systems, and the refractive index modulation can be as high as 0.10, enabling ultraefficient manufacturing of waveguide combiners for high-fidelity near-eye AR displays.}, archive = {J_JACS}, author = {Jie Chen and Wei Wei and Haiyan Peng and Mingli Ni and Hongxi Guo and Dengfu Lu and Yonggui Liao and Xingping Zhou and Zhong’an Li and Xiaolin Xie}, doi = {10.1021/jacs.5c06053}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22335--22343}, shortjournal = {J. Am. Chem. Soc.}, title = {Initiation-confined holographic photopolymerization under visible light}, volume = {147}, year = {2025}, }
• (2025). Nitrite causes nitrosative stress to iron sulfur clusters. JACS, 147(26), 22329--22334. (www)

  @article{ , abstract = {Nitric oxide (NO), produced by nitrite reductases or nitric oxide synthases, performs vital roles in signaling and the immune response. Iron sulfur (FeS) clusters are known targets for NO induced degradation, serving as sensors to trigger cellular responses. However, this FeS reactivity is proposed as NO specific, with no demonstrated reactivity toward nitrite, a soluble NO storage molecule. We demonstrate that synthetic FeS clusters supported by various ligands undergo facile nitrosylation by nitrite in the presence of a reductant, evidencing the nitrite reductase reactivity for FeS clusters. Moreover, a mononitrosylated Fe 4 S 4 cluster, [tempS 3 Fe 4 S 4 (NO)] 2– , can be readily synthesized by this approach, enabling further investigation into the FeS cluster repair and decomposition under NO induced oxidative stress.}, archive = {J_JACS}, author = {Subhadeep Bera and Arijeet Ghude and Vincent J. Catalano and Jean-Marie Mouesca and Ricardo García-Serres and Leslie J. Murray}, doi = {10.1021/jacs.5c05636}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22329--22334}, shortjournal = {J. Am. Chem. Soc.}, title = {Nitrite causes nitrosative stress to iron sulfur clusters}, volume = {147}, year = {2025}, }
• (2025). Mechanistic studies of catalytic o2-to-H2O2 conversion at a single cobalt site. JACS, 147(26), 22322--22328. (www)

  @article{ , abstract = {Understanding oxygen reduction reaction (ORR) mechanisms is of fundamental significance. Although metal hydrosuperoxos and metal hydroperoxos are considered to be key intermediates in ORR, these two species as well as their reaction natures are poorly understood because they are highly active with various reaction pathways. Herein, we report on the mechanistic studies of the ORR with Co II porphyrin 1 . Complex 1 is selective for catalytic O 2 -to-H 2 O 2 conversion with decamethylferrocene as the reductant and HClO 4 as the proton source. By employing the molecular pocket of 1 to stabilize the O 2 -adducts, we characterized Co III -hydrosuperoxo, [Co III (O 2 • H)] + , and Co III -hydroperoxo, [Co III (O 2 H)], studied the one-electron reduction of [Co III (O 2 • H)] + to generate [Co III (O 2 H)], and revealed a proton transfer–electron transfer (PTET) pathway for [Co III (O 2 H)] to generate Co II and H 2 O 2 . This work is therefore significant to confirm the key role of [Co III (O 2 • H)] + and [Co III (O 2 H)] in the catalytic ORR cycle and to establish a PTET pathway of [Co III (O 2 H)] to give H 2 O 2 .}, archive = {J_JACS}, author = {Tao Liu and Jia Meng and Haonan Qin and Mengchun Zhang and Ning Sun and Benxing Mei and Huamin Li and Xue-Peng Zhang and Jun Li and Rui Cao}, doi = {10.1021/jacs.5c04848}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22322--22328}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic studies of catalytic o2-to-H2O2 conversion at a single cobalt site}, volume = {147}, year = {2025}, }
• (2025). C–H functionalization via single atom metathesis of C–H and C–X bonds. JACS, 147(26), 22314--22321. (www)

  @article{ , abstract = {Metathesis and reversible catalytic reactions are fundamentally intriguing and powerful tools in modern synthetic chemistry. While most reversible catalytic reactions are predicated on breaking and forming reactive functional groups, the ability to leverage the C–H bond as a functional group in metathesis reactions has proved to be exceptionally challenging. Here, we develop a C–H/C–X metathesis reaction through a radical swapping protocol where hydrogen and halogen are traded between molecules via reversible hydrogen atom transfer (HAT) and halogen atom transfer (XAT) that allows for mild C–H halogenation. The reversibility of this process allows for the selective dehalogenation of polyhalogenated products to form monohalogenated products. Leveraging the reversibility of this process, halogenated organic pollutants can also serve as halogen sources for C–H halogenation. In a broader context, this work establishes that incorporating reversible metathesis logic in C–H bond functionalization can provide complementary advantages in synthetic strategies.}, archive = {J_JACS}, author = {Tanner C. Jankins and Barnabé Berger and Françoise A. Aouane and Sergio Barbeira-Arán and Christophe Didier and Bettina Hürlimann and Claudius Zimmer and Bill Morandi}, doi = {10.1021/jacs.5c04754}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22314--22321}, shortjournal = {J. Am. Chem. Soc.}, title = {C–H functionalization via single atom metathesis of C–H and C–X bonds}, volume = {147}, year = {2025}, }
• (2025). Tellurium-induced noble-metal reactivity in CO2 hydrogenation catalysts. JACS, 147(26), 22309--22313. (www)

  @article{ , abstract = {The reverse water–gas shift (RWGS) reaction is a pivotal industrial process that is central to CO 2 utilization. It typically relies on rare platinum group metal catalysts and high temperatures (over 1000 °C). Here, we show that tellurium switches the reactivity of classical methanation-active transition metals (e.g., Co, Ni, Ru, Rh) to selectively promote the RWGS reaction at low temperatures (<450 °C). Te-doped Co and Ni on titania achieve near-equilibrium CO 2 conversions with high stability and CO selectivities exceeding 98%, rivaling those of Pt-based systems. Characterization reveals stable alloy formation that suppresses methanation and favors CO desorption. These findings position transition-metal tellurides as alternative catalysts for sustainable CO 2 conversion.}, archive = {J_JACS}, author = {Xiaoyu Zhou and Colin Hansen and Daniel Isler and Wei Zhou and James Paterson and Jamie Southouse and Christophe Copéret}, doi = {10.1021/jacs.5c04185}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22309--22313}, shortjournal = {J. Am. Chem. Soc.}, title = {Tellurium-induced noble-metal reactivity in CO2 hydrogenation catalysts}, volume = {147}, year = {2025}, }
• (2025). Aryne polymerization enabled by pyrazole-induced nucleophilic aromatic substitution. JACS, 147(26), 22302--22308. (www)

  @article{ , abstract = {Despite the widespread use of arynes in organic synthesis, their polymerization remains a significant challenge due to the intrinsic instability and short lifetime of aryne intermediates. Here, we report a method for aryne polymerization using a simple organonucleophile, N -arylpyrazole, as an initiator. This polymerization proceeds via a unique pyrazole-induced nucleophilic aromatic substitution mechanism, facilitating the formation of poly( ortho -arylene)s with narrow polydispersity and well-defined structures. The high chemical stability of N -arylpyrazole allows for a broader scope of applications, including aryne polymerization at the side chain of preformed polymers (graft polymerization) and the synthesis of star-shaped poly( ortho -arylene)s.}, archive = {J_JACS}, author = {Hayato Fujimoto and Shisato Yamamura and Mamoru Tobisu}, doi = {10.1021/jacs.5c03980}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22302--22308}, shortjournal = {J. Am. Chem. Soc.}, title = {Aryne polymerization enabled by pyrazole-induced nucleophilic aromatic substitution}, volume = {147}, year = {2025}, }
• (2025). Natural circular dichroism beyond chirality. JACS, 147(26), 22296--22301. (www)

  @article{ , abstract = {While natural optical activity in crystals belonging to specific achiral point groups has been predicted by symmetry arguments, birefringence hampers its measurement in the UV–vis energy ranges. Here we use X-rays to reveal natural circular dichroism at the K-edges of copper and iron coordination salts crystallizing in the achiral point groups 4̅2 m and 4̅ respectively. The experimental signals follow the angular dependence exactly as predicted by the symmetry of the point groups. In addition, an angular phase shift was observed for 4̅, which is explained by the crystalline a and b axes not being determined by the crystal point group but by the translation operations of the space group.}, archive = {J_JACS}, author = {Elen Duverger-Nédellec and Alessandro De Frenza and Patrick Rosa and Nazanin Kordestani and Marie-Anne Arrio and Amélie Juhin and Philippe Sainctavit and Nathan J. Yutronkie and Fabrice Wilhelm and Andrei Rogalev and Elizabeth A. Hillard}, doi = {10.1021/jacs.5c03574}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22296--22301}, shortjournal = {J. Am. Chem. Soc.}, title = {Natural circular dichroism beyond chirality}, volume = {147}, year = {2025}, }
• (2025). An α-helically folded α-aminoisobutyric acid (Aib) oligomer that assembles into a Metal–Peptide superhelical nanotube. JACS, 147(26), 22290--22295. (www)

  @article{ , abstract = {α,α-Disubstituted α-amino acids such as α-aminoisobutyric acid (Aib), in their polymeric structures, are known to form a 3 10 -helical conformation rather than an α-helical conformation, which is usually adopted by polymeric α-monosubstituted α-amino acids. Even α-helically folded Aib oligomers are unprecedented, although they have been predicted by theoretical calculations. In the present paper, we report the first α-helically folded Aib oligomer found in the course of our study on the construction of a metal–peptide framework, Aib MOF-1. This MOF was synthesized by Zn 2+ -mediated complexation of a pyridyl-functionalized Aib hexamer, Py-Aib 6 -Py, and 5-nitroisophthalate (nip 2– ). Single crystal X-ray diffraction of Aib MOF-1 ([Zn(nip)(Py-Aib 6 -Py)] n ) revealed that Py-Aib 6 -Py in Aib MOF-1 carried a C═O i → NH i+4 hydrogen bonding array characteristic of α-helices, which is distinct from Py-Aib 6 -Py alone adopting a 3 10 -helical conformation with a C═O i → NH i+3 hydrogen bonding array. The α-helical Py-Aib 6 -Py units in Aib MOF-1 assembled into a superhelical nanotubular architecture with a porous framework. When just the nitro group of the coligand nip 2– was changed to a tert -butyl group, an MOF ( Aib MOF-2) with a completely different structure formed, where the constituent Py-Aib 6 -Py units adopted only the 3 10 -helical conformation, just like Py-Aib 6 -Py in its crystalline structure.}, archive = {J_JACS}, author = {Wei Yuan and Jenny Pirillo and Yuh Hijikata and Takuzo Aida and Hiroshi Sato}, doi = {10.1021/jacs.5c03534}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22290--22295}, shortjournal = {J. Am. Chem. Soc.}, title = {An α-helically folded α-aminoisobutyric acid (Aib) oligomer that assembles into a Metal–Peptide superhelical nanotube}, volume = {147}, year = {2025}, }
• (2025). Subcellular analysis of fatty acid metabolism using organelle-selective click chemistry. JACS, 147(26), 22284--22289. (www)

  @article{ , abstract = {The structural diversity of the fatty acids esterified in organellar membrane lipids is thought to confer the characteristic physiological properties of the membranes. However, the abundance profiles of fatty acid derivatives are still poorly characterized at organelle-level spatial resolution. Here, we have developed a technology for organelle-specific labeling and quantitative analysis of fatty acid derivatives involving the metabolic incorporation of azide fatty acids and organelle-localizing clickable dyes. This approach was used to investigate palmitate- and oleate-derived lipids in different organelle membranes. The relative abundances of fatty acid-containing lipids were found to differ depending on the organelle and the structure of the fatty acid. In addition, organelle-specific temporal variations in fatty acid derivatives were revealed that are difficult to detect using conventional lipid analysis.}, archive = {J_JACS}, author = {Takami Kimura and Seita Kawamoto and Alma Fujisawa and Mao Yoshida and Yuying Shen and Masaki Tsuchiya and Tomonori Tamura and Itaru Hamachi}, doi = {10.1021/jacs.5c02871}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22284--22289}, shortjournal = {J. Am. Chem. Soc.}, title = {Subcellular analysis of fatty acid metabolism using organelle-selective click chemistry}, volume = {147}, year = {2025}, }
• (2025). Metal-bound heteroatom radicals: Advancing site-selective C–H functionalization. JACS, 147(26), 22269--22283. (www)

  @article{ , abstract = {Selective transformation of C–H bonds represents a frontier research area in synthetic chemistry. While the high reactivity of radicals provides an alternative and efficient pathway for C–H bond functionalization, controlling their selectivity─particularly in processes such as site-selective hydrogen atom abstraction (HAA)─remains a long-standing and unresolved challenge in radical chemistry, largely due to the lack of effective regulation strategies. This review deliberately avoids a comprehensive discussion of the field’s current state or landmark discoveries in C–H functionalization. Instead, by focusing on recent advances in metal-catalyzed, highly site-selective C–H bond transformations, this Perspective elucidates how metal-bound radicals enable precise hydrogen abstraction for targeted functionalization. This emerging paradigm offers innovative strategies for regulating radical behavior, potentially unlocking novel radical-mediated selective transformations─including but not limited to the precise functionalization of C–H bonds.}, archive = {J_JACS}, author = {Jiayuan Li and Tobias Blockhaus and Guosheng Liu}, doi = {10.1021/jacs.5c07456}, journal = {Journal of the American Chemical Society}, month = {7}, number = {26}, pages = {22269--22283}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal-bound heteroatom radicals: Advancing site-selective C–H functionalization}, volume = {147}, year = {2025}, }
• (2025). Correction to “Self-adaptive release of stem cell-derived exosomes from a multifunctional hydrogel for accelerating MRSA-infected diabetic wound repair”. JACS, 147(25), 22268. (www)

  @article{ , archive = {J_JACS}, author = {Xiang Wang and Jiantong Dong and Jingjing Kang and Xujing Chen and Xiaoqin Hong and Jiaming Chen and Wei Du and Hong Cai and Dingbin Liu}, doi = {10.1021/jacs.5c08198}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22268}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Self-adaptive release of stem cell-derived exosomes from a multifunctional hydrogel for accelerating MRSA-infected diabetic wound repair”}, volume = {147}, year = {2025}, }
• (2025). Ether rhodamines with enhanced hydrophilicity, fluorogenicity, and brightness for super-resolution imaging. JACS, 147(25), 22253--22267. (www)

  @article{ , abstract = {Rhodamine dyes are widely used fluorophores in super-resolution fluorescence imaging due to their exceptional optical properties and “aggregation-disaggregation” induced fluorogenic activation. However, their excessive lipophilicity often reduces brightness in aqueous environments and causes off-target staining, limiting their effectiveness in high-resolution imaging. To address these challenges, we introduce an ether-decorated N-terminal modification strategy for rhodamine and silicon-rhodamine (Si-rhodamine), replacing conventional N -alkyl groups. The ether chains enhance water solubility, decrease aggregate size, and improve fluorogenicity across a wide concentration range. Their flexible, hydrophilic structure forms a protective shield around the xanthene core, minimizing dye-water interactions and reducing fluorescence quenching. Additionally, the inductive effect of the ether chains decreases the electron-donating strength of the amino groups, suppressing quenching caused by twisted intramolecular charge transfer (TICT). These modifications collectively increase the quantum yields of ER and ESiR in water from 0.35 and 0.19 (for tetraethyl-substituted analogs) to 0.70 and 0.41, respectively. Probes derived from ER and ESiR exhibit outstanding fluorogenicity, enhanced signal-to-noise ratios, and improved resolution in complex aqueous environments, demonstrating superior performance in advanced super-resolution imaging techniques such as structured illumination microscopy (SIM), stimulated emission depletion (STED) microscopy, and single molecule localization microscopy (SMLM). This work introduces a rational fluorophore design strategy that enhances aqueous brightness, minimizes nonspecific staining, and enables high-contrast, high-resolution imaging across multiple super-resolution modalities.}, archive = {J_JACS}, author = {Xiangning Fang and Qinglong Qiao and Zhifeng Li and Hao-Kai Li and Yalin Huang and Dongjie Hou and Jie Chen and Ning Xu and Kai An and Wenchao Jiang and Yi Tao and Pengjun Bao and Yinchan Zhang and Zhimin Wu and Xiaogang Liu and Zhaochao Xu}, doi = {10.1021/jacs.5c08833}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22253--22267}, shortjournal = {J. Am. Chem. Soc.}, title = {Ether rhodamines with enhanced hydrophilicity, fluorogenicity, and brightness for super-resolution imaging}, volume = {147}, year = {2025}, }
• (2025). Simple strategies to quantify and control polymer threading into micropores. JACS, 147(25), 22245--22252. (www)

  @article{ , abstract = {Blends of polymers with microporous particles are essential to many modern technologies, including membranes, catalysts, nanocomposites, and porous liquids. However, the design space and performance of these technologies are substantially limited because it is difficult to quantify and control how polymers thread into the particles’ sub-2 nm micropores. Here, we address these issues with two new strategies. First, we show that traditional solution-state NMR can be used to directly monitor polymer chains and quantify their diffusivities as they thread into microporous particles from the surrounding solvent. This label-free, high-resolution, in situ monitoring is possible because once a polymer chain enters the particles, its NMR signal becomes invisible due to excessively slow molecular tumbling. Second, we show that threading rates can be tuned across at least 6 orders of magnitude─without changing the particle size, micropore topology, or polymer chain length─by rationally modifying the particles’ external surface with different coatings that form via noncovalent self-assembly after simple mixing. The strategies described here to quantify and control polymer threading are simple and generalizable to a wide range of polymer/particle combinations, solvents, temperatures, and concentrations; thus, they may spark advances in diverse technological and fundamental areas that rely on blends of polymers with microporous particles.}, archive = {J_JACS}, author = {Supreet Kaur and Benjamin Lesea-Pringle and Surya Marjit and Hyukhun Hong and Aqib Rahman and Boran Ma and Denize C. Favaro and Christopher DelRe}, doi = {10.1021/jacs.5c07556}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22245--22252}, shortjournal = {J. Am. Chem. Soc.}, title = {Simple strategies to quantify and control polymer threading into micropores}, volume = {147}, year = {2025}, }
• (2025). Criegee intermediates compete well with OH as a cleaning agent for atmospheric amides. JACS, 147(25), 22237--22244. (www)

  @article{ , abstract = {Elucidating the chemical kinetics of stabilized Criegee intermediates (sCIs) in the atmosphere is critically important for climate modeling. Here, we report a class of very rapid bimolecular reactions of two sCIs, namely, CH 2 OO and syn -CH 3 CHOO, with amides. We used electronic structure calculations and kinetics calculations to elucidate a universal mechanism by which the oxygen atom of the carbonyl group in an amide is added to the carbon atom of the COO group in the sCI with simultaneous transfer of the amide hydrogen to the terminal oxygen atom of the carbonyl oxide of the sCI. The barriers for the mechanism are submerged below reactants by ∼9 kcal/mol, which means that the tight transition state is not the rate-determining step, and the rate constants are determined by loose free energy bottlenecks between the reactants and the precursor complexes. We calculate the rate constants due to these loose and barrierless transition states by variable-reaction-coordinate variational transition-state theory. We find that bimolecular reactions of sCIs with amides are very rapid, with rate constants 1 to 5 × 10 –10 cm 3 molecule –1 s –1 , which is a factor of 2 faster than the rate constants of carboxylic acids with sCIs and 10 2 faster than the rate constants of OH reactions with amides. This has the consequence that, under a wide range of conditions, sCIs are the major sink for atmospheric amides, in contrast to the usual assumption that OH radicals are the dominant sinks.}, archive = {J_JACS}, author = {Bo Long and Chaolu Xie and Donald G. Truhlar}, doi = {10.1021/jacs.5c07439}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22237--22244}, shortjournal = {J. Am. Chem. Soc.}, title = {Criegee intermediates compete well with OH as a cleaning agent for atmospheric amides}, volume = {147}, year = {2025}, }
• (2025). Wavelength-orthogonal optodynamics to overcome the statistical limitations of interfacial photopolymerizations. JACS, 147(25), 22228--22236. (www)

  @article{ , abstract = {Presently, error correction of covalent bonds for the controlled synthesis of ordered multidimensional materials is largely restricted to thermal methods, which oftentimes require harsh reaction conditions. This limitation affects interfacial applications, for example, in emulsions that are central to many industrial applications in energy, healthcare, or foods. Herein, we introduce wavelength-orthogonal optodynamics, which enables photoinduced error correction and provides a mild alternative to conventional dynamic covalent chemistry. We demonstrate that the dynamic interplay between two wavelengths (440 and 370 nm) can be harnessed for the preferential cleavage of suboptimal linkages to induce major structural improvements in interfacial polymer shells of emulsions. This overwrites the inherent statistical limitations of conventional photopolymerizations, which traditionally result in highly heterogeneous and defective structures. Overall, the work exemplifies the opportunities of wavelength-orthogonal optodynamic chemistry for the generation and modification of organic materials and highlights the prospect of it to areas previously inaccessible to dynamic covalent synthesis.}, archive = {J_JACS}, author = {Georgios Toupalas and Timothy M. Swager}, doi = {10.1021/jacs.5c07305}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22228--22236}, shortjournal = {J. Am. Chem. Soc.}, title = {Wavelength-orthogonal optodynamics to overcome the statistical limitations of interfacial photopolymerizations}, volume = {147}, year = {2025}, }
• (2025). Unveiling structure-dynamic processes in crystals of 1D Cd(II) coordination polymers during the elastic flexible events. JACS, 147(25), 22219--22227. (www)

  @article{ , abstract = {Flexibility, an intriguing yet far from being a commonly observed property of single crystals, is highly sought after as it enables crystal application in innovative technologies. Here, we report on anisotropically elastic single crystals of two novel 1D coordination polymers (CPs) featuring bridging halides (Cl ( 1 ); Br ( 2 )) and pyrazinamide ligands that enabled the determination of the bending mechanism and exploration of their mechanical properties. The mechanism identified distinctly differs from the mechanisms of elastically flexible molecular crystals subjected to mechanical stress and 1D plastically deformable crystals under quasi-hydrostatic pressure, the mechanisms of reconfigurable crystals uncovered thus far. By mapping the structural modification across the bent crystal 1 using microfocus synchrotron radiation, we found that both the 1D structural spine (controlling the distance between the organic ligands) and the ligands themselves adapt to the changes in external conditions. While the spine expands through the modifications of the bridging angles, causing a consequent enlargement of the metal···metal distances as going from the interior to the exterior of the bend, the ligands rotate toward linearity with the bending face. In addition, the extent of changes along the two other crystal axes is brought into a connection with the relative energies of the weakest links and crystal stiffness in those directions.}, archive = {J_JACS}, author = {Marijana Đaković and Mateja Pisačić and Mladen Borovina and Ivan Kodrin and Adriana Kenđel and Tea Frey}, doi = {10.1021/jacs.5c07191}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22219--22227}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling structure-dynamic processes in crystals of 1D Cd(II) coordination polymers during the elastic flexible events}, volume = {147}, year = {2025}, }
• (2025). Enantiocontrolled azetidine library synthesis via strain-release functionalization of 1-azabicyclobutanes. JACS, 147(25), 22209--22218. (www)

  @article{ , abstract = {A simple, modular, and programmable approach to access complex stereopure azetidines through strain-release functionalization is disclosed. The synthetic methods developed enable the parallel synthesis of stereodefined azetidines that would be otherwise laborious to produce. Given the privileged nature of these structures, a set of stereoprobes for use in activity-based protein profiling was prepared and evaluated, revealing proteins in human cancer cells, which were liganded with clear stereo- and chemo-selectivity.}, archive = {J_JACS}, author = {Michael Bielecki and Molhm Nassir and Hayden A. Sharma and Nathanyal J. Truax and Nicholas Raheja and Ty M. Thompson and Tamara El-Hayek Ewing and Bruno Melillo and Benjamin F. Cravatt and Phil S. Baran}, doi = {10.1021/jacs.5c07227}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22209--22218}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantiocontrolled azetidine library synthesis via strain-release functionalization of 1-azabicyclobutanes}, volume = {147}, year = {2025}, }
• (2025). Open-shell species enabled diverse deoxygenative cyanofunctionalization of aldehydes under metal-free conditions. JACS, 147(25), 22201--22208. (www)

  @article{ , abstract = {The conversion of carbonyl compounds to functionalized nitriles enables both one-carbon homologation and rapid multifunctionalization, especially considering the diverse transformation potential of the cyano group. Herein, by simultaneously introducing a cyano and a suitable C–O activated group into carbonyl compounds, we successfully achieved an efficient deoxygenative cyanofunctionalization of unactivated aliphatic aldehydes via a free radical process. Due to the unique characteristics of the open-shell species, this protocol can readily facilitate a variety of bond formations to install alkyl ketone, alkenyl, allylic, halo, phosphorus, and sulfur groups. Additionally, a direct deoxygenative cyanation with excellent scope and functional group compatibility was demonstrated under mild conditions. The fact that there is no need for toxic cyanide salts or metal catalysts further enhances the practicality of this simple, modular method to access diverse nitrile compounds, providing an elegant strategy for the late-stage modification of complex molecules.}, archive = {J_JACS}, author = {Wenhao Xu and Xiaoqiang Wu and Yuanqiang Chen and Tao XU}, doi = {10.1021/jacs.5c07165}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22201--22208}, shortjournal = {J. Am. Chem. Soc.}, title = {Open-shell species enabled diverse deoxygenative cyanofunctionalization of aldehydes under metal-free conditions}, volume = {147}, year = {2025}, }
• (2025). Modulating solid-state photocycloaddition kinetics via ligand substituents and crystal structures in one-dimensional coordination polymers. JACS, 147(25), 22192--22200. (www)

  @article{ , abstract = {Understanding the kinetics of solid-state chemical reactions is critical for elucidating reaction mechanisms and enabling the rational design of functional materials. However, such investigations are often impeded by limited molecular mobility, restricted reactant interactions, and complex nucleation phenomena. In this study, we employ one-dimensional crystalline coordination polymers (CPs) as structurally ordered platforms to investigate the kinetics of [2 + 2] photocycloaddition reactions of embedded alkene substrates. By integrating nuclear magnetic resonance, fluorescence spectroscopy, laser scanning confocal microscopy, and theoretical calculations, we demonstrate that the electronegativity of substituents (−F, –Cl, –Br, –I) on carboxylate ligands strongly modulates reaction rates, with more electronegative groups accelerating the kinetics. Additionally, single-crystal CPs exhibit significantly enhanced reaction rates compared to stacked crystals, attributed to uniform light penetration and reduced spatial inhomogeneity. These findings position CPs as robust model systems for probing heterogeneous reaction kinetics and offer a new framework for understanding and optimizing olefin reactivity in solid-state environments.}, archive = {J_JACS}, author = {Yong Wang and Qiaoqiao Zhang and Xin-Yi Huang and Qi Liu and Jian-Ping Lang}, doi = {10.1021/jacs.5c06962}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22192--22200}, shortjournal = {J. Am. Chem. Soc.}, title = {Modulating solid-state photocycloaddition kinetics via ligand substituents and crystal structures in one-dimensional coordination polymers}, volume = {147}, year = {2025}, }
• (2025). Dinitrogen activation and cyanide release by the gas-phase cluster anions InNbC2–: Synergistic effects of the p-block indium and the d-block niobium. JACS, 147(25), 22185--22191. (www)

  @article{ , abstract = {Transforming N 2 into valuable C–N bond-containing products at room temperature is of great importance, yet it remains highly challenging because of the inherent inertness of N 2 and the complexity in designing effective catalytic active sites. In this study, we investigate the structure and reactivity of InNbC 2 – using mass spectrometry, photoelectron spectroscopy, and theoretical calculations. Remarkably, at room temperature, InNbC 2 – can completely cleave the N≡N triple bond to form two C–N bonds in the intermediate product Nb(CN) 2 – , accompanied by the release of the In atom. Subsequently, one cyanide (CN) molecule is liberated during the oxidation reaction of Nb(CN) 2 – with O 2 . Comparative analysis with the inert Nb 2 C 2 – cluster reveals two critical roles of the In atom in the N 2 reduction process: (1) the In atom enhances the negative charge on the Nb site, facilitating N 2 adsorption and reduction. (2) The In atom enables the flexible formation and cleavage of the In–Nb bond during the reaction. In this N 2 transformation, the metal atoms act as electron reservoirs, and the C 2 unit is another important electron donor during C–N bond generation. The formation of strong Nb–O bonds provides the driving force for releasing cyanide as the final product in the subsequent oxidation reaction. This work presents the first gas-phase example of a heteronuclear bimetallic anion, InNbC 2 – , capable of releasing cyanide as a product under thermochemical conditions. Our findings propose a novel strategy for designing N 2 transformation catalysts by integrating p-block main group metals with d-block transition metals, offering new insights into the activation and functionalization of N 2 .}, archive = {J_JACS}, author = {Xiao-Wang Li and Feng-Xiang Zhang and Xi-Guan Zhao and Qing-Yu Liu and Sheng-Gui He and Jia-Bi Ma}, doi = {10.1021/jacs.5c06920}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22185--22191}, shortjournal = {J. Am. Chem. Soc.}, title = {Dinitrogen activation and cyanide release by the gas-phase cluster anions InNbC2–: Synergistic effects of the p-block indium and the d-block niobium}, volume = {147}, year = {2025}, }
• (2025). Spin–Vibronic coupling enhanced intersystem crossing beyond el-sayed restrictions. JACS, 147(25), 22176--22184. (www)

  @article{ , abstract = {Intersystem crossing is a crucial photochemical process driven by spin–orbit coupling. With intersystem crossing at the forefront of photochemical advancements, there is significant motivation to design molecular systems that can dynamically modulate spin–orbit coupling strength. This work seeks to understand the unusually rapid intersystem crossing rates that occur in select organic molecular systems that do not contain heavy atoms to induce spin–orbit coupling. This work presents a case where intersystem crossing is enabled by symmetry-perturbation rather than through the lifting of El-Sayed restrictions. Computational results indicate that the intersystem crossing between the lowest-lying S ( n π*) and T (ππ*) excited states of dibutylaniline thiosquaraine can only occur through a symmetry-perturbing spin–vibronic mechanism. Our analysis helps provide new insight into how synthetic chemists, materials scientists, and chemical engineers might incorporate symmetry considerations in designing new heavy-atom-free molecular systems with a propensity for efficient intersystem crossing.}, archive = {J_JACS}, author = {Can Liao and Cecily Rosenbaum and Alexis M. Glaudin and Maxwell Taub and Rahoul Banerjee Ghosh and Sarah Pristash and Cody W. Schlenker and Xiaosong Li}, doi = {10.1021/jacs.5c06949}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22176--22184}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin–Vibronic coupling enhanced intersystem crossing beyond el-sayed restrictions}, volume = {147}, year = {2025}, }
• (2025). A nucleic acid prodrug that activates mitochondrial respiration, promotes stress resilience, and prolongs lifespan. JACS, 147(25), 22161--22175. (www)

  @article{ , abstract = {Mitochondrial dysfunction caused by aging leads to decreased energy metabolism, resulting in functional decline and increased frailty in multiple tissues. Strategies for protecting and activating mitochondria under stressful conditions are required to suppress aging and age-related diseases. However, it is challenging to develop drugs capable of boosting mitochondrial respiration and compensating for the reduced intracellular adenosine triphosphate (ATP) levels. In this study, we developed a prodrug that stimulates the metabolism of intracellular adenine nucleotides (AXP: adenosine monophosphate (AMP), adenosine diphosphate (ADP), and ATP). It enhances AMP-activated protein kinase activity, fatty acid oxidation, oxidative stress resistance, and mitochondrial respiration, thereby increasing the intracellular ATP levels. Furthermore, this prodrug markedly extended the lifespan of Caenorhabditis elegans . AXP-driven stimulation of cellular energy metabolism proposed herein represents a novel geroprotective strategy and paves the way for the development of bioenergetic-molecule therapeutics.}, archive = {J_JACS}, author = {Takahisa Anada and Michiharu Kawahara and Taisei Shimada and Ryotaro Kuroda and Hidenori Okamura and Daiki Setoyama and Fumi Nagatsugi and Yuya Kunisaki and Eriko Kage-Nakadai and Shingo Kobayashi and Masaru Tanaka}, doi = {10.1021/jacs.5c06772}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22161--22175}, shortjournal = {J. Am. Chem. Soc.}, title = {A nucleic acid prodrug that activates mitochondrial respiration, promotes stress resilience, and prolongs lifespan}, volume = {147}, year = {2025}, }
• (2025). Combining theory and experiment to map the atomic-level Structure–Energy pathways of adsorbate-mediated phase changes in a cooperatively flexible Metal–Organic framework. JACS, 147(25), 22141--22160. (www)

  @article{ , abstract = {An important subclass of metal–organic frameworks (MOFs) exhibits cooperative flexibility, wherein individual crystallites undergo global structural phase changes in response to external stimuli. Where cooperative flexibility results in reversible changes between crystalline states of distinct accessible porosity, these frameworks can exhibit rare yet desirable behaviors that cannot be explained by local dynamics alone. Yet, the chemical and structural origins of cooperative flexibility and how frameworks undergo these reversible phase changes at the atomic level remain poorly understood. Deliberate design for specific applications is therefore exceedingly difficult, and there is great impetus to develop a fundamental understanding of this phenomenon. Here, an effective and widely accessible computational approach is developed, which is designed to provide microscopic resolution via direct comparison to experimental data along the desorption-guided pathway. The strategy is applied to explain the desorption-induced phase change in an experimentally well-characterized framework, CdIF-13 ( sod -Cd(benzimidazolate) 2 ), where experiment alone was unable to resolve the atomistically detailed phase change landscape. Our findings reveal that the cooperative phase change pathways are adsorbate dependent with thermodynamics of intermediate structural states dictated by a nuanced interplay of ligand orientation, skeletal symmetry, and modes of surface adsorption. The results reveal that this isotropically flexible framework is “chaperoned” through a complex energy landscape by specific adsorbates, revealed by the reported computational approach with atomic-level insight and validated by experimentally determined structures. Thus, this work facilitates both understanding and future design of flexible materials for applications in gas storage, transport, delivery, and separation technologies.}, archive = {J_JACS}, author = {Katherine A. Forrest and Arijit Halder and C. Michael McGuirk and Brian Space}, doi = {10.1021/jacs.5c06728}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22141--22160}, shortjournal = {J. Am. Chem. Soc.}, title = {Combining theory and experiment to map the atomic-level Structure–Energy pathways of adsorbate-mediated phase changes in a cooperatively flexible Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Enhanced nanoconfinement of copper-organic interfaces within phthalocyanine frameworks for selective electroreduction of CO to acetate. JACS, 147(25), 22132--22140. (www)

  @article{ , abstract = {Acetate is an essential raw material in the chemical industry, supporting sustainable processes and efficient carbon utilization, driving interest in electrochemical CO-to-acetate conversion. However, this process is limited by catalyst instability and the complexity of the reaction pathway, making precise control difficult. Herein, we engineer nanoconfined copper-organic interfaces within a series of nucleophilic substituted heterocyclic copper phthalocyanine covalent organic frameworks (CuPc-COFs) with AA’ stacking configuration to selectively steer CO electroreduction toward acetate. This architecture stabilizes low-coordination Cu clusters─generated via partial reduction of phthalocyanine Cu sites─and fosters synergistic CuPc-Cu cluster interactions, creating an active interfacial microenvironment that enhances acetate selectivity. The optimized CuPc-COF achieves a Faradaic efficiency (FE) of 53.5% for acetate at −0.9 V vs RHE. Operando X-ray absorption spectroscopy (XAS) confirms the in situ formation of highly reactive copper-organic interfaces, while in situ FTIR spectroscopy and DFT calculations reveal that low-coordinated Cu clusters strengthen *CO bridge adsorption (*CO B ) and promote *COCO dimerization. Additionally, heterocyclic linkers provide electron donation, stabilizing the Cu clusters and improving the structural integrity. This work elucidates the critical role of nanoconfined interface engineering in C–C coupling and establishes a design paradigm for advanced CO electroreduction catalysts.}, archive = {J_JACS}, author = {Quanquan Yang and Yaqi Chen and Nengji Liu and Shengxu Li and Mengwei Chen and Wanzhen Zheng and Yubin Fu and Junyi Han and Raul D. Rodriguez and Yang Hou and Tao Zhang}, doi = {10.1021/jacs.5c06660}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22132--22140}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced nanoconfinement of copper-organic interfaces within phthalocyanine frameworks for selective electroreduction of CO to acetate}, volume = {147}, year = {2025}, }
• (2025). Rh-catalyzed asymmetric hydrogenation of 3-amino-4-alkyl/aryl disubstituted maleimides. JACS, 147(25), 22121--22131. (www)

  @article{ , abstract = {A highly efficient Rh-catalyzed asymmetric hydrogenation of rigid cyclic 3-amino-4-alkyl/aryl disubstituted maleimides has been developed for the first time by using 5,5′-bridged axially chiral biaryl diphosphine ligands (BridgePhos), whose dihedral angle can be controlled by modifying the length of the 5,5′-bridging chain. Both 4-aryl and alkyl-substituted substrates exhibit outstanding catalytic behavior using the BridgePhos-Rh catalyst with the most suitable dihedral angle, enabling the construction of chiral disubstituted succinimides with excellent yields (up to 99%) and stereoselectivities (up to 99% ee and >20:1 dr). Mechanistic studies based on the control experiments and DFT calculations indicated that the two added hydrogen atoms of the products originate from two different H 2 molecules and the hydrogenation proceeds via a H 2 σ-bond metathesis pathway for the alkane release in the hydrogenation cycle. This protocol can be performed on a gram-scale with a low catalyst loading (S/C = 5000) and allows stereodivergent access to all four stereoisomers. The resulting hydrogenation products offer several potential transformations, including the first asymmetric catalytic synthesis of moxifloxacin hydrochloride, a novel fluoroquinolone antibiotic developed by Bayer Pharmaceuticals, with high efficiency.}, archive = {J_JACS}, author = {Jianxun Ye and Yicong Luo and Yunnan Xu and Delong Liu and Wanbin Zhang}, doi = {10.1021/jacs.5c06618}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22121--22131}, shortjournal = {J. Am. Chem. Soc.}, title = {Rh-catalyzed asymmetric hydrogenation of 3-amino-4-alkyl/aryl disubstituted maleimides}, volume = {147}, year = {2025}, }
• (2025). Site- and energy-selective low-energy electron emission by X-rays in the aqueous phase. JACS, 147(25), 22115--22120. (www)

  @article{ , abstract = {Low-energy-electron emission from resonant Auger final states via intermolecular Coulombic decay (RA-ICD) has previously been described as a promising scenario for controlling radiation damage for medical purposes, but it has so far only been observed in prototypical atomic and molecular van der Waals dimers and clusters. Here, we report the experimental observation of RA-ICD in an aqueous solution. We show that for solvated Ca 2+ ions, the emission can be very efficiently controlled by tuning the photon energy of exciting X-rays to inner-shell resonances of the ions. Our results provide the next step from demonstrating RA-ICD in relatively simple prototype systems to understanding the relevance and potential applications of ICD in real-life scenarios.}, archive = {J_JACS}, author = {Dana Bloß and Rémi Dupuy and Florian Trinter and Isaak Unger and Noelle Walsh and Gunnar Öhrwall and Niklas Golchert and Gabriel Klassen and Adrian Krone and Yusaku Terao and Johannes H. Viehmann and Lasse Wülfing and Clemens Richter and Tillmann Buttersack and Lorenz S. Cederbaum and Uwe Hergenhahn and Olle Björneholm and Arno Ehresmann and Andreas Hans}, doi = {10.1021/jacs.5c06436}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22115--22120}, shortjournal = {J. Am. Chem. Soc.}, title = {Site- and energy-selective low-energy electron emission by X-rays in the aqueous phase}, volume = {147}, year = {2025}, }
• (2025). Atomic-scale dynamics of five-fold twin mediated coalescence: Pathway-dependent and defect-governed nonclassical growth mechanisms. JACS, 147(25), 22104--22114. (www)

  @article{ , abstract = {Defective crystals with distinct properties have been discovered in many systems. However, the growth mechanism of defective crystals is still poorly understood. Here, using a 5-fold twinned gold (Au) nanocrystal (NC) as a model system, three new coalescence pathways involving detwinning or twinning have been uncovered through atomic-scale dynamic observations in an aberration-corrected transmission electron microscope coupled with atomistic simulations. This demonstrates that beyond crystal size, coalescence growth dynamics involving 5-fold twins (5-FTs) are highly dependent on crystal defect density and the approach pathways of the crystals. When a 5-FT encounters a smaller 5-FT or a smaller NC in a face-to-face way, a new, larger 5-FT is produced at a relatively fast coalescence growth rate; while in a corner-to-corner way, the coalescence dynamics are more retarded and sluggish, which is conducive to the formation of complex multitwined structures rather than 5-FTs. This highlights that the planar defect density and crystal approach pathway influence the coalescence dynamics of crystals containing 5-FT. Moreover, a column-by-column grain boundary (GB) migration mechanism, which results in bent GBs, was also unveiled during the crystal coalescence process. These results enrich the general understanding of the crystal growth theory and provide new insights into the controllable fabrication of 5-FTs by crystal coalescence mechanisms.}, archive = {J_JACS}, author = {Hongshan Wang and Miriding Mutailipu and Loukya Boddapati and Amit Samanta and Francis Leonard Deepak and Junjie Li}, doi = {10.1021/jacs.5c06375}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22104--22114}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic-scale dynamics of five-fold twin mediated coalescence: Pathway-dependent and defect-governed nonclassical growth mechanisms}, volume = {147}, year = {2025}, }
• (2025). Regioselective hydropyridylation of heteroatom-functionalized internal alkenes by half-sandwich rare-earth catalysts. JACS, 147(25), 22092--22103. (www)

  @article{ , abstract = {Catalytic C–H alkylation of pyridines with unactivated internal alkenes containing heteroatom functional groups is, in principle, an ideal means for the synthesis of functionalized alkylpyridines, which are important heterocyclic structural motifs in many pharmaceuticals, agrochemicals, and biologically active compounds. However, such a transformation has remained undeveloped to date, probably due to the lack of suitable catalysts. Here we report a rare-earth-catalyzed C–H alkylation of pyridines with unactivated internal alkenes that leverages a wide array of native heteroatom functional groups, including ethers, thioethers, and tertiary amines, to serve as an efficient promoter for the regioselective hydropyridylation and hydropyridylmethylation of internal alkenes. This protocol provides an atom-efficient and straightforward approach for the selective synthesis of a new family of C2-alkylated pyridines with diverse ether, thioether, and tertiary amine functional groups, featuring 100% atom efficiency, broad substrate scope, high yield, and excellent regioselectivity. Experimental and computational studies reveal that the coordination of the heteroatom (O, S, or N) in internal alkenes to the catalyst metal center is crucial for achieving the unprecedented activity and regioselectivity.}, archive = {J_JACS}, author = {Gu Zhan and Tenggang Jiao and Shao-Jie Lou and Shuya Wang and Gen Luo and Masayoshi Nishiura and Zhaomin Hou and Xuefeng Cong}, doi = {10.1021/jacs.5c06117}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22092--22103}, shortjournal = {J. Am. Chem. Soc.}, title = {Regioselective hydropyridylation of heteroatom-functionalized internal alkenes by half-sandwich rare-earth catalysts}, volume = {147}, year = {2025}, }
• (2025). Spatially aligned binary single-site catalyst on defective SiO2 for cascading reactions. JACS, 147(25), 22084--22091. (www)

  @article{ , abstract = {Capitalizing on the success of single-atom catalysts (SACs), dual-atom catalysts (DACs) have emerged as a new frontier in heterogeneous catalysis. However, most SACs and DACs studies seek to uniformly distribute the catalytic sites on the support material, which can hinder their effectiveness in intricate multistep cascading reactions. Particularly, it is a grand challenge to precisely control the spatial distribution of two different single sites forming binary sites so that reactants and intermediates contact the catalytic sites in the exact sequence required by the reaction steps. Here, we report a new type of binary single-site catalyst, Cu 1 –Zr 1 @SiO 2 , with Cu 1 and Zr 1 sites spatially aligned with the reaction sequence of the cascade reactions. The catalyst is synthesized by a modified reverse microemulsion approach, with single Cu sites anchored by nonbridging oxygen hole centers, which were induced by doping single Zr sites into SiO 2 . Low-energy ion scattering spectroscopy (LEIS) reveals that the outermost surface of the catalyst contains only Cu single sites, while the Zr sites are dispersed in the bulk. The catalytic performance is demonstrated in ethanol conversion to butenes, a model cascade reaction which includes ethanol dehydrogenation and aldol condensation steps. The precisely spatially controlled binary sites enable ethanol to first undergo dehydrogenation to acetaldehyde on Cu sites, followed by aldol condensation of acetaldehyde on Zr sites. As a result, C 3+ olefins selectivity as high as 77.0% (56.0% selectivity of butenes) is achieved by suppressing ethylene formation.}, archive = {J_JACS}, author = {Juanjuan Yang and Yanran Cui and Ying Zhao and Stephen C. Purdy and Junyan Zhang and Haoyu Liu and Yanping Zheng and Lei Nie and Zhenglong Li}, doi = {10.1021/jacs.5c06007}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22084--22091}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatially aligned binary single-site catalyst on defective SiO2 for cascading reactions}, volume = {147}, year = {2025}, }
• (2025). Photoinduced copper-catalyzed enantioselective alkylalkynylation of alkenes via polarity-matched hydrogen atom transfer. JACS, 147(25), 22072--22083. (www)

  @article{ , abstract = {Achieving precise chemo-, regio-, and stereoselective functionalization of C(sp 3 )–H bonds in inexpensive and readily accessible chemical feedstocks continues to pose a significant challenge in synthetic chemistry. However, while significant efforts have centered on substrates bearing hydridic C(sp 3 )–H bonds, enantioselective radical transformations of abundant feedstocks containing protic C(sp 3 )–H bonds remain underdeveloped. In this work, we report a photoinduced copper-catalyzed enantioselective three-component alkylalkynylation of alkenes with a wide range of chemical feedstocks, including acetonitrile, ketones, esters, amides, ethers, and amines. The reaction employs modified aryl iodides as hydrogen atom transfer (HAT) reagents, in which aryl radicals with tunable philicity could selectively abstract either protic or hydridic C(sp 3 )–H bonds based on the polarity-match effect. The resulting carbon-centered radicals then undergo sequential radical addition with alkenes, followed by copper-catalyzed asymmetric C(sp 3 )–C(sp) cross-coupling with terminal alkynes, furnishing various chiral alkynes with excellent chemo-, regio-, and stereoselectivities. This protocol offers a straightforward and mild method to access synthetically valuable chiral molecules directly from widely available chemical feedstocks, highlighting its efficiency and broad applicability.}, archive = {J_JACS}, author = {Zhengze Wu and Kai Li and Mengxia Liao and Chunxiang Pan and Bin Yang and Xi Ma and Hengyu Huo and Binbin Tu and Guozhu Zhang and Rui Guo}, doi = {10.1021/jacs.5c06054}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22072--22083}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoinduced copper-catalyzed enantioselective alkylalkynylation of alkenes via polarity-matched hydrogen atom transfer}, volume = {147}, year = {2025}, }
• (2025). Balancing *CHO/*CO intermediate flux via carbonyl-hydroxyl motif synergy enables high-selectivity ethanol electrosynthesis from dilute CO2. JACS, 147(25), 22062--22071. (www)

  @article{ , abstract = {The electrochemical CO 2 reduction reaction (CO 2 RR) to ethanol represents a sustainable avenue to close the carbon cycle and produce renewable fuels, yet challenges persist in achieving high selectivity and activity under industrially relevant dilute CO 2 streams. Herein, we realize an efficient ethanol electrosynthesis by coating Cu catalysts with β-hydroxy ketone-based covalent organic polymers (COP CO+OH ), which not only activate CO 2 but also balance the *CHO/*CO flux at the catalyst–electrolyte interface. The COP CO+OH coated Cu NPs (Cu+COP CO+OH ) exhibits unprecedented FE EtOH of 54.2% in 0.5 M KHCO 3 , with a partial current density of 121.3 mA cm –2 . Crucially, using a dilute CO 2 feedstock (20% CO 2 ), it retains ∼40.8% FE EtOH , circumventing energy-intensive CO 2 purification. Through systematic experimental characterizations and density functional theory (DFT) calculations, we elucidate a unique organic motif synergy: carbonyl groups serve as CO 2 activation centers, while adjacent hydroxyl groups boost *H supply for *CO protonation to *CHO intermediates. This unique synergy enables a balanced *CHO/*CO flux, thereby creating an optimal environment favoring asymmetric *CHO–*CO coupling and preferentially stabilizing the *CHCOH intermediate toward ethanol production. Our investigations establish a universal design paradigm to bypass scaling relations in CO 2 RR through organic motif synergy, offering atomistic insights into steering complex reaction networks in CO 2 electroreduction.}, archive = {J_JACS}, author = {Pu Huang and Zhilong Yang and Kewei Zhai and Binbin Huang and Jing Zhou and Xinyu Sun and Yamei Lin and Jing Xu and Chengsi Pan and Yuming Dong and Yao Wang and Ying Zhang and Yang Lou and Hongwen Huang and Yongfa Zhu and Jiawei Zhang}, doi = {10.1021/jacs.5c05839}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22062--22071}, shortjournal = {J. Am. Chem. Soc.}, title = {Balancing *CHO/*CO intermediate flux via carbonyl-hydroxyl motif synergy enables high-selectivity ethanol electrosynthesis from dilute CO2}, volume = {147}, year = {2025}, }
• (2025). Intrinsically adaptive salicylaldimine: Mechanically and thermally induced switching between photochromism and photoluminescence. JACS, 147(25), 22053--22061. (www)

  @article{ , abstract = {Dynamically adaptive materials that respond to varying environmental stimuli have garnered significant attention due to their potential applications. Nevertheless, developing single-molecule-based intrinsically adaptive materials capable of responding to multiple stimuli remains a challenge. Herein, we present an intrinsically adaptive salicylaldimine 1 featuring a urea group, demonstrating versatile adaptations across three different stacking states in response to light, mechanical, and thermal stimuli, thus facilitating controllable switching between photochromism and photoluminescence. Such adaptations are enabled by intermolecular hydrogen bonds between urea groups, which play a crucial role in modulating molecular stacking configurations. Specifically, the pristine imine 1 in crystal I state exhibits fluorescence quenching but demonstrates visible-light-driven reversible photochromism. Mechanical grinding disrupts the robust intermolecular hydrogen bond, deactivating photochromism while activating photoluminescence. The resulting imine 1 powder in amorphous state displays bright fluorescence and can be reverted to the initial crystal I state either through exposure to ethanol vapor or thermal annealing of imine 1 at 60 °C. Remarkably, a new stable crystalline state, crystal II, emerges after the thermal annealing of imine 1 at an exceptionally high temperature of 240 °C with 21.5-fold fluorescence enhancement compared to imine 1 in crystal I state. These versatile adaptations underscore its potential for applications in anticounterfeiting, information encryption, and high-temperature recording. Overall, these findings provide valuable insights into strategies for the development of intrinsically adaptive systems and materials.}, archive = {J_JACS}, author = {Zhiyuan Han and Meixia He and Jean-Marie Lehn and Quan Li}, doi = {10.1021/jacs.5c05848}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22053--22061}, shortjournal = {J. Am. Chem. Soc.}, title = {Intrinsically adaptive salicylaldimine: Mechanically and thermally induced switching between photochromism and photoluminescence}, volume = {147}, year = {2025}, }
• (2025). Silicon: A surface dopant for stable alumina-supported PtGa propane dehydrogenation catalysts by favoring redox and carbon dynamics. JACS, 147(25), 22041--22052. (www)

  @article{ , abstract = {The exploitation of shale gas has stimulated the use of on-purpose propane dehydrogenation (PDH) technologies. These technologies rely on continuous and rapid catalyst regeneration to maintain high propene production. For Pt-based catalysts, metal promotors and additives, such as Ga and Si, have been shown to enhance the catalyst productivity and stability. While most studies have focused on understanding the role of Ga as a promoter, the effect and role of Si on the catalytic properties are less explored and understood. Therefore, tailored monometallic Pt and bimetallic Pt–Ga catalysts supported on alumina or Si-doped alumina are prepared via surface organometallic chemistry and evaluated under PDH conditions. The Pt catalyst containing both Ga and Si displays the highest propene productivity (1970 mol C3= mol Pt –1 h –1 after 2 h) and the lowest deactivation constant (0.31 h –1 after 2 h), pointing out the critical role of both Ga and Si. While scanning transmission electron microscopy coupled with energy-dispersive X-ray spectroscopy and X-ray absorption spectroscopy show that the catalyst structures of the as-reduced Pt–Ga catalysts are similar, postmortem analyses reveal that Si-doping of the alumina-supported Pt–Ga PDH catalyst modifies redox and carbon dynamics. This modification maintains Pt-active sites by yielding interfaces between Pt and GaO x domains along with a surface PtC structure that is correlated with increased structural dynamics and slower deactivation.}, archive = {J_JACS}, author = {Kazutaka Sakamoto and Milivoj Plodinec and Christoph R. Müller and Christophe Copéret}, doi = {10.1021/jacs.5c05862}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22041--22052}, shortjournal = {J. Am. Chem. Soc.}, title = {Silicon: A surface dopant for stable alumina-supported PtGa propane dehydrogenation catalysts by favoring redox and carbon dynamics}, volume = {147}, year = {2025}, }
• (2025). Unlocking the ambiphilicity of the boryl anion: Synthesis and reactivity of an anionic diazoborane. JACS, 147(25), 22033--22040. (www)

  @article{ , abstract = {Reported boryl anions (R 2 B – ) often exhibit n – p conjugation between the boron atom and adjacent heteroatoms, with their nucleophilicity being the primary focus. In this work, we present evidence that aryl-substituted boryl anions (Ar 2 B – ) can exhibit ambiphilicity. Specifically, the diazoborane anion [K(2.2.2-cryptand)] + Dmp(Mes)BN 2 – ( 3 , Dmp = 2,6-dimesitylphenyl, Mes = 2,4,6-trimethylphenyl) has been synthesized via diazo transfer using Carpino’s hydrazine as a reagent. Compound 3 exhibits a strong tendency to release dinitrogen, acting as a free boryl anion Dmp(Mes)B – source. Ligand exchange reactions with carbon monoxide and 2,6-xylyl isocyanide highlight the metallomimetic (ambiphilic) behavior of 3 . The ambiphilic nature of 3 further enables its reaction with nitrous oxide to yield an oxoborane anion (R 2 BO – ). Compound 3 also reacts with carbon dioxide to form the cycloaddition product R 2 B(N 2 CO 2 ) − ( 7 ). Additionally, the boryl-N 2 anion undergoes N 2 release upon heating with LiCl or irradiation, yielding different bond activation products. The underlying mechanisms of these reactions were investigated through in-depth DFT analysis.}, archive = {J_JACS}, author = {Chonghe Zhang and Junyi Wang and Xibao Zhang and Philipp Dabringhaus and Weiming Shi and Kevin Qian and Chun-Lin Deng and Christopher C. Cummins and Robert J. Gilliard, Jr.}, doi = {10.1021/jacs.5c05883}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22033--22040}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking the ambiphilicity of the boryl anion: Synthesis and reactivity of an anionic diazoborane}, volume = {147}, year = {2025}, }
• (2025). Iridium-catalyzed Z-selective asymmetric allylic substitution reaction via Z/E kinetic resolution. JACS, 147(25), 22024--22032. (www)

  @article{ , abstract = {Chiral Z -olefin molecules are much more challenging targets in organic synthesis due to their thermodynamically unfavorable nature compared with that of their corresponding E -olefin counterparts. Particularly, the transformations toward advanced chiral Z -olefin products from readily available E -olefin precursors are faced with huge difficulties associated with the energetic uphill process. A possible solution to this issue is taking advantage of the different kinetic behaviors between Z - and E -olefins. However, recognizing the different reactivities between Z - and E -olefins poses great challenges for molecular catalysis. Herein, we report an Ir-catalyzed Z -selective asymmetric allylic substitution using oxindoles as nucleophiles via the kinetic resolution of Z / E olefin mixtures. The higher reactivity of Z -allylic carbonates than their E -counterparts in this reaction manifold originates from the faster oxidative addition of Z -allylic carbonates to the Ir(I) catalyst and the faster nucleophilic attack to anti -π-allyl-Ir intermediates than that to syn -π-allyl-Ir intermediates by external nucleophiles. When coupled with photoinduced olefin E / Z isomerization, the same products are accessed from E -allylic carbonates in up to 97% yield with 96% ee and >19:1 Z / E ratio. The results reported in this study represent an unprecedented pattern in asymmetric Tsuji–Trost-type reactions, a class of fundamental transformations in organic synthesis, and provide a unique approach to advanced chiral Z -olefins.}, archive = {J_JACS}, author = {Yi-Ming Hou and Ru Jiang and Jiandong Liu and Chao Zheng and Shu-Li You}, doi = {10.1021/jacs.5c05792}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22024--22032}, shortjournal = {J. Am. Chem. Soc.}, title = {Iridium-catalyzed Z-selective asymmetric allylic substitution reaction via Z/E kinetic resolution}, volume = {147}, year = {2025}, }
• (2025). Oxyhydride synthesis through facile water dissociation on the electride intermetallic LaScSi. JACS, 147(25), 22015--22023. (www)

  @article{ , abstract = {The simultaneous presence of hydride (H – ) and oxide (O 2– ) anions in an inorganic material is thermodynamically challenging. Oxyhydrides have always been synthesized from an oxide precursor, by using high-temperature solid-state reaction using a mixture of oxide and hydride, topochemical reduction at mild temperatures, or high-pressure synthesis. Here, we introduce a novel and unprecedented synthesis route for transition metal oxyhydrides, where the starting material is not an oxide but an intermetallic compound, LaScSi. The topochemical synthesis of LaScSiO x H y ( x ≈ 0.5, y ≈ 1) occurs through water dissociation, highlighting the exceptional catalytic behavior of the electride-type parent material. The topochemical insertion of oxygen and hydrogen transforms LaScSi into a more two-dimensional material and modifies its electronic properties, altering its transport properties, from three-dimensional metallic to semimetallic. This innovative path to oxyhydrides is also of fundamental interest for catalysis: it could open the way for new methods of hydrogen production and storage, especially in water splitting, bypassing traditional processes such as electrolysis or photocatalysis.}, archive = {J_JACS}, author = {Khaled ALABD and Etienne GAUDIN and Antoine VILLESUZANNE and Baptiste VIGNOLLE and Etienne DURAND and Nathalie DARO and Emmanuelle SUARD and Clemens RITTER and Sophie TENCÉ}, doi = {10.1021/jacs.5c05760}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22015--22023}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxyhydride synthesis through facile water dissociation on the electride intermetallic LaScSi}, volume = {147}, year = {2025}, }
• (2025). Motion-controlled photocatalytic hydrogen evolution using microrobots designed with a single atomic-level precision. JACS, 147(25), 22003--22014. (www)

  @article{ , abstract = {The potential of hydrogen as a next-generation fuel has recently attracted a great deal of attention because it is considered a green fuel originating from renewable sources. Material sciences with the tools of nanoarchitectonics are targeting a wide variety of suitable photocatalysts of different materials, morphologies, and dimensionalities. Here, we present the concept of the photocatalytic hydrogen evolution reaction (HER) using microrobots: tiny autonomous devices possessing propulsion and photocatalytic abilities. The microrobots were derived from a black TiO 2 (bTiO 2 ) material that provided the photocatalytic properties that contributed not only to successful light-induced propulsion but also to the activity toward the HER. In the next step, the decoration with magnetic nanoparticles (NPs) enabled the navigation of microrobots (mag-bTiO 2 microrobots) in a magnetic field to enhance overall propulsion abilities and to allow their collection and consecutive reusability. As a result, mag-bTiO 2 microrobots showed efficiency as dynamic photocatalysts for the HER; the positive contribution of the “on-the-fly” mode was confirmed by a control experiment using mag-bTiO 2 microrobots as static photocatalysts. Furthermore, the overall efficiency of the HER was improved by decorating microrobots with atomic-level Pt species (mag-Pt-bTiO 2 microrobots). The findings of this proof-of-concept study demonstrate an alternative approach toward the photocatalytic HER and lay the basis for the next generation of nano/microrobots for energy conversion applications.}, archive = {J_JACS}, author = {Anna Jancik-Prochazkova and Riku Nakao and Yuichi Yamaguchi and Akihiko Kudo and Katsuhiko Ariga}, doi = {10.1021/jacs.5c05661}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {22003--22014}, shortjournal = {J. Am. Chem. Soc.}, title = {Motion-controlled photocatalytic hydrogen evolution using microrobots designed with a single atomic-level precision}, volume = {147}, year = {2025}, }
• (2025). Switching between limiting charge extraction regimes in an illuminated Semiconductor–Metal–Organic framework junction. JACS, 147(25), 21996--22002. (www)

  @article{ , abstract = {Surface modification is an effective method to realize high performance photoelectrodes. While current investigations mostly aim to leverage surface layers for improved charge carrier kinetics during charge separation, interfacial charge transfer, and decreased recombination, carrier transport within the surface layer is largely unattended. Herein, we explore this charge transport process on a model photocathode consisting of p-Si and GaP semiconductors (SCs) that are coated with a redox-active Zn-NDI (NDI = naphthalene diimide bis-pyrazolate) metal–organic framework (MOF) surface layer. The MOF layer is able to accept photogenerated electrons and support a large photovoltage of the underlying SC. In addition to well-established carrier generation and interfacial transfer processes that are frequently considered to control photocurrents, experimental photoelectrochemical data of the MOF@SC electrodes expose limitations that arise from electron transport in the surface layer coating. The transport-limited regime becomes relevant when the illumination intensity is gradually increased and is sensitive to the nature of the underlying semiconductor as well as the electrolyte. The phenomenon reported in this work is likely present in other surface-modified photoelectrodes with thick cocatalysts or redox-active polymer coatings but can easily be overlooked. In the MOF@SC construct, the transition between different limiting regimes can be visualized owing to the well-behaved cation-coupled photoelectron hopping transport in the MOF layer. These findings support the design and realization of efficient photoelectrodes.}, archive = {J_JACS}, author = {Amol Kumar and Jingguo Li and Anna M. Beiler and Sascha Ott}, doi = {10.1021/jacs.5c05700}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21996--22002}, shortjournal = {J. Am. Chem. Soc.}, title = {Switching between limiting charge extraction regimes in an illuminated Semiconductor–Metal–Organic framework junction}, volume = {147}, year = {2025}, }
• (2025). Atomic spreading and retraction of supported ultrasmall alloy nanoparticles under reactive oxygen at elevated temperatures. JACS, 147(25), 21985--21995. (www)

  @article{ , abstract = {The ability to control the morphology of supported alloy nanoparticles in an ultrasmall size range (≲5 nm) is challenging especially under reactive oxygen at elevated temperatures. The understanding of factors governing such nanoscale surface-dominated interfacial interactions and reactivities remains elusive since existing studies are mostly based on crystalline phases of larger-sized nanoparticles and the associated nanoparticle–support surface interactions. Here, we reveal a counterintuitive spreading and retraction phenomenon by in situ tracking of the spatiotemporal dynamics of alumina-supported ultrasmall ternary alloy nanoparticles under oxygen at different temperatures as a model system. This oxygen-induced spreading and retraction phenomenon exhibits “ebb-and-flow” like dynamic amorphous–crystalline phase duality. It correlates with the high-capacity oxygen breathing-like behavior and is shown to play a critical role in maintaining the stability of the supported ultrasmall nanoalloys using carbon monoxide oxidation by oxygen as a probe reaction. The findings hint at a potential exploration of the dynamic and potentially reversible characteristics of phase transformation for the design of catalysts under reactive conditions.}, archive = {J_JACS}, author = {Han-Wen Cheng and Shan Wang and Guanyu Chen and Dominic Caracciolo and Zhi-Peng Wu and Shiyao Shan and Ke Pei and Zhengwang Liu and Merry N. Madiou and Xiaowei Lv and Dong Dinh and Susan Lu and Zhengchen Wu and Wenbin You and Qianqian Li and Zihan Wang and Heyong He and Renchao Che and Chuan-Jian Zhong}, doi = {10.1021/jacs.5c05696}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21985--21995}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic spreading and retraction of supported ultrasmall alloy nanoparticles under reactive oxygen at elevated temperatures}, volume = {147}, year = {2025}, }
• (2025). Direct observation of secondary nucleation in huntingtin amyloid formation by high-speed atomic force microscopy. JACS, 147(25), 21973--21984. (www)

  @article{ , abstract = {Amyloid fibril formation is a hallmark of various neurodegenerative diseases such as Huntington’s (HD), Alzheimer’s, and Parkinson’s disease. The protein aggregation process involves slow nucleation events followed by rapid growth and elongation of formed fibrils. Understanding the pathways of amyloid formation is key to development of novel therapeutic agents that can interfere with the pathogenic protein misfolding events. Recent studies of aggregation by polypeptides from Alzheimer’s and Huntington’s disease have identified the importance of a poorly understood secondary nucleation process that may even be the dominant source of protein aggregate formation. Here, we focus on the polyglutamine-expansion disorder HD and employ mechanistic and structural studies to study different aspects of secondary nucleation in the aggregation of huntingtin Exon 1 (HttEx1). Notably, we apply high-speed atomic force microscopy (HS-AFM) to directly observe the process on the single-particle level and in real time. Our observations show unique features of the amyloid formation dynamics in real time, including secondary nucleation, elongation, and the formation of large bundles of fibrils as a result of nucleated branching. We examine the role of HttEx1 flanking segments during the aggregation process, revealing that the N-terminal Htt NT segment exhibits a clear primary nucleation-aggregation-enhancing ability; however, it does not seem to induce or affect the secondary nucleation process. The obtained results illuminate the complex aggregation process of HttEx1 and have implications for attempts to inhibit or modulate it for therapeutic purposes.}, archive = {J_JACS}, author = {Chris van Ewijk and Greeshma Jain and Yari K. Knelissen and Sourav Maity and Patrick C. A. van der Wel and Wouter H. Roos}, doi = {10.1021/jacs.5c05571}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21973--21984}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct observation of secondary nucleation in huntingtin amyloid formation by high-speed atomic force microscopy}, volume = {147}, year = {2025}, }
• (2025). Ultrastable copper carboxylate Metal–Organic frameworks. JACS, 147(25), 21961--21972. (www)

  @article{ , abstract = {Direct synthesis of acid–base-stable copper carboxylate metal–organic frameworks (MOFs) is of great significance but faces substantial challenges. Herein, a nanoenvelope strategy was proposed to protect the copper paddle-wheel cluster in the assembly between Cu(II) and 4,4′,4″,4‴-(1,3,6,8-pyrenetetrayl)tetrakis-benzoic acid (H 4 TBAPy) through AB stacking. This structure unexpectedly restricted the access of water to the Cu–O bonds, creating one of the most stable MOFs in water (240 days, RT) as well as in acid and base solutions (pH from 0 to 13). Water vapor adsorption experiments, density functional theory (DFT) calculations, and radial distribution function (RDF) analyses further confirmed the high water resistance of Cu 2 TBAPy. Moreover, excellent separation for xylene isomers was achieved, with a resolution of 18.2 (meta-xylene/para-xylene) and a durability of 31 months, which surpassed all previous materials. Xylene isomer impurities were separated with a detection limit as low as 1.33 pg. The remarkable stability of Cu 2 TBAPy offers valuable guidance for the design and synthesis of highly water-stable copper carboxylate MOFs.}, archive = {J_JACS}, author = {Han Yang and Ming Xu and Min Mao and Lei Gao and Hao Zhang and Sha-Sha Meng and Wen-Qi Tang and Yu-Hao Gu and Shuai Yuan and Ling-Mei Liu and Zhi-Yuan Gu}, doi = {10.1021/jacs.5c05507}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21961--21972}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrastable copper carboxylate Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Bis(trifluoromethyl)carborhodamines: Highly fluorogenic, far-red to near-infrared dyes for live cell fluorescence microscopy, activity-based sensing, and single-molecule microscopy. JACS, 147(25), 21950--21960. (www)

  @article{ , abstract = {Synthetic fluorophores built on a classic rhodamine scaffold are essential for modern microscopy. An attractive feature of synthetic fluorophores is their potential to access long-wavelength excitation and emission profiles (>650 nm) that are difficult to achieve through genetically encoded methods like fluorescent proteins. Here, we present a new strategy to achieve excitation and emission above 650 nm: bis(trifluoromethyl)carborhodamine dyes, or BF dyes. In BF dyes, the geminal methyl groups of carborhodamines are replaced with trifluoromethyl (CF 3 ) groups. This accomplishes two things. First, CF 3 groups substantially red shift in the optical profile by over 90 nm compared to classic, oxygen-bridged rhodamine dyes, resulting in a dye framework with excitation and emission profiles >650 nm and high brightness (extinction coefficient >140,000 M –1 cm –1 and fluorescent quantum yield of 33%). Second, CF 3 groups render BF dyes fluorogenic, by shifting the position of the open-closed equilibrium of the colorless lactone and colored zwitterion form, resulting in up to a 30-fold improvement in fluorogenicity compared to silicon-bridged rhodamines. In this paper, we present the design and computational analysis of BF dyes; synthetic studies to access over a dozen new BF dyes through a unique, late-stage functionalization strategy; spectra characterization; and applications in advanced fluorescence microscopy including no-wash intracellular labeling, functional imaging with chemigenetic indicators, and single molecule tracking in living cells. Together, this report shows that bis(trifluoromethyl)carborhodamine dyes provide a complementary approach to achieving long-wavelength, fluorogenic dyes for live cell microscopy that do not rely on dimethyl silicon rhodamines.}, archive = {J_JACS}, author = {Nels C. Gerstner and Jack T. McCann and Julia G. Martin and Katharine M Henn and Kathrin Riske and Sathvik Anantakrishnan and Thomas G.W. Graham and Xavier Darzacq and Evan W. Miller}, doi = {10.1021/jacs.5c05473}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21950--21960}, shortjournal = {J. Am. Chem. Soc.}, title = {Bis(trifluoromethyl)carborhodamines: Highly fluorogenic, far-red to near-infrared dyes for live cell fluorescence microscopy, activity-based sensing, and single-molecule microscopy}, volume = {147}, year = {2025}, }
• (2025). Energy gap law-harnessing design of highly second near-infrared emissive 34π-annulated porphyrinoids for in vivo imaging. JACS, 147(25), 21940--21949. (www)

  @article{ , abstract = {NIR-II fluorophores (1000–1700 nm) are pivotal for biomedical imaging, offering deep-tissue penetration and high signal-to-noise ratios but suffer from low quantum yields (QY < 0.01%) beyond 1200 nm. To date, most reported NIR-II small-molecule dyes are derived from polymethine and xanthene frameworks. However, achieving NIR-II chromophores with sufficient QYs remains challenging, as the energy gap law dictates that internal conversion-governed by the emission energy gap and reorganization energy-dominates nonradiative decay. To address this, we designed a novel pseudo-2D molecular framework: 34 π-electron annulated porphyrinoids (Scheme 1), engineered to minimize reorganization energy. These structures achieve emission wavelengths up to 1290 nm with QYs of 1.10–6.14%. Density functional theory (DFT) calculations were performed to unravel the photophysical mechanisms underlying these behaviors, showing that the reorganization energy is as small as 10.5 meV for these dyes, which validates our design. The optimized molecular structures and the stacking geometry of these porphyrinoids in the nanoparticle form were also elaborated by DFT. The intense NIR-II fluorescence (>1200 nm) enables high-resolution in vivo vascular imaging, further enhanced by AI-driven imaging algorithms to significantly improve image quality.}, archive = {J_JACS}, author = {Yi-Chen Tsai and Yan-Chang Chen and Hsiu-Feng Lu and Kai-Min Chan and Syue-Liang Lin and Pin-Xuan Lin and Ricardas Rotomskis and Simona Steponkiene and Tung-Kung Wu and Ming-Hsien Chan and Ja-an Annie Ho and Yu-Fen Huang and Chao-Ping Hsu and Yang-Hsiang Chan}, doi = {10.1021/jacs.5c05151}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21940--21949}, shortjournal = {J. Am. Chem. Soc.}, title = {Energy gap law-harnessing design of highly second near-infrared emissive 34π-annulated porphyrinoids for in vivo imaging}, volume = {147}, year = {2025}, }
• (2025). Tuning covalent organic frameworks for nucleic acid loading: Toward creating a hierarchical artificial cell. JACS, 147(25), 21926--21939. (www)

  @article{ , abstract = {Bottom-up artificial cells have been widely studied in fundamental life sciences and other valuable applications. However, common one-pot encapsulation construction strategies usually result in oversimplified structure. Herein, we successfully constructed a nucleus structure based on covalent organic frameworks (COFs) using two different spatiotemporal strategies for linear or circular DNAs, which was further combined with cell-free transcription and translation (CFTT) to construct an artificial cell. Linear DNAs could be adsorbed through the pore structures of the COFs. Circular plasmids could be encapsulated inside the COF structure through a template sacrifice method (COFcap-1). The pore sizes and microenvironment were crucial to the CFTT efficiency. Three artificial nucleus logic gates were constructed and realized information transmission between different artificial organelles. Finally, the DNAs adsorbed on the COFs were successfully encapsulated inside liposomes to construct artificial cells with the nucleus structure. This study not only investigates new applications of COFs but also opens up a new avenue toward constructing artificial cells with high hierarchy in structure using porous materials.}, archive = {J_JACS}, author = {Yiming Wang and Chen Wang and Yunlong Zheng and Heng Hu and Yao Chen and Yuan Lu}, doi = {10.1021/jacs.5c05406}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21926--21939}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning covalent organic frameworks for nucleic acid loading: Toward creating a hierarchical artificial cell}, volume = {147}, year = {2025}, }
• (2025). Turing-patterned catalyst-ionomer architectures for enhanced mass transport in anion exchange membrane fuel cells. JACS, 147(25), 21916--21925. (www)

  @article{ , abstract = {The membrane electrode assembly, a core component of anion exchange membrane fuel cells (AEMFCs), faces critical challenges in maintaining operational stability under fluctuating humidity conditions due to the insufficient environmental adaptability of conventional catalyst layers (CLs). Typically, ionomers within CLs simultaneously serve as ionic conductors and structural binders. However, their random distribution often leads to transport bottlenecks that compromise the triple-phase interface effectiveness. Herein, we introduce a molecular engineering strategy to construct Turing-patterned ionomer networks through precisely controlled cross-linking chemistry. Advanced microstructural characterization (transmission electron microscopy and atomic force microscopy) confirms the formation of a distinctive pendant-cross-linked architecture with periodic nanochannels (∼8 nm width), establishing interconnected pathways for simultaneous ion, water, and O 2 transport under low-humidity operating conditions. Combined theoretical modeling and electrochemical diagnostics reveal that this Turing-patterned architecture effectively reduces mass transport resistance compared to conventional systems while maintaining better single-cell durability. The engineered CL enables AEMFCs to achieve a record-high peak power density of 1.39 W cm –2 under practical low relative humidity (70 °C, 60% RH, 0.1 MPa backpressure).}, archive = {J_JACS}, author = {Xian Liang and Weisheng Yu and Longlong Sun and Wenfeng Li and Yan Xu and Zhiru Liu and Mai Xu and Xiaolin Ge and Quan Liu and Liang Wu and Tongwen Xu}, doi = {10.1021/jacs.5c05281}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21916--21925}, shortjournal = {J. Am. Chem. Soc.}, title = {Turing-patterned catalyst-ionomer architectures for enhanced mass transport in anion exchange membrane fuel cells}, volume = {147}, year = {2025}, }
• (2025). A minimalist design for a dual-catalyst system for high-efficiency conversion of waste plastics into liquid fuel products. JACS, 147(25), 21907--21915. (www)

  @article{ , abstract = {Chemical conversion of waste plastics into valuable products holds immense significance for pollution control and resource conservation. Dual-catalyst systems exhibit improved overall efficiency compared with conventional bifunctional catalysts in hydrocracking processes, but they continue to grapple with the issues of high noble metal loadings and the necessity for meticulously controlled synthesis steps. Herein, we propose a minimalist design for a dual-catalyst system that combines exceptional catalytic efficiency, minimal noble metal consumption, and a streamlined synthesis process. Specifically, Ce-modified HY (CeHY) and CeO 2 -supported Rh (Rh–CeO 2 ) were directly blended as catalysts for low-density polyethylene (LDPE) hydrocracking. This blend achieves an ultrahigh liquid fuel formation rate of 3132 g/g noble metal /h, surpassing the previously reported dual-catalyst systems. Mechanistic analysis reveals that the enhanced performance mainly originates from unique interactions between CeO 2 and Rh, which allows the coexistence of Rh single atoms (Rh 1 ) and Rh nanoparticles (Rh n ). These served as active sites for adsorbing olefin intermediates and activating H 2 , respectively, thereby promoting the hydrogenation step. More significantly, considering the structural similarity between CeHY and commercial fluid catalytic cracking (FCC) catalysts, we further performed the catalysis using SOY-8 (a commercial FCC catalyst) and Rh–CeO 2 , achieving equally excellent catalytic performance. The following 40-fold scale-up experiment firmly confirms the practical application prospect of our physically mixed catalytic system.}, archive = {J_JACS}, author = {Xueting Wu and Xinyi Liu and Ye Song and Wei Liu and Ruiping Deng and Xiang Chu and Shuyan Song and Hongjie Zhang and Xiao Wang}, doi = {10.1021/jacs.5c05246}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21907--21915}, shortjournal = {J. Am. Chem. Soc.}, title = {A minimalist design for a dual-catalyst system for high-efficiency conversion of waste plastics into liquid fuel products}, volume = {147}, year = {2025}, }
• (2025). Structural basis and rational design of nucleotide analogue inhibitor evading the SARS-CoV-2 proofreading enzyme. JACS, 147(25), 21896--21906. (www)

  @article{ , abstract = {All coronaviruses (CoVs) encode an exoribonuclease in nonstructural protein nsp14 (nsp14 ExoN), which is required for the excision of mismatched nucleotides or nucleotide analogues (NAs) that are incorporated into nascent RNA. Here, we investigated the mechanism by which NAs evade SARS-CoV-2 nsp14 ExoN cleavage using chemically synthesized RNA with NAs incorporated at the 3′ end. Nsp14 ExoN exhibited significantly attenuated activity on RNA with sofosbuvir monophosphate (SMP) compared with natural nucleotides, remdesivir/molnupiravir monophosphate, and, in particular, AT-9010 monophosphate (ATMP), which has the same chemically modified ribose moiety as SMP, incorporated at the 3′ end. Cryo-electron microscopy structures of nsp10/14 bound to RNA-SMP/-ATMP and mutagenesis studies revealed the essential roles of H95/Q145/F146 in recognizing the base moiety and thus pulling the NAs into a favored conformation for cleavage. Therefore, NAs may evade nsp14 ExoN cleavage by having (1) a base that does not interact with H95, Q145, or F146 and (2) a chemically modified ribose. Guided by this hypothesis, two NAs were designed to effectively resist nsp14 ExoN cleavage. These results inform the rational design of anti-CoV NAs.}, archive = {J_JACS}, author = {Junbo Wang and Yufan Pan and Yixiao Liu and Bo Huang and Ge Jin and Lejin Zhang and Feng Zhou and Xiaoyu Chang and Yucen Huang and Liming Yan and Yuanchen Dong and Zihe Rao and Dongsheng Liu and Zhiyong Lou}, doi = {10.1021/jacs.5c05014}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21896--21906}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural basis and rational design of nucleotide analogue inhibitor evading the SARS-CoV-2 proofreading enzyme}, volume = {147}, year = {2025}, }
• (2025). Overcoming the electrolyte-derived interphase through sequential reactions for stable lithium metal anode. JACS, 147(25), 21885--21895. (www)

  @article{ , abstract = {Lithium metal batteries hold significant promise for achieving energy densities beyond 400 Wh kg –1 . However, the uncontrolled decomposition of solvent molecules and salt anions leads to a heterogeneous electrolyte-derived solid electrolyte interphase (SEI), resulting in nonuniform Li-ion diffusion and uncontrolled dendrite growth, which severely compromises cycling stability. Herein, we propose a sequential reactions strategy that enables precise SEI regulation through finely controlled chemical and electrochemical processes, overcoming the limitations of conventional electrolyte-driven decomposition. A reactive polymer, sulfurized polyethylenimine, is designed to chemically induce the formation of an Li 2 S layer on the lithium metal surface, ensuring homogeneous Li-ion transport. Subsequently, a Li 2 S/Li 3 N intermediate layer, generated by electrochemical reactions, accelerates Li-ion migration. Shielded by the unreacted organic layer, the tailored SEI maintains robust structural integrity. Even under lean electrolyte (1.35 g Ah –1 ) and high areal capacity (6.0 mAh cm –2 ), a 3.4 Ah LiNi 0.8 Co 0.1 Mn 0.1 O 2 ||Li pouch cell employing this well-controlled SEI achieves an ultrahigh specific energy of 480.5 Wh kg –1 with an impressive capacity retention of 85.9% after 100 cycles. These findings provide a new paradigm for rational SEI design via the regulation of sequential reactions, offering valuable insights into stabilizing Li metal anodes under practical conditions.}, archive = {J_JACS}, author = {Jiangning Liu and Baoyu Sun and Lijuan Zhao and Kefang Liu and Marija Demicoli and Jiangxuan Song}, doi = {10.1021/jacs.5c05084}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21885--21895}, shortjournal = {J. Am. Chem. Soc.}, title = {Overcoming the electrolyte-derived interphase through sequential reactions for stable lithium metal anode}, volume = {147}, year = {2025}, }
• (2025). Hydrophobic cation-immobilized covalent organic frameworks enable selective and stable electrosynthesis of ethylene from CO2. JACS, 147(25), 21877--21884. (www)

  @article{ , abstract = {The electrochemical reduction of CO 2 (CO 2 RR) offers a promising strategy for the synthesis of multicarbon fuels and chemicals. However, the highly dynamic gas/electrolyte/catalyst interface, where ions and reactant molecules exchange in a disorderly manner, restricts the electrocatalytic selectivity and stability. Herein, we immobilize quaternary ammonium cations onto covalent organic frameworks (COFs) to tailor the interface environment for boosting the electrosynthesis of ethylene. We find that the hydrophobic and microporous structures of the COFs enable fast CO 2 transport and rational H 2 O distribution, while the migration of cations is elegantly tailored through the Donnan effect. As a result, the COF-based electrode delivers a Faradaic efficiency of 46.8% and a high partial current density of 374.2 mA cm –2 for ethylene. A developed COF-based practical zero-gap membrane electrode assembly electrolyzer is further demonstrated with stable ethylene production over 89.6 h. In situ spectra and density functional theoretical calculations unveil that the cationic COFs further enhance the local electric field strength, resulting in stronger *CO adsorption and a boosted *CO dimerization rate. Our study provides a new avenue to enhance multicarbon production via tuning the cathode local mass and charge transfer.}, archive = {J_JACS}, author = {Zhengyi Qian and Youxing Liu and Zheng Lin and Na Ye and Yingjun Tan and Fei Liu and Yu Gu and Qizheng Huang and Hongyu Guo and Mingchuan Luo and Shaojun Guo}, doi = {10.1021/jacs.5c05120}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21877--21884}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrophobic cation-immobilized covalent organic frameworks enable selective and stable electrosynthesis of ethylene from CO2}, volume = {147}, year = {2025}, }
• (2025). Rational molecular design of aryl-lithium reagent enables precise chemical prelithiation of graphite anodes for achieving ideal 100% initial coulombic efficiency. JACS, 147(25), 21865--21876. (www)

  @article{ , abstract = {Prelithiation is a recognized strategy to enhance the initial Coulombic efficiency (ICE) and energy density of lithium-ion batteries (LIBs). However, existing methods generally suffer from insufficient lithiation precision, poor spatial homogeneity, and limited operational feasibility. Here, a molecular customized prelithiation reagent, 1-methyl-naphthalene-lithium/2-methyl tetrahydrofuran ( E mNaph-Li Θ = 0.21 V vs Li + /Li), is designed to lithiate graphite anode to its threshold potential for irreversible Li-storage ( E Gr-irr = 0.22 V vs Li + /Li), thereby achieving an ideal ICE of 100%. The well-matched potentials of E mNaph-Li Θ and E Gr-irr enable self-terminating prelithiation upon reaching equilibrium states, precisely eliminating irreversible lithium loss while avoiding the stringent control of lithium dosages or durations required by traditional methods. Combined microstructural and computational analyses reveal that the spontaneous formation of Stage-IV lithium-graphite intercalation compounds ( E stage-IV Li-GIC Θ = 0.22 V) drives the growth of spatially uniform, inorganic-rich solid–electrolyte interphases (SEI) with accelerated Li + transport kinetics. Full cells incorporating prelithiated electrodes demonstrate marked improvements in ICE, capacity retention, and energy density. In addition, the universality of this potential-matching approach is demonstrated for hard carbon and silicon/carbon anodes. Our work advances the understanding of graphite intercalation chemistry and provides a scalable, customizable approach to precise prelithiation in LIBs.}, archive = {J_JACS}, author = {Ran Tan and Kexin Liu and Xiaolong Zhu and Siyu Yang and Qian Zhang and Juzheng Zhang and Zu Chang and Pengcheng Chai and Xuanze Wang and Olivier Fontaine and Xinping Ai and Jiangfeng Qian}, doi = {10.1021/jacs.5c04997}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21865--21876}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational molecular design of aryl-lithium reagent enables precise chemical prelithiation of graphite anodes for achieving ideal 100% initial coulombic efficiency}, volume = {147}, year = {2025}, }
• (2025). Pore-space-partition-oriented sandwich platinum array confined in a Metal–Organic framework for boosting overall water splitting. JACS, 147(25), 21855--21864. (www)

  @article{ , abstract = {The atomic-level dispersion of noble metals in porous materials is prospective for highly efficient catalyst systems but is still inscrutable. Inspired by sandwich compounds, platinum (Pt) atoms were rationally confined within a metal–organic framework (MOF) through pore space partition by conjugate interactions between Pt and parallel-distributed aromatic pore partitioners, forming 1D infinite Pt arrays. By regulating the distance between adjacent aromatic rings from 7 to 4.5 to 3 Å (∼ the diameter of the Pt atom), the particle size in sandwich Pt arrays decreased in a linear fashion with the Pt electronic orbital simultaneously regulated by a pore partitioner, MOF nodes, and near noble atoms, as revealed by AC high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, and theoretical simulations. The optimized MOF pore endows the Pt@MOF-BCP material with highly efficient utilization of Pt sites, best electron transmission efficiency, and excellent catalytic stability. At 10 mA·cm –2 , an optimal Pt@MOF-BCP catalyst only needs ultralow overpotentials of 2.5 mV for hydrogen evolution reaction in the acidic electrolyte and 265 mV for oxygen evolution reaction in the alkaline electrolyte, exhibiting exceptional difunctional electrocatalytic performance superior to most benchmark catalysts. Remarkably, the cell voltage of Pt@MOF-BCP was dramatically reduced to 1.47 V at 10 mA·cm –2 in practical application.}, archive = {J_JACS}, author = {Jia-Min Huo and Ying Wang and Ze-Lin Ma and Jie Meng and Tian-Shu He and Bo-Lin Sun and Shu-Ni Li and Quan-Guo Zhai}, doi = {10.1021/jacs.5c04935}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21855--21864}, shortjournal = {J. Am. Chem. Soc.}, title = {Pore-space-partition-oriented sandwich platinum array confined in a Metal–Organic framework for boosting overall water splitting}, volume = {147}, year = {2025}, }
• (2025). In situ encapsulation of cationic [2]Catenane in a stable zirconium Metal–Organic framework. JACS, 147(25), 21844--21854. (www)

  @article{ , abstract = {As an emerging class of porous supports, metal–organic frameworks (MOFs) can host multifarious guests to realize diverse applications. Among the guest-introducing approaches, the in situ encapsulation method is unique in its ability to incorporate a diverse range of guests, from small organic molecules and metal clusters to proteins and even more complicated guests. Previous investigations have focused on guests that are either neutral or negatively charged. The realization of the in situ encapsulation of cationic catenanes in MOFs under mild conditions, however, has rarely been investigated. Herein, we have accomplished in situ encapsulation of a cationic catenane (DA[2]C) within UiO-66-F 4 ─a MOF consisting of Zr 6 nodes and tetrafluoroterephthalic acid ligands─at room temperature using H 2 O as a green solvent. Theoretical calculations elaborated that tetrafluoroterephthalic acid ligands interact strongly with the cationic DA[2]C. This observation is a result of electrostatic interactions between carboxylate anions and DA[2]C cations as well as the attraction of electronegative F atoms in tetrafluoroterephthalic acid to the cations. As a proof-of-concept application, the DA[2]C·4Cl/UiO-66-F 4 composite demonstrated heterogeneous catalytic detoxification of 2-chloroethyl ethyl sulfide to the sulfoxide with a complete conversion rate (>99%) and high selectivity (>97%). This method could also be extended to other organic cationic molecules, including dibenzyl benzoimidazoloimidazole chloride and a pyrene-functionalized cyclobis(paraquat- p -phenylene), rendering it as a universal platform for constructing host–guest MOF systems with various applications.}, archive = {J_JACS}, author = {Shuliang Yang and Isil Akpinar and Olga A. Syzgantseva and Maria A. Syzgantseva and Xuesong Li and Guangcheng Wu and Chandra S. Azad and Han Han and Xiaoliang Wang and Tianwei Xue and Li Peng and Yong Wu and Ruihua Zhang and Long Zhang and Tae-woo Kwon and Liang Feng and Yang Jiao and J. Fraser Stoddart}, doi = {10.1021/jacs.5c04895}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21844--21854}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ encapsulation of cationic [2]Catenane in a stable zirconium Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Functionalized porous polymer networks as high-performance PFAS adsorbents. JACS, 147(25), 21832--21843. (www)

  @article{ , abstract = {Toxic per- and polyfluoroalkyl substances (PFAS) are now found in nearly every water source on the planet. Exposure to these molecules can have negative health consequences, but the low concentration of PFAS relative to other solutes in water makes their removal challenging. Adsorbents offer a promising treatment route, but often exhibit low selectivities and removal capacities, as well as slow kinetics. The performance in these metrics can be improved by chemically optimizing PFAS binding sites and maximizing PFAS–adsorbent interactions. To explore how to achieve this, a porous polymer network solid (PPN-6, also known as PAF-1) was postsynthetically modified with various chemical moieties capable of leveraging unique combinations of electrostatic, hydrogen-bonding, hydrophobic, and fluorophilic interactions with PFAS molecules. Batch adsorption experiments and computational studies revealed that electrostatic and hydrogen-bonding interactions drive short-chain PFAS adsorption, while hydrophobic and fluorophilic interactions improve long-chain PFAS adsorption. In complex water matrices, a combination of electrostatic and fluorophilic interactions led to the greatest total PFAS removal. The best-performing material, functionalized with a fluorinated alkylammonium (PPN-6-FNDMB), selectively adsorbs PFAS with high capacity (up to 4.0 mmol/g) and rapid kinetics (equilibrium reached in <30 s). Furthermore, PPN-6-FNDMB outperforms several commercial adsorbents, achieving near-complete removal of 21 different PFAS from a groundwater sample collected at a US Air Force base. The PFAS could subsequently be desorbed from PPN-6-FNDMB, concentrating them by a factor of over 50 times. The recycled PPN-6-FNDMB could then be reused with minimal losses in long-chain PFAS adsorption capacity over four cycles.}, archive = {J_JACS}, author = {Ethan R. Pezoulas and Bahareh Tajdini and Yeongnam Ko and Adam A. Uliana and Raynald Giovine and Hiroyasu Furukawa and Hooman Vatankhah and Jonas Börgel and Ki Chul Kim and Christopher Bellona and Jeffrey R. Long}, doi = {10.1021/jacs.5c04689}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21832--21843}, shortjournal = {J. Am. Chem. Soc.}, title = {Functionalized porous polymer networks as high-performance PFAS adsorbents}, volume = {147}, year = {2025}, }
• (2025). Asparaginyl ligases with engineered substrate specificity for controlled, sequential transpeptidation reactions. JACS, 147(25), 21824--21831. (www)

  @article{ , abstract = {Transpeptidases are valuable enzymes for peptide and protein engineering due to their ease of use and highly defined substrate specificities. Asparaginyl ligases are a class of highly efficient transpeptidases. Engineered asparaginyl ligases with orthogonal substrate specificities would provide access to new types of sequential transpeptidation regimes, but no such engineered variants have been reported thus far. Here, we engineer the widely used asparaginyl ligase Oa AEP1 for altered substrate specificity. We find that a single amino acid substitution, Y188A, facilitates the recognition of a substrate sequence that is essentially unmodified by the parent enzyme or an alternative Y188W mutant. This orthogonality enables controlled sequential reactions for the generation of a dual N- and C-terminally labeled protein and the one-pot synthesis of two distinct cyclic peptides from a single linear synthetic peptide precursor. Introducing the equivalent mutation in a consensus-designed asparaginyl ligase facilitates similarly altered substrate specificity, suggesting that the Tyr188 residue is a general determinant of the asparaginyl ligase substrate specificity.}, archive = {J_JACS}, author = {Yan Zhou and Simon J. de Veer and Tristan J. Tyler and Yufei Chen and Thomas Durek and David J. Craik and Fabian B. H. Rehm}, doi = {10.1021/jacs.5c04693}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21824--21831}, shortjournal = {J. Am. Chem. Soc.}, title = {Asparaginyl ligases with engineered substrate specificity for controlled, sequential transpeptidation reactions}, volume = {147}, year = {2025}, }
• (2025). Ring expansions of 1,2-amino alcohols to amine heterocycles enabled by proton-coupled electron transfer. JACS, 147(25), 21818--21823. (www)

  @article{ , abstract = {Biologically active molecules are often composed of ring structures that precisely position functional groups to enable target-specific interactions. The iterative permutation of these structural arrangements is central to the modern drug discovery process, necessitating de novo synthesis to access isomeric compounds with distinct biological properties. However, methods to interconvert saturated ring systems remain limited. Here we report a general method for the peripheral-to-core nitrogen internalization of amino cycloalkanols to access N-heterocycles of various oxidation states. In this process, an excited-state iridium chromophore and weak Brønsted base cooperatively promote the endergonic redox isomerization of cyclic amino alcohols to linear amine-containing products that undergo in situ cyclization. This strategy enables the expansion, contraction, and carbon-to-nitrogen substitution of cyclic amino alcohols, providing access to structurally distinct heterocyclic scaffolds.}, archive = {J_JACS}, author = {Danny Q. Thach and Robert R. Knowles}, doi = {10.1021/jacs.5c04694}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21818--21823}, shortjournal = {J. Am. Chem. Soc.}, title = {Ring expansions of 1,2-amino alcohols to amine heterocycles enabled by proton-coupled electron transfer}, volume = {147}, year = {2025}, }
• (2025). High-connected ternary Metal–Organic framework platform: Synthesis, structure, and methane storage capacity. JACS, 147(25), 21811--21817. (www)

  @article{ , abstract = {Design and synthesis of a single metal–organic framework (MOF) that simultaneously achieves high gravimetric and volumetric working capacities for methane storage are crucial for advancing the use of natural gas as a vehicular fuel. However, this presents a significant challenge due to the inherent trade-off effect between the gravimetric and volumetric methane adsorption capacities of a single porous material. Herein, we initially synthesized a novel pyridine-carboxylic acid ligand and combined it with a trimeric iron cluster along with a series of dicarboxylic acid ligands of varying lengths or functionalities. Employing a dual-solvent system and dual-modulator solvothermal principles, we successfully constructed a 9-c ternary MOF platform. X-ray diffraction analysis reveals that the structures all feature an ncb -type topological network with a cage-channel biporous hierarchy. Through a multistep solvent exchange followed by supercritical carbon dioxide drying method, we successfully activated this series of materials, achieving substantial porosity, with pore volumes exceeding 1.90 cm 3 g –1 , gravimetric surface areas surpassing 4800 m 2 g –1 , and volumetric surface areas greater than 1600 m 2 cm –3 . High-pressure methane adsorption tests at 80 bar demonstrated that the series of materials exhibited a high total gravimetric and volumetric methane adsorption capacity. Notably, when the testing temperature was lowered to 273 K, these materials showed significant increases in total gravimetric and volumetric methane adsorption. Particularly, the Fe- ncb -TPDC-II constructed using the longest dicarboxylate linker achieved gravimetric and volumetric methane storage working capacities of 0.533 g g –1 and 232 cm 3 (STP) cm –3 , respectively, performing exceptionally well compared to reported porous materials under similar conditions.}, archive = {J_JACS}, author = {Jie Zhou and Ya-Nan Ma and Yu-Feng Zhang and Bin Zheng and Ke Zheng and Shan Liu and Xin-Ai Guo and Yue-Biao Zhang and Dong-Xu Xue}, doi = {10.1021/jacs.5c04567}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21811--21817}, shortjournal = {J. Am. Chem. Soc.}, title = {High-connected ternary Metal–Organic framework platform: Synthesis, structure, and methane storage capacity}, volume = {147}, year = {2025}, }
• (2025). Temperature variation of the local structure and dihydrogen bonds in ammonia borane. JACS, 147(25), 21803--21810. (www)

  @article{ , abstract = {Because ammonia borane (AB) exhibits a high hydrogen storage density derived from dihydrogen bonds, it has the potential to be a safe, lightweight, and compact hydrogen storage material. In the tetragonal phase at around room temperature, the hydrogen occupancy is low, and the atomic arrangement and electron density distribution have not been clarified. Therefore, the hydrogen storage properties, including the decomposition reaction mechanism, which proceeds from ∼373 K, also remain unclear. In this study, neutron/X-ray total scattering measurements were performed on AB above and below its phase-transition temperature of 225 K, and the disordered atomic arrangement of hydrogen in the tetragonal phase was clarified by reverse Monte Carlo modeling of the obtained pair distribution function. In addition, the charge of each atom was quantitatively investigated by first-principles calculations and Bader charge analysis. Hydrogen in AB was orderly arranged, forming N–H δ + ···H δ− –B dihydrogen bonds in the low-temperature orthorhombic phase; however, in the room-temperature tetragonal phase, where the hydrogen atoms were disorderly arranged, the distribution of negatively charged hydrido-like H δ− atoms coordinated to boron extended toward neutral. This situation shows that the dihydrogen bonds are unstable, which may lead to the decomposition of AB.}, archive = {J_JACS}, author = {Kazutaka Ikeda and Yoshihiro Shimizu and Tessui Nakagawa and Akihiko Machida and Hyunjeong Kim and Kouji Sakaki and Koji Ohara and Hidetoshi Ohshita and Toshiya Otomo}, doi = {10.1021/jacs.5c04566}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21803--21810}, shortjournal = {J. Am. Chem. Soc.}, title = {Temperature variation of the local structure and dihydrogen bonds in ammonia borane}, volume = {147}, year = {2025}, }
• (2025). Subnanometer pt catalysts encapsulated in MEL zeolite mesocrystals for h2 production from methylcyclohexane dehydrogenation. JACS, 147(25), 21789--21802. (www)

  @article{ , abstract = {Modulating the microenvironment of zeolite-encapsulated subnanometer metal active sites represents a frontier in the design of solid catalysts because of its marked impacts on the catalytic properties. Different from most prior works, which mainly focus on tuning the particle size and chemical composition of the encapsulated metal species, the present work focuses on the modulation of the morphology of the zeolite support to effectively stabilize subnanometer Pt clusters for H 2 production from the dehydrogenation of methylcyclohexane to toluene. By confining Pt clusters in the perpendicularly connected 10MR channels of MEL zeolite mesocrystals, we can maintain sufficient confinement of the zeolite framework to stabilize Pt clusters against sintering and to facilitate mass transport properties of the methylcyclohexane and toluene molecules, resulting in a markedly high specific H 2 production rate, excellent stability against sintering and coke deposition, and exceptionally low concentration of CH 4 impurity in the outlet H 2 .}, archive = {J_JACS}, author = {Hongtao Wang and Kailang Li and Miguel Lopez-Haro and Carlo Marini and Zhe He and Minghao Gao and Liang Zhang and Lichen Liu}, doi = {10.1021/jacs.5c04618}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21789--21802}, shortjournal = {J. Am. Chem. Soc.}, title = {Subnanometer pt catalysts encapsulated in MEL zeolite mesocrystals for h2 production from methylcyclohexane dehydrogenation}, volume = {147}, year = {2025}, }
• (2025). Growth of monolayer WS2 lateral homojunctions via in situ domain engineering. JACS, 147(25), 21778--21788. (www)

  @article{ , abstract = {Two-dimensional (2D) lateral homojunctions possess unique geometries and properties distinct from those of other heterostructures, including perfect lattice matching and clean carrier diffusion channels, showing great potential in beyond-silicon nanoelectronics. However, the direct growth of 2D lateral homojunctions within the same crystal phase and layer remains challenging due to the limited choice of elements. Here, we report the epitaxy growth of semiconducting monolayer WS 2 lateral homojunctions by in situ domain engineering during chemical vapor deposition (CVD). Domain-selective defects independently modulate the electronic structures of different regions, enabling the integration of intrinsic D-/E-mode field-effect transistors within one channel. Moreover, multiple characterizations demonstrated that optimized band alignment with an ideal lattice match exists at the interface, endowing homojunctions with strong diode-like characteristics. Benefiting from the unique atomic structures, the monolayer homojunctions were used to construct homo-NMOS logic devices. The sub-1 nm-thick inverter with good rail-to-rail operation shows a peak voltage gain of 12, a dynamic delay time about 135 μs, and a peak power consumption as low as 1.3 nW. This approach paves a new way for in situ engineering both defect configurations and distributions within atomic layers, offering comprehensive understanding of 2D landscape as well as accelerating their potential applications.}, archive = {J_JACS}, author = {Qilong Cui and Hongwei Shou and Chuanqiang Wu and Bijun Tang and Wen Zhu and Yuyang Cao and Wei Jiang and Pengjun Zhang and Ruijie Wang and Zhanfeng Liu and Shiqiang Wei and Shuangming Chen and Binghui Ge and Xiaojun Wu and Zheng Liu and Li Song}, doi = {10.1021/jacs.5c04546}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21778--21788}, shortjournal = {J. Am. Chem. Soc.}, title = {Growth of monolayer WS2 lateral homojunctions via in situ domain engineering}, volume = {147}, year = {2025}, }
• (2025). Directing the C–N coupling pathway enables efficient urea electrosynthesis. JACS, 147(25), 21764--21777. (www)

  @article{ , abstract = {Electrocatalytic synthesis of urea presents a promising approach to closing the artificial nitrogen cycle. However, a major challenge arises from the sluggish C–N coupling step in urea formation compared to other competing electrochemical steps involving nitrate and CO 2 reduction, ultimately limiting the urea selectivity and energy efficiency during the coelectroreduction of nitrate and CO 2 . In this study, we identify *NO 2 as a key intermediate that governs urea activity and selectivity as it can either undergo hydrogenation or couple with CO 2 to form the desired C–N bond. Our theoretical investigations reveal that a decrease in the adsorption energy of *NO 2 on Cu can suppress *NO 2 hydrogenation while enhancing its coupling with CO 2 to favor C–N bond formation. We further discover that doping of Cu with boron increases the energy requirement for *NO 2 hydrogenation and lowers the energy barrier for C–N coupling involved in the formation of *NO 2 CO 2 . Encouragingly, with the synthesized boron-doped Cu catalysts, we achieve a high urea Faradaic efficiency exceeding 80% at a low overpotential of −0.22 V vs the reversible hydrogen electrode, along with a substantial urea production rate of 101.2 μmol h –1 cm –2 . In contrast, the pristine Cu only shows a low urea selectivity (19%) and production rate (<20 μmol h –1 cm –2 ) under identical conditions. Furthermore, a comprehensive life-cycle assessment underscores the significance of abundant nitrate sources for urea electrosynthesis. This work introduces an effective approach for selective and efficient urea synthesis, offering valuable insights into C–N coupling and guiding the design of energy-efficient electrocatalysts for urea production.}, archive = {J_JACS}, author = {Bihao Hu and Ruihu Lu and Wenlong Wang and Yifan Zhou and Dhayananthan Kalpana Devi Jaswanthi and Zhe Wu and Ziyun Wang and Lei Wang}, doi = {10.1021/jacs.5c04483}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21764--21777}, shortjournal = {J. Am. Chem. Soc.}, title = {Directing the C–N coupling pathway enables efficient urea electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). A tailored quinoline-locked covalent organic framework for metal-free photocatalytic α-amino C–H annulation. JACS, 147(25), 21754--21763. (www)

  @article{ , abstract = {Metal-free α-amino C–H annulation via photocatalysis stands as a pioneering strategy for accessing heterocyclic compounds. Imine-linked covalent organic frameworks (ILCOFs), known for their photonic excitation potential, have been underutilized in C–H annulation due to inherent photochemical instability and inefficient C–H activation. Here, we propose a novel locking strategy using chlorotrimethylsilane-catalyzed cyclization to convert ILCOF- n into stable QLCOF- n with methylquinoline motifs, thereby establishing it as a robust photocatalytic platform for metal-free α-amino C–H annulation. This structural modulation preserves crystallinity, while enhancing structural robustness and optoelectronic properties versus parent ILCOFs. QLCOF- n demonstrates superior catalytic efficiency and stability over ILCOF- n , as validated by extensive scale-up and recycling experiments, as well as substrate derivatization across 22 examples. Further investigation explores strategies to enhance the photocatalytic efficiency, including synergistic integration of film catalysis and Bro̷nsted acid (BA) assistance. The apparent quantum yield (AQY) of the film at λ = 450 nm achieves an impressive value of 1.12 ± 0.08%. Mechanistic insights highlight the pivotal roles of amino carbon and superoxide anion (O 2 •– ) radicals in the annulation. This work establishes quinoline-locked QLCOFs as durable photocatalysts for sustainable C–H functionalization.}, archive = {J_JACS}, author = {Jing-Jun Li and Jia-Ying Liu and Shui-Ying Gao and Xue Yang and Rong Cao}, doi = {10.1021/jacs.5c04200}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21754--21763}, shortjournal = {J. Am. Chem. Soc.}, title = {A tailored quinoline-locked covalent organic framework for metal-free photocatalytic α-amino C–H annulation}, volume = {147}, year = {2025}, }
• (2025). Automatic discovery and optimal generation of amorphous high-entropy electrocatalysts. JACS, 147(25), 21743--21753. (www)

  @article{ , abstract = {Amorphous materials are ubiquitous in nature and are widely used for many industrial applications, including catalysis, energy storage, and environmental science. However, significant challenges remain in designing and optimizing amorphous high-entropy materials because of the lack of well-defined structure–activity relationships. Here, we use synthesis systems to discover and optimize amorphous high-entropy oxyhydroxide electrocatalysts within the entire design space for the alkaline oxygen evolution reaction. Amorphous high-entropy electrocatalysts are derived from ultrathin 2D coordination polymers composed of six nonprecious metal elements that were selected from top 16 candidate metal elements involved in oxygen evolution reaction (OER)-related literature searching, which can then be transformed in situ into amorphous oxyhydroxides. Leveraging machine learning (ML) techniques, we establish a composition–activity relationship and thereby identify an optimal composition group by traversing the entire design space (over 1,900,000 compositions). Our ML-model is validated by using 100 compositions in the high-activity region and 588 compositions in the low-activity region, which results in excellent recall values of nearly 100%. The predicted optimal amorphous high-entropy electrocatalyst demonstrates an ultralow overpotential of 159 mV at a current density of 10 mA cm –2 for the alkaline OER in a 1 M KOH while exhibiting ultralong durability 10,218 h under a practical current density of 1 A cm –2 in a 6 M KOH. Our work provides a general strategy for the automatic discovery and optimization of amorphous high-entropy oxyhydroxide electrocatalysts and could significantly impact the development of other amorphous high-entropy materials.}, archive = {J_JACS}, author = {Zhanwu Lei and Yan Huang and Yuanmin Zhu and Donglai Zhou and Yu Chen and Song Wang and Wanxia Li and Huirong Li and Xiaoke Xi and Yang Liu and Yuchen Zhang and Guozhen Zhang and Xiyu Li and Qing Zhu and Baicheng Zhang and Shuo Feng and Sheng Ye and Wensheng Yan and Shuo Zhang and Shuhong Jiao and Jun Jiang and Meng Gu and Ruiguo Cao and Yi Luo}, doi = {10.1021/jacs.5c04117}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21743--21753}, shortjournal = {J. Am. Chem. Soc.}, title = {Automatic discovery and optimal generation of amorphous high-entropy electrocatalysts}, volume = {147}, year = {2025}, }
• (2025). Quantitative determination of electronic effects in free radicals through open-shell hammett substituent constants. JACS, 147(25), 21735--21742. (www)

  @article{ , abstract = {Hammett substituent constants (σ), which quantify the electronic effects of functional groups, are widely used for predicting the properties of organic compounds and investigating reaction mechanisms. While these values have been obtained for a wide range of closed-shell substituents, measurements of analogous values for open-shell substituents are rare due to challenges associated with their short lifetimes. In this report, we developed a combined experimental and computational approach for quantifying the electronic properties of open-shell substituents based on changes in nitrile vibrational frequencies (ν(C≡N)). By coupling pulse radiolysis and time-resolved infrared spectroscopy (PR-TRIR), we measured ν(C≡N) IR bands of 30 para - and meta -substituted benzonitriles bearing C-, N-, and S-centered radicals. A linear scaling relationship was obtained between these experimental values and values obtained from DFT calculations. Using these computed values, two different Hammett constants, σ m , and σ p + , were determined for a series of C-, N-, O-, S-, Si-, and B-centered radicals. The differences between σ m and σ p + values enable the separate evaluation of inductive and resonance effects in these open-shell substituents. The results suggest that there are three classes of radicals: one is electron withdrawing (σ m , σ p + > 0), one is electron donating (σ m , σ p + < 0), and one is inductively withdrawing but resonance donating (σ m > 0, σ p + < 0). Our study represents a general approach to the analysis of the electronic properties of open-shell species and has potential applications in a wide range of molecular processes involving free radical intermediates.}, archive = {J_JACS}, author = {Eve Yuanwei Xu and Alberto Castanedo and Nick Y. Shin and Lakshmy Kannadi Valloli and David C. Grills and Matthew J. Bird and Robert R. Knowles}, doi = {10.1021/jacs.5c04058}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21735--21742}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantitative determination of electronic effects in free radicals through open-shell hammett substituent constants}, volume = {147}, year = {2025}, }
• (2025). Linear anion chain-assembled nonporous swelling molecular sieve for benchmark C2–C4 hydrocarbon separations. JACS, 147(25), 21725--21734. (www)

  @article{ , abstract = {Designing ideal materials with simultaneously high selectivity, high capacity, fast kinetics, and moderate regeneration for hydrocarbon separations remains challenging, restricting the advance of nonthermal-driven gas separation technologies. Herein, we reported a nonporous ClO 4 – -functionalized swelling molecular sieve CuClO 4 bipy·H 2 O that is assembled with 1D metal–organic linear chains via water-mediated hydrogen bonding. Destroying the hydrogen-bond network that connects linear chains enables the transformation from nonporous to adaptive porous structures upon gas exposure via chain shift, as indicated by Rietveld refinement of the structure of gas-loaded CuClO 4 bipy. The easily and rapidly reversible swelling nature of CuClO 4 bipy enables its fast kinetics and easy regeneration under ambient conditions. Meanwhile, in situ DRIFTS and ex situ Raman experiments reveal that the coordinated ClO 4 – anions and Cu open metal sites within CuClO 4 bipy endow the swelling structure with specific recognition ability toward molecules (e.g., acetylene, propyne, and butadiene) while excluding other molecules (e.g., alkanes, alkenes, and carbon dioxide), establishing CuClO 4 bipy as a new benchmark material for C2–C4 hydrocarbon separation. The work unveils the strategy of swelling molecular sieves with optimal thermodynamic and kinetic behaviors for challenging gas separations.}, archive = {J_JACS}, author = {Dengzhuo Zhou and Biao Meng and Zhensong Qiu and Xiaoling Liu and Jiyu Cui and Peixin Zhang and Rimin You and Tangyin Wu and Xian Suo and Xiaofei Lu and Yu Zhou and Jun Wang and Xili Cui and Lifeng Yang and Huabin Xing}, doi = {10.1021/jacs.5c03723}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21725--21734}, shortjournal = {J. Am. Chem. Soc.}, title = {Linear anion chain-assembled nonporous swelling molecular sieve for benchmark C2–C4 hydrocarbon separations}, volume = {147}, year = {2025}, }
• (2025). Pressure-induced dome-like superconductivity and unusual charge-density-wave-like transition in Th2Cu4As5. JACS, 147(25), 21718--21724. (www)

  @article{ , abstract = {The recently discovered Cu 4 As 3 -type material Th 2 Cu 4 As 5 has been reported to exhibit both superconductivity and charge density wave (CDW) orders. These two electronic phenomena might originate from distinct structural units in Th 2 Cu 4 As 5 , providing a unique platform to investigate the interplay between superconductivity and CDW. In this work, we carried out high-pressure electrical transport and X-ray diffraction measurements to track the evolution of the CDW and superconductivity at high pressure. Superconductivity can initially be enhanced upon the suppression of the CDW transition and then gradually decrease with increasing pressure after the CDW transition is completely suppressed, displaying a characteristic dome-like behavior. More intriguingly, a 2 × 2 × 5 superlattice appears at pressures exceeding 8 GPa, which coincides with the sudden loss of superconductivity. This observation indicates the presence of an unusual possible CDW state that may be linked to the Cu 4 As 3 superconducting layer. Our results unveil versatile CDW states in pressurized Th 2 Cu 4 As 5 , which provide us with a rare platform to investigate the interplay of multiple electronic ordered states.}, archive = {J_JACS}, author = {Yuqing Zhang and Ye Yang and Xikai Wen and Zhigang Gui and Yikang Li and Yanjun Li and Qingyuan Liu and Jiaojiao Meng and Cao Wang and Guang-Han Cao and Jianjun Ying and Xianhui Chen}, doi = {10.1021/jacs.5c03714}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21718--21724}, shortjournal = {J. Am. Chem. Soc.}, title = {Pressure-induced dome-like superconductivity and unusual charge-density-wave-like transition in Th2Cu4As5}, volume = {147}, year = {2025}, }
• (2025). Theoretical insight into proton-coupled energy transfer in an anthracene-phenol-pyridine triad. JACS, 147(25), 21708--21717. (www)

  @article{ , abstract = {Proton-coupled energy transfer (PCEnT) refers to a photochemical process in which the transfer of electronic excitation energy between donor and acceptor molecules is coupled to a proton transfer reaction. Herein, we apply our recently developed nonadiabatic PCEnT theory to an anthracene-phenol-pyridine triad system. For this system, electronic excitation energy is transferred from the anthracene to the phenol-pyridine, in conjunction with proton transfer from the phenol to the pyridine. Thus, the PCEnT reaction corresponds to the transition from the local excited state of the anthracene (LES) to the local electron–proton transfer (LEPT) state of the phenol-pyridine. With most input quantities determined from first-principles calculations, our theory reproduces the experimentally measured PCEnT rate constant. We analyzed the contributions from different electron–proton vibronic states to the PCEnT rate constant (the LES to LEPT state) and the acceptor absorption spectrum (the ground state to LEPT state). For the triad, PCEnT occurs in the absence of detectable spectral overlap between the donor emission and acceptor absorption spectra, even though conventional energy transfer theories require adequate spectral overlap. In this case, the LEPT vibronic state that dominates the PCEnT process contributes negligibly to the acceptor absorption spectrum due to the small Franck–Condon overlap associated with proton transfer. Energy transfer in PCEnT requires accompanying proton transfer to lower the energy of the LEPT state and enable sufficient spectral overlap that overcomes the small proton vibrational wave function overlap associated with proton transfer. This work enhances fundamental understanding of the PCEnT process and provides guidance for the design of other types of PCEnT systems.}, archive = {J_JACS}, author = {Kai Cui and Sharon Hammes-Schiffer}, doi = {10.1021/jacs.5c03866}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21708--21717}, shortjournal = {J. Am. Chem. Soc.}, title = {Theoretical insight into proton-coupled energy transfer in an anthracene-phenol-pyridine triad}, volume = {147}, year = {2025}, }
• (2025). Reductively induced aryl transmetalation: An alternative catalytically relevant ni-catalyzed biaryl coupling mechanism. JACS, 147(25), 21697--21707. (www)

  @article{ , abstract = {Ni-catalyzed cross-electrophile coupling (XEC) reactions have gained prominence for the construction of C–C bonds. Prior studies of XEC routes to biaryls have invoked several different mechanisms for the formation of key Ni(Ar) 2 intermediates. Here, we provide evidence for a previously unrecognized pathway involving reductively induced transmetalation between Ni I (Ar) and Ni II (Ar)X species. Chemical and electrochemical reduction of ( t Bu bpy)Ni II (2-tolyl)Br ( t Bu bpy = 4,4′-di- tert -butyl-2,2′-bipyridine) to ( t Bu bpy)Ni I (2-tolyl) is shown to initiate rapid transmetalation of the 2-tolyl ligand to a second equivalent of ( t Bu bpy)Ni II (2-tolyl)Br, affording ( t Bu bpy)Ni II (2-tolyl) 2 and ( t Bu bpy)Ni I Br as well-defined products. Experimental and computational data show that the Ni I -to-Ni II transmetalation mechanism is much more favorable than Ni II -to-Ni II transmetalation. Oxidation of ( t Bu bpy)Ni II (2-tolyl)Br results in rapid reductive elimination of 2-tolyl-Br, rather than promoting the analogous oxidatively induced Ni II /Ni III transmetalation. The Ni II (2-tolyl) 2 product of Ni I -to-Ni II transmetalation is stable at room temperature, while sterically less encumbered Ni II (Ar) 2 species undergo rapid reductive elimination to afford biaryl and a Ni 0 byproduct. The latter species can serve as a source of electrons to promote further transmetalation and biaryl formation. The unhindered complex ( t Bu bpy)Ni II (4-CF 3 -phenyl)Br undergoes biaryl formation in the absence of added reductant; however, kinetic analysis reveals an induction period and autocatalytic time course. Addition of catalytic quantities of a cobaltocene-based reductant eliminates the induction period and accelerates biaryl formation, consistent with the Ni I -to-Ni II transmetalation pathway. The results of this study provide a new rationale for previously reported results in the literature and introduce an alternative pathway to consider in the development of Ni-catalyzed biaryl coupling reactions.}, archive = {J_JACS}, author = {Antonio Romero-Arenas and Mihai V. Popescu and McKenna K. Goetz and Rashi Bhatnagar and Hamed Goljani and Buwanila T. Punchihewa and Kyana M. Sanders and Ilia A. Guzei and Mohammad Rafiee and Daniel J. Weix and Robert S. Paton and Shannon S. Stahl}, doi = {10.1021/jacs.5c03643}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21697--21707}, shortjournal = {J. Am. Chem. Soc.}, title = {Reductively induced aryl transmetalation: An alternative catalytically relevant ni-catalyzed biaryl coupling mechanism}, volume = {147}, year = {2025}, }
• (2025). Discovery of high-capacity asymmetric three-stage redox reactions of iodine for aqueous batteries. JACS, 147(25), 21686--21696. (www)

  @article{ , abstract = {Iodine-based batteries have emerged prominently in grid energy storage due to their cost-effectiveness and versatility. However, traditional iodine cathodes featuring I – /I 0 mechanisms struggle to meet the current demands for high-energy-density batteries, considering their limited specific capacity and voltage. Here, we discover a unique eight-electron-transfer asymmetric three-stage conversion of iodine facilitated by the formation of interhalogens. This mechanism involves a three-stage sequential charging from I – /I 0 , to I 0 /ICl 2 – , and finally ICl 2 – /ICl 4 – , with the prolonged third charging plateau significantly enhancing the specific capacity to 809.2 mAh g –1 of I 2 . During discharge, the cathode undergoes highly reversible but asymmetric conversions, with ICl 3 – as the intermediate. The mechanism is achieved by a regulated “chloride-in-acid” electrolyte with interlocking H-bond structures, which effectively reduces the free water content and stabilizes the interhalogen species. The iodine–hydrogen gas battery demonstrates stable cycling performance with an average Coulombic efficiency exceeding 98.2% for over 1000 cycles and an increased voltage from 0.47 to 0.75 V compared with the I – /I 0 mechanism, which can be further enhanced to 1.43 V by utilizing zinc anode. This study broadens the application of interhalogen chemistry into conversion reactions, presenting great prospects for high-energy-density aqueous batteries.}, archive = {J_JACS}, author = {Zehui Xie and Zaichun Liu and Hu Hong and Kai Du and Ruihao Luo and Muhammad Sajid and Zhengxin Zhu and Taoli Jiang and Mingming Wang and Yahan Meng and Weiping Wang and Jingwen Xu and Yuxiang Hu and Wei Chen}, doi = {10.1021/jacs.5c03581}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21686--21696}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of high-capacity asymmetric three-stage redox reactions of iodine for aqueous batteries}, volume = {147}, year = {2025}, }
• (2025). Cation-driven modulation of interfacial solvation structures for enhanced alkaline hydrogen oxidation kinetics. JACS, 147(25), 21672--21685. (www)

  @article{ , abstract = {The role of interfacial water and hydrogen-bonding structures in an electric double layer (EDL) in alkaline hydrogen oxidation reaction (HOR) kinetics has garnered widespread attention. However, the dynamic evolution of alkali metal cations (AM + ), as key components in EDL, and their impact on interfacial solvation structure and alkaline HOR kinetics remain poorly understood. Here, based on the Ni 3 S 2 -island-encapsulated Ni (Ni 3 S 2 /Ni) catalyst, we demonstrate that the AM + arrangement in the EDL can be regulated by the potential of zero charge (PZC) of the electrode, which in turn controls the associated solvation environment (i.e., the ordering of interfacial water and hydrogen-bonding network). Ab initio molecular dynamics simulations, in situ surface-enhanced infrared absorption spectroscopy, and electrochemical experiments indicate that the introduction of Ni 3 S 2 fosters a lower PZC for Ni 3 S 2 /Ni, which thus promotes a less crowded cation arrangement and more disordered interfacial water structures, ultimately contributing to the accelerated shuttling of H + /OH – across the EDL through a more interconnected H-bonding network, thereby leading to a reduced energy barrier of proton-coupled electron transfer (PCET) and enhanced HOR kinetics under alkaline electrolytes. This molecular-level picture is further supported by the unconventional cation dependence of HOR activities on Ni 3 S 2 /Ni (i.e., KOH > NaOH > LiOH) by which we reveal a new mechanistic insight; that is, the coordination of the Ni 3 S 2 island with a partially desolvated K + cation (Ni 3 S 2 -K + ) promotes dynamic evolution of cation-solvated water into strongly hydrogen-bonded water on adjacent Ni, significantly accelerating the proton transfer process. This work highlights the dominant role of AM + in controlling the EDL structure and PCET kinetics in alkaline HOR.}, archive = {J_JACS}, author = {Yana Men and Xiaomei Men and Peng Li and Lei Li and Xiaoyan Wang and Xiaozhi Su and Leijie Zhang and Shengli Chen and Wei Luo}, doi = {10.1021/jacs.5c03433}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21672--21685}, shortjournal = {J. Am. Chem. Soc.}, title = {Cation-driven modulation of interfacial solvation structures for enhanced alkaline hydrogen oxidation kinetics}, volume = {147}, year = {2025}, }
• (2025). Investigation of americium-containing phosphates, silicates, borates, molybdates, and fluorides synthesized via high-temperature flux crystal growth. JACS, 147(25), 21659--21671. (www)

  @article{ , abstract = {The crystal chemistry of americium-containing extended structures was investigated, and several classes of americium-containing solid-state oxide materials were obtained in single-crystal form via high-temperature flux crystal growth. This enabled the structural characterization of rare examples of ternary, quaternary, and penternary americium-containing silicates K 3 Am (Si 2 O 7 ) and Cs 6 Am 2 Si 21 O 48 , phosphates Na 3 Am (PO 4 ) 2 and K 3 Am (PO 4 ) 2 , borates Ba 3 Am 2 (BO 3 ) 4 and AmBO 3 , borate halides Ca 5 Am(BO 3 ) 4 Cl, molybdates Li 0.5 Am 0.5 MoO 4 , and fluorides CsAm 2 F 7 . Using these crystallographic data, the ionic radii of Am 3+ with coordination numbers of six (0.975 Å), seven (1.052 Å), and nine (1.162 Å) were established. A maximum entropy method (MEM) analysis was performed on the single-crystal X-ray diffraction data that were collected for K 3 Nd(PO 4 ) 2 /K 3 Am(PO 4 ) 2 , K 3 NdSi 2 O 7 /K 3 AmSi 2 O 7 , and NdBO 3 /AmBO 3 , to qualitatively compare the ionicities of the Nd–O and Am–O bonds. Raman spectroscopy data were collected on single crystals of K 3 Am(PO 4 ) 2 and compared to the calculated Raman spectrum of K 3 Am(PO 4 ) 2 obtained from DFT calculations.}, archive = {J_JACS}, author = {Travis K. Deason and Hunter B. Tisdale and Adrian T. Hines and Gregory Morrison and Yunping Zhoujin and Mark D. Smith and Theodore M. Besmann and Amir M. Mofrad and Shanna L. Estes and Jake W. Amoroso and David P. DiPrete and Hans-Conrad zur Loye}, doi = {10.1021/jacs.5c03457}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21659--21671}, shortjournal = {J. Am. Chem. Soc.}, title = {Investigation of americium-containing phosphates, silicates, borates, molybdates, and fluorides synthesized via high-temperature flux crystal growth}, volume = {147}, year = {2025}, }
• (2025). Biomimetic Metal–Organic nanotubular host for straight-chain fatty acids recognition. JACS, 147(25), 21649--21658. (www)

  @article{ , abstract = {Subtle structural variations among fatty acids significantly influence their biological roles and health effects. However, molecular recognition of their long, flexible, and chemically inert hydrocarbon chains remains a challenge. Inspired by natural fatty acid-binding proteins (FABPs), we designed and synthesized nanotubular metallo-cavitands, termed metal–organic pillars, through the coordination-driven assembly of pillararene-derived ligands with Ag(I) salts. These biomimetic hosts feature continuous interior channels exceeding 2.6 nm, selectively binding long-chain fatty acids through precise size and shape complementarity. Saturated and trans fatty acids, with linear conformations, are effectively encapsulated and stabilized by C–H···π and van der Waals interactions. In contrast, coiled cis -polyunsaturated fatty acids, such as docosahexaenoic acid (DHA), cannot be accommodated due to structural incompatibility. This work highlights the ability of artificial receptors to emulate the recognition capabilities of natural proteins, enabling the targeting of “bad” fatty acids associated with adverse health effects.}, archive = {J_JACS}, author = {Rong Chang and Hongliang Ye and Xue Dong and Xiao-Yu Cao and Andrew C.-H. Sue}, doi = {10.1021/jacs.5c03334}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21649--21658}, shortjournal = {J. Am. Chem. Soc.}, title = {Biomimetic Metal–Organic nanotubular host for straight-chain fatty acids recognition}, volume = {147}, year = {2025}, }
• (2025). Designing reversible photoswitching azobenzene-modified nucleotide for controlling biological function. JACS, 147(25), 21638--21648. (www)

  @article{ , abstract = {RNA plays vital roles in numerous normal and diseased cellular functions and processes. Reversible photoregulation of oligonucleotide’s structure and function is a powerful strategy for both regulating biological processes and developing novel RNA-based therapeutics. Herein, we designed an azobenzene-modified cytidine phosphoramidite and synthesized a series of oligoribonucleotides containing this photoswitchable residue. We validated the reversible photoisomerization in both ribonucleoside and oligoribonucleotide contexts and studied the overall impact of this cytidine modification through all-atom molecular dynamics (MD) simulations and UV melting experiments. We also showed that the modified oligoribonucleotide can switch the reverse transcription (RT) process upon light irradiation in the presence of various RT enzymes. In addition, the optical control mechanism of the HIV reverse transcriptase-mediated RT process was elucidated by MD simulation. This new chemical biology toolset enables reversible optical control of RNA structures and functions for gene regulation and novel drug development.}, archive = {J_JACS}, author = {Juncheng Li and Jinxi Du and Weiwei He and Ibrahim O. Adelakun and Miao Zhong and Savia Boyer and Ya Ying Zheng and Qishan Lin and Serdal Kirmizialtin and Jia Sheng and Ting Wang}, doi = {10.1021/jacs.5c03252}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21638--21648}, shortjournal = {J. Am. Chem. Soc.}, title = {Designing reversible photoswitching azobenzene-modified nucleotide for controlling biological function}, volume = {147}, year = {2025}, }
• (2025). Self-assembly of Alkynylplatinum(II) complexes for sialic acid detection and differentiation of cancer cells from normal cells. JACS, 147(25), 21629--21637. (www)

  @article{ , abstract = {A series of platinum(II) complexes incorporating a histidine moiety and/or positively charged group has been designed and synthesized to explore the specific binding between platinum(II) complexes and the analyte and their sensing ability. The specific hydrogen bonding between the histidine moiety and sialic acids, and the electrostatic interaction between the positively charged trimethylammonium group of the platinum(II) complexes and negatively charged carboxylate groups of sialic acids have been found to enhance the binding affinity. The supramolecular assembly of platinum(II) complexes upon binding to sialic acids induces remarkable luminescence changes due to noncovalent Pt(II) ··· Pt(II) and π–π stacking interactions, achieving sensing and visualization of sialic acids. A novel luminescence assay has been developed to differentiate cancer cells from normal cells based on the supramolecular assembly of platinum(II) complexes upon binding to a high level of sialic acids due to its excellent imaging ability toward sialic acids in live cells. The complexes have been adopted to visualize the variation of sialic acids in live cells after treatment with enzymes to remove sialic acids, paving the way for screening of novel anticancer agents. The present sensing strategy for differentiating cancer cells from normal cells facilitates early diagnosis and therapeutic guidance.}, archive = {J_JACS}, author = {Jungu Guo and Eric Ka-Ho Wong and Guang-Xi Xu and Angela Sin-Yee Law and Michael Ho-Yeung Chan and Jonathan Lam and Ziyong Chen and Kenneth Kam-Wing Lo and Vivian Wing-Wah Yam}, doi = {10.1021/jacs.5c03210}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21629--21637}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-assembly of Alkynylplatinum(II) complexes for sialic acid detection and differentiation of cancer cells from normal cells}, volume = {147}, year = {2025}, }
• (2025). Identification of active regions in a catalyst layer on a gas diffusion electrode in the electroreduction of CO2. JACS, 147(25), 21621--21628. (www)

  @article{ , abstract = {Although a gas diffusion electrode (GDE) has been widely employed in the electrochemical CO 2 reduction reaction (CO 2 RR) to effectively mitigate mass transport limitations, knowledge of the active region within the catalyst layer on the GDE remains incomplete. In this work, we employed a thin layer of Bi as a reporter to identify the active region within the Ag catalyst layer by taking advantage of the distinct selectivity of these two metals in the CO 2 RR. Through manipulating the position of the Bi layer within the Ag layer, we showed that at 100 mA cm –2 , the active region was located between 150 and 600 nm from the PTFE substrate. Current density, feed gas humidity, and the hydrophobicity of the substrate were found to impact both the location and thickness of the active region. Further, operando Raman spectroscopy capable of characterizing the cross-section of the catalyst layer was developed to locate the active region inside the catalyst layer.}, archive = {J_JACS}, author = {Qiwen Sun and Yuze Zheng and Jin Wang and Yao Ye and Linke Fu and Haocheng Xiong and Huanjun Song and Xiaoxia Chang and Bingjun Xu}, doi = {10.1021/jacs.5c03143}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21621--21628}, shortjournal = {J. Am. Chem. Soc.}, title = {Identification of active regions in a catalyst layer on a gas diffusion electrode in the electroreduction of CO2}, volume = {147}, year = {2025}, }
• (2025). A fast neural network for isotopic charge state assignment. JACS, 147(25), 21610--21620. (www)

  @article{ , abstract = {Electrospray ionization (ESI) mass spectrometry is an essential technique for chemical analysis in a range of fields. In ESI, analytes can produce multiple charge states, which must be correctly assigned for identification. Existing approaches to charge state assignment can suffer from limited accuracy or poor speed. Here, we developed a fast neural network to perform isotopic envelope charge assignment. The performance of our algorithm, IsoDec, was demonstrated on top-down proteomics spectra collected on diverse instruments. On these highly complex individual spectra, we found that IsoDec correctly assigns more features compared to existing software tools while simultaneously providing improved speed and accuracy. Importantly, this performance enhancement stems directly from the neural network charge assignment approach and not simply from improved scoring and filtering of isotopic envelopes. Finally, when applied to large top-down proteomics data sets, we discovered that database searching of the IsoDec deconvolution output produces proteoform-spectrum matches with a better combination of coverage and accuracy. Overall, IsoDec provides a compelling demonstration of the potential of lightweight neural networks in mass spectrometry data analysis for diverse applications.}, archive = {J_JACS}, author = {John G. Pavek and Nicholas E. Bollis and Josiah Grimes and Michael R. Shortreed and Lloyd M. Smith and Michael T. Marty}, doi = {10.1021/jacs.5c03162}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21610--21620}, shortjournal = {J. Am. Chem. Soc.}, title = {A fast neural network for isotopic charge state assignment}, volume = {147}, year = {2025}, }
• (2025). Collective biosynthesis of plant spirooxindole alkaloids through enzyme discovery and engineering. JACS, 147(25), 21600--21609. (www)

  @article{ , abstract = {Collective synthesis is a well-established strategy to produce natural product collections from common intermediates. Extending this concept to enzymatic systems, collective biosynthesis offers a sustainable approach to diverse molecular collections but faces distinct challenges, including incomplete pathway knowledge and narrow substrate specificity of biosynthetic enzymes. Here, we overcome these limitations through enzyme discovery and protein engineering to achieve collective biosynthesis of spirooxindole alkaloids, an important class of natural products with diverse biological activities. We identified two key enzymes that catalyze enzymatic epimerization, working sequentially with a previously discovered cytochrome P450 enzyme to fully elucidate the biosynthetic pathway of pentacyclic spirooxindole alkaloids. Structure-guided engineering enhanced substrate recognition capability, enabling collective biosynthesis of 12 tetracyclic and pentacyclic spirooxindole natural products. We also generated new-to-nature fluorinated and deuterated derivatives through precursor-directed biosynthesis. This work provides crucial insights into plant spirooxindole alkaloid biosynthesis while establishing a powerful approach for sustainable production of complex natural products.}, archive = {J_JACS}, author = {Danni Chu and Hongkui Wang and Zhiwen Nie and Kang-Li Li and Jiaqing Cao and Meijing Yang and Qin Yin and Yang Gu and Yindi Jiang}, doi = {10.1021/jacs.5c02990}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21600--21609}, shortjournal = {J. Am. Chem. Soc.}, title = {Collective biosynthesis of plant spirooxindole alkaloids through enzyme discovery and engineering}, volume = {147}, year = {2025}, }
• (2025). Motion of molecules in supramolecular scaffolds enhances bone regeneration. JACS, 147(25), 21586--21599. (www)

  @article{ , abstract = {The regeneration of human tissues is a great scientific challenge and a critical factor to achieve a long healthspan and prevent disabilities due to injury or disease. Materials chemistry can contribute to this goal with the development of bioactive supramolecular systems that can signal cells for regeneration. Recent work in our laboratory using in vivo models of spinal cord injury and cartilage regeneration has demonstrated that the motion of bioactive molecules in supramolecular scaffolds enhances receptor signaling. We report here on a novel molecular strategy to control supramolecular motion in filamentous assemblies using bone regeneration as a functional target. The supramolecular assemblies are composed of monomers that arrange, by design, with either parallel or antiparallel β-sheets, and some of them contain a terminal peptide sequence that binds BMP-2. We found that parallel β-sheet supramolecular assemblies promote greater osteogenic differentiation of progenitor cells in vitro relative to antiparallel assemblies, as well as superior quality of newly regenerated bone in a rat model of spinal fusion. Furthermore, these assemblies drastically reduce the dangerous supraphysiological dose of BMP-2 used clinically for spinal fusion. We attribute the enhanced bioactivity to the weaker nature of hydrogen bonds in parallel relative to antiparallel β-sheet assemblies, which in turn allows greater supramolecular motion and cell signaling of the growth factor-binding molecules.}, archive = {J_JACS}, author = {Ruomeng Qiu and Wei Ji and Zaida Álvarez and Hiroaki Sai and Zijun Gao and Feng Chen and Alexander A Linton and Nicholas J. Lanzetta and Alyssa M. Goodwin and Hogan J. Brecount and Jinyuan Li and Jacqueline Inglis and Steven Kurapaty and Stuart R. Stock and Wellington K. Hsu and Liam C. Palmer and Erin L. Hsu and Samuel I. Stupp}, doi = {10.1021/jacs.5c02930}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21586--21599}, shortjournal = {J. Am. Chem. Soc.}, title = {Motion of molecules in supramolecular scaffolds enhances bone regeneration}, volume = {147}, year = {2025}, }
• (2025). How a single atom influences the spatiotemporal response of flexible MOFs: Insights from theory and experiment. JACS, 147(25), 21575--21585. (www)

  @article{ , abstract = {Flexible metal–organic frameworks (MOFs) are porous materials exhibiting spatiotemporal responses to environmental changes, which significantly affect their sorption properties and offer potential technological breakthroughs. In this study, we investigate two isostructural thiazolo[5,4- d ]thiazolate MOFs, UAM-1S and UAM-1O, which differ by a single atom, sulfur or oxygen, in the angular dicarboxylate group. Despite this subtle modification, the materials trigger distinct structural adaptation mechanisms: a continuous in UAM-1S and a discrete in UAM-1O. Using a combination of experimental and theoretical approaches, including microcrystal electron diffraction and DFT analysis, we reveal the factors driving different transition mechanism. Appropriate treatment of UAM-1O, combined with single-crystal X-ray diffraction analysis, revealed the structure of the explosive metastable open phase, corroborating theoretical predictions. Furthermore, a time-resolved in situ powder X-ray diffraction data set was collected under varying CO 2 at pressures exceeding the cp-op structural transition pressure at 195 K, enabling the application of the Kolmogorov–Johnson–Mehl–Avrami equation to analyze the kinetics of adsorption. Holistically, our work enhances the understanding of the key factors responsible for the time-dependent response of flexible materials with implications for the design of dynamic materials.}, archive = {J_JACS}, author = {Szymon K Sobczak and Bartosz Mazur and Maura Malinska and Filip Formalik and Volodymyr Bon and Azat Khadiev and Stefan Kaskel and Bogdan Kuchta and Agnieszka M Janiak and Kornel Roztocki}, doi = {10.1021/jacs.5c02552}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21575--21585}, shortjournal = {J. Am. Chem. Soc.}, title = {How a single atom influences the spatiotemporal response of flexible MOFs: Insights from theory and experiment}, volume = {147}, year = {2025}, }
• (2025). In-cell approach to evaluate e3 ligases for use in targeted protein degradation. JACS, 147(25), 21560--21574. (www)

  @article{ , abstract = {A major challenge in evaluating the suitability of ∼700 known and putative E3 ligases for target protein degradation (TPD) is the lack of ligase-specific binders. Here, we use genetic code expansion (GCE) to express in living cells an E3 ligase with a site-specifically encoded, tetrazine-containing noncanonical amino acid (Tet-ncAA). Then, using click chemistry, we conjugate the incorporated Tet with a strained trans -cyclooctene (sTCO) tethered to a neosubstrate protein binder. The resulting covalent E3 ligase–binder construct can then be evaluated for the TPD of the neosubstrate. We first demonstrate that cereblon (CRBN) has a rather high plasticity for TPD by studying CRBN containing Tet-ncAA at a variety of surface positions. When these CRBN forms are covalently tethered to an sTCO-linker-JQ1 reagent, they all successfully recruit BRD2/4 for degradation, with the efficiency depending on the placement of the Tet-ncAA and the linker length. The results highlight the ability of this approach to map E3 surfaces and identify optimal TPD interfaces and pockets. Applying this strategy to speckle-type POZ protein (SPOP), an E3 ligase with no known specific ligand, we demonstrate that multiple sites on its surface can support TPD, revealing the potential for PROTAC-type development. This E3-ligand-free degrader (ELF degrader) platform preserves the native state of E3 ligases, enables the interrogation of any E3 surface region in live cells, and is applicable to a broad range of E3 ligases. ELF degraders represent a versatile approach to define functional degron sites, guide degrader design, and unlock new E3 ligases, those without known ligands, for therapeutic applications.}, archive = {J_JACS}, author = {Yunan Zheng and Anamika Singh and Zeqi Niu and Violeta Marin and Jonathon Young and Paul Richardson and Marcus L. Hemshorn and Richard B. Cooley and P. Andrew Karplus and Kedar Puvar and Scott E. Warder and Anil Vasudevan and Justin M. Reitsma and Ryan A. Mehl}, doi = {10.1021/jacs.5c02741}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21560--21574}, shortjournal = {J. Am. Chem. Soc.}, title = {In-cell approach to evaluate e3 ligases for use in targeted protein degradation}, volume = {147}, year = {2025}, }
• (2025). Identification of actionable targeted protein degradation effector sites through site-specific ligand incorporation-induced proximity (SLIP). JACS, 147(25), 21549--21559. (www)

  @article{ , abstract = {Targeted protein degradation (TPD) is a rapidly emerging and potentially transformative therapeutic modality. However, the large majority of >600 known ubiquitin ligases have yet to be exploited as TPD effectors by proteolysis-targeting chimeras (PROTACs) or molecular glue degraders (MGDs). We report here a chemical–genetic platform, Site-specific Ligand Incorporation-induced Proximity (SLIP), to identify actionable (“PROTACable”) sites on any potential effector protein in intact cells. SLIP uses genetic code expansion to encode copper-free “click” ligation at a specific effector site in intact cells, enabling the in situ formation of a covalent PROTAC-effector conjugate against a target protein of interest. Modification at actionable effector sites drives degradation of the targeted protein, establishing the potential of these sites for TPD. Using SLIP, we systematically screened dozens of sites across E3 ligases and E2 enzymes from diverse classes, identifying multiple novel potentially PROTACable effector sites which are competent for TPD. SLIP adds a powerful approach to the proximity-induced pharmacology (PIP) toolbox, enabling future effector ligand discovery to fully enable TPD and other emerging PIP modalities.}, archive = {J_JACS}, author = {Zhangping Xiao and Efthymios S. Gavriil and Fangyuan Cao and Xinyue Zhang and Stan Xiaogang Li and Sergei Kotelnikov and Patrycja Michalska and Friederike Marte and Chloe Huang and Yudi Lu and Yunxuan Zhang and Erika Bernardini and Dima Kozakov and Edward W. Tate}, doi = {10.1021/jacs.5c01420}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21549--21559}, shortjournal = {J. Am. Chem. Soc.}, title = {Identification of actionable targeted protein degradation effector sites through site-specific ligand incorporation-induced proximity (SLIP)}, volume = {147}, year = {2025}, }
• (2025). Isomerization of poly(ethylene glycol): A strategy for the evasion of anti-PEG antibody recognition. JACS, 147(25), 21538--21548. (www)

  @article{ , abstract = {PEGylation, the conjugation of poly(ethylene glycol) (PEG) to nanocarriers or protein-based active pharmaceutical ingredients (APIs), is a key strategy in nanomedicine to extend the circulation time of therapeutics in the bloodstream based on the stealth effect of PEG. However, the growing prevalence of anti-PEG antibodies in the population can lead to pronounced immune responses upon drug administration and accelerated blood clearance of PEGylated drugs, resulting in the loss of the stealth effect. We introduce the randomized PEG (rPEG) technology designed to strongly reduce the antigenicity of PEG while preserving its core benefits. This conceptually novel approach is based on an introduction of hydrophilic side chains along the PEG backbone. The synthesis is performed via anionic ring-opening copolymerization of ethylene oxide (EO) and glycidyl methyl ether (GME), resulting in constitutional isomers of PEG. By optimization of the reaction conditions, an ideally random distribution of the side chains in the polymer backbone could be achieved. Since previous studies show a relation between polymer chain regularity and immune system response, our approach specifically aims at introducing an irregular comonomer sequence via copolymerization, while translating the hydrophilicity and low toxicity of PEG to rPEG. Biocompatibility was evaluated using peripheral blood mononuclear cells (PBMC). Increasing the GME content in the copolymers did not decrease cell viability. Furthermore, all rPEG samples did not show complement activation in vitro at all tested concentrations. Enzyme-linked immunosorbent assays (ELISA) utilizing backbone- and end group-selective anti-PEG antibodies showed drastically reduced recognition and antibody binding for the constitutional isomers of PEG.}, archive = {J_JACS}, author = {Philip Dreier and Rebecca Matthes and Fabian Fuß and Julian Schmidt and Dominik Schulz and Gregor M. Linden and Ramona D. Barent and Sandra Schüttner and Barry W. Neun and Edward Cedrone and Marina A. Dobrovolskaia and Matthias Bros and Holger Frey}, doi = {10.1021/jacs.5c02716}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21538--21548}, shortjournal = {J. Am. Chem. Soc.}, title = {Isomerization of poly(ethylene glycol): A strategy for the evasion of anti-PEG antibody recognition}, volume = {147}, year = {2025}, }
• (2025). Assembling a metastable electron fence within gold-zeolite interfaces for boosted propylene epoxidation. JACS, 147(25), 21526--21537. (www)

  @article{ , abstract = {Selective oxidation of hydrocarbons represents a cornerstone reaction in the chemical industry, yet achieving both high activity and selectivity remains challenging. Gold catalysts, renowned for their resistance to overoxidation, are hindered by poor oxygen activation. Here, we develop an “electron fence” strategy to overcome these limitations and enhance the oxidation performances of a conventional gold/zeolite catalyst, which achieves a record-breaking propylene epoxidation rate of 502.6 g·kg cat –1 ·h –1 . By controlling the reduction dynamics and phase separation of immiscible Au–Rh precursors, we engineer a metastable “Hamburger” heterostructure with Rh atomic layers intercalated at the Au-zeolite interface. These interfacial Rh atoms serve as an electron fence and embank electrons within Au, enabling a valence-state transition from Au m+ to Au n– . Such electron confinement simultaneously addresses the hydrogen and oxygen activation challenges inherent in traditional Au catalysts, significantly promoting the pivotal generation of hydroperoxyl radicals for selective oxidation. Further fine-tuning the Au–Rh ratio prevents catalyst restructuring that causes propylene overhydrogenation to propane on the ball-cup structure, or overoxidation to CO 2 on Janus configuration. Hence, leveraging the above electronic and geometric promotions, this electron-fence Au–Rh catalyst achieves a two-order-of-magnitude enhancement in epoxidation rates. Such an electron-fence strategy can be extended to propane hydro-oxidation to acetone with simultaneously enhanced activity and selectivity.}, archive = {J_JACS}, author = {Qianhong Wang and Keng Sang and Changzheng Hong and Zhihua Zhang and Changwei Liu and Wenyao Chen and Chenxin Wu and Yuxia Zhong and Lina Li and Lei Hua and Xinggui Zhou and De Chen and Weikang Yuan and Xuezhi Duan}, doi = {10.1021/jacs.5c02753}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21526--21537}, shortjournal = {J. Am. Chem. Soc.}, title = {Assembling a metastable electron fence within gold-zeolite interfaces for boosted propylene epoxidation}, volume = {147}, year = {2025}, }
• (2025). Covalent recruitment of NEDD4 for targeted protein degradation: Rational design of small molecular degraders. JACS, 147(25), 21512--21525. (www)

  @article{ , abstract = {Targeted protein degradation (TPD) has emerged as a promising therapeutic strategy for treating various diseases. However, current small molecule degraders predominantly rely on a limited set of E3 ubiquitin ligases, such as CRBN and VHL, which restricts their applications. Here, we report that incorporation of the 2 H -azirine chemical handle into the EGFR L858R/T790M/C797S inhibitor induced remarkable degradation of the targeted protein. Proteomic profiling and functional validation confirmed that the NEDD4 E3 ligase was covalently recruited by 2 H -azirine through engagement of C1286 residue, facilitating target degradation. Furthermore, the 2 H -azirine moiety demonstrated versatility by acting as a small molecular degrader when conjugated to various ligands, effectively mediating the degradation of CDK4, PDE5, BTK and Brd4. More importantly, using the identical protein ligand scaffold, we demonstrated that the 2 H -azirine based probe can degrade proteins resistant to degradation by CRBN or VHL recruitment. This approach provides a rational strategy for developing novel small molecular degraders that target alternative E3 ubiquitin ligases. Notably, these degraders significantly outperformed their parent kinase inhibitor in suppressing cancer cell growth.}, archive = {J_JACS}, author = {Xiaoqiang He and Shihan Zeng and Yalei Wen and Tao Yang and Chaoming Huang and Yifang Li and Zhang Zhang and Ke Ding and Tongzheng Liu and Yi Tan and Zhengqiu Li}, doi = {10.1021/jacs.4c18083}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21512--21525}, shortjournal = {J. Am. Chem. Soc.}, title = {Covalent recruitment of NEDD4 for targeted protein degradation: Rational design of small molecular degraders}, volume = {147}, year = {2025}, }
• (2025). Limitations in determining oxidation states in condensed matter at the subnanometric scale. JACS, 147(25), 21501--21511. (www)

  @article{ , abstract = {The oxidation state is a fundamental chemical concept commonly employed to rationalize, classify, and predict the chemical reactivity of a variety of compounds. Understanding and defining the elemental oxidation state of solid materials at the atomic level becomes increasingly complex as their physical dimensions are reduced from tens of nanometers─where properties are still dominated by bulk or outer atomic crystal plane characteristics, to the subnanometric limit. In this work, we highlight the significant limitations in determining even a basic quantity, such as the oxidation state, when oxidized low-nuclearity mass-selected clusters are investigated by means of X-ray photoelectron spectroscopy (XPS), widely recognized as the elective approach to resolve different oxidations states. The lack of crystalline order in these nanoclusters, unlike that in periodic bulk systems and in solid surfaces, leads to a broad distribution of measured core levels, as shown in the case study of W nanoclusters. These cannot be unambiguously assigned to a valence state based solely on the knowledge of bulk matter behavior but need close comparison with specific theoretical modeling. Our results emphasize the substantial challenges inherent in understanding the unique properties of nanoscale materials, particularly in making a rigorous and quantitative determination of a fundamental property that takes a relevant role in many chemical processes, and represent crucial knowledge for advancing technologies that rely on the miniaturization of matter in various processes.}, archive = {J_JACS}, author = {Deborah Perco and Monica Pozzo and Andrea Berti and Federico Loi and Paolo Lacovig and Silvano Lizzit and Aras Kartouzian and Ueli Heiz and Dario Alfè and Alessandro Baraldi}, doi = {10.1021/jacs.5c02242}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21501--21511}, shortjournal = {J. Am. Chem. Soc.}, title = {Limitations in determining oxidation states in condensed matter at the subnanometric scale}, volume = {147}, year = {2025}, }
• (2025). Accelerated recombination reaction through interfacial FeIV=O accumulation on photoanode surfaces. JACS, 147(25), 21492--21500. (www)

  @article{ , abstract = {The observation of third-order water oxidation kinetics by Fe IV =O accumulation at the semiconductor–electrolyte interface is a milestone for understanding the four-electron transfer reaction mechanism. However, the consequences of such Fe IV =O accumulation for the associated recombination reaction kinetics at the interface have not been fully explored so far. Here, we observe fast second-order recombination reaction kinetics for Fe IV =O as the result of its accumulation at the model hematite–electrolyte interface, compared to the first-order recombination reaction kinetics for a lesser amount of available Fe IV =O . We refer to this phenomenon as “accumulation-accelerated recombination (AAR)” and highlight the adverse role of Fe IV =O accumulation at the interface. Further, we demonstrate that this fast second-order AAR could be slowed down to first-order kinetics by (i) deprotonation of the metal oxide surface; (ii) evacuating the conduction band electrons; and (iii) partial substitution of Fe IV =O with less active Co IV =O species. Such an insight is vital not only for understanding the efficiency loss mechanisms at the semiconductor–electrolyte interface but also for interpreting the interfacial behavior of photovoltaic systems and photocatalysts.}, archive = {J_JACS}, author = {Jingguo Li and Hang Chen and Siqin Liu and Yu Wang and Wenchao Wan and Yonggui Zhao and Carlos A. Triana and Zihao Xu and Greta R. Patzke}, doi = {10.1021/jacs.5c02231}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21492--21500}, shortjournal = {J. Am. Chem. Soc.}, title = {Accelerated recombination reaction through interfacial FeIV=O accumulation on photoanode surfaces}, volume = {147}, year = {2025}, }
• (2025). Tuning the supramolecular polymerization and cell response of ureidopyrimidinone monomers by pushing the hydrophobic threshold. JACS, 147(25), 21478--21491. (www)

  @article{ , abstract = {Understanding the assembly of small molecules in aqueous media is crucial for the development of adaptive biomaterials. The mechanical properties of supramolecular networks, including stiffness and stress relaxation, play a key role in cellular spreading and can be tuned via formulation strategies or monomer design. Here, we demonstrate the modulation of supramolecular polymerization and cellular response of ureidopyrimidinone (UPy) monomers in water by tailoring the length of the alkyl spacer within the monomer structure. A library of four UPy derivatives with varying hydrophilic–hydrophobic balances was synthesized by using an optimized synthetic approach. The assembly behavior and dynamics of the supramolecular polymers were investigated both in solution and gel states using a wide range of techniques. The results revealed that the alkyl spacer length significantly affects the supramolecular polymer dynamics, kinetics, and stability. Monomers with 6 and 8 methylene units formed dynamic elongated structures, while those with 10 and 12 units yielded robust and stable bundled fibers. In the gel state, a physical cross-linker was required for gel formation. The gels formed by the monomers featuring 8 and 10 methylene units exhibited optimal mechanical properties, promoting the spreading of human normal dermal fibroblasts in both 2D and 3D cultures. These findings highlight the impact of the monomer architecture on the properties of UPy supramolecular systems, paving the way for the rational design of biomaterials with tunable properties.}, archive = {J_JACS}, author = {Riccardo Bellan and Martin G. T. A. Rutten and Xianwen Lou and Chloe M. Wallace and Maritza M. Rovers and Andrew J. Smith and Marcel H. P. van Genderen and Dave J. Adams and Patricia Y. W. Dankers}, doi = {10.1021/jacs.5c01445}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21478--21491}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the supramolecular polymerization and cell response of ureidopyrimidinone monomers by pushing the hydrophobic threshold}, volume = {147}, year = {2025}, }
• (2025). Photoswitchable arylazopyrazole-functionalized ag8 nanoclusters with light-modulated photoluminescence. JACS, 147(25), 21468--21477. (www)

  @article{ , abstract = {Smart molecular photoswitches are an important member in the realm of artificial materials, which can exhibit distinct physicochemical properties under photoirradiation, yet light-driven silver nanocluster switches have been scarcely exploited due to their intrinsic photoinstability. Herein, two photostable isostructural photoresponsive Ag 8 nanoclusters ( Ag8a and Ag8b ) with a bicapped triangular prismatic Ag 8 core protected by the ternary ligands of arylazopyrazole, aryl-thiolate, and diphosphine have been synthesized and characterized comprehensively. The introduction of arylazopyrazole augments a fresh functionality to the silver nanocluster, realizing photoisomerization switched photoluminescence. The Ag 8 nanoclusters can be reversibly isomerized between trans and cis conformations with quite high efficiency under UV and visible light irradiation, respectively, which can occur in both solid and solution states and be conveniently monitored by time-dependent UV–Vis spectroscopy. More interestingly, the trans – cis isomerization process is accompanied by a significant bathochromic shift of the emission band from orange to red. This work not only presents a strategic guidance for synthesizing photoresponsive silver nanoclusters but also provides a new opportunity for developing photoswitchable fluorescent materials.}, archive = {J_JACS}, author = {Tianyang Xu and Wei-Dan Si and Chengkai Zhang and Bao-Liang Han and Zhi Wang and Chen-Ho Tung and Di Sun}, doi = {10.1021/jacs.5c01348}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21468--21477}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoswitchable arylazopyrazole-functionalized ag8 nanoclusters with light-modulated photoluminescence}, volume = {147}, year = {2025}, }
• (2025). Controlled/″Living″ click polymerization with possible bidirectional chain-growth propagation during polyaddition. JACS, 147(25), 21459--21467. (www)

  @article{ , abstract = {In this work, we found a new class of controlled/″living″ polymerization system, which proceeds bidirectional fashion using click reaction of AB monomer bearing azide and alkyne functionalities in a single molecule. The click polymerization of the AB monomer proceeded well using both azide and alkyne initiators in a well-controlled manner in either growth direction to afford polymers with predetermined molecular weights and narrow molecular weight distributions, as well as the terminal structures inherited from the initiator. Especially, the polymerizations with the difunctional initiators provided well-defined linear polymers with azide or alkyne groups at both termini. This approach also allows for polymerization control over the second monomer to give a block copolymer.}, archive = {J_JACS}, author = {Satoshi Sakai and Takuya Nakamura and Seiichiro Uchida and Yuto Nakauchi and Mineto Uchiyama and Tomohiro Kubo and Masami Kamigaito and Kotaro Satoh}, doi = {10.1021/jacs.5c01247}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21459--21467}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlled/″Living″ click polymerization with possible bidirectional chain-growth propagation during polyaddition}, volume = {147}, year = {2025}, }
• (2025). Unraveling photo-driven h2 production with a bio-inspired NiFe complex: Revealing an unexpected hydrogen atom source. JACS, 147(25), 21451--21458. (www)

  @article{ , abstract = {Developing efficient photocatalytic systems for sustainable H 2 production is a crucial step toward reducing dependence on fossil fuels. While extensive research over the past two decades has focused on bioinspired FeFe catalysts, NiFe-based systems remain largely unexplored. This study addresses that gap by introducing the first heterodinuclear NiFe complex capable of catalyzing H 2 production under photoassisted conditions. The catalyst demonstrates remarkable performance, achieving a turnover frequency of 2750 h –1 and a turnover number of up to 41200. A comprehensive mechanistic investigation, supported by EPR and labeling experiments, reveals that the photodriven catalytic pathway differs from the electrocatalytic mechanism. Under photoassisted conditions, BIH not only serves as a sacrificial electron donor, but its oxidized form, BIH ·+ , also acts as a hydrogen atom donor, directly contributing to the high activity of this system. These findings highlight the dual role of BIH in photoassisted catalysis, extending beyond its specific application in H 2 production to other reactions of interest, such as CO 2 reduction.}, archive = {J_JACS}, author = {Irene Suarez-Antuna and Noémie Lalaoui and Emilien Chaigne-Tarlotin and Florian Molton and Frédérique Loiseau and Carole Duboc}, doi = {10.1021/jacs.5c01329}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21451--21458}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling photo-driven h2 production with a bio-inspired NiFe complex: Revealing an unexpected hydrogen atom source}, volume = {147}, year = {2025}, }
• (2025). A coupled organic solar battery with 12.1% efficiency. JACS, 147(25), 21443--21450. (www)

  @article{ , abstract = {Coupled solar batteries enable direct solar-to-electrochemical energy storage but show low efficiencies due to insufficient solar spectrum utilization. Here, we report the exciton-coupled redox reactions over molecular photoelectrochemical materials for wide-spectrum, high-efficiency, coupled organic solar batteries. The molecular materials are prescreened to match the redox potential with visible light photovoltage for band-edge excitons utilization. The combination of strong donor–acceptor structure with external ion polarization enables long-lived superband gap excitons under ultraviolet light for hot exciton redox reactions, while the incorporation of photothermal molecular motifs further realizes in-band near-infrared energy utilization by the photothermal exciton–photon coupling. A record-high solar-to-electrochemical energy storage efficiency of 12.1% and an exchange photocurrent of 11.2 mA cm –2 at 0.93 V were achieved under full-spectrum illumination. The long-term stable operation of the manufactured upscalable (∼200 cm 2 ) tandem device under natural sunlight further demonstrates the potential of coupled organic solar batteries as a commercially viable system for practical applications.}, archive = {J_JACS}, author = {Xiang Zhang and Lei Jiao and Weiqiang Guo and Zhiwei Xiao and Enbo Zhou and Yan-Xi Tan and Yangyang Feng and Daqiang Yuan and Yaobing Wang}, doi = {10.1021/jacs.5c00662}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21443--21450}, shortjournal = {J. Am. Chem. Soc.}, title = {A coupled organic solar battery with 12.1% efficiency}, volume = {147}, year = {2025}, }
• (2025). Selective mass accumulation at the Metal–Polymer bridging interface for efficient nitrate electroreduction to ammonia and zn-nitrate batteries. JACS, 147(25), 21432--21442. (www)

  @article{ , abstract = {The electrochemical conversion of nitrate (NO 3 – ), a common nitrogen source in industrial wastewater and contaminated groundwater, into ammonia (NH 3 ), signifies an approach to wastewater treatment and NH 3 production. Nevertheless, its selectivity and activity at low NO 3 – concentrations and industrial current densities are constrained by limited mass transfer around the electrode. Here, we report a metal–polymer bridging interface constructed by anchoring Cu/Cu 2 O nanoparticles onto a two-dimensional (2D) Cu-based benzene dicarboxylate (CuBDC) coordination polymer via in situ electroreduction (denoted as E-CuBDC). This interface weakens the electrostatic repulsion and regulates the distribution/migration of NO 3 – and H 2 O, creating a Janus NO 3 – -rich and H 2 O-poor domain near the catalyst surface. Operando characterizations and theoretical simulations indicate that the metal–polymer bridging interface selectively accumulates NO 3 – and reduces the energy barrier toward the reduction of *NH 2 OH to *NH 2 , overcoming the mass transfer limitations at a low NO 3 – concentration. E-CuBDC exhibits a high Faradaic efficiency (FE) of over 90% across wide NO 3 – concentrations (7.1–100 mM NO 3 – ) and high applied voltages. Additionally, it achieved stable NH 3 production over 100 h at ampere-level current densities. When applied in a Zn–NO 3 – system, this newly developed E-CuBDC catalyst demonstrates an outstanding power density and FE for NH 3 production, showcasing its great potential for large-scale electrochemical conversion and storage systems. This study presents a generalizable strategy for constructing metal–polymer interfaces to regulate interfacial mass transport.}, archive = {J_JACS}, author = {Guojie Chao and Wei Zong and Jiexin Zhu and Haifeng Wang and Kaibin Chu and Hele Guo and Jian Wang and Yuhang Dai and Xuan Gao and Longxiang Liu and Fei Guo and Ivan P. Parkin and Wei Luo and Paul R. Shearing and Longsheng Zhang and Guanjie He and Tianxi Liu}, doi = {10.1021/jacs.5c00400}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21432--21442}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective mass accumulation at the Metal–Polymer bridging interface for efficient nitrate electroreduction to ammonia and zn-nitrate batteries}, volume = {147}, year = {2025}, }
• (2025). Excited state dynamics of odd [n]Cumulenes: Chain length and conformational effects. JACS, 147(25), 21419--21431. (www)

  @article{ , abstract = {Over the past decades, carbon allotropes have been extensively studied and applied to various technological applications due to their unique electronic and optical properties. Contemporary research has focused on quasi-1D, 2D, and 3D materials. On the other hand, the synthesis and isolation of carbyne as the 1D sp-hybridized carbon nanostructure remains elusive. Significant effort has been directed toward synthesis and study of carbon atomic wires (CAWs) as finite analogues of carbyne. The properties of CAWs composed of alkyne building blocks (oligoynes and polyynes) have provided glimpses of the potential properties of carbyne, while the synthesis and study of the alternative structure of CAWs, [ n ]cumulenes, remains in its infancy. Herein, we present an in-depth photophysical investigation of three odd [ n ]cumulenes ( n = 3, 5, 7) assisted by quantum-chemical calculations. In contrast to the oligoynes, the photophysical properties of cumulenic carbon chains are dramatically impacted by both length and conformational effects of terminal end groups. We demonstrate how the subtle control over rotational motion with respect to the terminal CC bonds of cumulenes alters their electronic ground and excited states as well as dominating the photophysical deactivation cascade.}, archive = {J_JACS}, author = {Tobias Ullrich and Bozheng Sun and Yanwen Yang and Christoph M. Schüßlbauer and Michael J. Ferguson and Daniele Fazzi and Fabrizia Negri and Matteo Tommasini and Rik R. Tykwinski and Dirk M. Guldi}, doi = {10.1021/jacs.5c00147}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21419--21431}, shortjournal = {J. Am. Chem. Soc.}, title = {Excited state dynamics of odd [n]Cumulenes: Chain length and conformational effects}, volume = {147}, year = {2025}, }
• (2025). Proton-transfer kinetics at Liquid–Liquid interfaces. JACS, 147(25), 21408--21418. (www)

  @article{ , abstract = {Proton transfer at electrochemical interfaces is fundamentally important across science and technology, yet kinetic measurements of this elementary step at electrode|electrolyte interfaces are convoluted with other electron-transfer steps and by inhomogeneous electrode surfaces. We use facilitated proton transfer at the interface between two immiscible electrolyte solutions (ITIES) as a platform to study proton-transfer kinetics in the absence of interfacial electron transfer and without the defects at solid|electrolyte interfaces. Diffusion-controlled micropipette voltammetry revealed that 2,6-diphenylpyridine (DPP) facilitates proton transfer across the HCl(aq)|trifluorotoluene interface, while voltammetry at nanopipette-supported interfaces yielded activation-controlled ion-transfer currents. We extract kinetic parameters k app 0 and α app , 3.0 ± 1.8 cm/s and 0.3 ± 0.2, respectively, for DPP-facilitated proton transfer by fitting quasi-reversible voltammograms to a mixed diffusive-kinetic model. Finite-element simulations highlighted regimes of direct proton transfer and sequential proton transfer, where the current divided between these two possible pathways was shown to favor direct proton transfer when the neutral partitioning step DPP(org) → DPP(aq) was rate-determining. Atomistic molecular-dynamics simulations were used to compute the free energy change to move DPP and its protonated analogue within, and across, the liquid|liquid interface. The most-likely location for proton transfer is predicted to be in the surface region where significant interpenetration of the two liquids occurs. Understanding the kinetics of ion transfer at the ITIES illustrated here is important in the development of general theories of ion transfer in electrochemical science and technology.}, archive = {J_JACS}, author = {Nick D’Antona and Joseph Kelly and Nadia Barnard and Shane Ardo and Yixian Wang and Yogesh Surendranath and Thomas E. Markland and Paul A. Kempler and Shannon W. Boettcher}, doi = {10.1021/jacs.4c18349}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21408--21418}, shortjournal = {J. Am. Chem. Soc.}, title = {Proton-transfer kinetics at Liquid–Liquid interfaces}, volume = {147}, year = {2025}, }
• (2025). Chemotype- and target-driven genome mining for a new natural product inhibitor of bacterial peptide deformylase. JACS, 147(25), 21400--21407. (www)

  @article{ , abstract = {Antibiotics are essential for modern medicine, but their use drives the evolution of antimicrobial resistance (AMR) that limits the long-term efficacy of any one drug. To keep pace with AMR and preserve our ability to treat bacterial infections, it is essential that we identify antibiotics with new structures and targets that are not affected by clinical resistance. Historically, most developmental candidates for antibiotics have come from microbial natural products, as they feature chemical structures and biological activities that have been honed over millions of years of evolution. Unfortunately, as classical bioactivity screens for natural product discovery are blind to the pharmacological properties of their hits, they often identify molecules with functional groups that limit their utility as drugs. One prominent example is actinonin, an inhibitor of bacterial peptide deformylase (PDF) whose activity is dependent on a hydroxamate moiety associated with toxicity in vivo . The abundance of bacterial genomes now presents an opportunity for target-based natural product discovery, where biosynthetic pathways can be mined for molecules that possess desired activities but lack known pharmacophores. Here, we use bioinformatics to lead a chemotype-sensitive, target-based search for natural product inhibitors of bacterial PDF that lack the conserved metal chelating group. We describe the discovery, heterologous expression, biosynthesis, total synthesis, and activity of the gammanonins: actinonin homologues from Gammaproteobacteria. Moving forward, we hope this chemotype- and target-driven approach will help to expedite the discovery of new leads for antibiotic development.}, archive = {J_JACS}, author = {Jonas H. Costa-Martini and Eva E. Adams and Chad W. Johnston}, doi = {10.1021/jacs.4c17876}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21400--21407}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemotype- and target-driven genome mining for a new natural product inhibitor of bacterial peptide deformylase}, volume = {147}, year = {2025}, }
• (2025). Nanoparticles selectively regulate the generation and scavenging of multiple reactive oxygen species at designated locations and states. JACS, 147(25), 21385--21399. (www)

  @article{ , abstract = {Photodynamic therapy (PDT) is recognized as a promising therapeutic modality for cancer, psoriasis, bacterial infection, atherosclerosis, and other diseases, yet confronts persistent challenges of oxygen dependency, limited diversity of reactive oxygen species (ROS), and collateral photodamage to healthy tissues. Here, we report that unlike traditional PDT, near-infrared-activated Prussian blue nanoparticles (PBs) uniquely interact with hydrogen peroxide (H 2 O 2 ) to concurrently generate hydroxyl radicals (·OH), hydroperoxyl radicals (·OOH), and singlet oxygen ( 1 O 2 ) through an oxygen-independent pathway, thereby compensating for the damage and selectivity differences between distinct ROS. PB, H 2 O 2 , and light are the three essential factors for producing ROS. Furthermore, PBs exhibit the ability to scavenge H 2 O 2 , ·OH, and ·OOH, thereby maintaining the redox homeostasis and showing negligible phototoxicity in normal tissues. Intriguingly, light irradiation enables PBs to selectively regulate both generation and scavenging of ROS. PB shows a powerful capability to selectively regulate the generation and scavenging of ROS at the designated location and time. Proof-of-concept validation through an infected wound murine model reveals that PBs’ exceptional therapeutic efficacy, achieving unprecedented healing outcomes. The discovery of PB as a special photosensitizer holds promise for enriching the fundamental understanding of PDT, overcoming its inherent limitations, and advancing the development of next-generation PDT strategies.}, archive = {J_JACS}, author = {Xiaojun Cai and Moran Huang and Wujie Qiu and Xue Xie and Jianrong Wu and Hui Qin and Lei Wang and Wei Gao and Yuanyi Zheng}, doi = {10.1021/jacs.4c17687}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21385--21399}, shortjournal = {J. Am. Chem. Soc.}, title = {Nanoparticles selectively regulate the generation and scavenging of multiple reactive oxygen species at designated locations and states}, volume = {147}, year = {2025}, }
• (2025). Pinpointing chemomechanical origins of na cathode degradation. JACS, 147(25), 21375--21384. (www)

  @article{ , abstract = {The performance and longevity of sodium-ion batteries are heavily influenced by cathode degradation, particularly under high-voltage cycling. Despite ongoing research, the interplay between chemical and mechanical processes remains unclear. Here, we investigated the degradation mechanisms of an O3-NaLi 1/9 Ni 2/9 Fe 2/9 Mn 4/9 O 2 (NLNFM) cathode material using synchrotron-based nanoresolution chemical imaging. Oxygen loss at high voltages was identified as the primary trigger, causing unwanted phase transformations, disrupting sodium intercalation, and leading to capacity fade. Fluorine incorporation during cycling also induced stress and particle cracking, accelerating degradation. By analyzing particles of different sizes, we revealed distinct degradation pathways: small particles experience severe side reactions during early cycling due to their high specific surface area, while large particles develop progressive structural damage during extended cycling from intraparticle heterogeneity and stress. These findings highlight the particle-size-dependent nature of cathode degradation and inform strategies such as particle size optimization, doping, micromorphology design, and stress-tolerant structures to mitigate capacity fade in sodium-ion batteries.}, archive = {J_JACS}, author = {Tianxiao Sun and Bin Wu and Shimao Deng and Yu-Jie Guo and Ji-Lei Shi and Xing Zhang and Xiaofeng Shi and Guannan Qian and Jian Wang and Piero Pianetta and Jigang Zhou and Yu-Guo Guo and Yijin Liu}, doi = {10.1021/jacs.4c14571}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21375--21384}, shortjournal = {J. Am. Chem. Soc.}, title = {Pinpointing chemomechanical origins of na cathode degradation}, volume = {147}, year = {2025}, }
• (2025). Generation of rare sugars by electrochemical oxidation of d-glucose using boron-doped diamond electrode. JACS, 147(25), 21363--21374. (www)

  @article{ , abstract = {The electrochemical oxidation of biomass for the production of value-added chemicals represents a promising approach in the field of sustainable chemistry. In this study, we investigated the electrochemical conversion of d -glucose, a biomass-derived compound, using boron-doped diamond (BDD) electrodes under constant applied current (10 mA) or potentials (1.5–3.0 V vs Ag/AgCl). The reaction products were analyzed using high-performance liquid chromatography (HPLC) and liquid chromatography/mass spectrometry (LC/MS) measurements, employing both p -aminobenzoic acid ethyl ester (ABEE) and l -tryptophan amide labeling methods to enable characterization. The results demonstrated that the BDD electrodes achieved 95.9% d -glucose degradation and successfully generated various rare sugars, including d -arabinose (0.126 mmol/L), d -erythrose (0.0544 mmol/L), d -glyceraldehyde, and l -glyceraldehyde (combined 0.148 mmol/L). Under identical conditions, Pt electrodes as a control showed only 10.2% d -glucose degradation with significantly lower rare sugar yields. The applied potential significantly influenced the product distribution, with optimal rare sugar production observed at 2.5 V vs Ag/AgCl, reflecting a balance between glucose oxidation and product degradation. Mechanistic studies suggest that the formation of rare sugars involves a series of oxidation and decarboxylation reactions, facilitated by electrochemically generated active species. The superior performance of the BDD electrodes is attributed to their wide potential window, efficient generation of oxidizing species, and unique surface characteristics. This research provides new insights into the electrochemical transformation of biomass-derived compounds and demonstrates the potential for sustainable production of high-value rare sugars, opening avenues for applications in food science, pharmaceuticals, and green chemistry.}, archive = {J_JACS}, author = {Kio Kawakatsu and Sho Usuki and Tiangao Jiang and Naoko Taki and Yuma Uesaka and Haru Togawa and Shanhu Liu and Yasuaki Einaga and Kazuya Nakata}, doi = {10.1021/jacs.4c17553}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21363--21374}, shortjournal = {J. Am. Chem. Soc.}, title = {Generation of rare sugars by electrochemical oxidation of d-glucose using boron-doped diamond electrode}, volume = {147}, year = {2025}, }
• (2025). A linear metallocene of Sc(II) supported by [C5Me4(SiMe2tBu)]1– ligands. JACS, 147(25), 21357--21362. (www)

  @article{ , abstract = {Reduction of [C 5 Me 4 (SiMe 2 t Bu)] 2 ScI with KC 8 generates the first example of a neutral, linear metallocene of scandium analogous to ferrocene, namely [C 5 Me 4 (SiMe 2 t Bu)] 2 Sc. X-ray diffraction studies, spectroscopic analyses, and DFT calculations are consistent with a Sc(II) complex. [C 5 Me 4 (SiMe 2 t Bu)] 2 Sc reacts reversibly with N 2 to provide the end-on (N═N) 2– complex {[C 5 Me 4 (SiMe 2 t Bu)] 2 Sc} 2 (μ-η 1 :η 1 -N 2 ) and gives a rare example of a crystallographically characterizable Sc(III) terminal hydroxide, namely [C 5 Me 4 (SiMe 2 t Bu)] 2 Sc(OH), as a hydrolysis product. The analogous linear Ca(II) metallocene [C 5 Me 4 (SiMe 2 t Bu)] 2 Ca was synthesized and characterized for comparison.}, archive = {J_JACS}, author = {Joseph Q. Nguyen and Ahmadreza Rajabi and Anthony J. Wang and Joseph W. Ziller and Filipp Furche and William J. Evans}, doi = {10.1021/jacs.5c07237}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21357--21362}, shortjournal = {J. Am. Chem. Soc.}, title = {A linear metallocene of Sc(II) supported by [C5Me4(SiMe2tBu)]1– ligands}, volume = {147}, year = {2025}, }
• (2025). Harnessing the electron-withdrawing inductive effect of one-component ionizable amphiphilic janus dendrimers unveils cation−π interactions and their important roles to targeted mRNA delivery. JACS, 147(25), 21347--21356. (www)

  @article{ , abstract = {It is expected that current medicine will be complemented or even replaced with genetic nanomedicine, which relies on the targeted delivery of nucleic acids. Delivery of mRNA is accomplished using viral and synthetic four-component vectors which deliver the nucleic acid predominantly to the liver. Our laboratories elaborated a one-component ionizable amphiphilic Janus dendrimer (IAJD) which targets the delivery of mRNA and, therefore, is complementary to viral and synthetic vectors. Here we report the study of a library of IAJDs containing derivatives of the natural gallic acid (GA) as branched hydrophobic domain and two ionizable amines connected via four linker length. The linker length mediates an electron-withdrawing inductive effect, which changes the p K a of the IAJDs. The same p K a trend was observed in a previously reported pentaerythritol (PE)-library, which has structures identical to those of the GA-library except that it does not contain the aromatic ring. Unpredictable, the GA-library of IAJDs has consistently higher p K a values than the PE-library, although the linker length-p K a dependence follows the same trend in both libraries. This trend indicates an unexpected cation−π interaction which explains some advantages of GA-IAJDs, including the 10 9 p/s total luciferase activity reported here.}, archive = {J_JACS}, author = {Mahwish Arshad and Elena N. Atochina-Vasserman and Devendra S. Maurya and Juncheng Lu and Nathan Ona and Jessica A. Vasserman and Brieyanna C. McWilliams and Houping Ni and Sydni Berkihiser and Wook-Jin Park and Drew Weissman and Virgil Percec}, doi = {10.1021/jacs.5c07232}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21347--21356}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing the electron-withdrawing inductive effect of one-component ionizable amphiphilic janus dendrimers unveils cation−π interactions and their important roles to targeted mRNA delivery}, volume = {147}, year = {2025}, }
• (2025). Pathway to P(V)-stereogenic phosphoramidates by enantioselective yttrium catalysis. JACS, 147(25), 21339--21346. (www)

  @article{ , abstract = {P-stereogenic phosphoramidates prove essential in agrochemicals and medicines, but their construction remains a challenge for enantioselective catalysis. We describe a Yttrium-catalyzed desymmetrization supported by Feng-ligands. An achiral oxazolidinyl phosphorodichloridate undergoes enantioselective nucleophilic substitution with phenols at ambient temperatures, followed by a stereospecific addition with amines in one pot. The resulting P-stereogenic phosphoramidate serves as a trifunctional building block to access diverse P-(V) motifs, enabling the stereodivergent synthesis of protected ProTides and the first stereoselective total synthesis of phosmidosine.}, archive = {J_JACS}, author = {Brian S. Daniels and Bryan G. Blackburn and Silas J. Scribner and Vy M. Dong}, doi = {10.1021/jacs.5c06639}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21339--21346}, shortjournal = {J. Am. Chem. Soc.}, title = {Pathway to P(V)-stereogenic phosphoramidates by enantioselective yttrium catalysis}, volume = {147}, year = {2025}, }
• (2025). Topochemical ring-opening polymerization of an oxathianethione. JACS, 147(25), 21331--21338. (www)

  @article{ , abstract = {Single crystals of an enantiopure oxathianethione ( OTT ) were found to spontaneously convert to the corresponding polymer ( POTT ) through topochemical ring-opening polymerization (topoROP). The polymerization proceeds quantitatively and stereospecifically to give crystalline POTT with high molecular weights. The resulting POTT crystals were suitable for structure determination through X-ray crystallography to reveal polymers with right-handed helices with an antiparallel arrangement of polymer chains. Control studies support a concerted nucleophilic substitution mechanism that proceeds in the absence of radical intermediates, and the polymerization is suppressed when the monomer is randomly organized in an amorphous glass. Overall, this represents a distinct class of topochemical polymerization that opens new opportunities to prepare highly crystalline sulfur-containing materials.}, archive = {J_JACS}, author = {Alvaro Calderón-Díaz and Liam Ordner and Maximilian G. Bernbeck and Matteo Palesati and Mark Weber and Natalie Stingelin and Will R. Gutekunst}, doi = {10.1021/jacs.5c06180}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21331--21338}, shortjournal = {J. Am. Chem. Soc.}, title = {Topochemical ring-opening polymerization of an oxathianethione}, volume = {147}, year = {2025}, }
• (2025). Benchmarking the reactivity of caged Iron(IV)-oxo sites within Metal–Organic frameworks. JACS, 147(25), 21325--21330. (www)

  @article{ , abstract = {Three recently reported iron-containing metal–organic frameworks, FeZn 4 (prv) 4 (btdd) 3 (Fe- 1 ), Fe 1.8 Zn 3.2 (prv) 4 (btdd) 3 (Fe 1.8 - 1 ), and FeZn 4 (moba) 4 (btdd) 3 (Fe- 2 ) (Hprv = pyruvic acid, Hmoba = 3,3-dimethyl-2-oxobutanoic acid, and H 2 btdd = bis(1 H -1,2,3-triazolo[4,5- b ],[4′,5′- i ])dibenzo[1,4]dioxin), that react with O 2 at low temperatures to generate high-spin ( S = 2) ferryl species provide an unprecedented opportunity to explore the effects of spin state and site-isolation on hydrocarbon oxidation reaction mechanisms. These reagents oxidize the radical clock substrate norcarane, yielding radical lifetimes in the low nanosecond regime, consistent with a diffusion-limited rebound mechanism. Rebound products derived from ligands on the iron centers inside the framework are detected and recapitulate chemistry seen in the structurally related α-ketoglutarate-dependent dioxygenases such as TauD, which also generate high-spin ( S = 2) ferryl intermediates. Framework models indicate that productive reactions occur when norcarane approaches the ferryl species from the larger of the two pores of the MFU-4 l -type framework.}, archive = {J_JACS}, author = {Jonas Börgel and Yuan Cao and Ran Gao and Daniel C. Y. Leong and Rachel Narehood Austin and John T. Groves and Jeffrey R. Long}, doi = {10.1021/jacs.5c05557}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21325--21330}, shortjournal = {J. Am. Chem. Soc.}, title = {Benchmarking the reactivity of caged Iron(IV)-oxo sites within Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Chemical mapping of Nanoparticle–Ligand interfaces in optical nanocavities. JACS, 147(25), 21319--21324. (www)

  @article{ , abstract = {Understanding processes in photon–phonon scattering, absorption, and chemical reactions in optical nanocavities is important for single-molecule sensors, single-photon emitters, and photocatalysis. However, the influence of electromagnetic fields, charge transfer, and molecular geometry is challenging to probe by ensemble-averaged spectroscopic techniques over multiple nanocavities. Photoinduced force microscopy (PiFM), which measures photoinduced polarizability under infrared excitation of a sample in the nanocavity between the scanning probe microscopy tip and sample surface, is used here for simultaneous nanoscale topological and chemical characterization. First-principles density functional theory (DFT) simulations of the vibrational spectra of gold nanoparticle surfaces functionalized with benzenedithiol (Au-BDT) elucidate molecular orientation, charge transfer, and oxidation state for understanding molecular and adatom reconfiguration in optical nanocavities in response to external fields.}, archive = {J_JACS}, author = {Chloe E. Groome and Hector Pascual-Herrero and Meagan E. Hill and Zhe Wang and Mariia Stepanova and Sahar Sharifzadeh and Maxim R. Shcherbakov and Ruqian Wu and Regina Ragan}, doi = {10.1021/jacs.5c05582}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21319--21324}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemical mapping of Nanoparticle–Ligand interfaces in optical nanocavities}, volume = {147}, year = {2025}, }
• (2025). Description of the electronic structure of oxyhemoglobin using fe L-edge X-ray absorption spectroscopy. JACS, 147(25), 21313--21318. (www)

  @article{ , abstract = {The electronic structure of oxyhemoglobin has been controversial since the discovery of the compound’s diamagnetism in 1936. This study uses partial fluorescence yield Fe L-edge X-ray absorption spectroscopy (XAS) in the 3s→2p fluorescence on oxyhemoglobin solutions, measured using a transition-edge sensor detector, to obtain a quantitative experimental description of the electronic structure of the O 2 -bound iron site. The spectrum is very different from typical low-spin Fe II and Fe III heme spectra, and multiplet simulations indicate a mixed ground configuration with ∼57% low-spin Fe III and ∼43% low-spin Fe II character. This is also very different from the Fe II character found for the picket-fence porphyrin model complex. The oxyhemoglobin L-edge XAS data further show that the O 2 ligand engages in a weak σ- but strong π-bond with the iron ion, leading to the overall strong Fe–O 2 bond required for O 2 transport.}, archive = {J_JACS}, author = {Augustin Braun and Charles J. Titus and Leland B. Gee and Michael L. Baker and Max D. J. Waters and James J. Yan and Sang-Jun Lee and Dennis Nordlund and William B. Doriese and Galen C. O’Neil and Daniel R. Schmidt and Daniel S. Swetz and Joel N. Ullom and Kent D. Irwin and Edward I. Solomon}, doi = {10.1021/jacs.5c05261}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21313--21318}, shortjournal = {J. Am. Chem. Soc.}, title = {Description of the electronic structure of oxyhemoglobin using fe L-edge X-ray absorption spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Electrokinetic detection of single-molecule phosphorylation. JACS, 147(25), 21308--21312. (www)

  @article{ , abstract = {Current single-molecule fluorescence experiments lack direct sensitivity to molecular phosphorylation states. We show that electrokinetic properties measured with an anti-Brownian trap resolve the number of phosphorylated sites on individual biomolecules and can monitor phosphorylation cycles with single kinase turnovers. As an application, we directly visualize the rate-limiting step in the kinase catalytic cycle.}, archive = {J_JACS}, author = {Quan Wang}, doi = {10.1021/jacs.5c05073}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21308--21312}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrokinetic detection of single-molecule phosphorylation}, volume = {147}, year = {2025}, }
• (2025). Keteniminium-mediated postpolymerization modification: Unlocking emergent properties in polyacrylamides. JACS, 147(25), 21302--21307. (www)

  @article{ , abstract = {Postpolymerization modification (PPM) is a powerful strategy for expanding the functionality of synthetic polymers beyond what is accessible through direct polymerization. Current PPM approaches for poly(acrylamide)s often require activated monomers or strong metal nucleophiles, thus limiting their accessibility. Herein, we present an amide activation strategy that enabled the direct PPM of unactivated poly(acrylamide)s via keteniminium ion intermediates. Treatment of poly(dialkylacrylamide)s with trifluoromethanesulfonic anhydride (Tf 2 O) resulted in the generation of keteniminium ions that, upon nucleophilic quenching, enabled selective conversion of pendant amides to aryl ketones. Molecular characterization confirmed the formation of poly(acrylamide- co -vinyl ketone) random copolymers with tunable functionalities. Interestingly, copolymers composed of aryl vinyl ketone repeat units underwent controlled photodegradation under UV irradiation, including broad spectrum sunlight, due to Norrish Type II radical fragmentation at the ketone units. This strategy provides a new approach to the PPM of unactivated polymers that leverages unique reactive intermediates, expands the scope of poly(acrylamide) functionalization, and introduces a new path toward designing degradable synthetic polymers with emergent properties.}, archive = {J_JACS}, author = {Kasun Wekasinghe and Stephanie A. Castillo and Jaina R. Bemis and Aaron J. Teator}, doi = {10.1021/jacs.5c04964}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21302--21307}, shortjournal = {J. Am. Chem. Soc.}, title = {Keteniminium-mediated postpolymerization modification: Unlocking emergent properties in polyacrylamides}, volume = {147}, year = {2025}, }
• (2025). Surface enhanced nuclear magnetic resonance spectroscopy at Solid–Liquid interfaces using overhauser dynamic nuclear polarization. JACS, 147(25), 21297--21301. (www)

  @article{ , abstract = {While solid–liquid interfaces are ubiquitous, detecting the associated surface sites under ambient conditions remains a grand challenge. Here, we demonstrate an approach to efficiently enhance the NMR signals of solid surfaces at the solid–liquid interface at ambient temperature that is based on exchange mediated Overhauser effect dynamic nuclear polarization (OE-DNP). We use this approach to obtain DNP enhancements for the 31 P signals of PPh 3 ligands interacting with Rh(I) surface sites, in prototypical silica-supported materials prepared via surface organometallic chemistry. Efficient enhancement (ε i ) is obtained under ambient conditions simultaneously at the surface (ε surface = 20–30) and in solution (ε solution up to 50), enabling detection of species both at the surface and in solution, opening the possibility to monitor surface and interfacial chemistry.}, archive = {J_JACS}, author = {Yu Rao and Domenico Gioffrè and Marcel Levien and Michael Wörle and Pragati Pandey and Marinella Mazzanti and Christophe Copéret and Lyndon Emsley}, doi = {10.1021/jacs.5c04452}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21297--21301}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface enhanced nuclear magnetic resonance spectroscopy at Solid–Liquid interfaces using overhauser dynamic nuclear polarization}, volume = {147}, year = {2025}, }
• (2025). Chemoselective electrochemical coupling of thioethers and primary amines for accessing sulfilimines and sulfoximines. JACS, 147(25), 21290--21296. (www)

  @article{ , abstract = {We report the electrooxidative coupling of thioethers with primary alkylamines, furnishing structurally diverse sulfilimines and sulfoximines including unconventional isopeptides. Cyclic voltammetry and control experiments revealed that modulating the protonation states of reactants and products is key to achieving chemoselective oxidation.}, archive = {J_JACS}, author = {Sukwoo Lee and Jonas Rein and Evan A. Weingarten and Song Lin}, doi = {10.1021/jacs.5c04012}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21290--21296}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemoselective electrochemical coupling of thioethers and primary amines for accessing sulfilimines and sulfoximines}, volume = {147}, year = {2025}, }
• (2025). Resistance gene-guided genome mining reveals RPL10 as the target of ligustrone a. JACS, 147(25), 21284--21289. (www)

  @article{ , abstract = {The ribosome is essential for protein synthesis and targeting its function serves as a platform for many therapies. Resistance gene-guided genome mining for a priori target identification has emerged as a useful workflow in natural product drug discovery, allowing for identification of a compound’s target before the time-consuming work of isolation and characterization is performed. In this work, we identify the previously unknown lig biosynthetic gene cluster (BGC) which contains a predicted resistance gene that shares sequence identity with the gene for human ribosomal protein RPL10. Through both heterologous expression and in situ BGC engineering, we identify ligustrone A ( 1 ) as this BGC’s product. Utilizing chemical genetics and chemoproteomics, we validate that 1 engages RPL10. Taken together, via resistance gene-guided mining we both discover a new target for a known natural product and elucidate its biosynthesis.}, archive = {J_JACS}, author = {Danielle A. Yee and Ross D. Overacker and Michelle F. Grau and Amber Cornelius and Adrianne Pigula and Daniel Mummau and Thomas Pavey and Cynthia Bailey and Clarence Hue Lok Yeung and Lawrence S. Hon and Joseph E. Spraker and Sheena Li and Bruno Perlatti and Samuel K. Oteng-Pabi and Henry H. Le and Colin J. B. Harvey}, doi = {10.1021/jacs.5c03802}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21284--21289}, shortjournal = {J. Am. Chem. Soc.}, title = {Resistance gene-guided genome mining reveals RPL10 as the target of ligustrone a}, volume = {147}, year = {2025}, }
• (2025). Self-adaptive catalysts for CO2 electroreduction. JACS, 147(25), 21267--21283. (www)

  @article{ , abstract = {The electrochemical conversion of CO 2 into value-added chemicals and fuels is considered a promising solution to address energy shortages and environmental pollution problems. However, uncontrollable reconstruction of catalysts during electrolysis often occurs. It remains a challenge to design and develop efficient and stable electrocatalytic systems. Self-adaptive electrocatalyst, which possesses self-regulating capabilities under reaction conditions, has great potential to overcome this challenge. In recent years, substantial progress has been made in utilizing in situ / operando characterization techniques and theoretical simulations to identify reaction sites and explore catalytic mechanisms. There is an urgent need to incorporate these advancements to guide the design of self-adaptive electrocatalysts. In this perspective, we discuss the necessity and effective strategies for constructing self-adaptive catalysts. Subsequently, we systematically summarize the mechanisms of self-adaptive electrocatalysts based on representative research advancements and highlight the beneficial effects of catalyst adaptive transformation on catalyst structure, catalytic activity, and reaction pathway regulation. Finally, we present prospects and suggestions for the future development of CO 2 reduction, from the perspectives of self-adaptive catalyst development, advanced characterization techniques, and intelligent catalytic platforms.}, archive = {J_JACS}, author = {Libing Zhang and Chaofeng Zheng and Xiaofu Sun and Buxing Han}, doi = {10.1021/jacs.5c06091}, journal = {Journal of the American Chemical Society}, month = {6}, number = {25}, pages = {21267--21283}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-adaptive catalysts for CO2 electroreduction}, volume = {147}, year = {2025}, }
• (2025). Correction to “Magnetite nanodiscs activate mechanotransductive calcium signaling in diverse cell types”. JACS, 147(24), 21266. (www)

  @article{ , archive = {J_JACS}, author = {Jacob L. Beckham and Ye Ji Kim and Emmanuel Vargas Paniagua and Noah Kent and Keisuke Nagao and Sharmelee Selvaraji and Florian Koehler and Elian Malkin and Xavier Smith and Anthony Tabet and Sehoon Kang and Polina Anikeeva}, doi = {10.1021/jacs.5c08071}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21266}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Magnetite nanodiscs activate mechanotransductive calcium signaling in diverse cell types”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Broadly applicable Copper(I)-catalyzed alkyne semihydrogenation and hydrogenation of α,β-unsaturated amides enabled by bifunctional iminopyridine ligands”. JACS, 147(24), 21264--21265. (www)

  @article{ , archive = {J_JACS}, author = {Mahadeb Gorai and Jonas H. Franzen and Philipp Rotering and Tobias Rüffer and Fabian Dielmann and Johannes F. Teichert}, doi = {10.1021/jacs.5c07662}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21264--21265}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Broadly applicable Copper(I)-catalyzed alkyne semihydrogenation and hydrogenation of α,β-unsaturated amides enabled by bifunctional iminopyridine ligands”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Copper chelate targeting externalized phosphatidylserine inhibits PD-l1 expression and enhances cancer immunotherapy”. JACS, 147(24), 21263. (www)

  @article{ , archive = {J_JACS}, author = {Fan Gao and Wei You and Lei Zhang and Ai-Zong Shen and Guang Chen and Ze Zhang and Xuan Nie and Lei Xia and Wei-Qiang Huang and Long-Hai Wang and Chun-Yan Hong and Da-Long Yin and Ye-Zi You}, doi = {10.1021/jacs.5c07516}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21263}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Copper chelate targeting externalized phosphatidylserine inhibits PD-l1 expression and enhances cancer immunotherapy”}, volume = {147}, year = {2025}, }
• (2025). Benzotriazole and poly(vinylidene fluoride) synergistically promote the selectivity of carbon dioxide reduction on copper toward c2 products. JACS, 147(24), 21252--21262. (www)

  @article{ , abstract = {Electrochemical reduction of carbon dioxide (CO 2 RR) to valuable chemicals offers a promising solution to mitigate CO 2 emissions and address the energy crisis. Surface modification of the catalyst surface with small molecules or polymers could modulate the product selectivity of the CO 2 RR. If a properly chosen polymer and molecule were combined together, a significant improvement in the CO 2 RR might be realized. Herein, we demonstrate that sequential coating of Cu catalyst with benzotriazole (BTA) and poly(vinylidene fluoride) (PVDF) significantly enhances the product selectivity toward C 2 species. The Faradaic efficiency (FE) of C 2 hydrocarbons increased from 49 to 70% at −1.05 V vs the reversible hydrogen electrode (RHE) in an H-type electrochemical cell, with stable performance maintained over 10 h. The coated BTA molecules could enhance the CO 2 RR activity and promote the production of C 2 species, while the PVDF layer prevents the BTA molecules from dissolving/detaching and regulates the surface coverage of *CO and *H intermediates. This dual-layer modification strategy provides a simple and effective approach to improve the Faradaic efficiencies (FEs) of the CO 2 RR on Cu. Furthermore, this strategy may be integrated with other strategies to further optimize the CO 2 RR performance, offering a versatile pathway for advancing sustainable energy conversion technologies.}, archive = {J_JACS}, author = {Chengcheng Zhu and Zhongyan Gong and Xinya Chen and Lu Jiang and Haonan Chen and Furong Qiao and Qinghua Liu and Yaning Liu and Gang Lu}, doi = {10.1021/jacs.5c08179}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21252--21262}, shortjournal = {J. Am. Chem. Soc.}, title = {Benzotriazole and poly(vinylidene fluoride) synergistically promote the selectivity of carbon dioxide reduction on copper toward c2 products}, volume = {147}, year = {2025}, }
• (2025). Transient dipole strategy boosts highly oriented self-assembled monolayers for organic solar cells approaching 21% efficiency. JACS, 147(24), 21241--21251. (www)

  @article{ , abstract = {Self-assembled monolayers (SAMs) based on carbazole with minimal parasitic absorption, such as the most widely used [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz), dominate the high-performance hole transport layer (HTL) for conventional organic solar cells (OSCs). However, the small dipole moment of the 2PACz molecules results in weak molecular dipole–dipole interactions, leading to disordered dipole orientation and restricting work function modulation, which causes serious interfacial energy loss. Here, we grafted thiophene groups at both ends of the carbazole in 2PACz to obtain an SAM material (Th-Cz), which formed a transient resonance structure during thermal annealing, resulting in a twice-enlarged dipole moment. This strengthened molecular dipole–dipole interactions, facilitating ordered arrangement and dipole orientation of the Th-Cz film, contributing to a higher work function, which enhanced hole extraction and suppressed energy losses at the SAM/active layer interface. Additionally, van der Waals interactions between Th-Cz and the donors enabled the donor crystallizing before the acceptor, and this phenomenon is different from the cocrystallization observed in 2PACz-based active layers. This manipulation of crystallization dynamics favors vertical phase separation with a donor-rich phase at the bottom of active layers, leading to balanced charge-carrier mobilities. The resultant OSCs based on PM6:Y6 and D18-Cl:N3:AT-β2O with Th-Cz as HTL achieved power conversion efficiencies (PCEs) of 19.34% and 20.91% (certified 20.67%), respectively, setting a record PCE for the PM6:Y6-based OSCs and achieving the highest certified PCE for single-junction OSCs to date. Notably, Th-Cz also demonstrated exceptional compatibility with flexible OSCs, delivering a record PCE of 19.63%.}, archive = {J_JACS}, author = {Hongyu Mou and Yue Yin and Haiyang Chen and Jiacheng Xu and Junyuan Ding and Chen Ju and Juan Zhu and Yingyi Wang and Weijie Chen and Guiying Xu and Tianjiao Zhang and Jia Li and Yaowen Li and Yongfang Li}, doi = {10.1021/jacs.5c08124}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21241--21251}, shortjournal = {J. Am. Chem. Soc.}, title = {Transient dipole strategy boosts highly oriented self-assembled monolayers for organic solar cells approaching 21% efficiency}, volume = {147}, year = {2025}, }
• (2025). Axial chlorine engineering of p-block antimony atomic sites boosts oxygen reduction. JACS, 147(24), 21231--21240. (www)

  @article{ , abstract = {The main-group metals characterized by closed d shells are generally regarded as catalytically inert for oxygen reduction reactions (ORR) due to the delocalized valence orbitals. Modulating the coordination environment of metal sites is critical to gaining highly active electrocatalysts for ORR. Herein, atomically dispersed Sb site catalysts were successfully constructed with SbN 4 –Cl configuration for highly efficient ORR. Density functional theory (DFT) calculations reveal that the introduction of an axial Cl ligand regulates the p electron structure of the Sb active center, thereby alleviating the binding energy of the HO* intermediate and lowering the energy barrier of the ORR process. Remarkably, the as-prepared SbN 4 Cl/NC catalysts exhibited excellent ORR activity with a half-wave potential ( E 1/2 ) of 0.921 V and exceptional durability, superior to most 3d transition-metal-based single-atom catalysts and commercial Pt/C. Moreover, Zn–air battery tests also verified the outstanding discharge performance and ultralong charge/discharge durability of SbN 4 Cl/NC catalysts, demonstrating significant promise for energy storage and conversion applications.}, archive = {J_JACS}, author = {Yanmin Hu and Shuwen Niu and Zedong Zhang and Tingting Chao and Tonghui Zhao and Ge Yu and Fangyao Zhou and Xiao Liang and Huile Jin and Zhengkun Yang and Dingsheng Wang and Wei Chen and Yadong Li}, doi = {10.1021/jacs.5c07459}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21231--21240}, shortjournal = {J. Am. Chem. Soc.}, title = {Axial chlorine engineering of p-block antimony atomic sites boosts oxygen reduction}, volume = {147}, year = {2025}, }
• (2025). Band gap engineering and metastable phase discovery in Cu2BaSnS4–xSex nanocrystals via topotactic anion exchange. JACS, 147(24), 21219--21230. (www)

  @article{ , abstract = {Earth-abundant multinary inorganic chalcogenides, such as Cu 2 BaSnS 4– x Se x (CBTSSe), have emerged as promising absorbers for next-generation solar cells. However, accessing colloidal CBTSSe nanocrystals, including metastable polymorphs with more favorable optoelectronic properties, remains a critical synthetic challenge. Herein, we report the first use of topotactic anion exchange to access metastable crystal structures in soft chemistry syntheses. By varying the stoichiometry of selenium precursor, we directly synthesize Cu 2 BaSnS 4– x Se x (0 ≤ x ≤ 4) nanocrystals with a broad band gap tunability of 1.51–2.04 eV. At x = 4, a new metastable trigonal phase of Cu 2 BaSnSe 4 is isolated. This phase arises via an in situ topotactic anion exchange from sulfur-rich Cu 2 BaSnS 4– x Se x intermediates, while retaining both the cation sublattice and overall nanocrystal morphology. The trigonal Cu 2 BaSnSe 4 exhibits a nearly direct band gap that is 280 meV lower than its thermodynamically stable orthorhombic counterpart, aligning more closely with the optimal band gap for single-junction solar cells. In contrast, a postsynthetic anion exchange route leads to the thermodynamically preferred orthorhombic polymorph, pointing to the critical nature of the in situ transformation. Our findings open a versatile pathway for both polymorphic and morphological control in colloidal nanocrystals, expanding the synthetic design space for new optoelectronic materials.}, archive = {J_JACS}, author = {Zhaohong Sun and Yizhen Chen and Richard L. Brutchey}, doi = {10.1021/jacs.5c07324}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21219--21230}, shortjournal = {J. Am. Chem. Soc.}, title = {Band gap engineering and metastable phase discovery in Cu2BaSnS4–xSex nanocrystals via topotactic anion exchange}, volume = {147}, year = {2025}, }
• (2025). Iron-catalyzed enantioconvergent amination of alcohols. JACS, 147(24), 21209--21218. (www)

  @article{ , abstract = {Owing to the prevalence of chiral amines in natural products and pharmaceuticals, we developed an iron-catalyzed borrowing hydrogen enantioconvergent amination of alcohols in the presence of chiral phosphoric acid. This protocol effectively converts a range of secondary alcohols and amines, tolerating numerous functional groups, including hydroxyl, cyano, ester, and boronate groups, into chiral amines with high to excellent yields (up to 99%) and enantioselectivities (up to 99% ee). Notably, the compatibility with peptides, including di- and tripeptides, offers new possibilities for exploring chemical transformations in biological contexts. Mechanistic studies revealed a hydrogen-borrowing pathway, with DFT calculations further elucidating the crucial role of the chiral environment (pocket) in controlling enantioselectivity.}, archive = {J_JACS}, author = {Fan Sun and Bo-Xuan Yao and Siyi Wang and Bolin Ji and Shao-Fei Ni and Weiping Liu}, doi = {10.1021/jacs.5c07101}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21209--21218}, shortjournal = {J. Am. Chem. Soc.}, title = {Iron-catalyzed enantioconvergent amination of alcohols}, volume = {147}, year = {2025}, }
• (2025). Smart energy-storing DNA hydrogel for on-demand laser-free photoimmunotherapy of melanoma. JACS, 147(24), 21194--21208. (www)

  @article{ , abstract = {Photoimmunotherapy, which synergizes phototherapy and immunotherapy, holds significant potential for cancer treatment but demands more precise and effective strategies. Herein, we present a smart DNA hydrogel with energy-storing capabilities that responds to multiple tumor markers, enabling laser-free, on-demand photoimmunotherapy for localized melanoma treatment. The hydrogel is constructed from two single-stranded DNA chains via rolling-circle amplification, incorporating aptamers (Apt PD-1), oligonucleotides (CpG ODNs), and recognition sites for the Hha I endonuclease, enabling a controlled release of the photodynamic module. This module, composed of the AS1411 aptamer, a photosensitizer, and energy-storing persistent luminescent nanoparticles, facilitates selective tumor cell uptake and glutathione-triggered phototherapy in the absence of external irradiation, generating tumor-associated antigens for immunotherapy. Upon specific binding to T cells, Apt PD-1 blocks PD-1 receptors, promoting the release of CpG ODNs to enhance immunotherapy. In a murine melanoma model, the photoimmunotherapy system achieved a tumor inhibition rate of 73.3%. This laser-free, on-demand strategy based on the energy-storing DNA hydrogel offers a precise approach to cancer therapy and highlights the potential of DNA materials in advancing precision medicine.}, archive = {J_JACS}, author = {Huaixin Zhao and Lijun Wang and Sen Yang and Zhuiyun Li and Xiaocui Guo and Chen Zuo and Guoming Xie and Chi Yao and Dayong Yang}, doi = {10.1021/jacs.5c06905}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21194--21208}, shortjournal = {J. Am. Chem. Soc.}, title = {Smart energy-storing DNA hydrogel for on-demand laser-free photoimmunotherapy of melanoma}, volume = {147}, year = {2025}, }
• (2025). Synthetic CRISPR networks driven by transcription factors via structure-switching DNA translators. JACS, 147(24), 21184--21193. (www)

  @article{ , abstract = {CRISPR-Cas systems have advanced many domains in life sciences, enabling diverse applications in gene editing, diagnostics, and biosensing. Here, we introduce a platform that leverages transcription factors (TFs) to regulate CRISPR-Cas12a trans-cleavage activity via engineered DNA translators. These dynamic DNA structures respond to TF binding by switching conformations, modulating Cas12a activity. Using TATA-binding protein and Myc-Max as TF models, we optimized DNA translators for precise and tunable control with rapid response kinetics. We demonstrated the platform’s specificity and versatility by integrating TF-induced regulation into synthetic biology networks, including the activation of a fluorogenic RNA aptamer (Mango III) and the creation of an artificial multimolecular communication pathway between Cas12a and Cas13a. This work establishes TFs as effective regulators of CRISPR-Cas systems, enabling novel protein-nucleic acid communication channels, showing potential for novel synthetic biology applications.}, archive = {J_JACS}, author = {Luca Capelli and Sofia Marzari and Elena Spezzani and Alessandro Bertucci}, doi = {10.1021/jacs.5c06913}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21184--21193}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthetic CRISPR networks driven by transcription factors via structure-switching DNA translators}, volume = {147}, year = {2025}, }
• (2025). Montmorillonite-based oral vaccine for colorectal cancer immunotherapy through mucosal immune activation. JACS, 147(24), 21170--21183. (www)

  @article{ , abstract = {Mucosal cancer, a kind of malignancy originating in mucosal tissues and affecting various organs, such as colorectal cancer, is a major health challenge worldwide. Effective activation of mucosal immunity is crucial for its prevention and treatment. However, conventional vaccines administered subcutaneously or intramuscularly often fail to stimulate a robust immune response against mucosal cancer. In contrast, oral mucosal vaccines can harness the extensive mucosal surfaces of the gut for immune activation. Here, we developed an oral tumor therapeutic vaccine using manganese-rich montmorillonite nanosheets (Mn-MMT@OVA) with promising potential for colorectal cancer immunotherapy. Upon oral administration, the vaccine adheres to the intestinal mucosa and forms a vaccine depot that gradually releases antigens and Mn 2+ . These ions eliminate immune tolerance and activate robust mucosal immunity by cGAS-STING pathway stimulation. The mucosal imprinted effector immune cells migrate to the colonic mucosa and increase the level of cytotoxic T cell infiltration within the colorectal tumor via the mucosal homing effect, resulting in a marked inhibition of colorectal tumor growth. This work provides valuable insights into immune treatment against mucosal cancer and highlights the potential of oral mucosal tumor vaccines for therapeutic development.}, archive = {J_JACS}, author = {Jie Yang and Ya-Xuan Zhu and Zhixin Chen and Zeyang Tian and Han Lin and Jianlin Shi}, doi = {10.1021/jacs.5c06776}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21170--21183}, shortjournal = {J. Am. Chem. Soc.}, title = {Montmorillonite-based oral vaccine for colorectal cancer immunotherapy through mucosal immune activation}, volume = {147}, year = {2025}, }
• (2025). Water-hydroxyl wetting monolayer predicted and realized on a hydrophobic metal surface. JACS, 147(24), 21162--21169. (www)

  @article{ , abstract = {Water adsorption on metal surfaces is ubiquitous in broad natural and technological settings. However, elucidating this phenomenon is often challenging due to difficulties in accurately determining the morphology and understanding the chemistry of adsorbed water networks. Here, we report a significant discovery of the water-hydroxyl (H 2 O–OH) wetting monolayer, which has long been deemed possible only on hydrophilic metal surfaces, now realized on an archetypal hydrophobic metal surface, Ag(111). Ab initio structure searches predicted a hexagonal hydrogen-bonded network comprising alternating H 2 O and OH units; ensuing low-energy-electron-assisted synthesis in concert with extensive characterization and computational simulation provided compelling evidence of an H 2 O–OH monolayer realized on the Ag(111) surface, with remarkable stability up to near room temperature. Our finding brings new insights into the intriguing chemistry of H 2 O–OH overlayers on metal surfaces, and the electron-assisted synthesis opens a unique pathway toward creating delicate molecular networks.}, archive = {J_JACS}, author = {Meiling Xu and Qiaoxiao Zhao and Zijia Liu and Xuegao Hu and Jisong Gao and Pengyue Gao and Yiming Zhang and Yinwei Li and Dong Li and Zhicheng Gao and Kehui Wu and Lan Chen and Changfeng Chen and Yanchao Wang and Yanming Ma and Baojie Feng}, doi = {10.1021/jacs.5c06679}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21162--21169}, shortjournal = {J. Am. Chem. Soc.}, title = {Water-hydroxyl wetting monolayer predicted and realized on a hydrophobic metal surface}, volume = {147}, year = {2025}, }
• (2025). Aromaticity in a palladium-capped al6 trigonal prismatic cluster. JACS, 147(24), 21153--21161. (www)

  @article{ , abstract = {Aromaticity, a fundamental concept for understanding molecular stability, has long been established in organic chemistry. However, isolating examples of all-metal aromaticity has remained a rare achievement, despite its initial proposal in an Al 4 cluster two decades ago. In this study, we successfully isolated and characterized the first all-metal aluminum cluster with a trigonal prismatic geometry. X-ray crystallography reveals that each rectangular face of the Al 6 trigonal prism is capped by a Pd atom, which is further stabilized by six chelating monoanionic ligands and two counter potassium ions. The Pd-capped Al 6 trigonal prismatic cluster features three 3c–2e σ bonds in each of the top and bottom Al 3 layers, and a unique 6c–2e π–π interacting bond connecting the two Al 3 faces. Quantum chemical calculations provide strong evidence for aromaticity in the Pd-capped Al 6 trigonal prism. This discovery not only extends the concept of aromaticity to polyhedral aluminum clusters but also opens new avenues for the synthesis and exploration of novel all-metal aromatic systems.}, archive = {J_JACS}, author = {Pengfei Chen and Jiaxin Chen and Yue Zhao and Jing Ma and Jin Xie and Congqing Zhu and Zhenyang Lin and Qin Zhu}, doi = {10.1021/jacs.5c06541}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21153--21161}, shortjournal = {J. Am. Chem. Soc.}, title = {Aromaticity in a palladium-capped al6 trigonal prismatic cluster}, volume = {147}, year = {2025}, }
• (2025). Transformation of pyridines into 2D and 3D fused bicyclic heterocycles. JACS, 147(24), 21143--21152. (www)

  @article{ , abstract = {Skeletal editing of heteroarenes in complex molecules represents a transformative synthetic strategy that transcends the limitations of conventional peripheral functionalization, enabling the profound structural diversification of molecular frameworks. Here, we demonstrate a powerful metal-free approach for converting pyridines into planar (2D) and three-dimensional (3D) fused bicyclic heterocycles through a precisely orchestrated process of nucleophilic addition, 6π-electrocyclic ring opening/ring closure, and fused ring formation. This methodology exploits the unique reactivity of N -pyridinium salts with hydrazine nucleophiles, accommodating diverse functional groups in a sequential one-pot protocol. In addition, a modified procedure enabled the synthesis of C3-brominated heterocyclic scaffolds. The synthetic utility is further demonstrated by successful late-stage modifications of structurally complex bioactive molecules. Comprehensive mechanistic investigations, including the isolation of key intermediates and computational studies, offer critical insights into the reaction pathway. Our findings establish a versatile platform for the strategic reconstruction of pyridine cores, significantly expanding the accessible chemical space. Notably, the newly synthesized pyrazolopyridazine scaffolds exhibit low-micromolar inhibitory activity over JNK1, positioning them as promising candidates with a substantial medicinal chemistry value for further optimization. This bioactivity validation underscores how our findings establish a versatile platform for the strategic reconstruction of pyridine cores, considerably expanding the accessible chemical space for drug discovery.}, archive = {J_JACS}, author = {Xiangzhang Tao and Hyeonsoo Han and Jinwook Jeong and Dongwook Kim and Sungwoo Hong}, doi = {10.1021/jacs.5c06469}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21143--21152}, shortjournal = {J. Am. Chem. Soc.}, title = {Transformation of pyridines into 2D and 3D fused bicyclic heterocycles}, volume = {147}, year = {2025}, }
• (2025). Development of sclareol- and sclareolide-based chemoenzymatic approaches to ring intact and seco limonoids. JACS, 147(24), 21131--21142. (www)

  @article{ , abstract = {The limonoids are a family of tetranortriterpenoids that share a steroid-like ring system with a conserved 3′-substituted furan moiety. The family exhibits a high degree of structural diversity arising from extensive oxidations and skeletal rearrangements. This account chronicles the evolution of our chemoenzymatic strategy toward various limonoids from two feedstock terpenes, sclareol and sclareolide. An initial route starting from sclareol successfully delivered the limonoid tetracyclic skeleton but was deemed to lack the versatility to access more oxidized family members. A second-generation strategy that commenced from sclareolide was conceived to allow convergent access to gedunin, Corey’s protolimonoid, nimbocinol and azadiradione. Finally, the strategy was further extended to the synthesis of two ring- seco limonoids, methyl angolensate and mexicanolide.}, archive = {J_JACS}, author = {Fang Chen and Jian Li and Hans Renata}, doi = {10.1021/jacs.5c06404}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21131--21142}, shortjournal = {J. Am. Chem. Soc.}, title = {Development of sclareol- and sclareolide-based chemoenzymatic approaches to ring intact and seco limonoids}, volume = {147}, year = {2025}, }
• (2025). All-heteroatom-substituted carbon spiro stereocenters: Synthesis, resolution, enantiomeric stability, and absolute configuration. JACS, 147(24), 21121--21130. (www)

  @article{ , abstract = {Chiral tetra-heterosubstituted methanes (i.e., tetraoxa and azatrioxa carbon spiro stereocenters) are synthesized under CpRu catalysis, using cyclic carbonates and carbamates as substrates and α-diazo-β-ketoesters as reagents. Single enantiomers, isolated by chiral stationary phase chromatography, display chiroptical properties, from g abs ∼10 –5 to ∼10 –4 , which, together with TD-DFT calculations, provide robust absolute configuration assignments. Crystalline spiro diastereomers were also obtained, confirming further the structural and configurational assignments. Using enantioselective dynamic chromatography, remarkable enantiomerization barriers were determined for the ortho-carbonates and ortho-carbamates, with values of up to 27.6 and 34.6 kcal/mol (half-lives 227 days and >84,000 years at 25 °C, respectively). DFT further elucidates the origin of this large difference pointing toward preferred C–O or C–N bond cleavages in the rate-determining step of the S N 1-like mechanism.}, archive = {J_JACS}, author = {Olivier Viudes and Céline Besnard and Alexander F. Siegle and Oliver Trapp and Thomas Bürgi and Gennaro Pescitelli and Jérôme Lacour}, doi = {10.1021/jacs.5c06394}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21121--21130}, shortjournal = {J. Am. Chem. Soc.}, title = {All-heteroatom-substituted carbon spiro stereocenters: Synthesis, resolution, enantiomeric stability, and absolute configuration}, volume = {147}, year = {2025}, }
• (2025). Unraveling polymorphic control in the solid-state [2 + 2] cycloaddition of vitamin k3: Insights from single-crystal irradiation. JACS, 147(24), 21109--21120. (www)

  @article{ , abstract = {The solid-state [2 + 2] cycloaddition of vitamin K 3 (VK3) polymorphs has been systematically reexamined, overcoming the limitations of powder-based studies by focusing on single-crystal behavior. Using THz micro-Raman and FTIR-ATR vibrational spectroscopies combined with X-ray diffraction and solid-state density functional theory (DFT) calculations, we unveil distinct photoreactivity and stereoselectivity in both polymorphs. Monochromatic irradiation at the absorption tail preserved the crystal integrity, enabling a detailed investigation of the reaction outcomes. While both polymorphs undergo photoreaction, their transformations proceed via distinct crystal-to-crystal processes, yielding cis-syn and cis-anti dimers selectively. The photochemical pathway to the formation of the cis -isomers is analyzed by quantum mechanical calculations. These findings highlight the critical role of polymorphism in solid-state photochemistry while questioning the conventional dichotomy between defect-driven and purely topochemical mechanisms.}, archive = {J_JACS}, author = {Fabio Loprete and Lorenzo Pandolfi and Andrea Giunchi and Sara Pandolfi and Simone d’Agostino and Riccardo Tarroni and Patrizio Graziosi and Raffaele G. Della Valle and Tommaso Salzillo and Elisabetta Venuti}, doi = {10.1021/jacs.5c06303}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21109--21120}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling polymorphic control in the solid-state [2 + 2] cycloaddition of vitamin k3: Insights from single-crystal irradiation}, volume = {147}, year = {2025}, }
• (2025). Cobalt-catalyzed enantioconvergent decarboxylative N-alkylation. JACS, 147(24), 21097--21108. (www)

  @article{ , abstract = {Introduction of alkyl substituents onto nucleophilic nitrogen atoms in amines is a central synthetic strategy for increasing molecular complexity and structural diversity in medicinal chemistry, organic synthesis, and materials science. Although the direct transfer of a stereogenic alkyl group onto a nitrogen atom by N-alkylation is one of the most efficient approaches to asymmetric C( sp 3 )–N bond formation, few methods are available for the enantioconvergent N-alkylation of amines with racemic alkyl transfer reagents. We report herein a previously unexplored enantioconvergent decarboxylative N-alkylation of aromatic amines with racemic carboxylic acids. The reaction is enabled by a merger of acridine photocatalysis with Co(salen)-catalyzed asymmetric radical–polar crossover (RPC). The study provides a simple synthetic segue to medicinally and synthetically valuable α-chiral benzylic amines and unravels the structural, electronic, and bonding effects that govern the stereocontrol imparted by the privileged Co(salen)-based asymmetric RPC catalytic system.}, archive = {J_JACS}, author = {Siwen Huang and Ramon Trevino and Dishun Zuo and Xin Tian and Wenhan Yang and William B. Hughes and Seth O. Fremin and Arka Porey and Vy T. B. Nguyen and Bo Gao and Xiyuan Xu and Babu Raj Dhungana and Yingqian Jiang and Yao Sun and Chao Huang and Min He and Chandan Giri and Shree Krishna Dhakal and Bin Qin and Yongxiang Liu and Maosheng Cheng and Oleg V. Larionov and Shengfei Jin}, doi = {10.1021/jacs.5c06317}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21097--21108}, shortjournal = {J. Am. Chem. Soc.}, title = {Cobalt-catalyzed enantioconvergent decarboxylative N-alkylation}, volume = {147}, year = {2025}, }
• (2025). Crystalline and stable hierarchical porous conjugated organic framework as an ideal platform for electrosynthesis. JACS, 147(24), 21089--21096. (www)

  @article{ , abstract = {Fully π-conjugated organic frameworks (π-COFs) have attracted considerable attention due to their enhanced stability and conductivity compared to conventional covalent organic frameworks (COFs). Here, we report the synthesis of a crystalline and stable hierarchical porous π-COF (polyphthalocyanine, HPPc) and demonstrate its potential as an ideal electrosynthesis platform. The as-synthesized crystalline HPPc possesses a high surface area (∼324 m 2 g –1 ), plentiful inherent micropores (1.4 nm), along with hard-template-induced, uniform, and interconnected mesopores (35 nm). This dual-porosity design can lead to improved active site dispersion and mass diffusion. Moreover, the long-range ordering brought by high crystallinity enables the precise customization of active sites as needed. Anchored with nickel and cobalt atoms, the optimized catalyst exhibits an outstanding oxygen evolution reaction performance, including a competitive overpotential of 305 mV at 10 mA cm –2 and a low Tafel slope of 40 mV dec –1 , significantly surpassing commercial RuO 2 . This work opens a new avenue for the rational design and synthesis of chemically stable and crystalline hierarchical porous π-COFs for various applications.}, archive = {J_JACS}, author = {Hongfei Wu and Sixing Yin and Hao Zhang and Haitao Xu and Yan Luo and Feng Li and Dongyuan Zhao}, doi = {10.1021/jacs.5c06338}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21089--21096}, shortjournal = {J. Am. Chem. Soc.}, title = {Crystalline and stable hierarchical porous conjugated organic framework as an ideal platform for electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Data-driven design of random heteropolypeptides as synthetic polyclonal antibodies. JACS, 147(24), 21077--21088. (www)

  @article{ , abstract = {Antibodies are indispensable in biomedicine. However, conventional antibody development faces challenges, including high costs and lengthy production timelines spanning months. Here, we present a data-driven workflow for engineering random heteropolypeptides (RHPs) as synthetic polyclonal antibodies (SpAbs) with programmable binding properties. By combining high-throughput synthesis of selenopolypeptide derivatives with algorithm-assisted optimization, we rapidly identified SpAbs targeting human interferon-α (IFN) and tumor necrosis factor-α (TNF-α) within 2 weeks. The SpAbs exhibited binding affinities comparable to natural antibodies, with the top candidate achieving a dissociation constant of 7.9 nM for TNF-α and 418-fold selectivity over human serum albumin, effectively neutralizing TNF-α-induced cytotoxicity. Liquid-phase electron microscopy revealed flexible, intrinsically disordered protein-like conformations and folding-upon-binding dynamics. This study establishes a robust framework for SpAb discovery, demonstrating that sequence-independent RHPs can serve as functional antibody mimics with tunable binding properties, rapid optimization, and broad potential in diagnostics and therapeutics.}, archive = {J_JACS}, author = {Haisen Zhou and Guangqi Wu and Zuo Zhang and Zhen Zhu and Tanfeng Zhao and Qiankang Zhou and Haolin Chen and Zhenzhong Zhao and Yuanhao Dai and Xiaodong Jing and Wei Ji and Xuehai Yan and Lijiang Yang and Yiqin Gao and Huan Wang and Hua Lu}, doi = {10.1021/jacs.5c06240}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21077--21088}, shortjournal = {J. Am. Chem. Soc.}, title = {Data-driven design of random heteropolypeptides as synthetic polyclonal antibodies}, volume = {147}, year = {2025}, }
• (2025). Oxygen-vacancies-ordering triggered large ferroelectric polarization in CaTiO3 thin films. JACS, 147(24), 21068--21076. (www)

  @article{ , abstract = {Regulating the rich paraelectric materials into the ferroelectric state is currently urgent due to the scarcity of intrinsic ferroelectric materials for practical applications. As a paradigmatic perovskite, CaTiO 3 is an incipient ferroelectric but hard to induce polarity due to the strong tilting of the oxygen octahedron as the antiferrodistortion. Herein, we report a prominent room-temperature ferroelectric CaTiO 3 thin film triggered by oxygen vacancies ordering, the maximum and remanent polarizations reaching up to 68 μC·cm –2 and to 13 μC·cm –2 , respectively, as the excellent level in perovskite incipient ferroelectrics to date. The synchrotron X-ray diffraction (XRD), reciprocal space mapping (RSM), and transmission Electron Microscope (TEM) investigations reveal that bulk-like and ferroelectric phases coexist in the film. Scanning transmission electron microscopy (STEM) images and electric diffractions clearly show that the oxygen vacancies orient along [0–11] in the ferroelectric phase. Such ordered oxygen vacancies soften the tilting of oxygen octahedron, leading to the off-center displacements of Ti 4+ along an out-of-plane direction. It raises the suppression of antiferrodistortion and brings excellent ferroelectric performance. The current breakthrough of CaTiO 3 room-temperature ferroelectric may provide a prospect to explore nonpolar perovskites and will enrich ferroelectric families.}, archive = {J_JACS}, author = {Mingdi Yang and Shan Li and Jiaqi Li and Zhen Wang and Zonglin Lv and Chuanrui Huo and Hongwei Wang and Yilin Wang and Qinghua Zhang and Jun Miao and Qiang Li and Xianran Xing}, doi = {10.1021/jacs.5c06244}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21068--21076}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxygen-vacancies-ordering triggered large ferroelectric polarization in CaTiO3 thin films}, volume = {147}, year = {2025}, }
• (2025). Photocatalysis at the Molecule/Metal oxide interface is driven by asymmetric photocarrier transfer: Ab initio quantum dynamics simulation. JACS, 147(24), 21060--21067. (www)

  @article{ , abstract = {The photocatalytic efficiency of a molecule/metal oxide interface critically depends on the dynamic competition between forward carrier transfer to the molecule and reverse transfer to the substrate. Using CH 3 O – /TiO 2 as a prototypical system and employing nonadiabatic molecular dynamics simulations with hybrid density functional theory, we reveal the complete cascade of atomistic processes following photoexcitation. Our results demonstrate that accurately predicting carrier dynamics in photocatalysis requires a comprehensive understanding of the full photochemical sequence involves carrier trapping, post-trapping stabilization, and subsequent dissociation. In the trapping process, despite an unfavorable 0.55 eV HOMO-VBM offset under static conditions that would suggest minimal hole trapping, thermal fluctuations dynamically modulate adsorbate–substrate hybridization, enabling transient photogenerated hole capture. Critically, when trapped hole stabilization occurs via CH 3 O · radical formation, the reverse transfer time scale dramatically extends from sub-10 fs to sub-10 ps, a rise of 3 orders of magnitude. This radical state elevates the trap-state energy, suppressing reverse transfer and extending carrier lifetimes sufficiently to enable subsequent chemistry. The metastable radical further reduces the C–H dissociation barrier, driving spontaneous photodecomposition via proton-coupled charge transfer. Our findings reconcile long-standing theory-experiment discrepancies by demonstrating that a dual energy alignment framework in the molecule/metal oxide interface: initial charge capture requires pretrapping energy matching, while post-trapping stabilization via chemical intermediates creates an energetic asymmetry that effectively suppresses carrier dissipation. This mechanistic understanding of interfacial charge dynamics provides fundamental design principles for the rational development of high-efficiency photocatalytic systems.}, archive = {J_JACS}, author = {Siyi Wu and Jianzheng Ma and Changwei Zhang and Oleg V. Prezhdo and Jin Zhao and Xin-Gao Gong and Weibin Chu}, doi = {10.1021/jacs.5c06155}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21060--21067}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalysis at the Molecule/Metal oxide interface is driven by asymmetric photocarrier transfer: Ab initio quantum dynamics simulation}, volume = {147}, year = {2025}, }
• (2025). Intramolecular N–O bond formation for the synthesis of N-alkyl and N-aryl isoxazolidines. JACS, 147(24), 21053--21059. (www)

  @article{ , abstract = {We describe the synthesis of a series of readily assembled, variously substituted 3-(4-trifluoromethyl-2-nitrobenzenesulfonamido)alkyl silylperoxides and their conversion to the corresponding isoxazolidines in moderate to high yield by intramolecular N–O bond formation on removal of the sulfonamide protecting group. Cyclization with N–O bond formation was dependent on steric hindrance of the electrophilic silylperoxides, with primary systems cyclizing directly during the course of sulfonamide cleavage with thiolate anions. Secondary silyl peroxides, on the other hand, were best cyclized by warming in the presence of hexafluoroisopropanol after desulfonylation, while tertiary silylperoxides required deprotonation of the intermediate amine. Tertiary benzylic peroxides underwent cyclization by a novel mechanism, with the formation of intermediate trifluoromethylnitrophenyl peroxides, during the course of fluoride-mediated desilylation. The cyclization was extended to include the formation of a simple oxazine, but extrapolation to the formation of an oxazepine was foiled by competing Kornblum DeLaMare fragmentation at the level of the intermediate aminoperoxide.}, archive = {J_JACS}, author = {Margaret Solecki and David Crich}, doi = {10.1021/jacs.5c06061}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21053--21059}, shortjournal = {J. Am. Chem. Soc.}, title = {Intramolecular N–O bond formation for the synthesis of N-alkyl and N-aryl isoxazolidines}, volume = {147}, year = {2025}, }
• (2025). Fully conjugated thiophene-fused oligo-BODIPYs: A class of intensely near-infrared absorbing, arc-shaped materials with up to 31 linearly-fused rings. JACS, 147(24), 21041--21052. (www)

  @article{ , abstract = {Structurally well-defined large π-conjugated systems attract significant interest in molecular materials both for their unique electronic/photophysical properties and unexplored structure–property relationships arising from synthetic challenges. Herein, we address this challenge by leveraging a series of polycondensed π-system doping with B, N and S heteroatoms. In our approach, a series of fully conjugated thiophene-fused oligo-BODIPYs with atomic precision have been efficiently synthesized through the combination of intermolecular S N Ar reactions followed by intramolecular aromatic oxidative couplings from halogenated BODIPY precursors. The largest architecture is a fully fused BODIPY octamer, featuring a coplanar backbone of 31 linearly fused rings. The extended π-conjugation causes a dramatic shift of the absorption event from about 500 nm (monomer) to 822 nm (octamer) with extremely high molar absorptivities reaching 800,000 M –1 cm –1 , as well as maintaining intense fluorescence intensity (Φ FL up to 0.32), long triplet lifetime (τ T = 0.61–15.4 μs), efficient triplet quantum yields (Φ T = 0.24–0.81) and good singlet oxygen generation abilities. More interestingly, due to the weak aromaticity of thiophene, oligo-BODIPYs exhibit triplet state localization as their conjugation length increases, where the triplet energy remains constant while the singlet energy decreases significantly. Notably, intense near-infrared thermally activated delayed fluorescence (TADF) is observed even in tetramers, hexamers, and octamers. Our findings not only present a new series of heteroatom-doped condensed π-systems but also establish a precise regulation mechanism for singlet–triplet energy levels in molecules with large rigid π-conjugated structures. Furthermore, this work provides a novel strategy for designing next-generation TADF molecules with narrowband emission.}, archive = {J_JACS}, author = {Qingbao Gong and Jinsong Shao and Wanwan Li and Xing Guo and Shizhang Ling and Yun Wu and Yaxiong Wei and Xinsheng Xu and Xiaochun Jiang and Lijuan Jiao and Erhong Hao}, doi = {10.1021/jacs.5c05873}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21041--21052}, shortjournal = {J. Am. Chem. Soc.}, title = {Fully conjugated thiophene-fused oligo-BODIPYs: A class of intensely near-infrared absorbing, arc-shaped materials with up to 31 linearly-fused rings}, volume = {147}, year = {2025}, }
• (2025). Elucidating the activity of electrochemical nitrate reduction: High-valent anionic intermediates as kinetic gatekeepers. JACS, 147(24), 21032--21040. (www)

  @article{ , abstract = {The persistent paradox in electrochemical nitrate reduction (NO 3 – RR)─the requirement of high overpotentials despite its highly exothermic nature─remains a critical roadblock for efficient ammonia electrosynthesis. Here, we resolve this conundrum by identifying a high-valent anionic intermediate as kinetic gatekeepers during the nitrate reduction on a single-atom catalyst by using AIMD simulations under explicit solvation and electrode potentials. Employing our self-developed constant-potential thermodynamic integration method, we reveal a stark kinetic barrier dichotomy: while the reaction is thermodynamically favorable governed by the N–O break, the protonation to oxygen at a low anionic state necessitates substantial activation energy. Mechanistic analysis uncovers that electrode polarization preactivates *NO 3 – into a metastable high-valent *NO 3 2– intermediate, which serves as the key step to the following protonation process. Crucially, this intermediate’s stabilization requires a highly negative potential, directly linking its formation to the observed overpotential. Furthermore, molecular dynamics simulations also demonstrate that K + cations play a key role in electrostatically stabilizing the adsorption of negatively charged NO 3 – onto the negatively polarized cathode. This work calls for the urgent reconsideration of conventional nitrate reduction mechanisms and the exigency of refined interface design principles for improved nitrate electrocatalysis.}, archive = {J_JACS}, author = {Sheng-Jie Qian and Hao Cao and Xin-Mao Lv and Jun Li and Yang-Gang Wang}, doi = {10.1021/jacs.5c05728}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21032--21040}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating the activity of electrochemical nitrate reduction: High-valent anionic intermediates as kinetic gatekeepers}, volume = {147}, year = {2025}, }
• (2025). Pb:Sn ratio-driven polytypism and band modulation in photoresponsive hexagonal perovskitoids. JACS, 147(24), 21014--21031. (www)

  @article{ , abstract = {Three-dimensional (3D) perovskites of the formula AMX 3 are known for their excellent optoelectronic properties, but their design is limited by the narrow range of A-site cations that can template the 3D corner-sharing structure, and many of the viable options have already been explored. These materials also face structural instability under environmental conditions. In contrast, 3D hexagonal perovskitoids, with the same chemical formula, may offer enhanced stability and richer structural diversity through a range of corner- and face-sharing octahedral configuration options, providing greater opportunities for structural design; however, challenges such as synthesis complexity and wide band gaps have hindered optoelectronic performance achieved to date. Herein, we synthesized a structural homologous series of mixed-metal hexagonal perovskitoids with the formula APb 1– x Sn x I 3 ( x = 0, 0.25, 0.50, 0.75, 1; A = ethylammonium, guanidinium) and identified three polytypes (9R, 12R, 6H) using single-crystal X-ray diffraction (SCXRD). These structures exhibited increasing corner-sharing connectivity with higher Sn content, revealing a previously unobserved relationship between metal composition and structural evolution in perovskitoid materials. The incorporation of Sn reduced the band gap (tunable from 2.51 to 1.87 eV) and drove structural transformations, a trend seen also in density functional theory (DFT) calculations, which suggest a thermodynamic preference for Pb at face-sharing sites and Sn at corner-sharing sites. DFT band structure calculations and optical spectroscopy also reveal an anomalous behavior in these materials, which we term polytypic band modulation. This phenomenon combines conventional band bowing with the structural transformations that occur as Sn content increases, as observed in the band gap and in photoluminescence spectra. Photodiodes fabricated from thin films of these materials exhibited stable and pronounced photoresponses across various light intensities over time. The combination of templating 3D perovskitoids with multiple cations and alloying Pb and Sn suggests a vastly underexplored phase space that offers new parameters to tune perovskitoids.}, archive = {J_JACS}, author = {Taylor E. Wiggins and Abdulaziz S. R. Bati and Mikaël Kepenekian and Robert P. Reynolds and Stefan Zeiske and Anastasia D. Pournara and Cheng Liu and Yi Yang and Xianfu Zhang and Isaiah W. Gilley and Bin Chen and Jacky Even and Edward H. Sargent and Mercouri G. Kanatzidis}, doi = {10.1021/jacs.5c05714}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21014--21031}, shortjournal = {J. Am. Chem. Soc.}, title = {Pb:Sn ratio-driven polytypism and band modulation in photoresponsive hexagonal perovskitoids}, volume = {147}, year = {2025}, }
• (2025). Unraveling double-exchange effect coupling spin modulation of Sr2Fe1.5Mo0.5O6-δ electrocatalyst for solid oxide cells. JACS, 147(24), 21003--21013. (www)

  @article{ , abstract = {Perovskites are promising electrocatalysts for solid oxide cells (SOCs) due to their tunable structures. The reactivity/stability can be effectively enhanced by tuning the spin, whereas few studies have been able to elucidate the correlation between spin and reactivity/stability. Herein, the double-exchange effect coupling spin modulation is studied for Sr 2 Fe 1.3 Ni 0.2 Mo 0.5 O 6 , which exhibits a current density of 2.48 A cm –2 with high stability at 800 °C and 1.5 V as the cathode in CO 2 reduction. Based on Mössbauer spectroscopy, X-ray absorption spectroscopy, and density functional theory calculations, it is revealed that the doped Ni induces an additional double-exchange effect with enhanced conductivity coupling spin modulation. It produces high-spin Fe 4+ ( t 2g 3 e g 1 ) with vacant e g orbitals which can accommodate additional electrons from the lone pairs of oxygen, thus facilitating CO 2 reduction by enhancing CO 2 adsorption and weakening CO adsorption. This work provides a general strategy for the design of SOC electrocatalysts.}, archive = {J_JACS}, author = {Yuanfeng Liao and Jun Liu and Hao Chen and Yan Yi and Xiuan Xi and Jianwen Liu and Lei Wang and Jiujun Zhang and Xian-Zhu Fu and Jing-Li Luo}, doi = {10.1021/jacs.5c05525}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {21003--21013}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling double-exchange effect coupling spin modulation of Sr2Fe1.5Mo0.5O6-δ electrocatalyst for solid oxide cells}, volume = {147}, year = {2025}, }
• (2025). Phototriggered LYTAC: Photoactive bispecific aptamer chimera enhances targeted degradation of membrane protein through regulating cell autophagy. JACS, 147(24), 20989--21002. (www)

  @article{ , abstract = {Regulating membrane protein abundance through Lysosome Targeting Chimera (LYTAC) holds significant promise in addressing various diseases. However, the precise structural control of LYTAC molecules and how to improve their treatment efficacy remain elusive. In this study, we develop a multifunctional phototriggered LYTAC platform, named PT-LYTAC, to enhance targeted protein degradation using a photoactive bispecific aptamer chimera (PBAC). PBAC is designed with a precise modular approach that integrates an NIR photosensitive molecule into a bispecific aptamer chimera. Taking advantage of the low molecular weight and easy synthesis of the DNA aptamers, PBAC can efficiently transport the therapeutically relevant membrane protein PTK7 to lysosomes for degradation through the lysosomal pathway. Moreover, our investigation reveals that the multifunctional PT-LYTAC platform, enabled by DNA aptamers, promotes protein degradation by modulating cellular autophagy. By the combination of targeted protein degradation and spatiotemporally controllable regulation of intracellular oxidative stress, the function of tumor cells can be significantly inhibited. Under NIR laser irradiation, PT-LYTAC completely suppresses colorectal cancer growth with just one dose and a single laser treatment, all without any apparent side effects. We anticipate that this novel PT-LYTAC will expand the use of DNA-based LYTAC drugs and provide a new dimension for targeted protein degradation.}, archive = {J_JACS}, author = {Rongjun Zhang and Changjie Yang and Xiaobo Gao and Zhenyang He and Ding-Kun Ji and Weihong Tan}, doi = {10.1021/jacs.5c05456}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20989--21002}, shortjournal = {J. Am. Chem. Soc.}, title = {Phototriggered LYTAC: Photoactive bispecific aptamer chimera enhances targeted degradation of membrane protein through regulating cell autophagy}, volume = {147}, year = {2025}, }
• (2025). β-thioglycosylation from unactivated carbohydrates. JACS, 147(24), 20978--20988. (www)

  @article{ , abstract = {Thioglycosides are prominent glycosides in biology and drug discovery because of their unique physicochemical and biological properties. The stereoselective construction of thioglycosides from unactivated carbohydrates has been historically challenging. Herein, we unearthed an S N 2 strategy with anomeric non-prefunctionalized glycosyl donors to achieve β-stereoconvergent thioglycosylation, featuring in situ activation–acceptor integration via designed reagents. The thioglycosylating reagent featured an iminium motif of a six-electron/four-center system, not only activating the anomeric hydroxyl groups but also facilitating reversible convergence from β to α anomer, which enabled the stereospecific S N 2 coupling from the β-face via the intimate ion pair of the imine cation and sulfide anion. The adjustable assembly of sp 3 -, sp 2 -, and sp-type sulfur acceptors was comprehensively achieved with a 130-membered library of β-thioglycosides for overwhelming functional group compatibility and β-selectivity. Click linkages have been successfully realized for alkenyl/alkynyl thioglycosides with diversely functional molecules via site-selective methionine bioconjugation and azide–alkyne cycloaddition.}, archive = {J_JACS}, author = {Hao Li and Weigen Du and Chengliang Li and Leiyang Bai and Xuefeng Jiang}, doi = {10.1021/jacs.5c05414}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20978--20988}, shortjournal = {J. Am. Chem. Soc.}, title = {β-thioglycosylation from unactivated carbohydrates}, volume = {147}, year = {2025}, }
• (2025). CO2 conversion enhancement by hydrophobic cation additives is nearly exclusive at the undercoordinated sites of metal surfaces. JACS, 147(24), 20967--20977. (www)

  @article{ , abstract = {Modifying the composition of the interfacial liquid, the region in contact with a charged solid, has emerged as a complementary strategy to enhance CO 2 electroconversion kinetics by creating a more favorable catalytic environment. This can be accomplished by using hydrophobic cation additives like the cetyltrimethylammonium. Here, we demonstrate that the enhancement effects of cetyltrimethylammonium are highly confined to undercoordinated metal sites. Advanced surface characterization and quantitative analysis with the polycrystalline Ag catalyst reveal that cetyltrimethylammonium enhances the CO 2 -to-CO turnover frequency of undercoordinated sites by nearly 2 orders of magnitude, while the rest of the other sites exhibit only a 2-fold increase. Ultimately, in the presence of cetyltrimethylammonium, the intrinsic activity of undercoordinated Ag sites surpasses that of the rest by more than 3 orders of magnitude. Since these sites constitute only a small fraction of the total surface and are highly susceptible to blockage by other species, even nanomolar concentrations of impurity metals in solution can completely nullify the overall enhancement effects, as observed for both CO and formate production with Ag and Sn as catalysts, respectively. These findings highlight the significant site-dependent nature of environmental adjustments near catalytic surfaces, an aspect previously overlooked, and the need for a deeper understanding of the interplay between surfaces and near-surface environments to further advance electrocatalytic systems for CO 2 and beyond.}, archive = {J_JACS}, author = {Rani Baidoun and Yidong Hua and Joseph Nicolas and Dohyung Kim}, doi = {10.1021/jacs.5c05352}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20967--20977}, shortjournal = {J. Am. Chem. Soc.}, title = {CO2 conversion enhancement by hydrophobic cation additives is nearly exclusive at the undercoordinated sites of metal surfaces}, volume = {147}, year = {2025}, }
• (2025). Silicon rhodamine-catalyzed near-infrared light-induced photodecaging of ortho-nitrobenzyl groups in vitro and in vivo. JACS, 147(24), 20957--20966. (www)

  @article{ , abstract = {The ortho-nitrobenzyl (ONB) group is one of the most widely utilized photocages for spatiotemporal control of biological processes via the light-triggered activation of small molecules and macromolecules. However, a significant limitation is that ONB photocages typically absorb in the UV/blue light region, which is phototoxic to living systems and exhibits limited tissue penetration. In this study, we present a novel approach for near-infrared (NIR) light-triggered photodecaging of the ONB core using silicon rhodamine (SiR) as a photoredox catalyst. The reaction efficiently uncages ONB substrates under 660 nm light irradiation, achieving high yields across a diverse range of substrates, including amino acids, nucleotides, prodrugs, bioactive small molecules, caged fluorescent dyes, and proteins. Mechanistic studies demonstrate that the uncaging reaction proceeds through nitroreduction via a single electron transfer mechanism, followed by an electron cascade-triggered self-immolation process. The reaction has been successfully applied in both mammalian cells and bacteria. Furthermore, we developed a NIR light-activated prodrug release protocol for antibody–drug conjugates (ADCs) targeting noninternalizable cancer cell surface markers and demonstrated the utility of this approach in a tumor-bearing mouse model.}, archive = {J_JACS}, author = {Xiaosa Yan and Jia-Hui Zhao and Qing Wang and Wenjing Wang and Yanchao Ding and Yutong Zhou and Gang Chen and Juanjuan Du and Weiren Huang and Ling Chu}, doi = {10.1021/jacs.5c04942}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20957--20966}, shortjournal = {J. Am. Chem. Soc.}, title = {Silicon rhodamine-catalyzed near-infrared light-induced photodecaging of ortho-nitrobenzyl groups in vitro and in vivo}, volume = {147}, year = {2025}, }
• (2025). Divergent asymmetric dialkylation of dienoic acids with carbonyls and zinc reagents via tandem ni(0) and Ni(II) catalysis. JACS, 147(24), 20947--20956. (www)

  @article{ , abstract = {Reductive elimination of dialkyl Ni(II) species for the enantioselective construction of a C(sp 3 )–C(sp 3 ) bond represents a fundamental challenge due to the low oxidative ability of the Ni(II) ion. Here we report that a Ni(0) complex can perform as a π-Lewis base to activate the 2,4-dienoic carboxylate salts formed in situ with zinc reagents, such as dimethylzinc, and undergo vinylogous addition to carbonyls α-regioselectively and stereoselectively. After transmetalation with another organometallic reagent, the resultant alkyl allylic nickel(II) species readily undertake reductive elimination to finally forge two C(sp 3 )–C(sp 3 ) bonds, even with switchable diastereodivergence and α,β- or α,δ-regiodivergence via ligand or substrate control. A self-assembled dinuclear Zn cage framework is believed to enhance the latter process through an intriguing outer-sphere π-acidic activation mode.}, archive = {J_JACS}, author = {Shun-Zhong Tan and Dai-Fu Zhang and Lei Zhu and Qin Ouyang and Wei Du and Ying-Chun Chen}, doi = {10.1021/jacs.5c05284}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20947--20956}, shortjournal = {J. Am. Chem. Soc.}, title = {Divergent asymmetric dialkylation of dienoic acids with carbonyls and zinc reagents via tandem ni(0) and Ni(II) catalysis}, volume = {147}, year = {2025}, }
• (2025). Efficient aminations of aryl halides by a Cu(II) catalyst. JACS, 147(24), 20939--20946. (www)

  @article{ , abstract = {Aminations of aryl halides catalyzed by copper complexes with ancillary ligands have become valuable for the formation of anilines, and the mechanisms for these reactions have been shown to occur by a Cu(I)/(III) cycle. We show that the coupling of aryl and heteroaryl bromides with a range of nitrogen nucleophiles, including hydrazine hydrate and complex amines, occurs with copper and a simple dianionic, dimethylpyrrole-based oxalohydrazido ligand by a cycle in which Cu(II) complexes of this ligand are the resting state and an active, low-valent, catalytic intermediate. These couplings involving Cu(II) occur in many cases with just 0.1–0.2 mol % catalyst and take place under air, due to the absence of Cu(I) that is less stable to disproportionation and to air. Kinetic profiles and EPR spectroscopy of reactions initiated with Cu(I) and Cu(II) precursors provide strong evidence that both systems react through an active Cu(II) complex, thereby indicating that a recently uncovered mechanistic manifold for copper-catalyzed couplings of phenoxides with oxalamide ligands is also followed for the coupling of nitrogen nucleophiles catalyzed by copper complexes of oxalohydrazido ligands.}, archive = {J_JACS}, author = {Christina N. Pierson and Teresa Horak and Willi M. Amberg and Ritwika Ray and Guodong Rao and Timothy M. Pinkhassik and Serena M. Fantasia and Stephan M. Rummelt and Kurt Püntener and R. David Britt and John F. Hartwig}, doi = {10.1021/jacs.5c05210}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20939--20946}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient aminations of aryl halides by a Cu(II) catalyst}, volume = {147}, year = {2025}, }
• (2025). Polarization-ordered tandem in superlattice promoting C–N photocatalytic cross-coupling. JACS, 147(24), 20930--20938. (www)

  @article{ , abstract = {Transition metal-catalyzed C–N cross-coupling reactions are pivotal in synthesizing pharmaceuticals and agrochemicals. Nickel catalysts, while cost-effective, suffer from rapid deactivation via reductive elimination, leading to reaction instability. Photocatalysis using photogenerated charge carriers offers a promising solution to mitigate metal catalyst deactivation, yet their efficacy remains constrained by inefficient electron–hole separation, which reduces the overall catalytic performance. Herein, we propose a polarization-ordered tandem strategy to integrate multiple continuous charge carrier drivers into superlattice photocatalysts, enabling efficient charge carrier separation over a broader spatial range. Taking Bi 4 TaO 8 Cl–Bi 2 YO 4 Cl superlattice as an example, aberration-corrected electron microscopy and atomic-resolution elemental mapping confirm the successful construction of the superlattice structure. Combined with fluorescence spectroscopy, Kelvin probe spectroscopy, and ultrafast spectroscopy, our results indicate that the ordered polarization tandem between the constituent layers significantly lowers the exciton binding energy, improving carrier transfer efficiency and charge separation. Consequently, efficient electron–hole separation effectively suppresses nickel deactivation during C–N coupling reactions. Bi 4 TaO 8 Cl–Bi 2 YO 4 Cl can achieve a high conversion (99%) and selectivity (99%) to couple pyrrolidine and 4-bromobenzonitrile under visible light within 2 h. The presented strategy not only effectively mitigates the deactivation of transition metal catalysts in C–N coupling reactions but also opens new avenues for enhancing the efficiency of traditional photocatalytic processes.}, archive = {J_JACS}, author = {Huiyi Li and Qinglong Wu and Lei Li and Liang Sun and Min Ge and Qilong Liu and Chong Xiao and Qun Zhang and Yi Xie}, doi = {10.1021/jacs.5c05186}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20930--20938}, shortjournal = {J. Am. Chem. Soc.}, title = {Polarization-ordered tandem in superlattice promoting C–N photocatalytic cross-coupling}, volume = {147}, year = {2025}, }
• (2025). Single-molecule macrocyclic carrier overcomes the direct transmembrane of medium-sized cargoes. JACS, 147(24), 20919--20929. (www)

  @article{ , abstract = {Direct transmembrane transport plays an important role in the biomedical field. Although well-established methods exist for the direct membrane transport of small-sized cargoes (e.g., water and ions) and large-sized cargoes (e.g., proteins, DNAs, polysaccharides), they are challenging to directly apply to medium-sized cargoes (e.g., drugs, probes, oligopeptides, and growth hormones). Here, we present a negatively charged single molecular carrier, carboxyl-modified azocalix[6]arene (CAC6A), as a direct transmembrane tool that facilitates the transport of medium-sized cargoes. The cellular uptake pathway of CAC6A was identified using pharmacological inhibitors, and the direct transmembrane transport was confirmed. Further mechanistic transport investigations reveal that the modification group at the upper rim, the cavity size, and the appropriate amphiphilicity of CAC6A promote direct membrane transport. Combined with the hypoxia-responsive property, CAC6A achieved the targeted release of the payload. The findings in this work may lead to the development of macrocycle-based transmembrane systems with broad applications in biomedicine, diagnostics, and sensing.}, archive = {J_JACS}, author = {Xiaoxue Hou and Xin-Yue Hu and Yang Wang and Huan-Yu Wang and Yu-Chen Pan and Jie Chen and Juan-Juan Li and Ze-Han Wang and Fan Huang and Jianfeng Liu and Dong-Sheng Guo}, doi = {10.1021/jacs.5c04866}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20919--20929}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-molecule macrocyclic carrier overcomes the direct transmembrane of medium-sized cargoes}, volume = {147}, year = {2025}, }
• (2025). Discovery of a two-step enzyme cascade converting aspartate to aminomalonate in peptide natural product biosynthesis. JACS, 147(24), 20909--20918. (www)

  @article{ , abstract = {Aminomalonic acid (Ama) is found in various natural products and protein hydrolysates of multiple organisms, but the understanding of its biosynthetic origin remains largely limited. By exploiting a biosynthetic gene cluster for ribosomally synthesized and post–translationally modified peptides (RiPPs), which are rich sources of new enzyme chemistry, we identified a novel two-enzyme pathway for Ama biosynthesis. This biosynthetic pathway, mediated by an Fe(II)/2-oxoglutarate-dependent oxygenase (Fe(II)/2OG), SmaO, and an atypical Fe(II)-dependent histidine-aspartate (HD) domain enzyme, SmaX, converts aspartate (Asp) to β-hydroxyaspartic acid (Hya) intermediate and ultimately to Ama. These tandem enzymatic reactions─hydroxylation of the carbon next to an acid functional group and subsequent four-electron oxidative bond cleavage in α-hydroxy acid─are similar to those associated with other known HD domain oxygenases, PhnZ and TmpB. However, SmaX also exhibits unique features, such as C–C bond cleavage in α-hydroxycarboxylate using a single Fe cofactor, in contrast to the C–P bond cleavage using a mixed-valent diiron cofactor in PhnZ and TmpB. Bioinformatic analysis reveals that this two-enzyme cascade may be present in various biosynthetic pathways for peptide natural products, including RiPPs and nonribosomal peptides (NRPs). Collectively, our study demonstrates the presence of a novel Ama biosynthetic pathway and suggests its widespread distribution in peptide natural product biosynthesis.}, archive = {J_JACS}, author = {Hye Won Kim and Sangwook Kang and Sihyeon Kim and Hyunbin Lee and Yegang Hur and Woon Ju Song and Dong-Chan Oh and Seokhee Kim}, doi = {10.1021/jacs.5c05071}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20909--20918}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of a two-step enzyme cascade converting aspartate to aminomalonate in peptide natural product biosynthesis}, volume = {147}, year = {2025}, }
• (2025). Solvent-directed assembly of π-stacked 3D Metal–Organic frameworks with tunable conductivity enhanced by c60 encapsulation. JACS, 147(24), 20899--20908. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) with tunable structures and unique host–guest chemistry have emerged as promising candidates for conductive materials. However, the tunability of conductivity and porosity in conductive MOFs, as well as their interrelationship, still lacks a systematic study. Herein, we report the synthesis of a series of 3D copper MOFs (NU-4000 to NU-4003) using a triphenylene-based hexatopic carboxylate linker. By modulating the ratio of mixed solvents, distinct structural topologies and π–π stacking arrangements were achieved, resulting in electrical conductivities ranging from insulators (<10 –6 S/cm) to semiconductors (10 –8 ∼10 2 S/cm). Among them, NU-4003 features continuous π–π stacking and exhibits a conductivity of 1.7 × 10 –6 S/cm. To further enhance the conductivity, we encapsulated C 60 , a strong electron acceptor, within the circular channels of NU-4003, resulting in a remarkable conductivity increase to 140 S/cm with approximately 100% pore occupancy. Even at lower C 60 loadings that leave 54% of the pore volume accessible, the conductivity remains exceptionally high at 104 S/cm. This represents an eight-order magnitude enhancement and positions NU-4003-C 60 as one of the most conductive 3D MOFs reported to date. This work integrates two charge transport pathways (through-space and electron donor-acceptor interactions) into a single MOF host–guest material, achieving a significant enhancement in conductivity. This study demonstrates the potential of combining host–guest chemistry and π–π stacking to design conductive MOFs with permanent porosity maintained, providing a blueprint for the development of next-generation materials for electronic and energy-related applications.}, archive = {J_JACS}, author = {Xianhui Tang and Xijun Wang and Shengyi Su and Xiaoliang Wang and Haomiao Xie and Timothy Y.-Z. Li and Wei Gong and Lei Jia and Enping Du and Ke Xie and Yan Liu and Kent O. Kirlikovali and Edward H. Sargent and Yong Cui and Omar K. Farha}, doi = {10.1021/jacs.5c04897}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20899--20908}, shortjournal = {J. Am. Chem. Soc.}, title = {Solvent-directed assembly of π-stacked 3D Metal–Organic frameworks with tunable conductivity enhanced by c60 encapsulation}, volume = {147}, year = {2025}, }
• (2025). Superionic ionic conductor discovery via multiscale topological learning. JACS, 147(24), 20888--20898. (www)

  @article{ , abstract = {Lithium superionic conductors (LSICs) are crucial for next-generation solid-state batteries, offering exceptional ionic conductivity and enhanced safety for renewable energy and electric vehicles. However, their discovery is extremely challenging due to the vast chemical space, limited labeled data, and understanding of complex structure–function relationships required for optimizing ion transport. This study introduces a multiscale topological learning (MTL) framework that integrates algebraic topology and unsupervised learning to efficiently tackle these challenges. By modeling lithium-only and lithium-free substructures, the framework extracts multiscale topological features and introduces two topological screening metrics, cycle density and minimum connectivity distance, to ensure structural connectivity and ion diffusion compatibility. Promising candidates are clustered via unsupervised algorithms to identify those that resemble known superionic conductors. For final refinement, candidates that pass chemical screening undergo ab initio molecular dynamics simulations for validation. This approach led to the discovery of 14 novel LSICs, four of which have been independently validated in recent experiments. This success accelerates the identification of LSICs and demonstrates broad adaptability, offering a scalable tool for addressing complex material discovery challenges.}, archive = {J_JACS}, author = {Dong Chen and Bingxu Wang and Shunning Li and Wentao Zhang and Kai Yang and Yongli Song and Guo-Wei Wei and Feng Pan}, doi = {10.1021/jacs.5c04828}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20888--20898}, shortjournal = {J. Am. Chem. Soc.}, title = {Superionic ionic conductor discovery via multiscale topological learning}, volume = {147}, year = {2025}, }
• (2025). In and out: Shuttling atoms in covalent nanocrystals, from synthesis in molten salts to water-splitting electrocatalysis. JACS, 147(24), 20878--20887. (www)

  @article{ , abstract = {Postsynthetic transformations are key to the colloidal synthesis of functional nanocrystals by offering a way to complex shapes, heterostructures, and chemical compositions. They however remain inaccessible to whole families of solids, especially those relying on covalent bonds, which crystallize at temperatures that common solvents cannot stand. Herein we show that in inorganic molten salts above 500 °C, such transformations can be triggered to deliver metallo-covalent nanocrystals previously unattainable. By incorporating silicon and phosphorus into metal nanoparticles, we synthesize nickel silicophosphide nanocrystals and demonstrate how distinct chemical bonds involving silicon or phosphorus drive their electrocatalytic properties for alkaline water oxidation and hydrogen evolution. These bonds also determine the synthesis pathway, from sequential incorporation of p -block elements to topotactic transformations not reported before. The ability to run such complex postsynthetic reactions of nanoparticles into molten salts paves the way to increasing complexity in compositions and chemical bonding in nanocrystals for energy conversion.}, archive = {J_JACS}, author = {Yang Song and Anissa Ghoridi and Fernando Igoa Saldaña and Isabel Gómez-Recio and Daniel Janisch and Edouard de Rolland Dalon and Dominique Thiaudière and Maria Luisa Ruiz-González and José M. González-Calbet and Benedikt Lassalle-Kaiser and Andrea Zitolo and Christel Laberty-Robert and David Portehault}, doi = {10.1021/jacs.5c04741}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20878--20887}, shortjournal = {J. Am. Chem. Soc.}, title = {In and out: Shuttling atoms in covalent nanocrystals, from synthesis in molten salts to water-splitting electrocatalysis}, volume = {147}, year = {2025}, }
• (2025). 99Ru solid-state nuclear magnetic resonance spectroscopy of organometallic compounds: Linking nuclear magnetic resonance parameters with Metal–Ligand bonding. JACS, 147(24), 20865--20877. (www)

  @article{ , abstract = {This study introduces 99 Ru solid-state NMR (SSNMR) spectroscopy, along with relativistic density functional theory (DFT) calculations of 99 Ru chemical shift and electric field gradient (EFG) tensors and their analysis with localized molecular orbitals, as a versatile tool to elucidate relationships between SSNMR spectra and Ru-ligand bonding in organometallic compounds. 99 Ru is a very challenging target for analysis by SSNMR. Robust experimental protocols were developed for the acquisition of ultrawideline 99 Ru SSNMR spectra for stationary samples with unprecedented signal-to-noise ratios and uniformity. The 99 Ru EFG and chemical shift tensors determined from these spectra are complemented by DFT-based analyses of the contributions of individual bond-, lone-pair-, and core-shell-orbitals to the NMR interaction tensors, which highlight their relationships with Ru-ligand bonding and electronic structure. These experimental and computational protocols are anticipated to prove fruitful for the characterization of a wide range of Ru-containing compounds, with applications to catalysis, advanced materials, and electronic devices.}, archive = {J_JACS}, author = {Sean T. Holmes and Yijue Xu and Adam B. Philips and Sara Termos and James J. Kimball and Jochen Autschbach and Robert W. Schurko}, doi = {10.1021/jacs.5c04759}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20865--20877}, shortjournal = {J. Am. Chem. Soc.}, title = {99Ru solid-state nuclear magnetic resonance spectroscopy of organometallic compounds: Linking nuclear magnetic resonance parameters with Metal–Ligand bonding}, volume = {147}, year = {2025}, }
• (2025). Three-dimensional bicarbazole-based covalent organic frameworks as efficient yeager-type photocatalysts for H2O2 generation in a two-phase system. JACS, 147(24), 20855--20864. (www)

  @article{ , abstract = {Photocatalytic reduction of oxygen to hydrogen peroxide (H 2 O 2 ) represents an attractive solar-to-chemical conversion pathway. Nevertheless, it remains a significant challenge to achieve efficient H 2 O 2 photosynthesis while simultaneously mitigating photocorrosion of the catalysts owing to the presence of superoxide radicals ( • O 2 – ) and the accumulation of photoexcited holes (h + ). In the present work, a 1,2,3,4-tetrahydroisoquinoline (THIQ)-water two-phase system was developed to achieve high-efficiency and durable production of H 2 O 2 by suppressing • O 2 – intermediates and rapidly consuming h + . The • O 2 – -free direct two-electron oxygen reduction reaction (2e – ORR) to H 2 O 2 was accomplished on special three-dimensional (3D) covalent organic framework (COF) metal-free photocatalysts consisting of bicarbazole units (BCTB) as electron donors and thiazole (BT) or triazine (TAPT) as electron acceptors (COF-BCTB-BT or COF-BCTB-TAPT). The unique structures endow them with a high H 2 O 2 production rate in the water phase of ∼33.2 mmol g cat. –1 h –1 over COF-BCTB-BT. In the other organic phase, the photoexcited h + was also efficiently consumed by semidehydrogenation of THIQ (THIQ-SDR) to 3,4-dihydroisoquinoline (DHIQ). Theoretical calculations revealed a Yeager-type four-step direct 2e – ORR mechanism over two COFs, with a lower energy barrier of *O–O to *O–OH for COF-BCTB-BT. A four-step mechanism of the THIQ-SDR to DHIQ was also suggested. This work provides an impressive Yeager-type two-phase H 2 O 2 photosynthesis strategy over high-efficiency 3D bis-heterocyclic COF photocatalysts, effectively suppressing both • O 2 – formation and h + accumulation.}, archive = {J_JACS}, author = {Aiguo Kong and Tao Yang and Hai Yan and Xinxin Chen and Yue Chen and Fangyuan Kang and Qichun Zhang and Rui Liu}, doi = {10.1021/jacs.5c04447}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20855--20864}, shortjournal = {J. Am. Chem. Soc.}, title = {Three-dimensional bicarbazole-based covalent organic frameworks as efficient yeager-type photocatalysts for H2O2 generation in a two-phase system}, volume = {147}, year = {2025}, }
• (2025). Introducing prism[4]arene: A macrocycle with enantiomerically resolvable inherent chirality and intriguing chiroptical properties. JACS, 147(24), 20843--20854. (www)

  @article{ , abstract = {This study presents the first report of an inherently chiral prismarene with resolved enantiomers. Prism[4]arenes, synthesized via a thermodynamic template approach using a tailor-made selective cation, effectively maintain their chirality due to their strained macrorings and narrow annuli, which prevent the flipping of naphthalene rings. The solid-state structure of the synthesized PrS[4] iPe revealed a racemic crystal composed of all-p R and all-p S enantiomeric pairs, forming supramolecular polymeric chains of homochiral molecules interlinked by intermolecular host–guest interactions. Both enantiomers were resolved by using chiral high-performance liquid chromatography (HPLC), and their chiroptical properties were thoroughly investigated. Configurational assignment was achieved through time-dependent density functional theory (TDDFT) computations alongside electronic circular dichroism/ultraviolet–visible (ECD/UV–vis) spectral analysis. Notably, the circularly polarized luminescence (CPL) properties exhibited a significant dissymmetry ratio of 0.008 for these prism[4]arenes, due to electric and magnetic dipole transition moments both directed along the cylinder axis. Furthermore, the ability of PrS[4] iPe to achieve enantioselective recognition with chiral ammonium guests was demonstrated.}, archive = {J_JACS}, author = {Paolo Della Sala and Carmen Talotta and Margherita De Rosa and Stefano Superchi and Ernesto Santoro and Silvano Geremia and Neal Hickey and Marco Fusè and Sergio Abbate and Giuseppe Mazzeo and Giovanna Longhi and Carmine Gaeta}, doi = {10.1021/jacs.5c04512}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20843--20854}, shortjournal = {J. Am. Chem. Soc.}, title = {Introducing prism[4]arene: A macrocycle with enantiomerically resolvable inherent chirality and intriguing chiroptical properties}, volume = {147}, year = {2025}, }
• (2025). A near-infrared-II luminescent and photoactive Vanadium(II) complex with a 760 ns excited state lifetime. JACS, 147(24), 20833--20842. (www)

  @article{ , abstract = {Ruthenium and iridium are key components in the most important applications of photoactive complexes, namely, light-emitting devices, photocatalysis, bioimaging, biosensing, and photodynamic therapy. Especially, near-infrared (NIR) emissive materials are required in fiber-optic telecommunications, anticounterfeit inks, night-vision readable displays, and bioimaging. Replacing rare and expensive precious metals with more abundant first-row transition metals is of great interest; however, photophysical properties and the chemical stability of 3d metal complexes are often insufficient. Here, we tackle these challenges with a nonprecious metal polypyridine vanadium(II) complex that shows emission above 1300 nm with excited state lifetimes of up to 760 ns. Strong light absorption in the visible spectral region and exceptional stability in the presence of oxygen enable photocatalysis in water and acetonitrile using green to orange-red light for excitation. This study unravels a new design principle for NIR-II luminescent and photoactive complexes based on the abundant first-row transition metal vanadium.}, archive = {J_JACS}, author = {Alexandra König and Robert Naumann and Christoph Förster and Jan Klett and Katja Heinze}, doi = {10.1021/jacs.5c04471}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20833--20842}, shortjournal = {J. Am. Chem. Soc.}, title = {A near-infrared-II luminescent and photoactive Vanadium(II) complex with a 760 ns excited state lifetime}, volume = {147}, year = {2025}, }
• (2025). Molecular design of unimolecular tetra-receptor agonists. JACS, 147(24), 20819--20832. (www)

  @article{ , abstract = {Peptide hormone-receptor interactions serve as critical regulators of metabolic homeostasis, a paradigm exemplified by the clinical efficacy of glucagon-like peptide-1 (GLP-1) receptor agonists. Building upon this framework, strategic design has yielded unimolecular dual and triple agonists targeting GLP-1R, glucose-dependent insulinotropic polypeptide receptor (GIPR), and glucagon receptor (GcgR), leveraging the sequence homology within the cognate native ligands of the class B G protein-coupled receptor (GPCR) family. However, the integration of Y2 receptor (Y2R) agonism─engaged by peptide YY (PYY) and belonging to the structurally divergent class A GPCR family─has remained an unaddressed challenge due to the topological and sequence disparities between these receptor classes. Y2R activation plays a pivotal role in appetite suppression, potentiating the metabolic benefits conferred by GLP-1R, GIPR, and GcgR agonism. Here, we report first-in-class, unprecedented tetra-agonists with high potency at GLP-1R, GIPR, GcgR, and Y2R. The chimeric peptides overcome the intrinsic sequence constraints imposed by class A and class B GPCR divergence, demonstrating the feasibility of rationally designed agonism mediated by single agents across receptor families. Lipidation of this template is well tolerated enhancing the promise of therapeutic viability. Furthermore, we show that biased agonism at GLP-1R selectively boosts cyclic AMP (cAMP) signaling while minimizing β-arrestin recruitment, thereby decoupling receptor desensitization from metabolic efficacy. Additionally, we introduce a tunable framework to modulate β-arrestin engagement without compromising cAMP potency, providing insight into the fine-tuning of GPCR-mediated signaling for next-generation peptide therapeutics.}, archive = {J_JACS}, author = {Tristan C. Dinsmore and Jacob E. Cortigiano and Siyuan Xiang and Marina V. Spenciner and Alexandra R. Dobbins and Richard L. Zhao and Brett M. Waldman and Martin Beinborn and Krishna Kumar}, doi = {10.1021/jacs.5c04095}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20819--20832}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular design of unimolecular tetra-receptor agonists}, volume = {147}, year = {2025}, }
• (2025). Rapid C–S+ bond cleavage via 1,6-benzyl elimination for traceless modification of bioactive peptides. JACS, 147(24), 20807--20818. (www)

  @article{ , abstract = {Peptides and proteins are invaluable therapeutics and biological tools, where stimuli-responsive and fully reversible conjugation chemistry is essential to advances in drug delivery systems and chemical biology. However, methods that allow precise conjugation, efficient regulation of biochemical functions, and customized recovery of parent peptides remain underdeveloped. Here, we introduce a straightforward yet powerful reversible chemical strategy targeting methionine (Met), a widespread yet low abundance amino acid in peptides and proteins. By selectively alkylating Met-containing peptides under weakly acidic conditions, we form a stable C–S + bond, which can be cleaved rapidly via 1,6-benzyl elimination upon stimulus. This versatile chemistry is demonstrated in diverse applications: (i) PEGylated prodrugs of antimicrobial peptides with reduced toxicity and enhanced enzymatic stability, (ii) esterase-responsive peptide–peptide inhibitor conjugates (PPICs) with improved cell membrane permeability and therapeutic effects, (iii) reversibly stapled peptides with switchable conformations for targeting both intra- and extracellular sites, and (iv) bioorthogonal control of C-terminal Met-caged neuropeptides. Overall, this work describes, for the first time, a valuable traceless modification strategy that promises to greatly benefit the peptide community and advance the field of chemical biology.}, archive = {J_JACS}, author = {Yu Chai and Can Yu and Zhi Chen and Wenbin Duan and Huanwen Chen and Xunxiang Qiu and Zhengyang Xu and Shengzhang Liu and Anastasia Danilenko and Gilles Frison and Valérie Alezra and Emeric Miclet and Xiang Li and Yang Wan}, doi = {10.1021/jacs.5c04329}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20807--20818}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid C–S+ bond cleavage via 1,6-benzyl elimination for traceless modification of bioactive peptides}, volume = {147}, year = {2025}, }
• (2025). Strong and switchable magneto-optical effect in air-stable chiral DyIII complexes with magnetic anisotropy. JACS, 147(24), 20799--20806. (www)

  @article{ , abstract = {Assembling chiral and magnetic units at a molecular level is a key to achieving a strong magneto-optical (MO) effect, especially for lanthanide complexes with a specific 4 f electronic configuration. However, the f – f transitions are generally restricted by selection rules, making the observation of the MO response extremely challenging. Herein, we reported the synthesis of two highly air-stable chiral Dy III complexes 1- R and 1- S , with a pair of tailored chelating chiral ligands. Besides magnetization dynamics in a wide temperature range, the magnetic circular dichroism (MCD) of 1- R and 1- S shows remarkable MO responses of f – f transitions of Dy III centers in the vis–NIR region, and CD spectra of 1- R and 1- S provide the first experimental observation of room-temperature CD peaks corresponding to the f – f transition of Dy III at 450 nm. Importantly, the direction of CD signals from 700 to 1100 nm can be reversibly switched by external magnetic fields. Mechanism study reveals that the strong magnetic anisotropy of the Dy III center is a key to inducing the remarkable room-temperature MO effect. This work not only provides a facile way to construct air-stable magnetic and chiral complexes but also gains insights into the influence of magnetic anisotropy on the strong MO effect in a wide spectrum range at room temperature.}, archive = {J_JACS}, author = {Yuewei Wu and Ze-Yu Ruan and Chengcheng Zhang and Jia-Nan Chen and Xin-Yi Wang and Zhonghang Chen and Xiaoshuang Gou and Wenlong Lan and Xiang-Jian Kong and Jun-Liang Liu and Peng Cheng and Wei Shi}, doi = {10.1021/jacs.5c04297}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20799--20806}, shortjournal = {J. Am. Chem. Soc.}, title = {Strong and switchable magneto-optical effect in air-stable chiral DyIII complexes with magnetic anisotropy}, volume = {147}, year = {2025}, }
• (2025). In situ coupling of MHz acoustic waves for the synthesis of hierarchical UiO-66 Metal–Organic frameworks. JACS, 147(24), 20790--20798. (www)

  @article{ , abstract = {Engineering the physical properties of metal–organic frameworks (MOFs) to improve their performance has been a key focus area for establishing their use in a variety of applications. While some synthesis strategies have shown promise in this regard, a method that can simultaneously give rise to unique properties in the MOF structure across multiple dimensions (e.g., the nano-, meso-, and macro-scales), which can be critical for a number of practical applications, has never been reported. Herein, we report an acoustomicrofluidic platform that concurrently facilitates such multiscale manipulation of the MOFs’ physical properties. In just several minutes at room temperature, large ( O (10–100 μm)) monolithic superstructures of UiO-66 MOFs (a MOF model with excellent stability) can be synthesized with highly desirable properties. These properties include hierarchical (micro- and meso-scale) porosity and nanoscale framework-level defects, all of which are absent in conventional-prepared UiO-66 with solvothermal synthesis. We show (as examples of the benefits of simultaneously enhancing the MOF properties on multiple dimensional levels) their practical application for simultaneous capture and degradation of large dye molecules, and for UV photodetection with superior responsivity.}, archive = {J_JACS}, author = {Javad Khosravi Farsani and Omid Mazaheri and Enrico Della Gaspera and Ravichandar Babarao and Sandeep G. Rajan and Joseph J. Richardson and Amgad R. Rezk and Leslie Y. Yeo}, doi = {10.1021/jacs.5c04345}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20790--20798}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ coupling of MHz acoustic waves for the synthesis of hierarchical UiO-66 Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Tuning exciton coupling of non-conjugated cyanine dimers for efficient photodynamic immunotherapy. JACS, 147(24), 20778--20789. (www)

  @article{ , abstract = {Cyanine dyes usually serve as good fluorescence probes but not as efficient photosensitizers owing to the spin-forbidden intersystem crossing process and short excited-state lifetime. Nevertheless, the structure-derived energy release from the excited state could enable dyes to function efficiently. In this work, we developed cyanine dimers ( 2 o -Cy , 2 m -Cy , and 2 p -Cy ) based on exciton coupling effects by connecting two Cy5.5 molecules at the N -indole site with nonconjugated ortho / meta / para -bis(bromomethyl)benzene linkers. These dimers exhibited significantly enhanced molar extinction coefficients (32–45 × 10 4 M cm –1 ) as well as satisfactory triplet excited-state quantum yields (32–44%) and lifetimes (10.6–11.9 μs), leading to a substantially enhanced reactive oxygen species production along with efficient antitumor activity under both normoxic and hypoxic conditions. Furthermore, 2 p -Cy NPs ablated primary tumors, inhibited distant tumor growth, and prevented metastatic regrowth via photoinduced innate immune activation. This dimer-based strategy represents a powerful approach to develop high-performance photosensitive dyes for antitumor photodynamic immunotherapy.}, archive = {J_JACS}, author = {Hua Gu and Puan Yuan and Juan Zhang and Xiang Xia and Qingze Pan and Wenkai Liu and Xueze Zhao and Wen Sun and Jianjun Du and Jiangli Fan and Xiaojun Peng}, doi = {10.1021/jacs.5c04044}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20778--20789}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning exciton coupling of non-conjugated cyanine dimers for efficient photodynamic immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Homochiral single crystals of helical polymer nanotubes: Synthesis and application. JACS, 147(24), 20770--20777. (www)

  @article{ , abstract = {The construction of helical polymer nanotubes with precise structure and enhanced stability remains a formidable challenge in synthetic chemistry, as it requires a complex balance of covalent and noncovalent interactions for hierarchical assembly. Herein, we report a hierarchical self-assembly strategy for the single-crystal synthesis of homochiral helical polymer nanotubes from simple, commercially available achiral monomers via synergistic dynamic covalent chemistry and noncovalent interactions. This one-pot process integrates the in situ formation of boroxine-based dynamic covalent bonds (B–O and B–N) to establish the polymer backbone, longitudinal hydrogen bonding (C≡N···H–N) to induce helical coiling, and π–π stacking to stabilize the enclosed nanotubular architecture. Through single-crystal X-ray diffraction and circular dichroism (CD) spectroscopy, we elucidate a crystallization-induced helical (CIH) nanotubulization mechanism, wherein linear polymer chains undergo supramolecular reorganization into homochiral helices during crystallization. The resulting nanotubes exhibit intrinsic chirality, hydrophilicity, aqueous stability, and strong photoluminescence properties. This work establishes a scalable, modular platform for synthesizing crystalline helical nanomaterials, bridging the gap between covalent polymer synthesis and nanotube design engineering for advanced optoelectronic and enantioselective applications.}, archive = {J_JACS}, author = {Yinghua Yu and Si-Hao Shen and Jian-Bing Chen and Qing-Rong Ding and Hai-Xia Zhang and Jian Zhang}, doi = {10.1021/jacs.5c04285}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20770--20777}, shortjournal = {J. Am. Chem. Soc.}, title = {Homochiral single crystals of helical polymer nanotubes: Synthesis and application}, volume = {147}, year = {2025}, }
• (2025). Molecular-level tailoring of energy structure in ternary conjugated polymers with a built-in ru-complex catalyst for efficient CO2 reduction photocatalysis. JACS, 147(24), 20759--20769. (www)

  @article{ , abstract = {Efficient catalytic CO 2 conversion by harnessing visible-light energy is a substantial challenge for sustainability. Photocatalytic materials consisting of light absorbers and catalysts have been extensively developed. However, efficient photocatalytic systems have so far relied on the use of precious metal-based compounds or materials as light-absorbing components, primarily because of their long-lived photoexcited states. Herein, we report the design principles of ternary conjugated polymers as a metal-free light absorber with a built-in metal complex catalyst for substantially activating CO 2 reduction photocatalysis. The ternary conjugated system enabled exceedingly flexible tuning of their energy structure, which is beneficial for long-range charge separation by manipulating the photoexcited electrons to the site-selectively introduced molecular catalyst center. The key cascade energy structure was tailored, and its impacts on photocatalysis were unveiled by using both spectroscopic experiments and theoretical calculations. The precise molecular design resulted in very active visible-light CO 2 reduction, even without the aid of a precious metal-based light absorber, recording an external quantum efficiency up to 32.2% and producing a concentrated formate (∼0.48 M).}, archive = {J_JACS}, author = {Kotaro Ishihara and Akinobu Nakada and Hajime Suzuki and Akira Yamakata and Osamu Tomita and Akinori Saeki and Ryu Abe}, doi = {10.1021/jacs.5c04222}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20759--20769}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular-level tailoring of energy structure in ternary conjugated polymers with a built-in ru-complex catalyst for efficient CO2 reduction photocatalysis}, volume = {147}, year = {2025}, }
• (2025). Hard–Soft Acid–Base theory explains photoexcited carrier dynamics in Porphyrin/CNT nanohybrids: Time-domain atomistic analysis. JACS, 147(24), 20748--20758. (www)

  @article{ , abstract = {We employ the fundamental chemical concepts of hard–soft acid–base to formulate general principles governing excited-state dynamics in zinc porphyrin (ZnP)/carbon nanotube (CNT) hybrids for energy photoconversion. Atomistic quantum dynamics simulations demonstrate that electron-withdrawing and donating substituents at the ZnP β-pyrrolic position strongly influence the dynamics. ZnP photoexcitation produces subpicosecond electron transfer (ET) from ZnP to CNT, in agreement with the experiment. Substitutions of CN by H and t Bu accelerate the ET. The trend is directly related to the hard–soft acid–base concept because the soft–soft interaction between the t Bu-ZnP acid and the mild CNT base enhances the donor–acceptor coupling. Longer coherence and more active vibrational modes facilitate the ET in t Bu-ZnP/CNT. Electron–hole recombination in CN-ZnP/CNT occurs on a hundred picosecond time scale, nicely corroborated by the experiment. The exciton lifetime is extended beyond a nanosecond by the substitutions. The soft–soft interaction in t Bu-ZnP/CNT increases the splitting between the highest occupied orbitals of the two subsystems, reduces their mixing, and decreases nonadiabatic coupling between the ground and excited states. Rapid decoherence and involvement of low-frequency vibrations favor longer lifetimes. Our investigation reveals that larger p K a of the β-pyrrolic acid gives rapid ET and slow recombination and provides detailed mechanistic information, essential for future optoelectronic applications.}, archive = {J_JACS}, author = {Uttam Chowdhury and Shrabanti Mondal and Subhajit Dey and Md Habib and Ritabrata Sarkar and Shriya Gumber and Pabitra Chattopadhyay and Pranab Sarkar and Oleg Prezhdo and Sougata Pal}, doi = {10.1021/jacs.5c04270}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20748--20758}, shortjournal = {J. Am. Chem. Soc.}, title = {Hard–Soft Acid–Base theory explains photoexcited carrier dynamics in Porphyrin/CNT nanohybrids: Time-domain atomistic analysis}, volume = {147}, year = {2025}, }
• (2025). Consecutive multiphoton-mediated defluorinative amination of fluoroarenes. JACS, 147(24), 20735--20747. (www)

  @article{ , abstract = {Traditional nucleophilic aromatic substitution (S N Ar) is a versatile tool for the construction of molecular complexity in (hetero)aromatic systems for fluoroarenes. However, it generally necessitates harsh reaction conditions to achieve the products. To overcome these drawbacks, we developed a robust and general method using a new strongly oxidizing photocatalyst, HATCN. The photocatalyst HATCN, built on a large π-delocalized aromatic core, can afford multiple stable redox states upon visible-light excitation and successive reductions under very mild potential. This modularity in affording multiple redox states proved instrumental in steering the aromatic defluorinative amination of fluorobenzenes. During the mechanistic study of this S N Ar reaction, it is apparent that altogether three photons are invested to conduct the full catalytic process, which is so far elusive in photochemically driven catalytic cycles. The two stable redox states of the photocatalyst are capable of oxidizing two substrate molecules that translates in the substrate versatility by accessing electron-neutral, electron-poor, and heterocyclic variants, which were previously inaccessible using established methods. Intriguingly, while the neutral and monoanionic HATCN acts as an oxidant, direduced HATCN behaves as a reductant. The critical evaluation of these redox states has been substantiated by intermediate redox-state isolation, along with a series of control reactions. Eventually, the cubic dependence of reaction rate on photon intensity demonstrated the consecutive three photon involvement in overall catalysis. The high efficiency of this oxidizing photocatalyst directly stems from its redox flexibility, which also translates to its unique mechanistic paradigm, involving multiphotons for the catalytic process.}, archive = {J_JACS}, author = {Argha Saha and Monojit Roy and Shyamali Maji and Gourab Rana and Debabrata Maiti and Debashis Adhikari}, doi = {10.1021/jacs.5c04164}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20735--20747}, shortjournal = {J. Am. Chem. Soc.}, title = {Consecutive multiphoton-mediated defluorinative amination of fluoroarenes}, volume = {147}, year = {2025}, }
• (2025). The intricate nonribosomal assembly of a potent antifungal lipopeptide from the burkholderia cepacia complex. JACS, 147(24), 20725--20734. (www)

  @article{ , abstract = {The Burkholderia cepacia complex (BCC) is a group of Gram-negative bacteria known for their pathogenicity to patients suffering from cystic fibrosis (CF). The BCC-belonging strain B. pyrrocinia BC11 (formerly B. cepacia BC11) produces AFC-BC11, a compound with strong activity against phytopathogenic fungi. In this contribution, we report on the unprecedented N -acyl-tetrapeptide structure and antifungal potency of this natural product. We further provide insights into central steps of its biosynthesis mediated by a nonclassical nonribosomal peptide synthesis machinery lacking condensation domains. With the involvement of a sole acyl/peptidyl carrier protein AfcK, an acyltransferase AfcL and coenzyme A, the growing acyl-peptide chain is shuffled between different thioester carriers during the intricate biosynthetic assembly. The knowledge of the AFC-BC11 structure may contribute to the development of antifungals against phytopathogens and, with the afc gene cluster being conserved in various Burkholderia strains, possibly to an understanding of the human pathogenesis of the BCC.}, archive = {J_JACS}, author = {Lei Zhong and Agnes Mühlenweg and Dou Hong and Sarah Yammine and Annette Poch and Dingchang Xu and Yasemin Kirimlioglu and Lisa Großgloß and Malo Boulanger and Franziska Graeger and Maria Seidel and Manuel Gemander and Grit Walther and Sebastian Kemper and Tam Dang and Monique Royer and Andi Mainz and Stéphane Cociancich and Roderich D. Süssmuth}, doi = {10.1021/jacs.5c04167}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20725--20734}, shortjournal = {J. Am. Chem. Soc.}, title = {The intricate nonribosomal assembly of a potent antifungal lipopeptide from the burkholderia cepacia complex}, volume = {147}, year = {2025}, }
• (2025). Lattice oxygen mechanism induced on nickel sites by cl– adsorption for efficient seawater oxidation reaction. JACS, 147(24), 20716--20724. (www)

  @article{ , abstract = {Efficient seawater oxidation reaction is crucial for advancing hydrogen fuel production. Developing highly efficient oxygen evolution reaction (OER) catalysts that follow the lattice oxygen mechanism (LOM) can effectively mitigate undesirable chloride oxidation side reactions in seawater electrolysis and reduce energy consumption. Herein, we propose a Cl – -mediation strategy that is able to shift the OER mechanism from the adsorbate evolution mechanism (AEM) to LOM on nickel sites. By loading highly dispersed Ir onto Ni-based precursors (e.g., NiSe, Ni(OH) 2 , NiS 2 and NiSOH), we exploit the robust coordination interaction between Ir and Cl – in seawater to establish a Cl–Ir–O–Ni electron-withdrawing chain from Ni to Cl, which strengthens Ni–O covalency in situ during the OER, thereby activating lattice oxygen around the Ni sites in seawater. As a result, the Cl-modified Ir/NiOOH-Se@Cl catalyst requires an overpotential of only 313 mV to achieve an OER current density of 0.5 A cm –2 , demonstrating a reduction of 147 mV compared to that in alkaline condition (Ir/NiOOH-Se@OH) and also maintaining stable operation at 0.5 A cm –2 for 500 h. Our work provides a novel and intriguing concept for regulating local lattice oxygen activity toward developing highly efficient oxygen electrocatalysts for clean energy productions.}, archive = {J_JACS}, author = {Qihao Sha and Tianshu Gao and Li Yan and Wei-Hsuan Hung and Ching-Yu Chiang and Daojin Zhou and Bin Liu and Yun Kuang and Xiaoming Sun}, doi = {10.1021/jacs.5c04206}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20716--20724}, shortjournal = {J. Am. Chem. Soc.}, title = {Lattice oxygen mechanism induced on nickel sites by cl– adsorption for efficient seawater oxidation reaction}, volume = {147}, year = {2025}, }
• (2025). Iridium polypyridyl carboxylates as excited-state PCET catalysts for the functionalization of unactivated C–H bonds. JACS, 147(24), 20703--20715. (www)

  @article{ , abstract = {The design of catalysts capable of functionalizing unactivated C(sp 3 )–H bonds remains a significant goal in synthetic organic chemistry. Herein, we present a novel set of iridium polypyridyl complexes bearing pendent Brønsted basic carboxylates that become potent hydrogen atom abstraction catalysts upon visible light irradiation. Thermochemical and spectroscopic characterization reveal that these excited-state complexes exhibit bond dissociation free energies (BDFEs) of up to 105 kcal mol –1 with long excited-state lifetimes. We demonstrate that these complexes can catalyze C–H alkylation reactions in which the Ir carboxylate mediates both C–H abstraction and formation steps. Mechanistic, spectroscopic, and computational studies are consistent with C−H abstraction proceeding through an excited-state proton-coupled electron transfer (PCET) step. The modular nature of these Ir polypyridyl complexes establishes a foundation for designing tunable and efficient C–H functionalization catalysts based on covalent tethering of excited-state oxidants and bases.}, archive = {J_JACS}, author = {Diego A. Granados and Y. Emily Du and Shiloh J. Andersson and Avery Cirincione-Lynch and Kai Cui and Adam Reinhold and Philip D. Jeffrey and Gregory D. Scholes and Sharon Hammes-Schiffer and Robert R. Knowles}, doi = {10.1021/jacs.5c04000}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20703--20715}, shortjournal = {J. Am. Chem. Soc.}, title = {Iridium polypyridyl carboxylates as excited-state PCET catalysts for the functionalization of unactivated C–H bonds}, volume = {147}, year = {2025}, }
• (2025). Design rules to engineer the spin structure of cr4+ molecular qubits via matrix modularity. JACS, 147(24), 20693--20702. (www)

  @article{ , abstract = {Using a multilevel computational approach, we predict the zero-field splitting (ZFS) parameters of Cr(IV) molecular qubits with unprecedented accuracy, obtaining results in excellent agreement with experiments. We then apply the protocol to Cr(IV) molecular color centers embedded in non-isostructural tin host matrices. We show that by simply altering the matrix composition, one can effectively modify the relative energies of the spin sublevels, thus enabling a fine-tuning of the qubit’s magnetic anisotropy for optimal performance in quantum technologies. We identify two effects influencing matrix design: the molecular symmetry of the qubit and the presence of inhomogeneous electrostatic fields arising from the chemical composition of the matrix. Finally, we compute spin-coherence times and discuss their sensitivity to the matrix environment through the ZFS parameters. Our work provides predictive strategies for tailoring the spin structure and coherence properties of molecular color centers through a rational control of their matrix environment.}, archive = {J_JACS}, author = {Lorenzo Baldinelli and Diego Sorbelli and Michael Toriyama and Giovanni Bistoni and Filippo De Angelis and Giulia Galli}, doi = {10.1021/jacs.5c04004}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20693--20702}, shortjournal = {J. Am. Chem. Soc.}, title = {Design rules to engineer the spin structure of cr4+ molecular qubits via matrix modularity}, volume = {147}, year = {2025}, }
• (2025). Iridium-catalyzed nitrene-mediated enantioselective 1,2-hydride shift enabled by attractive noncovalent interactions for chiral δ-lactam synthesis. JACS, 147(24), 20680--20692. (www)

  @article{ , abstract = {In modern organic chemistry, 1,2-hydride shifts of carbocations are generally considered to be highly rapid processes, typically exhibiting activation barriers of ∼2–4 kcal/mol─significantly faster than conventional S N 1 or E1 reactions. Consequently, achieving a catalytic enantioselective 1,2-hydride shift remains a significant challenge. Herein, we introduce a nitrene-mediated strategy that generates carbocation intermediates through intramolecular metal-nitrenoid transfer to alkenes, followed by a ligand-enabled, stereocontrolled, and accelerated 1,2-hydride shift facilitated by attractive noncovalent interactions. This methodology yields δ-lactams bearing contiguous γ,δ-stereocenters with excellent yields, diastereoselectivities, and enantioselectivities (most examples >95% ee, >20:1 dr). The versatility of this catalytic enantioselective carbocation rearrangement platform is demonstrated by its mild reaction conditions and wide substrate scope, accommodating diverse nucleophiles, including carbon, oxygen, and nitrogen-based species, as well as biologically relevant molecules. Mechanistic investigations revealed that the enantioselective 1,2-hydride shift serves as the stereodetermining step, driven by attractive noncovalent interactions. Complementary computational studies further demonstrated that enhanced C–H···π interactions play a critical role by increasing the interaction energy, which directs the reaction pathway and ensures high stereoselectivity.}, archive = {J_JACS}, author = {Qian-Kun Fan and Zi-Qian Bai and Gang He and Gong Chen and Hao Wang}, doi = {10.1021/jacs.5c03919}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20680--20692}, shortjournal = {J. Am. Chem. Soc.}, title = {Iridium-catalyzed nitrene-mediated enantioselective 1,2-hydride shift enabled by attractive noncovalent interactions for chiral δ-lactam synthesis}, volume = {147}, year = {2025}, }
• (2025). Ultrasound-triggered activation of p-azidobenzyloxycarbonyl-based prodrugs via radical-mediated cascade elimination. JACS, 147(24), 20667--20679. (www)

  @article{ , abstract = {Selective prodrug activation at tumor sites through noninvasive external stimuli represents a promising strategy in enhancing the therapeutic index. Here, we report a p -azidobenzyloxycarbonyl (PAzBC)-based prodrug platform activated by physiotherapy-grade ultrasound (2.0 W/cm 2 , 1 MHz) through radical-mediated cascade elimination. Mechanistic studies reveal that ultrasound initiates single-electron-transfer (SET) and hydrogen-atom-transfer (HAT) processes, enabling efficient azide-to-amine reduction. This activation is further amplified by superoxide anion radicals generated via acoustic sensitizers, as confirmed by DFT calculations and radical trapping experiments. The PAzBC platform demonstrates broad applicability with diverse drug functionalities (amino, hydroxyl, sulfhydryl), achieving >99% azide reduction efficiency and approximately 40% active drug release under optimized sonication conditions. Cellular studies reveal a 4.1–115.5-fold reduction in prodrug toxicity and a 11.9–169.5-fold enhancement in selective activation, highlighting its potential for clinical translation. This work establishes a robust platform for spatiotemporally controlled drug delivery, advancing the field of ultrasound-mediated precision cancer therapy.}, archive = {J_JACS}, author = {Hang Xu and Mengfei Zheng and Daping Ye and Junyan An and Zhilin Liu and Zhaohui Tang and Xuesi Chen}, doi = {10.1021/jacs.5c03878}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20667--20679}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrasound-triggered activation of p-azidobenzyloxycarbonyl-based prodrugs via radical-mediated cascade elimination}, volume = {147}, year = {2025}, }
• (2025). Phosphorus(III)-compatible asymmetric Suzuki–Miyaura cross-coupling (P-ASMC) reaction. JACS, 147(24), 20657--20666. (www)

  @article{ , abstract = {The Suzuki–Miyaura cross-coupling (SMC) is a cornerstone method in the synthesis of biaryls. The enantioselective variant of this reaction typically involves an exogenous chiral ligand to induce enantioselectivity. Nonetheless, the application of coupling partners adorned with phosphorus(III) functionalities has been hindered by their strong coordination with transition metals and the challenges in identifying compatible chiral ligands. Here, we report the development of a P(III)-compatible asymmetric Suzuki–Miyaura cross-coupling (P-ASMC) reaction that enables the one-step assembly of axially chiral biaryl monophosphines. Employing a palladium catalyst, an achiral phosphine, and a chiral phosphine ligand, ortho -bromo-substituted arylphosphines undergo coupling with aryl boronate esters, demonstrating high reactivity and enantioselectivity. The resultant atropisomers exhibit exceptional efficacy as ligands in enantioselective palladium, rhodium, and gold catalysis, highlighting the practical promise of the P-ASMC reaction. Comprehensive experimental and computational studies have elucidated the reaction pathway and identified key factors contributing to cluster inhibition and enantioinduction.}, archive = {J_JACS}, author = {Lei Wu and Chengzhi Ge and Minyan Wang and Zhuangzhi Shi}, doi = {10.1021/jacs.5c03816}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20657--20666}, shortjournal = {J. Am. Chem. Soc.}, title = {Phosphorus(III)-compatible asymmetric Suzuki–Miyaura cross-coupling (P-ASMC) reaction}, volume = {147}, year = {2025}, }
• (2025). Proton-modulated nickel hydride electrocatalysis for the hydrogenation of unsaturated bonds and olefin isomerization. JACS, 147(24), 20644--20656. (www)

  @article{ , abstract = {Transition-metal hydrides stand as indispensable intermediates in both energy conversion and organic synthesis. Their electrochemical generation represents a compelling sustainable approach, enabling precise control over the reactivity and expanding the scope of electrocatalytic hydrogenation and isomerization. However, a major challenge in Ni-catalyzed electrochemical hydrogenation is the competing hydrogen evolution reaction (HER), which has led to various innovative strategies aimed at circumventing Ni–H formation. Here, we pursued an alternative approach by designing a bifunctional ligand with a pendant amine moiety to promote Ni–H formation. This design enabled selective (semi)hydrogenation of a diverse range of substrates, including terminal and internal alkynes, alkenes, and aldehydes, achieving an unprecedented substrate scope. Remarkably, we also demonstrated tunable positional selectivity for olefin isomerization by employing different types of proton sources. Our hydrogenation and isomerization method also exhibits excellent functional group tolerance, streamlining access to pharmaceuticals and their derivatives. Computational studies revealed the crucial, noninnocent role of the proton source in modulating metal hydride selectivity, either through hydrogen bonding, direct protonation of the pendant amine, or facilitation of protodemetalation.}, archive = {J_JACS}, author = {Xue Song and Yuan-Qiong Huang and Bodi Zhao and Hanshuo Wu and Xiaotian Qi and Jianchun Wang}, doi = {10.1021/jacs.5c03821}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20644--20656}, shortjournal = {J. Am. Chem. Soc.}, title = {Proton-modulated nickel hydride electrocatalysis for the hydrogenation of unsaturated bonds and olefin isomerization}, volume = {147}, year = {2025}, }
• (2025). Insights into the mechanisms of sugar acceptor selectivity of plant flavonoid apiosyltransferases. JACS, 147(24), 20631--20643. (www)

  @article{ , abstract = {Flavonoid apiosides are widely distributed in cereals, fruits, vegetables, and medicinal herbs and play critical roles in human health. Their facile and efficient synthesis has been a hot but challenging topic in the fields of both organic chemistry and biosynthesis. However, very few apiosyltransferases (ApiGTs) have been reported thus far. Here, we report the first flavonoid apiosyltransferase (CaApiGT) capable of catalyzing the 2″- O -apiosylation of flavonoid 3- O -glycosides in chickpea ( Cicer arietinum ). Moreover, we identify PcApiGT from parsley ( Petroselinum crispum ), which catalyzes the 2″- O -apiosylation of flavonoid 7-/4′- O -glycosides. To dissect the mechanisms underlying their different sugar acceptor selectivity, we obtain 10 complex crystal structures of CaApiGT and PcApiGT with resolutions ranging from 1.55 to 2.65 Å, including CaApiGT/UDP, 6 ternary structures of CaApiGT/UDP/sugar acceptors, PcApiGT/UDP, and 2 ternary structures of PcApiGT/UDP/sugar acceptors. Structural analyses, theoretical calculations, and site-directed mutagenesis indicate that flavonoid 3- O -glycosides and 7- O -glycosides exhibit a T-shape and streamline shape, respectively, and fit the active pockets of CaApiGT and PcApiGT. Moreover, the sugar acceptor selectivity of these two apiosyltransferases is determined by a key α-helix. In CaApiGT, this α-helix contains multiple polar amino acids, particularly a threonine residue at its end. Using this α-helix motif as a marker, we further characterize four apiosyltransferases from Leguminosae plants that exhibit functional similarity to CaApiGT. This work unravels detailed sugar acceptor selectivity mechanisms of plant apiosyltransferases and provides efficient biocatalysts for the synthesis of flavonoid apiosides.}, archive = {J_JACS}, author = {Hao-Tian Wang and Zi-Long Wang and Nian-Hang Chen and Wei Huang and Jian-Lin Zou and Yun-Gang Tian and Guo Ye and Jian Huang and Ruibo Wu and Min Ye}, doi = {10.1021/jacs.5c03771}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20631--20643}, shortjournal = {J. Am. Chem. Soc.}, title = {Insights into the mechanisms of sugar acceptor selectivity of plant flavonoid apiosyltransferases}, volume = {147}, year = {2025}, }
• (2025). An oriented polymer in a dynamic microsolution pierces molecular rings: An approach toward polyrotaxane synthesis under precise kinetic control. JACS, 147(24), 20612--20630. (www)

  @article{ , abstract = {In this study, we demonstrated host–guest chemistry under dynamic conditions using a polymer–ring system as a model. We found that a Hagen–Poiseuille flow drives a guest polymer into the cavities of ring hosts repeatedly, in a manner distinct from self-threading under thermodynamic equilibrium. Using poly(ethylene glycol) (PEG) and γ-cyclodextrin (γ-CD) as a representative polymer–ring system, two PEG units were threaded into γ-CD in a head-to-tail fashion, forming extremely long pseudodouble-stranded polyrotaxane (DS-PR) nanofibers. These novel DS-PR structures further assembled hierarchically through facial hydrogen bonding, resulting in micrometer-scale crystalline fibers. We systematically investigated the influence of solution motion on host–guest interactions by varying hydrodynamic parameters (e.g., total flow rate, channel geometry, and channel length) and structural parameters (e.g., polymer length and γ-CD/PEG ratio). Remarkably, the forward end of the PEG chain preferentially pierced the wider rim of the γ-CD. Based on these observations, we devised an active-threading mechanism, wherein the end of the PEG chain pierces multiple rings while satisfying both energetic and steric requirements, with the microflow channel acting as a catalyst to accelerate host–guest interaction. Finally, we explored the possibility of cothreading α- and γ-CD units onto a single PEG chain. Notably, overcoming the classical “lock-and-key” paradigm of host–guest chemistry, the observed “piercing effect” enabled the same PEG chain to thread into two differently sized CDs depending on the α-CD/γ-CD ratio in solution.}, archive = {J_JACS}, author = {Munenori Numata and Kaori Tanaka and Atsushi Asai and Mamoru Matsushita and Hiroshi Yoneda and Shoki Tanaka and Takuya Fukai and Hiroka Taguchi and Yoshihiro Kikkawa}, doi = {10.1021/jacs.5c03550}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20612--20630}, shortjournal = {J. Am. Chem. Soc.}, title = {An oriented polymer in a dynamic microsolution pierces molecular rings: An approach toward polyrotaxane synthesis under precise kinetic control}, volume = {147}, year = {2025}, }
• (2025). Breaking the scaling relationship in water oxidation enabled by the electron buffering effect of the fullerene network. JACS, 147(24), 20600--20611. (www)

  @article{ , abstract = {The scaling relationship among reaction intermediates with strongly correlated adsorption energy in the oxygen evolution reaction (OER) severely restricts the energy-conversion efficiency of water electrolysis. For the conventional adsorbate evolution mechanism, breaking the scaling relationship remains challenging, as it is difficult to modulate the adsorption of multiple intermediates on a specific active site simultaneously. Herein, we utilize the electron buffering effect of a two-dimensional fullerene network (C 60 NET) to dynamically tune the electronic structure of the iridium (Ir) active site with the change of adsorbed intermediates, which can tailor the adsorption strength of intermediates from multistep reactions and break the adsorption-energy scaling relationships among *OOH, *O, and *OH. The C 60 NET-buffered Ir nanocluster catalyst exhibits excellent OER activity with a low overpotential of 237 mV and stability over 600 h at 10 mA cm –2 , outperforming graphene-supported Ir nanoclusters and commercial IrO x , attributed to the breaking of the linear scaling relationship enabled by the unique ability to reversibly accept and donate electrons of C 60 NET.}, archive = {J_JACS}, author = {Xiang Chen and Hao Ma and Xing Wang and Hongqiang Jin and Yao Wu and Sibo Wang and Yukun Xiao and Rui Jiang and Yumin Da and Lei Fan and Yuanmiao Sun and Shibo Xi and Yanwei Lum and Qian He and Hexing Li and Dongming Liu and Shangfeng Yang and Wei Chen}, doi = {10.1021/jacs.5c03577}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20600--20611}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking the scaling relationship in water oxidation enabled by the electron buffering effect of the fullerene network}, volume = {147}, year = {2025}, }
• (2025). Enhancing Magnon–Magnon coupling strength to 0.6 GHz in Dion–Jacobson Cu(II)-hybrid perovskites by tuning the topology of ligands. JACS, 147(24), 20590--20599. (www)

  @article{ , abstract = {Copper(II) hybrid organic–inorganic perovskites (HOIPs) offer a unique platform to explore magnetic interactions responsible for ferro- or antiferromagnetic order; yet, their potential for coherent magnon dynamics, a cornerstone of spintronic technologies, remains underdeveloped. Unlike conventional ferromagnets, the structural parameters influencing magnon generation, propagation, and control in HOIPs are poorly understood. Here, we engineer interlayer and intralayer exchange interactions in A-type Dion–Jacobson (DJ) phase Cu(II)-based HOIPs to achieve robust magnon–magnon coupling. By incorporating short, planar organic ligands, we realize a coupling strength of 0.6 GHz, a hallmark of strong interactions vital for dynamic spin-wave manipulation. Landau–Lifshitz–Gilbert simulations and density functional theory (DFT) reveal that interlayer antiferromagnetic exchange and intralayer easy-plane anisotropy jointly dictate the coupling strength in Cu(II)-halide HOIPs. This work demonstrates how the organic ligand topology can be strategically tailored to modulate magnetic exchange pathways, enabling precise control over spin-wave phenomena.}, archive = {J_JACS}, author = {Weixin He and Luwen Jiang and Yali Yang and Walter P. D. Wong and Yunzhe Ke and Shiyue Sun and Shuaishuai Ding and Wenping Hu and Ramanathan Mahendiran and Kian Ping Loh}, doi = {10.1021/jacs.5c03517}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20590--20599}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing Magnon–Magnon coupling strength to 0.6 GHz in Dion–Jacobson Cu(II)-hybrid perovskites by tuning the topology of ligands}, volume = {147}, year = {2025}, }
• (2025). Molecular thermal engine based on a highly flexible elastic crystal. JACS, 147(24), 20582--20589. (www)

  @article{ , abstract = {Materials that exhibit actuation behavior in response to external stimuli have a wide range of applications owing to their ability to convert input energy into mechanical work. Light and chemicals are common sources of input energy. However, actuation using thermal energy from ambient-temperature sources remains challenging. In this study, we introduce novel elastic crystals composed of dodecylated porphyrin molecules that exhibit high flexibility and deformation in response to temperature changes. When a crystal is loaded with a small weight and positioned between high- and low-temperature heat sources, it exhibited continuous, large, and rapid oscillations. These oscillations persisted for at least 160 h, corresponding to 3.9 million deformation cycles, as long as the temperature difference was maintained. This study presents the first example of a molecular crystal functioning as an engine that can extract kinetic energy from static and ambient-temperature sources.}, archive = {J_JACS}, author = {Hinako Kato and Yoji Horii and Chiharu Watanabe and Toshiyuki Sasaki and Kouhei Ichiyanagi and Mariko Noguchi and Hiroki Fujimori and Taro Yamamoto and Hal Suzuki and Yuichi Hirai and Takahito Ohmura and Keigo Yano and Shotaro Hayashi and Takashi Kajiwara}, doi = {10.1021/jacs.5c03529}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20582--20589}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular thermal engine based on a highly flexible elastic crystal}, volume = {147}, year = {2025}, }
• (2025). Reinvestigation of the C-glycoside synthase in alnumycin biosynthesis reveals a conserved mechanism of C–C bond formation. JACS, 147(24), 20571--20581. (www)

  @article{ , abstract = {C -Nucleosides are defined by their unusual C–C glycosidic linkage between the nucleobase and the monosaccharide moiety, which distinguishes them from common N -nucleosides. Several enzymes have been identified to catalyze this atypical C–C bond formation. For instance, YeiN catalyzes the reversible cleavage of pseudouridine 5′-phosphate, yielding ribose 5-phosphate (R5P) and uracil via a Schiff base intermediate formed between R5P and an active-site lysine residue. In alnumycin biosynthesis, the C–C glycosidic bond between R5P and a naphthoquinone heterocycle, prealnumycin, has been shown to be installed by AlnA. While AlnA shares 41% sequence identity with YeiN, a distinct mechanism involving an ene-diol tautomer of R5P had been proposed based on previous biochemical studies and X-ray crystallography. Herein, the mechanism of AlnA is reevaluated using juglone (5-hydroxy-1,4-naphthalenedione) as a prealnumycin analog. By employing isotopologues and protein mass spectrometry, the involvement of an ene-diol intermediate and an alternative Morita–Baylis–Hillman mechanism in AlnA catalysis can both be ruled out. Further analysis of juglone reactivity showed that it can be reduced either enzymatically when coupled to glucose oxidase or nonenzymatically through autoreduction yielding 1,4,5-naphthalenetriol. This hydroquinone derivative of juglone serves as the true substrate of AlnA such that the C -glycosylation mechanism is no different from that of YeiN. These findings unravel the correct substrate of the C -glycoside synthase AlnA and unify the mechanisms of AlnA, YeiN, and other C -glycoside synthases. These results highlight that accurate substrate identification is essential for mechanistic study of enzyme catalysis and call for a reevaluation of the biosynthetic pathway of alnumycin and other naphthoquinone-derived natural products.}, archive = {J_JACS}, author = {Daan Ren and Yu-Hsuan Lee and Hung-wen Liu}, doi = {10.1021/jacs.5c03469}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20571--20581}, shortjournal = {J. Am. Chem. Soc.}, title = {Reinvestigation of the C-glycoside synthase in alnumycin biosynthesis reveals a conserved mechanism of C–C bond formation}, volume = {147}, year = {2025}, }
• (2025). Electrochromic rutile with dynamically tailored surfaces in formaldehyde-mediated hydroxylamine electrosynthesis. JACS, 147(24), 20559--20570. (www)

  @article{ , abstract = {Electrocatalytic nitrate reduction is an attractive route for sustainable hydroxylamine synthesis, but its selectivity is limited by over-reduction and competing hydrogen evolution, highlighting the need for in-depth mechanistic understanding to guide catalyst design. Here, we systematically investigate the electrochemical synthesis of hydroxylamine via a formaldehyde-mediated method on titanium oxides. An electrochromic rutile array prepared via a wet-chemical route achieved a Faradaic efficiency (FE) of 92.6% (for formaldehyde oxime) and a corresponding yield rate of up to 2085 μmol cm –2 h –1 under ambient conditions. Mechanistic studies reveal that the electrochromism is a macroscopic manifestation of the protonation of O b (bridging oxygen) sites and the formation of O v (oxygen vacancies) and Ti 3+ , which act as proton “sponges” and electron reservoirs. Formaldehyde not only serves as the capturing agent but also helps to stabilize *NH 2 OH through molecular tuning, thereby achieving high selectivity. Through formaldehyde-nitrate electro-reforming, hydrogen, formic acid, and hydroxylamine can be coproduced at 200 mA cm –2 under an ultralow cell voltage of 0.78 V. This work links the catalytic performance of hydroxylamine electrosynthesis to the dynamic surface of titanium oxides, offering insights into selectivity control in nitrate electroreduction and providing a green, cost-effective alternative to conventional hydroxylamine synthesis.}, archive = {J_JACS}, author = {Jiaqi Zhang and Erbo Zhao and Chou-Hung Hsueh and Weng-Chon Max Cheong and Xin Tan and Chuhao Liu and Xiang Liu and Jinxin Wang and Hai Xiao and Chen Chen}, doi = {10.1021/jacs.5c03124}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20559--20570}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochromic rutile with dynamically tailored surfaces in formaldehyde-mediated hydroxylamine electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Unexpected SO2 photooxidation on quantum-sized carbon. JACS, 147(24), 20548--20558. (www)

  @article{ , abstract = {Surface photochemistry of carbon quantum dots (CQD) under atmospheric conditions remains poorly understood. Here, we systematically investigate the photoreactivity of CQD in the presence of SO 2 and reveal that CQD photoageing and its interaction with SO 2 occur independently of O 2 . Through a combined experimental and theoretical approach, we demonstrate that these unexpected surface reactions are driven by unique energy transfer and photocatalytic processes induced by photoexcited CQD. Key reactive intermediates─photogenerated hole, hydroxyl radical, sulfite radical, and carbon-centered radical─are identified as critical drivers of CQD surface photooxidation. This discovery provides new insights into the unresolved atmospheric photochemistry of flame-formed fresh soot, advances our understanding of photocatalytic processes on synthetic nanosized carbon materials, and offers clues to the origins of sulfated carbonaceous chondrites in interstellar media.}, archive = {J_JACS}, author = {Peng Zhang and Liang Wang and Huazhang Guo and Hao Li and Shuying Wang and Yulong Shan and Tianzeng Chen and Biwu Chu and Qingxin Ma and Yonghong Wang and Yunbo Yu and Minghong Wu and Joseph S. Francisco and Hong He}, doi = {10.1021/jacs.5c03177}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20548--20558}, shortjournal = {J. Am. Chem. Soc.}, title = {Unexpected SO2 photooxidation on quantum-sized carbon}, volume = {147}, year = {2025}, }
• (2025). Self-generative singlet oxygen (1O2)-initiated chemical modification of nuclear DNAs combats tumor drug resistance. JACS, 147(24), 20534--20547. (www)

  @article{ , abstract = {Multidrug resistance (MDR) is one of the major problems in cancer treatment. Overcoming MDR to achieve effective cancer treatment remains a huge challenge. Here, we proposed a self-generative singlet oxygen ( 1 O 2 )-initiated chemical modification of nuclear DNAs (SiCMoND) approach to kill multidrug-resistant tumor synergizing with chemotherapy. A tumor-targeted “nano-bomb” FA(CT- f T-Dox) was rationally fabricated by encapsulating the complex of Cu 2+ with tetrakis(4-carboxyphenyl) porphyrin) (Cu-TCPP) as a 1 O 2 generator and a doxorubicin (Dox) prodrug tailed with a furan-containing positively charged peptide ( f TAT-Dox) within the micelles of FA-PEG 5000 -PCL 3000 and mPEG 5000 -PCL 3000 . When FA(CT- f T-Dox) nanoparticles accumulated at the tumor site, they could undergo disassembly in the tumor microenvironment (TME) specifically to release Cu-TCPP and f TAT-Dox simultaneously. Taking advantage of the features of Cu-TCPP that can convert tumor-abundant H 2 O 2 into 1 O 2 and f TAT-Dox that can readily penetrate the cell membrane into the nucleus, chemical modification of nuclear DNAs was realized through the covalent cyclization reaction between furan and nucleobases of nuclear DNAs under the ignition of self-generative 1 O 2 , which leads to significant DNA damage and enhanced therapeutic susceptibility. More notably, the sustained release of Dox within the nucleus greatly inhibits DNA transcription and translation leading to severe cancer cell apoptosis. In vivo studies in a multidrug-resistant MCF-7/ADR tumor model showed that the antitumor efficacy of FA(CT- f T-Dox) was 1.6-fold higher than FA(CT-T-Dox) without DNA modification functionality with a tumor suppression efficiency of 83.3%. This SiCMoND-assisting chemotherapy strategy provides a promising antitumor therapeutic modality and opens new avenues for battling multidrug-resistant tumors.}, archive = {J_JACS}, author = {Anna Wang and Yuqi Zhang and Yurong Fan and Zhongsheng Zhao and Zhengzhong Lv and Yirui Guo and Miao Li and Yan Chen and Lihua Hu and Danyang Ji and Xiaju Cheng and Haibin Shi}, doi = {10.1021/jacs.5c02826}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20534--20547}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-generative singlet oxygen (1O2)-initiated chemical modification of nuclear DNAs combats tumor drug resistance}, volume = {147}, year = {2025}, }
• (2025). Near-infrared light-driven condensation using branched two-photon-absorbing organic photocatalysts with viscosity-dependent properties. JACS, 147(24), 20525--20533. (www)

  @article{ , abstract = {Most reported photocatalytic systems that primarily rely on the absorption of ultraviolet (UV) and short visible light irradiation face significant limitations, including shallow penetration in reaction media, competing absorption with substrates and catalysts, and incompatibility with light-sensitive molecules. These drawbacks can be largely avoided if the same reaction can be operated under near-infrared (NIR) light irradiation. Herein, we report a novel family of branched pyridinium-based photocatalysts designed with elegant donor-π-acceptor (D-π-A) architectures and exceptional two-photon absorption (TPA) capabilities in the deep-red and NIR regions. Among the three designed complexes, MPP-3arm demonstrates a remarkable TPA cross section and hence efficient NIR-driven photocatalytic condensation of aromatic diamines and aldehydes. Notably, it also exhibits a unique viscosity-dependent photocatalytic performance, attributed to restricted rotational mobility in a highly viscous environment, a feature rarely explored in organic photocatalysis. Overall, this study presents the design of multibranched organic TPA photocatalysts and their potential of overcoming the limitations encountered in conventional photocatalysis, thus unlocking new opportunities in NIR light-driven chemical synthesis.}, archive = {J_JACS}, author = {Chuang Han and Bidyut Kumar Kundu and Rui Chen and Pragti and Prasenjit Srivastava and Christopher G. Elles and Yujie Sun}, doi = {10.1021/jacs.5c02797}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20525--20533}, shortjournal = {J. Am. Chem. Soc.}, title = {Near-infrared light-driven condensation using branched two-photon-absorbing organic photocatalysts with viscosity-dependent properties}, volume = {147}, year = {2025}, }
• (2025). Covalent destabilizing degrader of AR and AR-v7 in androgen-independent prostate cancer cells. JACS, 147(24), 20512--20524. (www)

  @article{ , abstract = {Androgen-independent prostate cancers, correlated with heightened aggressiveness and poor prognosis, are caused by mutations or deletions in the androgen receptor (AR) or the expression of truncated variants of AR that are constitutively activated. Currently, drugs and drug candidates against AR target the steroid-binding domain to antagonize or degrade AR. However, these compounds cannot therapeutically access largely intrinsically disordered truncated splice variants of AR, such as AR-V7, which only possess the N-terminal transactivation domain and DNA-binding domain and are missing the ligand-binding domain. Targeting intrinsically disordered regions within transcription factors has remained challenging and is considered “undruggable”. Herein, we leverage a cysteine-reactive covalent ligand library in a cellular screen to identify the degraders of AR and AR-V7 in androgen-independent prostate cancer cells. We identified a covalent compound, EN1441, that selectively degrades AR and AR-V7 in a proteasome-dependent manner through direct covalent targeting of intrinsically disordered cysteine C125 in the N-terminal transactivation domain of AR and AR-V7. EN1441 causes significant and selective destabilization of AR and AR-V7, leading to the aggregation of AR/AR-V7 and subsequent proteasome-mediated degradation. Consistent with targeting both AR and AR-V7, we find that EN1441 completely inhibits total AR transcriptional activity in androgen-independent prostate cancer cells expressing both AR and AR-V7 compared with AR antagonists or degraders that only target the ligand-binding domain of full-length AR, such as enzalutamide and ARV-110. Our results put forth a pathfinder molecule EN1441 that targets an intrinsically disordered cysteine within AR to destabilize, degrade, and inhibit both AR and AR-V7 in androgen-independent prostate cancer cells and highlights the utility of covalent ligand discovery approaches in directly targeting, destabilizing, inhibiting, and degrading classically undruggable transcription factor targets.}, archive = {J_JACS}, author = {Charlotte M. Zammit and Cory M. Nadel and Ying Lin and Sajjan Koirala and Elnaz Ahani and Patrick Ryan Potts and Daniel K. Nomura}, doi = {10.1021/jacs.5c02801}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20512--20524}, shortjournal = {J. Am. Chem. Soc.}, title = {Covalent destabilizing degrader of AR and AR-v7 in androgen-independent prostate cancer cells}, volume = {147}, year = {2025}, }
• (2025). Elevating nitrate reduction through the mastery of hierarchical hydrogen-bond networks. JACS, 147(24), 20504--20511. (www)

  @article{ , abstract = {To effectively resolve environmental and industrial dilemmas, electrochemical reduction of nitrate (NO 3 – ) to ammonia (NH 3 ) offers a brilliant strategy for tackling pollution and creating economic value, but the scarcity and reduced reactivity of available interfacial water and reactive adsorbates represent ongoing obstacles. Here, we reform the water–ion networks via electrolyte concentration manipulation and electrode construction on atomically flat Au single-crystal surfaces. With the combination of in situ Raman spectroscopy and multifidelity theoretical simulations, we pinpoint H 2 O with dual hydrogen-bond donors as an observable indicator for nitrate electroreduction (NO 3 RR). A hierarchical configuration characterized by structured Li + ·NO 3 – planes coupled with enriched hydrogen-bond networks is verified to streamline the reactive intermediates activation and proton transport, thus synergistically boosting NO 3 RR. We highlight the cooperative modulation of the interfacial water–ion interactions and the hydrogen-bond networks in optimizing NO 3 RR. Our findings unveil microscale viewpoint of synergy between the local ion–water interactions and connectivity of the hydrogen-bonding network.}, archive = {J_JACS}, author = {Ru-Yu Zhou and Shisheng Zheng and Xuan Liu and Yao-Hui Wang and Shunning Li and Xinzhe Yang and Feng Pan and Jian-Feng Li}, doi = {10.1021/jacs.5c02540}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20504--20511}, shortjournal = {J. Am. Chem. Soc.}, title = {Elevating nitrate reduction through the mastery of hierarchical hydrogen-bond networks}, volume = {147}, year = {2025}, }
• (2025). Highly efficient assembly-line production of long-chain hydrocarbons via Fischer–Tropsch synthesis over Ru/TiO2 catalysts. JACS, 147(24), 20493--20503. (www)

  @article{ , abstract = {The assembly-line strategy serves as an effective way for optimizing tandem steps in the fields of enzyme catalysis and homogeneous catalysis. Herein, we rationally construct efficient Ru/TiO 2 catalysts for an important industrial heterogeneous reaction of Fischer–Tropsch synthesis (FTS), involving CO dissociation, hydrogenation, and C–C coupling complex processes. These catalysts feature an “assembly-line” structure composed of oxygen vacancies (O v ), interfacial Ru (Ru I δ+ at Ru I δ+ –O v –Ti 3+ ), and exposed Ru (Ru E 0 ) sites. Both experimental and theoretical results demonstrate that Ru I δ+ sites with the assistance of O v primarily contribute to CO dissociation and hydrogenation to C1 monomers (workshop 1), while Ru E 0 sites predominantly drive the above intermediates to C–C coupling for carbon chain growth (workshop 2). We interestingly discover that besides the performance of the two workshops themselves, their efficient coordination is key to improve the activity and long-chain hydrocarbon selectivity in FTS. Optimizing this trisite catalytic system via tuning the prereduction time of the TiO 2 support robustly achieves an ultrahigh FTS activity (180.8 mol CO mol Ru –1 h –1 ) while maintaining an impressive C 5+ selectivity (90.1%), outperforming the vast majority of state-of-the-art Ru-based FTS catalysts. This work not only clearly clarifies the synergistic mechanisms of multiple active sites but also offers valuable guidance for the application of the assembly-line strategy in complex heterogeneous catalysis reactions.}, archive = {J_JACS}, author = {Dejian Zhao and Shuaishuai Lyu and Qingpeng Cheng and Yunhao Liu and Pengwei Zhao and Qicheng Zhang and Yingtian Zhang and Yu Pan and Xiaoshen Li and Shaohui Xiong and Zhihong Wang and Xingang Li}, doi = {10.1021/jacs.5c02684}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20493--20503}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly efficient assembly-line production of long-chain hydrocarbons via Fischer–Tropsch synthesis over Ru/TiO2 catalysts}, volume = {147}, year = {2025}, }
• (2025). The binding affinities of serum proteins to nanoparticles. JACS, 147(24), 20475--20492. (www)

  @article{ , abstract = {Nanoparticles can be coated with targeting ligands to deliver medical agents to specific cells. Serum protein adsorption affects the binding of nanoparticles to target cells. We hypothesized that serum proteins and target receptors compete for binding to nanoparticles. We tested the serum protein binding affinity of 251 nanoparticle designs. Here, we discovered that the binding affinities of serum proteins and receptors to a nanoparticle determine whether it can bind to target cells. We developed and validated a quantitative metric, the binding ratio, to identify nanoparticle designs that can bind to targets in serum with 90% sensitivity and 88% specificity. Using the binding ratio as a numerical guideline for nanoparticle design enabled us to improve the efficiency of nanoparticle binding to target cellular receptors.}, archive = {J_JACS}, author = {Benjamin P. Stordy and Zahra Sepahi and Gabriel D. Patrón and Wei Yang and Alexander D. Goodson and Colin Blackadar and Anthony J. Tavares and Guanyou Lin and Ayden Malekjahani and Bill Ling and Rashmi Ravichandran and Derrick R. Hicks and Mikhail G. Shapiro and Miqin Zhang and Neil P. King and David Baker and Luis A. Ricardez-Sandoval and Warren C. W. Chan}, doi = {10.1021/jacs.5c02576}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20475--20492}, shortjournal = {J. Am. Chem. Soc.}, title = {The binding affinities of serum proteins to nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Click-controlled photo-uncaging: Click-assembly of platinum-based photoactive protecting groups for light-triggered bioactive molecule release. JACS, 147(24), 20466--20474. (www)

  @article{ , abstract = {We introduce click-controlled photouncaging, an innovative approach that synergizes click ligation with photocleavage to achieve biorthogonal, light-triggered bioactive molecule release across visible to near-infrared (NIR) wavelengths. Central to this approach is a novel amine protection and deprotection strategy utilizing Pt(IV) complexes. In this strategy, an azide-bearing clickable Pt(IV) moiety acts as a protecting group for amine-containing molecules (the ″cargo″) via a carbamate linkage. Subsequently, click ligation with a DBCO-tagged fluorescent antenna positions the antenna near the Pt(IV) core, transforming it into a photoactive protecting group (PPG) that can be fine-tuned to respond to visible or NIR light. When exposed to light, the antenna drives the photoreduction of the Pt(IV) linker, triggering deprotection and subsequently releasing the cargo molecule. To validate this approach, three Pt(IV) complexes were synthesized featuring amine-containing fluorescent reporters (coumarin, BODIPY) and a therapeutic molecule (Exatecan), and their functionality was validated in solution and cell cultures. Overall, this work introduces a novel, user-friendly, and versatile chemical tool for bioorthogonal, light-controlled activation of molecules in complex biological environments.}, archive = {J_JACS}, author = {Arpit Sharma and Wjdan Jogadi and Man Kshetri and Suha Alqarni and Md Al Amin and May Cheline and Bishal Pokhrel and Shirin Akter and Zexin Lin and Jimin Park and Jordan Solmen and Jordan Caraway and Megan Brattley and Hao Shen and Yao-Rong Zheng}, doi = {10.1021/jacs.5c02579}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20466--20474}, shortjournal = {J. Am. Chem. Soc.}, title = {Click-controlled photo-uncaging: Click-assembly of platinum-based photoactive protecting groups for light-triggered bioactive molecule release}, volume = {147}, year = {2025}, }
• (2025). From nonclassical to classical: Crystallization seeds reshape nucleation mechanisms. JACS, 147(24), 20456--20465. (www)

  @article{ , abstract = {Crystalline seeds are widely employed in crystallization to accelerate nucleation and control product polymorphs; yet, their impact on nucleation mechanisms remains poorly understood. While homogeneous nucleation of crystals from solution often proceeds through nonclassical pathways involving amorphous intermediates, it is unclear how seeds that promote heterogeneous nucleation reshape these mechanisms and govern polymorph selection. Here, we provide the first direct evidence that crystalline seeds can bypass the need for amorphous intermediates as nucleation sites, converting nonclassical nucleation mechanisms into classical, monomer-by-monomer crystallization pathways. Using molecular dynamics simulations of zeolite synthesis, we uncover a complex reaction network of competing nucleation processes mediated by intermediate interfacial polymorphs. The interplay between thermodynamic stability and kinetic favorability of these interfacial polymorphs dictates nucleation outcomes, creating a dynamic balance between the interfacial polymorph stability and crystallization rates. Furthermore, we show that the synthesis environment─whether monomers or aggregates serve as reactants─profoundly impacts these pathways. At moderate supersaturation, seeds eliminate amorphous intermediates and promote classical nucleation, whereas high supersaturation or aggregate-based reactants favor nonclassical pathways, even in the presence of seeds. These findings establish a general framework for understanding how seeds govern crystallization mechanisms, with broad implications for controlling nucleation kinetics, polymorph selection, and material properties. While focused on zeolites, this work reveals insights that may be applicable to biominerals, pharmaceuticals, functional materials, and catalysts, providing a basis for engineering crystallization pathways in diverse applications.}, archive = {J_JACS}, author = {Carlos Chu-Jon and Eli Martinez and Andressa A. Bertolazzo and Aditya Koneru and Subramanian K.R.S. Sankaranarayanan and Jeffrey D. Rimer and Valeria Molinero}, doi = {10.1021/jacs.5c02580}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20456--20465}, shortjournal = {J. Am. Chem. Soc.}, title = {From nonclassical to classical: Crystallization seeds reshape nucleation mechanisms}, volume = {147}, year = {2025}, }
• (2025). An alternative mechanism for C–C desaturation underscores a dual-controlled mechanism for the fate of radical intermediate in Iron(II)- and 2-(Oxo)glutarate-dependent oxygenase DfmD. JACS, 147(24), 20442--20455. (www)

  @article{ , abstract = {The C(sp 3 )–C(sp 3 ) desaturation catalyzed by iron(II)- and 2-(oxo)glutarate-dependent(Fe/2OG) oxygenase is a key step in the biosynthesis and modification of natural products. Similar to other C–H functionalization processes, the reaction is initiated by the active Fe(IV)-oxo species, which abstracts a hydrogen atom from the C–H bond. However, Fe/2OG desaturase suppresses the thermodynamically favored OH-rebound process. This is enigmatic since the substrate-cofactor disposition appears to be a favorable process which involves C–H activation followed by OH rebound. To decipher the mechanism, we studied here the biosynthesis of dehydrofosmidomycin by DfmD, an Fe/2OG enzyme that catalyzes the biosynthesis of the natural product through desaturation, rearrangement, and demethylation reactions. This study employed biochemical, crystallographic, and computational analysis of the reaction. Unlike the sequential hydrogen-atom transfer (HAT) mechanism and cation-dependent mechanism, our study reveals an alternative mechanism for C–C desaturation. This mechanism involves the formation of a three-member ring intermediate oxaphosphiran. We found that the thermodynamically favored formation of oxaphosphiran reduced the barrier for the desaturation reaction. Additionally, the H-bonding network disfavors the OH-rebound pathway. As such, this dual action of the enzyme enables the selective desaturation reaction while bypassing the hydroxylation process. This mechanism highlights the importance of protein machinery as a means of controlling the reactivity and selectivity of radical species.}, archive = {J_JACS}, author = {Xuan Zhang and Lanteng Wang and Jia Liu and Tzu-Yu Chen and Shengheng Yan and Wei-chen Chang and Sason Shaik and Jiahai Zhou and Binju Wang}, doi = {10.1021/jacs.5c02361}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20442--20455}, shortjournal = {J. Am. Chem. Soc.}, title = {An alternative mechanism for C–C desaturation underscores a dual-controlled mechanism for the fate of radical intermediate in Iron(II)- and 2-(Oxo)glutarate-dependent oxygenase DfmD}, volume = {147}, year = {2025}, }
• (2025). Ultrafast cointercalation chemistry for low-temperature sodium-ion batteries. JACS, 147(24), 20431--20441. (www)

  @article{ , abstract = {Sodium-ion batteries (SIBs) offer a sustainable and promising solution for large-scale energy storage because of their low cost and abundant element resources, especially in cold environments, where traditional batteries struggle. The cointercalation chemistry for graphite anode presents a potential avenue due to its fast intercalation kinetics, but it faces significant challenges at low temperatures. Herein, we first unravel a previously overlooked desolvation behavior in the cointercalation system, a key factor in performance decay under low temperatures. We propose a novel two-step reaction mechanism involving partial desolvation and interlayer diffusion for the cointercalation chemistry, which demonstrates the challenge of single-solvent solvation structures in achieving overall kinetics. Based on this, we developed an electrolyte composed of solvents with strong and weak solvation capabilities to accelerate the above two dynamic processes. Benefiting from the unique dual-solvent solvation structure, fast partial desolvation is realized by the easy removal of weakly solvating solvents, while rapid interlayer diffusion is driven by solvated Na + with strong solvents, verified by solid-state nuclear magnetic resonance (ss-NMR). The assembled battery shows an ultrahigh capacity retention of up to ∼90.0% at −30 °C compared with that at room temperature at 1 C. Under this temperature, the battery still shows excellent rate performance with a high capacity maintenance of ∼ 84% for the rate increasing from 0.1 to 5 C.}, archive = {J_JACS}, author = {Yongqi Chen and Likun Chen and Zhe Dong and Chenjie Lou and Zhuo Han and Xudong Li and Guanyou Xiao and Wei Lv and Yan-Bing He and Feiyu Kang and Ming Liu}, doi = {10.1021/jacs.5c02229}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20431--20441}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrafast cointercalation chemistry for low-temperature sodium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Topochemical synthesis, micro-electron diffraction (3D ED), and electron beam-initiated topotactic dimer splitting of cis,syn-thymine dimer crystals. JACS, 147(24), 20426--20430. (www)

  @article{ , abstract = {A solid-state photochemical reaction of crystalline thymine hydrate ( TH ) resulted in a clean topochemical transformation into the cis-syn-dimer ( TD ), matching the structure as the one responsible for most UV lesions in DNA. Microcrystals of TD grown by drop casting piperidine solutions in a TEM grid made it possible to determine their structure by microelectron diffraction (3D ED) and to confirm expectations that an in situ electron-beam ionization reaction could result in a topotactic dimer splitting that, in this case, retains single-crystal-to-single-crystal character up to ca. 30% conversion. The packing structure of dimer TD and the as formed monomer T displays a novel trimeric hydrogen bonding motif, and the latter represents a new crystal phase. Beyond interesting analogies between single crystals of T and TD , and DNA, such as templated dimer formation and electron-transfer-induced repair, this work is a rare example of an electron beam-induced chemical reaction in the crystalline solid state.}, archive = {J_JACS}, author = {Krzysztof A. Konieczny and Rishika Rai and Lukáš Palatinus and Miguel A. Garcia-Garibay}, doi = {10.1021/jacs.5c02209}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20426--20430}, shortjournal = {J. Am. Chem. Soc.}, title = {Topochemical synthesis, micro-electron diffraction (3D ED), and electron beam-initiated topotactic dimer splitting of cis,syn-thymine dimer crystals}, volume = {147}, year = {2025}, }
• (2025). Room-temperature catalyst-free ammonia decomposition for hydrogen production on water microdroplets. JACS, 147(24), 20417--20425. (www)

  @article{ , abstract = {Ammonia has been considered a viable carbon-free hydrogen carrier, yet its decomposition to hydrogen mainly relies on noble-metal-based catalysts and high temperatures. Here, through leveraging extraordinary physicochemical properties at the gas–liquid interface of water microdroplets, we present a catalyst-free and scalable approach for hydrogen production from ammonia under ambient conditions. A maximum hydrogen evolution rate of 226.8 μmol/h was observed, which outperformed most conventional catalytic methods at room temperature. Comprehensive experimental investigations and theoretical calculations revealed the underlying ammonia splitting mechanisms: hydroxyl radical and hydrogen radical, generated at the gas–liquid interface of microdroplets, synergistically triggered the interfacial ammonia decomposition following a thermodynamically favorable redox pathway, and the reaction rates can be enhanced by the high electric fields and reactants concentration accumulation at the gas–liquid interface. This work provides a new paradigm for green hydrogen production, advancing microdroplet chemistry and a sustainable hydrogen society.}, archive = {J_JACS}, author = {Kejian Li and Bingxing Zhang and Deming Xia and Zhengwei Ye and Yuyang Pan and Joseph S. Francisco and Zetian Mi}, doi = {10.1021/jacs.5c02072}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20417--20425}, shortjournal = {J. Am. Chem. Soc.}, title = {Room-temperature catalyst-free ammonia decomposition for hydrogen production on water microdroplets}, volume = {147}, year = {2025}, }
• (2025). Cation-assisted water oxidation with crown ether-based covalent organic frameworks. JACS, 147(24), 20406--20416. (www)

  @article{ , abstract = {Covalent organic framework (COF)-based electrocatalysts for water oxidation are usually designed by inducing polarization into an organic framework. The most common methodology “heteroatom insertion” suffers from lower catalytic activity than metalated systems. Herein, we introduce a strategy of polarity induction into organic frameworks by complexing electrolyte’s alkali metal using crown ether. We have synthesized a series of porous crystalline COFs with different sizes of crown ether units, having different alkali metal binding abilities. COF-catalysts having crown ethers in their backbone show oxygen and hydrogen evolution (OER and HER) performance in alkaline electrolytes. Electrocatalytic performances of various COF-catalysts have also been studied while changing the alkali metal of the electrolyte solution. The most efficient catalyst B18C achieved a current density of 20 and 100 mA cm –2 at an overpotential (η 20 and η 100 ) of 287 ± 1 and 362 ± 8 mV (for the OER) in 1 M KOH (pH = 13.6), with good electrocatalytic stability (16 h chronopotentiometry study showed a 2 mV potential change at 25 mA cm –2 current density). Notably, B18C COF also exhibited good OER performance in 1 M K 2 SO 4 (pH = 6.3) with an overpotential (η 20 ) of 471 mV. Additionally, a promising alkaline HER activity of B18C (η 20 = 310 ± 5 mV) leads to an overall water–splitting performance in 1 M KOH ( E cell = 1.784 V @ 20 mA cm –2 ).}, archive = {J_JACS}, author = {Hiranmoy Pal and Arun Karmakar and Arnab Sadhukhan and Rahul Kumar Sharma and Srayasee Paul and Matthew A. Addicoat and Yusuke Nishiyama and Biswarup Pathak and Subrata Kundu and Rahul Banerjee}, doi = {10.1021/jacs.5c02083}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20406--20416}, shortjournal = {J. Am. Chem. Soc.}, title = {Cation-assisted water oxidation with crown ether-based covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). High-throughput multiplexed quantification of molecules by aptamer sequencing (Apt-seq) in single cells. JACS, 147(24), 20394--20405. (www)

  @article{ , abstract = {The advent of high-throughput sequencing technologies is transforming life sciences into a quantitative paradigm. However, existing sequencing technologies for nondirectly sequencable molecules, such as antibody-sequencing and glycan-sequencing, face certain challenges, including the complexity of antibody-oligonucleotide conjugation procedures, potential steric hindrance, and the labor-intensive chemoenzymatic labeling. Aptamers, as directly sequencable nucleic acids, offer exceptional specificity, broad target range, and small size, making them ideal tools for multimodal molecular profiling. In this work, we present Apt-seq, an aptamer-based, high-throughput platform for multimodal omics quantification at single-cell resolution. This integrative strategy─termed Aptomics─enables parallel profiling of cell surface proteins, glycans, and mRNA. The feasibility of the platform was validated using commercial cell lines, demonstrating strong concordance between sequencing data and flow cytometry results at both bulk and single-cell levels. When applied to complex clinical samples, Apt-seq exhibited exceptional sensitivity and enabled the precise profiling of tumor heterogeneity. Notably, the platform identified a subpopulation of tumor cells with elevated PTK7 surface expression, a marker of stemness. These findings underscore the role of PTK7 in tumor stemness and its potential as a stem-like biomarker. Moreover, using an aptamer targeting sialic acid, we tracked the dynamic changes in sialylation during T cell differentiation, observing an increase in sialic acid levels as resting T cells transitioned into functional T cells, followed by a subsequent decline upon maturity. Collectively, we have developed a new form of multiomics, termed Aptomics, which employs aptamers to enable the sequencing of molecules that are not directly sequenceable, such as proteins and glycans, etc. Apt-seq enables the simultaneous quantitation of both directly and nondirectly sequencable molecules, offering a versatile and scalable platform for the comprehensive quantification of molecules of life in complex biological systems and advancing quantitative science.}, archive = {J_JACS}, author = {Xiaoqiu Wu and Xinrui Lin and Xiangqi Ma and Huidong Huang and Dengwei Zhang and Yuqing Liu and Rui Cheng and Jia Song and Lifei Zhang and Yamin Tan and Ruizi Peng and Tao Bing and Qin Wu and Weihong Tan}, doi = {10.1021/jacs.5c01296}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20394--20405}, shortjournal = {J. Am. Chem. Soc.}, title = {High-throughput multiplexed quantification of molecules by aptamer sequencing (Apt-seq) in single cells}, volume = {147}, year = {2025}, }
• (2025). Spectroscopic and biochemical characterization of the noncanonical radical SAM enzyme ArsL, involved in arsinothricin biosynthesis. JACS, 147(24), 20381--20393. (www)

  @article{ , abstract = {Radical SAM enzymes are the most widespread biocatalysts. These metalloenzymes, using S -adenosyl- l -methionine (SAM) and a [4Fe-4S] cluster as central cofactors, catalyze a broad range of chemically challenging transformations. The vast majority of radical SAM enzymes initiate their reaction by the homolytic cleavage of the SAM C5′–S bond and the generation of the central 5′-deoxyadenosyl radical (5′-dA·). In this study, by combining spectroscopic approaches with labeling and biochemical analyses, we show that ArsL, the key enzyme in the biosynthesis of the arsenic-containing antibiotic arsinothricin, catalyzes a unique reaction: the addition of the 3-amino-3-carboxypropyl radical (ACP·) to As(III). Remarkably, by exploiting several radical trapping strategies, we demonstrate that in sharp contrast to canonical radical SAM enzymes ArsL cleaves the SAM Cγ-S bond. In addition, using electron paramagnetic resonance (EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopies, we establish that ArsL has a unique SAM binding mode, consistent with its catalytic properties and predicted structure. Notably, EPR and HYSCORE analyses support that SAM interacts with the radical SAM [4Fe-4S] cluster in an uncharacteristic conformation to form ACP·. Collectively, our study reveals that members of the superfamily of radical SAM enzymes are able to finely tune the binding of the SAM cofactor in order to perform unique chemistries.}, archive = {J_JACS}, author = {Mickaël Mauger and Alain Guillot and Maryam Seif-Eddine and Stéphane Grimaldi and Alhosna Benjdia and Olivier Berteau}, doi = {10.1021/jacs.5c01006}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20381--20393}, shortjournal = {J. Am. Chem. Soc.}, title = {Spectroscopic and biochemical characterization of the noncanonical radical SAM enzyme ArsL, involved in arsinothricin biosynthesis}, volume = {147}, year = {2025}, }
• (2025). 3D printable materials with visible light triggered photochromism and room temperature phosphorescence. JACS, 147(24), 20372--20380. (www)

  @article{ , abstract = {Light-responsive organic functional materials, especially photochromic materials and room temperature phosphorescence (RTP) materials, have emerged as key players recently for driving advancements in various cutting-edge optical applications. Most of them exhibit a single functional property upon ultraviolet (UV) light irradiation, while visible light triggered functional materials are still scarce. Herein, we have designed three triphenylethylene materials with visible light triggered photochromism and RTP dual-functional properties via a local rigidity design strategy and host–guest strategy and successfully fabricated 3D structures through digital light processing 3D printing methods. The extended π-conjugation structure of triphenylethylene derivatives in the ring-closed forms by introducing dibenzothiophene into the triphenylethylene skeleton influenced the redshift of the absorption peaks and excitation spectra. The halogens and twisted molecules create abundant intermolecular interactions that stabilize the triplet exciton and reduce energy, leading to visible light triggered photochromism and RTP. Taking advantage of the great convenience of excitation light in the visible range, these dual-functional 3D printed materials can be used to create individualized structures. This study not only opens up a strategy for developing functional photosensitive materials that combine photochromism and RTP properties but also provides our insight into optical multichannel information storage with high resolution.}, archive = {J_JACS}, author = {Yuxin Xiao and Jiahui Li and Zihe Song and Jimeng Liao and Mingyao Shen and Tao Yu and Wei Huang}, doi = {10.1021/jacs.5c00976}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20372--20380}, shortjournal = {J. Am. Chem. Soc.}, title = {3D printable materials with visible light triggered photochromism and room temperature phosphorescence}, volume = {147}, year = {2025}, }
• (2025). Asymmetric bimetallic catalysis enabled alkenyl Z/E mutual isomerization. JACS, 147(24), 20359--20371. (www)

  @article{ , abstract = {Olefins are fundamental functional groups present in numerous molecules, and the geometrical configuration of the C═C bonds often plays a critical role in determining the properties of these compounds. Alkenyl geometrical isomerization is, in principle, one of the most efficient approaches for accessing stereodefined olefins. While some progress has been made in achieving unidirectional Z → E or E → Z conversion via olefin geometrical isomerization, there remains a strong demand for controllable, bidirectional geometrical isomerization of C═C bonds. Herein, we present a method for Z / E mutual isomerization of alkenyl groups by using a Pd/Cu catalytic system. This process involves Pd-mediated π–σ–π interconversion followed by selective trapping of the π-allyl-Pd intermediates with N -metalated azomethine ylides generated by a chiral Cu-catalyst. The reaction enables the synthesis of chiral non-natural amino acid derivatives bearing Z - and E -alkenyl groups in an enantio- and Z / E -divergent manner, achieving yields of up to 92%, > 20:1 Z / E or E / Z , and >99% ee. Furthermore, the reaction is scalable to gram quantities, and the resulting products can be transformed into valuable molecules adorned with Z - or E -alkenyl groups. Computational studies show that the bimetallic catalytic system better distinguishes among eight stereoisomers of π-allyl-Pd intermediates than the monometallic system, which results in exceptional Z / E -selectivity of the products. This method offers a robust protocol for synthesizing Z - or E -trisubstituted olefins bearing a chiral motif utilizing a readily available Z / E -mixture of substrates.}, archive = {J_JACS}, author = {Guanlin Li and Ziyun Lai and En Zheng and Yicong Luo and Yuwen Sun and Rui Ding and Panpan Li and Qi Kong and Xiaohong Huo and Shengming Ma and Wanbin Zhang}, doi = {10.1021/jacs.5c00484}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20359--20371}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric bimetallic catalysis enabled alkenyl Z/E mutual isomerization}, volume = {147}, year = {2025}, }
• (2025). Enhancement of lithium-ion conductivity in liquid crystalline block copolymer electrolyte by electric field alignment. JACS, 147(24), 20347--20358. (www)

  @article{ , abstract = {A block copolymer electrolyte (BCPE) with a liquid crystal and a lithium-ion conductive phase is investigated to assess the influence of an external applied electric field on the bulk morphology and the resulting electrochemical performance. For this purpose, the controlled synthesis of poly(10-[(4-cyano-4′-biphenyl)oxy] decatyl methacrylate)- block -(methoxy-poly(ethylene glycol) methacrylate- co -glycidyl methacrylate) [P(MALC)- b -P(PEGMA- co -GM)] block copolymer is performed by reversible addition–fragmentation transfer polymerization. The BCPE containing lithium bis(trifluoromethanesulfonyl)imide as the salt is drop-cast and crosslinked inside an alternating or direct current electric field. Transmission electron microscopy and small-angle X-ray scattering are utilized to study the phase behavior of BCPE and assess the influence of the electric field on the spatial orientation of the microdomains. A hierarchical lam-in-CYL nanostructure with the perpendicular orientation of the mesogenic smectic layers (lam) with respect to the BCPE cylinders (CYL) long axis is identified. Interestingly, the BCPE cast with electric field treatment gives rise to highly ordered cylindrical structures in comparison to the same BCPE without electric field treatment, which in turn exhibits a poorly ordered worm-like morphology. Consequently, a consistent improvement of the ionic conductivity is observed for the electric field-treated polymer, reaching ionic conductivities up to 4.7·10 –5 S·cm –1 at 60 °C, compared to 6.1·10 –6 S·cm –1 at the same temperature for the polymer electrolyte cast without an electric field. Surprisingly, for most of the investigated systems, the BCPE microstructure aligns perpendicular to the applied stimuli, which is explained by the movement of the whole liquid crystalline layer rather than by individual mesogen reorientation.}, archive = {J_JACS}, author = {Isaac Álvarez Moisés and Monika Król and Garance Keus and Zhenni He and Alessandro Innocenti and Stefano Passerini and Janne Ruokolainen and Jean-François Gohy}, doi = {10.1021/jacs.5c00278}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20347--20358}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancement of lithium-ion conductivity in liquid crystalline block copolymer electrolyte by electric field alignment}, volume = {147}, year = {2025}, }
• (2025). Spin manipulation of single nitroxide radical on au(111) by selective coordination. JACS, 147(24), 20338--20346. (www)

  @article{ , abstract = {Organic radicals are promising candidates for constructing molecule-based magnetic materials. Despite the achievements of various radical ligand-containing complex materials, tuning the spin state of organic radicals at the single-molecule level on surfaces remains a challenge. In this study, the spin state of the DPBIN molecule, a derivative of 1,4-di(pyridine-3-yl)benzene bearing two imino-nitroxide radicals in para positions, is tuned by selective coordination with Au, Ni, and Fe centers on the Au(111) surface. The DPBIN molecules provide nitroxide oxygen atoms as ligand atoms in the Au and Fe coordination structures, where the spin of the DPBIN molecules is quenched. By contrast, the nitroxide oxygen atoms are not involved in coordination with Ni atoms; thus, the spin is preserved in this structure. Scanning tunneling microscopy (STM) and spectroscopy (STS) are employed to characterize the geometric structures and spin states of these coordination structures at the atomic level. Interestingly, this spin-manipulation method demonstrates a broader applicability to other metal coordination systems. This research deepens our understanding of the effect of selective coordination on radical spins.}, archive = {J_JACS}, author = {Yansong Wang and Xin Li and Meng-Xiang Wu and Jie Li and Xueyan Wang and Wenjie Dong and Ziyong Shen and Yang He and Yajie Zhang and Xueliang Shi and Hai-Bo Yang and Shimin Hou and Kai Wu and Song Gao and Yongfeng Wang}, doi = {10.1021/jacs.5c00342}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20338--20346}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin manipulation of single nitroxide radical on au(111) by selective coordination}, volume = {147}, year = {2025}, }
• (2025). Dual molecular catalyst-based tandem that enables electrocatalytic CO2−Formaldehyde−Methanol cascade conversion. JACS, 147(24), 20329--20337. (www)

  @article{ , abstract = {Electrocatalytic CO 2 reduction into multielectron products is a promising approach for carbon capture and utilization. Recently, cobalt phthalocyanine (CoPc)-based molecular catalysts have shown potential competence toward electrochemical conversion of CO 2 to methanol, a 6e − /6H + product. Yet, despite the recent advancements, CoPc’s tendency to aggregate and the weak CO-intermediate binding generally limit its electrocatalytic activity and selectivity. Herein, we demonstrate that a metal−organic framework (MOF) could be used to construct a tandem electrocatalytic system via immobilization of 2 types of molecular catalysts (CoPc and Fe-porphyrin). Notably, the MOF-based tandem achieves a 3-fold increase in electrocatalytic CO 2 -to-methanol activity and selectivity compared to a CoPc-only MOF-based catalyst (up to 18% methanol faradaic efficiency at 25 mA/cm 2 ). Additionally, operando spectroscopy and electrochemical analysis show that unlike typical tandem systems, the MOF-based tandem operates uniquely by using a reactive intermediate different from CO (i.e., formaldehyde). Hence, this proof-of-concept approach offers a new means to design molecular electrocatalytic schemes capable of driving complex proton-coupled electron transfer reactions.}, archive = {J_JACS}, author = {Arnab Ghatak and G. Shiva Shanker and Yanai Pearlmutter and Adi Fryder and Ran Shimoni and Idan Hod}, doi = {10.1021/jacs.5c00316}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20329--20337}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual molecular catalyst-based tandem that enables electrocatalytic CO2−Formaldehyde−Methanol cascade conversion}, volume = {147}, year = {2025}, }
• (2025). Spin-state effect of tetrahedron-coordinated single-atom catalysts on CO2 electroreduction. JACS, 147(24), 20318--20328. (www)

  @article{ , abstract = {Spin state of active sites is one of the most influencing factors for the catalytic performance of electrocatalysts. To date, most modulations are conducted on non-tetrahedrally coordinated metal sites, while tetrahedron-coordinated single-atom catalysts (TCSACs) have not been investigated yet. This article presents a correlation between the spin state of TCSACs and their activities toward CO 2 electroreduction. TCSACs are made using ZnO as the substrate. The spin states of metal sites of TCSACs modulate the interactions between the catalyst and adsorbed intermediates. A volcano relationship is found between the transition metal (TM) magnetic moments and the limiting potential ( U L ) of the CO 2 reduction reaction. Spin-state analysis indicates that the intermediate spin state of TMs is more favorable for the adsorption and conversion of CO 2 . Optimal interaction between the TM-t 2 orbitals of the intermediate spin and the adsorbed molecule-p z orbitals significantly improves the catalytic activity of the TCSACs. As a result, Fe-TCSAC achieves a high FE CO of 91.6% at −0.9 V vs RHE. These results provide a theoretical basis and guidelines for the spin-state effects of tetrahedron-coordinated single-atom catalysts.}, archive = {J_JACS}, author = {Yuan Liu and Xixi Ren and Jiajun Wang and Haozhi Wang and Zexiang Yin and Yang Wang and Wenjie Huang and Xiaolin Hu and Zhichuan J. Xu and Yida Deng}, doi = {10.1021/jacs.4c18550}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20318--20328}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin-state effect of tetrahedron-coordinated single-atom catalysts on CO2 electroreduction}, volume = {147}, year = {2025}, }
• (2025). Long-range resonant charge transport through open-shell Donor–Acceptor macromolecules. JACS, 147(24), 20310--20317. (www)

  @article{ , abstract = {A grand challenge in molecular electronics is the development of molecular materials that can facilitate efficient long-range charge transport. Research spanning more than two decades has been fueled by the prospects of creating a new generation of miniaturized electronic technologies based on molecules whose synthetic tunability offers tailored electronic properties and functions unattainable with conventional electronic materials. However, current design paradigms produce molecules that exhibit off-resonant transport under low bias, which limits the conductance of molecular materials to unsatisfactorily low levels─several orders of magnitude below the conductance quantum 1 G 0 ─and often results in an exponential decay in conductance with length. Here, we demonstrate a chemically robust, air-stable, and highly tunable molecular wire platform comprised of open-shell donor–acceptor macromolecules that exhibit remarkably high conductance close to 1 G 0 over a length surpassing 20 nm under low bias, with no discernible decay with length. Single-molecule transport measurements and ab initio calculations show that the ultralong-range resonant transport arises from extended π-conjugation, a narrow bandgap, and diradical character, which synergistically enables excellent alignment of frontier molecular orbitals with the electrode Fermi energy. The implementation of this long-sought-after transport regime within molecular materials offers new opportunities for the integration of manifold properties within emerging nanoelectronic technologies.}, archive = {J_JACS}, author = {Shaocheng Shen and Mehrdad Shiri and Paramasivam Mahalingam and Chaolong Tang and Tyler Bills and Alexander J. Bushnell and Tanya A. Balandin and Leopoldo Mejía and Haixin Zhang and Bingqian Xu and Ignacio Franco and Jason D. Azoulay and Kun Wang}, doi = {10.1021/jacs.4c18150}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20310--20317}, shortjournal = {J. Am. Chem. Soc.}, title = {Long-range resonant charge transport through open-shell Donor–Acceptor macromolecules}, volume = {147}, year = {2025}, }
• (2025). Conformer-sensitive nuclear dynamics of the ammonia dimer cation probed by femtosecond time-resolved coulomb explosion. JACS, 147(24), 20302--20309. (www)

  @article{ , abstract = {Unlike in the liquid phase, the debate of whether and how hydrogen-bonded structures exist in neutral ammonia dimer (NH 3 ) 2 in the gas phase has been ongoing for several decades. Here, we distinguish the structures of neutral ammonia dimers with and without hydrogen bonds by photoionization because the ions inherit initial structures from the neutral dimers and lead to significantly different Coulomb explosion channels in our pump–probe experiment, i.e., the direct dissociation (NH 3 + + NH 3 + ) and indirect dissociation with proton migration (NH 2 + + NH 4 + ). With quantum chemical and molecular dynamics simulation, we showcase that these two different Coulomb explosion channels originate from the ammonia dimer cations with different structures. The dimer cations without hydrogen bonds correlate with the direct Coulomb explosion channel. In contrast, dimer cations with hydrogen bonds are likely to undergo ultrafast proton migration in ∼48 fs, which has no potential barrier and correlate with the indirect dissociation channel in the Coulomb explosion. The 48 fs characteristic time is used to exclude the slower indirect dissociation initiated from non-H-bonded cations. Our work demonstrates a highly sensitive approach to probe weakly bonded and fluxional structures of gas-phase molecular clusters by utilizing both channel and time resolutions of Coulomb explosion.}, archive = {J_JACS}, author = {Jiguo Wang and Xiaoyu Mi and Zhou Liang and Bowen Dong and Yongkai Deng and Ming Zhang and Zheng Li and Yunquan Liu}, doi = {10.1021/jacs.4c18084}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20302--20309}, shortjournal = {J. Am. Chem. Soc.}, title = {Conformer-sensitive nuclear dynamics of the ammonia dimer cation probed by femtosecond time-resolved coulomb explosion}, volume = {147}, year = {2025}, }
• (2025). Tuning the directional solubility of ionic liquids through multicomponent ions for low-temperature desalination. JACS, 147(24), 20294--20301. (www)

  @article{ , abstract = {Directional solvent extraction (DSE) is an emerging technology capable of utilizing low-temperature heat sources (e.g., waste heat) for desalination, but the identification of high-performing directional solvents remains a significant unmet need hindering its broader implementation. Herein, we report the design of thermoresponsive ionic liquids with multicomponent ions as a powerful class of directional solvents. Our studies revealed that freshwater yield and ion rejection rates for [choline][NTf 2 ] were greatly enhanced by the addition of [choline][OH]. Molecular simulations highlight the importance of balancing hydrophilicity and hydrophobicity through the addition of polar, protic functional groups in the development of a reliable structure–function relationship toward identifying an optimal ionic liquid-based directional solvent. The newly developed ionic liquid directional solvents may significantly advance the DSE technology to solve the global water shortage challenge.}, archive = {J_JACS}, author = {Gregory M. Durling and Tye Milazzo and Eliseo Marin-Rimoldi and Jonathan A. Ouimet and William A. Phillip and Edward J. Maginn and Tengfei Luo and Brandon L. Ashfeld}, doi = {10.1021/jacs.4c16294}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20294--20301}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the directional solubility of ionic liquids through multicomponent ions for low-temperature desalination}, volume = {147}, year = {2025}, }
• (2025). Peptide recognition sequence guides catalytic side chain cross-linking of plant peptides by copper-dependent cyclases. JACS, 147(24), 20284--20293. (www)

  @article{ , abstract = {Side chain cross-linking of amino acids is a challenging oxidative enzymatic reaction that has largely been confined to heme and iron sulfur cluster containing enzymes. However, the recent discovery of plant BURP-domain peptide cyclases (BpCs) responsible for the biosynthesis of burpitide natural products has demonstrated that copper-dependent enzymes are able to generate similar cross-links. For example, ArbB2 is responsible for the formation of a Tyr-phenol-O to Leu-C β bond observed in arabipeptin A, a cyclopeptide alkaloid isolated from the well-known plant Coffea arabica . To investigate this intriguing enzyme family in more detail, we developed minimal peptide substrates for ArbB2, which enabled quantitative studies. By examining reductant dependence, we achieved catalytic turnover for the first time in this enzyme family, which allowed for kinetic, mutational, substrate scope, and multicore processing analyses. Additionally, we established the dioxygen dependence and confirmed the absence of hydrogen peroxide as a side product in the catalytic system. Finally, we extended our study to other BpCs involved in cyclopeptide alkaloid biosynthesis, demonstrating that our findings apply across additional members of this enzyme family. Ultimately, this work provides fundamental insights into a new, widespread family of copper-dependent peptide cyclases and lays the groundwork for future mechanistic investigations.}, archive = {J_JACS}, author = {Stella T. Lima and Michael A. Pasquale and M. Rafiul O. K. Noyon and Elizabeth A. Clark and Corinne R. Laws and Shabnam Hematian and Jonathan R. Chekan}, doi = {10.1021/jacs.4c15470}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20284--20293}, shortjournal = {J. Am. Chem. Soc.}, title = {Peptide recognition sequence guides catalytic side chain cross-linking of plant peptides by copper-dependent cyclases}, volume = {147}, year = {2025}, }
• (2025). X-ray-induced photodegradation of hydrogels by the incorporation of X-ray-activated long persistent luminescent nanoparticles. JACS, 147(24), 20273--20283. (www)

  @article{ , abstract = {The development of on-demand degradable hydrogels remains an important challenge. Even though photodegradable hydrogels offer spatiotemporal control over degradation, it is difficult to use ultraviolet, visible, or near-infrared light as a tool for noninvasive triggering in vivo due to the poor tissue-penetration capacity. In contrast, X-ray irradiation can penetrate deep tissue and has virtually no penetration limitations for biological soft tissues. In this study, we propose an X-ray-photodegradation cascade system for hydrogel degradation by incorporating X-ray-activated persistent luminescence nanoparticles (X-PLNPs) into photodegradable hydrogels. A photodegradable 9,10-dialkoxyanthracene-based cross-linker was synthesized and used to prepare photodegradable hydrogels, of which the degradation behavior can be triggered by visible green light. Next, Tb 3+ -doped β-NaLuF 4 was introduced as an X-PLNP that can convert X-rays into visible light centered at 544 nm. The afterglow can even be detected for 4 × 10 3 s after switching off the X-ray irradiation. The X-ray-induced green light emission was demonstrated to trigger photodegradation of the hydrogel. This proof-of-concept system for X-ray irradiation-induced on-demand hydrogel degradation was used to demonstrate X-ray-sensitive drug delivery inside a chicken breast as the in vitro tissue model. As this X-ray-induced cascade degradation of hydrogels can penetrate deep tissues, it is a promising platform for future in vivo applications requiring on-demand triggered hydrogel degradation, such as drug delivery or removal of hydrogel patches, hydrogel adhesives, or hydrogel tissue engineering scaffolds. It should, however, be noted that the hydrogel’s X-ray and photoresponsiveness should be further improved to enable future in vivo use.}, archive = {J_JACS}, author = {Shanshan Li and Hailei Zhang and Jiaying Zhong and Bo Zhang and Kaiming Zhang and Yuangong Zhang and Leipeng Li and Yanmin Yang and Yonggang Wu and Richard Hoogenboom}, doi = {10.1021/jacs.4c14477}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20273--20283}, shortjournal = {J. Am. Chem. Soc.}, title = {X-ray-induced photodegradation of hydrogels by the incorporation of X-ray-activated long persistent luminescent nanoparticles}, volume = {147}, year = {2025}, }
• (2025). C–C bond cleavage in the late-stage biosynthesis of huperzine alkaloids occurs via enzymatic retro-aza-prins reaction. JACS, 147(24), 20265--20272. (www)

  @article{ , abstract = {The demand for novel enzyme-catalyzed reactions in chemical synthesis has spurred the development of many new-to-nature reactions. Additionally, detailed analysis of biosynthetic pathways can uncover unprecedented chemical/enzymatic mechanisms. In this study, we revisited the catalytic mechanism of the 2-oxoglutarate-dependent dioxygenase Pt2OGD-1, involved in the biosynthesis of huperzine alkaloids. Our experimental and computational investigations uncovered a previously unknown enzymatic C–C bond cleavage in the piperidine ring of the alkaloid scaffold, resembling an oxidative retro-aza-Prins reaction. Here, this transformation is initiated by hydrogen abstraction, followed by electron transfer at the 4-position of the heterocycle, triggering ring opening and finally resulting in the loss of a carbon atom as formaldehyde. This discovery expands the toolbox of reactions, enhances our understanding of these enzymes, and may facilitate their application in the biotechnological production of pharmaceutically relevant alkaloid scaffolds as well as the development of biocatalysts with similar activities.}, archive = {J_JACS}, author = {Stefan E. Payer and Mario Prejanò and Philipp Kögl and Tamara Reiter and Eva-Maria Pferschy-Wenzig and Fahmi Himo and Wolfgang Kroutil}, doi = {10.1021/jacs.4c10410}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20265--20272}, shortjournal = {J. Am. Chem. Soc.}, title = {C–C bond cleavage in the late-stage biosynthesis of huperzine alkaloids occurs via enzymatic retro-aza-prins reaction}, volume = {147}, year = {2025}, }
• (2025). Alkyl fluoride synthesis via cu-mediated deacetylative fluorination. JACS, 147(24), 20257--20264. (www)

  @article{ , abstract = {Given the increasing demand for diverse alkyl fluorides for various applications, it would be beneficial to enrich the fluorination toolbox by including more kinds of common functional groups, such as ketones, as fluoride surrogates. Here we report a Cu-mediated deacylative fluorination approach that can convert a wide range of methyl ketones to the corresponding alkyl fluorides. The reaction is enabled by a ketone activation reagent and a nucleophilic fluoride source. It features broad functional group tolerance, capability for the late-stage fluorination, fluoro-annulation, synthesis of α,α-dideuterated fluorides, and degree-controlled synthesis of mono-, di-, and trifluoro alkanes from a single ketone starting material. The computational studies suggest interesting Cu(III)-mediated C–F bond forming pathways via either fluorine atom transfer or an S N 2 process.}, archive = {J_JACS}, author = {Zining Zhang and Kezhi Chen and Peng Liu and Guangbin Dong}, doi = {10.1021/jacs.5c08175}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20257--20264}, shortjournal = {J. Am. Chem. Soc.}, title = {Alkyl fluoride synthesis via cu-mediated deacetylative fluorination}, volume = {147}, year = {2025}, }
• (2025). Strained cyclic alkyl(amino)carbene-stabilized tetraatomic silicon(0) cluster. JACS, 147(24), 20251--20256. (www)

  @article{ , abstract = {Lewis-base-stabilized silicon species in the zero oxidation state are crucial for transforming elemental silicon into valuable compounds. The synthesis of a cyclic tetraatomic silicon(0) cluster, stabilized by four-membered cyclic alkyl(amino) carbenes, is reported. It is a versatile one, two, or four silicon atom source, demonstrating cluster isomerization or fragmentation.}, archive = {J_JACS}, author = {Rahul Kumar Siwatch and Zheng Jie Glenn Ng and Jia-Jun Sean Lim and Zheng-Feng Zhang and Ming-Der Su and Cheuk-Wai So}, doi = {10.1021/jacs.5c07275}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20251--20256}, shortjournal = {J. Am. Chem. Soc.}, title = {Strained cyclic alkyl(amino)carbene-stabilized tetraatomic silicon(0) cluster}, volume = {147}, year = {2025}, }
• (2025). The isopropylstilbene precursor cinnamic acid inhibits anthraquinone pigment production by targeting AntI. JACS, 147(24), 20246--20250. (www)

  @article{ , abstract = {Photorhabdus strains, Gram-negative bacteria pathogenic to insect larvae, produce two signature compounds: the multifunctional isopropylstilbene (IPS), known for its antibiotic, insecticidal, and immunosuppressive activities, and orange-to-red pigmented anthraquinones (AQs), which attenuate oxidative stress. Here, we demonstrate an inverse correlation between the production of AQs and cinnamic acid (CA), the primary precursor for IPS formation in the model strain P. laumondii TTO1. Metabolic and proteomic analyses following CA treatment show that CA inhibits AntI, a key enzyme in the final step of AQ-256 biosynthesis. The crystal structure of AntI in complex with CA reveals that cinnamic acid functions as a competitive inhibitor by inducing specific structural rearrangements in the lyase, resulting in noncovalent, reversible inhibition. These findings provide atomic insights into the intricate regulatory control of pigment biosynthesis and the production of bioactive compounds.}, archive = {J_JACS}, author = {Li Su and Maximilian Schmalhofer and Gina L. C. Grammbitter and Nicole Paczia and Timo Glatter and Michael Groll and Helge B. Bode}, doi = {10.1021/jacs.5c07388}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20246--20250}, shortjournal = {J. Am. Chem. Soc.}, title = {The isopropylstilbene precursor cinnamic acid inhibits anthraquinone pigment production by targeting AntI}, volume = {147}, year = {2025}, }
• (2025). Divergent total syntheses of rearranged steroids swinhoeisterols A–C. JACS, 147(24), 20239--20245. (www)

  @article{ , abstract = {Swinhoeisterols A–C are 13(14→8),14(8→7)-di abeo -steroids possessing an intriguing 6/6/5/7 tetracyclic core framework and potent inhibitory activity against the histone acetyltransferase p300. Herein we report their divergent total syntheses from readily available ( S )-Wieland–Miescher ketone. A tandem Negishi/Heck cross-coupling of a chloroenol triflate was developed to install the labile methylenecyclopentene motif using a silyl-tethered homoallylic zinc reagent that was carefully designed to suppress undesired [Pd]–H insertion. Furthermore, a Baran reductive olefin coupling of a diene, a rarely used radical donor, with a tethered acrylonitrile group allowed for the simultaneous construction of the seven-membered ring and two contiguous stereocenters, including a quaternary carbon center.}, archive = {J_JACS}, author = {Ganlin Huang and Xinliang Zhang and Yu-Cheng Gu and Jinghan Gui}, doi = {10.1021/jacs.5c07053}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20239--20245}, shortjournal = {J. Am. Chem. Soc.}, title = {Divergent total syntheses of rearranged steroids swinhoeisterols A–C}, volume = {147}, year = {2025}, }
• (2025). Palladium-catalyzed methylene β-C–H fluorination of native amides. JACS, 147(24), 20233--20238. (www)

  @article{ , abstract = {Selective fluorination of C( sp 3 )–H bonds is a highly valuable transformation in organic synthesis and drug discovery. However, achieving methylene C–H fluorination of native substrates remains a significant challenge, as it typically requires external directing groups to facilitate catalyst-substrate binding. Herein, we report a ligand-accelerated Pd-catalyzed methylene β-C–H fluorination of native amides using a bidentate neutral amide-pyridone ligand. This ligand design features the enhancement of catalyst-substrate interactions via stabilization of the cationic palladium center and acceleration of methylene C–H activation, enabling the stereo- and site-selective fluorination of native amides under relatively mild conditions. Notably, Pd(II)-catalyzed methylene C–H activation of weakly coordinating native amides has not been reported to date. This method is compatible with native amides derived from selected drug molecules and Weinreb amides, demonstrating potential utility in drug discovery and other applications.}, archive = {J_JACS}, author = {Yi-Hao Li and Jin-Quan Yu}, doi = {10.1021/jacs.5c06237}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20233--20238}, shortjournal = {J. Am. Chem. Soc.}, title = {Palladium-catalyzed methylene β-C–H fluorination of native amides}, volume = {147}, year = {2025}, }
• (2025). Photoinduced copper-catalyzed enantioselective allylic C(sp3)–H oxygenation of acyclic terminal olefins enabled by SphenBOX. JACS, 147(24), 20225--20232. (www)

  @article{ , abstract = {Although the copper-catalyzed allylic C(sp 3 )–H oxygenation (Kharasch–Sosnovsky reaction) is a powerful transformation known for over a half century, its enantioselective version has been developed with drawbacks. High enantioselectivity was not achieved for acyclic terminal olefins and tertiary C–H bonds. Here we have addressed these long-standing challenges enabled by the design of new SphenBOX ligands. When combined with photocatalysis, a range of valuable allylic esters can be obtained directly from terminal olefins and carboxylic acids with high efficiency, regioselectivity, and enantioselectivity. Unprecedented enantioconvergent oxygenation of allylic tertiary C(sp 3 )–H bonds is demonstrated, allowing construction of quaternary stereocenters with high enantioselectivity. Structural analysis indicates that SphenBOX features a compact chiral pocket that may contribute to its superior performance.}, archive = {J_JACS}, author = {Xu-Kuan Qi and Qiang Dai and Yangyi Gu and Kwan Shing Lau and Herman H. Y. Sung and Ian D. Williams and Zhenyang Lin and Chaoshen Zhang and Jianwei Sun}, doi = {10.1021/jacs.5c06136}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20225--20232}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoinduced copper-catalyzed enantioselective allylic C(sp3)–H oxygenation of acyclic terminal olefins enabled by SphenBOX}, volume = {147}, year = {2025}, }
• (2025). Net-coded organic building blocks for the reticular assembly of high-connectivity Metal–Organic frameworks. JACS, 147(24), 20218--20224. (www)

  @article{ , abstract = {High-connectivity metal–organic frameworks (MOFs) are of great importance in reticular chemistry because of the designed synthesis by judicious selection of organic and inorganic building blocks. However, it remains a challenge to synthesize well-defined polytopic organic linkers with a connectivity ≥ 12. Here we report the synthesis of (4,12)-connected shp - and (6,12)-connected alb -MOFs─denoted as Cu-HDTB- shp , In-HDTB- shp , Fe-HDTB- alb , and Zr-HDTB- alb ─by assembly of a 12-connected dodecacarboxylate ligand and preselected inorganic nodes. This dodecacarboxylate ligand, a feasible net-coded organic building block encoding geometric information on the targeted high-connectivity net, allows the rational synthesis of MOFs based on the shp - and alb -derived nets, including rare node-morphing ceh and key nets. Fe-HDTB- alb and Zr-HDTB- alb , on account of the right pore structures, can potentially be applied to natural gas upgrading. This net-coded strategy presents a significant step toward the rational synthesis of high-connectivity framework structures with molecular-level precision.}, archive = {J_JACS}, author = {Jian Yang and Zhi Zhang and Yutong Jiang and Yuanlong Zhong and Zhenning Yang and Zhijie Chen}, doi = {10.1021/jacs.5c06012}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20218--20224}, shortjournal = {J. Am. Chem. Soc.}, title = {Net-coded organic building blocks for the reticular assembly of high-connectivity Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Vanadium-mediated carbon isotope exchange of terminal alkenes. JACS, 147(24), 20212--20217. (www)

  @article{ , abstract = {The incorporation of carbon isotopes into bioactive compounds is of great importance in chemistry, biology, and medicine. Especially valuable are catalytic procedures that rely on a limited collection of available labeled materials. Recently we introduced a conceptually novel solution to carbon isotope exchange (CIE) for terminal olefins based on the preference of V alkylidenes for degenerate metathesis. However, the previous report utilized a V catalyst that suffered from functional group tolerance due to the high electrophilicity of the V center, making it impractical for biological compounds. Herein, we utilized V catalysts containing electron-donating groups to overcome those challenges. We utilize isotopically labeled substituted styrene as a labeled ═ 13 CH 2 moiety source, prepared from 13 C-labeled iodomethane. The isotope source can be easily removed from the reaction mixture, recovered, and reused. A diverse range of terminal alkenes, including bioactive molecules, were tested to showcase the capabilities and limitations of the developed method.}, archive = {J_JACS}, author = {Vasilisa Krivovicheva and Madhu Sudhana Reddy Gangireddy and Anqi Liu and Leonardo B. Maya and Alexander M. Mebel and Konstantin V. Bukhryakov}, doi = {10.1021/jacs.5c05880}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20212--20217}, shortjournal = {J. Am. Chem. Soc.}, title = {Vanadium-mediated carbon isotope exchange of terminal alkenes}, volume = {147}, year = {2025}, }
• (2025). Light-driven lithium extraction from mixtures of alkali cations using an azobipyridine ligand. JACS, 147(24), 20205--20211. (www)

  @article{ , abstract = {Humanity’s replacement of fossil-fuel energy with renewable electricity will require extensive deployment of lithium batteries, which necessitates an increase in the rate of production of this vital metal. Current extraction methods from brines and ores are very energy-intensive, as are recycling methods. Here we report a novel Li 5 L 2 sandwich structure in which five lithium ions are bound between the azobipyridine groups of two pentagonal ligands. The geometry of these ligands leads to the selectivity for binding Li + in the presence of Na + and K + . Upon illumination, the trans -azobipyridine moieties of the ligands isomerize to their cis form, promoting the release of free Li + as the sandwich comes apart. The selective complexation of Li + , and its photostimulated release, were used as the basis of a cycle for selectively extracting and releasing Li + ions from a mixture with Na + and K + . Solar energy may thus be used directly to purify this metal, which is essential for storing increasingly cheap electricity produced through renewable means.}, archive = {J_JACS}, author = {Yuyin Du and Amit Ghosh and Paula C. P. Teeuwen and David J. Wales and Jonathan R. Nitschke}, doi = {10.1021/jacs.5c05885}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20205--20211}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-driven lithium extraction from mixtures of alkali cations using an azobipyridine ligand}, volume = {147}, year = {2025}, }
• (2025). Concise syntheses of lycojapomine alkaloids enabled by radical dearomatization of a pyrrole. JACS, 147(24), 20200--20204. (www)

  @article{ , abstract = {We disclose the first total syntheses of the complex alkaloids Lycojapomine A and B. Our synthetic strategy is built on a dearomatization and stepwise functionalization of a pyrrole starting material, constructing the three-dimensional structure of the target around it. This is enabled by a high-yielding photoinduced primary radical addition from the N -hydroxy phthalimide ester and a subsequent silver-catalyzed 5-endo-dig and Aza-silyl-Prins annulation cascade. Divergent control over an aldol reaction yields both Lycojapomines A and B in an efficient manner, without the need for any excess protecting groups.}, archive = {J_JACS}, author = {Benjamin M. Gross and Brian M. Stoltz}, doi = {10.1021/jacs.5c05721}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20200--20204}, shortjournal = {J. Am. Chem. Soc.}, title = {Concise syntheses of lycojapomine alkaloids enabled by radical dearomatization of a pyrrole}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic cyclohexanone oxime synthesis from ambient air and KA oil. JACS, 147(24), 20194--20199. (www)

  @article{ , abstract = {Photocatalysis offers a sustainable alternative for cyclohexanone oxime synthesis. However, multielectron and multiproton chemical transformations and synergic C–N coupling have posed tremendous barriers. To overcome these challenges, we intimately integrate quantum dot (QD) photocatalysts with a molecular iron–polypyridine complex and achieve photocatalytic cyclohexanone oxime formation for the first time. Mechanistic studies reveal that the close contact between CdS QDs and molecular iron–polypyridine complex boosts rapid photogenerated electron transfer to drive fast and continuous NO x – reduction. Simultaneously, photogenerated holes perform cyclohexanol oxidation to cyclohexanone coordinated to CdS QDs. More strikingly, the controllable formation and coordination with NH 2 OH intermediate by the molecular complex enable synergic C–N coupling for cyclohexanone oxime synthesis with near-unity NO x – conversion and 82.5 ± 1.7% selectivity. Through tandem plasma-driven N 2 oxidation and photocatalysis, 0.395 g of cyclohexanone oxime is obtained from ambient air and ketone–alcohol (KA) oil, which offers a competitive candidate for cyclohexanone oxime synthesis and encourages value-added nitrogenous chemical transformation from abundant resource molecules.}, archive = {J_JACS}, author = {Shu-Lin Meng and Chen Zhang and Jia-Hao Li and Chen-Ho Tung and Li-Zhu Wu}, doi = {10.1021/jacs.5c03187}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20194--20199}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic cyclohexanone oxime synthesis from ambient air and KA oil}, volume = {147}, year = {2025}, }
• (2025). Radical oxidation of the 2-deoxyribosyl moiety of DNA: Characterization of unique strand breaks with 5′-carboxylate termini. JACS, 147(24), 20189--20193. (www)

  @article{ , abstract = {Hydroxyl radicals and other reactive species attack DNA to produce an array of nucleobase and 2-deoxyribose lesions. Here, we have characterized novel oxidatively induced modifications of the sugar moiety that arise from initial H atom abstraction at the C5′ position. In the presence of O 2 , C5′-centered alkyl radicals transform into the corresponding peroxyl radicals. Ultimately, this leads to strand breaks with a modified nucleoside at the 5′-terminus. In addition to the well-known 5′-aldehyde products, we have characterized novel 5′-carboxylate products. This damage represents about 25% of the corresponding 5′-aldehyde nucleosides. We also characterized two tandem lesions, whose formation can be explained by the addition of intermediate 5′-peroxyl radicals to the C8 position of the attached purine base. The modifications were detected by UPLC-MS/MS upon exposure of DNA to ionizing radiation, Fenton reagents, and alkylperoxyl radicals.}, archive = {J_JACS}, author = {Gabriel Robert and J. Richard Wagner}, doi = {10.1021/jacs.5c00674}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20189--20193}, shortjournal = {J. Am. Chem. Soc.}, title = {Radical oxidation of the 2-deoxyribosyl moiety of DNA: Characterization of unique strand breaks with 5′-carboxylate termini}, volume = {147}, year = {2025}, }
• (2025). Elucidating energy conversion pathways at Biotic/Abiotic interfaces in Microbe–Semiconductor hybrids. JACS, 147(24), 20171--20188. (www)

  @article{ , abstract = {Biotic/abiotic hybrid systems integrating microbes with light-absorbing semiconductor materials offer promising solutions for sustainable energy conversion and value-added chemical production. In this Perspective, we discuss the mechanistic insights into upstream energy conversion processes at the biotic–abiotic interfaces, underscoring their pivotal roles in determining biohybrid performance. We explore how biological, physicochemical, and electrochemical characterization techniques have advanced our understanding of energy conversion pathways and electron transport mechanisms within these complex systems. Moreover, we emphasize the growing importance of spatiotemporally resolved imaging in linking biological activity to physicochemical dynamics at the single-cell level. Moving forward, we propose that interdisciplinary collaborations and innovative methodologies will be critical in deepening the mechanistic understanding and unlocking the full potential of artificial photosynthetic biohybrid systems.}, archive = {J_JACS}, author = {Weidong Zhang and Chenwei Xiong and Peng Chen and Bing Fu and Xianwen Mao}, doi = {10.1021/jacs.5c02838}, journal = {Journal of the American Chemical Society}, month = {6}, number = {24}, pages = {20171--20188}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating energy conversion pathways at Biotic/Abiotic interfaces in Microbe–Semiconductor hybrids}, volume = {147}, year = {2025}, }
• (2025). Correction to “Chemoselective silver-catalyzed nitrene transfer: Tunable syntheses of azepines and cyclic carbamimidates. JACS, 147(23), 20170. (www)

  @article{ , archive = {J_JACS}, author = {Emily Z. Schroeder and Chenxi Lin and Yun Hu and Zhen-Yao Dai and Amory F. Griffin and Thomas S. Hotvedt and Ilia A. Guzei and Jennifer M. Schomaker}, doi = {10.1021/jacs.5c08158}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20170}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Chemoselective silver-catalyzed nitrene transfer: Tunable syntheses of azepines and cyclic carbamimidates}, volume = {147}, year = {2025}, }
• (2025). Correction to “Electrocatalytic oxidation of ammonia by (Salen)ruthenium(III) ammine complexes: Direct evidence for a Ruthenium(VI) nitrido active intermediate”. JACS, 147(23), 20168--20169. (www)

  @article{ , archive = {J_JACS}, author = {Jianhui Xie and Tingting Yang and Longzhu Hong and Hui Li and Bing Li and Zhenguo Guo and Yingying Liu and Tai-Chu Lau}, doi = {10.1021/jacs.5c08147}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20168--20169}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Electrocatalytic oxidation of ammonia by (Salen)ruthenium(III) ammine complexes: Direct evidence for a Ruthenium(VI) nitrido active intermediate”}, volume = {147}, year = {2025}, }
• (2025). Mechanism-guided development of directed C–H functionalization of bicyclo[1.1.1]pentanes. JACS, 147(23), 20159--20167. (www)

  @article{ , abstract = {This report describes a detailed study of the palladium-mediated directed C(2)–H functionalization of bicyclo[1.1.1]pentanes (BCPs). Previous attempts to achieve this transformation were reported as unsuccessful. To understand why, a combination of stoichiometric organometallic experiments (to isolate and study the coordination chemistry of these substrates), H/D exchange (to directly probe the C–H activation step), and DFT calculations (to predict optimal directing groups and supporting ligands) was conducted. Collectively, these revealed that cyclometalation at Pd(II) is kinetically facile but thermodynamically unfavorable with aminoquinoline as a directing group and acetonitrile as a supporting ligand. However, changing to a pyridine N-oxide directing group or dimethyl sulfoxide (DMSO) supporting ligand enabled the isolation of stable BCP palladacycles. The functionalization of these complexes was low-yielding with two-electron aryl iodide oxidants. However, moving to single-electron reactions (using in situ-generated aryl radicals) or to electrophilic functionalization (using I 2 ) resulted in synthetically useful yields of C(2)-functionalized products at room temperature. This C–H functionalization approach was leveraged to access derivatives of a key intermediate in the synthesis of bioisosteric analogues of the angiotensin II receptor blocker telmisartan. A four-step sequence from commercially available BCP carboxylic acids, involving directing group installation, cyclopalladation, C(2) arylation, and directing group cleavage, afforded a comparable or improved overall yield, step-count, and functional group compatibility relative to state-of-the-art synthetic approaches. Overall, these studies uncovered a mild Pd-mediated route for the C(2)-diversification of the BCP scaffold. In addition, the lessons learned herein provide a blueprint for achieving directed C–H functionalization of a broader array of strained ring benzene bioisosteres.}, archive = {J_JACS}, author = {Alexander Bunnell and Michael W. Milbauer and Julia Viana Bento and S. Maryamdokht Taimoory and Paul M. Zimmerman and Dipannita Kalyani and Tiffany Piou and Melanie S. Sanford}, doi = {10.1021/jacs.5c07190}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20159--20167}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanism-guided development of directed C–H functionalization of bicyclo[1.1.1]pentanes}, volume = {147}, year = {2025}, }
• (2025). Bioinspired amine-guided polyphenol coatings for selective bacterial disruption and osseointegration on orthopedic implants. JACS, 147(23), 20144--20158. (www)

  @article{ , abstract = {Implant-related infections and inadequate osseointegration pose significant challenges in orthopedic surgery. However, current surface modification strategies are generally complex or necessitate harsh synthesis conditions, thereby limiting their versatility. We developed a facile, one-step method to fabricate a stable polyphenol-based coating on titanium using amine-directed self-polymerization. Amine forms covalent bonds with polyphenol, enhancing the coating stability, as confirmed by molecular dynamics simulations. This bioinspired coating eliminated over 90% of Staphylococcus aureus and Escherichia coli by disrupting bacterial chemotaxis and FTSI protein expression of the cell wall, thereby impairing bacterial respiration and interfering with proton and electron transfer in bacterial membranes, which could selectively eliminate pathogenic bacteria through a contact-killing mechanism without any negative effect on mammalian cells. It also promoted the growth and differentiation of bone mesenchymal cells via the Wnt/β-catenin pathway. Additionally, The bioinspired coating modulated macrophages toward a pro-repair M2 polarization. In cell-bacteria competitive coculture experiments, the coating exhibited superior antibacterial efficacy. In vivo studies demonstrate a 50% improvement in osseointegration in infected bone models. This approach is versatile and can be applied to various implant materials, offering a scalable solution for next-generation medical devices.}, archive = {J_JACS}, author = {Meizhou Sun and Chi Xu and Ruonan Wu and Yiyan Ke and Xiaokang Ding and Nana Zhao and Wei Geng and Yujie Sun and Shun Duan and Fu-Jian Xu}, doi = {10.1021/jacs.5c07074}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20144--20158}, shortjournal = {J. Am. Chem. Soc.}, title = {Bioinspired amine-guided polyphenol coatings for selective bacterial disruption and osseointegration on orthopedic implants}, volume = {147}, year = {2025}, }
• (2025). Design and structural elucidation of glycopeptide fibrils: Emulating glycosaminoglycan functions for biomedical applications. JACS, 147(23), 20132--20143. (www)

  @article{ , abstract = {Glycosaminoglycans (GAGs) are essential polysaccharides crucial for various cellular functions, such as cell proliferation, migration, and differentiation. However, their complex structure and variability from natural sources pose challenges for functional studies and therapeutic applications. In this study, we engineered a glycopeptide that assembles into fibrils, emulating the functional attributes of GAGs. Utilizing cryo-EM, we elucidated the atomic structure of the designed glycopeptide fibril, which is composed of three identical protofilaments intertwined into a left-handed helix and held together by a variety of intermolecular interactions. Remarkably, the functional sugar units, glucuronic acids, are orderly positioned on the fibril surface, making them readily accessible to the solvent. This distinctive spatial configuration allows the designed glycopeptide fibril to effectively mimic key GAG functionalities, including the promotion of cell proliferation, cell migration, and osteogenic differentiation. Our findings offer a structural framework for designing glycan functionalities on glycopeptide fibrils and open avenues for developing glycopeptide-based materials with versatile biological activities. This work further enhances the potential of these materials for applications in therapeutic and regenerative medicine.}, archive = {J_JACS}, author = {Wencheng Xia and Zhongxin Xu and Hui Dong and Shengnan Zhang and Changdong He and Dan Li and Bo Sun and Bin Dai and Suwei Dong and Cong Liu}, doi = {10.1021/jacs.5c07039}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20132--20143}, shortjournal = {J. Am. Chem. Soc.}, title = {Design and structural elucidation of glycopeptide fibrils: Emulating glycosaminoglycan functions for biomedical applications}, volume = {147}, year = {2025}, }
• (2025). Carbon-atom scavengers enable divergent, selective carbon deletion of azaarenes. JACS, 147(23), 20120--20131. (www)

  @article{ , abstract = {Divergent synthesis is a powerful strategy that provides simultaneous access to multiple derivatives of a given substrate. However, the emerging developments in skeletal editing have largely delivered methods that lack this potential for diversification. Herein, we report the serendipitous discovery of reagent-controlled selective deletion of C3 or C2 carbon atoms of quinolines, affording indoles. An initial observation that an impurity in commercial samples of DBU promoted cyclization of a benzoxazepine-derived imidate led to the identification of indoline and aminoethanol as C3- and C2-selective carbon-atom scavengers, respectively. These two methods successfully convert a broad scope of quinolines and related azaarenes to the corresponding indoles and azaindoles, enabling divergent carbon deletion. In-depth mechanistic studies support the HFIP-promoted ring opening of 3,1-benzoxazepines to amidine intermediates as a rate-determining step, while providing insights into the selectivity afforded by indoline. These methods and their associated mechanisms offer a blueprint for the rational design of reagent-controlled, divergent skeletal edits.}, archive = {J_JACS}, author = {Jisoo Woo and Tergitë Zeqiri and Alec H. Christian and Michael C. Ryan and Mark D. Levin}, doi = {10.1021/jacs.5c06577}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20120--20131}, shortjournal = {J. Am. Chem. Soc.}, title = {Carbon-atom scavengers enable divergent, selective carbon deletion of azaarenes}, volume = {147}, year = {2025}, }
• (2025). Gradient protein thin-film-based bragg’s mirror. JACS, 147(23), 20109--20119. (www)

  @article{ , abstract = {Conventional structural color sensors with an even thickness can hardly detect tiny structural changes caused by analytes at extremely low concentrations. Herein, we construct a gradient protein thin-film-based Bragg’s mirror, which reveals a highly effective signaling translation from the 3D gradient surface to 2D interference patterns and thus realizes an extremely high sub 0.5 Å of spatial resolution by using a simple CCD camera, exhibiting 1000-fold improvement than the color recognition. Bragg’s mirror consists of responsive “core–shell” structural protein nanocrystals, which is applied for sensing humidity and putrescine vapor through adsorption–swelling and crystallization–swelling mechanisms, respectively. Through an exposure-development strategy, we successfully demonstrated the real-time monitoring of seafood spoilage in high-humidity environments. Compared to professional spectrometer-based reflectance measurements, our Bragg pattern analysis shows 2.6–5× sensitivity improvement in both detection modes. This work introduces a means to open the door to types of high-performance and low-cost colorimetric sensors that are competitive with and offer greater functionality than bulky/expensive modern optical sensors.}, archive = {J_JACS}, author = {Fei Tao and Yali Li and Qian Han and Shuting Miao and Yongchun Liu and Hao Ren and Peng Yang}, doi = {10.1021/jacs.5c06430}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20109--20119}, shortjournal = {J. Am. Chem. Soc.}, title = {Gradient protein thin-film-based bragg’s mirror}, volume = {147}, year = {2025}, }
• (2025). Piercing molecular graphenes: Precision synthesis and photophysics of NBN-edged porous molecular carbons. JACS, 147(23), 20098--20108. (www)

  @article{ , abstract = {Bottom-up solution-phase synthesis of atomically precise porous nanographenes is a challenging endeavor. In particular, molecular carbons with multiple pores and heteroatoms remain unknown. Herein, we report three porous molecular carbons ( 2PNG , 3PNG , and 7PNG ) with precise NBN-doped zigzag edges, in which 7PNG possesses seven pores. X-ray crystallographic diffraction and scanning tunneling microscopy reveal their unique pore structures and self-assembly behaviors. Interestingly, the HOMO–LUMO overlap of these molecules gradually decreases as the size of the molecule increases, which induces peripheral-to-core excitations and promotes intersystem crossing. Steady-state and transient spectroscopy, along with DFT calculations, reveal the excited-state dynamics and the size-dependent energy-transfer mechanism in these NBN-doped molecular systems. Our study describes a new strategy for producing minimal wave function overlaps at almost planar geometry by segmenting the electronic structures of molecular graphene by insertion of pores, forcing the excitation to occur between the periphery and the core, with great potential for new phosphorescent and delayed fluorescence emitters.}, archive = {J_JACS}, author = {Yang Yu and Asier Izu and José M. Marín Beloqui and Shammi Rana and Kunal S. Mali and Steven De Feyter and David Casanova and Juan Casado and Junzhi Liu}, doi = {10.1021/jacs.5c06175}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20098--20108}, shortjournal = {J. Am. Chem. Soc.}, title = {Piercing molecular graphenes: Precision synthesis and photophysics of NBN-edged porous molecular carbons}, volume = {147}, year = {2025}, }
• (2025). Unveiling ultra-high ionic conductivity in W-doped Na3SbS4: Grain boundary effects and pure bulk transport. JACS, 147(23), 20092--20097. (www)

  @article{ , abstract = {W-doped Na 3 SbS 4 is a promising solid electrolyte for all-solid-state sodium batteries, exhibiting a sodium (Na + ) ionic conductivity higher than 30 mS cm –1 (A. Hayashi, N. Masuzawa, S. Yubuchi, F. Tsuji, C. Hotehama, A. Sakuda, M. Tatsumisago, Nat. Commun. 2019, 10, 5266). This exceptional conductivity arises primarily from the introduction of sodium ion vacancies (V′ Na ) via supervalent substitution of Sb 5+ with W 6+ . Using low-temperature impedance spectroscopy down to T = 113 K (−160 °C), we demonstrate that previously reported room temperature conductivities of Na 2.9 Sb 0.9 W 0.1 S 4 are influenced by grain boundary resistances, which can only be effectively separated from the total conductivity at such low temperatures. Our results indicate that the pure Na + bulk conductivity can reach 96 mS cm –1 (D σ = 0.98 × 10 –10 m 2 s –1 ) at room temperature, as extrapolated from accurately measured low-temperature data (1.8 mS cm –1 at –130 °C). Our study suggests that further minimizing detrimental grain boundary effects enables extraordinarily fast long-range Na + ion transport in this sulfide.}, archive = {J_JACS}, author = {Jana Königsreiter and Bernhard Gadermaier and H. Martin R. Wilkening}, doi = {10.1021/jacs.5c05842}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20092--20097}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling ultra-high ionic conductivity in W-doped Na3SbS4: Grain boundary effects and pure bulk transport}, volume = {147}, year = {2025}, }
• (2025). Formation mechanism of polycatenane by direct catenation. JACS, 147(23), 20082--20091. (www)

  @article{ , abstract = {Polycatenanes, a novel class of polymers consisting of interlocked macrocyclic monomers, have attracted significant attention. However, the mechanism of formation of polycatenanes through direct catenation remains poorly understood. Herein, we explore the structural diversity and unique chain termination mechanism inherent to polycatenanes. Unlike conventional linear polymers, a linear polycatenane exhibits a variety of topological configurations, with chain growth terminated upon the formation of completely interwoven structures. This intrinsic termination, characterized by the probability q , necessitates a modification of the classical Carothers equation to accurately determine the number-average degree of polymerization (DP n ). Using the importance of sampling-based Monte Carlo algorithms, we have investigated the influence of the interaction strength ϵ between monomers and the cavity size l (σ) of a monomer on the termination probability q . Our findings reveal that stronger intermolecular interactions increase q , while a larger cavity size promotes higher-order catenation with a lower q . To achieve polycatenanes with higher DP n , we propose two strategies employing directional interactions and introducing steric hindrance to prevent the formation of completely interwoven structures. These approaches enable the synthesis of polycatenanes with sustained reactivity, offering new pathways for the design of polymers with sophisticated topologies and configurations.}, archive = {J_JACS}, author = {Weihao Wang and Zhenghong Chen and Shaodong Zhang}, doi = {10.1021/jacs.5c05684}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20082--20091}, shortjournal = {J. Am. Chem. Soc.}, title = {Formation mechanism of polycatenane by direct catenation}, volume = {147}, year = {2025}, }
• (2025). Planarity is not plain: Closed- vs open-shell reactivity of a structurally constrained, doubly reduced arylborane toward fluorobenzenes. JACS, 147(23), 20071--20081. (www)

  @article{ , abstract = {The ability to activate small molecules is imparted to 9,10-dihydro-9,10-diboraanthracenes (DBAs) through the injection of two electrons. We report on the activation of fluorobenzenes C 6 F n H 6– n by the doubly reduced, structurally constrained DBA [ 1 ] 2– in THF ( n : 1,3,4,5,6). Compound 1 is a 9,10-diphenyl DBA, forced into planarity by methylene bridges between the phenyl substituents and the DBA core. This rigidity results in enhanced stability under ambient conditions and an elevated planar-to-pyramidal reorganization energy upon boron tetracoordination, unlocking new reactivity. The dianion salts M 2 [ 1 ] were synthesized in excellent yields by stirring neutral 1 with alkali metals M in THF (M: Li, Na, K); comproportionation of Li 2 [ 1 ] with 1 generates the blue radical salt Li[ 1 ], characterized by EPR spectroscopy and X-ray diffraction. While Li 2 [ 1 ] is inert toward C 6 FH 5 up to 120 °C, it reacts with 1,3,5-C 6 F 3 H 3 at 100 °C to yield a B(sp 2 )/B(sp 3 ) adduct with a difluorophenyl ligand (Li[ 2 ]). Treatment of Li 2 [ 1 ] with 1 eq. of C 6 F 5 H or C 6 F 6 induces selective monohydrodefluorination, occurring in parallel with the formation of a unique B(sp 2 )/B(sp 3 ) tetrahydrofuran-2-yl adduct (Li[ 3 ]). The three isomers of C 6 F 4 H 2 represent intermediate cases, where the competition between trifluorophenyl- and tetrahydrofuran-2-yl-adduct formation is governed by the relative positions of the F substituents and the nature of the countercation (M + : Li + , K + ). Through experimental and quantum-chemical studies, we unveil the underlying reaction mechanisms and show that Li 2 [ 1 ] acts either as a B-centered nucleophile in an S N Ar-type conversion (low benzene fluorination) or as a reducing agent in a single-electron transfer/H atom abstraction sequence (high benzene fluorination).}, archive = {J_JACS}, author = {Christoph D. Buch and Alexander Virovets and Eugenia Peresypkina and Burkhard Endeward and Hans-Wolfram Lerner and Felipe Fantuzzi and Shigehiro Yamaguchi and Matthias Wagner}, doi = {10.1021/jacs.5c05588}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20071--20081}, shortjournal = {J. Am. Chem. Soc.}, title = {Planarity is not plain: Closed- vs open-shell reactivity of a structurally constrained, doubly reduced arylborane toward fluorobenzenes}, volume = {147}, year = {2025}, }
• (2025). Electrical detection of magnetic perturbations through the magnetoelectric effect of a molecular spin triangle. JACS, 147(23), 20063--20070. (www)

  @article{ , abstract = {Dielectric and magnetoelectric (ME) studies were conducted on polycrystalline samples of the molecular spin triangle [Fe 3 O(O 2 CPh) 6 (py) 3 ]ClO 4 ·py ( Fe 3 ) and on its diamagnetic isostructural Ga III analogue ( Ga 3 ). Dielectric studies revealed a thermally activated process between approximately 15–60 K, attributed to the freezing-unfreezing of the crystallographically disordered pyridine solvates, with a paraelectric behavior above ∼68 K. Magnetoelectric studies revealed a second-order ME effect for Fe 3 , which remained significant above liquid-nitrogen temperatures. Similar experiments on Ga 3 allowed to control for the instrumental baseline response and to confirm the origin of the signal as the ME effect of Fe 3 . The thermal evolution of the ME coupling coefficient (α ME ) showed no discontinuities around the temperature of the freezing–unfreezing processes, indicating that it is unrelated to them. These latter are assigned the disordered-diamagnetic sublattice consisting of the pyridine solvates and perchlorate counteranions. In turn, the ME coupling is assigned to the ordered-magnetic sublattice consisting of the Fe 3 trinuclear cations. These results demonstrate that Fe 3 can directly transform magnetic perturbations to electric signals at the single-molecule level, without the need of structural transformations or long-range magnetic ordering.}, archive = {J_JACS}, author = {Balwant Singh Chauhan and Ratnamala Chatterjee and Philippe Turek and Athanassios K. Boudalis}, doi = {10.1021/jacs.5c05601}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20063--20070}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrical detection of magnetic perturbations through the magnetoelectric effect of a molecular spin triangle}, volume = {147}, year = {2025}, }
• (2025). Synthesis of a stable tricobalt carbide cluster. JACS, 147(23), 20056--20062. (www)

  @article{ , abstract = {We report the synthesis and characterization of the anionic tricobalt carbide cluster [( Ftbs L)Co 3 (μ 3 –C)] − . The source of the carbide ligand is a phosphorus ylide (R 2 MePCH 2 ; R = Me, Ph) which substitutes pyridine in the all-cobalt(II) cluster ( Ftbs L)Co 3 (py) to afford the ylide adduct ( Ftbs L)Co 3 (CH 2 PMeR 2 ). Deprotonation affords the anionic diylide cluster [( Ftbs L)Co 3 (κ 2 -η 1 :η 1 –(CH 2 ) 2 PR 2 )] − which eliminates MePR 2 upon heating to furnish the anionic methylidyne cluster [( Ftbs L)Co 3 (μ 3 –CH)] − . Oxidation of the anionic methylidyne complex with ferrocenium hexafluorophosphate generates the diamagnetic methylidyne complex ( Ftbs L)Co 3 (μ 3 –CH). The methylidyne ligand can be deprotonated with Li- or KN(SiMe 3 ) 2 to afford carbide complexes ( Ftbs L)Co 3 (μ 4 –C)Li(OEt 2 ) or [K(C 222 )][( Ftbs L)Co 3 (μ 3 –C)], respectively. Isotopic enrichment of the carbide with 13 C reveals downfield-shifted 13 C NMR chemical shifts (δ/ppm) of 389, Co 3 (μ 3 – C H); 731, Co 3 (μ 4 – C Li); and 769, Co 3 (μ 3 – C ) − ; the latter of which is the most downfield resonance for a transition metal carbide reported to date.}, archive = {J_JACS}, author = {Nicholas P. Litak and Shao-Liang Zheng and Dongtao Cui and Theodore A. Betley}, doi = {10.1021/jacs.5c04760}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20056--20062}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of a stable tricobalt carbide cluster}, volume = {147}, year = {2025}, }
• (2025). Concentration-driven ring expansion metathesis polymerization via tunable ring transfer processes. JACS, 147(23), 20045--20055. (www)

  @article{ , abstract = {Ring expansion metathesis polymerization (REMP) is a robust and versatile method used to access polymeric cyclic architectures for applications in biomedicine, electronics, and performance engineering. Cyclic Ru-benzylidene REMP catalyst CB6 demonstrates higher stability and polymerization rates compared to other Ru-based systems. However, CB6 also exhibits an unusual molar mass evolution profile where high-molar-mass cyclic polymers are produced at early time points followed by a gradual decrease in molar mass. For broad cyclic polymer applications to be fully realized, a mechanistic understanding of REMP is crucial. In this work, we investigate the polymerization profiles of CB6 using a series of mechanistic studies to probe the requisite ring transfer steps envisaged for such a polymerization profile. Furthermore, our studies reveal an intricate relationship between reaction concentration and experimental molar mass. These collective studies demonstrate CB6 ’s role not only as an initiator but also as a catalytic ring transfer agent. Overall, we showcase a new toolkit by which to control REMP that will allow further optimization of catalyst design and the creation of novel cyclic materials.}, archive = {J_JACS}, author = {Meredith N. Pomfret and Nicholas P. Serck and Lucy P. Miller and Matthew R. Golder}, doi = {10.1021/jacs.5c05347}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20045--20055}, shortjournal = {J. Am. Chem. Soc.}, title = {Concentration-driven ring expansion metathesis polymerization via tunable ring transfer processes}, volume = {147}, year = {2025}, }
• (2025). Fluorescence visualization of strain by Tetraphenylethylene/Ruthenium complex three-dimensional covalent organic framework assemblies. JACS, 147(23), 20033--20044. (www)

  @article{ , abstract = {Dynamic visualization of strain and its distribution in materials are still challenging. Herein, dual-fluorophore three-dimensional covalent organic frameworks (3D-COFs) and the PEGylated 3D-COFs (PEG-3D-COFs) were synthesized for the construction of physically interacted assemblies to realize fluorescence imaging on not only strain distribution but also strain-related surface friction and flow velocity distributions in various media including polymer elastomers, organic or aqueous dispersions. The responsiveness arises from the controllability of the aggregation structure of 3D-COFs and PEG-3D-COFs, showing concentration-dependent morphology and photoluminescence, and meanwhile having a concentration-deformation equivalence on the structural evolution dynamics which drives the color change of the COF emission in the solids and liquids with high sensitivity and reversibility, whenever the superstructure of the COF assemblies is affected by the applied strain on the matrices. The report will inspire further efforts to construct responsive COFs for optical measurement aims.}, archive = {J_JACS}, author = {Yingying Ren and Wenze Wu and Yuxuan Lu and Jiwei Li and Yang Liu and Haiqiang Jin and Xiaoyi Li and Xiaozhong Qu and Zhenzhong Yang}, doi = {10.1021/jacs.5c05354}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20033--20044}, shortjournal = {J. Am. Chem. Soc.}, title = {Fluorescence visualization of strain by Tetraphenylethylene/Ruthenium complex three-dimensional covalent organic framework assemblies}, volume = {147}, year = {2025}, }
• (2025). Unraveling ultrafast li-ion dynamics in the solid electrolyte LiTi2(PS4)3 by NMR down to cryogenic temperatures. JACS, 147(23), 20023--20032. (www)

  @article{ , abstract = {Self-diffusion processes of small atoms or ions play a crucial role in many areas of research. The unique crystal structure of LiTi 2 (PS 4 ) 3 (LTPS) presents a variety of energetically inequivalent diffusion pathways for small Li + charge carriers and has resulted in one of the highest Li + diffusion coefficients. Investigating these pathways individually at the atomic scale poses significant challenges, especially for probing jump processes. In this study, we utilized nuclear spin relaxation techniques down to cryogenic temperatures (10 K) to reveal unprecedented details about both long-range and short-range Li + dynamics. The temperature-dependent 7 Li NMR spin–lattice relaxation (SLR) rate exhibits a series of diffusion-induced peaks, allowing the extraction of activation energies and jump rates. Due to the exceptionally fast localized Li + exchange processes in LTPS, temperatures as low as 50 K are required to freeze Li + dynamics, on the SLR time scale, entirely within the ring-like cages of the LTPS structure.}, archive = {J_JACS}, author = {Denise Tapler and Bernhard Gadermaier and Jonas Spychala and Florian Stainer and Annika Marko and Jana Königsreiter and Katharina Hogrefe and Paul Heitjans and H. Martin R. Wilkening}, doi = {10.1021/jacs.5c05253}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20023--20032}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling ultrafast li-ion dynamics in the solid electrolyte LiTi2(PS4)3 by NMR down to cryogenic temperatures}, volume = {147}, year = {2025}, }
• (2025). Nanoplasmonic isosbestics uncover mesoscale assembly of gold nanoparticles on soft templates. JACS, 147(23), 20008--20022. (www)

  @article{ , abstract = {Assembly of plasmonic nanoparticles (NPs) generates unique optical properties through coupling of the localized surface plasmon resonance (LSPR) of individual NPs. However, precisely controlling and monitoring how mesoscale assembly dictates final optical properties remain key challenges in designing advanced plasmonic materials. Here, we introduce “nanoplasmonic isosbestics” as optical descriptors of the mesoscale organization of gold nanoparticles (AuNPs) on soft templates. Unlike isosbestic points in molecular spectroscopy, which describe chemical equilibria, our numerical simulations demonstrate that nanoplasmonic isosbestics emerge from the coexistence of individual AuNPs and AuNP clusters, where the interparticle spacing determines the isosbestic wavelength. By templating AuNP assembly onto synthetic free-standing lipid bilayers with tunable membrane rigidity, we experimentally achieve precise control over interparticle spacing and prove that it is mirrored by univocal modulation of the isosbestic wavelength. This provides a fundamental understanding of the structure–function relationship in plasmonic systems, linking, for the first time, nanoplasmonic isosbestics to interparticle spacing and equilibrium structure in plasmonic assemblies. On the analytical perspective, nanoplasmonic isosbestics provide noninvasive optical fingerprints of the templates, opening to appealing applications. As a proof of concept, we apply this approach to profile the stiffness of two extracellular vesicle (EVs) classes─mesenchymal stem cell (MSC)-derived and red blood cell-derived EVs─both recognized for their biological and translational potential.}, archive = {J_JACS}, author = {Jacopo Cardellini and Ilaria De Santis and Giuseppe Emanuele Lio and Marco Brucale and Francesco Valle and Virginia Catani and Ilenia Mastrolia and Marta Calabria and Massimo Dominici and Andrea Zendrini and Annalisa Radeghieri and Lucia Paolini and Paolo Bergese and Lucrezia Caselli and Debora Berti and Costanza Montis}, doi = {10.1021/jacs.5c05189}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {20008--20022}, shortjournal = {J. Am. Chem. Soc.}, title = {Nanoplasmonic isosbestics uncover mesoscale assembly of gold nanoparticles on soft templates}, volume = {147}, year = {2025}, }
• (2025). Achieving diverse CO2 conversions through on-demand installation of multivariate catalytic sites into one prototypical Metal–Organic framework. JACS, 147(23), 19996--20007. (www)

  @article{ , abstract = {The programmable design and construction of multirole or swing-role metal–organic frameworks (MR/SR-MOFs) for variable CO 2 conversions are appealing for green and sustainable chemistry. Herein, we describe a facile MR/SR-MOF synthetic strategy for on-demand engineering of the catalytic pore spaces in a primitive MOF for diverse CO 2 chemical fixation. Distinct functional groups can be precisely and quantitively immobilized into prototypical LIFM-28 ( proto -LIFM-28) by virtue of postsynthesis based on its solid-state dynamic attribute, generating different catalytic pore spaces suitable for hydrosilylation, N -methylation, cycloaddition, and cyclization reactions of CO 2 . Remarkably, the resultant LIFM-DSL-3 carrying amino and CO 2 -masked N -heterocyclic carbene (NHC–CO 2 ) sites presents an excellent hydrosilylation performance with complete Ph 2 SiH 2 conversion (>99%) and high silyl methoxide (SMO) selectivity (95%) under atmospheric CO 2 pressure, achieving an extraordinary turnover number (TON) of 4367 and a turnover frequency (TOF) of 6221 h –1 beneficial for efficient methanol release upon hydrolysis. Moreover, an exceptionally high N -methylation efficiency is obtained for CO 2 transformation via N -methylation. This work demonstrates how to design MR/SR-MOFs as a multivariate catalytic platform for the cost-saving multirole and swing-role applications through on-demand manipulation and installation of active sites into a single MOF matrix without de novo synthesis.}, archive = {J_JACS}, author = {Songlin Deng and Yang-Yang Xiong and Cheng-Xia Chen and Qing-Hua Dai and Yin-Xian Chen and Wei Geng and Zi-Ying Liang and Wei-Lun Ruan and Zhang-Wen Wei and Mihail Barboiu and Cheng-Yong Su}, doi = {10.1021/jacs.5c05028}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19996--20007}, shortjournal = {J. Am. Chem. Soc.}, title = {Achieving diverse CO2 conversions through on-demand installation of multivariate catalytic sites into one prototypical Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Reagent-regulated organocatalytic enantiodivergent synthesis of chiral sulfinimidate esters. JACS, 147(23), 19986--19995. (www)

  @article{ , abstract = {Achiral parameter-regulated enantiodivergent synthesis of chiral sulfur compounds has rarely been reported. Driven by the increasing importance of aza-sulfur stereogenic centers in drug discovery, we present herein organocatalytic tandem enantioselective chlorination and nucleophilic substitution for the synthesis of chiral sulfinimidate esters. The enantiopreference is modulated by N -chlorophthalimide (NCP) and trichloroisocyanuric acid (TCCA) with the same enantiomer of chiral pentanidium catalyst, and both enantiomers of sulfinimidate esters are obtained with high enantiocontrol. Notably, the reactions with TCCA are very fast and completed in 5 min, and the efficiency is well maintained for gram-scale synthesis. The resulting sulfinimidate esters are versatile precursors for diverse aza-S(IV) and S(VI) stereogenic centers. Studies on the enantiodivergent mechanism reveal that the sulfur stereogenic center is inverted twice in reactions with NCP, and only a single inversion is verified with TCCA, representing a novel strategy for enantiodivergent catalysis.}, archive = {J_JACS}, author = {Wei-Long Cui and Luoqiang Zhang and Chu Liu and Junjia Su and Hao-Ran Zhang and Ronggang Ma and Daiqiang Jian and Wanxing Xiang and Xinyi Ye and Xin Zhang}, doi = {10.1021/jacs.5c05035}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19986--19995}, shortjournal = {J. Am. Chem. Soc.}, title = {Reagent-regulated organocatalytic enantiodivergent synthesis of chiral sulfinimidate esters}, volume = {147}, year = {2025}, }
• (2025). Cathode-induced C–H bond heterolysis for olefin isomerization and applications in electrocarboxylation. JACS, 147(23), 19976--19985. (www)

  @article{ , abstract = {Olefin isomerization can not only convert terminal olefins into higher-value internal olefins but also serve as a bridge to connect with the functionalization reaction. However, traditional isomerization methods, such as base-mediated and transition-metal-mediated approaches, still face challenges like harsh conditions, low trans / cis ( E / Z ) ratios, unrecyclable metals, and industrial scalability. Herein, we report that the C–H bond could be activated at the cathode to form hydride ions (H – ) and carbon radicals, which could initiate olefin isomerization via a radical mechanism without base or metal catalyst assistance. Through this new mechanism, various substrates, including chemicals with significant industrial demand, could be effectively converted into internal olefins with high yields, excellent E / Z ratios, and scalability, all while requiring only a catalytic amount of electrons. Furthermore, this electrochemical isomerization system was successfully applied to overcome the challenge of electrocarboxylation of nonconjugated olefins and carbon dioxide (CO 2 ) by isomerizing nonconjugated olefins to conjugated olefins. This work makes a significant contribution to chemical science for C–H bond activation, and opens a new way for olefin isomerization with promising applications in electrochemical isomerization-functionalization reaction.}, archive = {J_JACS}, author = {Mengke Dong and Shuaiqiang Jia and Xiao Chen and Jiapeng Jiao and Cheng Xue and Zhanghui Xia and Hailian Cheng and Ting Deng and Chunjun Chen and Kaiwu Dong and Haihong Wu and Mingyuan He and Buxing Han}, doi = {10.1021/jacs.5c04952}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19976--19985}, shortjournal = {J. Am. Chem. Soc.}, title = {Cathode-induced C–H bond heterolysis for olefin isomerization and applications in electrocarboxylation}, volume = {147}, year = {2025}, }
• (2025). Crystallographic visualization of distinct iodic aggregations in isostructural Metal–Organic frameworks. JACS, 147(23), 19968--19975. (www)

  @article{ , abstract = {Precisely determining the location of adsorbed molecules is essential for illuminating the mechanisms underlying molecular confinement within porous metal–organic frameworks (MOFs). Here, we present the pore-filling and reactive adsorption of iodine in ALP-MOF-1 and its isostructural redox-active ALP-MOF-2. The adsorbed iodine molecules (I 2 ) are unaffected by Zn(II) in ALP-MOF-1 and are exclusively confined into an unusual three-dimensional (3D) iodine aggregation due to the 3D cross-linked pore topology and multiple I 2 -framework interactions. Conversely, in ALP-MOF-2, the adsorbed I 2 enables the oxidation of Co(II) to Co(III), which is accompanied by the reduction of I 2 to I 3 – and the formation of I 5 – and I 2 during continuous I 2 loading. Identification of distinct iodine adsorption processes in ALP-MOF-1 and −2 motivated tuning of the metal ion composition to adjust the adsorption mechanism. The iodic aggregations in both MOFs are unambiguously confirmed by the combination of single crystal X-ray diffraction and spectroscopic characterization. The presence of multiple adsorption sites facilitate rapid iodine uptake of ∼179 wt % in ALP-MOF-1 and ∼150 wt % in ALP-MOF-2 within ∼5 h, which could be advantageous for applications requiring rapid and energy-efficient iodine capture.}, archive = {J_JACS}, author = {Yi Han and Yiwen He and Yin-Ke Fu and Hongliang Huang and Hongdong Li and Jiong-Peng Zhao and Lei Wang and Qian Niu and Nathaniel L. Rosi}, doi = {10.1021/jacs.5c04910}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19968--19975}, shortjournal = {J. Am. Chem. Soc.}, title = {Crystallographic visualization of distinct iodic aggregations in isostructural Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Polarization-induced breaching of the Liquid/Liquid interface formed with water-in-salt electrolytes. JACS, 147(23), 19959--19967. (www)

  @article{ , abstract = {The solvation properties of water-in-salt electrolytes (WiSEs) have been extensively studied by spectroscopic and computational means and were shown to impart them with unique chemical and physical properties when compared to more classical superconcentrated aqueous solutions. More specifically, the formation of ionic aggregates in solutions containing a large concentration of TFSI anions was shown to alter the water and anion reactivity at electrochemical interfaces, often improving the performance of aqueous rechargeable batteries. However, insights into the role of the WiSE solvation structure on ion transfer at electrochemical interfaces are scarce. Herein, interfaces between two immiscible electrolytes (ITIESs) are used to study the energetics for ion transfer between aqueous LiCl and LiTFSI solutions and dichloroethane. Combining electrochemical measurements at microinterfaces with metadynamics molecular dynamics (MD) simulations, the effect of solvation properties on the energy for transferring Li + and Cl – /TFSI – ions across the liquid/liquid interface was studied. While increasing the LiCl concentration increases the amount of ion pairs, it only marginally impacts the ion transfer energy. Instead, using large LiTFSI concentrations at which ionic aggregates are formed, ion transfer across the liquid/liquid interface shows a unique behavior that departs from that observed for polarizable or nonpolarizable interfaces. Ions do not freely cross the interface, with a transfer energy found to be ≈8–10 kcal/mol. However, upon polarization, ionic aggregates are found to breach the liquid/liquid interface, locally mixing both solutions. We believe that such a finding calls for reevaluating our current understanding of ion transfer across chemical interfaces in superconcentrated electrolytes, including liquid/liquid interfaces used in membrane-less electrochemical systems.}, archive = {J_JACS}, author = {Lihao Feng and Michael Goldstein and Yang Wang and Udayan Mohanty and Alexis Grimaud}, doi = {10.1021/jacs.5c04832}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19959--19967}, shortjournal = {J. Am. Chem. Soc.}, title = {Polarization-induced breaching of the Liquid/Liquid interface formed with water-in-salt electrolytes}, volume = {147}, year = {2025}, }
• (2025). Effective near-infrared triplet emitter based on hetero-Metal–Metal interaction. JACS, 147(23), 19949--19958. (www)

  @article{ , abstract = {Incorporating metal–metal (M–M) interactions into excited states of closed-shell d 8 and d 10 metal complexes is an effective strategy in the design of near-infrared (NIR) phosphorescent materials. While extensive studies have focused on homometallic M-M-bonded excited states, the potential of heterometallic interactions remains relatively underexplored. Herein, we report a series of heterometallic Rh(I)–Pt(II) double salt complexes that achieve efficient NIR phosphorescence, with emission peak energy spanning 830–980 nm and room-temperature quantum yield up to 23%. In this system, the Rh(I) center lowers the emission energy, while the Pt(II) center enhances spin–orbit coupling (SOC) via its heavy-atom effect. The resulting materials exhibit an outstanding waveguiding performance in the NIR spectral region. Combined spectroscopic and time-dependent density functional theory (TDDFT) analyses reveal that the Rh(I)–Pt(II) interaction directly modulates the excited state character, enhancing the radiative decay while suppressing nonradiative decay pathways. This work establishes heterometallic M–M cooperativity as a design principle for high-performance NIR phosphorescence, opening avenues for tailored NIR phosphorescent materials beyond conventional homometallic frameworks.}, archive = {J_JACS}, author = {Ning Zhou and Yangbo Zhang and Xiong Wang and Peng Yang and Wei Lu and Qingyun Wan}, doi = {10.1021/jacs.5c04585}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19949--19958}, shortjournal = {J. Am. Chem. Soc.}, title = {Effective near-infrared triplet emitter based on hetero-Metal–Metal interaction}, volume = {147}, year = {2025}, }
• (2025). Sterically induced acceleration of aryl halide activation by pd(0): A radical alternative to 2-electron oxidative addition. JACS, 147(23), 19941--19948. (www)

  @article{ , abstract = {The first elementary step of Pd (0) -catalyzed cross-coupling involves the activation of an aryl halide by a Pd (0) catalyst, which is widely assumed to proceed in a formal 2-electron process, involving concerted cleavage of the aryl halide bond and formation of an aryl-Pd bond as to generate a Pd (II) complex. Contrary to common reactivity assumptions under this mechanistic manifold, we observed that severe steric hindrance in the aryl halide and catalyst did not inhibit the thermal activation of the aryl halide but instead greatly accelerated it, giving full conversion of an ortho , ortho- di- tert -butyl-substituted aryl bromide in 1 min at room temperature on gram scale with a bulky Pd (0) catalyst. Our mechanistic data revealed that a 1-electron-based halogen abstraction by Pd (0) is operative in such sterically demanding settings.}, archive = {J_JACS}, author = {Daniel Hupperich and Jaime Ponce-de-León and Ignacio Funes-Ardoiz and Theresa Sperger and Franziska Schoenebeck}, doi = {10.1021/jacs.5c04407}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19941--19948}, shortjournal = {J. Am. Chem. Soc.}, title = {Sterically induced acceleration of aryl halide activation by pd(0): A radical alternative to 2-electron oxidative addition}, volume = {147}, year = {2025}, }
• (2025). A molecule assembly route to simultaneously detoxify platinum sites and disentangle reactant transport paths in proton exchange membrane fuel cells. JACS, 147(23), 19931--19940. (www)

  @article{ , abstract = {Substantially reducing the platinum (Pt) usage is essential for large-scale application of proton exchange membrane fuel cells (PEMFCs), a key hydrogen-energy technology promising a carbon-neutral future. Currently, the low-Pt PEMFCs suffer from sluggish reaction and transport kinetics in the cathodic catalyst layers (CCLs) caused by the adsorption of perfluorinated sulfonic acid (PFSA) ionomers to Pt via the side chains and the accompanying uneven PFSA aggregation. Herein, we demonstrate, through detailed physical and electrochemical characterizations and molecular dynamics simulations, that β-cyclodextrin with a unique chemical and geometric structure can effectively address these issues through a molecule assembly route. On one side, β-cyclodextrin forms a hydrogen-bonded molecular assembly with PFSA, which effectively mitigates sulfonate poisoning to Pt, produces ordered hydrophilic domains for rapid proton transport, and at the same time increases the porosity crossing CCL. On the other side, the hydrophobic β-cyclodextrin nanocavities provide ideal O 2 diffusion paths. The thus formed CCL and Pt/ionomer interface with enriched catalytic sites, and well-segregated and ordered O 2 and proton transport channels, remarkably boost the fuel cell performance.}, archive = {J_JACS}, author = {Meihua Tang and Huangli Yan and Zhenying Zheng and Hao Zhang and Chengwen Yu and Bin Liu and Shengli Chen}, doi = {10.1021/jacs.5c04479}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19931--19940}, shortjournal = {J. Am. Chem. Soc.}, title = {A molecule assembly route to simultaneously detoxify platinum sites and disentangle reactant transport paths in proton exchange membrane fuel cells}, volume = {147}, year = {2025}, }
• (2025). Shifting gears: Photochromic Metal–Organic frameworks with stimulus-adaptable performance. JACS, 147(23), 19918--19930. (www)

  @article{ , abstract = {The tunability of the reaction parameter space is probed in the presented work through photoswitch-directed energy and charge transfer pathways induced by organic chromophores, hierarchically organized within a well-defined, light-harvesting metal–organic framework. Unique matrix-imposed changes in photoswitch photophysical properties, including the first report of visible light-induced photoisomerization of a spiropyran derivative, illustrate the critical synergy between the selected matrix and the photoresponsive compound. Moreover, the confined space of the utilized porous matrix allowed for mimicking isomerization kinetics of integrated sterically demanding photochromic moieties in solution. More importantly, such photoisomerization suppresses the charge transfer processes in favor of resonance energy transfer pathways instead. The demonstrated ability to shift between multiple relaxation pathways (e.g., charge transfer, energy transfer, or photoluminescence) as a function of the excitation wavelength resulted in photoswitch-directed tailoring of model phosphinylation reaction outcomes. Thus, incorporating spiropyran moieties within the framework allows for visible light to be harvested and funneled toward either a ligand-based reactive center or an acceptor molecule such as a photochromic unit. Moreover, the framework’s chemical activity was promoted exclusively by organic linkers without the participation of metal nodes, the addition of (co)catalysts, or the use of harsh conditions at room temperature. Overall, this work paves the way for the development of stimulus-responsive platforms, for which chemical activity could be controlled through a photochromic moiety.}, archive = {J_JACS}, author = {Johanna Haimerl and Grace C. Thaggard and Buddhima K. P. Maldeni Kankanamalage and Raphael Bühler and Jaewoong Lim and Kyoung Chul Park and Julien Warnan and Roland A. Fischer and Natalia B. Shustova}, doi = {10.1021/jacs.5c04466}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19918--19930}, shortjournal = {J. Am. Chem. Soc.}, title = {Shifting gears: Photochromic Metal–Organic frameworks with stimulus-adaptable performance}, volume = {147}, year = {2025}, }
• (2025). Ambiphilic reactivity of iridium complexes with N-heterocyclic vinylidene ligands. JACS, 147(23), 19911--19917. (www)

  @article{ , abstract = {Room-temperature stable diazoolefins provide access to a unique class of carbon-donor ligands: N -heterocyclic vinylidenes. Herein, we describe iridium complexes with terminal N -heterocyclic vinylidene ligands. Cationic complexes of type [Cp*IrClL]X (X = SbF 6 , OTf; L = N -heterocyclic vinylidene) were obtained by reaction of (Cp*IrCl 2 ) 2 with an N -heterocyclic diazoolefin, followed by chloride abstraction. Reduction instead of chloride abstraction gave a neutral Cp*IrL complex with a “pogo stick” geometry. Crystallographic analyses of the complexes revealed very short iridium–carbon bonds, suggesting partial carbyne character. The vinylidene ligands display ambiphilic reactivity. The cationic complex forms covalent adducts with halides and pseudohalides, whereas the neutral complex reacts with electrophiles. These transformations generate rare carbon-donor species, including anionic N -heterocyclic olefins with pronounced carbene character or a side-on bound alkylidene ketene.}, archive = {J_JACS}, author = {Tak Hin Wong and Paul Varava and Farzaneh Fadaei-Tirani and Rosario Scopelliti and Kay Severin}, doi = {10.1021/jacs.5c04371}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19911--19917}, shortjournal = {J. Am. Chem. Soc.}, title = {Ambiphilic reactivity of iridium complexes with N-heterocyclic vinylidene ligands}, volume = {147}, year = {2025}, }
• (2025). Structure–Emission property relationship of bilayer 2D hybrid perovskites. JACS, 147(23), 19902--19910. (www)

  @article{ , abstract = {Two-dimensional hybrid perovskites (2D-PVKs) have shown great promise for optoelectronic applications. However, the structure-emission property relationship of 2D-PVKs, particularly those with multiple octahedral layers in the metal-halide lattice ( n > 1), is not fully understood. Here we combine experimental and theoretical studies to investigate a series of bilayer ( n = 2) 2D-PVK crystals in both Ruddlesden–Popper (RP) and Dion–Jacobson (DJ) phases. Our results reveal that DJ-phase crystals exhibit a higher degree of octahedral lattice distortion compared with RP-phase crystals, with this distortion scaling inversely with interlayer spacing. Such octahedral distortion leads to (1) lower formation energies for iodine vacancies that act as nonradiative recombination centers, thereby reducing light emission yields, and (2) local inversion asymmetry that impacts electronic band structure and light emission properties. Among all the studied crystals, the DJ-phase crystal based on 4-(aminomethyl)piperidinium cations demonstrates the largest intra- and interoctahedral distortions, leading to inversion asymmetry that causes significant Rashba band splitting and circular-polarization dependent photoluminescence at room temperature. Our results provide insights into the development of 2D-PVKs for future optoelectronic/spintronic applications.}, archive = {J_JACS}, author = {Yumeng Song and Yifan Zhou and Congcong Chen and Kezhou Fan and Zhen Wang and Yu Guo and Ziming Chen and Lingling Mao and Jun Yin and Philip C. Y. Chow}, doi = {10.1021/jacs.5c04417}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19902--19910}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure–Emission property relationship of bilayer 2D hybrid perovskites}, volume = {147}, year = {2025}, }
• (2025). Visualization and quantification of base-level SO2 in live cells without intracellular background interference using sensitive 19F-NMR. JACS, 147(23), 19893--19901. (www)

  @article{ , abstract = {Sulfur dioxide (SO 2 ), as an endogenous gasotransmitter, is involved in a variety of physiological processes in living systems, however, distinction and quantification of base-level SO 2 in live cells pose great challenges for the current analytical techniques. We report an efficient way to visualize and quantify base-level SO 2 in different live mammalian cells by 19 F-NMR. This method relies on a high-performance 19 F-probe ( P1-CF 3 ) that reacts with the reactive sulfur species (RSS) in the generation of distinct chemical shift profiles, which are well-resolved in the NMR spectrum. The quantitative reaction of the 19 F-probe with SO 2 is fast and produces a stable addition product that is well distinguishable between the intra- and extracellular environment. The high performance of this method discloses that the base-level SO 2 in live cells varies greatly in different cell lines. The high accuracy and precision of RSS measurement by the reactive 19 F NMR probe allow simultaneous quantification of base-level SO 2 in living cells and culture medium in real time without interference from other RSS and potential competitors and also without background signals.}, archive = {J_JACS}, author = {Chao-Yu Cui and Bin Li and Xing Zhang and Shu-Li Guo and Bin-Bin Pan and Xun-Cheng Su}, doi = {10.1021/jacs.5c04351}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19893--19901}, shortjournal = {J. Am. Chem. Soc.}, title = {Visualization and quantification of base-level SO2 in live cells without intracellular background interference using sensitive 19F-NMR}, volume = {147}, year = {2025}, }
• (2025). Anti-heavy-atom effect observed in near-infrared emissive bimetallic nanoclusters Au28Cu12X4Cl4 (X = cl, br, and i). JACS, 147(23), 19886--19892. (www)

  @article{ , abstract = {Metal nanoclusters with high photoluminescence quantum yield (PLQY) in the near-infrared region (NIR) have attracted considerable interest, and the elucidation of their structure–property relationships and luminescence mechanisms facilitates rational synthesis and practical applications. The direct reduction of alkynyl-gold precursors and copper salts leads to the formation of a series of face-centered cubic bimetallic nanoclusters Au 28 Cu 12 X 4 Cl 4 ( X = Cl, Br, and I), which exhibits strong NIR emission (∼850 nm) with PLQY being 14, 10, and 8% in the solution at room temperature, respectively. In contrast to the well-known heavy-atom effect, when the four chlorides in the Au 24 Cu 4 core are replaced with bromides or iodides, the luminescence of Au 28 Cu 12 X 4 Cl 4 is not enhanced but diminished instead. Excited-state dynamics studies reveal that heavier halogen atoms have a negligible effect on the intersystem crossing rate. Instead, their larger atomic sizes lead to an expansion of the cluster cores, which increases nonradiative transition rates and reduces PLQY. This is the first observation of an anti-heavy-atom effect in luminescent nanoclusters.}, archive = {J_JACS}, author = {Feng Hu and Zhen-Chao Long and Fangming Zhao and Wan-Qi Shi and Meng Zhou and Quan-Ming Wang}, doi = {10.1021/jacs.5c04083}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19886--19892}, shortjournal = {J. Am. Chem. Soc.}, title = {Anti-heavy-atom effect observed in near-infrared emissive bimetallic nanoclusters Au28Cu12X4Cl4 (X = cl, br, and i)}, volume = {147}, year = {2025}, }
• (2025). Enhanced THz emission and chirality control in van der waals ferromagnetic FePd2Te2/Pt heterostructures. JACS, 147(23), 19878--19885. (www)

  @article{ , abstract = {Two-dimensional (2D) magnetic materials, with their unique van der Waals (vdW) layered structure, tunable magnetism, and strong spin–orbit coupling, are promising for spintronic applications like terahertz (THz) emitters. Our study investigates the THz radiation properties of the newly discovered vdW ferromagnet FePd 2 Te 2 , which features a one-dimensional Fe zigzag chain structure and strong in-plane uniaxial anisotropy. Using ultrafast reflective THz emission spectroscopy (TES), we demonstrate that the paramagnetic FePd 2 Te 2 produces weak THz emission at room temperature. However, when capped with a 3 nm Pt layer, the THz emission intensity is significantly enhanced, attributed to spin-to-charge conversion (SCC) via the inverse spin Hall effect (ISHE). In the FePd 2 Te 2 /Pt heterostructure, the THz emission intensity is closely linked to the spin texture induced by crystal twinning in FePd 2 Te 2 and depends on the polarization angle of the pump laser. Two mechanisms for the photoexcited spin current generation are identified: one from spin-polarized hot electrons at the FePd 2 Te 2 /Pt interface, and the other, which is dominant, from angular momentum transfer through a nonlinear optical effect that induces impulsive magnetization. These findings provide valuable insights into the spin dynamics of 2D materials and open avenues for high-density, low-power THz spintronic device development based on advanced 2D vdW magnets.}, archive = {J_JACS}, author = {Jiali Zhang and Bingxian Shi and Haoran Xu and Yiwen Song and Yuqing Zou and Ziyang Li and Hongtao Dai and Yuna Song and Qingyuan Jin and Peng Cheng and Zuanming Jin and Zongzhi Zhang}, doi = {10.1021/jacs.5c04284}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19878--19885}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced THz emission and chirality control in van der waals ferromagnetic FePd2Te2/Pt heterostructures}, volume = {147}, year = {2025}, }
• (2025). Low-energy photoelectron spectroscopy and scattering from aqueous solutions and the role of solute surface activity. JACS, 147(23), 19868--19877. (www)

  @article{ , abstract = {Experimental insights into low-kinetic-energy electron scattering in aqueous solutions are essential for an improved understanding of electron-driven chemistry and radiobiology, and the development and informed application of aqueous-phase electron-based spectroscopy and dichroism methods. Generally, in aqueous environments and for electron kinetic energies below 12–15 eV, significant and, thus far, incompletely understood low-energy-transfer inelastic electron scattering with solvent molecules preponderates. This leads to cascades of tens-of-meV kinetic-energy losses that distort nascent photoelectron spectra, prevent direct and accurate electron-binding-energy measurements, and limit possibilities to determine electron-scattering cross sections at especially low electron kinetic energies. Here, we quantify aqueous-phase inelastic-scattering-based energy losses using 1–30 eV kinetic energy photoelectrons and liquid-jet photoemission spectroscopy, specifically by photoionizing an exemplary surface-active solute and comparing the results with those from the homogeneously distributed aqueous solvent. Thereby, we identify a general ≳17 eV electron-kinetic-energy requirement for the direct and accurate measurement of aqueous-phase electron binding energies, irrespective of interfacial concentration profiles. Further, at electron kinetic energies from 10 eV down to a few-eV above the ionization threshold, we observe and quantify lower degrees of scattering for photoelectrons generated from surface-active solutes, allowing moderately distorted surface-active-solute photoemission peaks to be resolved down to just few-eV electron kinetic energies. These results demonstrate that liquid-jet photoemission spectroscopy can be used to probe interfacial surface-active-solute dynamics and dichroism effects close to ionization thresholds, in stark contrast to similar experiments on homogeneously distributed solution components. Furthermore, they offer novel insights into low-electron-kinetic-energy scattering in aqueous environments, thereby addressing the current lack of reliable experimental data in this critical energy range.}, archive = {J_JACS}, author = {Stephan Thürmer and Dominik Stemer and Florian Trinter and Igor Yu Kiyan and Bernd Winter and Iain Wilkinson}, doi = {10.1021/jacs.5c04263}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19868--19877}, shortjournal = {J. Am. Chem. Soc.}, title = {Low-energy photoelectron spectroscopy and scattering from aqueous solutions and the role of solute surface activity}, volume = {147}, year = {2025}, }
• (2025). Unveiling the solvation chemistry and surface effects on CO2 reduction reaction pathways in nonaqueous Li–CO2 batteries. JACS, 147(23), 19859--19867. (www)

  @article{ , abstract = {Achieving highly reversible Li–CO 2 batteries requires efficient and reversible CO 2 redox reactions. However, the CO 2 reduction reaction (CO 2 RR) mechanism during discharge in nonaqueous electrolytes, strongly influenced by the solvent environment and surface structure, remains unclear. Here, we systematically investigate the CO 2 RR on atomically flat Au( hkl ) single crystal surfaces, providing direct spectral evidence of vital surface/intermediate species using in situ Raman spectroscopy. Our findings, combined with theoretical calculations, reveal that high-donor-number (DN) electrolytes facilitate a solution-mediated pathway, where Li + forms stable solvation structures with solvent molecules that react with *CO 2 – to produce CO and Li 2 CO 3 . Conversely, low-DN electrolytes promote a surface-mediated pathway due to limited solvation, enhancing direct Li + –*CO 2 – interactions on the electrode surface. Among the various Au( hkl ) surfaces, Au(110) shows superior catalytic activity, greatly enhancing *CO 2 – activation. This research offers crucial insights into the interplay between solvent chemistry and surface structure in the CO 2 RR, guiding future Li–CO 2 batteries optimization.}, archive = {J_JACS}, author = {Fan Gao and Mu-Fei Yue and Daniel Wun Fung Cheung and Weimin Yang and Zhi-Feng He and Yu Gu and Shisheng Zheng and Xiaobin Zhong and Siyuan Ma and Wei-Ping Chen and Jing-Hua Tian and Jin-Chao Dong and Jian-Feng Li}, doi = {10.1021/jacs.5c04157}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19859--19867}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling the solvation chemistry and surface effects on CO2 reduction reaction pathways in nonaqueous Li–CO2 batteries}, volume = {147}, year = {2025}, }
• (2025). Herzberg type-I or type-II predissociation dynamics at the conical intersection: Bifurcation into adiabatic or nonadiabatic pathway. JACS, 147(23), 19851--19858. (www)

  @article{ , abstract = {Bifurcation dynamics into Herzberg type-I and type-II predissociation pathways at the conical intersection have been characterized in terms of their distinct reaction rates and energy-disposal dynamics from the picosecond time-resolved product state distributions measured at multiple S 1 /S 2 vibronic states of thioanisole (C 6 H 5 SCH 3 ). Electronic predissociation (type-I) occurs on a faster time scale and leads to the larger translational energies being released to the fragments (C 6 H 5 S • + • CH 3 ) compared to the vibrational predissociation (type-II). While type-II dominates at the S 1 zero-point level, the type-I quantum yield increases sharply near the S 1 /S 2 conical intersection, which is consistent with the striking dynamic resonance observed for the reactive flux in the proximity of the conical intersection. Nonadiabatic product yield at the asymptotic limit was found to be enhanced predominantly through the type-I channel, suggesting that the quantum-mechanical nature of the reactive flux prepared near the first S 1 /S 2 conical intersection is likely to be retained at the second S 0 /S 2 conical intersection encountered in the later stage as there is little time to be altered during the ultrafast S-CH 3 bond extension on the repulsive potential energy curve linking two conical intersections, enabling nonadiabatic control over product yields through the state-selection of the reactive flux.}, archive = {J_JACS}, author = {Kyung Chul Woo and Sang Kyu Kim}, doi = {10.1021/jacs.5c03968}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19851--19858}, shortjournal = {J. Am. Chem. Soc.}, title = {Herzberg type-I or type-II predissociation dynamics at the conical intersection: Bifurcation into adiabatic or nonadiabatic pathway}, volume = {147}, year = {2025}, }
• (2025). Open the pores: Particles with fully accessible hierarchical pore networks by controlling phase separation in confinement. JACS, 147(23), 19841--19850. (www)

  @article{ , abstract = {Hierarchical porous materials combine large surface area with efficient mass transport, in particular when macropores directly connect mesopores. Polymerization-induced spinodal decomposition of poly(ethylene glycol) and tetraethyl orthosilicate can produce such macro-mesoporous material in bulk. However, the confinement of this spinodal decomposition process to emulsion droplets typically produces porous particles with a dense silica shell that blocks pore accessibility. Here, we address this issue by controlling the interfacial energies of the two phases undergoing spinodal decomposition within the emulsion droplet. We use surfactant mixtures to induce neutral wetting to prevent shell formation and generate particles with fully open, accessible and interconnected pore systems. Lattice Boltzmann simulations corroborate the experimental findings and underline that neutral wetting conditions with a contact angle to the continuous phase of ∼90° for both phases are essential to form open surface pores. Our work provides a simple strategy for producing hierarchical porous particles with controlled surface and bulk porosity between ∼200 and ∼6000 nm, expanding their potential for applications in catalysis, separation technologies, and adsorption.}, archive = {J_JACS}, author = {Umair Sultan and Alexander Götz and Nicolas Salcedo and Lukas Sandner and Johannes Martinus Peter Beunen and Alexander Kichigin and Carola Vorndran and Paolo Malgaretti and Benjamin Apeleo Zubiri and Matthias Thommes and Jens Harting and Erdmann Spiecker and Nicolas Vogel}, doi = {10.1021/jacs.5c03923}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19841--19850}, shortjournal = {J. Am. Chem. Soc.}, title = {Open the pores: Particles with fully accessible hierarchical pore networks by controlling phase separation in confinement}, volume = {147}, year = {2025}, }
• (2025). Electrodepositing textured sn film as a highly reversible anode for aqueous batteries. JACS, 147(23), 19829--19840. (www)

  @article{ , abstract = {Electrodepositing metal materials in large capacity, at low potential, and with high reversibility serves as the foundation for any aqueous rechargeable battery chemistry to realize the promises of high energy, low cost, and high safety. However, such a foundation is not solid because of the natural tendency of metals to form irregular, nonplanar, and often dendritic morphologies during electrochemical crystallization, which is further amplified in an acidic environment due to the faster kinetics of the coupled proton and mass-transport processes between hydrated metal ions and free metal atoms. As a typical representative, tin metal (Sn 0 ) has potential to achieve high energy in acidic batteries, but its nonuniform large-particle morphology, obtained from traditional electrodeposition, leads to dead Sn 0 formation and deteriorating reversibility, accompanied by the sustained hydrogen evolution reaction (HER) and active Sn 0 loss. Here, we report quaternary onium salts as effective interfacial cocations that, via selective adsorption, steadily texturize Sn 0 deposition along the (211) plane, which is intrinsically inert to the HER, thus regulating the film deposition process by favoring the formation of planar Sn 0 film. Such Sn 0 film brings exceptional reversibility in acidic electrolytes, which translates into sustained cycling stability at applicable areal capacities in both anode-half cells (∼1500 deposition/dissolution cycles at 5 mAh cm –2 ) and full cells (350 charge/discharge cycles at 5 mAh cm –2 ). Textured electrodeposition with intrinsic HER-suppression capability provides a universal solution for diverse metal anode materials in rechargeable energy-dense aqueous batteries.}, archive = {J_JACS}, author = {Haozhe Zhang and Yanxia Yu and Diyu Xu and Minghao Zhang and Chen-Jui Huang and Jianxin Wang and Hao Liu and Fan Yang and Mingqian Li and Di-Jia Liu and Xihong Lu and Kang Xu and Ying Shirley Meng}, doi = {10.1021/jacs.5c03861}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19829--19840}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrodepositing textured sn film as a highly reversible anode for aqueous batteries}, volume = {147}, year = {2025}, }
• (2025). Degradable diblock copolymer vesicles via radical ring-opening polymerization-induced self-assembly in aqueous media. JACS, 147(23), 19817--19828. (www)

  @article{ , abstract = {The development of degradable polymeric vesicles is essential for next-generation controlled delivery systems and responsive materials, particularly for therapy and diagnostics. However, achieving precise control over their synthesis and degradation behavior remains a significant challenge. Herein we report the synthesis of degradable diblock copolymer vesicles via radical ring-opening polymerization-induced self-assembly (rROPISA) in aqueous media. This approach employs radical ring-opening copolymerization (rROP) of a thionolactone with a water-miscible vinyl monomer to introduce cleavable thioester groups within the membrane-forming polymer chains. More specifically, a water-soluble poly( N , N -dimethylacrylamide) (PDMAC) precursor is chain-extended by statistically copolymerizing dibenzo[ c , e ]oxepane-5-thione (DOT) with 2-methoxyethyl acrylate (MEA) using a reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization formulation. The disparity in reactivity between DOT and MEA is addressed using a comonomer-starved feed strategy, with MEA acting as a cosolvent for the water-insoluble DOT. This controlled feeding approach ensures a more uniform distribution of DOT repeat units within the hydrophobic core block, significantly improves copolymer composition control, enables DOT incorporation of up to ∼4 mol %, and enhances overall comonomer conversion. Compared to conventional one-shot batch syntheses, this strategy yielded vesicles with superior degradation profiles. Morphological characterization using cryogenic transmission electron microscopy (cryo-TEM), dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) confirmed the formation of well-defined vesicles. Hydrolytic degradation studies conducted in mildly basic aqueous media led to vesicle disintegration, as indicated by cryo-TEM, DLS, and SAXS analyses. Importantly, size exclusion chromatography (SEC) analysis revealed the formation of significantly shorter copolymer chains and final molecular weight distributions comparable to that of the nondegradable PDMAC precursor, indicating efficient hydrolytic degradation of the membrane-forming P(MEA- stat -DOT) block. This study provides valuable insights regarding the rational design of degradable vinyl-based diblock copolymer vesicles, which augurs well for potential biomedical applications.}, archive = {J_JACS}, author = {Panagiotis G. Georgiou and Thomas J. Neal and Mark A. Newell and Kyle S. Hepburn and Joshua J. S. Tyler and Matthew A. H. Farmer and Priyanka Chohan and Peter J. Roth and Julien Nicolas and Steven P. Armes}, doi = {10.1021/jacs.5c03744}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19817--19828}, shortjournal = {J. Am. Chem. Soc.}, title = {Degradable diblock copolymer vesicles via radical ring-opening polymerization-induced self-assembly in aqueous media}, volume = {147}, year = {2025}, }
• (2025). Fully exposed cu clusters with ru single atoms synergy for high-performance acetylene semihydrogenation. JACS, 147(23), 19808--19816. (www)

  @article{ , abstract = {Semihydrogenation of acetylene is an essential process in the ethylene industry for removing acetylene impurities and ensuring the production of polymer-grade ethylene. Atomically dispersed Cu catalysts have attracted significant attention due to their cost-effectiveness and catalytic potential. However, the inherently weak hydrogen dissociation ability of Cu results in low catalytic activity, necessitating elevated reaction temperatures, which limit its practical applicability. To overcome this limitation, we design a Ru single-atom-decorated, fully exposed Cu cluster catalyst (Ru 1 Cu n /SiO 2 ) that exhibits outstanding performance in semihydrogenation of acetylene, achieving 100% acetylene conversion with 98% ethylene selectivity at 170 °C. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS) confirm the atomic dispersion of Ru and the structural evolution of Cu clusters. H 2 –D 2 exchange and temperature-programmed desorption (TPD) experiments reveal that Ru modification significantly enhances the hydrogen dissociation ability of the catalyst while tuning acetylene adsorption. Density functional theory (DFT) calculations further demonstrate that the Ru single atoms and Cu nanoclusters create a synergistic catalytic interface that markedly promotes hydrogen activation and lowers the energy barrier of the rate-determining step. This study provides fundamental insights into the rational design of atomically dispersed bimetallic catalysts and offers a new strategy for the efficient and selective acetylene hydrogenation.}, archive = {J_JACS}, author = {Chengquan Sui and Wanni Dong and Maolin Wang and Fei Huang and Shengling Xiang and Hui Wang and Jiawei Chen and Chengyu Li and Mi Peng and Ning Wang and Geng Sun and Ding Ma and Hongyang Liu}, doi = {10.1021/jacs.5c03713}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19808--19816}, shortjournal = {J. Am. Chem. Soc.}, title = {Fully exposed cu clusters with ru single atoms synergy for high-performance acetylene semihydrogenation}, volume = {147}, year = {2025}, }
• (2025). Divergent mechanisms of SSZ-39 crystallization using structurally similar but chemically distinct organic structure-directing agents. JACS, 147(23), 19796--19807. (www)

  @article{ , abstract = {The role of an organic structure-directing agent on zeolite crystallization is conventionally interpreted based on the final, bulk crystal structure. However, few studies have examined their effect on the dynamics of zeolite crystal growth and restructuring, particularly with respect to the interzeolite transformations that are increasingly being exploited in zeolite synthesis. Herein, we compare two organic structure-directing agents that both direct the formation of the small-pore zeolite SSZ-39 (AEI). The organics have nearly identical molecular structures but exhibit distinct chemical compositions by virtue of a single heteroatom substitution. Our findings reveal that the organics have a dramatic impact on the crystallization kinetics, physicochemical properties, and catalytic performance of zeolite AEI prepared by the transformation of zeolite FAU parent crystals. The conventional quaternary ammonium structure-directing agent, “Pippy”, produces a distinct intermediate metastable structure with defects and anisotropic crystal shape that transitions into relatively thick zeolite AEI platelets with compromised hydrothermal stability. This transition is accompanied by an unusual morphological evolution from rod-like to platelet crystals that defies common Ostwald ripening processes. We demonstrate that a new quaternary ammonium-ether structure-directing agent, “Morphy”, produces thinner platelets of zeolite AEI and bypasses the defective intermediate observed for the conventional organic. Syntheses with Morphy produce a more hydrothermally stable product, which exhibits superior activity in the NH 3 selective catalytic reduction of NO x used as a benchmark reaction for assessing structure–performance relationships.}, archive = {J_JACS}, author = {Zhiyin Niu and Taimin Yang and Alyssa McNarney and Luke Tufaro and Simon M. Vornholt and Hadi Bourji and Jia Lv and Michael P. Harold and Jeremy C. Palmer and Bradley F. Chmelka and Karena W. Chapman and Roger Moulton and Jeffrey D. Rimer}, doi = {10.1021/jacs.5c03712}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19796--19807}, shortjournal = {J. Am. Chem. Soc.}, title = {Divergent mechanisms of SSZ-39 crystallization using structurally similar but chemically distinct organic structure-directing agents}, volume = {147}, year = {2025}, }
• (2025). Manipulating hydrocarbon chain-melting transitions in dialkylammonium halide barocaloric materials through desymmetrization. JACS, 147(23), 19788--19795. (www)

  @article{ , abstract = {Layered materials containing hydrocarbon bilayers capable of transitioning between an ordered and partially disordered state can exhibit large temperature and entropy changes─termed barocaloric effects─in response to a change in hydrostatic pressure. These barocaloric materials can, in principle, be used to drive heating and cooling cycles with higher efficiency and less environmental impact than conventional fluorocarbon refrigerants. However, much remains to be understood about how to manipulate the thermodynamics and kinetics of hydrocarbon order–disorder, or “chain-melting”, transitions in the solid state in order to design materials with properties tailored for specific thermal applications. Here, we report a chain desymmetrization strategy to modulate the phase-change behavior of a new family of asymmetric dialkylammonium halide salts. In particular, we demonstrate that chain desymmetrization can lead to reduced phase-change thermal hysteresis while maintaining large entropy changes. This translates to a significant reduction in the pressure required to reversibly drive nonzero entropy changes, with asymmetric dialkylammonium salts able to access reversible entropy changes at pressures nearly 80% lower than their symmetric counterparts. This work expands the scope of chain-melting materials that exhibit strong barocaloric effects and offers insights into the factors that influence the reversibility of barocaloric materials.}, archive = {J_JACS}, author = {Faith E. Chen and Jason D. Braun and Jinyoung Seo and Hailey J. Hurd and Malia B. Wenny and Shao-Liang Zheng and Jason J. Calvin and Craig M. Brown and Jarad A. Mason}, doi = {10.1021/jacs.5c03705}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19788--19795}, shortjournal = {J. Am. Chem. Soc.}, title = {Manipulating hydrocarbon chain-melting transitions in dialkylammonium halide barocaloric materials through desymmetrization}, volume = {147}, year = {2025}, }
• (2025). Stable isotopic labeling of dimethylallyl pyrophosphate (DMAPP) reveals compartmentalization of isoprenoid biosynthesis during sporulation in bacillus subtilis. JACS, 147(23), 19777--19787. (www)

  @article{ , abstract = {Isoprenoids are essential metabolites whose biosynthesis originates from two five-carbon (C 5 ) isomers, isopentenyl pyrophosphate (IPP) and dimethylallyl pyrophosphate (DMAPP). Although these isomers serve as the core substrates for isoprenoid biosynthesis, tracking their independent incorporation into downstream metabolites is difficult due to the lack of available chemical tools. To address this issue, we have developed a cell-permeant, stable isotope-labeled analog of DMAPP that employs self-immolating esters to mask the β-phosphate, allowing for efficient cellular uptake and direct forward isotopic labeling of downstream products of DMAPP in Bacillus subtilis . We demonstrate that 13 C-labeled, ester-protected DMAPP ( 13 C 3 SIE-DMAPP) achieves significant incorporation into menaquinone-7 (MK-7), regardless of inhibition of endogenous production of IPP and DMAPP. By knocking out isopentenyl pyrophosphate isomerase (IPPI) expression, we achieve specific 13 C isotopic labeling exclusively at DMAPP-derived positions of MK-7 and demonstrate that IPPI overexpression enables B. subtilis to utilize DMAPP as its sole isoprenoid source. Finally, we tracked DMAPP incorporation during the transition from vegetative growth to sporulation, revealing compartment-specific isotope labeling patterns that underscore the metabolic independence of isoprenoid metabolism in the mother cell and endospore during sporulation in B. subtilis . The introduction of this stable isotope-labeled DMAPP facilitates the tracking of DMAPP-derived metabolites in native biological contexts and opens new avenues for studying prenyl metabolism, terpene biosynthetic pathways, and the regulatory mechanisms governing cellular isoprenoid pools.}, archive = {J_JACS}, author = {Dillon P. McBee and Zackary N. Hulsey and Makayla R. Hedges and Joshua A. Baccile}, doi = {10.1021/jacs.5c03639}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19777--19787}, shortjournal = {J. Am. Chem. Soc.}, title = {Stable isotopic labeling of dimethylallyl pyrophosphate (DMAPP) reveals compartmentalization of isoprenoid biosynthesis during sporulation in bacillus subtilis}, volume = {147}, year = {2025}, }
• (2025). One-pot multisubstrate screening for asymmetric catalysis enabled by 19F NMR-based simultaneous chiral analysis. JACS, 147(23), 19770--19776. (www)

  @article{ , abstract = {Exploring a diverse chemical space is essential for advancing asymmetric synthesis. The complexity of the chirality-determining processes often requires resource-intensive optimization campaigns across multiple substrates. Although one-pot multisubstrate screening offers a promising solution for high-throughput screening (HTS), a persistent challenge lies in the accurate and efficient analysis of complex reaction mixtures, which has traditionally relied on chromatography-based techniques with limited resolution. In this work, we present a rapid multisubstrate screening workflow that utilizes 19 F NMR spectroscopy for simultaneous chiral analysis. By employing an NMR-shifting cobalt reagent, we accurately determined both yields and enantiomeric excesses for up to 21 different substrates in a single reaction mixture during the ruthenium-catalyzed asymmetric reductive amination of ketones. This method facilitates precise chiral analysis through dynamic peak shifts and splitting in 19 F NMR spectra induced by the shift reagent. This approach accelerates the evaluation of structure-selectivity relationships, offering valuable mechanistic insights into enantio-determining processes.}, archive = {J_JACS}, author = {Donghun Kim and Gyeongseon Choi and Hyunwoo Kim}, doi = {10.1021/jacs.5c03446}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19770--19776}, shortjournal = {J. Am. Chem. Soc.}, title = {One-pot multisubstrate screening for asymmetric catalysis enabled by 19F NMR-based simultaneous chiral analysis}, volume = {147}, year = {2025}, }
• (2025). Chemically recyclable poly(tetrathioorthocarbonate)s: Combining high refractive index and abbe number. JACS, 147(23), 19762--19769. (www)

  @article{ , abstract = {Polymers with high refractive index ( n ) and Abbe number ( v D ) have the potential to be used in advanced optical devices. However, fabricating such materials is challenging because of the inherent trade-off between light refraction and dispersion. Herein, we present an efficient strategy for synthesizing sulfur-rich polymers with tetrathioorthocarbonate as the functional group through the alternating copolymerization of thiiranes and cyclic trithiocarbonates in a controlled fashion. Notably, the tetrathioorthocarbonates with features of high sulfur content, cyclic structure, and free C═S bonds afforded excellent optical properties with an n under 589.3 nm of 1.706, v D of 40.9, and optical transparency of 90%. Density functional theory calculations of the copolymerization process suggest that the high selectivity of poly(tetrathioorthocarbonate)s (PTOCs) originates from the thermodynamically unfavorable elimination of trithiocarbonate anions. In particular, PTOCs can be recycled to the original thiiranes and cyclic trithiocarbonates via spiro intermediates by simple pyrolysis.}, archive = {J_JACS}, author = {Jin-Zhuo Zhao and Tian-Jun Yue and Bai-Hao Ren and Yi-Xuan Ma and Xiao-Bing Lu and Wei-Min Ren}, doi = {10.1021/jacs.5c03424}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19762--19769}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemically recyclable poly(tetrathioorthocarbonate)s: Combining high refractive index and abbe number}, volume = {147}, year = {2025}, }
• (2025). Amplification of asymmetry for dynamic helical polymers through 1:1 Host–Guest interactions: Theoretical models for majority rule and sergeants and soldiers effects. JACS, 147(23), 19751--19761. (www)

  @article{ , abstract = {Amplification of asymmetry (chiral amplification) is one of the distinctive phenomena of dynamic helical polymers whose helical sense excess is significantly enhanced with a small amount of chiral units through the strong cooperative interactions among the monomer units. The Ising model for the amplification of asymmetry in the dynamic helical copolymers bearing the chiral side chains has been well-established. However, the theoretical models have not yet been developed for the amplification of asymmetry in the dynamic helical polymers induced by noncovalent intermolecular (host–guest) interactions of the achiral side chains with the chiral/chiral (majority rule effect) and chiral/achiral (sergeants and soldiers effect) guest molecules. In this work, we propose the theoretical models for two types of 1:1 host–guest interactions: the majority rule effect type 1:1 host–guest interaction (MRHG) and sergeants and soldiers effect type 1:1 host–guest interaction (SSHG) models, in which each twisting unit of the dynamic helical polymers is assumed to interact with one guest molecule. The excess energy of the helical reversal state (Δ G r ), per unit energy favoring one helical state over the other (2Δ G h ), and enantioselectivity (α) can be effectively determined using the MRHG model. Moreover, it was revealed that the chiral solvation model reported by Green, Morawetz, and co-workers is a particular solution of the SSHG model.}, archive = {J_JACS}, author = {Nozomu Suzuki and Daisuke Taura and Yusuke Furuta}, doi = {10.1021/jacs.5c03406}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19751--19761}, shortjournal = {J. Am. Chem. Soc.}, title = {Amplification of asymmetry for dynamic helical polymers through 1:1 Host–Guest interactions: Theoretical models for majority rule and sergeants and soldiers effects}, volume = {147}, year = {2025}, }
• (2025). Revisiting the hunter-sanders model for π–π interactions. JACS, 147(23), 19738--19750. (www)

  @article{ , abstract = {The “Hunter-Sanders model” ( J. Am. Chem. Soc. 1990, 112 , 5525) is foundational to many chemists’ understanding of interactions between aromatic systems. Carter-Fenk and Herbert ( Chem. Sci ., 2020, 11 , 6758) recently upended that understanding by showing that the driving force for aromatic systems to adopt parallel displaced geometries arises from steric, not Coulombic, repulsion of the π-electron clouds. Carter-Fenk and Herbert also claimed to show that the original Hunter-Sanders potential fails to predict the geometries of a range of parallel and T-shaped dimers. Closer inspection reveals that the data supporting this latter claim are flawed. Correctly implemented, the Hunter-Sanders potential provides qualitatively correct predictions for these systems and performs particularly well for the T-shaped benzene dimer. Moreover, it predicts the preferred displacement direction for some stacked heterocyclic dimers and accurately captures the impact of a diverse group of substituents on the benzene sandwich dimer. This is inclusive of the fact that all substituents enhance stacking interactions in this geometry. Ironically, for substituted benzene dimers, the Hunter-Sanders potential provides data in accord with our Local, Direct Interaction Model but in contrast with the so-called “Hunter-Sanders model.” At the same time, the Hunter-Sanders potential struggles to capture heteroatom and substituent effects in parallel displaced geometries in which the heteroatom/substituent is located over the other ring, leading to qualitatively incorrect predictions of the preferred displacement direction of substituted benzene dimers. Overall, many aspects of the Hunter-Sanders potential are flawed; however, others appear qualitatively correct.}, archive = {J_JACS}, author = {Steven E. Wheeler}, doi = {10.1021/jacs.5c03169}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19738--19750}, shortjournal = {J. Am. Chem. Soc.}, title = {Revisiting the hunter-sanders model for π–π interactions}, volume = {147}, year = {2025}, }
• (2025). Theoretical insights into the resonant suppression effect in vibrational polariton chemistry. JACS, 147(23), 19727--19737. (www)

  @article{ , abstract = {Recent experiments demonstrated the possibilities of modifying ground-state chemical reaction rates by placing an ensemble of molecules in an optical microcavity through a resonant coupling between the cavity mode and molecular vibrations. Typical VSC experiments operate in the absence of any light source. The VSC-induced rate constant suppression occurs under the resonance condition when the cavity frequency matches the molecular vibrational frequency, and only under the normal incidence when considering in-plane momentum inside a Fabry–Pérot cavity. In this work, we use quantum dynamics simulations and analytic theories to provide valuable insights into observed VSC phenomena, including the resonance behavior, the nonlinear change of the rate constant when increasing Rabi splitting, modification of both reactive enthalpy and entropy, and a reason why, with a very low barrier, there is a lack of the cavity modification. The analytic theory also exhibits the normal incidence condition and collective coupling effects.}, archive = {J_JACS}, author = {Sebastian Montillo Vega and Wenxiang Ying and Pengfei Huo}, doi = {10.1021/jacs.5c03182}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19727--19737}, shortjournal = {J. Am. Chem. Soc.}, title = {Theoretical insights into the resonant suppression effect in vibrational polariton chemistry}, volume = {147}, year = {2025}, }
• (2025). Oxaborole-functionalized sialylated glycan probe for high-fidelity fluorescence imaging of cancer tissue. JACS, 147(23), 19718--19726. (www)

  @article{ , abstract = {Cell surface glycosylation performs a pivotal role in various biological processes, impacting cellular communication, immune response, and disease mechanisms. Glycomes on cell surfaces vary significantly, presenting viable biomarkers for identifying cell types and their states. Thus, the development of fluorescent probes to rapidly detect glycans is of great importance for disease diagnosis and the biomarker-mediated delivery of therapeutic agents. Herein, we introduce an oxaborole-based fluorescent probe (SLY), designed to recognize sialylated glycans on cell surfaces, facilitating cell distinction. This probe demonstrates pronounced selectivity for HepG2 and HT29 cells, which overexpress sialyl Lewis x and sialyl Lewis a, respectively, in contrast to cells that do not overexpress these Lewis antigens. Mechanistic studies revealed that the probe binds to sialic acid present on these Lewis antigens and internalizes into the cell via caveolae-mediated endocytosis, ultimately localizing in the mitochondria. Remarkably, the distinct selectivity of this probe allows for the identification of the cancerous regions within the liver at cellular resolution. Our newly developed probe holds immense potential in distinguishing cell types and advancing cancer diagnostics and fluorescence-guided surgery.}, archive = {J_JACS}, author = {Kwangwook Ko and Min Gao and Sourav Sarkar and Haw-Young Kwon and Young-Tae Chang}, doi = {10.1021/jacs.5c03020}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19718--19726}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxaborole-functionalized sialylated glycan probe for high-fidelity fluorescence imaging of cancer tissue}, volume = {147}, year = {2025}, }
• (2025). Triclinic liquid crystal of counter-rotating squashed double helices in a side-chain polymer. JACS, 147(23), 19711--19717. (www)

  @article{ , abstract = {A polysiloxane with tris-alkoxy-ended rod-like mesogenic side groups forms an unusually low-symmetry antiferrochiral liquid crystal, space group P 1̅ , consisting of distorted left- and right-handed double-helices containing alternating splay and twist sections. The unit cell contains two double-helical columns. On faster cooling, a closely related metastable orthorhombic structure is formed, symmetry Fddd , with 8 double helices per cell.}, archive = {J_JACS}, author = {Yi-nan Xue and Ya-xin Li and Yu-min Tang and Shu-gui Yang and Ruo-yin Jia and Liliana Cseh and Feng Liu and Xiang-bing Zeng and Goran Ungar}, doi = {10.1021/jacs.5c02663}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19711--19717}, shortjournal = {J. Am. Chem. Soc.}, title = {Triclinic liquid crystal of counter-rotating squashed double helices in a side-chain polymer}, volume = {147}, year = {2025}, }
• (2025). Evidence of heteroepitaxy and solid solutions in lattice matched ternary covalent organic framework systems. JACS, 147(23), 19702--19710. (www)

  @article{ , abstract = {Covalent organic frameworks (COFs) are crystalline, porous materials with the possibility for broad applications, but their structural diversity remains constrained by simple net topologies, limiting functional versatility. To address this challenge, we developed a strategy for incorporating linkers with normally mismatched geometries, exemplified by a [4-c + 2-c + 3-c] system incorporating pentagonal motifs for 2D tiling. Central to this approach is the derivation of a length ratio parameter, α, which provides a quantitative guide for evaluating the compatibility of linkers in ternary systems. Investigating a model system with close to ideal α, we demonstrate that precise size matching enables the formation of localized solid solutions and heteroepitaxial interfaces, as seen by transmission electron microscopy. These findings showcase a pathway for expanding the structural and functional complexity of COFs, opening new avenues for tailored material design.}, archive = {J_JACS}, author = {Alena Winter and Juliane Lange and Farzad Hamdi and Panagiotis L. Kastritis and Frederik Haase}, doi = {10.1021/jacs.5c02502}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19702--19710}, shortjournal = {J. Am. Chem. Soc.}, title = {Evidence of heteroepitaxy and solid solutions in lattice matched ternary covalent organic framework systems}, volume = {147}, year = {2025}, }
• (2025). Chemically engineered affinity protein drugs for covalent targeted cancer therapy. JACS, 147(23), 19687--19701. (www)

  @article{ , abstract = {Affinity proteins are multiple types of well-explored small scaffold proteins with excellent tumor targeting performance. However, due to their small size, the balance between rapid blood clearance and efficient tumor accumulation remains a challenge for their clinical application. The covalent targeting mode, endowing the affinity proteins with an irreversible binding ability to their receptor and then decoupling the pharmacodynamic effect from pharmacokinetics, may provide a promising solution for clinical applications of affinity proteins. Herein, we develop a chemical modification strategy to construct covalently targeted affinity protein drugs. Through the chemical attachment with a sulfur(VI) fluoride exchange (SuFEx) chemistry-based maleimide-substituted aryl fluorosulfate (MFS) linker, the engineered affinity protein acquires the capacity to covalently link with its targeting receptor. As a proof of concept, the MFS linker modified affibody-protein drug elicited over 72% covalent binding to the target human epidermal growth factor receptor 2 (HER2) and 185% higher cell uptake than that of the noncovalent control in vitro . In mice, the tumor retention capacity of the covalent affibody-protein drug was 2.01 times greater than that of the control group, ultimately resulting in nearly complete inhibition of tumor growth. Similar enhanced therapeutic efficacy was also obtained in another MFS linker-armed monobody-protein drug targeting the epidermal growth factor receptor (EGFR). In brief, this facile chemical modification strategy provides a general platform for preparing covalently targeted affinity protein drugs, potentially accelerating the application of protein therapeutics in diverse diseases.}, archive = {J_JACS}, author = {Xuelin Xia and Wenhui Gao and Xiaoyuan Yang and Wei Huang and Xiao-Xia Xia and Deyue Yan}, doi = {10.1021/jacs.5c02212}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19687--19701}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemically engineered affinity protein drugs for covalent targeted cancer therapy}, volume = {147}, year = {2025}, }
• (2025). Iodine-induced redirection of active sources in cu-based catalysts during efficient and stable water oxidation. JACS, 147(23), 19675--19686. (www)

  @article{ , abstract = {Enhancing the mechanistic regulation of the oxygen evolution reaction (OER) is crucial for developing efficient and stable electrocatalysts. However, the dynamic variation of surface structure during the electrocatalytic process limits the accurate identification of the active source and underlying reaction mechanism. Herein, we report an iodine-doping strategy to direct the reconstruction of active species in CuS catalysts toward an unconventional oxygen vacancy oxidation mechanism, thereby overcoming the activity and stability limitations. Mechanistic analysis indicates that the electronic manipulation, weak coordination of Cu–S bonds, and lattice distortion induced by iodine-doping facilitate the thermodynamically favorable Cu 2+ to Cu 3+ oxidation during OER. The decisively formed oxygen vacancies are emphasized as a genuine active source to promote hydroxyl adsorption, with hypervalent Cu species acting as auxiliary sites to accelerate deprotonation by strengthening Cu–O covalent. Consequently, the optimal iodine-doped CuS exhibits a reduced overpotential of 189 mV at 10 mA cm –2 and superb stability prolonging to 1250 h. When used as a bifunctional electrode in a membrane electrode assembly electrolyzer, it also exhibits a low voltage of 1.65 V at 1 A cm –2 , with electrolysis durability of 480 h and a low hydrogen cost of US$1.70/kg H 2 , outperforming the 2026 targets set by the U.S. Department of Energy.}, archive = {J_JACS}, author = {Mingzheng Gu and Ling Jiang and Hao Wang and Qiao Chen and Yixin Hao and Linlin Li and Feng Hu and Xiaojun Zhang and Yuping Wu and Guangfeng Wang and Shengjie Peng}, doi = {10.1021/jacs.5c01897}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19675--19686}, shortjournal = {J. Am. Chem. Soc.}, title = {Iodine-induced redirection of active sources in cu-based catalysts during efficient and stable water oxidation}, volume = {147}, year = {2025}, }
• (2025). An ethynyl-linked sp-carbon-conjugated covalent organic framework through sonogashira cross-coupling reactions. JACS, 147(23), 19667--19674. (www)

  @article{ , abstract = {We report the synthesis of ethynyl-linked covalent organic frameworks through microinterfacial polymerization with Sonogashira cross-coupling reactions of 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin (TEPP) and 5,10,15,20-tetrakis(4-bromophenyl)porphyrin (TBPP). This framework consists of extended two-dimensional tetragonal layers with porphyrin knots and ethynyl (−C≡C−) linkers and constitutes layered frameworks with an AB-stacking mode, creating periodically ordered porphyrin arrays and one-dimensional microporous channels. The ethynyl-linked porphyrin framework features a broad absorption spectrum that covers the entire visible region and extends to the infrared zone exceeding 1400 nm, exhibits a low optical bandgap of 1.32 eV, and is photoconductive, generating prominent photocurrent. The micropores formed by the AB stacking are highly accessible, enabling iodine uptake, CO 2 capture, and Li + confinement. Remarkably, the Li + -confined frameworks exhibit Li + conductivity of 2.1 × 10 –5 S cm –1 at 100 °C under anhydrous conditions and achieve an exceptional Li + conductivity of 3.9 × 10 –3 S cm –1 at a relative humidity of 98%. Temperature-dependent experiments revealed that Li + conduction is facilitated by a low-energy barrier hopping mechanism. We envision that our ethynyl linkage strategy will not only develop novel sp-carbon-conjugated frameworks but also enable unprecedented functions.}, archive = {J_JACS}, author = {Hao Yang and Shanshan Tao and Shuyue He and Donglin Jiang}, doi = {10.1021/jacs.5c01709}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19667--19674}, shortjournal = {J. Am. Chem. Soc.}, title = {An ethynyl-linked sp-carbon-conjugated covalent organic framework through sonogashira cross-coupling reactions}, volume = {147}, year = {2025}, }
• (2025). Kinetic dissection of proton-coupled conformational transitions in nucleic acids by integrating pH-dependent NMR and chemical modifications. JACS, 147(23), 19643--19666. (www)

  @article{ , abstract = {Proton-coupled conformational transitions play fundamental roles in nucleic acid recognition, catalysis, and folding, yet the kinetic mechanisms underlying these multistep protonation reactions remain unknown. Here, we present an approach to resolve the dominant kinetic pathway and rate-limiting step, which combines NMR chemical exchange measurements with chemical perturbations that shift p K a or modulate conformational equilibria. Applying the approach to three nucleic acid systems, we find the microscopic protonation step to be a diffusion-limited proton transfer reaction ( k prot ∼ 10 11 M –1 s –1 ), 2 orders of magnitude faster than diffusion-limited ligand-binding. For an A + –C mismatch in duplex DNA, protonation was the rate-limiting step occurring after the conformational change at a diffusion-limited k on ∼ 10 11 M –1 s –1 via conformational selection of the wobble conformation, which forms rapidly and in significant abundance in the neutral ensemble. In RNA, the A–C wobble was sparsely populated in the neutral ensemble. The apparent k on was 2 orders of magnitude slower, and the reaction followed an induced-fit mechanism, where the unpaired adenine was initially protonated, followed by rate-limiting intrahelical flipping. The apparent k on was 5 orders of magnitude slower for the protonated G( syn )–C + Hoogsteen conformation in duplex DNA in which cytosine protonation was rate-limiting occurring after the conformational change via conformational selection of an energetically disfavored G( syn )–C intermediate. These kinetic models quantitatively predicted the impact of pH shifts and chemical modifications on reaction kinetics. Our findings reveal how differences in nucleic acid conformational ensembles can drive diverse kinetic responses to pH changes and chemical modifications, even in binding reactions involving the simplest ligand: the proton.}, archive = {J_JACS}, author = {Yeongjoon Lee and Rohit Roy and Stephanie Gu and Subin B. Shetty and Atul K. Rangadurai and Hashim M. Al-Hashimi}, doi = {10.1021/jacs.5c01663}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19643--19666}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetic dissection of proton-coupled conformational transitions in nucleic acids by integrating pH-dependent NMR and chemical modifications}, volume = {147}, year = {2025}, }
• (2025). Nickel-mediated radical capture: Evidence for a concerted inner-sphere mechanism. JACS, 147(23), 19632--19642. (www)

  @article{ , abstract = {Nickel catalysis enables cross-coupling of a broad scope of C(sp 3 ) moieties by mediating carbon–carbon bond formation from carbon-centered radicals. A widely proposed mechanism involves stepwise radical capture by a nickel(II) complex that forms a nickel(III) intermediate. The alternative pathway, a concerted radical capture and carbon–carbon bond formation, has been largely overlooked. This study investigates the ligand effect and kinetics of nickel-mediated radical capture and reductive elimination, which provide evidence to distinguish between stepwise and concerted pathways. Through radical clock experiments, spectroscopic investigation, electrochemical studies, and multivariate linear regression analysis of a series of [(pybox)Ni(Ar)]BAr F 4 complexes, we established a strong correlation between the rate of radical capture and HOMO and LUMO energies, along with positive charge stabilization at nickel and the aryl actor ligand. These data rule out the stepwise formation of a nickel(III) intermediate and support a concerted pathway. Redox-active nitrogen ligands and nonredox-active phosphine ligands exhibit contrasting reactivity, with only redox-active ligands facilitating radical capture and carbon–carbon bond formation. This critical role of ligand redox activity can be attributed to the participation of the LUMO in bond cleavage and formation. Among redox-active ligands, bidentate and tridentate ligands exhibit similar rates, suggesting a consistent mechanism with relatively minimal ancillary ligand effect. Our results highlight the critical interplay between ligand electronics, sterics, and orbital contributions, offering valuable design principles for nickel-catalyzed cross-coupling reactions involving radical intermediates.}, archive = {J_JACS}, author = {Ethan H. Spielvogel and Jonathan Yuan and Norah M. Hoffmann and Tianning Diao}, doi = {10.1021/jacs.5c01554}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19632--19642}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-mediated radical capture: Evidence for a concerted inner-sphere mechanism}, volume = {147}, year = {2025}, }
• (2025). Domino effect of catalysis: Coherence between reaction network and catalyst restructuring accelerating surface carburization for CO2 hydrogenation. JACS, 147(23), 19622--19631. (www)

  @article{ , abstract = {Dynamic carburization is a common and important phenomenon in many industrial reactions. Finding the critical factor governing this process is significant for catalyst optimization, which is complicated due to the coherence between catalyst dynamics and reaction dynamics. In this work, we manipulate the in situ formation of fast carburization on the Pd-FeO x surface by revealing a domino effect between the reaction network and catalyst restructuring during long-term CO 2 hydrogenation reaction. We prepared catalysts of three sizes (5Pd-FeO x , 0.5Pd-FeO x , 0.05Pd-FeO x ) and found that the large size of Pd NP (5Pd-FeO x ) induces the reactive metal–support interaction, following the in situ Pd 3 Fe formation, the reaction route change, the fast surface carburization (Fe 5 C 2 ), and finally the superior catalytic performance. Among these changes, we identify that in situ alloying instead of the apparent size difference is crucial for the formation of the active Fe 5 C 2 phase. As a proof of concept, we further design a presynthesized Pd 3 Fe alloy on FeO x and find an enhanced activity with reduced Pd loading by controlled fast carburization. This work not only demonstrates the controllability of dynamic carburization but also presents a benchmark of optimizing catalysts through the comprehensive understanding of in situ catalyst changes.}, archive = {J_JACS}, author = {Pengfei Du and Yafeng Zhang and Rui Qi and Qingqing Gu and Xiaoyan Xu and Aiqin Wang and Beien Zhu and Bing Yang and Tao Zhang}, doi = {10.1021/jacs.5c01435}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19622--19631}, shortjournal = {J. Am. Chem. Soc.}, title = {Domino effect of catalysis: Coherence between reaction network and catalyst restructuring accelerating surface carburization for CO2 hydrogenation}, volume = {147}, year = {2025}, }
• (2025). Atmospheric pressure synthesis of ultrathin monoclinic FeCr2S4 crystals with robust antiferromagnetism. JACS, 147(23), 19614--19621. (www)

  @article{ , abstract = {The synthesis of unconventional phases in two-dimensional (2D) materials can unlock unique properties not readily observed in their bulk counterparts. Recently, the naturally occurring monoclinic phase of FeCr 2 S 4 , which forms under extremely high pressure, has been discovered in meteorites. However, the properties of this unconventional phase have not yet been explored. Here, we have designed a phase-selective synthesis approach to grow 2D monoclinic FeCr 2 S 4 crystals at atmospheric pressure under sulfur-deficient conditions, based on the sulfur content-dependent phase transition that we revealed. By combining theoretical calculations with transport measurements and variable-temperature polarized Raman spectroscopy, we revealed that the monoclinic phase of FeCr 2 S 4 is an antiferromagnetic semiconductor with a thickness-independent Néel temperature ( T N ) of ∼240 ± 10 K (determined from the inflection point in the resistance–temperature curve), due to the nonlayered structure inherent to FeCr 2 S 4 . The robust antiferromagnetism in 2D monoclinic FeCr 2 S 4 crystals allowed us to construct ferrimagnetic/antiferromagnetic junctions using FeCr 2 S 4 crystals with different phases, which exhibited an exchange bias field of up to 228 Oe at 50 K. Furthermore, a magnetic tunnel junction (MTJ) fabricated with 2D FeCr 2 S 4 showed a storage field window of 925 Oe at 50 K, surpassing conventional 2D layered heterostructures. The high- T N characteristics that are independent of thickness, coupled with a strong exchange bias effect, position 2D antiferromagnetic monoclinic FeCr 2 S 4 crystals as a promising 2D component for future spintronic devices.}, archive = {J_JACS}, author = {Lei Liu and Qin Yu and Juanxia Wu and Jing Xia and Dong Wang and Liming Xie and Yuansha Chen and Liying Jiao}, doi = {10.1021/jacs.5c00935}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19614--19621}, shortjournal = {J. Am. Chem. Soc.}, title = {Atmospheric pressure synthesis of ultrathin monoclinic FeCr2S4 crystals with robust antiferromagnetism}, volume = {147}, year = {2025}, }
• (2025). Developing pharmaceutically relevant pd-catalyzed C–N coupling reactivity models leveraging high-throughput experimentation. JACS, 147(23), 19602--19613. (www)

  @article{ , abstract = {This manuscript presents machine learning models for Pd-catalyzed C–N couplings constructed using a large, pharmaceutically relevant, structurally diverse dataset (4204 unique products) generated de novo using high-throughput experimentation. The dataset generation was enabled by the discovery of novel nanomole scale compatible automation friendly C–N coupling reaction conditions using LiOTMS as the base. The large dataset enabled the systematic evaluation of model performance using five different data-splitting strategies that were carefully designed to assess the models’ ability to both interpolate and extrapolate. The models exhibit high predictive performance across all splits as gauged by standard metrics. In addition, the models predicted with high accuracy the outcome of validation libraries that were outside the scope of the training set. Employing these models in the context of medicinal chemistry campaigns should result in significant enrichment of successful C–N couplings.}, archive = {J_JACS}, author = {Seung Kyun Ha and Dipannita Kalyani and Michael S. West and Jessica Xu and Yu-hong Lam and Thomas Struble and Spencer Dreher and Shane W. Krska and Stephen L. Buchwald and Klavs F. Jensen}, doi = {10.1021/jacs.5c00933}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19602--19613}, shortjournal = {J. Am. Chem. Soc.}, title = {Developing pharmaceutically relevant pd-catalyzed C–N coupling reactivity models leveraging high-throughput experimentation}, volume = {147}, year = {2025}, }
• (2025). Microdroplet surface drives and accelerates proton-controlled, size-dependent nitrate photolysis. JACS, 147(23), 19595--19601. (www)

  @article{ , abstract = {Particulate nitrate photolysis regenerates reactive oxidized nitrogen species (HONO and NO x ) in the atmosphere, influencing tropospheric ozone, atmospheric oxidation capacity, and particulate matter formation. However, reported nitrate photolysis rates vary by orders of magnitude, and the roles of protons and the air–water interface in accelerating nitrate photolysis in deliquesced aerosols (i.e., microdroplets) remain unclear. Using confocal Raman spectroscopy and aerosol optical tweezer, we measured nitrate photolysis rate coefficients ( j ) in microdroplets, ranging from 5.28 × 10 –8 to 9.07 × 10 –6 s –1 , depending on pH (3.2–7.4) and radius (3.7 μm to 6.0 mm). j remained pH-independent under proton-sufficient conditions (pH < 6.5) but decreased with increasing pH under proton-deficient conditions (pH > 6.5), resolving discrepancies in previous studies. Moreover, we identified a tipping-point radius ( r * = 706 μm), below which j scales inversely with the droplet radius and above which j plateaus at the aqueous bulk value (6.73 ± 2.12 × 10 –8 s –1 ). These findings demonstrate that nitrate photolysis occurs predominantly at the air–water interface in microdroplets. With the atmospheric aerosol pH and radii typically below these tipping points (pH* = 6.5, r * = 706 μm), the surface-driven size-dependent photolysis likely explains the variations in atmospheric particulate nitrate photolysis rates.}, archive = {J_JACS}, author = {Xiaowu Zhang and Qishen Huang and Yu-Xin Liu and Jiayi Yin and Shu-Feng Pang and Pai Liu and Yun-Hong Zhang and Maofa Ge}, doi = {10.1021/jacs.5c00720}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19595--19601}, shortjournal = {J. Am. Chem. Soc.}, title = {Microdroplet surface drives and accelerates proton-controlled, size-dependent nitrate photolysis}, volume = {147}, year = {2025}, }
• (2025). Cooperative Organosulfur/Photoredox catalysis enables radical-polar crossover C(sp3)–N coupling via inner-sphere electron shuttling. JACS, 147(23), 19583--19594. (www)

  @article{ , abstract = {Radical-polar crossover (RPC) is a valuable mechanistic tool for revitalizing traditional radical and polar chemistries by integrating them. However, transitioning from radical to polar pathways across multiple redox events requires precise redox potential matching between the reaction components (catalysts and substrates), which inherently limits the scope of these transformations. Here, we present a cooperative catalytic platform that diverts the key RPC mechanism from outer-sphere to inner-sphere manifolds, enabling C(sp 3 )–N coupling of redox active esters with otherwise oxidizable (hetero)arylamines. The key to success is the identification of organosulfur catalyst capable of selectively shuttling electrons between the photocatalyst and the incipient radical in preference to competing arylamine oxidation. Experimental and computational studies reveal that the tailored organosulfur catalyst plays a crucial role in steering the post-radical generation steps to guide the desired reaction trajectory for C(sp 3 )–N bond formation. This method displays good functional group compatibility and chemoselectivity, providing an efficient route to functionally rich secondary and tertiary arylamines. The virtue of this method was further demonstrated by late-stage applications for synthesizing medically relevant nitrogen-containing compounds.}, archive = {J_JACS}, author = {Youngeun Hong and Changkyu Park and Junseong Jang and Minseok Oh and Dongwook Kim and Seunghoon Lee and Seung Youn Hong}, doi = {10.1021/jacs.5c00352}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19583--19594}, shortjournal = {J. Am. Chem. Soc.}, title = {Cooperative Organosulfur/Photoredox catalysis enables radical-polar crossover C(sp3)–N coupling via inner-sphere electron shuttling}, volume = {147}, year = {2025}, }
• (2025). On-surface synthesis of a large-scale 2D MOF with competing π–d Ferromagnetic/Antiferromagnetic order. JACS, 147(23), 19575--19582. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) represent an interesting class of versatile materials with important properties, including magnetism. However, the synthesis of atomically precise large-scale 2D MOFs with nontrivial strong magnetic coupling represents a current research challenge. In this regard, we report on the synthesis of a high-quality large-scale 2D MOF, with strong π–d magnetic exchange coupling. To this aim, we present a new two-step synthetic approach that consists of the initial formation of an extended supramolecular organic framework on a Au(111) surface, establishing the large-scale order of organic ligands and their subsequent metalation by single cobalt atoms assisted by annealing. Moreover, we show that the usage of radical asymmetric organic ligands enables us to form a magnetic 2D MOF with strong π–d electron interactions. According to the multireference calculations, the 2D MOF shows complex spin interactions beyond the traditional superexchange mechanism, with the interplay between antiferromagnetic and ferromagnetic couplings. We anticipate that this synthetic strategy can be adapted to different approaches, such as liquid interfaces or insulating substrates, to synthesize high-quality 2D MOFs. Accompanied by the high control with atomic precision over the magnetic properties of the ligands and metals, this approach enables the formation of large-scale 2D MOFs with complex spin interactions, which will open new avenues in the field of 2D magnetic materials.}, archive = {J_JACS}, author = {Federico Frezza and Manish Kumar and Ana Sánchez-Grande and Diego Soler-Polo and Manuel Carrera and Oleksandr Stetsovych and Pingo Mutombo and David Curiel and Pavel Jelínek}, doi = {10.1021/jacs.4c17993}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19575--19582}, shortjournal = {J. Am. Chem. Soc.}, title = {On-surface synthesis of a large-scale 2D MOF with competing π–d Ferromagnetic/Antiferromagnetic order}, volume = {147}, year = {2025}, }
• (2025). Water cooperativity impacts aromatic interactions in the aggregation of benzene with water. JACS, 147(23), 19568--19574. (www)

  @article{ , abstract = {The interactions between water and aromatic rings are pervasive across various scientific and technological disciplines, including biochemistry, materials science, and environmental chemistry. In this study, we combine broadband rotational spectroscopy and quantum-chemical calculations to reveal detailed structural and binding motifs in the aggregation of benzene, as the prototypical aromatic molecule, in the presence of a few water molecules. The benzene dimer and trimer structures with up to two water molecules are conclusively identified through isotopic substitution. We observe that the π-stacking interactions are substituted by more favorable CH···π contacts, allowing the insertion of water molecules acting as bridges between aromatic rings. This induces a shortening of the O···O distances for the complexes with two water molecules compared to that of the isolated water dimer. A many-body decomposition analysis of the interaction energy reveals the interactions of water with the aromatic partners through three-body contributions. While in the prototypical hydrogen-bonded pure water clusters this contribution amounts to 20–25% of the total interaction energy, we observe a significant contribution on the order of 10% in the interactions with the benzene rings. These results experimentally rationalize the binding strength of π-systems with water.}, archive = {J_JACS}, author = {Amanda L. Steber and Farha S. Hussain and Alberto Lesarri and Timothy S. Zwier and Brooks H. Pate and Luca Evangelisti and Cristóbal Pérez}, doi = {10.1021/jacs.4c17315}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19568--19574}, shortjournal = {J. Am. Chem. Soc.}, title = {Water cooperativity impacts aromatic interactions in the aggregation of benzene with water}, volume = {147}, year = {2025}, }
• (2025). Enantioselective β-C(sp3)–H nucleophilic tosylation of native amides: A synthetic platform for chiral methyl stereocenters. JACS, 147(23), 19559--19567. (www)

  @article{ , abstract = {Enantioselective oxygenation of unactivated C(sp 3 )–H bonds via asymmetric metalation remains an unsolved challenge. Herein we report the development of a Pd-catalyzed, enantioselective C(sp 3 )–H tosylation of native amides with NaOTs as the nucleophile, representing a rare example of enantioselective C–H functionalization with a nucleophilic coupling partner. High enantioselectivity in this reaction is achieved by chiral monoprotected amino sulfonamide (MPASA) ligands. Substantial enhancement of the enantioselectivity by silver salt additives was also observed. Through desymmetrization of the readily available isopropyl moiety, structurally diverse β-tosylated amides bearing an α-methyl stereocenter were obtained with high yield and enantioselectivity, which complements the current enzymatic method for making Roche ester chiral synthon. The tosylated products are highly versatile chiral building blocks for further diversifications with nitrogen, oxygen, and other nucleophiles, thus providing a platform for constructing chiral methyl stereocenters.}, archive = {J_JACS}, author = {Yuxin Ouyang and D. Quang Phan and Nikita Chekshin and Yi-Hao Li and Jennifer X. Qiao and Martin D. Eastgate and Jin-Quan Yu}, doi = {10.1021/jacs.4c17267}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19559--19567}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective β-C(sp3)–H nucleophilic tosylation of native amides: A synthetic platform for chiral methyl stereocenters}, volume = {147}, year = {2025}, }
• (2025). A multi-threshold micelle improves tumor accumulation and STING immunotherapy. JACS, 147(23), 19547--19558. (www)

  @article{ , abstract = {Stimulator of interferon genes (STING) is a critical innate immune protein that potentiates anticancer immunity. An adjuvanted micelle, PC7A, directly binds to STING and coordinates robust immune signaling after local tumor delivery but is not optimized for intravenous administration. To improve systemic delivery, we engineered a hybrid, STING-activating micelle (HySTING) composed of an immune-stimulating polymer, PEG- b -PC7A (p K a = 6.9), and a secondary carrier polymer with a lower p K a . HySTING variants (HySTING 6.2 , HySTING 5.2 , and HySTING 4.2 ─subscript denotes secondary p K a ) show stepwise ultra-pH-sensitivity at each polymer’s individual p K a despite forming a single micellar architecture. HySTING micelles maintain the pharmacological properties of PC7A (i.e., STING-activation and membrane-destabilization) in bone marrow-derived monocytes and cancer cell lines, respectively. In mice, the hybrid formulations drastically improve blood circulation half-life from <1 h (PC7A) to 18 h (HySTING 5.2 ) after intravenous administration. The improved circulation results in significantly higher tumor accumulation of HySTING 6.2 (17-fold) and HySTING 5.2 (6-fold) as compared to PC7A nanoparticles. Further, we screened a panel of cyclic dinucleotides (CDNs) and discovered thiol substitutions in CDN linkers improved micelle encapsulation and stability. We identified a HySTING IACS–8803 formulation with improved tumor growth inhibition in a CT26 murine colon carcinoma model and synergy with anti-programmed cell death-1 (αPD-1) antibody. Overall, the multithreshold pH-sensitivity of HySTING improves tumor biodistribution and efficacy, enabling intravenous STING immunotherapy against cancer.}, archive = {J_JACS}, author = {Zachary T. Bennett and Animeshasavithri Krishnamurthy and Shuyue Ye and Vijay S. Basava and Qiang Feng and Gang Huang and Baran D. Sumer and Jinming Gao}, doi = {10.1021/jacs.4c17082}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19547--19558}, shortjournal = {J. Am. Chem. Soc.}, title = {A multi-threshold micelle improves tumor accumulation and STING immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Stereoselectivity of aminoacyl-RNA loop-closing ligation. JACS, 147(23), 19539--19546. (www)

  @article{ , abstract = {The origin of amino acid homochirality remains an unresolved question in the origin of life. The requirement of enantiopure nucleotides for nonenzymatic RNA copying strongly suggests that the homochirality of nucleotides and RNA arose early. However, this leaves open the question of whether and how homochiral RNA subsequently imposes biological homochirality on other metabolites, including amino acids. Previous studies have reported moderate stereoselectivity for various aminoacyl-RNA transfer reactions. Here, we examine aminoacyl-RNA loop-closing ligation, a reaction that “captures” aminoacylated RNA in a stable phosphoramidate product, such that the amino acid bridges two nucleotides in the RNA backbone. We find that the rate of this reaction is much higher for RNA aminoacylated with L-amino acids than for RNA aminoacylated with D-amino acids. We present an RNA sequence that nearly exclusively captures L-amino acids in loop-closing ligation. Finally, we demonstrate that ligation of aminoacyl-L-RNA results in an inverse stereoselectivity for D-amino acids. The observed stereochemical link between D-RNA and L-amino acids in the synthesis of RNA stem-loops containing bridging amino acids constitutes a stereoselective structure-building process. We suggest that this process led to a selection for the evolution of aminoacyl-RNA synthetase ribozymes that were selective for L-amino acids, thereby setting the stage for the subsequent evolution of homochiral peptides and, ultimately, protein synthesis.}, archive = {J_JACS}, author = {Shannon Kim and Marco Todisco and Aleksandar Radakovic and Jack W. Szostak}, doi = {10.1021/jacs.4c16905}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19539--19546}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereoselectivity of aminoacyl-RNA loop-closing ligation}, volume = {147}, year = {2025}, }
• (2025). On-surface synthesis of a ferromagnetic molecular spin trimer. JACS, 147(23), 19530--19538. (www)

  @article{ , abstract = {Triangulenes are prototypical examples of open-shell nanographenes. Their magnetic properties, arising from the presence of unpaired π electrons, can be extensively tuned by modifying their size and shape or by introducing heteroatoms. Different triangulene derivatives have been designed and synthesized in recent years thanks to the development of on-surface synthesis strategies. Triangulene-based nanostructures with polyradical character, hosting several interacting spin units, can be challenging to fabricate but are particularly interesting for potential applications in carbon-based spintronics. Here, we combine pristine and N-doped triangulenes into a more complex nanographene, TTAT , predicted to possess three unpaired π electrons delocalized along the zigzag periphery. We generate the molecule on a Au(111) surface and detect direct fingerprints of multiradical coupling and high-spin state using scanning tunneling microscopy and spectroscopy. With the support of theoretical calculations, we show that its three radical units are localized at distinct parts of the molecule and couple via symmetric ferromagnetic interactions, which result in a S = 3/2 ground state, thus demonstrating the realization of a molecular ferromagnetic Heisenberg spin trimer.}, archive = {J_JACS}, author = {Alessio Vegliante and Manuel Vilas-Varela and Ricardo Ortiz and Francisco Romero Lara and Manish Kumar and Lucía Gómez-Rodrigo and Stefano Trivini and Fabian Schulz and Diego Soler-Polo and Hassan Ahmoum and Emilio Artacho and Thomas Frederiksen and Pavel Jelínek and Jose Ignacio Pascual and Diego Peña}, doi = {10.1021/jacs.4c15736}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19530--19538}, shortjournal = {J. Am. Chem. Soc.}, title = {On-surface synthesis of a ferromagnetic molecular spin trimer}, volume = {147}, year = {2025}, }
• (2025). Bridged boranoanthracenes: Precursors for free oxoboranes through aromatization-driven oxidative extrusion. JACS, 147(23), 19520--19529. (www)

  @article{ , abstract = {We introduce a novel class of boranobornadiene derivatives, termed boranoanthracene, along with an in-depth study of their structures and reactivities. Using these versatile precursors, we propose a fundamentally novel mechanism for generating free oxoborane species. This pathway enables the formation of aminoxoborane species, which are rarely reported in the literature. The proposed mechanism unfolds via the coordination of an oxygen -Lewis base (dimethyl sulfoxide) to the boron center, triggering a fragmentation cascade propelled by oxidative aromatization. A detailed experimental analysis, NMR measurements, and DFT calculations provide a strong evidence supporting our findings. We explored three distinct reactivities of these species: first, the insertion of oxoborane species into B–C bonds, representing, to the best of our knowledge, the first example of this reactivity. Second, we demonstrated the [3 + 2] cycloaddition reaction of oxoboranes with nitrones, offering viable access to new boranoheterocycles. Third, we reported the first example of a [5 + 2] cycloaddition between oxoboranes and azomethine imines, leading to the formation of a seven-membered boracycle. The diverse reactivities and facile generation of aminoxoboranes highlight their immense potential as versatile tools in organic chemistry.}, archive = {J_JACS}, author = {Stav Deri and Moran Feller and Shibaram Panda and Batya Blank and Mark A. Iron and Yael Diskin-Posner and Liat Avram and Linda J. W. Shimon and Rakesh Mondal and Samer Gnaim}, doi = {10.1021/jacs.4c15496}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19520--19529}, shortjournal = {J. Am. Chem. Soc.}, title = {Bridged boranoanthracenes: Precursors for free oxoboranes through aromatization-driven oxidative extrusion}, volume = {147}, year = {2025}, }
• (2025). Tailoring chloride solid electrolytes for reversible redox. JACS, 147(23), 19508--19519. (www)

  @article{ , abstract = {Solid-state electrolytes enable next-generation batteries that can theoretically deliver higher energy densities while improving device safety. However, when fabricating cathodes for all-solid-state batteries, solid-state electrolytes must be combined with the active materials in high weight fractions in order to achieve sufficient ionic percolation within the cathode composite. This requirement drastically hinders the practicality of solid-state batteries as the solid-state electrolyte is conventionally designed to be electrochemically inactive and is effectively electrochemical “dead weight”, lowering both the gravimetric and volumetric energy density of the cell. In this work, a well-known solid-state electrolyte, Na 2 ZrCl 6 , is modified by aliovalent substitution of inactive Zr 4+ cations with redox-active M 5+ ( M = Nb or Ta) cations to create a series of Na 2– x M x Zr 1– x Cl 6 solid solutions that possess both high ionic conductivities and active sites for Na + storage. The Na + intercalation mechanisms of these solid-solution materials, in addition to those of the Na M Cl 6 end-member materials, are elucidated in this work. It was discovered that both the niobium- and tantalum-containing chlorides exhibit rather high electrochemical potentials (2.2–2.8 V vs Na 9 Sn 4 ), making them ideal catholytes to pair with commonly used oxide cathode materials like NaCrO 2 . This synergistic pairing leads to a cathode composite with an 83–102% increase in energy density and 39–81% improvement in areal discharge capacity compared to a redox-innocent solid electrolyte. This approach highlights the benefits of designing and employing redox-active solid-state electrolytes that can reversibly intercalate charge-carrying cations, opening up a broad new avenue for solid-state electrolyte discovery and solid-state battery design.}, archive = {J_JACS}, author = {Phillip Ridley and George Duong and Sarah L. Ko and Jin An Sam Oh and Grayson Deysher and Kent J. Griffith and Ying Shirley Meng}, doi = {10.1021/jacs.4c14670}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19508--19519}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailoring chloride solid electrolytes for reversible redox}, volume = {147}, year = {2025}, }
• (2025). Symmetry and asymmetry in mutations and memory retention during the evolutionary growth of carbon nanotubes. JACS, 147(23), 19498--19507. (www)

  @article{ , abstract = {Symmetry is a motif featured in almost all areas of science, and understanding the mechanism of symmetry breaking is challenging. Similar to mutations that disrupt symmetry in evolution, defects in materials offer insight into symmetry breaking. Here, we investigate symmetry in intragenerational mutations and symmetry breaking in transgenerational mutations in the evolutionary growth system of carbon nanotubes (CNTs). Mutations caused by pentagon–heptagon (5–7) pairs in different conformations shorten the lifespans of single-walled carbon nanotubes (SWNTs) by acting as time markers during growth. Symmetric distributions are observed for intragenerational mutations from ( n , m ) to ( n + i , m – i ) (where i ∈ caslon Z) with different appearance orders of pentagon and heptagon. Such symmetry breaks occur in transgenerational mutations. Intragenerational mutations occur multiple times on a SWNT, oscillating regularly between i and – i until termination occurs. These types and effects are retained in the form of memory to encode SWNTs during subsequent growth, resulting in a length reduction after each mutation. Our results provide a profound understanding of symmetry breaking and memory retention and offer guidance for the controlled synthesis of materials.}, archive = {J_JACS}, author = {Lin Chai and Yaxiong Yu and Hao Xiong and Xiao Chen and Wenjie Zhang and He Ren and Yaxin Jiang and Yukang Zhu and Chenxi Zhang and Zhenxing Zhu and Qinghong Yuan and Fei Wei}, doi = {10.1021/jacs.4c10400}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19498--19507}, shortjournal = {J. Am. Chem. Soc.}, title = {Symmetry and asymmetry in mutations and memory retention during the evolutionary growth of carbon nanotubes}, volume = {147}, year = {2025}, }
• (2025). Iridium-catalyzed asymmetric hydrogenation of aryl(4-hydroxyphenyl)ketones. JACS, 147(23), 19491--19497. (www)

  @article{ , abstract = {Asymmetric hydrogenation of diaryl ketones is challenging, particularly when the two aromatic rings have very similar steric hindrances, such as those in para -substituted diaryl ketones. In this study, we developed a catalyst that can distinguish between para -hydroxyl phenyl and other para -substituted aryl rings in diaryl ketones. Using this catalyst, a variety of chiral diarylcarbinols were synthesized with high yield and high enantioselectivity. DFT studies revealed that noncovalent interactions such as π–π stacking and C–H···π interactions between the substrate and catalyst play a crucial role in controlling the stereochemistry.}, archive = {J_JACS}, author = {Zheng Wang and Li-Yuan Xue and Yue Xu and Qi-Lin Zhou}, doi = {10.1021/jacs.5c06149}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19491--19497}, shortjournal = {J. Am. Chem. Soc.}, title = {Iridium-catalyzed asymmetric hydrogenation of aryl(4-hydroxyphenyl)ketones}, volume = {147}, year = {2025}, }
• (2025). Retrofitting PMMA with a thermal trigger for efficient depolymerization. JACS, 147(23), 19485--19490. (www)

  @article{ , abstract = {This work reports an efficient closed-loop bulk depolymerization method applicable to commercially available PMMA. Acid hydrolysis (<10%) and subsequent esterification with N -hydroxyphthalimide are used to incorporate a thermally sensitive trigger that allows efficient depolymerization of PMMA at a temperature lower than conventionally employed. We showed that this strategy is applicable to model PMMA homopolymers with molecular weights ranging from 28 to 1140 kg/mol. The same method was used for efficient bulk depolymerization (∼70%) of commercially available PMMA ( M n = 439 kg/mol), supporting the efficacy of this work for practical applications. Furthermore, we demonstrate that this method can be leveraged to generate depolymerizable polymer networks. The depolymerization approach reported here holds potential to mitigate polymethacrylate waste and maintain a sustainable polymer economy.}, archive = {J_JACS}, author = {Rhys W. Hughes and Tanmoy Maity and Timothée Sergent and Alex H. Balzer and Isabella S. Zastrow and Mansi S. Patel and Leah M. Baker and Payson M. Keown and LaShanda T. J. Korley and Brent S. Sumerlin}, doi = {10.1021/jacs.5c05879}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19485--19490}, shortjournal = {J. Am. Chem. Soc.}, title = {Retrofitting PMMA with a thermal trigger for efficient depolymerization}, volume = {147}, year = {2025}, }
• (2025). Formally stereoretentive SN1 reactions of homoallylic tertiary alcohols via nonclassical carbocation. JACS, 147(23), 19478--19484. (www)

  @article{ , abstract = {We present a stereoretentive nucleophilic substitution of homoallylic tertiary alcohols via the formation of a nonclassical cyclopropyl carbinyl (CPC) carbocation intermediate. This strategy enables the creation of highly congested tertiary centers with preserved stereocontrol, addressing the typical challenges of carbocation instability and reactivity in S N 1 mechanisms. The stabilization of the CPC intermediate is crucial for achieving precise regio- and stereoselectivity, significantly enhancing the utility of S N 1-type mechanisms in complex molecule synthesis.}, archive = {J_JACS}, author = {Kaushalendra Patel and Leonie Wilczek and Francesco Calogero and Ilan Marek}, doi = {10.1021/jacs.5c05680}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19478--19484}, shortjournal = {J. Am. Chem. Soc.}, title = {Formally stereoretentive SN1 reactions of homoallylic tertiary alcohols via nonclassical carbocation}, volume = {147}, year = {2025}, }
• (2025). Photoelectrochemical tandem chlorination of sp3 C–H bond in Seawater/Chloroform two-phase electrolyte system by ti-doped Fe2O3 photoanode. JACS, 147(23), 19472--19477. (www)

  @article{ , abstract = {C–H bond activation is a fundamental challenge in organic synthesis, and various routes have been explored. Among them, halogenation has played an important role in producing valuable intermediates. We report a novel photoelectrochemical (PEC) tandem C–H chlorination using a Ti-doped Fe 2 O 3 (Ti:Fe 2 O 3 ) photoanode in a two-phase electrolyte system consisting of natural seawater and a chloroform organic phase. This system enables the in situ generation of Cl 2 via the chlorine evolution reaction (CER) with near 100% Faradaic efficiency (FE) while suppressing the competing oxygen evolution reaction (OER). The generated Cl 2 undergoes photolytic cleavage, forming chlorine radicals that selectively chlorinate sp 3 C–H bonds in toluene, cyclohexane, and ethylbenzene with 100% regioselectivity. This work demonstrates the feasibility of seawater-based PEC halogenation and provides a sustainable strategy for selective C–H functionalization in organic synthesis.}, archive = {J_JACS}, author = {Sang Youn Chae and Adeel Mehmood and Eun Duck Park}, doi = {10.1021/jacs.5c05100}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19472--19477}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoelectrochemical tandem chlorination of sp3 C–H bond in Seawater/Chloroform two-phase electrolyte system by ti-doped Fe2O3 photoanode}, volume = {147}, year = {2025}, }
• (2025). A nitrilium-type N-heterocyclic aryne. JACS, 147(23), 19465--19471. (www)

  @article{ , abstract = {The first solution-phase synthesis and reactivity of a nitrilium-type N -hetaryne are described. The 1,2-azaborine-derived 1,6-BN-aryne 2 exhibits [4 + 2], [3 + 2], and [2 + 2] cycloadditions and electrophilic aromatic substitution (EAS) reactivity. The observed regio- and diastereoselectivities of the cycloaddition and EAS products are consistent with a polarized aryne/nitrilium species. The free 1,6-BN-aryne 2 was isolated and characterized under matrix isolation conditions. A Lewis structure description where the 1,6-BN-aryne 2 resonates between two limiting (ketenimine (dominant) vs nitrilium) forms is consistent with DFT calculations. New 1,2-azaborine structures that are functionalized at the C6- and N-positions, including highly strained derivatives that were previously not accessible, can now be accessed using 1,6-BN-aryne 2 as a versatile synthetic building block.}, archive = {J_JACS}, author = {Marisol Alvarado and Lauren Tran and Christina Tönshoff and Bo Li and Clovis Darrigan and Hugues Preud’homme and Anna Chrostowska and Holger F. Bettinger and Shih-Yuan Liu}, doi = {10.1021/jacs.5c05146}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19465--19471}, shortjournal = {J. Am. Chem. Soc.}, title = {A nitrilium-type N-heterocyclic aryne}, volume = {147}, year = {2025}, }
• (2025). Stereodivergent four-component reactions via rh-carbynoids. JACS, 147(23), 19458--19464. (www)

  @article{ , abstract = {Multicomponent reactions (MCRs) provide a robust platform for the modular assembly of structurally complex molecules, while higher-order MCRs (≥4 components) exponentially expand the accessible chemical space. Although Rh-carbynoids exhibit significant potential for developing higher-order MCRs due to their unique reactivity, their application in asymmetric four-component reactions (4CRs) has been hindered by competing nucleophilic reactivities and stereochemical control. Herein, we overcome these challenges by integrating N - and C -nucleophiles and report an asymmetric 4CR involving hypervalent iodine diazo reagents, carbamates, N,N -dialkylanilines, and imines. This strategy represents the first asymmetric 4CR utilizing Rh-carbynoids, achieving the sequential formation of C(sp 3 )–N, C(sp 3 )–C(sp 2 ), and C(sp 3 )–C(sp 3 ) bonds at a single carbon center. The method provides stereodivergent access to α,β-diamino-3-arylpropanoic acid derivatives bearing two contiguous stereocenters with good yields and exceptional enantioselectivity.}, archive = {J_JACS}, author = {Jian Luo and Yinwu Li and Haiqing Wang and Gengxin Liu and Zhenghui Kang and Yu Qian and Zhuofeng Ke and Xiang Fu and Wenhao Hu}, doi = {10.1021/jacs.5c04924}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19458--19464}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereodivergent four-component reactions via rh-carbynoids}, volume = {147}, year = {2025}, }
• (2025). Persistent boryl radicals as highly reducing photoredox catalysts for debrominative borylations. JACS, 147(23), 19450--19457. (www)

  @article{ , abstract = {Organic free radicals are commonly perceived to be highly reactive species with short lifetimes, yet there are many examples that defy this convention by displaying remarkable stability. Although these persistent radicals can be relatively unreactive in their ground states, photoexcitation can generate highly reactive excited states. Despite this, they have found limited application as reagents or catalysts in photochemical reactions. Here we report the identification of persistent boryl-bipyridine radicals that function as highly reducing photoredox catalysts. These radicals, which are generated by simply mixing a bipyridine with a diboron reagent, were found to possess excited state reduction potentials that rival the most powerful photoreductants reported to date. We show that this class of doublet state photoredox catalyst can promote borylations of alkyl bromides and various other transformations.}, archive = {J_JACS}, author = {Jingjing Wu and Hui Wang and Huaquan Fang and Kevin C. Wang and Deborin Ghosh and Valerio Fasano and Adam Noble and Varinder K. Aggarwal}, doi = {10.1021/jacs.5c03864}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19450--19457}, shortjournal = {J. Am. Chem. Soc.}, title = {Persistent boryl radicals as highly reducing photoredox catalysts for debrominative borylations}, volume = {147}, year = {2025}, }
• (2025). Molecular steganography using multistate photoswitchable hydrazones. JACS, 147(23), 19444--19449. (www)

  @article{ , abstract = {The development of photochromic compounds that can have multiaddressable and -stable states is desirable for imparting multistate responses in soft materials. Here, we report on two such photochromes, composed of para -NO 2 - and pentafluoro-phenyl functionalized hydrazones connected nonsymmetrically through an isosorbide linker, which exhibit highly efficient, orthogonal, and sequential switching. We took advantage of these properties and the multistability of the four different isomeric states (i.e., ZZ , ZE , EZ , and EE ) to control the photophysical properties of nematic liquid crystals (LCs). Doping the switches into 5CB, followed by switching to the EE state, triggered an unusual cholesteric to focal conic phase transition. We used this property to modulate the opacity of the LC films, resulting in a molecular steganography application.}, archive = {J_JACS}, author = {Brandon Balamut and Ivan Aprahamian}, doi = {10.1021/jacs.5c03668}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19444--19449}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular steganography using multistate photoswitchable hydrazones}, volume = {147}, year = {2025}, }
• (2025). Rapid oxygen atom transfer at a catalysis-relevant Ni(I)–Alkyl complex with N2O. JACS, 147(23), 19438--19443. (www)

  @article{ , abstract = {To improve our understanding of Ni-catalyzed alcohol formation with N 2 O, a catalytically relevant Ni(I)–alkyl was synthesized and characterized (EPR, NMR). The complex, prepared via comproportionation and transmetalation, reacted with N 2 O at ambient temperature within 1 min, producing alcohol and N 2 . This contrasts sharply with slower reactions of (bpy)NiEt 2 (12 h) and catalytic systems (22 h). Theoretical studies suggest a stepwise organometallic Baeyer–Villiger mechanism via a Ni(II)–oxyl intermediate. The high reactivity of Ni(I)–alkyl challenges the notion of N 2 O’s inertness, highlighting its potential as a versatile oxidant in synthesis.}, archive = {J_JACS}, author = {Ana Mateos-Calbet and Paolo Cleto Bruzzese and Markella Aliki Mermigki and Alexander Schnegg and Dimitrios A. Pantazis and Josep Cornella}, doi = {10.1021/jacs.5c03351}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19438--19443}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid oxygen atom transfer at a catalysis-relevant Ni(I)–Alkyl complex with N2O}, volume = {147}, year = {2025}, }
• (2025). Pushing the boundaries of resolution in solid-state nuclear magnetic resonance of biomolecules with 160 kHz magic-angle spinning. JACS, 147(23), 19433--19437. (www)

  @article{ , abstract = {We present ultrafast magic-angle spinning (MAS) at 160 kHz in solid-state nuclear magnetic resonance (NMR), demonstrating unprecedented spectral quality and coherence lifetimes in proton-detected experiments on biomolecular systems. By optimizing experimental and sample conditions and utilizing advanced filling and handling tools, we achieve superior resolution on both microcrystalline and membrane-reconstituted proteins, paving the way for new applications in structural biology.}, archive = {J_JACS}, author = {Zhiyu Sun and Claire Ollier and Adrienn Rancz and Batiste Thienpont and Kristof Grohe and Lukas Becker and Armin Purea and Frank Engelke and Sebastian Wegner and James Sturgis and Tatyana Polenova and Tanguy Le Marchand and Guido Pintacuda}, doi = {10.1021/jacs.5c02466}, journal = {Journal of the American Chemical Society}, month = {6}, number = {23}, pages = {19433--19437}, shortjournal = {J. Am. Chem. Soc.}, title = {Pushing the boundaries of resolution in solid-state nuclear magnetic resonance of biomolecules with 160 kHz magic-angle spinning}, volume = {147}, year = {2025}, }
• (2025). Correction to “Hierarchical copper with inherent hydrophobicity mitigates electrode flooding for high-rate CO2 electroreduction to multicarbon products”. JACS, 147(22), 19432. (www)

  @article{ , archive = {J_JACS}, author = {Zhuang-Zhuang Niu and Fei-Yue Gao and Xiao-Long Zhang and Peng-Peng Yang and Ren Liu and Li-Ping Chi and Zhi-Zheng Wu and Shuai Qin and Xingxing Yu and Min-Rui Gao}, doi = {10.1021/jacs.5c05166}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19432}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Hierarchical copper with inherent hydrophobicity mitigates electrode flooding for high-rate CO2 electroreduction to multicarbon products”}, volume = {147}, year = {2025}, }
• (2025). Stereoselective 1,3-cyclotelomerization of butadiene with dienophiles under nickel catalysis. JACS, 147(22), 19421--19431. (www)

  @article{ , abstract = {The discovery of new chemoselectivity with readily accessible chemicals is important to expand the reaction space for modern chemistry. For dienes and dienophiles, most people will naturally use them to carry out the classic Diels–Alder reaction to construct six-membered cyclic compounds. Here, we demonstrated a chemoselective coupling of butadiene with dienophiles through stereoselective 1,3-cyclotelomerization. By utilizing robust Ni/IPr catalysis, valuable bicyclic products were created with high regio- and chemoselectivities under mild conditions. Asymmetric cyclotelomerization enabled by the chiral NHC ligand was also performed, generating enantioenriched bicyclic compounds. The reaction mechanism was also investigated via experiments and density functional theory (DFT) calculations, which indicate that the reaction might start with oxidative cyclometalation between two molecules of 1,3-diene and Ni(0) species, followed by a [3 + 2]-cycloaddition between nickelacycle and dienophile. The products can undergo a variety of intricate transformations, which emphasizes the potential applications of this strategy. It is hoped that the discovery of this protocol will further inspire people to rethink classic organic reactions.}, archive = {J_JACS}, author = {Ying Li and Li-Ming Zhang and Xue-Ting Li and Heng Liu and Ting-Ting Song and Ding-Wei Ji and Qing-An Chen}, doi = {10.1021/jacs.5c06414}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19421--19431}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereoselective 1,3-cyclotelomerization of butadiene with dienophiles under nickel catalysis}, volume = {147}, year = {2025}, }
• (2025). Current amplification driven by reversible redox cycling in a thin-layer reactor using boron-doped diamond electrodes. JACS, 147(22), 19413--19420. (www)

  @article{ , abstract = {Current amplification plays an essential role in electrochemistry by improving the productivity of the electrochemical production of industrial materials and enhancing the sensitivity of environmental and biomedical sensing. Various approaches have been explored to enhance steady-state current, such as thin-layer reactors, microelectrodes, and rotating-disk electrodes. Thin-layer reactors have several advantages, including the ability to generate larger currents using bulk-sized electrodes and simple fabrication processes. In this study, we developed a thin-layer reactor using boron-doped diamond (BDD) electrodes with an interelectrode distance of several tens of micrometers, which is comparable to the thickness of a diffusion layer. The use of BDD electrodes enabled reversible redox cycling in the thin-layer reactor, resulting in more than 2-fold current amplification compared to conventional thin-layer reactors. This effect was observed only when BDD electrodes were used for both the working and counter electrodes, and the interelectrode distance was 200 μm and below. Based on the experimental results of the present study, we propose a novel concentration profile model and reaction mechanism for BDD thin-layer reactors that cannot be explained by conventional thin-layer reactor models. The model involves a three-step reversible redox cycle: (1) consumption of reduced species and generation of oxidized species at the working electrode, (2) regeneration of reduced species at the counter electrode, and (3) resupply of reduced species to the working electrode. The BDD thin-layer reactor also demonstrated twice the sensitivity, and a detection limit one-tenth those of the conventional bulk-reactor in electrochemical detection based on the proposed model.}, archive = {J_JACS}, author = {Kana Asai and Atsushi Otake and Keita Ando and Yasuaki Einaga}, doi = {10.1021/jacs.5c06207}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19413--19420}, shortjournal = {J. Am. Chem. Soc.}, title = {Current amplification driven by reversible redox cycling in a thin-layer reactor using boron-doped diamond electrodes}, volume = {147}, year = {2025}, }
• (2025). Unlocking epoxide radical anion reactivity for asymmetric cross-coupling by copper metallaphotoredox. JACS, 147(22), 19400--19412. (www)

  @article{ , abstract = {The ability to tame radical anions that feature both an unpaired spin and a charge is critical for synthetic chemistry, enabling the construction of diverse chemical bonds via unique reaction pathways and promoting advances in the area of synthesis. In this regard, C(sp 3 )-rich epoxide radical anions are particularly attractive but often elusive, highly reactive intermediates. Classic methods to access epoxide radical anions exploit single-electron chemistry by using dissolving alkali, sacrificial electrodes, or redox metals. However, these methods are often prohibitive because of reagent safety issues and over-reduction, limiting their wide implementation, especially in asymmetric synthesis. Herein, we realize a copper metallaphotoredox platform to unlock epoxide radical anion reactivity, allowing the controlled generation of epoxide radical anions and their enantioconvergent cross-coupling with diverse, readily available partners via distonic radical anion intermediates. These discoveries permit highly regio-, chemo-, and enantioselective hydrocyanation and hydroalkynylation, thereby providing a general solution to the challenge of epoxide radical anion-mediated enantioselective chemical diversification.}, archive = {J_JACS}, author = {Fan Teng and Zi-Qing Li and Zhi-Cheng Mao and Zhihan Zhang and Min Jiang and Wen-Jing Xiao and Jia-Rong Chen}, doi = {10.1021/jacs.5c05957}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19400--19412}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking epoxide radical anion reactivity for asymmetric cross-coupling by copper metallaphotoredox}, volume = {147}, year = {2025}, }
• (2025). Surface-controlled TiO2 nanocrystals with catalytically active single-site co incorporation for the oxygen evolution reaction. JACS, 147(22), 19391--19399. (www)

  @article{ , abstract = {The design of advanced electrocatalysts is often hindered by uncertainties in identifying and controlling the active surfaces and catalytic centers within heterogeneous materials. Here we present the synthesis of single-site Co catalysts, substitutionally doped into surface-controlled TiO 2 anatase nanocrystals, aimed at enhancing the oxygen evolution reaction (OER). Grand canonical quantum mechanics calculations reveal that the kinetics of the OER, following an adsorbate evolution mechanism, is markedly influenced by the coordination environment of Co. The simulations suggest significantly higher turnover frequencies when Co is doped into the (001) surface of TiO 2 compared to the (101) surface. Consistent with the computational findings, experimental results show that Co-doped TiO 2 (Co-TiO 2 ) nanoplates with selectively exposed {001} surfaces exhibit enhanced current densities and turnover frequencies compared to Co-TiO 2 nanobipyramids with {101} surfaces. This study highlights the synergy between theoretical calculations and precision synthesis in the development of more effective catalysts.}, archive = {J_JACS}, author = {Chang Liu and Soonho Kwon and Perrin Godbold and Grayson Johnson and Sooyeon Hwang and Chengjun Sun and Hua Zhou and William A. Goddard, III and Sen Zhang}, doi = {10.1021/jacs.5c05795}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19391--19399}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface-controlled TiO2 nanocrystals with catalytically active single-site co incorporation for the oxygen evolution reaction}, volume = {147}, year = {2025}, }
• (2025). Measurements of local pH gradients for electrocatalysts in the oxygen evolution reaction by electrochemiluminescence. JACS, 147(22), 19380--19390. (www)

  @article{ , abstract = {An accurate understanding of the mechanism of the oxygen evolution reaction (OER) is crucial for catalyst design in the hydrogen energy industry. Despite significant advancements in microscopic pH detection, selective, sensitive, speedy, and reliable detection of local pH gradients near the catalysts during the OER remains elusive. Here, we pioneer an electrochemiluminescence (ECL) method for local pH detection during the OER. For this purpose, a new class of ECL emitters based on ECL resonance energy transfer was theoretically predicted and facilely synthesized by grafting functional fluorescent dyes onto noble 2D carbon nitride. By positioning one of the as-prepared ECL emitters with pH-responsibility neighboring the OER catalysts, local pH gradient generation near the catalysts could be qualitatively measured in real-time with a subsecond resolution. It provided details of the reaction mechanism of the OER and unveiled the catalyst degrading pathway caused by proton accumulation. Besides, the average proton generation rate on the catalyst was also extractable from the local pH measurement as a quantitative descriptor of the OER reaction rate. Owing to the high designability of the grafting method, this study opens up new strategies for studying reaction mechanisms and detecting intermediates.}, archive = {J_JACS}, author = {Yu Wang and Sijia Zhou and Yongjun Zheng and Yongji Wang and Yuhua Hou and Kaiqing Wu and Chaofeng Huang and Songqin Liu and Yanfei Shen and Ran Chen and Yuanjian Zhang}, doi = {10.1021/jacs.5c04896}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19380--19390}, shortjournal = {J. Am. Chem. Soc.}, title = {Measurements of local pH gradients for electrocatalysts in the oxygen evolution reaction by electrochemiluminescence}, volume = {147}, year = {2025}, }
• (2025). Elucidating charge carrier reactivity, conversion, and degradation in n-doped oligo- and poly(benzodifurandione). JACS, 147(22), 19372--19379. (www)

  @article{ , abstract = {n-Doped poly(benzodifurandione) (n-PBDF) has gained significant attention due to its solution processability and high electrical conductivity. However, the nature of charge carriers in n-PBDF remains poorly understood. In this study, we investigated a series of oligo(benzodifurandiones) (BFD1, BFD2, and BFD3), using previously reported BFD1 and BFD2 alongside newly synthesized BFD3, with a particular focus on the charged species of BFD3. Neutral BFD3 was successfully reduced to its hydride-adduct anion (BFD3H – ), radical anion (BFD3 •– ), and dianion (BFD3 2– ), the latter two behaving similarly to polarons and bipolarons respectively in n-PBDF. We conducted a characterization of their optical, electrochemical, and structural properties, and examined their interconversion and reactivity. Mass spectrometry analysis and absorption spectroscopy revealed that the BFD3 2– backbone undergoes degradation when further reduced, with proposed structural assignments for several degradation products. Notably, similar reactivity and degradation pathways were also identified in the polymeric system n-PBDF. These findings provide critical insights into the stability and reactivity of n-type charge carriers in π-conjugated polymers, establishing a foundation for future strategies to optimize doping levels and mitigate degradation in n-type organic electronic materials.}, archive = {J_JACS}, author = {Jinhyo Hwang and Xiaojuan Ni and Michael F. Espenship and Kan Tang and Junxiang Zhang and Aniruddha Basu and Suman Kuila and Stephen Barlow and Seth R. Marder and Jean-Luc Brédas and Julia Laskin and Jianguo Mei}, doi = {10.1021/jacs.5c05722}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19372--19379}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating charge carrier reactivity, conversion, and degradation in n-doped oligo- and poly(benzodifurandione)}, volume = {147}, year = {2025}, }
• (2025). Controlling the conductivity of cyclo[8]pyrrole polyiodide cocrystals via minor substituent group changes. JACS, 147(22), 19364--19371. (www)

  @article{ , abstract = {Substituent group modifications can influence the conductivity of organic materials. However, achieving several orders of magnitude increases in conductivity through minor substituent changes remains a challenge. Here, we report the observation of such large changes in cocrystals of cyclo[8]pyrroles and polyiodides. Two cocrystals were prepared, one from all-ethyl-substituted cyclo[8]pyrrole ( 1 •+ ), which forms a 2D stacked structure [( 1 •+ ) 2 ⊃(I 7 ) − • (I 24 ) − ], and the other from a methyl–ethyl-substituted analogue ( 2 •+ ), which yields a 3D layered structure [ 2 •+ • (I 16 ) − ]. The methyl–ethyl-substituted cocrystal exhibited an approximately 1000-fold higher conductivity (6.1 × 10 –1 S/cm) than its all-ethyl counterpart (4.2 × 10 –4 S/cm). Cocrystal [ 2 •+ • (I 16 ) − ] demonstrated good stability, retaining the bulk of its conductivity after being exposed to air for four months or upon heating to 100 °C. The present findings highlight how substituent effects, a molecular feature readily amenable to modification, can have a profound effect on cocrystal conductivity. This work thus sets the stage for further optimization of high-performance organic conductors.}, archive = {J_JACS}, author = {Yu-Dong Yang and Mingwan Leng and Qian Zhang and Xingchen Jin and Calvin V. Chau and Jian Yang and Serhii Vasylevskyi and Graeme Henkelman and Han-Yuan Gong and Lei Fang and Jonathan L. Sessler}, doi = {10.1021/jacs.5c05723}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19364--19371}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlling the conductivity of cyclo[8]pyrrole polyiodide cocrystals via minor substituent group changes}, volume = {147}, year = {2025}, }
• (2025). One-for-all photoactivatable manganese-based carbon monoxide-releasing molecules (CORMs) for synergistic therapy of mycobacterial infection. JACS, 147(22), 19353--19363. (www)

  @article{ , abstract = {Tuberculosis presents a severe threat to human health. It is of crucial importance to develop novel and effective treatments to combat mycobacterial infections, especially those caused by drug-resistant bacteria. In this study, a tricarbonyl manganese(I) complex ( Mn-PTP ) was synthesized for the purpose of conducting synergistic therapy against mycobacterial infection. When subjected to white light irradiation, Mn-PTP generated multiple reactive species, including type I/II combined reactive oxygen species (ROS), carbon monoxide (CO), the toxic ligand PTP , and manganese oxides (MnO X ) with catalase-like ability. The antibacterial experiment demonstrated that irradiated Mn-PTP exhibited specific antibacterial effects on Mycobacterium smegmatis ( M. smegmatis ). It was found to cause damage to the bacterial membrane and effectively eradicate biofilms. Moreover, the in vivo experiment revealed that the photoactive Mn-PTP could promote the healing process of M. smegmatis -infected skin wounds. This study pioneers innovative frameworks for developing one-for-all small-molecule pharmaceuticals capable of enabling synergistic therapeutic strategies against mycobacterial infections.}, archive = {J_JACS}, author = {Yingru Lai and Liu Wang and Hongbiao Ma and Zhi Chen and Haorui Wu and Guoqing Wen and Xuan Wu and Bole Yu and Dan Li and Guotao Yuan and Huaiyi Huang and Pingyu Zhang}, doi = {10.1021/jacs.5c05490}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19353--19363}, shortjournal = {J. Am. Chem. Soc.}, title = {One-for-all photoactivatable manganese-based carbon monoxide-releasing molecules (CORMs) for synergistic therapy of mycobacterial infection}, volume = {147}, year = {2025}, }
• (2025). Multiple secondary bond-mediated C–N coupling over N-doped carbon electrocatalysts. JACS, 147(22), 19342--19352. (www)

  @article{ , abstract = {Electrocatalytic C–N reductive coupling offers a sustainable and eco-friendly approach to producing value-added oximes. The challenge lies in the overstrong chemisorption of N-containing intermediates and carbonyl compounds on metal-based catalysts, which causes low Faradaic efficiency and yield rates, as well as undesired byproducts. Here, we propose a multiple secondary bond-mediated strategy for C–N coupling toward benzaldoxime on a nitrogen-doped graphene-like carbon catalyst (NC). Integrating theoretical and experimental analyses, we demonstrate that the graphitic-N–C sites in NC promote nitrite reduction into hydroxylamine via weak electrostatic interaction. Moreover, the hydrogen bonds and π–π stacking interactions among NC, hydroxylamine, and benzaldehyde synergistically enrich the key intermediates on the catalyst surface and inhibit the side reactions, leading to a highly selective C–N coupling process. Remarkably, the NC catalyst achieves a high Faradaic efficiency of 73 ± 1% and a yield rate of 6.8 ± 0.1 mol h –1 m –2 for benzaldoxime electrosynthesis at an economically viable current density of 0.1 A cm –2 , as revealed by technoeconomic analysis. Our results demonstrate an appealing route for high-performance C–N coupling with enhanced economic feasibility.}, archive = {J_JACS}, author = {Xiaoying Lu and Ze-Cheng Yao and Xinbo Ma and Zhuo-Qi Shi and Liang Ding and Jiaju Fu and Zhen-Hua Lyu and Zhe Jiang and Shu-Qi Wang and Ji Yang and Xiaoxia Chang and Bingjun Xu and Jin-Song Hu}, doi = {10.1021/jacs.5c05466}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19342--19352}, shortjournal = {J. Am. Chem. Soc.}, title = {Multiple secondary bond-mediated C–N coupling over N-doped carbon electrocatalysts}, volume = {147}, year = {2025}, }
• (2025). Non-aqueous binary and ternary nHF·Base fluoride reagents: Characterization of structure, properties, and reactivity. JACS, 147(22), 19329--19341. (www)

  @article{ , abstract = {Binary and ternary n HF·base mixtures are an important class of nucleophilic fluorinating reagents used in myriad fluorination reactions. These reagents are soluble in organic media, and by varying n , the reactivity of fluoride can be controlled and tuned. Of particularly frequent utility are the ternary mixtures of n HF·amine, in which the binary 9HF·py and 3HF·NEt 3 mixtures are combined, the ratio ( n ) of which has a strong influence on the reaction yields and selectivity. The structure, properties, and reactivity of these non-aqueous ionic liquid mixtures vary considerably with n . Herein, we disclose a combined experimental and theoretical study aimed at characterizing binary and ternary n HF·base mixtures. We have measured the concentration of components, their Hammett acidity H 0 , nucleophilicity, and basicity, while using theory to calculate the lowest energy size and structure of the clusters formed at different ratios of HF to base and analyzed the noncovalent interactions present. The quantification of properties and enhanced understanding presented should facilitate the further development and use of this important family of fluorination reagents.}, archive = {J_JACS}, author = {Stephen G. Sweeting and Alastair J. J. Lennox}, doi = {10.1021/jacs.5c05472}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19329--19341}, shortjournal = {J. Am. Chem. Soc.}, title = {Non-aqueous binary and ternary nHF·Base fluoride reagents: Characterization of structure, properties, and reactivity}, volume = {147}, year = {2025}, }
• (2025). Sterically controlled cyclobutane-dioxetane ultrabright afterglow nanosystem for cyclic therapy of choroidal neovascularization in mice. JACS, 147(22), 19315--19328. (www)

  @article{ , abstract = {Afterglow occurring after light excitation ceases offers a safer light source to the laser-activated verteporfin therapy approved by the FDA for choroidal neovascularization (CNV). However, conventional afterglow molecules, especially adamantane-dioxetanes with high steric hindrance, exhibit limited chemiexcitation, restricting electron transfer and diminishing therapeutic effects. Here, we constructed ultrabright afterglow nanosystems by integrating low-hindrance cyclobutane moieties into the dioxetane framework. Among these cyclobutane substituents, the benzyl oxocyclobutane-dioxetane is the brightest afterglow molecule due to its lowest hindrance, showing 35.7 times faster relative chemiexcitation rate and 59 times higher afterglow intensity than adamantane-dioxetane, alongside a three-order-of-magnitude increase in total afterglow emission. Consequently, at the equivalent concentration, the benzyl oxocyclobutane-dioxetane-based nanosystem produces nearly five times more singlet oxygen than free verteporfin. In a CNV mouse model, cyclic treatment with our nanosystem reduced lesion areas by 64.9%, outperforming the 39.3% reduction achieved by free verteporfin counterpart. By eliminating the need for laser activation, this strategy minimizes ocular damage, providing a safe and effective treatment for CNV and other retinal disorders.}, archive = {J_JACS}, author = {Jiawei Zhang and Haoliang Shi and Xuan Qin and Pengcheng Wang and Yufan Ling and Xiangbowen Jin and Mingyue Cui and Bin Song and Houyu Wang and Yao He}, doi = {10.1021/jacs.5c05187}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19315--19328}, shortjournal = {J. Am. Chem. Soc.}, title = {Sterically controlled cyclobutane-dioxetane ultrabright afterglow nanosystem for cyclic therapy of choroidal neovascularization in mice}, volume = {147}, year = {2025}, }
• (2025). Aromaticity localization effects in polycyclic aromatic hydrocarbons for discovering narrowband fluorescence materials. JACS, 147(22), 19305--19314. (www)

  @article{ , abstract = {Achieving narrowband fluorescence in polycyclic aromatic hydrocarbons (PAHs) is crucial for ultrahigh-definition organic light-emitting diodes (UD-OLEDs), yet the underlying structure–property relationships that dictate emission bandwidth remain insufficiently understood. In this study, we introduce aromaticity localization as a predictive framework for identifying narrowband emitters. Using nucleus-independent chemical shift (NICS) analysis, we uncover a strong correlation between localized aromaticity and reduced vibrational coupling, demonstrating that restricting π-electron delocalization effectively suppresses shoulder peaks, thereby minimizing spectral broadening. To validate this concept, we designed a new class of imine-amine-type PAHs (IA-PAHs) that integrates electron-deficient imine and electron-rich amine units, generating a multiple-resonance-type electronic structure. Building on a steric-hindrance-guided C–H activation strategy, we precisely controlled the regioselectivity of pyridine fusion within the triphenylamine framework, leading to the discovery of narrowband red-emitting II-b and green-emitting III-c featuring localized aromaticity. Notably, II-b exhibited an exceptionally narrowband red emission at 660 nm with a full width at half-maximum of only 35 nm (0.10 eV). OLEDs incorporating II-b demonstrated high efficiency with minimal roll-off and fully met the stringent BT.2020 red standard, with Commission Internationale de l’Eclairage (CIE) coordinates of [0.71, 0.29]. This work not only establishes aromaticity localization as an empirical and intuitive design principle for narrowband fluorophores but also represents a significant advancement in deep-red narrowband OLED technology, setting a new benchmark for conventional fluorescent emitters.}, archive = {J_JACS}, author = {Yimin Wu and Junjie Liu and Ge Yang and Zhengyang Bin and Jingsong You}, doi = {10.1021/jacs.5c05112}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19305--19314}, shortjournal = {J. Am. Chem. Soc.}, title = {Aromaticity localization effects in polycyclic aromatic hydrocarbons for discovering narrowband fluorescence materials}, volume = {147}, year = {2025}, }
• (2025). Electronic structure modulation in GeTe by hg and sb codoping leads to high thermoelectric performance. JACS, 147(22), 19296--19304. (www)

  @article{ , abstract = {Electronic band convergence and the introduction of doping-induced midgap states near the Fermi level offer a compelling mechanism for modulating the electronic structure to achieve high thermoelectric performance. Germanium telluride (GeTe), with its unique crystal and electronic structure, holds great promise for thermoelectric (TE) power generation. However, a high p-type carrier concentration coupled with high lattice thermal conductivity limits its TE performance. Herein, we report an impressive thermoelectric figure of merit (zT) of ∼2.4 (∼2.6 with Dulong–Petit C p ) at 727 K in Hg and Sb codoped GeTe, achieved through the synergistic effects of electronic structure optimization and lattice thermal conductivity reduction. Hg doping in GeTe boosts the Seebeck coefficient by facilitating the valence band convergence. Importantly, a hybridized midgap band emerges upon Hg doping, through the antibonding interaction of Hg 6s and p orbitals of Te and Ge. Further codoping of Sb makes the midgap state more localized and shifts the E F up to pin the midgap electronic band, resulting in an enhanced electronic density of states near E F , as validated by first-principles density functional theory (DFT) calculations of the electronic band structure and experimental Pisarenko analysis. This leads to a significant enhancement of the Seebeck coefficient in Hg and Sb codoped GeTe. Further, when Hg doping exceeds the solid solution limit, it forms HgTe nanoprecipitates in the GeTe matrix, suppressing the lattice thermal conductivity. We have constructed a double-leg TE device using the developed material as a p-type leg, which exhibits a promising output power density of 0.77 W/cm 2 for the Δ T = 440 K, underscoring the material’s potential for high-performance TE applications.}, archive = {J_JACS}, author = {Paribesh Acharyya and Animesh Das and Raagya Arora and Manisha Samanta and Subarna Das and Tanmoy Ghosh and Umesh V. Waghmare and Kanishka Biswas}, doi = {10.1021/jacs.5c05116}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19296--19304}, shortjournal = {J. Am. Chem. Soc.}, title = {Electronic structure modulation in GeTe by hg and sb codoping leads to high thermoelectric performance}, volume = {147}, year = {2025}, }
• (2025). Adenosine-triggered dynamic and transient aptamer-based networks integrated in liposome protocell assemblies. JACS, 147(22), 19282--19295. (www)

  @article{ , abstract = {The development of transient dissipative nucleic-acid–based reaction circuits and constitutional dynamic networks attracts growing interest as a means of emulating native dynamic reaction circuits. Recent efforts applying enzymes, DNAzymes, or light as catalysts controlling the transient, dissipative functions of DNA networks and circuits were reported. Moreover, the integration of the dynamic networks in protocell assemblies and the identification of potential applications are challenging objectives. Here, we introduce the adenosine (AD) aptamer subunit complex coupled with adenosine deaminase (ADA) as a versatile recognition/catalytic framework for driving transient allosterically AD-stabilized DNAzyme circuits or dissipative AD-stabilized constitutional dynamic networks. In addition, the AD/ADA-driven transient frameworks are integrated into liposome assemblies as protocell models. Functionalized liposomes carrying allosterically ATP-stabilized DNAzymes cleaving EGR-1 mRNA are fused with MCF-7 breast cancer cells, demonstrating effective gene therapy and selective apoptosis of cancer cells.}, archive = {J_JACS}, author = {Yu Ouyang and Yang Sung Sohn and Xinghua Chen and Rachel Nechushtai and Eli Pikarsky and Fan Xia and Fujian Huang and Itamar Willner}, doi = {10.1021/jacs.5c05090}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19282--19295}, shortjournal = {J. Am. Chem. Soc.}, title = {Adenosine-triggered dynamic and transient aptamer-based networks integrated in liposome protocell assemblies}, volume = {147}, year = {2025}, }
• (2025). An electric molecular faraday cage. JACS, 147(22), 19272--19281. (www)

  @article{ , abstract = {Faraday cages are essential tools for protecting conducting materials from unwanted electromagnetic radiation by redistributing charges around the cage’s exterior. When integrated into nanoscale molecular circuits, particularly those with well-defined inner cavity structures, Faraday cages isolate guest molecules from external influences, thereby improving device stability and performance. The design of molecular Faraday cages involves the intersection of molecular electronics and supramolecular chemistry with the goal of safeguarding internal molecules from harmful substances. In this study, we introduce an X-shaped octacationic cyclophane, XCage 8+ , as an electric molecular Faraday cage. Its spacious binding cavity allows for the encapsulation of perylene diimide molecular wires. The shielding effectiveness of XCage 8+ was confirmed through electrochemical gating, demonstrating that electric fields are shielded effectively. The findings of this study provide valuable insights that could inspire the development of innovative strategies for enhancing device stability and performance at the supramolecular level, paving the way for further progress in the fields of molecular electronics and quantum devices.}, archive = {J_JACS}, author = {Ping Zhou and Kai Cheng and Kai Qu and Leng Wang and Chen Hu and Wenqi Liu and Hongliang Chen}, doi = {10.1021/jacs.5c05038}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19272--19281}, shortjournal = {J. Am. Chem. Soc.}, title = {An electric molecular faraday cage}, volume = {147}, year = {2025}, }
• (2025). Topology-directed cage engineering in MOFs for efficient C2H2/CO2/C2H4 separation. JACS, 147(22), 19262--19271. (www)

  @article{ , abstract = {Cage-based porous materials, leveraging their unique “confined windows–expanded cavities” synergistic architecture, have demonstrated remarkable advantages in the field of gas adsorption and separation. This study presents a topology-directed in situ assembly strategy that successfully constructs metal–organic frameworks with tailored pore structures. Using the distinctive cage-channel soc topological frameworks as a template, by innovatively reversing the roles of traditional nodes and linkers, we employed the conformationally flexible hexa-pyridine ligands as six-connected nodes and utilized undercoordinated Cu 2+ as five-connected linkers, in combination with halogen anions (F – , Cl – , and Br – ) as two-connected topological “blockers”, resulting in the successful synthesis of three MOF materials ( LNU-H1 , LNU-H2 , and LNU-H3 ) featuring an unprecedented jcq topological network. These materials exhibit a unique “confined window–expanded cavity” synergistic structure, achieving complete closure of linear channels. Notably, LNU-H1 demonstrated exceptional performance in the separation of ternary C 2 H 2 /CO 2 /C 2 H 4 gas mixtures, as validated by dynamic breakthrough experiments under industrially relevant conditions. This study not only confirms the effectiveness of the topology-directed pore engineering approach but also provides new insights into the development of advanced, energy-efficient functional materials for gas separation applications.}, archive = {J_JACS}, author = {Yuejiang Han and Chunqing Ji and Yuning Lou and Ran Li and Mingyao He and Daqiang Yuan and Zhengbo Han}, doi = {10.1021/jacs.5c05068}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19262--19271}, shortjournal = {J. Am. Chem. Soc.}, title = {Topology-directed cage engineering in MOFs for efficient C2H2/CO2/C2H4 separation}, volume = {147}, year = {2025}, }
• (2025). Structural basis for medium-chain Dehydrogenase/Reductase-catalyzed reductive cyclization in polycyclic tetramate macrolactam biosynthesis. JACS, 147(22), 19253--19261. (www)

  @article{ , abstract = {Few enzymes are known to catalyze reductive cyclizations via nucleophile-mediated C–C bond formation. Medium-chain dehydrogenases/reductases (MDRs) typically function as dehydrogenases or reductases. However, a distinct subclass of MDRs involved in polycyclic tetramate macrolactam (PoTeM) biosynthesis catalyzes reductive cyclizations via hydride-mediated C–C bond formation. Here, we present the apo and substrate-bound structures of OX4 and CftD, two enzymes responsible for the third ring formation in PoTeMs biosynthesis. Structural and mutational analysis reveal a catalytic mechanism wherein OX4 initiates a NADPH-dependent 1,6-reduction, followed by cyclization to form the C11–C22 bond, water-mediated protonation of the C7-carbonyl oxygen, and a final tautomerization to produce the cyclized product. Precise substrate positioning and stabilization of the enolate intermediate by the conserved residue W260 are critical for catalysis. These findings represent the first structural and mechanistic understanding of this newly identified cyclase subgroup and offer promising new avenues for enzyme engineering and natural product biosynthesis.}, archive = {J_JACS}, author = {Xiangqian Xie and Fan Li and Yanxin Mu and Mengyao Lu and Jie Luo and Haoxin Wang and Yuemao Shen and Liangcheng Du and Deyu Zhu and Yaoyao Li}, doi = {10.1021/jacs.5c04971}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19253--19261}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural basis for medium-chain Dehydrogenase/Reductase-catalyzed reductive cyclization in polycyclic tetramate macrolactam biosynthesis}, volume = {147}, year = {2025}, }
• (2025). Visualizing size-dependent dynamics of CeO2−δ{100}-supported CoOx nanoparticles under CO2 hydrogenation conditions. JACS, 147(22), 19239--19252. (www)

  @article{ , abstract = {Carbon dioxide is a major greenhouse gas. In order to optimize processes focused on its chemical valorization, one needs detailed information about the effects of CO 2 and/or CO 2 /H 2 mixtures on the structure and morphology of metal/oxide catalysts. In this study, the evolution of a catalyst with cobalt supported on CeO 2 -cube nanostructures under CO 2 hydrogenation conditions was investigated by using a set of in situ characterization techniques (X-ray absorption fine structure, X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, and environmental transmission electron microscopy (TEM)). The {100} facets of the ceria support displayed an unexpectedly high stability due to strong interactions with the aggregates of cobalt oxide. A significant influence of interfacial bonding between CoO x and CeO 2−δ {100} is evident through a clear preference in the orientation of CoO x nanoparticles (NPs) with respect to the substrate. For initially reduced Co/CeO 2 -cube nanostructures, a kinetically controlled oxidation of cobalt upon the introduction of CO 2 was observed during the early stages of CO 2 hydrogenation. Environmental TEM revealed the size-dependent morphological behavior of cobalt oxide NPs due to strong interactions with the CeO 2 {100} surface. When the environment was switched from H 2 to a mixture of H 2 and CO 2 at 250 °C, small CoO x NPs (in the largest dimension < 2.5 nm) rapidly transformed from a pyramidal three-dimensional (3D) form to a planar, monatomic layer attached to the concurrently oxidized CeO 2−δ {100} surface. This maximizes the number of sites available for the binding of CO 2 or reaction intermediates. The shape transformation reflected the oxophilic character of cobalt and strong metal–support interactions. The removal of CO 2 from the gas phase led to a reduction of the cobalt oxide NPs by hydrogen and a reversible two-dimensional → 3D transformation. In contrast, no significant morphological changes, apart from further oxidation, were observed for big CoO x NPs (in the largest dimension > 3 nm). These trends are not seen for nanoparticles of noble metals. The observed morphological and structural changes in the small CoO x NPs affected the stability of reaction intermediates and modified the selectivity of the CoO x /CeO 2 catalyst system for methane production.}, archive = {J_JACS}, author = {Kaixi Deng and Yuxi Wang and Patricia Pérez-Bailac and Wenqian Xu and Jordi Llorca and Arturo Martinez-Arias and Dmitri N. Zakharov and José A. Rodriguez}, doi = {10.1021/jacs.5c04901}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19239--19252}, shortjournal = {J. Am. Chem. Soc.}, title = {Visualizing size-dependent dynamics of CeO2−δ{100}-supported CoOx nanoparticles under CO2 hydrogenation conditions}, volume = {147}, year = {2025}, }
• (2025). Biosourced functional hydroxybenzoate-co-lactide polymers with antimicrobial activity. JACS, 147(22), 19230--19238. (www)

  @article{ , abstract = {Antimicrobial resistance is an urgent global health challenge, and compounds that address this issue have attracted significant attention. In particular, bioderived molecules that possess natural antimicrobial properties can be useful to prepare active macromolecules that are degradable. In this work, a 4-(methyl/allyl/benzyl)oxy-6-(H/alkyl)-2-oxy-benzoate- co -lactide-based polymer library was designed and studied for antimicrobial activity. The monomer precursors were heterologously produced and purified from an engineered fungal host, chemically modified with 4-(methyl/allyl/benzyl)oxy substituents, and ring-closed to form the 3-methyl-5 H -benzo[ e ][1,4]dioxepine-2,5(3 H )-diones. The polymers were synthesized by ring-opening polymerization using a 3-O urea/1-methyl-2,3,4,6,7,8-hexahydro-1H-pyrimido[1,2- a ]pyrimidine catalytic system and 3-methyl-butan-1-ol as the initiator. Polymers at different degrees of polymerization were prepared by varying the [monomer]/[initiator] (M/I = 5–30) and tested for activity against the pathogen Staphylococcus aureus . Polymers were identified that were antimicrobial and disrupted biofilms while maintaining good in vitro biocompatibility. The degradability of the polymers was confirmed. Overall, these results demonstrate the power of utilizing a combination of synthetic biology and chemistry to produce functional and degradable polymers that are potent inhibitors of the Gram-positive bacterium S. aureus , with potential applications in medicine.}, archive = {J_JACS}, author = {Pedro Salas-Ambrosio and Shelby Vexler and Rajalakshmi P Sivasankaran and Niko Vlahakis and Ryan S. Lai and Colin Johnson and Sophia I. Baas-Maynard and Daniel S. Min and Haillie Lower and Abigail G. Doyle and Yi Tang and Jose A. Rodriguez and Irene A. Chen and Javier Read de Alaniz and Heather D. Maynard}, doi = {10.1021/jacs.5c04624}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19230--19238}, shortjournal = {J. Am. Chem. Soc.}, title = {Biosourced functional hydroxybenzoate-co-lactide polymers with antimicrobial activity}, volume = {147}, year = {2025}, }
• (2025). Mixed-flux techniques for rational synthesis and structural control in silver chalcogenides. JACS, 147(22), 19217--19229. (www)

  @article{ , abstract = {The functionality of materials is intrinsically linked to their structures, an axiom encapsulated in the principle of structure–property relationships. The pinnacle of materials design is the tailoring of its structure for a specific function, which requires the ability of rational synthesis and the development of synthesis science. This idea, however, remains elusive for the synthesis of complex extended solids. A major obstacle is the difficulty in using established chemical principles selectively to control reaction paths and favor certain structural patterns over numerous other possible results. In this context, we are developing a synthesis science approach that facilitates the control of the structure and bonding to create new structures. This is achieved by employing a two-component flux consisting of mixed hydroxides and halides as the reaction medium. This enables reaction conditions that allow better control of the structure dimensionality and composition by manipulating the temperature and solvent basicity (via the flux component ratio). We demonstrate the efficacy of this method in controlling their structural motifs to arrive at 23 unreported compositions and 6 unique structure types. These materials are expected to exhibit a broad range of properties, from metallic to semiconducting, with calculations suggesting the potential for emergent phenomena such as Dirac semimetals. The reaction paths afforded by these mixed fluxes establish a direct correlation between the synthetic variables and properties, providing significant insight into a broadly applicable approach for new materials.}, archive = {J_JACS}, author = {Xiuquan Zhou and Luqing Wang and Hengdi Zhao and Venkata Surya Chaitanya Kolluru and Wenqian Xu and Tieyan Chang and Yu-Sheng Chen and Jianguo Wen and Maria K. Y. Chan and Duck Young Chung and Mercouri G. Kanatzidis}, doi = {10.1021/jacs.5c04757}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19217--19229}, shortjournal = {J. Am. Chem. Soc.}, title = {Mixed-flux techniques for rational synthesis and structural control in silver chalcogenides}, volume = {147}, year = {2025}, }
• (2025). Dual-atom catalysts for the oxygen reduction reaction: Unraveling atomic structures under reaction conditions. JACS, 147(22), 19210--19216. (www)

  @article{ , abstract = {Metal–nitrogen–carbon (M–N–C, M = Mn, Fe, Co, Ni, Cu, Zn, and Pt) dual-atom catalysts (DACs) show great potential for the oxygen reduction reaction (ORR) at the cathode of proton exchange membrane fuel cells (PEMFCs). During catalytic reactions, multiple reactants and intermediates interact with the active sites, yet understanding their dynamic structural evolution under the operating conditions remains challenging. In this study, we analyze 186 heteronuclear FeM–N–C DACs using ab initio thermodynamic phase diagrams and find that OH-ligated structures become predominant at higher applied potentials. This indicates that catalytic activity is governed by electrochemically modified metal sites rather than by the bare structures. We further investigate the catalytic mechanism of these ligated structures and reveal that the ORR limiting potential can be efficiently predicted from the phase diagrams. Among the 186 DACs studied, 29 were found to outperform Pt-based catalysts, with FeCo–N–C DACs demonstrating the highest activity. Our computational predictions align well with experimental observations, highlighting the crucial role of dynamic structural changes under reaction conditions in enhancing the electrocatalytic performance of DACs.}, archive = {J_JACS}, author = {Courtney Brea and Guoxiang Hu}, doi = {10.1021/jacs.5c04776}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19210--19216}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual-atom catalysts for the oxygen reduction reaction: Unraveling atomic structures under reaction conditions}, volume = {147}, year = {2025}, }
• (2025). Ferroelectric-like polarization switching in plastic crystalline succinonitrile. JACS, 147(22), 19200--19209. (www)

  @article{ , abstract = {An intermediate state of the plastic crystal (PC) phase between solid and liquid has attracted much attention due to its potential applications for ionic conductors, ferroelectrics, and barocaloric materials. In general, it has been considered difficult to maintain a polarized orientation state in the PC phase due to the loss of orientational order caused by the isotropic rotation of molecules. In this study, we succeeded in realizing a unique polarized orientation state in the PC phase of sucinonitrile ( SN ), which exhibits hysteresis in the polarization–electric field ( P – E ) curve. In the PC phase, the trans and gauche conformations coexist, and the conformation and orientation of the molecules change in response to an external electric field. Interestingly, the polarization state in the PC phase relaxes upon removal of the electric field and does not exhibit the nonvolatile memory effects seen in conventional ferroelectrics. However, two different polarization mechanisms emerge due to the molecular orientational and conformational degrees of freedom. As a result, a characteristic double P – E hysteresis behavior with two different coercive fields, which is not observed in conventional ferroelectrics, is observed. This result provides an important guideline for the design of organic materials for the realization of next-generation multilevel memory.}, archive = {J_JACS}, author = {Nozomi Onodera and Shun Dekura and Tetsu Sato and Miyu Mashiko and Takuya Kurihara and Motohiro Mizuno and Tomoyuki Akutagawa}, doi = {10.1021/jacs.5c04778}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19200--19209}, shortjournal = {J. Am. Chem. Soc.}, title = {Ferroelectric-like polarization switching in plastic crystalline succinonitrile}, volume = {147}, year = {2025}, }
• (2025). A mechanism-based strategy for controlling CH4 and CO selectivities in CO2–H2 reactions on dispersed ru, co, and ni nanoparticles. JACS, 147(22), 19185--19199. (www)

  @article{ , abstract = {The formation of CO as an intermediate in the conversion of CO 2 –H 2 to CH 4 and its strong binding on dispersed Ru, Co, and Ni nanoparticles inhibit rates of CO and CH 4 formation but to different extents. CO 2 conversion rates decrease and CH 4 selectivities increase as CO concentration gradients evolve axially along the catalyst bed and radially within diffusion-limited porous aggregates. These trends and their interpretation in terms of the identity and kinetic relevance of surface-catalyzed elementary steps enable mechanism-based strategies for selectivity control through the purposeful introduction of CO pressures into inlet CO 2 –H 2 streams. This strategy exploits the stronger CO inhibition of its formation (from CO 2 ) than its conversion (to CH 4 ), which causes the selective inhibition of CO 2 conversion relative to CH 4 formation. The presence of CO at levels accurately prescribed by the mechanism-derived rate equations, similar in functional form on Ru, Co, and Ni nanoparticles, and by diffusion-convection-reaction models that account for CO gradients at the bed and aggregate scales led to the exclusive formation of CH 4 and to the elimination of CO gradients at both scales, as evident from measured rates and selectivities for CO 2 –H 2 reactions on Ru, Co, and Ni nanoparticles over a broad and practical range of temperature (483–573 K), reactant pressures (4–1100 kPa CO 2 ; 8–820 kPa H 2 ), and nanoparticle diameter (2–30 nm). This mechanism-based strategy enables the exclusive formation of CH 4 from CO 2 –H 2 reactants, irrespective of reaction conditions or nanoparticle composition (Ru, Co, Ni) and size, without requiring complex catalyst architectures or intricate synthesis protocols.}, archive = {J_JACS}, author = {Wenshuo Hu and Gregory L. Tate and Enrique Iglesia}, doi = {10.1021/jacs.5c04698}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19185--19199}, shortjournal = {J. Am. Chem. Soc.}, title = {A mechanism-based strategy for controlling CH4 and CO selectivities in CO2–H2 reactions on dispersed ru, co, and ni nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Direct access to benzofurans and indoles from ethylene with 2-Methylphenols/Anilines through iridium-catalyzed dehydrogenative annulation. JACS, 147(22), 19178--19184. (www)

  @article{ , abstract = {The direct conversion of o -cresol and 2-methylphenols to 2-methylbenzofurans was achieved by an Ir/DTBE-DPPE-catalyzed reaction under an atmosphere of ethylene (1 atm). The reaction involves the initial selective formation of a C–C bond at the benzylic C(sp 3 )–H bond of 2-methylphenols with ethylene without the accommodation of the C(sp 2 )–H bonds at the 6-positions, which is followed by subsequent C–O bond-forming annulation along with associated dehydrogenation and double bond migration steps. The reaction conditions also allowed for the direct conversion of o -toluidine and 2-methylanilines into 2-methylindoles.}, archive = {J_JACS}, author = {Kaito Yagi and Toshimichi Ohmura and Michinori Suginome}, doi = {10.1021/jacs.5c04631}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19178--19184}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct access to benzofurans and indoles from ethylene with 2-Methylphenols/Anilines through iridium-catalyzed dehydrogenative annulation}, volume = {147}, year = {2025}, }
• (2025). High-curvature interfaces induce nondegenerate splitting of d-orbital energy levels for enhanced catalytic activity. JACS, 147(22), 19166--19177. (www)

  @article{ , abstract = {The construction of hierarchical pores, especially mesopores, usually leads to abundant interfaces with high curvature, while the recognition of the impact of interface curvature upon intrinsic reactivity is yet limited. In this work, a large number of high-curvature interfaces were identified in the as-synthesized mesoporous catalysts (Cu/Ni-MNC-T x , MNC = mesoporous nitrogen-doped carbon) through advanced three-dimensional reconstruction technologies. It was further confirmed that high-curvature interfaces can induce nondegenerate splitting of d -orbital energy levels in the affixing metal sites. As a result, Cu/Ni-MNC-T 60 exhibited a significantly reduced apparent activation energy (from 102.7 to 52.8 kJ·mol –1 ) and remarkably promoted intrinsic activity (reduced energy barriers by 60%) in the hydrogenation of furfural. DFT calculations revealed that the abundant high-curvature interfaces of Cu/Ni-MNC-T 60 accomplished a parallel adsorption of furfural on Cu sites and also facilitated H 2 splitting on Ni sites. Furthermore, in the rate-determining step, the C–OH bond of the key *fur–CH 2 OH intermediate not only exhibited an impaired electron enrichment at the nearby oxygen end but also displayed an elongated bond length, indicating effective C–OH bond activation with the reduced hydrogenation energy barrier. The application feasibility of such a promotion mechanism was additionally verified by the considerable hydrogenation performances of Cu/Ni-MNC-T 60 for a wide scope of aldehydes.}, archive = {J_JACS}, author = {Xin Zhao and Yueshuai Wang and Jie Wen and Lijia Cao and Fengliang Wang and Kaisen Lei and Ruiqi Fang and Linan Zhou and Yingwei Li}, doi = {10.1021/jacs.5c04321}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19166--19177}, shortjournal = {J. Am. Chem. Soc.}, title = {High-curvature interfaces induce nondegenerate splitting of d-orbital energy levels for enhanced catalytic activity}, volume = {147}, year = {2025}, }
• (2025). Electrodeposition of magnonic v(tetracyanoethylene)2 thin films. JACS, 147(22), 19157--19165. (www)

  @article{ , abstract = {Molecule-based magnetic materials have been identified as promising candidates for application in magnonic technologies, owing not only to their solution processability but also because they can exhibit narrow ferromagnetic resonance (FMR) linewidths and low Gilbert damping coefficients─crucial prerequisites for the transmission of coherent magnons over macroscopic distances. In particular, V(TCNE) 2 , a compound with a three-dimensional network structure composed of vanadium(II) centers linked by tetracyanoethylene (TCNE •– ) radical anions, displays magnonic properties comparable to yttrium iron garnet, the quintessential magnonic material in the field. However, existing solution and chemical vapor deposition methods for synthesizing V(TCNE) 2 require the use of highly reactive zero-valent molecular vanadium precursors, stymying research on this important material. Herein, we report a facile electrochemical method for the deposition of thin films of V(TCNE) 2 using readily obtainable and stable divalent vanadium precursors and TCNE •– anions generated by electrochemical reduction. Magnetization measurements reveal that the films exhibit ferrimagnetic ordering above room temperature, consistent with V(TCNE) 2 films synthesized via other methods. Moreover, the electrodeposited films exhibit narrow FMR linewidths as low as 17.5 G and a low Gilbert damping coefficient of 1.1 × 10 –3 , values that are on par with some currently integrated metallic magnonic materials. More generally, these results demonstrate that electrodeposition can provide a straightforward means of generating high-performance magnonic materials using readily available molecular precursors.}, archive = {J_JACS}, author = {Ryan A. Murphy and Kennedy C. McCone and Robert Claassen and Ellen Holmgren and Ezekiel Johnston-Halperin and Jeffrey R. Long}, doi = {10.1021/jacs.5c04610}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19157--19165}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrodeposition of magnonic v(tetracyanoethylene)2 thin films}, volume = {147}, year = {2025}, }
• (2025). Area-controllable nanoplatelets from rapid photocontrolled living crystallization-driven self-assembly of an alternating copolymer. JACS, 147(22), 19148--19156. (www)

  @article{ , abstract = {Photocontrolled living self-assembly has attracted considerable interest due to its noninvasive, remote control, and real-time features; however, it has remained much less explored compared to other stimuli-responsive self-assembly systems. Here, a novel photocontrolled living crystallization-driven self-assembly (P-CDSA) system was constructed by employing an alternating copolymer, poly((hexylthienyl stiff-stilbene)- alt -poly(ethylene glycol)) containing photosensitive stiff-stilbene derivative, as the precursor. The photoinduced trans -to- cis isomerization of the stiff-stilbene derivative segments could occur quickly upon 365 nm light irradiation, leading to a rapid P-CDSA process producing size-controllable nanoplatelets within 2 min at room temperature. Taking advantage of the repetitive characteristic of alternating copolymers, the nanoplatelet morphology was independent of the molecular weight (MW) and its distribution ( Đ ) of the copolymer. The areas of the nanoplatelets were precisely controlled by adjusting the unimer-to-seed mass ratio, following a linear relationship. Additionally, the lengths of the major and minor axes followed a sublinear growth trend, enabling tailored nanoplatelet dimensions. The area could also be programmed by sequential light on/off switching, showing a linear dependence on light irradiation time. This study demonstrates the first example of photocontrolled two-dimensional CDSA and opens a new avenue for controlling over the area of 2D architectures.}, archive = {J_JACS}, author = {Jiacheng Zhang and Tianyu Xiao and Zhilin Liu and Yucheng Yin and Chen Li and Fugui Xu and Yiyong Mai}, doi = {10.1021/jacs.5c04537}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19148--19156}, shortjournal = {J. Am. Chem. Soc.}, title = {Area-controllable nanoplatelets from rapid photocontrolled living crystallization-driven self-assembly of an alternating copolymer}, volume = {147}, year = {2025}, }
• (2025). Guanine crystallization by particle attachment. JACS, 147(22), 19139--19147. (www)

  @article{ , abstract = {Understanding how crystals nucleate is a key goal in materials, biomineralization, and chemistry. Many inorganic materials are known to crystallize “nonclassically” by particle attachment. However, a molecular-level understanding of small molecule crystallization is hampered by the complexity and time scales of nucleation events, which are often too large to simulate and too small to observe. Here, by combining unbiased molecular dynamics simulations and in situ experiments, we uncover this nucleation “blind spot” to elucidate the nonclassical crystallization mechanism of the nucleobase, guanine. The multi-step nucleation process begins with stacked guanine clusters, whose H-bonding and π-stacking arrangement progressively orders as they attach into nanoscopic fibers (observed by simulation and electron microscopy), partially ordered bundles, and finally, 3D periodic crystals. This work provides a foundation for understanding how organisms exquisitely control the formation of guanine and other molecular crystals, which are used ubiquitously in biology as optical and nitrogen-storage materials.}, archive = {J_JACS}, author = {Shashanka S. Indri and Florian M. Dietrich and Avital Wagner and Michal Hartstein and Einat Nativ-Roth and Mariela J. Pavan and Leeor Kronik and Matteo Salvalaglio and Benjamin A. Palmer}, doi = {10.1021/jacs.5c04543}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19139--19147}, shortjournal = {J. Am. Chem. Soc.}, title = {Guanine crystallization by particle attachment}, volume = {147}, year = {2025}, }
• (2025). Discovery of an interlocked and interwoven molecular topology in nanocarbons via dynamic C–C bond formation. JACS, 147(22), 19132--19138. (www)

  @article{ , abstract = {Topologically complex carbon nanostructures are an exciting but largely unexplored class of materials due to their challenging synthesis. Previous methods are low yielding because they rely on irreversible C sp 2 –C sp 2 bond formation, which necessitates complex templating strategies to enforce entanglement. Here, reversible zirconocene coupling of alkynes is developed as a new method to access complex molecular topologies, where dynamic C–C bond formation facilitates entanglement under thermodynamic control, allowing the use of simple precursors without the need for preassembly. This strategy enables the scalable, high-yield synthesis of three topologically distinct nanocarbons, including the serendipitous discovery of a structure containing a new topological motif that was not previously identified or realized synthetically. This motif, consisting of an unusual combination of interlocking and interweaving, was recognized to be generalizable to a new topological class of molecules, introduced here as perplexanes.}, archive = {J_JACS}, author = {Harrison M. Bergman and Angela T. Fan and Christopher G. Jones and August J. Rothenberger and Kunal K. Jha and Rex C. Handford and Hosea M. Nelson and Yi Liu and T. Don Tilley}, doi = {10.1021/jacs.5c04268}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19132--19138}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of an interlocked and interwoven molecular topology in nanocarbons via dynamic C–C bond formation}, volume = {147}, year = {2025}, }
• (2025). Spatial configuration-guided design of covalent organic framework-based artificial metalloantioxidases for inhibiting inflammatory cascades and regulating bone homeostasis. JACS, 147(22), 19113--19131. (www)

  @article{ , abstract = {Intense oxidative stress in bone tissues can trigger the hyperactivation of neutrophils, thereby causing inflammatory cascades to deteriorate bone homeostasis. Here, inspired by the catalytic centers of natural antioxidases, we introduce the spatial configuration-guided design of covalent organic framework (COF)-based artificial metalloantioxidases for inhibiting inflammatory cascades and regulating bone homeostasis. Specifically, the hexaiminohexaazatrinaphthalene COF with ruthenium coordination (S-HACOF-Ru), featuring electron-rich centers with a spatial configuration, demonstrates exceptional antioxidase-like reactive oxygen species (ROS) scavenging capabilities for efficiently mitigating the oxidative stress. As a result, S-HACOF-Ru efficiently prevents the generation of neutrophil extracellular traps and inhibits the release of myeloperoxidase (MPO). By preventing MPO-induced activation of nuclear factor-kappa B and inhibiting proinflammatory macrophage polarization, S-HACOF-Ru successfully blocks the neutrophil-macrophage inflammatory cascades. This intervention promotes bone homeostasis by a shift from bone resorption to tissue regeneration, which can efficiently inhibit alveolar bone loss in periodontal tissues and reverse cartilage damage in ankle joint cavities. We propose that this design strategy provides an intriguing avenue for developing new artificial antioxidases and biocatalytic materials with potential applications in treating a wide range of chronic inflammatory diseases.}, archive = {J_JACS}, author = {Yaxin Xie and Qian Li and Lingyi Huang and Peiqi Wang and Ting Wang and Mingru Bai and Jiusi Guo and Wei Geng and Xiaolin Wang and Wei Qiao and Xianglong Han and Chong Cheng}, doi = {10.1021/jacs.5c04242}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19113--19131}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatial configuration-guided design of covalent organic framework-based artificial metalloantioxidases for inhibiting inflammatory cascades and regulating bone homeostasis}, volume = {147}, year = {2025}, }
• (2025). Orientational geometry, surface density, and binding free energy of intermediates as full descriptors for electrochemical CO2 reduction at metal surfaces. JACS, 147(22), 19101--19112. (www)

  @article{ , abstract = {Metal catalysts for the electrochemical CO 2 reduction reaction (CO 2 RR) have attracted widespread attention due to their high catalytic efficiency, stability, broad product diversity, and ease of preparation. Studies show that the product distribution and yield of the electrochemical CO 2 RR on metal surfaces result from the metal’s binding energy of an intermediate adsorbed CO (*CO). However, reaction pathways could be manipulated by other thermodynamic parameters, such as orientation and surface density. In this work, the CO 2 RR on Au electrode surfaces was comprehensively analyzed using high-performance in situ electrochemical sum-frequency generation (EC-SFG) spectroscopy. The improved signal intensities allowed the reaction to be monitored with a fast time resolution, extracting key thermodynamic and kinetic features from the experiments. Our EC-SFG spectrometer allowed the comprehensive analysis of the potential-dependent polarized SFG signal, allowing us to quantify *CO orientation at the Au electrode surface as a function of applied potential. These experimental results were then used to determine the maximum surface density and binding energies of the *CO intermediate in a self-contained analysis. These EC-SFG experiments enabled us to quantify the reaction rate constant for the system. We then discuss how the binding energy, orientation angle, and absolute surface density of an intermediate should be fully considered in understanding its thermodynamic behaviors in the CO 2 RR. This work demonstrates the potential of high-efficiency EC-SFG spectroscopy to provide an all-inclusive analysis of the CO 2 RR on metal surfaces and opens the door for other catalysts to be investigated using this technique to determine the best system for efficient electrocatalysis.}, archive = {J_JACS}, author = {Hui Wang and Haley Fisher and Zhi-Chao Huang-Fu and Jesse B. Brown and Tong Zhang and Fuzhan Song and Yuqin Qian and Yi Rao}, doi = {10.1021/jacs.5c04276}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19101--19112}, shortjournal = {J. Am. Chem. Soc.}, title = {Orientational geometry, surface density, and binding free energy of intermediates as full descriptors for electrochemical CO2 reduction at metal surfaces}, volume = {147}, year = {2025}, }
• (2025). Photo- and copper-catalyzed enantioselective oxidation of benzylic C(sp3)–H bonds. JACS, 147(22), 19093--19100. (www)

  @article{ , abstract = {Here, we report a photo- and copper-catalyzed enantioselective oxidation of benzylic C(sp 3 )–H bonds using N -hydroxyphthalimide as the oxygenated reagent. The reaction proceeds under mild conditions and does not require excess substrates or oxidants. The oxidation products can be readily transformed into chiral benzylic alcohols or hydroxylamines. Preliminary mechanism studies suggest that the oxidation reaction proceeds via a free radical mechanism.}, archive = {J_JACS}, author = {Fu Li and Xian-Ming Liu and Jia-Bin Pan and Ling Dai and Yin Yang and Li-Jun Xiao and Chao Fan and Qi-Lin Zhou}, doi = {10.1021/jacs.5c04142}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19093--19100}, shortjournal = {J. Am. Chem. Soc.}, title = {Photo- and copper-catalyzed enantioselective oxidation of benzylic C(sp3)–H bonds}, volume = {147}, year = {2025}, }
• (2025). Nanoscale origin of the soft-to-hard short-circuit transition in inorganic solid-state electrolytes. JACS, 147(22), 19084--19092. (www)

  @article{ , abstract = {Understanding and overcoming the chemomechanical failures of polycrystalline inorganic solid-state electrolytes (SSEs) are critical for next-generation all-solid-state batteries. Yet, so far, the nanoscale origin of SSEs’ chemomechanical failure under operation conditions remains a mystery. Here, by using in situ electron microscopy, we decipher the nanoscale origin of the soft-to-hard short-circuit transition─a conventionally underestimated failure mechanism─caused by electronic leakage-induced Li 0 precipitation in SSEs. For the first time, we directly visualize stochastic Li 0 interconnection-induced soft short circuits, during which the SSEs undergo the transition from a nominal electronic insulator to a state exhibiting memristor-like nonlinear conduction (electronic leakages), ultimately evolving into hard short circuits. Furthermore, we first capture intragranular cracking caused by Li 0 penetration, demonstrating that fully wetted Li 0 can fracture polycrystalline oxide SSEs via a liquid-metal embrittlement-like mechanism. Guided by these insights, we show that incorporating an electronically insulating and mechanically resilient 3D polymer network into an inorganic/polymer composite SSE effectively suppresses Li 0 precipitation, interconnection, and short circuits, significantly enhancing its electrochemical stability. Our work, by elucidating the soft-to-hard short-circuit transition kinetics of SSEs, offers new insights into their nanoscale failure mechanisms.}, archive = {J_JACS}, author = {Chunyang Wang and Yubin He and Peichao Zou and Qi He and Ju Li and Huolin L. Xin}, doi = {10.1021/jacs.5c04113}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19084--19092}, shortjournal = {J. Am. Chem. Soc.}, title = {Nanoscale origin of the soft-to-hard short-circuit transition in inorganic solid-state electrolytes}, volume = {147}, year = {2025}, }
• (2025). Tunable self-assembly of decanuclear Ni(II) carbonato clusters with a hydroxyquinolinato shell: Robust porous networks with reversible solvent-/Temperature-driven phase transitions and selective gas separation. JACS, 147(22), 19073--19083. (www)

  @article{ , abstract = {The utilization of molecular metal clusters as building units of noncovalent porous materials (NPMs) is a promising strategy, combining the versatile functionality of organic and inorganic subunits with the softness and flexibility of molecular solids controlled by noncovalent interactions. However, the development of robust porous functional frameworks based on self-assembly driven by noncovalent forces is still highly challenging. Herein, we report the synthesis and characterization of a discrete decanuclear Ni(II) hydroxyquinolinato-carbonato cluster, [Ni 10 (μ 6 -CO 3 ) 4 (L) 12 ], which, depending on the crystallization conditions, self-assembles into either of two microporous frameworks: diamondoid WUT-1(Ni) and pyrite WUT-2(Ni) . The transitions between both polymorphs can also be selectively triggered by temperature or exposure to vapors of a particular organic solvent, which is accompanied by the easy recovery of crystallinity by the materials from the noncrystalline phase. Moreover, both materials show excellent robustness toward various chemical environments, including air/moisture and water stability, and demonstrate interesting gas adsorption properties. Remarkably, WUT-1(Ni) exhibits significant enhancement in gas uptake compared to the previously reported isostructural Zn(II) analogue, WUT-1(Zn) , representing one of the highest H 2 uptakes among NPMs. In turn, tighter voids of the ultramicroporous WUT-2(Ni) framework facilitate selective interactions with gas molecules, resulting in outstanding selectivity in the adsorption of CO 2 over CH 4 and N 2 . The presented studies demonstrate the profound role of the character of metal centers on the self-assembly of isostructural nanoclusters as well as properties of the resulting microporous frameworks.}, archive = {J_JACS}, author = {Katarzyna Sołtys-Brzostek and Kamil Sokołowski and Iwona Justyniak and Aurelia Li and David Fairen-Jimenez and Alicja Supeł and Michał Terlecki and Janusz Lewiński}, doi = {10.1021/jacs.5c04096}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19073--19083}, shortjournal = {J. Am. Chem. Soc.}, title = {Tunable self-assembly of decanuclear Ni(II) carbonato clusters with a hydroxyquinolinato shell: Robust porous networks with reversible solvent-/Temperature-driven phase transitions and selective gas separation}, volume = {147}, year = {2025}, }
• (2025). ATP-ion complexation and lithium’s bioactive form in cellular solutions. JACS, 147(22), 19061--19072. (www)

  @article{ , abstract = {Lithium (Li + ) is a first-line therapy for millions of people with bipolar disorder. However, the molecular mechanism underlying Li + ’s action remains unclear. Here we resolve a key issue concerning its bioactive form that is central to all hypotheses proposed to explain its therapeutic action─under cellular conditions, it is unclear as to what fraction of Li + is free vs bound to ATP. We address this using molecular dynamics (MD) simulations and kinetic modeling. The polarizable force field (AMOEBA-HFC) employed in MD is benchmarked against quantum mechanical and experimental data, including local ion-ligand interactions, aqueous phase ion properties, and ion-ATP binding free energies. The kinetic model is built using observations from MD and parametrized using MD and experimental data. We discover that Mg 2+ -bound ATP (ATP·Mg) has two binding sites for monovalent cations, and both sites can be loaded simultaneously. In Li + ’s absence, ATP·Mg predominantly exists as a ternary or quaternary complex with Na + and/or K + ions. Li + also competes for these two sites. Although its standard affinity is stronger than Na + and K + , its loading its limited by its low therapeutic concentration. Nevertheless, the extent of Li + loading increases with ATP levels, and 50% of Li + can be sequestered by ATP·Mg at physiological extremes. This means that both Li + forms can be present in high fractions, providing a basis to investigate molecular modes of Li + action. Overall, our work provides new structural, thermodynamic, and kinetic insights into how ATP binds ions in cellular solutions, also revealing Li’s bioactive form.}, archive = {J_JACS}, author = {Julian M. Delgado and Peter S. Klein and Sameer Varma}, doi = {10.1021/jacs.5c04061}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19061--19072}, shortjournal = {J. Am. Chem. Soc.}, title = {ATP-ion complexation and lithium’s bioactive form in cellular solutions}, volume = {147}, year = {2025}, }
• (2025). One-step radical-induced synthesis of graft copolymers for effective compatibilization of polyethylene and polypropylene. JACS, 147(22), 19052--19060. (www)

  @article{ , abstract = {The synthesis of copolymers from high-density polyethylene (HDPE) and isotactic polypropylene ( i PP) has gained increasing attention due to their ability to improve the recycling of incompatible mixed polyolefin waste feed streams. Herein, we report a new radical grafting process that yields HDPE- g - i PP copolymers from HDPE and i PP by using a commercially available peroxide. Tensile testing of brittle 70/30 HDPE/ i PP mixtures with these graft copolymers added showed promising compatibilization, improving the elongation at break of the blends from 20% up to 1080%. Detailed kinetic studies coupled with thermal and rheological characterization revealed optimized conditions for HDPE and i PP macroradical coupling and a deeper understanding of the grafting reaction. This optimization yielded HDPE- g - i PP copolymers that compatibilize HDPE and i PP blends at loadings as low as 2.5 wt %. The versatility of this macroradical grafting reaction was demonstrated by preparing an effective compatibilizer from untreated postconsumer waste plastics.}, archive = {J_JACS}, author = {Moritz Kränzlein and Shilin Cui and Jenny Hu and Anne M. LaPointe and Brett P. Fors and Geoffrey W. Coates}, doi = {10.1021/jacs.5c03869}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19052--19060}, shortjournal = {J. Am. Chem. Soc.}, title = {One-step radical-induced synthesis of graft copolymers for effective compatibilization of polyethylene and polypropylene}, volume = {147}, year = {2025}, }
• (2025). Hyperpolarized 13C NMR by dissolution DNP enables snapshot detection of degradation products in lithium-ion battery electrolytes. JACS, 147(22), 19039--19051. (www)

  @article{ , abstract = {Dissolution Dynamic Nuclear Polarization (dDNP) is a powerful hyperpolarization technique enabling sensitivity gains beyond 4 orders of magnitude in solution nuclear magnetic resonance (NMR). Over the last decades, researchers’ efforts have led to an extension of dDNP applications in numerous research fields. Lithium-ion batteries are one of the most widespread types of rechargeable batteries, which calls for a deeper understanding of the various physicochemical mechanisms involved in making them more efficient, safe, and sustainable. One of the key challenges lies in better understanding the degradation of the battery electrolyte to mitigate it, as it can significantly impact the battery’s performance. While NMR has been used in attempts to understand these mechanisms, notably by investigating the degradation products, the intrinsic lack of sensitivity of this technique, combined with the limited accessible volume of such compounds, makes its application often challenging. In this work, we combine several state-of-the-art dDNP methodologies, including the use of recently introduced hyperpolarizing polymers (HYPOPs), to acquire hyperpolarized 13 C NMR spectra of battery electrolytes. We show that we can successfully detect 13 C signals on formulated battery electrolyte solutions in different degradation stages on a 600 MHz spectrometer, with sensitivity gains of up to 3 orders of magnitude. This work paves the way for studying lithium-ion battery electrolyte degradation under real usage conditions (cycling, thermal aging, air exposure, etc.) with a 13 C detection limit below the micromolar range. This methodology has the potential to provide new insights into degradation mechanisms and the role and effectiveness of additives to mitigate electrolyte degradation.}, archive = {J_JACS}, author = {Chloé Gioiosa and Ekaterina V. Pokochueva and Julien Dieterich and James Tolchard and Charlotte Bocquelet and Mohamed Ayman Ennachet and Nghia Le and Laurent Veyre and Damien Montarnal and Anne Lesage and Ségolène Laage and Simon Pondaven and Sami Jannin}, doi = {10.1021/jacs.5c03773}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19039--19051}, shortjournal = {J. Am. Chem. Soc.}, title = {Hyperpolarized 13C NMR by dissolution DNP enables snapshot detection of degradation products in lithium-ion battery electrolytes}, volume = {147}, year = {2025}, }
• (2025). Suppressing phase transitions and high-pressure amorphization through tethered organic cations in organochalcogenide-halide perovskites. JACS, 147(22), 19026--19038. (www)

  @article{ , abstract = {Polymorphism, where the same composition adopts different structures, is abundant in perovskites, with numerous phase transitions occurring as a function of temperature and pressure. The APbX 3 perovskites (A = monovalent cation; X = Cl – , Br – , I – ) show such phase transitions near ambient conditions, significantly impacting their optoelectronic device performance and stability. Herein, we show that the recently reported organochalcogenide-halide perovskites (RCh)PbX 2 (RCh = + NH 3 (CH 2 ) 2 S – , + NH 3 (CH 2 ) 2 Se – ; X = Cl – , Br – ) featuring an organic A-site cation that is covalently linked to the inorganic framework, show no phase transitions with temperature from 4 to 423 K and with pressure from 0 to 40 GPa. Furthermore, the RCh-perovskites remain crystalline even at 40 GPa, in striking contrast to AMX 3 (M = Pb, Sn) perovskites that rapidly become amorphous at pressures above ca. 5 GPa. By alloying RCh or the similar-sized ethylammonium as impurities into a (CH 3 NH 3 )PbBr 3 host, we find that the enhanced phase integrity of the RCh-perovskites may be attributed mostly to the covalent attachment of the A-site cation, which impedes octahedral tilting, a primary avenue for phase transitions. We also track the rotational isomerization of the RCh ligands with pressure, finding that the trans -to- gauche isomerization enables a shrinking A-site cavity volume, without drastic changes to the inorganic framework. Unlike the dynamic disorder seen in hybrid perovskite A-site cations, this static rotational isomerism appears to be unaffected by temperature from 93 to 373 K. The exceptional structural integrity of the RCh-perovskites motivates the design of similar strategies to impede phase transitions in technologically important perovskite compositions.}, archive = {J_JACS}, author = {Jiayi Li and Jan Hofmann and Robert M. Stolz and Jiajia Wen and Christina R. Deschene and Hannah Bartels and Zhenxian Liu and Alberto Salleo and Yu Lin and Karena W. Chapman and Hemamala I. Karunadasa}, doi = {10.1021/jacs.5c03696}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19026--19038}, shortjournal = {J. Am. Chem. Soc.}, title = {Suppressing phase transitions and high-pressure amorphization through tethered organic cations in organochalcogenide-halide perovskites}, volume = {147}, year = {2025}, }
• (2025). In situ monitoring of molten chloride salt chemistry and corrosion using a microelectrode. JACS, 147(22), 19013--19025. (www)

  @article{ , abstract = {This study investigated, for the first time, the applicability of a borosilicate glass-coated tungsten microelectrode for in situ monitoring of localized surface electrochemical processes, such as corrosion. The diffusion of Eu 3+ ions was analyzed via cyclic voltammetry from 400 to 550 °C. The microelectrode consistently overestimated diffusion coefficients compared to the macroelectrode results due to additional intrinsic glass electrode current (IGEC) originating from the borosilicate glass coating, as confirmed by EIS. Further analysis revealed that the effective capacitance of the borosilicate glass increases with temperature, and corrected diffusion values were obtained after subtracting the IGEC. To assess the microelectrode’s performance for novel high-temperature scanning electron-chemical microscopy applications, approach curve tests were conducted near insulating alumina and corroding Ni–20Cr surfaces. The current response depended strongly on approach speed and temperature. Approaching the insulating alumina at lower temperatures and faster speeds induced artifacts likely from convection-driven interference and limited ionic mobility. Near the corroding Ni–20Cr surface, slower approach speeds enhanced deposition effects at more negative potentials. Additionally, time-dependent OCP profiling near Ni–20Cr captured the evolution of local redox potential gradients. These results emphasize the need to carefully optimize operational parameters and highlight the potential of microelectrodes for localized electrochemical measurements in molten salt environments.}, archive = {J_JACS}, author = {Changkyu Kim and Adrien Couet}, doi = {10.1021/jacs.5c03651}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19013--19025}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ monitoring of molten chloride salt chemistry and corrosion using a microelectrode}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic phosphine-mediated deoxygenative [3 + 2] cycloaddition of α,β-unsaturated carbonyls and alkenes. JACS, 147(22), 19004--19012. (www)

  @article{ , abstract = {Tertiary phosphine is a powerful nucleophile that enables numerous synthetically important reactions. However, the exclusive reliance on a two-electron pathway has restricted the development of phosphine chemistry. We report here a visible light photocatalytic phosphine-mediated deoxygenative [3 + 2] cycloaddition of α,β-unsaturated carbonyls and activated alkenes, providing facile access to polysubstituted cyclopentenes from readily accessible starting materials in promising yields with good substrate scope. Mechanistic investigations corroborate the transient involvement of a phosphine radical cation and consequent α-addition (α to electron-withdrawing groups) to C–C double bonds due to the inherent electrophilicity of the radical cation, as opposed to the traditional nucleophilic β-addition of phosphine. The ensuing single electron transfer reduction, Michael addition, and 1,4-proton transfer cascade furnish a phosphorus ylide, which undergoes an intramolecular Wittig reaction to finish the construction of the cyclopentenes. This work demonstrates that tertiary phosphine can serve as a convenient reagent for carbonyl deoxygenation and act as a traceless directing group for controllable cross-coupling of two distinct alkenes, providing new avenues to expand the frontiers of phosphine chemistry and synthetic chemistry.}, archive = {J_JACS}, author = {Jiayan Qiu and Xuemei Zhang and Hanliang Zheng and Gangguo Zhu}, doi = {10.1021/jacs.5c03665}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {19004--19012}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic phosphine-mediated deoxygenative [3 + 2] cycloaddition of α,β-unsaturated carbonyls and alkenes}, volume = {147}, year = {2025}, }
• (2025). Modulating adsorption kinetics in a 3D-interconnected nanocavity framework with narrow apertures for enhanced propylene separation. JACS, 147(22), 18993--19003. (www)

  @article{ , abstract = {The energy-intensive distillation currently used for C 3 H 6 /C 3 H 8 separation─challenged by their small boiling point difference─could be improved via adsorption. However, most porous materials face a trade-off among C 3 H 6 adsorption capacity, selectivity, and kinetics. Herein, we report the synthesis and characterization of a novel metal–organic framework, denoted NiPz 4 Bim, constructed from a weak Lewis-base pyrazole-based ligand Pz 4 Bim and the weak Lewis-acid Ni 2+ , featuring 3D pore structures with nanocavities (∼1 nm) connected by very narrow apertures (∼5 Å). This framework enables efficient C 3 H 6 /C 3 H 8 separation by combining selective adsorption with enhanced diffusion kinetics for C 3 H 6 . Specifically, adsorption capacities at 298 K and 1 bar were recorded as 3.24 mmol g –1 for C 3 H 6 and 2.74 mmol g –1 for C 3 H 8 , with selectivity ratios of up to 2.42. Kinetic uptake analysis using the effective diffusion coefficient ( D′ ) revealed a significant difference in the adsorption rates of the two gases, corresponding to a kinetic selectivity of 51.96. Neutron powder diffraction, coupled with grand canonical Monte Carlo simulations and density functional theory calculations, directly visualizes the binding domains of adsorbed gases and the dynamics and energetics of the host–guest interactions. These studies reveal that the unique nanosized cavities with narrow apertures in NiPz 4 Bim facilitates van der Waals and π-π interactions with C 3 H 6 , enabling selective trapping over C 3 H 8 . Crucially, NiPz 4 Bim exhibits high stability and reusability in multicycle tests, demonstrating its practical viability. This work highlights the importance of pore-geometry engineering in framework materials for the efficient separation of structurally similar molecules, with immediate implications for sustainable olefin production.}, archive = {J_JACS}, author = {Long-Zhang Dong and Zi-Yi Liao and Ling-Xiang Bao and Ming-Chan Yang and Bo Bai and Bao Yuan and Run-Han Li and Ping Miao and Yong Yan and Ya-Qian Lan}, doi = {10.1021/jacs.5c03677}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18993--19003}, shortjournal = {J. Am. Chem. Soc.}, title = {Modulating adsorption kinetics in a 3D-interconnected nanocavity framework with narrow apertures for enhanced propylene separation}, volume = {147}, year = {2025}, }
• (2025). Breaking structural instability and orbital symmetry mismatch in p-block metal monochalcogenides for CO2 electroreduction via noninvasive van der waals doping. JACS, 147(22), 18982--18992. (www)

  @article{ , abstract = {P -block metal monochalcogenides (MX) adopting black phosphorus (BP)-like structures are promising electrocatalysts due to their abundant exposed metal sites and tunable electronic structures. However, their practical application is limited by structural instability arising from lone-pair electron-induced structural distortions, along with an inherent orbital symmetry mismatch with the frontier orbitals of small molecules (e.g., CO 2 ), reducing the activation efficiency. Here, we report a noninvasive doping strategy to overcome both structural instability and orbital symmetry mismatch in p -block metal monochalcogenides for efficient CO 2 electroreduction, through engineering a periodic van der Waals (vdW) superlattice, known as a misfit superlattice. These vdW superlattices with tunable sublayer ratios contain the catalytically active p -electron-rich MX sublayers and conductive transition metal dichalcogenide current collectors. Taking [BiS] 1 [TaS 2 ] 1 as a proof-of-concept, the presence of noninvasive vdW doping and ionic interactions between sublayers is crucial for modulating their electronic structures and stabilizing BiS sublayers by transforming the Bi into a higher valence state of Bi (2+δ) . Concurrently, interlayer noninvasive vdW doping induces uneven electron redistribution in Bi’s p -orbitals, breaking its orbital symmetry mismatch with the LUMO of CO 2 , thereby reducing the CO 2 activation barrier. In situ characterization and theoretical calculations reveal that the optimized Bi sites exhibit moderate adsorption for the *OCHO, endowing the superlattice with exceptional selectivity (>90%) for formate in CO 2 electroreduction. This work advances vdW superlattice engineering as a versatile platform for synergistically stabilizing layered p -block materials and tailoring their sublayer interactions and orbital symmetry alignment by leveraging noninvasive vdW doping, achieving optimal catalytic performance for the efficient electrochemical conversion of small molecules.}, archive = {J_JACS}, author = {Pengfei Li and Xu Han and Fangqi Yang and Ning Li and Meng-Xuan Li and Jing Li and Xiaoxu Zhao and Meng Zhao and Zejun Li and Wenping Hu and Jiong Lu}, doi = {10.1021/jacs.5c03556}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18982--18992}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking structural instability and orbital symmetry mismatch in p-block metal monochalcogenides for CO2 electroreduction via noninvasive van der waals doping}, volume = {147}, year = {2025}, }
• (2025). Harnessing dynamic supramolecular interactions for lanthanide detection via computational pattern recognition of magnetic resonance fingerprints. JACS, 147(22), 18972--18981. (www)

  @article{ , abstract = {The reliance of modern technology growth on lanthanides presents dual challenges: securing sustainable sources from natural or recycled materials and reducing environmental harm from waste discharge. However, the similar ionic radii, oxidation states, and binding affinities of Ln 3+ ions hinder their nondestructive detection in mixtures. Furthermore, the overlap of spectroscopic signals and the inapplicability for opaque solutions limit the harness of luminescent sensors for differentiating one Ln 3+ from another. Here, we introduce 19 F-paramagnetic guest exchange saturation transfer magnetic resonance fingerprinting ( 19 F-paraGEST MRF), a rapid signal acquisition, encoding, and analysis approach for detecting specific Ln 3+ in mixtures. Based on a small-sized experimental 19 F-paraGEST data set, we generated a de novo dictionary of ∼2500 combinations of Ln 3+ mixtures, resulting in ∼7,000,000 simulated 19 F-paraGEST MRF patterns of different Ln 3+ concentrations. This dictionary was later used for computational pattern recognition of experimental NMR signal evolutions (“fingerprints”), utilizing a rapid computational approach executable on a standard laptop within seconds. Hence, fast and reliable multiplexed lanthanide detection in complex mixtures was enabled. Demonstrated through the analysis of lanthanides’ content of permanent magnets from a hard disk drive, this MR-based method paves the way for broader applications of lanthanide detection in murky, nontransparent mixtures and further exploration of supramolecular sensors in diverse scenarios.}, archive = {J_JACS}, author = {Elad Goren and Balamurugan Subramani and Liat Avram and Alla H. Falkovich and Or Perlman and Amnon Bar-Shir}, doi = {10.1021/jacs.5c03583}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18972--18981}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing dynamic supramolecular interactions for lanthanide detection via computational pattern recognition of magnetic resonance fingerprints}, volume = {147}, year = {2025}, }
• (2025). Reticular structural diversification of zirconium Metal–Organic frameworks through angular ligand configuration control. JACS, 147(22), 18963--18971. (www)

  @article{ , abstract = {Reticular chemistry offers practical guidelines for enlarging and enriching the arsenal of metal–organic frameworks (MOFs). However, reticular expansion to access mesoporous structures remains challenging due to limitations in achieving precise control over both the size and configuration during building units’ extension. Herein, we combine ligand isomerization and functionalization strategies to regulate the ligand configuration by systematically replacing aryl C–H groups with N atoms, resulting in angular dicarboxylate ligands with various symmetries. The assembly between a 4,4′-(pyridine-2,6-diyl)dibenzoic acid ligand (1N, C 2 symmetry) and 12-connected Zr 6 cluster leads to the formation of a pseudo ftw topology framework (NU-2611), where one pair of nose-to-nose 1N ligands resembles a tetra-topic ligand. When a 6,6′-(1,3-phenylene)dinicotinic acid ligand (2N, C S symmetry) was used, another pseudo ftw network NU-2612 was obtained with a 2-fold framework interpenetration. Interestingly, the planar [2,2′:6′,2″-terpyridine]-5,5″-dicarboxylic acid ligand (3N, C 2 V symmetry) yielded an intriguing mesoporous Zr-MOF with kag topology. NU-2613 represents the first example of kag Zr-MOF designed to include large, well-defined mesopores. The diversity of these MOFs was further enhanced through post-synthetic metalation of linkers. Particularly, metalation of the chelating 3N ligand with Fe 3+ in NU-2613 enables efficient catalytic transformation within the functionalized channels. This work contributes insight into the reticular expansion of Zr-MOFs by finely-tuning the ligand planarity, advancing the structure diversification of mesoporous frameworks for specific applications.}, archive = {J_JACS}, author = {Xiang-Jing Kong and Haomiao Xie and Tao He and Jiayang Liu and Xiaoliang Wang and Zhihua Cheng and Kent O. Kirlikovali and Zi-Ming Ye and Omar K. Farha}, doi = {10.1021/jacs.5c03587}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18963--18971}, shortjournal = {J. Am. Chem. Soc.}, title = {Reticular structural diversification of zirconium Metal–Organic frameworks through angular ligand configuration control}, volume = {147}, year = {2025}, }
• (2025). Optimizing the mass transport and atomic fe intrinsic activity to achieve high-performing fuel cells. JACS, 147(22), 18953--18962. (www)

  @article{ , abstract = {Due to the insufficient three-phase interfaces and high oxygen transport resistance, the high intrinsic activity cannot be sufficiently utilized in practical proton-exchange membrane fuel cells (PEMFCs). The efficient transport of protons and reactants within the catalyst layers (CL) is largely influenced by the pore structure of the carbon support, hosting both metal sites and ionomers. Herein, we constructed a porous nanosheet Pt-free catalyst (Fe AC -N-SC) by selecting a highly nitrogen-rich GT-18 MOF via salt template to realize the improvement of PEMFC performance. The simulation and experimental results illustrate that the microstructure can benefit the homogeneous dispersion of ionomers and facilitate oxygen mass transport in the cathode CL, ultimately achieving efficient utilization of catalytic activities. The PEMFC assembled from the Fe AC -N-SC catalyst exhibited an outstanding peak power density of 1.1 W cm –2 and durability (61% power density retention after AST -30k cycles and 92% voltage retention after 100 h OCV test). DFT results demonstrated that the introduction of Fe atomic clusters can boost the intrinsic activity of ORR by regulating the electron distribution of single-atomic Fe–N 4 sites. This study reveals the relationship between CL design, mass transport, and electrode microstructure, which successfully exploits the intrinsic activity of cathode catalysts and enhances the power generation capacity.}, archive = {J_JACS}, author = {Haiyang Fan and Yarong Liu and Jiaxin Li and Zunhang Lv and Changli Wang and Rui Liu and Feilong Dong and Chongao Tian and Xiao Feng and Wenxiu Yang and Bo Wang}, doi = {10.1021/jacs.5c03499}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18953--18962}, shortjournal = {J. Am. Chem. Soc.}, title = {Optimizing the mass transport and atomic fe intrinsic activity to achieve high-performing fuel cells}, volume = {147}, year = {2025}, }
• (2025). Nickel-catalyzed adaptive migration-enabled asymmetric cross-hydrocarbonylation of unactivated alkenes. JACS, 147(22), 18944--18952. (www)

  @article{ , abstract = {Transition-metal-catalyzed regio- and enantioselective cross-coupling of alkyl metallic species has emerged as a cornerstone in modern organic synthesis, which enables the construction of carbon–carbon and carbon–heteroatom bonds with high precision to facilitate rapid access to important organic targets with molecular complexity. However, the selective formation and utilization of different alkyl metallic intermediates from one precursor under identical conditions remain unknown and challenging. Herein, a Ni-catalyzed adaptive migratory asymmetric cross-hydroacylation of unactivated alkenes for the synthesis of enantioenriched α-arylated ketones has been developed. One alkene serves as a precursor for two different alkyl metallic intermediates by adaptive migration, providing one of the most straightforward pathways to access enantioenriched α-arylated ketones.}, archive = {J_JACS}, author = {Yi-Ming Du and Jia-Ni Lin and Yu-Long Li and Qiong Yu and Wei Shu}, doi = {10.1021/jacs.5c03451}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18944--18952}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-catalyzed adaptive migration-enabled asymmetric cross-hydrocarbonylation of unactivated alkenes}, volume = {147}, year = {2025}, }
• (2025). In-situ gelled covalent organic framework membrane with vacancies-enhanced anhydrous proton conductivity. JACS, 147(22), 18934--18943. (www)

  @article{ , abstract = {The development of high-performance anhydrous proton-exchange membranes (APEMs) for electrochemical techniques remains a significant challenge. Covalent organic frameworks (COFs) offer a promising solution for APEMs due to their tunable channels and functionalizable skeletons. However, COFs are typically porous powders, which create extreme difficulties in processing them into self-standing APEMs, thereby limiting their practical applications. In this study, we propose a novel strategy for preparing COF-based APEMs for high-temperature proton exchange membrane fuel cell (HT-PEMFC) applications through acidification and gelation. In the gel, COF acts as both a gelling agent and proton trap, inhibits guest acid flow, and captures protons from the acid, leading to the formation of proton vacancies in the COF gel and greatly accelerating proton migration. As a result, COF gel membranes exhibit conductivities that far surpass that of the guest acid itself, exceeding 0.1 S cm –1 at temperatures above 140 °C, outperforming most reported COF materials. Notably, membrane electrode assemblies of HT-PEMFCs fabricated with a COF gel achieve a maximum power density of 150 mW cm –2 at 180 °C and anhydrous conditions. Our approach introduces an innovative strategy for the fabrication of self-standing COF-based APEMs, representing a significant breakthrough in the field of COF-based APEMs for fuel cell technology.}, archive = {J_JACS}, author = {Jin Zhang and Han Zhang and Ya-Ru Kong and Linlong Zhou and Siyao Li and Linzhou Zhuang and Nanwen Li and Xiao-Ming Ren and Zhi Xu}, doi = {10.1021/jacs.5c03311}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18934--18943}, shortjournal = {J. Am. Chem. Soc.}, title = {In-situ gelled covalent organic framework membrane with vacancies-enhanced anhydrous proton conductivity}, volume = {147}, year = {2025}, }
• (2025). Genome mining of isoindolinone-containing peptide natural products. JACS, 147(22), 18923--18933. (www)

  @article{ , abstract = {Peptide natural products (PNPs) are important sources of bioactive compounds. Recent studies have shown that oligopeptides or pseudopeptides can be synthesized by amide-bond-forming enzymes such as ATP-grasp enzymes and amide-bond synthetases (ABSs). By focusing on ATP-grasp enzymes as part of a conserved biosynthetic enzyme ensemble, genome mining of PNPs was performed on three biosynthetic gene clusters (BGCs) from diverse fungi, including Coccidioides immitis RS, the causative agent of valley fever. We demonstrate that the conserved enzymes synthesize a common dipeptide fragment, l -leucine- l - O -isoindolinone-homoserine ( l -Leu- l -Isd), which is modified and diversified into three PNPs ( 1 – 3 ) by associated enzymes in the three pathways. Pathway reconstitution and enzymatic assays led to the characterization of six ATP-grasp enzymes and ABSs that catalyze di-, tri-, and tetrapeptide formation. From the C. immitis BGC, a flavoenzyme catalyzing the direct oxidation of l -tryptophan to l -oxindolylalanine was discovered. Our work validates ATP-grasp enzymes and ABSs as leads to mine new PNPs and further showcases the biocatalytic potential of these enzymes in catalyzing amide-bond formation.}, archive = {J_JACS}, author = {Yalong Zhang and Lin Wu and Zuwei Wang and Wenyu Han and Tyler A. Kerr and Yi Tang}, doi = {10.1021/jacs.5c03321}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18923--18933}, shortjournal = {J. Am. Chem. Soc.}, title = {Genome mining of isoindolinone-containing peptide natural products}, volume = {147}, year = {2025}, }
• (2025). Concentration energy ion channels with molecular-structure dual recognition for sustainable environmental monitoring. JACS, 147(22), 18910--18922. (www)

  @article{ , abstract = {Pesticides are vital for crop and seafood production but leave persistent residues that pose risks to ecosystems and human health through bioaccumulation. The detection of pesticide residues requires highly sensitive and selective technologies. Herein, a nanochannel sensor capable of dual recognition of ionic charge and molecular conformation based on molecular imprinting technology (MIT) is presented, offering a significant improvement in selectivity and sensitivity over traditional nanopore sensors. The MIT-based nanochannels with imprinting sites tailored to pesticide molecules go beyond recognizing the molecular size and surface functional groups, enabling the detection of molecular configurations. In this research, the approach enables the detection of 10 pesticide molecules with detection limits (LODs) ranging from 12.9 to 26.9 pM, achieving two orders of magnitude lower than fluorescence-based methods. Density functional theory (DFT) and molecular dynamics (MD) simulations revealed hydrogen bonding as the dominant interaction in the imprinting process. This versatile nanochannel construction method, proposed for the first time, provides dual recognition capabilities and is expected to advance nanochannel sensing while promoting sustainable environmental development.}, archive = {J_JACS}, author = {Yeqing Xu and Abuduheiremu Awati and Shan Zhou and Runhao Zhang and Xin Zhang and Hui Zeng and Yaxin Guo and Yuanbo Song and Chengmin Hu and Lei Xie and Qirui Liang and Kang Liang and Lei Jiang and Dongyuan Zhao and Biao Kong}, doi = {10.1021/jacs.5c03283}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18910--18922}, shortjournal = {J. Am. Chem. Soc.}, title = {Concentration energy ion channels with molecular-structure dual recognition for sustainable environmental monitoring}, volume = {147}, year = {2025}, }
• (2025). Aza-michael Addition–Fragmentation ring-opening polymerization. JACS, 147(22), 18901--18909. (www)

  @article{ , abstract = {Cleaving the C(sp 3 )–N bonds in unstrained cyclic monomers for ring-opening polymerization remains a formidable challenge in polymer chemistry. Here, we report a novel strategy that integrates the cascade aza-Michael/retro-aza Michael reaction with a chain growth polymerization mechanism. For the first time, this approach cleaves the C(sp 3 )–N bond in less-strained cyclic monomers under ambient conditions, yielding cinnamate-containing polyamines with controlled molecular weight, narrow dispersity, and unexpected cis -stereoselectivity. A linear relationship between the number-average molecular weight and the conversion, high chain-end fidelity, and efficient chain extension proved excellent control over the polymerization process. In addition, density functional theory calculations were conducted to clarify the origin of the observed stereoselectivity. The versatility of this polymerization was further demonstrated through the copolymerization with aziridine monomers and the synthesis of sequence-controlled polymers. This protocol provides a new C–N cleavage pattern for ring-opening polymerization and would lead to a more useful synthetic pathway to polymers with main-chain functionalities.}, archive = {J_JACS}, author = {Dan Huang and Zhen Zhu and Derong Cao and Hanchu Huang}, doi = {10.1021/jacs.5c03181}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18901--18909}, shortjournal = {J. Am. Chem. Soc.}, title = {Aza-michael Addition–Fragmentation ring-opening polymerization}, volume = {147}, year = {2025}, }
• (2025). Orthogonal site-specific dual bioconjugation of aryl and alkyl thiols. JACS, 147(22), 18888--18900. (www)

  @article{ , abstract = {We introduce aryl thiols as nucleophiles for site-specific protein and antibody bioconjugation, which allows the orthogonal labeling of native cysteines for double modification strategies. In a high-yielding synthesis, we introduce aromatic thiol substituents in two amino acids (4-SH- L -Phe and 3-SH- L -Tyr), which can be site-specifically incorporated into the C -terminus of a protein using the enzyme tubulin tyrosine ligase (TTL, Tub-tag labeling). In particular, we found that 3-SH- L -tyrosine shows excellent water solubility and incorporation rates, similar to previously described Tyr-derivatives. 2D NMR experiments revealed a p K a value of 5.5 for the aryl thiol modality of 3-SH- L -tyrosine, which matches the pH-dependent reactivity profile toward thiol-selective ethynyl-triazolyl-phosphinate (ETP) electrophiles. Most importantly, we found that the addition of glutathione had no significant effect on the reaction between ETPs and the aryl thiol at pH 7.0 and below, supporting orthogonal reactivity between the aryl and alkyl thiols. We utilized these findings to develop an orthogonal thiol-selective dual bioconjugation protocol for proteins, featuring TTL-ligation to site-specifically incorporate the arylthiol-containing amino acid derivative, followed by aryl thiolate functionalization at pH 5.5 and subsequent conjugation of cysteines at pH 8.3. This dual bioconjugation strategy was used to generate a highly fluorescent photostabilized nanobody and a fully functionalized antibody-drug conjugate carrying two different cytotoxic payloads, which displays potent cytotoxicity toward cells carrying the target antigen in addition to a strong bystander effect.}, archive = {J_JACS}, author = {Mark A. R. de Geus and Christian E. Stieger and Jan Vincent V. Arafiles and Jean-Romain P. J. Lotthé and Peter Schmieder and Kristin Kemnitz-Hassanin and Beate Kindt and Heinrich Leonhardt and Saskia Schmitt and Marcus Gerlach and Dominik Schumacher and Jonas Helma and Marc-André Kasper and Christian P. R. Hackenberger}, doi = {10.1021/jacs.5c02981}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18888--18900}, shortjournal = {J. Am. Chem. Soc.}, title = {Orthogonal site-specific dual bioconjugation of aryl and alkyl thiols}, volume = {147}, year = {2025}, }
• (2025). UV-cross-linked DNA nanomaterials enable robust nanopatterning of folate ligands for enhanced cellular uptake. JACS, 147(22), 18876--18887. (www)

  @article{ , abstract = {The arrangement of ligands on a nanomaterial scaffold is a powerful approach to enhance targeted cellular delivery. However, nanomaterial-mediated delivery often employs imprecise ligand conjugation, limiting the exploration of optimal ligand density and spatial organization. To address these challenges, we developed DNA nanomaterials with precisely spaced folate ligands and rigidified them via a postassembly UV-based thymine cross-linking. These materials exhibit exceptional nuclease stability and maintain structural integrity both under biologically relevant conditions and during internalization into live HeLa cells. We used these nanomaterials as scaffolds for folate patterning and identified optimal modes of folate presentation for cellular uptake. Each step of the uptake process was probed, revealing the synergistic effects of structural stabilization and precise ligand patterning on the uptake mechanism, intracellular retention, and export dynamics. We then used our nanopatterned nanomaterials as delivery vectors for a gene-silencing nucleic acid payload. By integrating optimized ligand presentation and structural immobilization, we successfully achieved targeted gene silencing in folate receptor alpha-expressing cancer cells. This work showcases the effect that DNA nanostructure fidelity and rigidity have on the presentation of ligand moieties. It introduces UV cross-linking as a critical tool for structural stabilization of DNA nanomaterials, enabling applications in therapeutic delivery, diagnostics, and nanoscale cell surface engineering. In addition, this study reveals spatial principles of folate nanopatterning to enhance future targeted delivery systems with precision, stability, and biocompatibility.}, archive = {J_JACS}, author = {Tyler M. Brown and Daniel Saliba and Jakob Hartmann and Jathavan Asohan and Chihyu Yao and Trishalina Das and Hanadi F. Sleiman}, doi = {10.1021/jacs.5c02986}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18876--18887}, shortjournal = {J. Am. Chem. Soc.}, title = {UV-cross-linked DNA nanomaterials enable robust nanopatterning of folate ligands for enhanced cellular uptake}, volume = {147}, year = {2025}, }
• (2025). Operando two-dimensional solid-state NMR unveils dual-template collaboration and competition in SAPO-34 zeolite crystallization. JACS, 147(22), 18864--18875. (www)

  @article{ , abstract = {Unraveling the mechanism of zeolite crystallization, especially in a complex system containing dual-template agents, remains a critical challenge. In this work, we introduced, for the first time, novel operando two-dimensional (2D) solid-state NMR spectroscopy under extreme conditions of high temperature and high pressure, allowing for observations with atomic-level spatial and temporal resolution, thereby enabling unprecedented insights into the crystallization of SAPO-34 zeolite. By utilizing operando 2D 31 P{ 1 H} HETCOR, 27 Al{ 1 H} HMQC NMR techniques, we clarified the intricate cooperative and competitive interactions of dual-template agents and highlighted the synergistic effect between templates and hydroxyl groups during CHA zeolite crystallization. Furthermore, operando 1 H, 27 Al, and 31 P MAS NMR revealed a previously unreported induction period, which precedes intermediate formation. This innovative approach advances the understanding of molecular dynamics, crystallization mechanism, and synthesis method for zeolites, representing a significant leap forward in the field of operando two-dimensional solid-state NMR spectroscopy.}, archive = {J_JACS}, author = {Daoning Wu and Xinlong Yao and Lixin Liang and Quanzheng Deng and Lu Han and Guangjin Hou and Weili Dai}, doi = {10.1021/jacs.5c02853}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18864--18875}, shortjournal = {J. Am. Chem. Soc.}, title = {Operando two-dimensional solid-state NMR unveils dual-template collaboration and competition in SAPO-34 zeolite crystallization}, volume = {147}, year = {2025}, }
• (2025). Spontaneous fission of charged water nanodrops: Unveiling the stochastic nature of fission pathways and dynamics. JACS, 147(22), 18853--18863. (www)

  @article{ , abstract = {Fission of highly charged micrometer-sized and larger droplets has been investigated using optical methods, but until recently, direct measurements of spontaneous fission of submicrometer droplets have not been possible. Charge detection mass spectrometry is used to track the mass, charge, and energy per charge of aqueous nanodrops that undergo evaporative water loss while they are trapped for up to 4 s. 154 of the 846 trapped nanodrops (18.2%) with charges ranging from 44 to 158% of the Rayleigh limit underwent fission. Although these spontaneous fission processes are highly heterogeneous, four distinct fission pathways that occur over times ranging from a few ms to 100s of ms with ejection of just a few to hundreds of progeny droplets were identified. One is a “continuous” pathway in which many small progeny droplets with progressively less charge are sequentially emitted over the course of ∼25 to 150 ms. Prompt and sequential prompt pathways in which one or a limited number of progeny droplets carry away a significant fraction of the precursor charge are the most common. “Prefission” events in which emission of just a few charges prior to a larger prompt fission event occur for some nanodrops charged above the Rayleigh limit, and these events appear to have similarities to “foreshocks” that often occur shortly prior to major earthquakes.}, archive = {J_JACS}, author = {Veena S. Avadhani and Conner C. Harper and Zachary M. Miller and Evan R. Williams}, doi = {10.1021/jacs.5c02845}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18853--18863}, shortjournal = {J. Am. Chem. Soc.}, title = {Spontaneous fission of charged water nanodrops: Unveiling the stochastic nature of fission pathways and dynamics}, volume = {147}, year = {2025}, }
• (2025). Disorder-mediated ionic conductivity in irreducible solid electrolytes. JACS, 147(22), 18840--18852. (www)

  @article{ , abstract = {Solid-state batteries currently receive extensive attention due to their potential to outperform lithium-ion batteries in terms of energy density when featuring next-generation anodes such as lithium metal or silicon. However, most highly conducting solid electrolytes decompose at the low operating voltages of next-generation anodes leading to irreversible lithium loss and increased cell resistance. Such performance losses may be prevented by designing electrolytes which are thermodynamically stable at low operating voltages (anolytes). Here, we report on the discovery of a new family of irreducible (i.e., fully reduced ) electrolytes by mechanochemically dissolving lithium nitride into the Li 2 S antifluorite structure, yielding highly conducting crystalline Li 2+ x S 1– x N x phases reaching >0.2 mS cm –1 at ambient temperature. Combining impedance spectroscopy experiments and ab initio density functional theory calculations we clarify the mechanism by which the disordering of the sulfide and nitride ions in the anion sublattice boosts ionic conductivity in Li 2+ x S 1– x N x phases by a factor 10 5 compared to the Li 2 S host structure. This advance is achieved through a novel theoretical framework, leveraging percolation analysis with local-environment-specific activation energies and is widely applicable to disordered ion conductors. The same methodology allows us to rationalize how increasing nitrogen content in Li 2+ x S 1– x N x antifluorite-like samples leads to both increased ionic conductivity and lower conductivity-activation energy. These findings pave the way to understanding disordered solid electrolytes and eliminating decomposition-induced performance losses on the anode side in solid-state batteries.}, archive = {J_JACS}, author = {Victor Landgraf and Mengfu Tu and Wenxuan Zhao and Anastasia K. Lavrinenko and Zhu Cheng and Jef Canals and Joris de Leeuw and Swapna Ganapathy and Alexandros Vasileiadis and Marnix Wagemaker and Theodosios Famprikis}, doi = {10.1021/jacs.5c02784}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18840--18852}, shortjournal = {J. Am. Chem. Soc.}, title = {Disorder-mediated ionic conductivity in irreducible solid electrolytes}, volume = {147}, year = {2025}, }
• (2025). Spontaneous emergence of homochiral suspensions from racemic solutions via stochastic nucleation. JACS, 147(22), 18826--18839. (www)

  @article{ , abstract = {Homochirality represents a hallmark of life, and its emergence on the prebiotic Earth remains elusive. Here, we demonstrate a spontaneous pathway to homochirality, where a conglomerate-forming chiral species ( N -(2-methylbenzylidene)-phenylglycine amide, NMPA) evolves from an initial perfectly symmetric state, i.e., a racemic solution, to a fully homochiral state, where only enantiopure crystals of one handedness are present in the suspension. It entails first the establishment of supersaturated conditions, e.g., because of either solvent evaporation or cooling, then stochastic nucleation of enantiopure crystals as the symmetry-breaking event, and finally asymmetry amplification and complete deracemization via temperature fluctuations in a racemizing solution (thanks to the presence of the base 1,8- diazabicyclo[5.4.0]undec-7-en, DBU). After developing a stochastic modeling platform and an experimental setup, we confirm the plausibility of this pathway through both detailed simulations and laboratory experiments. We also show how from a variety of local homochiral states of different handedness a global homochiral state may emerge via merging and deracemizing. Because the external conditions triggering supersaturation creation, nucleation, and deracemization via temperature-cycling must have existed also on the prebiotic Earth, the proposed spontaneous pathway may have plausibly played a role in the emergence of life on Earth.}, archive = {J_JACS}, author = {Leif-Thore Deck and Mercedeh Sadat Hosseinalipour and Marco Mazzotti}, doi = {10.1021/jacs.5c02651}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18826--18839}, shortjournal = {J. Am. Chem. Soc.}, title = {Spontaneous emergence of homochiral suspensions from racemic solutions via stochastic nucleation}, volume = {147}, year = {2025}, }
• (2025). Single-pt-atom-decorated TiO2 nanorod arrays for photoelectrochemical C–H chlorination. JACS, 147(22), 18814--18825. (www)

  @article{ , abstract = {Photoelectrochemical (PEC) chloride oxidation reaction offers a green and sustainable approach for the synthesis of chlorinated chemicals, pesticides, pharmaceuticals/drugs, etc. However, until now, efficient PEC chloride activation remains highly challenging, primarily due to the lack of effective catalytically active reaction sites on the developed photoanodes. Herein, we construct a high-performance photoanode for PEC C–H chlorination by controllably embedding Pt single atoms onto positively charged TiO 2 nanorod arrays (denoted as Pt 1 - p -TiO 2 NRAs). The one-dimensional single-crystalline TiO 2 nanorods not only create a rapid electron transport pathway but also orthogonalize the light absorption and hole transport directions, effectively suppressing photogenerated electron–hole recombination. Furthermore, the positively charged TiO 2 nanorod surface induced by electrochemical reduction can facilitate the anchoring of single Pt atoms as C–H chlorination active sites onto TiO 2 and at the same time modulate the charge carrier dynamics. Consequently, high selectivity (up to 87%) and Faradaic efficiency (close to 60%) toward chlorination of organics are achieved over Pt 1 - p -TiO 2 NRAs using NaCl as the chlorine source under light illumination. PEC experiments and mechanistic investigations demonstrate that the single Pt atoms on TiO 2 nanorods can help to effectively separate photoexcited charge carriers and induce preferable chloride ions’ adsorption as well as electron transfer from Pt single atoms to TiO 2 nanorods to generate reactive chloride radicals (Cl•), which play a key role in PEC C–H chlorination.}, archive = {J_JACS}, author = {Ying Tao and Jie Ding and Zhenyuan Teng and Qingzhu Xu and Wei Ou and Hongli Sun and Shuangjun Li and Lei Yu and Guisheng Li and Bin Liu and Chenliang Su}, doi = {10.1021/jacs.5c02551}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18814--18825}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-pt-atom-decorated TiO2 nanorod arrays for photoelectrochemical C–H chlorination}, volume = {147}, year = {2025}, }
• (2025). Efficient self-sensitized photochemical CO2 reduction using [Re(bpy2+)(CO)3(I)]2+ and [Re(bpy2+)(CO)3(CH3CN)]3+ photocatalysts with pendent ammonium cations. JACS, 147(22), 18796--18813. (www)

  @article{ , abstract = {Rhenium(I) tricarbonyl complexes fac -[Re(bpy)(CO) 3 (L)] n+ are the classic examples of self-sensitized photocatalysts capable of the dual roles of light absorption and catalysis. In this work, a series of dicationic halido or tricationic solvento complexes fac -[Re(bpy 2+ )(CO) 3 X] n+ (PF 6 ) n (where X = Cl – or I – ( n = 2), or CH 3 CN ( n = 3) and bpy 2+ is bipyridine modified by two −CH 2 –(NMe 3 ) + tetra-alkylammonium cations) have been investigated as self-sensitized and sensitized CO 2 reduction photocatalysts. Four structural isomers differing in the cation position have been tested in N , N ′-dimethylacetamide solvent (DMA) using 1,3-dimethyl-2-phenyl-2,3-dihydro-1 H -benzimidazole (BIH) as the electron donor, and the position of the cationic pendants has a significant impact on the catalyst turnover number and quantum efficiency (ϕ). Up to 455 self-sensitized turnovers of CO and a high photon efficiency (ϕ CO ) of 22% have been achieved. Time-resolved infrared spectroscopy and theoretical calculations were used to characterize the catalytic cycle including the ligand exchange between one-electron reduced (OER) halido and solvento species as well as the binding of CO 2 to the putative two-electron reduced (TER) species. The CO 2 -reactive TER catalyst was formed by disproportionation or intramolecular electron transfer between two forms of the OER catalyst as indicated by the formation of the fully oxidized catalyst concurrent with CO 2 binding. When [Ru(bpy) 3 ] 2+ was used as a sensitizer, catalyst durability improved, and the selectivity toward formate increased as high as 3.3:1 over CO (total TON = 1370) due to acidification of the reaction, which promotes formation of the hydride intermediate, as BIH was consumed and deprotonated.}, archive = {J_JACS}, author = {Zongheng Wang and Laura Rotundo and Mehmed Z. Ertem and Dmitry E. Polyansky and Gerald F. Manbeck}, doi = {10.1021/jacs.5c02523}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18796--18813}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient self-sensitized photochemical CO2 reduction using [Re(bpy2+)(CO)3(I)]2+ and [Re(bpy2+)(CO)3(CH3CN)]3+ photocatalysts with pendent ammonium cations}, volume = {147}, year = {2025}, }
• (2025). Supramolecular polymorphism of the hydrogen-bonded c3-symmetrical hexadehydrotribenzo[12]annulene derivative. JACS, 147(22), 18783--18795. (www)

  @article{ , abstract = {The C 3 -symmetric hexadehydrotribenzo[12]annulene ( [12]DBA ) derivative ( 1a ) with three tetradecylamide (−NHCOC 14 H 29 ) chains capable of hydrogen-bonding interaction formed either a two-dimensional lamellar ( LM ) or a one-dimensional (1D) nanofiber ( NF ) molecular assembly, depending on the association state of the amide hydrogen bonds in the solution phase. The intermolecular amide hydrogen-bonding modes in the LM and NF structures were different from each other. The NF structure was metastable, 2.2 kJ mol –1 less stable than that of the LM structure, and was obtained through organogel formation. In CHCl 3 , 1a exhibited a 1D association behavior following the isodesmic model ( K = 2.18 × 10 3 M –1 ) due to intermolecular amide hydrogen bonds, whereas the presence of CH 3 CN inhibited this association state. The NF structure had larger amplitude dynamics about the polar amide group than that of the LM structure, undergoing a phase transition from the NF to the LM structure upon heating. The absorption spectra of NF and solid-state LM were different from each other, exhibiting different optical properties. The coexistence of intermolecular amide hydrogen bonds and van der Waals interactions among the C 3 -symmetric molecules resulted in polymorphic phenomena, where energetically similar molecular assemblies were expressed.}, archive = {J_JACS}, author = {Yotaro Kasahara and Takashi Takeda and Shun Dekura and Yoshiki Ishii and Hayato Anetai and Atsuro Takai and Ichiro Hisaki and Masayuki Takeuchi and Tomoyuki Akutagawa}, doi = {10.1021/jacs.5c02529}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18783--18795}, shortjournal = {J. Am. Chem. Soc.}, title = {Supramolecular polymorphism of the hydrogen-bonded c3-symmetrical hexadehydrotribenzo[12]annulene derivative}, volume = {147}, year = {2025}, }
• (2025). A designed zn2+ sensor domain transmits binding information to transmembrane histidine kinases. JACS, 147(22), 18770--18782. (www)

  @article{ , abstract = {Generating stimulus-responsive allosteric signaling de novo is a significant challenge in protein design. In natural systems like bacterial histidine kinases (HKs), signal transduction occurs when ligand binding initiates a signal that is amplified across biological membranes over long distances to induce large-scale rearrangements and phosphorylation relays. Here, we ask whether our understanding of protein design and multidomain, intramolecular signaling has progressed sufficiently to enable engineering of a HK with tunable de novo components. We generated de novo metal-binding sensor domains and substituted them for the native sensor domain of a transmembrane HK, affording chimeras that transduce signals initiated from a de novo sensor. Signaling depended on the designed sensor’s stability and the interdomain linker’s phase and length. These results show the usefulness of de novo design to elucidate the biochemical mechanisms and principles of transmembrane signaling.}, archive = {J_JACS}, author = {A. Katherine Hatstat and Rian Kormos and Vee Xu and Guoming Du and Lijun Liu and Shao-Qing Zhang and William F. DeGrado}, doi = {10.1021/jacs.5c02273}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18770--18782}, shortjournal = {J. Am. Chem. Soc.}, title = {A designed zn2+ sensor domain transmits binding information to transmembrane histidine kinases}, volume = {147}, year = {2025}, }
• (2025). Engineering spatial interface in supported molecular complexes for ampere-level electrocatalytic oxygen evolution. JACS, 147(22), 18760--18769. (www)

  @article{ , abstract = {Homogenized molecular complexes with active single sites hold great promise for electrocatalytic conversion processes. However, the influence of the spatial gap between coordination complexes and the carbon support on electron shuttling remains poorly understood. Herein, we demonstrate a supramolecular architectural strategy that leverages oxygen sites to strengthen the complex-support interactions, thereby elucidating the oxygen evolution reaction (OER) catalytic mechanism effected by the spatial gap. Experimental results reveal that the narrow gap would benefit electron shuttling and stabilize the molecular complexes, enabling the ampere-level current densities. Typically, the optimized biphenyl-4,4′-dicarboxylic acid-coordinated Fe–Ni complexes exhibit superior electrocatalytic performance with a current density of 1.5 A cm –2 and a mass activity of 41,206 A g Fe/Ni –1 at an overpotential of 0.33 V. Theoretical studies further demonstrate that the highly electrophilic oxygen bridging between iron and nickel sites would promote the formation of key intermediates on iron sites (Fe–OOH*). These findings demonstrate the significant roles of complex-support interactions in designing heterogeneous molecular complexes.}, archive = {J_JACS}, author = {Yun Gao and Chengdong Yang and Xiaobo Zheng and Zechao Zhuang and Jiarui Yang and Yuhai Dou and Jintao Zhang and Dingsheng Wang}, doi = {10.1021/jacs.5c02247}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18760--18769}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering spatial interface in supported molecular complexes for ampere-level electrocatalytic oxygen evolution}, volume = {147}, year = {2025}, }
• (2025). Applying active learning toward building a generalizable model for ni-photoredox cross-electrophile coupling of aryl and alkyl bromides. JACS, 147(22), 18747--18759. (www)

  @article{ , abstract = {When developing machine learning models for yield prediction, the two main challenges are effectively exploring condition space and substrate space. In this article, we disclose an approach for mapping the substrate space for Ni/photoredox-catalyzed cross-electrophile coupling of alkyl bromides and aryl bromides in a high-throughput experimentation (HTE) context. This model employs active learning (in particular, uncertainty querying) as a strategy to rapidly construct a yield model. Given the vastness of substrate space, we focused on an approach that builds an initial model and then uses a minimal data set to expand into new chemical spaces. In particular, we built a model for a virtual space of 22,240 compounds using less than 400 data points. We demonstrated that the model can be expanded to 33,312 compounds by adding information around 24 building blocks (<100 additional reactions). Comparing the active learning-based model to one constructed on randomly selected data showed that the active learning model was significantly better at predicting which reactions will be successful. A combination of density function theory (DFT) and difference Morgan fingerprints was employed to construct the random forest model. Feature importance analysis indicates that key DFT features that are related to the reaction mechanism (e.g., alkyl radical LUMO energy) were crucial for model performance and predictions on aryl bromides outside the training set. We anticipate that combining DFT featurization and uncertainty-based querying will help the synthetic organic community build predictive models in a data-efficient manner for other chemical reactions that feature large and diverse scopes.}, archive = {J_JACS}, author = {Lucas W. Souza and Nathan D. Ricke and Braden C. Chaffin and Mike E. Fortunato and Shutian Jiang and Cihan Soylu and Thomas C. Caya and Sii Hong Lau and Katherine A. Wieser and Abigail G. Doyle and Kian L. Tan}, doi = {10.1021/jacs.5c02218}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18747--18759}, shortjournal = {J. Am. Chem. Soc.}, title = {Applying active learning toward building a generalizable model for ni-photoredox cross-electrophile coupling of aryl and alkyl bromides}, volume = {147}, year = {2025}, }
• (2025). Isolated copper atoms boost *NO3 adsorption and active hydrogen retention over zinc oxide for ammonia electrosynthesis at ampere-level current densities. JACS, 147(22), 18737--18746. (www)

  @article{ , abstract = {The use of renewable electricity to drive the electroreduction of nitrate to ammonia can simultaneously achieve the green synthesis of ammonia and alleviate the environmental pollution of nitrate. However, the industrial requirement for ammonia synthesis with ampere-level current densities remains a grand challenge. In addition, the electroreduction of nitrate to ammonia reaction requires multiple steps of deoxygenation and hydrogenation of *NO 3 intermediates. Therefore, it is urgent to clarify the relationship between the adsorption strength of *NO 3 /*H (active hydrogen) intermediates and the catalytic activity. Herein, we achieved highly selective ammonia electrosynthesis at ampere-level current densities by anchoring atomically dispersed copper atoms on zinc oxide (ZnO) nanospheres (Cu 1 /ZnO). The synthesized Cu 1 /ZnO delivers a high NH 3 yield rate of 184.7 mg h –1 cm –2 with an NH 3 Faradaic efficiency of 96.1% and an NH 3 partial current density of 2.23 A cm –2 in a flow cell. Based on mechanistic studies, anchoring Cu single atoms over ZnO enhances the adsorption of the *NO 3 intermediate and the retention of *H generated by water dissociation, resulting in the decreased energy barrier of the rate-determining step of *NO-to-*NHO.}, archive = {J_JACS}, author = {Zhipeng Chen and Yusi Zhao and Haoran Huang and Gen Liu and Hongna Zhang and Yan Yan and Hongliang Li and Licheng Liu and Mingkai Liu and Dingsheng Wang and Jie Zeng}, doi = {10.1021/jacs.5c01863}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18737--18746}, shortjournal = {J. Am. Chem. Soc.}, title = {Isolated copper atoms boost *NO3 adsorption and active hydrogen retention over zinc oxide for ammonia electrosynthesis at ampere-level current densities}, volume = {147}, year = {2025}, }
• (2025). Caught in the middle: A rigid DNA label that provides an incisive picture of DNA conformational flexibility in Protein–DNA complexes. JACS, 147(22), 18723--18736. (www)

  @article{ , abstract = {Measurement of the conformation of DNA in protein–DNA complexes is important to decipher the role of the DNA conformation and dynamics in protein recognition and function. In this work, we report a rigid nucleotide-independent spin label that places paramagnetic Cu(II) within the DNA helix. The labeling strategy exploits the chelation of Cu(II) to two 8-aminoquinoline moieties, one in each strand. Because the rigidity of the probe avoids potentially confounding motions of the label itself, EPR signals can resolve 2–3 Å changes in interspin distance; the breadth of the distance distribution reports dynamic fluctuations from the most probable conformation. Continuous wave and pulsed electron paramagnetic resonance spectroscopy (EPR) shows that Cu(II) coordinates properly to the labeling sites. Measurements of the interspin dipolar interaction on DNA oligonucleotides with two labels placed at various distances demonstrate that the label provides accurate and narrow distance distributions sensitive to DNA conformation and flexibility. Molecular dynamics simulations support these interpretations. We utilized this label to measure the conformations of DNA when the type II restriction endonuclease Eco RV binds to its specific recognition sequence. The results provide in-solution evidence that the Eco RV endonuclease induces axial DNA bending in the absence of metal ions, contrary to a long-standing belief. Furthermore, the distance distribution narrows upon protein binding and even further on subsequent metal binding, implying that bound protein constrains the bending dynamics of DNA. This method provides a novel and accurate approach to assess DNA conformation and dynamics in solution.}, archive = {J_JACS}, author = {Joshua Casto and Shramana Palit and Anthony Little and Zikri Hasanbasri and Linda Jen-Jacobson and Sunil Saxena}, doi = {10.1021/jacs.5c01823}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18723--18736}, shortjournal = {J. Am. Chem. Soc.}, title = {Caught in the middle: A rigid DNA label that provides an incisive picture of DNA conformational flexibility in Protein–DNA complexes}, volume = {147}, year = {2025}, }
• (2025). Operando contactless EFISH study of the rate-determining step of light-driven water oxidation on TiO2 photoanodes. JACS, 147(22), 18712--18722. (www)

  @article{ , abstract = {For many slow solar-fuel-forming reactions, the accumulation of photogenerated minority carriers on the photoelectrode surface leads to light-induced band edge unpinning, affecting the junction properties by decreasing band bending in the semiconductor space charge layer and increasing the driving force of surface reactions in the electric double layer. In this study, we demonstrate a contactless operando electric field-induced second harmonic generation (EFISH) method for measuring the band bending change (δΔΦ SCR L ) on photoelectrodes upon photoexcitation. For n-doped rutile TiO 2 water oxidation photoanodes at pH 7, δΔΦ SCR L increases at more positive potentials or higher illumination power density until it reaches saturation values. We show that under fast mass transport conditions, δΔΦ SCR L is exclusively attributed to the accumulated charged rate-determining species that can be regarded as temporary surface states, and the relationship between the photocurrent and δΔΦ SCR L can be well modeled by assuming that hole trap states function as the reaction center. Kinetic isotope experiments identify proton-coupled electron transfer as the rate-determining step and suggest a possible chemical nature of the key intermediate. We demonstrate that light-induced band edge unpinning is a beneficial feature under high illumination conditions for oxygen evolution reaction on TiO 2 because it maintains the photon-to-current conversion efficiency by enhancing the surface reaction driving force, shedding light on the actual device application.}, archive = {J_JACS}, author = {Fengyi Zhao and Zihao Xu and Sa Suo and Yixuan Xu and Craig L. Hill and Djamaladdin G. Musaev and Tianquan Lian}, doi = {10.1021/jacs.5c01836}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18712--18722}, shortjournal = {J. Am. Chem. Soc.}, title = {Operando contactless EFISH study of the rate-determining step of light-driven water oxidation on TiO2 photoanodes}, volume = {147}, year = {2025}, }
• (2025). Evidence of ferroelectric distortions in topological crystalline insulators via transverse thermoelectric measurements. JACS, 147(22), 18704--18711. (www)

  @article{ , abstract = {The transverse thermoelectric (Nernst) effect is a powerful probe for studying the electronic and structural properties of materials. In this study, we employ transverse thermoelectric measurements to investigate the ferroelectric distortion in the topological crystalline insulator (TCI) Pb 0.60 Sn 0.40 Te, a compound derived from PbTe and SnTe, known for their exceptional thermoelectric performance and distinct ferroelectric properties. By leveraging Nernst measurements, we provide direct evidence of ferroelectric distortion in this TCI, corroborated by Shubnikov–de Haas quantum oscillations that confirm the presence of two topologically nontrivial Fermi pockets. Density functional theory calculations show that these pockets originate from the L and T points in the Brillouin zone of the distorted structure within the TCI phase. Raman spectroscopy further identifies a structural phase transition below 50 K, consistent with the quantum oscillation observations. This observation is further substantiated by temperature-dependent synchrotron X-ray pair distribution function analysis and transmission electron microscopy, which confirm the local off-centering of cations at low temperature. These findings underscore the potential of transverse thermoelectric measurements in unveiling ferroelectric distortions and their role in modulating topological quantum states, opening new directions for research into the synergy between ferroelectricity and topological phases.}, archive = {J_JACS}, author = {Pranav Negi and Bin He and Denis Ukolov and Sharona Horta and Krishnendu Maji and Ning Mao and Nikolai Peshcherenko and Premakumar Yanda and Mengyu Yao and Moinak Dutta and Iñigo Robredo and Mikel Iraola and Maia G. Vergniory and Peter Lemmens and Yang Zhang and Chandra Shekhar and Maria Ibáñez and Claudia Felser and Subhajit Roychowdhury}, doi = {10.1021/jacs.5c01700}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18704--18711}, shortjournal = {J. Am. Chem. Soc.}, title = {Evidence of ferroelectric distortions in topological crystalline insulators via transverse thermoelectric measurements}, volume = {147}, year = {2025}, }
• (2025). Inner-sphere electron transfer enabling highly reversible Mn2+/MnO2 conversion toward energy-dense electrolytic Zinc–Manganese batteries. JACS, 147(22), 18694--18703. (www)

  @article{ , abstract = {High-voltage electrolytic Zn//MnO 2 batteries show great potential for large-scale energy storage due to their affordability, eco-friendliness and high safety. However, their practical application is hindered by capacity losses due to incomplete MnO 2 dissolution. Herein, we propose the strategy by coupling a 1,4-benzoquinone (1,4-BQ)/hydroquinone (HQ) redox mediator pair with in situ modulation of MnO 2 electronic structure through electrolyte engineering to facilitate rapid and complete MnO 2 dissolution. During the charging and discharging processes, Al 3+ ions in the electrolyte enter MnO 2 lattice by co-deposition and intercalation, respectively. The incorporated Al 3+ ions effectively optimize the electronic structure of MnO 2 by lowering the valence state of localized Mn IV to Mn III , thereby facilitating the formation of inner-sphere complexes with HQ molecules. This transformation successfully shifts the dominant reaction mechanism between MnO 2 and the redox mediator from outer-sphere electron transfer (Mn IV –HQ) to inner-sphere electron transfer (Mn III –HQ). Consequently, complete MnO 2 dissolution can be achieved in the designed electrolyte even at an ultrahigh areal capacity of 50 mAh cm –2 . Furthermore, a 750-mAh electrolytic Zn//MnO 2 battery exhibits a capacity retention rate of 99% after 100 cycles, demonstrating the significance of regulating electron transfer mechanisms during MnO 2 dissolution through electrolyte coupling strategies.}, archive = {J_JACS}, author = {Weijie Fan and Siyu Tian and Liping Qin and Taghrid S. Alomar and Pengchao Ruan and Zeinhom M. El-Bahy and Najla AlMasoud and Bingan Lu and Jiang Zhou}, doi = {10.1021/jacs.5c01648}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18694--18703}, shortjournal = {J. Am. Chem. Soc.}, title = {Inner-sphere electron transfer enabling highly reversible Mn2+/MnO2 conversion toward energy-dense electrolytic Zinc–Manganese batteries}, volume = {147}, year = {2025}, }
• (2025). A solvatochromic near infrared fluorophore sensitive to the full amyloid beta aggregation pathway. JACS, 147(22), 18685--18693. (www)

  @article{ , abstract = {Alzheimer’s disease has long been associated with the aggregation of amyloid beta peptides (Aβ42) into macroscale plaques, although specific neurodegenerative agents have not been definitively identified. Much evidence has pointed to the soluble nanoscale oligomers that form early in the Aβ42 aggregation pathway, but there is little understanding of these structures, their mechanisms of formation, or how they grow into plaques. Here, we show that a solvatochromic fluorophore with near-infrared (NIR) emission can track synthetic Aβ42 aggregation through environment-sensitive spectral shifts from the earliest time points through plaque formation. This azide-functionalized phosphine oxide azetidine rhodol (Phazr-N 3 ) shows large polarity-dependent changes in fluorescence emission, with maxima shifting from 630 nm in toluene to 703 nm in aqueous buffer, and a maximum quantum yield of 62%. Upon induction of Aβ42 aggregation, we observe immediate solvatochromic changes in Phazr-N 3 fluorescence, with multiple apparent phases over 12 h, and which culminate before the onset of any major fluorescence changes of conformation-specific aggregation fluorophore thioflavin T. Solution anisotropy measurements show a low micromolar affinity of Phazr-N 3 for disordered, free Aβ42 in solution, and real-time measurements are consistent with rapid liquid–liquid phase separation and slow dehydration of the growing aggregate. Spectral imaging of synthetic plaques stained in the presence of live cells and lipid-binding protein albumin shows over 4000-fold Phazr-N 3 fluorescence intensity above background under no-wash conditions, and over 100-fold intensity above coplated microglial cells or a large excess of albumin. This use of a solvatochromic probe with structure-independent binding to free Aβ42 offers real-time, minimally invasive insight into the full Aβ42 aggregation pathway.}, archive = {J_JACS}, author = {Zeming Wang and Line G. Kristensen and Yen H. Ho and Yazhi Liu and Luis A. Valencia and Isha Nadig and Kyleigh L. Range and Behzad Rad and Corie Y. Ralston and Bruce E. Cohen}, doi = {10.1021/jacs.5c01512}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18685--18693}, shortjournal = {J. Am. Chem. Soc.}, title = {A solvatochromic near infrared fluorophore sensitive to the full amyloid beta aggregation pathway}, volume = {147}, year = {2025}, }
• (2025). Engineering supramolecular hydrogen bonding interactions into dynamic covalent polymers to obtain double dynamic biomaterials. JACS, 147(22), 18674--18684. (www)

  @article{ , abstract = {Inspired by dynamic systems in nature, we can introduce dynamics into synthetic biomaterials through dynamic covalent bonds or supramolecular interactions. Combining both types of dynamic interactions may allow for advanced and innovative networks with multiple levels of dynamicity. Here we present two types of solid materials consisting of either dynamic covalent imine bonds or a combination of these dynamic covalent bonds with supramolecular hydrogen bonding ureido-pyrimidinone (UPy) units to obtain double dynamic materials. We showed the facile synthesis and formulation of both materials at room temperature. The thermal and physical properties of each material are highly tunable by altering the ratio and type of cross-linker. Interestingly, we showed that minimal amounts of UPy units result in a drastic increase in material mechanics. Furthermore, we show that both types of materials are suitable as biomaterials through functionalization with cell-adhesive peptides, through either a dynamic covalent imine bond or a supramolecular UPy moiety.}, archive = {J_JACS}, author = {Jasper G. M. Aarts and Maritza M. Rovers and Martin G. T. A. Rutten and Patricia Y. W. Dankers}, doi = {10.1021/jacs.4c15102}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18674--18684}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering supramolecular hydrogen bonding interactions into dynamic covalent polymers to obtain double dynamic biomaterials}, volume = {147}, year = {2025}, }
• (2025). Toward chiral recognition by design: Uncovering the self-enantioresolving properties of chiral amine derivatives. JACS, 147(22), 18662--18673. (www)

  @article{ , abstract = {The study of chiral recognition phenomena is key for understanding biological processes, designing bioactive compounds, and for asymmetric catalysis and chiral analysis. In addition, phenomena related to the self-recognition of enantiomers are highly relevant in emergence-of-homochirality research and supramolecular chemistry. However, the design of molecules exhibiting chiral self-recognition remains challenging, and its observation is mainly based on serendipity. Here, we report a comprehensive study of the self-enantiorecognition properties of chiral amine-derived building blocks frequently encountered in organic synthesis. Through a structure−activity relationship study, multiple families of chiral amine derivatives, featuring self-complementary hydrogen-bond donor and acceptor groups, have been found to exhibit self-induced diastereomeric anisochronism (SIDA) by NMR analysis, a rather unexplored form of self-recognition of enantiomers. Our study suggests that the self-enantiorecognition properties of many common building blocks in asymmetric synthesis might have remained inadvertently unnoticed. We have also rationalized the origins of their SIDA effect and demonstrated their potential as an in situ probe for the determination of enantiomeric purity, the analysis of supramolecular interactions, and the study of reaction mechanisms. We anticipate that the principles outlined here will contribute to fostering the use of the SIDA effect in fundamental stereochemical studies, asymmetric synthesis, catalysis, and supramolecular chemistry.}, archive = {J_JACS}, author = {Anka Hagelschuer and Damián Padín and Vanda Dašková and Ben L. Feringa}, doi = {10.1021/jacs.5c01251}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18662--18673}, shortjournal = {J. Am. Chem. Soc.}, title = {Toward chiral recognition by design: Uncovering the self-enantioresolving properties of chiral amine derivatives}, volume = {147}, year = {2025}, }
• (2025). Mesoporous single-crystal high-entropy alloy. JACS, 147(22), 18651--18661. (www)

  @article{ , abstract = {Mesoporous high-entropy alloys (HEAs) represent a promising advancement in mesoporous metals, showing great potential for various applications. Their unique multi-metallic uniformity, strong structural features, and high surface-active-site exposure contribute to their practical catalytic ability. The catalytic efficiency of metal nanostructures depends on both their elemental compositions and crystallinity, with single-crystalline structures generally outperforming polycrystalline ones. However, synthesizing single-crystalline HEA nanostructures with defined mesoporosity remains challenging due to the complex fabrication process. This study introduces a block copolymer micelle-assisted soft-chemical strategy to create single-crystalline mesoporous HEAs (SCPHEAs). These structures feature uniformly sized mesopores that permeate the entire structure, maximizing the exposure of HEA active sites, enhancing material utilization, and facilitating efficient mass and charge transport. The optimized SCPHEAs exhibit excellent electrocatalytic performance in methanol oxidation reactions, surpassing polycrystalline mesoporous HEAs, commercial Pt–C, and various recently reported precious metal-based HEAs and conventional alloy electrocatalysts. This superior performance is attributed to a synergistic effect that results from surface charge redistribution among different atomic entities, which enhances the adsorption of methanol and water molecules and mitigates intermediate CO poisoning. Our synthesis method enables the design of a wide range of mesoporous HEAs with controllable morphology and crystallinity tailored for various catalytic applications and beyond.}, archive = {J_JACS}, author = {Ravi Nandan and Ho Ngoc Nam and Quan Manh Phung and Hiroki Nara and Joel Henzie and Yusuke Yamauchi}, doi = {10.1021/jacs.5c01260}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18651--18661}, shortjournal = {J. Am. Chem. Soc.}, title = {Mesoporous single-crystal high-entropy alloy}, volume = {147}, year = {2025}, }
• (2025). Establishing dual-interface built-in electric fields within janus heterostructures for cooperative photoredox catalysis. JACS, 147(22), 18637--18650. (www)

  @article{ , abstract = {Rationally designing nanostructures and comprehensively understanding the structure–property relationships are important for directional charge transfer. A general dual-interface built-in electric field (BIEF) regulation strategy is developed to synthesize the bifunctional ZnS/Sv-chalcogenide/Ti 3 C 2 heterostructure photocatalysts (Sv represents sulfur vacancies; chalcogenides include ZnIn 2 S 4 , CdS, and CdIn 2 S 4 ) consisting of a ZnS/chalcogenide S-scheme heterojunction and a Sv-chalcogenide/Ti 3 C 2 Schottky heterojunction. The ternary-component photocatalyst construction involves hollow core–shell heterostructure establishment via lateral epitaxy and chalcogenide-surface Ti 3 C 2 nanoparticle introduction via a defect-mediated heterocomponent anchorage. These nanoreactors integrate the strong intrinsic driving force and enhanced interfacial electronic coupling, leveraging resulting dual-interface BIEFs for precise carrier mobility control and robust redox performance feedback. The BIEF-induced ultrafast charge transfer features powerful photocarrier enrichment and feeble photocarrier recombination at the ZnS/ZnIn 2 S 4 S-scheme heterointerface as well as continuous steering of photocarrier localization and delocalized electron transport at the Sv-ZnIn 2 S 4 /Ti 3 C 2 Schottky heterointerface. Simultaneously, BIEF-induced targeted molecule catalysis is marked by complementary adsorption and selective activation of key intermediates. Representative ZnS/Sv-ZnIn 2 S 4 /Ti 3 C 2 demonstrates broad substrate compatibility and superhigh reactivity in cooperative biomass valorization and hydrogen evolution. This study provides a programmable framework for manipulating BIEFs by multicomponent ordered-space integration and interface engineering, elucidating the substantial impact of dual-interface BIEFs on carrier transport behavior and molecular catalytic behavior.}, archive = {J_JACS}, author = {Yi-Wen Han and Yu-Xin Zhang and Lei Ye and Tian-Jun Gong and Xue-Bin Lu and Ning Yan and Yao Fu}, doi = {10.1021/jacs.5c01171}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18637--18650}, shortjournal = {J. Am. Chem. Soc.}, title = {Establishing dual-interface built-in electric fields within janus heterostructures for cooperative photoredox catalysis}, volume = {147}, year = {2025}, }
• (2025). Responsive organoselenium dendritic polymers: From monodisperse dendrimers to self-assembled micelles for advanced therapeutic applications. JACS, 147(22), 18626--18636. (www)

  @article{ , abstract = {Selenium (Se) is a highly biologically active element, and its organic derivatives have attracted growing interest for their promising chemotherapeutic potential, largely due to their redox-modulating activity, which selectively affects cancer cells with high levels of reactive oxygen species (ROS). However, their high reactivity and susceptibility to spontaneous degradation limit their biomedical application. To harness their potential in the realm of nanomedicine, we present a new generation of therapeutically promising polymers that combine Se with 2,2-bis(methylol)propionic acid (bis-MPA)-based dendritic polymers, chosen for their high chemical versatility, low toxicity, and excellent biodegradability. Most examples in the literature about dendritic polymers feature dormant dendritic skeletons with active functional groups expressed only on their periphery, which severely limits their functional scope. In this work, monodisperse dendrimers and linear–dendritic (LD) polymers up to the third generation were developed, with the latter capable of self-assembling into dendritic micelles (∼20 nm). These systems feature Se at the dendritic core or peripheral branches in the form of monoselenide or diselenide bridges. Selenium incorporation demonstrated excellent compatibility with two key polyester synthetic approaches: anhydride chemistry and fluoride-promoted esterification (FPE). Both monoselenide and diselenide linkages introduced degradability and dynamic behavior in dendrimers and dendritic micelles. However, their biological activities differed significantly. Diselenide-containing dendrimers exhibited great anticancer potential against breast cancer cell lines, with IC 50 values in the micromolar range. Among these, first-generation Se dendrimers stood out due to their promising selectivity toward cancer cells. In contrast, dendritic polymers incorporating monoselenides retained the high biocompatibility characteristics of bis-MPA dendritic constructs.}, archive = {J_JACS}, author = {Natalia Sanz del Olmo and Jorge San Jacinto García and Yikai Yin and Ying Zhao and Moustapha Hassan and Michael Malkoch}, doi = {10.1021/jacs.5c00811}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18626--18636}, shortjournal = {J. Am. Chem. Soc.}, title = {Responsive organoselenium dendritic polymers: From monodisperse dendrimers to self-assembled micelles for advanced therapeutic applications}, volume = {147}, year = {2025}, }
• (2025). Asymmetric enantio-complementary synthesis of thioethers via ene-reductase-catalyzed C–C bond formation. JACS, 147(22), 18618--18625. (www)

  @article{ , abstract = {Enzymes are attractive catalysts due to their high chemo-, regio-, and enantioselectivity. In recent years, the application of enzymes in organic synthesis has expanded dramatically, especially for the synthesis of chiral alcohols and amines, two very important functional groups found in many active pharmaceutical ingredients (APIs). Indeed, many elegant routes employing such compounds have been described by industry. Yet, for the synthesis of chiral thiols and thioethers, likewise found in APIs albeit less ubiquitous, only very few biocatalytic syntheses have been reported, and stereocontrol has proved challenging. Here, we apply ene-reductases (EREDs), whose ability to initiate and control chemically challenging radical chemistries has recently emerged, to the synthesis of chiral thioethers from α-bromoacetophenones and pro-chiral vinyl sulfides, without requiring light. Depending on the choice of ERED either enantiomer of the product could be accessed. The highest conversion and selectivity were achieved with GluER T36A using fluorinated substrates, reaching up to 82% conversion and >99.5% ee . With α-bromoacetophenone and α-(methylthio)styrene, the reaction could be performed on a 100 mg scale, affording the product in a 46% isolated yield with a 93% ee . Finally, mechanistic studies were carried out using stopped-flow spectroscopy and protein mass spectrometry, providing insight into the preference of the enzyme for the intermolecular reaction. This work paves the way for new routes for the synthesis of thioether-containing compounds.}, archive = {J_JACS}, author = {Christian M. Heckmann and Derren J. Heyes and Martin Pabst and Edwin Otten and Nigel S. Scrutton and Caroline E. Paul}, doi = {10.1021/jacs.5c00761}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18618--18625}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric enantio-complementary synthesis of thioethers via ene-reductase-catalyzed C–C bond formation}, volume = {147}, year = {2025}, }
• (2025). Structure flexibility enabled by surface high-concentration titanium doping for durable lithium-ion battery cathodes. JACS, 147(22), 18606--18617. (www)

  @article{ , abstract = {Ni-rich layered oxides have emerged as the most promising cathode materials for next-generation lithium-ion batteries due to their high energy densities. However, their strain-related instabilities, for example, microcracks and rock-salt phase formation, present a significant threat to battery performance. In this study, we successfully stabilize the structure of LiNi 0.8 Co 0.1 Mn 0.1 O 2 using flexible TiO 6 octahedron units through high-concentration surface Ti doping. The TiO 6 octahedron can tolerate Jahn–Teller distortions of other neighboring structural units due to the absence of d electrons in Ti 4+ , allowing them to accommodate undesirable lattice distortions within the local domain and mitigate the lattice strain/changes. Compared with the conventional approach of increasing the rigidity of the layered structure, our strategy of using flexible TiO 6 structural units can fundamentally address the strain-related issues, contributing to significantly reduced lattice changes, especially along the c -direction (by 95.2%). This approach enables a high battery capacity (211.5 mAh g –1 at 0.1 C) and long battery durability of Ni-rich cathodes, surpassing most commercial products on the market. The strategy of surface optimization using flexible structural units to stabilize Ni-rich layered oxides can be broadly applied to other battery materials to address performance issues due to the similarities among layered-structured cathode materials.}, archive = {J_JACS}, author = {Jingxi Li and Gemeng Liang and Wei Zheng and Jinshuo Zou and Caoyu Wang and Jodie A Yuwono and Yameng Fan and Bernt Johannessen and Lars Thomsen and Sijiang Hu and Lei Jiang and Zaiping Guo}, doi = {10.1021/jacs.5c00789}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18606--18617}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure flexibility enabled by surface high-concentration titanium doping for durable lithium-ion battery cathodes}, volume = {147}, year = {2025}, }
• (2025). Amyloid oligomers: Expediting crystal growth and revisiting the corkscrew structures. JACS, 147(22), 18594--18605. (www)

  @article{ , abstract = {Crystallizing soluble amyloid oligomers (AOs) presents a major challenge in studying disease-related mutations associated with amyloid diseases. The G37R mutation in superoxide dismutase 1 (SOD1) is linked to early onset amyotrophic lateral sclerosis (ALS), yet its toxic mechanism remains unclear. The transient nature and low solubility of AOs often complicate the production of high-quality crystals required for X-ray crystallography (XRC) analysis. To address these challenges, we employ native ion mobility spectrometry-mass spectrometry (IMS-MS) to screen SOD1 peptides and examine correlations between structural features that reflect AO stability, their sequence length, and specific mutations. In particular, previous studies showed that the P28K mutation in SOD1(28–38) enhances solubility, thus allowing the capture of AO corkscrew structures for both SOD1(28–38) P28K and SOD1(28–38) P28K, G37R . Building on these findings, we expanded our screening to include SOD1 peptides with longer sequences, identifying structural features in IMS-MS spectra that correlate with improved crystallization potential. This approach enabled us to distinguish the stabilizing effects of G37R from those of P28K, culminating in the successful determination of the first crystal structure of the SOD1 corkscrew containing the native proline.}, archive = {J_JACS}, author = {Sarah S. Hirschbeck and Michael R. Sawaya and Edward T. Lindberg and Miranda N. Limbach and Joshua H. Jang and Kristi L. Lazar Cantrell and David S. Eisenberg and Thanh D. Do}, doi = {10.1021/jacs.5c00656}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18594--18605}, shortjournal = {J. Am. Chem. Soc.}, title = {Amyloid oligomers: Expediting crystal growth and revisiting the corkscrew structures}, volume = {147}, year = {2025}, }
• (2025). Determination of local structural and dynamic descriptors in doped oxides: The case of zr-doped ceria, a non-classical electrostrictor. JACS, 147(22), 18583--18593. (www)

  @article{ , abstract = {Non-classical electromechanical properties, such as large electrostriction stress coefficient and low dielectric constant in Zr-doped ceria and other doped cerium oxides, discovered in the last several years, are the focus of intense research as they indicate the existence of solids with unusually large anharmonicity of chemical bonds. Theoretical models of electrostriction mechanisms rely on the concept of elastic dipoles that are formed due to the local structural distortions around dopants. The structural, dynamic, and electronic descriptors of the pre-existing (at zero field) dipoles (as in aliovalent-doped ceria) and those dynamically formed under the electric field (as in isovalent-doped ceria) are unknown. Here, the characteristics of the local structure and dynamics of the dopant and host bonding environments were obtained by using the temperature-dependent X-ray absorption fine structure measurements. The candidate set of descriptors was identified in a quasiharmonic approximation for the nearest neighboring bonds between Zr (Ce) and the atoms in the first and second coordination shells. The descriptors included static bond length disorder, the anharmonicity of the effective pair potential, and effective force constants for the probed atomic pairs. The observation of significant Zr–O bond anharmonicity confirms previous first-principles calculations. The structural model, emerging from these simulations, emphasizes significant free volume around Zr in the oxygen cube, explaining both the mechanical anomaly (the decrease in Young’s modulus with Zr concentration) as well as correlating at least one descriptor (static disorder) to the measured electrostriction coefficient. This descriptor-based approach can be extended to studies under applied electric fields or stress in this and other materials.}, archive = {J_JACS}, author = {Tali Pechersky Savich and Kaifeng Zheng and Ryuichi Shimogawa and Prahlad K. Routh and Maxim Varenik and David Ehre and Igor Lubomirsky and Anatoly I. Frenkel}, doi = {10.1021/jacs.5c00391}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18583--18593}, shortjournal = {J. Am. Chem. Soc.}, title = {Determination of local structural and dynamic descriptors in doped oxides: The case of zr-doped ceria, a non-classical electrostrictor}, volume = {147}, year = {2025}, }
• (2025). Hydrogen bond interaction networks in the mixed pentamers of hydrogen sulfide and water. JACS, 147(22), 18576--18582. (www)

  @article{ , abstract = {The observation of gas-phase water clusters has been instrumental in understanding water aggregation and cooperativity, paving the way for solvation models in the bulk. However, the characterization of hydrogen sulfide self-aggregation is still largely unexplored. Here, we investigate two mixed pentamers of hydrogen sulfide and water to examine the influence of the weaker, dispersion-based and less directional interactions caused by hydrogen sulfide. Unprecedented structural resolution was obtained by combination of jet-cooled broadband rotational spectroscopy and quantum-chemical calculations. Specifically, we compare the 4:1 and 1:4 hydrogen sulfide - water pentamers, offering comparison with the prototype homoclusters. Important structural differences are revealed in the hydrogen sulfide clusters, which reorganize to compensate for the weaker sulfur-centered hydrogen bonds. The noncovalent interactions in the pentamers were rationalized using density functional theory and reduced electronic density calculations. Moreover, a comprehensive many-body decomposition energy analysis revealed significant variations in molecule two- and three-body contributions to the total interaction energy based on the relative proportions of H 2 O and H 2 S. These findings offer new insights into the distinct cooperative forces in water and hydrogen sulfide clusters. The results will improve our understanding and modeling of sulfur-centered hydrogen bonds, which may be useful across various research fields, including protein folding, molecular aggregation, materials science, and computational benchmarking.}, archive = {J_JACS}, author = {Pablo Pinacho and Cristóbal Pérez and Marcel Stahn and Rizalina T. Saragi and Andreas Hansen and Stefan Grimme and Alberto Lesarri and Melanie Schnell}, doi = {10.1021/jacs.4c18276}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18576--18582}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen bond interaction networks in the mixed pentamers of hydrogen sulfide and water}, volume = {147}, year = {2025}, }
• (2025). Stepwise reactions in the potassium and ammonia-intercalated iron selenide superconductor phase diagram followed by in situ powder diffraction. JACS, 147(22), 18563--18575. (www)

  @article{ , abstract = {Iron-based superconductors have attracted much attention for their high superconducting temperatures and high upper critical fields, which make them promising candidates for application as well as fundamentally important for our understanding of superconductivity. One feature of these superconductors is their ability to intercalate and deintercalate species from between their iron-containing layers, something not available in cuprate high-temperature superconductors or niobium-based conventional superconductors used in technologies. This provides an opportunity for switchable changes in the superconducting properties as a function of chemical conditions, but the resulting structures are often hard to characterize due to loss of crystallinity and sometimes the formation of multiphase products. Here, we explore both the synthesis and decomposition of potassium and ammonia-intercalated iron selenide superconductors through in situ powder X-ray diffraction. We report a complete phase diagram including two new solution-stable ammonia-rich phases and several metastable forms. We give accurate characterization of the reported ammonia-poor forms using a combination of neutron and X-ray powder diffraction, using an innovative supercell approach to describe the phase breadth within the samples. These results give rare insight into stepwise changes occurring in solids along multiple reaction pathways, which demonstrate the importance of in situ diffraction techniques.}, archive = {J_JACS}, author = {Simon J. Cassidy and Daniel N. Woodruff and Stefan J. Sedlmaier and Jack N. Blandy and Christina Reinhard and Oxana V. Magdysyuk and Andrew L. Goodwin and Silvia Ramos and Simon J. Clarke}, doi = {10.1021/jacs.5c00356}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18563--18575}, shortjournal = {J. Am. Chem. Soc.}, title = {Stepwise reactions in the potassium and ammonia-intercalated iron selenide superconductor phase diagram followed by in situ powder diffraction}, volume = {147}, year = {2025}, }
• (2025). Revealing the crucial roles of pore interconnectivity between zeolitic and nonzeolitic components in enhancing diffusion and catalytic efficiency of industrial zeolite-based catalysts. JACS, 147(22), 18550--18562. (www)

  @article{ , abstract = {One of the utmost targets for catalysis research is to meet social needs in a profitable manner. Zeolitic and “nonzeolitic components” (such as silica, alumina, amorphous aluminosilicate, clay, etc.), as indispensable constituents of an industrial catalyst, both actively participate in industrial processes like polyolefin catalytic cracking and residue fluid catalytic cracking. Yet, the main research activities focus mainly on the diffusion behaviors of a single zeolitic or nonzeolitic component. In this work, the pore interconnectivity between zeolitic and nonzeolitic components to better ensure the diffusion and migration of reaction intermediate products in between was systematically studied by adopting a series of ZSM-5@meso-SiO 2 core–shell mesostructures as models to mimic industrially applied multicomponent zeolite-based catalysts with varying pore interconnectivities between the zeolitic (ZSM-5) and nonzeolitic components (meso-SiO 2 ). Their distinctive differences in the multiscale diffusion behaviors and structure-performance relationships represent the following three summarized scenarios: (1) micro/mesopore orientation, (2) spatial distribution of components, and (3) micro/mesoporous relative pore sizes thereof. These reveal that a well-connected micro/mesopore network can effectively accelerate interfacial diffusion and fully enhance the catalytic efficiency of the zeolitic component, highlighting the foundational functions of pore interconnectivity between zeolitic and nonzeolitic components in terms of the significance of the free migration of reactant species in between.}, archive = {J_JACS}, author = {Yipu Xu and Peng Peng and Hanlixin Wang and Hao Xiong and Zhaochao Xu and Xiao Chen and Yanpeng Li and Anmin Zheng and Yingxu Wei and Zifeng Yan and Shutao Xu and Zhongmin Liu}, doi = {10.1021/jacs.5c00214}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18550--18562}, shortjournal = {J. Am. Chem. Soc.}, title = {Revealing the crucial roles of pore interconnectivity between zeolitic and nonzeolitic components in enhancing diffusion and catalytic efficiency of industrial zeolite-based catalysts}, volume = {147}, year = {2025}, }
• (2025). Carbon nanotubes for rechargeable Na/Cl2 batteries. JACS, 147(22), 18541--18549. (www)

  @article{ , abstract = {Rechargeable Na/Cl 2 batteries were developed for the first time using multiwalled carbon nanotube (MWCNT) positive electrodes in SOCl 2 -based electrolytes. At room temperature, these batteries delivered high cycling specific capacities up to 3500 mA h g –1 (normalized to CNT mass) with ∼3.9 V discharge voltage at up to 2 C rates over >140 cycles. In situ Raman spectroscopy experiments combined with real-time optical microscopy imaging revealed reversible formation and reduction of SCl 2 and S 2 Cl 2 species during battery operation, responsible for the additional plateaus to the main Cl – /Cl 2 redox reactions. Cryo-TEM revealed NaCl nanocrystals inside the hollow inner space of CNTs through battery cycling, suggesting Cl – /Cl 2 redox reactions reaching hollow CNTs likely through defects and open ends on MWCNTs. High-resolution electron energy loss spectroscopy (EELS) mapping revealed Cl uniformly distributed along CNTs in the charged state, suggesting CNTs as a novel carbon material to host Cl – /Cl 2 redox and store chlorine for reversible conversion between NaCl and Cl 2 and battery rechargeability.}, archive = {J_JACS}, author = {Peng Liang and Guanzhou Zhu and Weize Wang and Cheng-Liang Huang and Shu-Chi Wu and Jingwen Zhou and Xichen Zhou and Yan Wu and Shixin Wang and Mingyue Wang and Lei Zhang and Chan Cheong Ming and Jiachen Li and Feifei Wang and Mengdie Sun and Yuan-Yao Li and Bing-Joe Hwang and Hongjie Dai}, doi = {10.1021/jacs.4c18070}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18541--18549}, shortjournal = {J. Am. Chem. Soc.}, title = {Carbon nanotubes for rechargeable Na/Cl2 batteries}, volume = {147}, year = {2025}, }
• (2025). An adaptive palladium single-atom catalyst enabling reactivity switching between borylation and C–C coupling. JACS, 147(22), 18524--18540. (www)

  @article{ , abstract = {The development of single-atom catalysts (SACs) with site-specific and tunable catalytic functionalities remains a highly desirable yet challenging goal in catalysis. In this study, we report a SAC featuring anisotropic coordination cavities synthesized via a one-step polymerization of 2,6-diaminopyridine and cyanuric chloride. These cavities provide a robust framework for anchoring isolated Pd single atoms with exceptional stability. The unique broken symmetry of the catalyst’s local structure enables precise control over reaction pathways, allowing reactivity to be switched between distinct catalytic outcomes. Specifically, under tailored reaction conditions, the catalyst can either halt at the borylation step or proceed seamlessly to Suzuki coupling in a self-cascade process. Mechanistic studies unveil the pivotal role of Pd single atoms in driving key steps, including oxidative addition, base exchange, and reductive elimination. Furthermore, green metrics demonstrate the process’s sustainability, with minimized waste generation and reduced reliance on hazardous reagents in the self-cascade transformation. This work establishes an innovative benchmark in the field of single-atom catalysis: by enabling complex, multistep transformations via strategic activation of multiple functional groups, this catalyst exemplifies the potential of self-cascade processes to revolutionize synthetic chemistry via catalysis engineering.}, archive = {J_JACS}, author = {Vitthal B. Saptal and Clara Saetta and Adriana Laufenböck and Martin Sterrer and Ik Seon Kwon and Andrea Lucotti and Matteo Tommasini and Ondřej Tomanec and Aristides Bakandritsos and Giovanni Di Liberto and Gianfranco Pacchioni and Gianvito Vilé}, doi = {10.1021/jacs.4c17943}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18524--18540}, shortjournal = {J. Am. Chem. Soc.}, title = {An adaptive palladium single-atom catalyst enabling reactivity switching between borylation and C–C coupling}, volume = {147}, year = {2025}, }
• (2025). RNA editing-mediated correction of TP53 nonsense mutations via lipid nanoparticle-delivered circular ADAR-recruiting RNAs. JACS, 147(22), 18512--18523. (www)

  @article{ , abstract = {Nonsense mutations account for over 20% of disease-associated mutations, which refer to the occurrence of premature termination codons (PTCs) in gene sequences, resulting in truncated and dysfunctional proteins. Nonetheless, due to poor accessibility of precise target sites and the limitations of gene editing tools, there is still a lack of safe, effective, and site-specific approach for correction of nonsense mutations. Here, we designed a circular ADAR-recruiting RNA (Circ-arRNA) for the in vivo RNA editing-mediated repair of the TP53-W53X nonsense mutation. Compared with linear arRNA, Circ-RNA demonstrates strong intracellular stability and high efficiency for site-specific correction of the TP53-W53X nonsense mutant, with no detectable off-target effects on bystander bases. In triple-negative breast cancer TP53-W53X 4T1 cells and tumor-bearing mouse models, we used lipid nanoparticles (LNPs) to encapsulate and deliver Circ-arRNA, which achieved mutation correction efficiencies of 73.32 and 48.48%, respectively. Furthermore, Circ-arRNA LNPs effectively restored full-length p53 protein expression and its functional activity, significantly enhancing the sensitivity of tumor-bearing mice to paclitaxel chemotherapy. Our research demonstrated the safety and efficacy of LNP-based circular arRNA for specifically the repair of nonsense mutations in vivo, highlighting the immense potential of ADAR-mediated editing for correcting such mutations.}, archive = {J_JACS}, author = {Jinjin Wang and Wenjing Zhang and Shuguang Li and Wenjun Shi and Bingyu Li and Jingge Zhang and Yan Liang and Xucong Teng and Kaixiang Zhang}, doi = {10.1021/jacs.4c17920}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18512--18523}, shortjournal = {J. Am. Chem. Soc.}, title = {RNA editing-mediated correction of TP53 nonsense mutations via lipid nanoparticle-delivered circular ADAR-recruiting RNAs}, volume = {147}, year = {2025}, }
• (2025). Bis-allylic deuterated docosahexaenoic acid-esterified phospholipids resist in vivo peroxidation in rat brain. JACS, 147(22), 18504--18511. (www)

  @article{ , abstract = {The human central nervous system simultaneously has the most highly unsaturated fatty acids (HUFAs) and the highest metabolic rate among body tissue. Up to 1% of consumed O 2 is converted to reactive oxygen species (ROS) that cause unregulated damage to HUFA-rich membrane phospholipids (PLs). Docosahexaenoic acid (DHA) is the brain’s most unsaturated and abundant HUFA. Reinforcing the ROS-labile bis -allylic positions with deuterium (D-DHA) protects against oxidative damage in vitro and in vivo. We developed an LC–MS/MS method to detect ambient levels of nascent oxidation products of DHA and D-DHA containing PLs in vivo in rat brain lipid extracts. Multiple reaction monitoring (MRM)-triggered mass spectra confirmed D-DHA incorporation in D-DHA-fed rat brain PLs. DHA-PL nascent oxidation products add 2 O, consistent with known peroxidation reactions. In contrast, D-DHA oxidation is primarily detected as a single O addition, consistent with epoxidation. D-DHA-PL showed 20%–30% lower overall oxidation compared to DHA-PL. Our data are consistent with a mechanism of action whereby D-DHA blocks excess lipid peroxidation, leading to lower overall membrane damage. D-DHA is a unique therapeutic approach against neurodegenerative diseases where ROS-driven oxidation is implicated.}, archive = {J_JACS}, author = {Secilia Garza and Genevieve James and Hui Gyu Park and Paul R. S. Baker and Martin-Paul Agbaga and Vicki Ea and Mikhail S. Shchepinov and J. Thomas Brenna}, doi = {10.1021/jacs.4c17871}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18504--18511}, shortjournal = {J. Am. Chem. Soc.}, title = {Bis-allylic deuterated docosahexaenoic acid-esterified phospholipids resist in vivo peroxidation in rat brain}, volume = {147}, year = {2025}, }
• (2025). Insights into decoupled solar energy conversion and charge storage in a 2D covalent organic framework for solar battery function. JACS, 147(22), 18492--18503. (www)

  @article{ , abstract = {Decoupling solar energy conversion and storage in a single material offers a great advantage for off-grid applications. Herein, we disclose a two-dimensional naphthalenediimide (NDI)-based covalent organic framework (COF) exhibiting remarkable solar battery performance when used as a photoanode. Light-induced radicals are stabilized within the framework for several hours, offering on-demand charge extraction for electrical energy production. Our study reveals mechanistic insights into the long-term charge stabilization using optical spectroscopy and (photo)electrochemical measurements, in conjunction with density functional theory (DFT) simulations. Among several solvents, water provides the best dielectric screening and energetically favorable proton exchange to stabilize photoinduced radicals for more than 48 h without the need for additional metal cations. This study provides fundamental insights into the optoionic charge storage mechanism in NDI-COF, while introducing a highly tunable, nanoporous material platform that surpasses related materials, such as carbon nitrides, metal–organic frameworks (MOFs), or metal oxides, in terms of charge storage capacity. This study opens new perspectives for the design of optoionic charge-storing materials and the direct storage of solar energy to overcome the intermittency of solar irradiation.}, archive = {J_JACS}, author = {Bibhuti Bhusan Rath and Laura Fuchs and Friedrich Stemmler and Andrés Rodríguez-Camargo and Yang Wang and Maximilian F. X. Dorfner and Johann Olbrich and Joris van Slageren and Frank Ortmann and Bettina V. Lotsch}, doi = {10.1021/jacs.4c17642}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18492--18503}, shortjournal = {J. Am. Chem. Soc.}, title = {Insights into decoupled solar energy conversion and charge storage in a 2D covalent organic framework for solar battery function}, volume = {147}, year = {2025}, }
• (2025). High-efficiency organic mechanophosphorescence from a phenoselenazine phosphor for multiple applications. JACS, 147(22), 18484--18491. (www)

  @article{ , abstract = {Mechanoluminescence (ML) materials with phosphorescent characteristics hold significant potential for applications in pressure sensing and material damage inspection. However, currently reported mechanophosphorescence (MP) materials suffer from low luminescence efficiency and insufficient brightness. Herein, we report a piezoelectric material, p -BPM, with an exceptionally high phosphorescence efficiency of 61.4%, which is the highest value among reported pure organic MP materials. Benefiting from its excellent ML performance, we have developed a display device using crystals that allow for clear observation of the written letter paths (letters M and L), which have promising prospects in pressure-sensitive display. Amazingly, we also observed that the crystals produce bright ultrasound induced luminescence in the medium at a low ultrasonic operating frequency (40 kHz). The composite films of crystal and poly(butylene adipate- co -terephthalate) (PBAT) polymer exhibit significant tensile strength while maintaining effective MP. The composite films show good piezoelectric energy harvesting properties with a maximum open-circuit voltage of 0.47 V and short-circuit current of 0.046 μA, demonstrating promise for precise sonic location. This work will facilitate the development of highly efficient organic MP materials, expanding the potential in stress-monitoring, imaging, and marine robotics.}, archive = {J_JACS}, author = {Meijuan Ding and Meng Zhang and Anqi Lv and Qiuzhuo Dong and Yi Zhang and Wei Li and Zhongfu An and Wei Huang}, doi = {10.1021/jacs.4c17418}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18484--18491}, shortjournal = {J. Am. Chem. Soc.}, title = {High-efficiency organic mechanophosphorescence from a phenoselenazine phosphor for multiple applications}, volume = {147}, year = {2025}, }
• (2025). Dual-state ambipolar charge transport in antiaromatic [4]cyclodibenzopentalene single-molecule nanohoops. JACS, 147(22), 18475--18483. (www)

  @article{ , abstract = {Antiaromatic compounds are of great interest due to their narrow highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps, high reactivity, and enhanced charge mobility, yet their role in single-molecule electronics is still not well understood. Using electrochemically controlled scanning tunneling microscopy break junction (ECSTM-BJ) measurements, we compared the energy-alignment-dependent conductance of the aromatic [10]cycloparaphenylene ([10]CPP) and the antiaromatic [4]cyclodibenzopentalene ([4]CDBP). While [10]CPP showed a single conductance state via the HOMO, [4]CDBP exhibited two distinct states involving both the HOMO and LUMO. Our analysis and DFT calculations attribute this dual-state behavior to unique anchoring mode and energy-level realignment within a narrow HOMO-LUMO gap. This property enables electron- and hole-dominated pathways that depend on the anchoring configuration and coexist at a fixed gate potential. This phenomenon, also observed in the [4]CDBP⊃C 60 structure, highlights the potential of antiaromatic molecules for advanced molecular electronics.}, archive = {J_JACS}, author = {Sai Feng and Renad Almughathawi and Andrej Weber and Songjun Hou and Chengyang Zhang and Jan S. Wössner and Birgit Esser and Colin Lambert and Qingqing Wu and Yueqi Li and Jinghong Li}, doi = {10.1021/jacs.4c17115}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18475--18483}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual-state ambipolar charge transport in antiaromatic [4]cyclodibenzopentalene single-molecule nanohoops}, volume = {147}, year = {2025}, }
• (2025). TRPM8 protein dynamics correlates with ligand structure and cellular function. JACS, 147(22), 18460--18474. (www)

  @article{ , abstract = {Protein dynamics has emerged as a key feature associated with function in various systems. Here, NMR-based studies coupled with computational cheminformatics and cellular function are leveraged to identify a relationship between human cold and menthol receptor TRPM8 dynamics, chemical structure, and cellular potency. TRPM8 is a validated target for a variety of pain indications but generally has been clinically limited by on-target side effects, impacting thermosensing and thermoregulation. This study shows that cheminformatic analysis of a TRPM8 regulating small-molecule ligand library correlates with cellular function. Electrophysiology studies further validate the relationship and show a correlation between the chemical structure and functional features such as compound potency. Solution NMR studies of the TRPM8 voltage sensing-like domain, which houses the canonical menthol ligand binding site, show that ligand binding conformationally selects NMR-detected TRPM8 dynamics in a manner that quantitatively correlates with the chemical structure. The relationship between chemical structure and protein dynamics can be used predictively, where a chemical structure is predictive of dynamics in a latent reduced dimensionality space. Moreover, the robustness of the conformational selection of the dynamic ensemble is evaluated by varying related and divergent chemotypes, signal-to-noise sensitivity, and sample bias. Taken together, this study identifies that protein dynamics can serve as a quantifiable bridge between the chemical structure and cellular function, which has implications for drug discovery in difficult systems.}, archive = {J_JACS}, author = {Mubark D. Mebrat and Dustin D. Luu and Jacob K. Hilton and Minjoo Kim and Kaitlyn Parrott and Brian R. Cherry and Marcia Levitus and V. Blair Journigan and Wade D. Van Horn}, doi = {10.1021/jacs.4c09435}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18460--18474}, shortjournal = {J. Am. Chem. Soc.}, title = {TRPM8 protein dynamics correlates with ligand structure and cellular function}, volume = {147}, year = {2025}, }
• (2025). Water clustering modulates activity and enables hydrogenated product formation during carbon monoxide electroreduction in aprotic media. JACS, 147(22), 18445--18459. (www)

  @article{ , abstract = {Water solvation plays a critical role in a wide range of electrochemical transformations, but its role is often convoluted since water is typically used as both a solvent and a proton source. Here, we experimentally control water speciation and activity using aprotic solvent media during the carbon monoxide reduction reaction (CORR). Remarkably, we show that aprotic solvents that support microheterogeneous water–water clusters lead to significant amounts of CORR products (methane and ethylene) with a maximum ethylene Faradaic efficiency of 22% in acetonitrile (χ H 2 O = 0.2). In contrast, microhomogeneous systems–where water integrates into the solvents’ intermolecular binding network and has lower activity–primarily support the undesired hydrogen evolution reaction (HER). Insights gained expand our understanding of water activity and nonaqueous electrolyte design for other important transformation reactions beyond CO reduction, such as CO2RR and HER.}, archive = {J_JACS}, author = {Hannah Fejzić and Ritesh Kumar and Reginaldo J. Gomes and Lilin He and Theodore J. Houser and Jaemin Kim and Matin Mohebi and Nora Molten and Chibueze V. Amanchukwu}, doi = {10.1021/jacs.4c07865}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18445--18459}, shortjournal = {J. Am. Chem. Soc.}, title = {Water clustering modulates activity and enables hydrogenated product formation during carbon monoxide electroreduction in aprotic media}, volume = {147}, year = {2025}, }
• (2025). Kharasch-type haloalkylation of alkenes by photoinduced copper catalysis. JACS, 147(22), 18438--18444. (www)

  @article{ , abstract = {The simultaneous construction of C–C and C–X bonds in a single step facilitates multistep synthesis through rapid carbon chain growth and subsequent transformations of halide functionalities. Traditional Kharasch addition requires simple polyhalogenated compounds or those with electron-withdrawing groups at the α-carbon. Herein, we present a Kharasch-type reaction utilizing a broad range of carboxylic acid-derived redox-active esters as the alkyl source, which enables the efficient introduction of highly functionalized alkyl groups. Our method produces α-halo carbonyls that enable versatile nucleophilic substitutions for synthesizing valuable compounds, such as unnatural α-amino acids.}, archive = {J_JACS}, author = {Yuan Cai and Mahiob Dawor and Gaurav Gaurav and Tobias Ritter}, doi = {10.1021/jacs.5c05699}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18438--18444}, shortjournal = {J. Am. Chem. Soc.}, title = {Kharasch-type haloalkylation of alkenes by photoinduced copper catalysis}, volume = {147}, year = {2025}, }
• (2025). Diboron-incorporated indenofluorene: Isolation of crystalline neutral and reduced states of 6,12-diboraindeno[1,2-b]fluorene. JACS, 147(22), 18431--18437. (www)

  @article{ , abstract = {The synthesis and redox transformations of 6,12-diboraindeno[1,2- b ]fluorene (DBIF)─a pentacyclic π-system with diboron incorporation─are reported. In notable contrast to the all-hydrocarbon indenofluorenes, a ligand coordination and reduction strategy allows tuning of the electronic structure across four redox states. Accordingly, we introduce an 18π e – neutral DBIF, a 20π e – diradical, a 21π e – radical anion, and a 22π e – dianion, all of which have been isolated and structurally authenticated. The diradicals exhibit diradical character of up to 77% and possess open-shell singlet ground states with thermally accessible triplet states.}, archive = {J_JACS}, author = {Bi Youan E. Tra and Yujie Zhao and Andrew Molino and Yifu Ouyang and Chun-Lin Deng and Colleen McAloon and Noah D. McMillion and Heechan Kim and Chonghe Zhang and Peter Müller and Robert G. Griffin and Robert J. Gilliard, Jr.}, doi = {10.1021/jacs.5c04487}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18431--18437}, shortjournal = {J. Am. Chem. Soc.}, title = {Diboron-incorporated indenofluorene: Isolation of crystalline neutral and reduced states of 6,12-diboraindeno[1,2-b]fluorene}, volume = {147}, year = {2025}, }
• (2025). Molecular design for optically induced magnetization: Targeting excited state orbital degeneracy in Tungsten(V) complexes. JACS, 147(22), 18424--18430. (www)

  @article{ , abstract = {The rise of quantum information science has spurred chemists to prepare new molecules that serve as useful building blocks in quantum technologies of the future. Implementation of molecular spin-based qubits requires new methods to induce high spin polarization of samples. Herein, we report design criteria to develop axially symmetric spin-1/2 molecules amenable to optically induced magnetization (OIM), a technique using circularly polarized (CP) excitation to deliver spin polarization. We apply these criteria to develop a series of tungsten(V) chalcogenide complexes that are demonstrated to have large spin-sensitive responses to CP light using magnetic circular dichroism (MCD) that could allow up to ∼20% spin polarization through OIM. Pulsed electron paramagnetic resonance (EPR) spectra reveal these systems have improved relaxation times over molecules like K 2 IrCl 6 , a species recently investigated by OIM, and field-swept electron spin–echo (FS-ESE) experiments show they have a remarkable lack of anisotropy in their phase-memory T m times. The design criteria are general and point toward future ways to improve OIM-initializable qubits.}, archive = {J_JACS}, author = {Ian E. Ramsier and Alysia Mandato and Sunil Saxena and Wesley J. Transue}, doi = {10.1021/jacs.5c03783}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18424--18430}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular design for optically induced magnetization: Targeting excited state orbital degeneracy in Tungsten(V) complexes}, volume = {147}, year = {2025}, }
• (2025). Structure directing acid-amine salt films for imine-linked covalent organic framework films by chemical vapor deposition. JACS, 147(22), 18419--18423. (www)

  @article{ , abstract = {While the chemical vapor deposition (CVD) process promises high-quality films of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs), strategic approaches are limited. Here we report a new strategic approach to synthesizing imine-linked COF films through acid-amine salt films by CVD. Acids are known to catalyze imine condensation between amines and aldehydes in the solution phase and have been believed to do the same in the vapor phase reaction. Upon the attempts to synthesize COF-LZU1 thin films using p -phenylenediamine, 1,3,5-triformylbenzene, by CVD, highly crystalline and smooth COF-LZU1 films are obtained only in the presence of p -toluenesulfonic acid, proving the conventional role of acid during vapor phase imine condensation. The COF-LZU1 film has a mixed orientation according to the structure analysis by grazing-incidence wide-angle X-ray scattering. In contrast, amorphous films with a face-on orientation were obtained in the absence of an acid. The role of acid in modulating structure is confirmed from the reaction using a different acid, benzenesulfonic acid, which results in the COF-LZU1 film having an edge-on orientation. The control experiments using benzoic acid and succinic acid that failed to make either acid-amine salt or COF films explain that the acid-amine-salt film formation is crucial to the formation of imine-linked COF films by CVD. Our findings not only explain the limited kinds of active acids for imine condensation in the vapor phase but also widen the field for the facile synthesis of highly crystalline COF films by CVD and the structure control of COF films through the combination of an acid-amine salt.}, archive = {J_JACS}, author = {Yelim Son and Hee Cheul Choi}, doi = {10.1021/jacs.5c03798}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18419--18423}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure directing acid-amine salt films for imine-linked covalent organic framework films by chemical vapor deposition}, volume = {147}, year = {2025}, }
• (2025). Stabilization of condensate interfaces using dynamic protein insertion. JACS, 147(22), 18412--18418. (www)

  @article{ , abstract = {Coacervates have been widely used to mimic membraneless organelles (MLOs). However, coacervates without a membrane or stabilizing surface do not feature the same level of stability as MLOs. This study shows that specifically engineered surface-active proteins can interact with the interface of polypeptide coacervates, conferring resistance to coacervate dissolution and fusion. Modulating the molecular characteristics of these coacervate stabilizing proteins highlighted that their dimerization aids in achieving effective interface stabilizers. Cryo-TEM imaging showed a densely packed protein monolayer at the coacervate-liquid interface, while single-molecule super-resolution microscopy captured the dynamic nature of this protein layer, with the proteins rapidly (un)docking and moving across the coacervate interface within milliseconds. These findings suggest a dynamic form of coacervate stabilization driven by transient protein interactions at the condensate interface. This unique form of coacervate stabilization not only provides a new approach to developing stable and dynamically exchanging synthetic condensate systems but, as model systems, can also significantly contribute to our understanding of the mechanisms underlying the temporal stability of MLOs in nature.}, archive = {J_JACS}, author = {Yannick H. A. Leurs and Sanne N. Giezen and Yudong Li and Willem van den Hout and Jay Beeren and Linn J. M. van den Aker and Ilja K. Voets and Jan C. M. van Hest and Luc Brunsveld}, doi = {10.1021/jacs.5c03740}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18412--18418}, shortjournal = {J. Am. Chem. Soc.}, title = {Stabilization of condensate interfaces using dynamic protein insertion}, volume = {147}, year = {2025}, }
• (2025). 3-selective pyridine fluorination via zincke imine intermediates. JACS, 147(22), 18406--18411. (www)

  @article{ , abstract = {Fluorine substitution is a widely used approach to improve the properties of drugs bearing aromatic rings and has spawned numerous new methods for C–F bond formation. Reactions employing C–H bond precursors are particularly valuable, but pyridine-applicable variants are rare, especially at the C3-position. We developed an approach using ring-opened Zincke imines that undergo regioselective C–F bond formation with electrophilic fluorination reagents, resulting in C3-fluoropyridines after ring closure. This process can accommodate a wide range of pyridine substitution patterns, tolerates various appended functional groups, and is viable for the late-stage fluorination of pyridine-containing drugs.}, archive = {J_JACS}, author = {Marie A. Hart and Benjamin J. H. Uhlenbruck and Jeffrey N. Levy and Andrew McNally}, doi = {10.1021/jacs.5c03091}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18406--18411}, shortjournal = {J. Am. Chem. Soc.}, title = {3-selective pyridine fluorination via zincke imine intermediates}, volume = {147}, year = {2025}, }
• (2025). Copper-catalyzed formal aldehydic C–H borylation enabled by an sp2–sp3 diboron reagent. JACS, 147(22), 18397--18405. (www)

  @article{ , abstract = {We have developed a copper-catalyzed formal aldehydic C–H borylation using a neutral sp 2 –sp 3 diboron reagent, LBH 2 –Bpin (where L is a σ-donor), leading to the one-pot synthesis of diverse acylboranes. Notably, the BH moieties in the acylborane can be further used to construct boracycles. This protocol enables straightforward functional group (FG) replacement of commercial medicines with an acylboron motif. Detailed mechanistic studies and DFT calculations reveal a synergistic hydride transfer pathway, which is promoted by the electron-rich nature of the LBH 2 fragment. This investigation highlights the potential of the new diboron reagent in accessing reaction modes that were previously unachievable.}, archive = {J_JACS}, author = {Jiaxin Lin and Peiqi Zhang and Xiangyu Lou and Zhenyang Lin and Hairong Lyu and Yangjian Quan}, doi = {10.1021/jacs.5c02718}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18397--18405}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper-catalyzed formal aldehydic C–H borylation enabled by an sp2–sp3 diboron reagent}, volume = {147}, year = {2025}, }
• (2025). Concise total synthesis of ambiguine p. JACS, 147(22), 18391--18396. (www)

  @article{ , abstract = {Ambiguine P ( 5 ) is a synthetically challenging representative of the hapalindole-type natural products. Inspired by the biosynthesis of this indole terpenoid family, we developed a Cope/Prins/Friedel–Crafts cascade, achieving a six-step synthesis of 5 from 2,2-dimethylcycloheptanone. Altered from the biosynthetic pathway, this cascade strategically commenced with a tricyclic indolenine derivative bearing a seven-membered ring, enabling efficient construction of the pentacyclic scaffold of 5 . The oxidation state was elevated through chlorination and hydroxylation in the final stage.}, archive = {J_JACS}, author = {Yifan Fei and Bo Fan and Zhigang Liu and Mengyu Ba and Zhongwen Cui and Peng Yang and Ang Li}, doi = {10.1021/jacs.5c00395}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18391--18396}, shortjournal = {J. Am. Chem. Soc.}, title = {Concise total synthesis of ambiguine p}, volume = {147}, year = {2025}, }
• (2025). Biocatalytic regulation of peptide self-assembly for biomineralization. JACS, 147(22), 18386--18390. (www)

  @article{ , abstract = {The production of functional hierarchical architectures through the biomineralization of a continuously secreted protein matrix is prevalent in nature; however, it remains challenging to mimic this dynamic aspect of the biomineralization process, especially in biological systems. Here we report the use of dynamically generated supramolecular assemblies of peptides for in situ biomimetic mineralization in live cells. Specifically, by integrating enzymatic regulation of inorganic phosphate concentration and enzyme-instructed self-assembly, we demonstrate a phosphorylated tripeptide that self-assembles into dynamic supramolecular nanofibers via enzymatic dephosphorylation to template biomineralization with the inorganic phosphate. This biomimetic mineralization results in the formation of peptide–inorganic hybrid nanocrystals, with tunable crystal size and calcium-to-phosphorus (Ca:P) ratio, regulated by enzyme activity. Cellular enzymes can instruct in situ biomineralization around mammalian cells, inducing cell aggregation and osteogenic differentiation. This work presents a novel strategy for mimicking the dynamic biomineralization of a protein matrix and regulating biomimetic mineralization in live cells to control the cell fate.}, archive = {J_JACS}, author = {Zhaoqianqi Feng and David J. Mooney}, doi = {10.1021/jacs.4c18331}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18386--18390}, shortjournal = {J. Am. Chem. Soc.}, title = {Biocatalytic regulation of peptide self-assembly for biomineralization}, volume = {147}, year = {2025}, }
• (2025). A supramolecular nanosheet assembled from carpyridines and water. JACS, 147(22), 18380--18385. (www)

  @article{ , abstract = {The use of water as a solvent to facilitate supramolecular self-assembly and polymerization is well-documented; however, it is rare that water acts as a monomer that undergoes polymerization. We report the formation of nanosheets composed of water and a saddle-shaped porphyrinoid macrocycle, carpyridine, which allows for linearly stacked, eclipsed columns within formed 2D structures. Self-assembling carpyridine monomers from solutions with different extents of wetness permit the formation of nanosheets that appear identical by microscopy. Structural analysis through electron diffraction reveals fundamental changes in the local organization. Under dry conditions, carpyridine stacks are formed through π–π interactions between curved surfaces, whereas in solutions containing greater quantities of water, a hydrogen-bonded water-to-carpyridine-core network is propagated throughout perfectly linear columns. The observed wet phase can be interconverted to a dry one through vapor annealing, indicating an accessible energy surface of polymorphism.}, archive = {J_JACS}, author = {Joseph F. Woods and Kai Zhang and Joëlle Peterschmitt and Olivier Blacque and Céline Besnard and Gustavo Santiso-Quinones and Laura Samperisi and Andreas Vargas Jentzsch and Michel Rickhaus}, doi = {10.1021/jacs.4c17024}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18380--18385}, shortjournal = {J. Am. Chem. Soc.}, title = {A supramolecular nanosheet assembled from carpyridines and water}, volume = {147}, year = {2025}, }
• (2025). The critical role of chemistry in advancing quantum information science. JACS, 147(22), 18374--18379. (www)

  @article{ , abstract = {Advancements in the field of Quantum Information Science (QIS) are expected to produce groundbreaking technologies in computing, sensing, and communications. These developments could have an impact on the economy and workforce of the United States. In order to achieve this vision and sustain U.S. leadership in QIS, however, a robust research enterprise needs to be established. Presently, QIS has reached an inflection point for new discoveries; searching for novel quantum molecular materials that are operational, practical, and efficient is now the new frontier. Since chemistry is the study of manipulating molecular properties across different lengths and time-scales, it has a tremendous opportunity to take a leading role in this untapped domain. Blending QIS and chemistry together will accelerate progress in designing new quantum molecular materials, developing novel measurement tools and techniques, and establishing new quantum computing standards. A recent National Academies of Sciences, Engineering, and Medicine (NASEM) report, Advancing Chemistry and Quantum Information Science , points to fundamental research areas at the interface of these two disciplines that should be pursued in the near-term. Here, a brief overview of these research directions as well as collaboration and infrastructure needs identified from the report are presented.}, archive = {J_JACS}, author = {Linda Nhon and Theodore Goodson, III}, doi = {10.1021/jacs.5c04128}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18374--18379}, shortjournal = {J. Am. Chem. Soc.}, title = {The critical role of chemistry in advancing quantum information science}, volume = {147}, year = {2025}, }
• (2025). Dynamic transcription machineries in protocells. JACS, 147(22), 18359--18373. (www)

  @article{ , abstract = {Transcription machineries play key roles in nature by regulating diverse cellular processes, including cell cycle progression, the control of intracellular metabolic balance, and cell differentiation and growth. These processes are regulated by the programmed transcription factor-mediated operation of transcription machineries and cellular environmental cues dictating spatiotemporal gene expression, demonstrating amplification and bistable, switchable, and transient dynamic features. Emulating these native pathways through artificial means not only advances the area of Systems Chemistry by providing principles for the evolution of life but also introduces novel catalytic and theranostic applications of the system. The perspective addresses recent advances in developing transcription-machinery-loaded protocell assemblies, consisting of liposomes, microdroplets, proteinsomes, and microcapsules. Stimuli-responsive transcription machineries integrated into liposomes, Fe 3+ -cross-linked tannic acid membranes, and nucleic acid-functionalized hydrogel microcapsules acting as protocells are triggered by light, redox agents, and switchable refiguration of transcription templates. Moreover, temporally modulated oscillatory transcription circuitries integrated in microemulsion droplets acting as protocells were demonstrated, and the transcription-guided transient assembly and disassembly of DNA nanotubes mimicking formation and dissociation of motor filaments in native cells was accomplished. In addition, the dynamic transcription-mediated diffusive signaling and communication of microdroplets and proteinosome-based protocell assemblies are presented. Future challenges of the topic and potential practical applications of these systems are addressed in the conclusion section.}, archive = {J_JACS}, author = {Jiantong Dong and Fan Xia and Fujian Huang and Itamar Willner}, doi = {10.1021/jacs.5c03622}, journal = {Journal of the American Chemical Society}, month = {6}, number = {22}, pages = {18359--18373}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic transcription machineries in protocells}, volume = {147}, year = {2025}, }
• (2025). A threose nucleic acid (TNA) enzyme catalyzing native 3′-5′ ligation of RNA. JACS, 147(21), 18349--18358. (www)

  @article{ , abstract = {Threose nucleic acid (TNA) is a synthetic genetic polymer of both prebiotic significance and practical utility. Identification of TNA molecules with enzymatic activities (TNAzymes) not only lends experimental support for TNA as a potential primitive catalyst but also offers intrinsically stable biotechnological and biomedical molecular tools. Here, we report the in vitro selection of TNAzymes capable of catalyzing the native 3′-5′ ligation of two RNA oligonucleotides. The Zn 2+ -dependent TNAzyme facilitates the formation of a canonical phosphoester bond between a terminal 3′-hydroxyl group on one substrate and a 5′-triphosphate on the other. Under optimal conditions (pH 7.3 and 23 °C), the TNAzyme exhibits a catalytic rate constant of 0.39 h –1 . Lastly, we demonstrate that the TNAzyme-catalyzed ligation of two RNA fragments could yield a functional RNA product such as a ribozyme. These findings showcase the potential role of TNA as a primordial catalyst during the emergence of the RNA world, as well as its prospective application in RNA synthesis.}, archive = {J_JACS}, author = {Juan Wang and Feng Han and Ye Zou and Mengqi Wang and Yao Wang and Jia-Yu Chen and Hanyang Yu}, doi = {10.1021/jacs.5c07235}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18349--18358}, shortjournal = {J. Am. Chem. Soc.}, title = {A threose nucleic acid (TNA) enzyme catalyzing native 3′-5′ ligation of RNA}, volume = {147}, year = {2025}, }
• (2025). In situ construction of amide-functionalized 2D conjugated Metal–Organic frameworks with multiple active sites for high-performance potassium-ion batteries. JACS, 147(21), 18338--18348. (www)

  @article{ , abstract = {Two-dimensional conjugated metal–organic frameworks (2D c -MOFs) represent a promising class of electrode materials for potassium-ion batteries (PIBs), attributed to their superior conductivity, large specific surface area, high charge carrier mobility, and tunable active sites. However, most reported 2D c -MOF-based cathode materials for PIBs usually encounter challenges, such as low specific capacity and inadequate cycling stability. In this context, we herein designed and synthesized a new hexahydroxy salicylamide ligand (6OH-HBB) via a straightforward two-step synthesis with a high yield of 93%, which was subsequently utilized to construct a 2D Cu-HBB-MOF with multiple active sites through an in situ metal coordination-induced planarization strategy. Thanks to its abundant active sites and large specific surface area, the Cu-HBB-MOF demonstrated an outstanding high initial capacity of 228.1 mA h g –1 at 0.2 A g –1 , surpassing most reported porous material-based PIBs. Furthermore, even at 5.0 A g –1 , the Cu-HBB-MOF exhibited a large reversible specific capacity of 103.6 mA h g –1 after 2500 cycles, simultaneously maintaining a low-capacity loss of only 0.011% per cycle and achieving a Coulombic efficiency up to 100%, demonstrating good long-term cycle stability. This work provides fundamental insights into engineering 2D c -MOFs with multisite functionality, charting a new course for developing high-performance MOF-based cathodes in next-generation energy storage systems.}, archive = {J_JACS}, author = {Xi Su and Linqi Cheng and Xiaoli Yan and Hanwen Zhang and Tangjun Wang and Heng-Guo Wang and Long Chen}, doi = {10.1021/jacs.5c07158}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18338--18348}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ construction of amide-functionalized 2D conjugated Metal–Organic frameworks with multiple active sites for high-performance potassium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Square-planar tetranuclear cluster-based high-symmetry coordination Metal–Organic polymers for efficient electrochemical nitrate reduction to ammonia. JACS, 147(21), 18327--18337. (www)

  @article{ , abstract = {Metal–organic polymers (MOPs) are gaining booming attention as atomically precise single-site catalysts for electrochemical nitrate-to-ammonia conversion owing to their regular structures and tunable functionalities. However, a molecular-level understanding is still lacking for the design of more efficient MOP electrocatalysts. Here, we report the construction of high-symmetry coordination MOPs ( Mn-TATB , Fe-TATB , and Co-TATB ), utilizing square-planar tetranuclear building units [M 4 (μ 4 -O)(CO 2 ) 8 ] (M = Mn, Fe, or Co) bridged by 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine (H 3 TATB) ligands. These MOPs possess distinct coordination motifs with well-defined porosity, high-density catalytic sites, accessible mass transfer channels, and nanoconfined chemical environments. Benefited from the unique metal–organic coordination framework, Co-TATB demonstrated a remarkable ammonia production Faradaic efficiency (FE NH3 ) of ∼98% across a wide potential range (−0.7 to −1.0 V (vs RHE)) in the electrocatalytic nitrate reduction reaction (NITRR) and maintained stable performance over a long duration when tested in a flow cell at an industrially relevant current density of ∼332.1 mA cm –2 . Furthermore, in situ spectroscopic analyses, combined with theoretical calculations, elucidate the intrinsic reaction pathway of the Co-TATB model during the NITRR process. These findings offer insightful perspectives on the strategic design of electrocatalysts with symmetrical configurations for the purification of nitrate-containing wastewater and the green synthesis of ammonia.}, archive = {J_JACS}, author = {Miao Wang and Ya-Ru Meng and Wenjie Xu and Tianyu Shen and Yunhao Wang and Qianchuan Yu and Chongjing Liu and Yuming Gu and Zuoxiu Tie and Zhanxi Fan and Jing-Lin Zuo and Jian Su and Zhong Jin}, doi = {10.1021/jacs.5c06650}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18327--18337}, shortjournal = {J. Am. Chem. Soc.}, title = {Square-planar tetranuclear cluster-based high-symmetry coordination Metal–Organic polymers for efficient electrochemical nitrate reduction to ammonia}, volume = {147}, year = {2025}, }
• (2025). Achieving efficient organic room-temperature phosphorescence through acceptor dendronization. JACS, 147(21), 18317--18326. (www)

  @article{ , abstract = {Organic room-temperature phosphorescence (RTP) materials hold significant promise for applications in optoelectronics, information security, and bioimaging. Recently, significant progress has been made in RTP materials and vacuum-deposited organic light-emitting diode (OLED) devices. However, the performance of solution-processed OLEDs is seriously lagging behind due to the lack of RTP molecular strategies that balance exciton stability and solution processability at the single-molecule scale. In this work, we propose an acceptor dendronization strategy for designing RTP materials and successfully achieving highly efficient and stable RTP emissions. This strategy can simultaneously enhance the various processes involved in RTP emission at the single-molecule level: increase the intersystem crossing channels, enhance the spin–orbit coupling constants between T 1 and S 0 , and suppress molecular motion. Consequently, it promotes intersystem crossing and triplet radiative transition while inhibiting nonradiative transition, thereby efficiently enhancing RTP emission. A proof-of-concept acceptor-dendronized dendrimer exhibits long phosphorescence lifetimes in the millisecond range in ambient solution and near 100% photoluminescent quantum yields in the doped films. This is the first reported RTP dendrimer to date. An OLED fabricated using this dendrimer in a sky-blue emission achieves an external quantum efficiency of 25.1%, which represents the state-of-the-art efficiency based on solution-processed RTP-OLEDs to date. Our findings offer definitive guidelines for the molecular engineering of RTP materials and pave the way for innovative RTP systems in diverse optoelectronic applications.}, archive = {J_JACS}, author = {Chensen Li and Zhenchen Lou and Minghui Wu and Fulong Ma and Xinmeng Chen and Haozhe Tan and Zonghang Liu and Feng Gao and Zijie Qiu and Zheng Zhao and Lianrui Hu and Guohua Xie and Maoqiu Li and Yumeng Guo and Zhongjie Ren and Song Zhang and Yuchao Liu and Shouke Yan and Zhen Li and Bo Xu and Ryan T. K. Kwok and Jacky W. Y. Lam and Ben Zhong Tang}, doi = {10.1021/jacs.5c06288}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18317--18326}, shortjournal = {J. Am. Chem. Soc.}, title = {Achieving efficient organic room-temperature phosphorescence through acceptor dendronization}, volume = {147}, year = {2025}, }
• (2025). A linear Dysprosium(II) metallocene with a high effective energy barrier and magnetic hysteresis up to 70 kelvin. JACS, 147(21), 18307--18316. (www)

  @article{ , abstract = {Dysprosium in the oxidation state +3 is ubiquitous in studies of single-molecule magnets (SMMs). In contrast, SMMs based on lanthanides in the oxidation state +2 are rare, and examples with both a high effective energy barrier to reversal of the magnetization and hysteresis with coercivity at high temperatures are extremely uncommon. Here, we show that one-electron reduction of the dysprosium(III) complex [(η 5 -C 5 i Pr 5 )Dy(η 5 -Cp*)(BH 4 )] (Cp* = C 5 Me 5 ) with KC 8 generates the linear dysprosium(II) metallocene [(η 5 -C 5 i Pr 5 )Dy(η 5 -Cp*)]. Magnetic measurements, ultraviolet/visible/near infrared (UV/vis/NIR) spectroscopy and theoretical calculations show that the dysprosium(II) center in [(η 5 -C 5 i Pr 5 )Dy(η 5 -Cp*)] adopts a 4f 9 (6s/5d) 1 configuration. Coupling of the 4f and 5d electrons in [(η 5 -C 5 i Pr 5 )Dy(η 5 -Cp*)] results in an effective magnetic moment of 11.38 μ B at 217 K, equaling the highest magnetic moment recorded for a mononuclear complex. AC and DC magnetic measurements establish the SMM properties of [(η 5 -C 5 i Pr 5 )Dy(η 5 -Cp*)], including an energy barrier of 1551 cm –1 , the largest yet reported for a divalent lanthanide SMM, and a 100-s blocking temperature of 62 K. Magnetic hysteresis measurements produce loops that remain open up to 70 K. Multireference calculations reveal that the eas y -axis of magnetization in the ground doublet of [(η 5 -C 5 i Pr 5 )Dy(η 5 -Cp*)] coincides with the molecular symmetry axis, and that this doublet has extremely strong axial character. The strong axiality results in Orbach relaxation probably occurring via the second-excited doublet. The SMM parameters and the theoretical insight suggest that the high effective barrier and blocking temperature are linked to the strong and perfectly axial crystal field experienced by the dysprosium(II) center.}, archive = {J_JACS}, author = {Ming Liu and Yan-Cong Chen and Huan Wang and Tao Shang and Ming-Liang Tong and Richard A. Layfield and Akseli Mansikkamäki and Fu-Sheng Guo}, doi = {10.1021/jacs.5c06222}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18307--18316}, shortjournal = {J. Am. Chem. Soc.}, title = {A linear Dysprosium(II) metallocene with a high effective energy barrier and magnetic hysteresis up to 70 kelvin}, volume = {147}, year = {2025}, }
• (2025). Single-atom ru-triggered lattice oxygen redox mechanism for enhanced acidic water oxidation. JACS, 147(21), 18295--18306. (www)

  @article{ , abstract = {Activating the oxygen anionic redox presents a promising avenue for developing highly active oxygen evolution reaction (OER) electrocatalysts for proton-exchange membrane water electrolyzers (PEMWE). Here, we engineered a lattice-confined Ru single atom dispersed on a lamellar manganese oxide (MnO 2 ) cation site. The strong Ru–O bond induced an upward shift in the O 2 p band, enhancing metal–oxygen covalency and reshaping the OER mechanism toward lattice oxygen oxidation pathway with increased activity. In situ spectral characterization combined with density functional theory (DFT) calculations revealed that electron transfer from Mn to Ru alleviates the Jahn–Teller effect within the MnO 6 octahedral structure, stabilizing the lattice. The layered Ru/MnO 2 architecture also promotes the rapid replenishment of oxygen vacancies, preventing structural collapse. As a result, the optimized Ru/MnO 2 electrocatalyst achieves an OER overpotential of only 179 mV at 10 mA cm –2 in 0.5 M H 2 SO 4 , along with exceptional durability over 1000 h at 100 mA cm –2 . Moreover, the Ru/MnO 2 -based PEM device requires only 1.71 V to reach 1 A cm –2 and shows a durability of 500 h at 500 mA cm –2 .}, archive = {J_JACS}, author = {Menghui Qi and Xiangbowen Du and Xiaoyun Shi and Suwen Wang and Bing Lu and Jiadong Chen and Shanjun Mao and Hao Zhang and Yong Wang}, doi = {10.1021/jacs.5c05752}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18295--18306}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-atom ru-triggered lattice oxygen redox mechanism for enhanced acidic water oxidation}, volume = {147}, year = {2025}, }
• (2025). Template-directed synthesis of recognition-encoded melamine oligomers using a base-filling strategy. JACS, 147(21), 18284--18294. (www)

  @article{ , abstract = {Replication of molecular information in nature is based on the synthesis of the backbone of the copy strand by polymerization of monomers bound to a template. An alternative strategy is to use a preassembled polymer backbone devoid of sequence information as the copy strand and to attach side chains in a sequence determined by binding to a template, i.e., base-filling. Base-filling strategies were investigated for template-directed synthesis of recognition-encoded melamine oligomers (REMO) using H-bond base-pairing interactions between 4-nitrophenol and phosphine oxide side chains. A template with three 4-nitrophenol H-bond donor recognition units was used with a blank copy strand equipped with three aldehyde groups for the reversible attachment of amine recognition units via dynamic imine chemistry. Equilibration of the template and blank strands in dichloromethane in the presence of benzylamine and a phosphine oxide recognition unit equipped with an amine resulted in selective incorporation (79%) of the phosphine oxide recognition unit into the resulting copy strand. Covalent attachment of the blank strand to the template with a diester linker increased the selectivity of the base-filling process to 85%, and carrying out the experiment in toluene further increased the selectivity to 92%. The imines in the copy strand were trapped by reduction, and cleavage of the ester linkages allowed recovery of the template strand along with the kinetically stable tris-phosphine oxide copy. Fidelity of templating is determined by the concentration of the template strand, the association constant for the base-pairing interaction, and the effective molarities of the intramolecular interactions in the duplex.}, archive = {J_JACS}, author = {Joseph T. Smith and Joaquin Baixeras Buye and Ben Iddon and Daniil O. Soloviev and Christopher A. Hunter}, doi = {10.1021/jacs.5c05681}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18284--18294}, shortjournal = {J. Am. Chem. Soc.}, title = {Template-directed synthesis of recognition-encoded melamine oligomers using a base-filling strategy}, volume = {147}, year = {2025}, }
• (2025). Ca7(TeO3)6(MoO4): A promising mid-infrared nonlinear optical crystal activated via a module-oriented dimensionality reduction strategy. JACS, 147(21), 18275--18283. (www)

  @article{ , abstract = {Nonlinear optical (NLO) materials are of fundamental interest in laser technologies, yet achieving high-performing NLO crystals remains a substantial challenge due to the inherent trade-offs in critical performance metrics. Here, we report a new quasi-zero-dimensional (0D) tellurite molybdate NLO crystal, Ca 7 (TeO 3 ) 6 (MoO 4 ) (CTMO), engineered via a module-oriented dimensionality reduction strategy. The identification of a record isolated Te–O to Mo–O group ratio of 6 in tellurite molybdates underscores an unparalleled structural configuration. Notably, CTMO exhibits the shortest UV cutoff edge of 266 nm accompanied by a record-breaking bandgap of 4.66 eV among all reported acentric molybdates, which endows CTMO with a high laser-induced damage threshold 42 times higher than that of AgGaS 2 . Moreover, it demonstrates the strongest second harmonic generation (SHG) response of approximately 8.6 × KDP among molybdates with bandgaps exceeding 4 eV, a desirable birefringence value of 0.092@1064 nm for an effective phase matching process, and an extended IR absorption edge beyond 7.0 μm. Structural and theoretical analyses reveal that the well-balanced activities of CTMO arise from the synergistic effects of densely packed [TeO 3 ] trigonal pyramids and well-aligned [MoO 4 ] modules. The discovery of CTMO facilitates the utilization of acentric oxides as mid-IR NLO crystals, and it provides a straightforward and effective approach toward the rational design of novel NLO crystals with enhanced overall performance.}, archive = {J_JACS}, author = {Tinghui Zhang and Fei Liang and Conggang Li and Ning Ye and Zhanggui Hu}, doi = {10.1021/jacs.5c05512}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18275--18283}, shortjournal = {J. Am. Chem. Soc.}, title = {Ca7(TeO3)6(MoO4): A promising mid-infrared nonlinear optical crystal activated via a module-oriented dimensionality reduction strategy}, volume = {147}, year = {2025}, }
• (2025). Synthesis of stable SnI2·xDMSO adducts toward efficient Tin–Lead perovskite solar cells. JACS, 147(21), 18267--18274. (www)

  @article{ , abstract = {Sn–Pb narrow-bandgap perovskites are indispensable for achieving highly efficient all-perovskite tandem solar cells as bottom subcells. However, facile oxidation of Sn 2+ into Sn 4+ leads to the poor precursor stability, which largely hinders the development of Sn–Pb perovskite solar cells (PSCs). Herein, we present a novel strategy to synthesize SnI 2 · x DMSO intermedium adducts in situ utilizing a mild one-to-one reaction between molecular SnI 4 and metallic Sn. This approach avoids the formation of low-coordinated SnI 2 · x DMSO clusters ( x ≤ 2), yielding highly coordinated SnI 2 · x DMSO ( x = 3) adducts with enhanced antioxidation ability. The resultant precursor showed outstanding stability and reproducibility. The aged precursor for 7 days maintains its initial properties. Consequently, the resulting Sn–Pb PSCs deliver an impressive efficiency of 22.64% and retain ∼ 90% of their initial value after maximum power point operation under simulated one-sun illumination in air for 530 h under encapsulation. Our finding provides an effective pathway to enhance the intrinsic antioxidant capacity of Sn 2+ in perovskite precursors, paving a way for the development of efficient and reproducible Sn–Pb PSCs.}, archive = {J_JACS}, author = {Zhenkai Zhu and Ciyu Ge and Dayu Liu and Qi Xu and Yongxin Zhu and Xuke Yang and Chong Dong and Xinzhi Zu and Shuwen Yan and Jun Wang and Zeyu Zhang and Shuping Pang and Juan Du and Long Hu and Dewei Chu and Ling Xu and Haisheng Song and Luying Li and Ying Zhou and Chao Chen and Jiang Tang}, doi = {10.1021/jacs.5c05430}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18267--18274}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of stable SnI2·xDMSO adducts toward efficient Tin–Lead perovskite solar cells}, volume = {147}, year = {2025}, }
• (2025). Ligand basicity modulates metal cation reduction potentials at colloidal cadmium chalcogenide quantum dot surfaces. JACS, 147(21), 18257--18266. (www)

  @article{ , abstract = {Reduction or oxidation reactions at colloidal semiconductor nanocrystal quantum dot (QD) surfaces are critical mechanistic steps for charge trapping or for photoinduced charge transfer. However, measuring and controlling the redox potentials of the surface is nontrivial. Here, monoanionic metal carbonyl complexes are used as electronically tunable X-type ligands for CdSe and CdS QD surfaces. IR spectroscopy of the frequencies of the C–O stretching vibrations of the anionic metal carbonyl species enable quantitative measurement of anion dissociation correlated to QD surface reduction. Spectral redox titration and spectroelectrochemical experiments show that coordination of more Lewis basic anions shifts the surface reduction potentials to more negative values, spanning a range of more than 1 V. Based on these results, complexation energies are a critical factor in controlling surface charge storage. This concept extends generally to other types of QD supporting ligands and to other QD materials. As proof-of-concept, anion exchange was used to control chemical surface reduction and photochemical electronic doping in CdSe QDs.}, archive = {J_JACS}, author = {Mawuli Degbevi and Wyatt L. Balliew and Kasuni U. Handunge and Allen G. Oliver and Emily Y. Tsui}, doi = {10.1021/jacs.5c05413}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18257--18266}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand basicity modulates metal cation reduction potentials at colloidal cadmium chalcogenide quantum dot surfaces}, volume = {147}, year = {2025}, }
• (2025). Programmable solid-state [2 + 2] photocycloadditions of dienes directed by structural control and wavelength selection. JACS, 147(21), 18249--18256. (www)

  @article{ , abstract = {Small differences in molecular or solid-state structure can afford significant differences in properties. Here, a diene derivative, 1,3-bis(( E )-2-bromostyryl)benzene (2Brm), is synthesized and crystallized into two unique solid-state forms, each exhibiting a different π–π stacking geometry, which imparts distinct reactivity and photoresponsivity. Upon exposure of the two solids to UV–Vis light, a [2 + 2] photocycloaddition occurs to afford regioisomeric products due to the difference in the stacking geometries of the dienes. From a single molecular precursor, we further demonstrate that under different wavelengths of light, the chemical functionality can be programmed into discrete and distinct products containing one, two, or three cyclobutane rings as well as oligomeric/polymeric products. Moreover, the two initial solid forms exhibit wavelength-dependent photomechanical behaviors (i.e., photosalience). This work demonstrates a rare, template-free, self-assembly-based strategy that enables access to a suite of discrete and oligomeric/polymeric products via regiocontrolled solid-state photocycloadditions and further presents potential routes toward the design of photoactuating materials.}, archive = {J_JACS}, author = {Liulei Ma and Gary C. George, III and Steven P. Kelley and Kristin M. Hutchins}, doi = {10.1021/jacs.5c05415}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18249--18256}, shortjournal = {J. Am. Chem. Soc.}, title = {Programmable solid-state [2 + 2] photocycloadditions of dienes directed by structural control and wavelength selection}, volume = {147}, year = {2025}, }
• (2025). Kinetic analysis of the redox-neutral catalytic mitsunobu reaction: Dehydration, kinetic barriers, and hopping between potential energy surfaces. JACS, 147(21), 18240--18248. (www)

  @article{ , abstract = {Denton’s redox-neutral catalytic Mitsunobu reaction is remarkable in that it translates a reaction traditionally driven by the consumption of sacrificial chemical reagents to an additive-free catalytic manifold. Rational attempts to improve the system have been met with only marginal improvements, and a lack of consensus concerning the rate-determining step continues to limit effective reaction development. Here, we analyze the reaction mechanism focusing on a critical, largely overlooked element: the removal of water using a Dean–Stark apparatus. Experimental analysis of the water removal process, coupled with extensive kinetic simulations, demonstrates that the overall rate of the reaction is intimately tied to the rate of water removal. This process can be viewed as a transition between potential energy surfaces and, consequently, subsequent steps of the reaction can progress spontaneously in the absence of water, allowing an explanation of how Le Chatelier’s principle, a thermodynamic effect, can have a profound kinetic influence over the rate of the reaction. We identify three bottlenecks in the reaction that inform catalyst design. Additionally, we (a) clarify the ongoing discussion regarding the rate-determining step, (b) provide clear advice concerning future reaction design taking into account the role of water and, (c) discuss the redox-neutral catalytic Mitsunobu reaction in the context of formally endergonic esterification reactions, noting parallels with ratchet mechanisms. Finally, we highlight general principles of catalyst/reaction design that emerge from our analysis and implement our findings to demonstrate a 50% rate acceleration resulting from improved water removal, a substantially greater reaction enhancement than previously obtained from computationally guided catalyst structural changes.}, archive = {J_JACS}, author = {Keith G. Andrews and Stefan Borsley}, doi = {10.1021/jacs.5c05404}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18240--18248}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetic analysis of the redox-neutral catalytic mitsunobu reaction: Dehydration, kinetic barriers, and hopping between potential energy surfaces}, volume = {147}, year = {2025}, }
• (2025). Small organic carbonic anhydrase IX ligands from DNA-encoded chemical libraries for tumor-targeted delivery of radionuclides. JACS, 147(21), 18230--18239. (www)

  @article{ , abstract = {Carbonic anhydrase IX (CAIX) is a membrane protein that is highly expressed in clear cell renal cell carcinoma (ccRCC) and in hypoxic tumors. Being virtually absent in most healthy tissues, CAIX became an attractive target for the selective delivery of diagnostic and therapeutic payloads. Here, we report the discovery and characterization of DNA-encoded chemical library (DEL)-derived CAIX ligands for radionuclide-based imaging applications. Methods: DELs were screened against CAIX and CAII to prioritize hits based on their selectivity and enrichment against CAIX. In vitro characterization of hits was performed by fluorescence polarization (FP), surface plasmon resonance (SPR), and flow cytometry. In vivo biodistribution studies of Lutetium-177 and Gallium-68-radiolabeled compounds were performed in SK-RC-52 tumor-bearing mice. Results: DEL-based CAIX ligands with different affinities and selectivities could be identified. Selectivity and high affinity toward the target correlated with higher tumor-to-organ ratios and improved tumor retention. The best candidate, named OncoCAIX, reached up to ∼55% injected dose per gram in SK-RC-52 lesions at early time points with very low healthy organ uptake (tumor-to-kidney ratio of >23). Conclusion: OncoCAIX demonstrated rapid and selective tumor uptake, which is a key feature for the development of radionuclide-based imaging agents for early and late-stage ccRCC and hypoxic tumors.}, archive = {J_JACS}, author = {Marco Müller and Tony Georgiev and Jacqueline Mock and Dario Neri and Samuele Cazzamalli and Sebastian Oehler}, doi = {10.1021/jacs.5c05198}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18230--18239}, shortjournal = {J. Am. Chem. Soc.}, title = {Small organic carbonic anhydrase IX ligands from DNA-encoded chemical libraries for tumor-targeted delivery of radionuclides}, volume = {147}, year = {2025}, }
• (2025). Design and synthesis of a cluster-based supramolecular reaction pump for the efficient catalysis of amination reactions. JACS, 147(21), 18219--18229. (www)

  @article{ , abstract = {Although discrete self-assembled cage compounds with single-metal centers mimicking natural bioreactors for catalysis have been extensively investigated, studies on those with multimetal active centers, i.e., cluster active centers (CACs), have been less explored. Herein, we present the design and synthesis of a novel cluster-based supramolecular reaction pump ( CSRP-1 ) featuring four CACs that facilitate catalysis. CSRP-1 holds a cationic supramolecular tetrahedral structure, comprising four WS 3 Cu 3 clusters, each positioned at one vertex and interconnected by dipyridyl linkers. Substrates, including aryl iodides or primary or secondary amines, enter the cage cavity by replacing N , N -dimethylformamide at the CACs through weak Cu···I/N interactions. This design leverages the coordinatively unsaturated Cu centers within each CAC to activate the substrates, resulting in efficient catalytic amination. CSRP-1 works like a dynamic pump, and upon completion of the reaction, the amine product is expelled from the cavity, allowing the catalytic cycle to repeat with maintained efficiency. Theoretical calculations complement the experimental findings, providing key insights into the catalytic mechanism and the synergistic role of the clusters and linkers. This work offers a new catalysis paradigm with broad applicability to various organic reactions.}, archive = {J_JACS}, author = {Yun-Hu Deng and Brendan F. Abrahams and Jian-Ping Lang}, doi = {10.1021/jacs.5c04980}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18219--18229}, shortjournal = {J. Am. Chem. Soc.}, title = {Design and synthesis of a cluster-based supramolecular reaction pump for the efficient catalysis of amination reactions}, volume = {147}, year = {2025}, }
• (2025). Reactive oxygen species-instructed supramolecular assemblies enable bioorthogonally activatable protein degradation for pancreatic cancer. JACS, 147(21), 18208--18218. (www)

  @article{ , abstract = {Proteolysis-Targeting Chimeras (PROTACs) represent a transformative therapeutic platform for targeted protein degradation across diverse disease indications. However, their potent catalytic activity in normal tissues raises significant concerns regarding off-target toxicity. Here, we present a novel supramolecular self-assembly platform for the bioorthogonal control of PROTAC prodrug activation, enabling tumor-specific protein degradation with minimized systemic toxicity. By exploiting the overproduction of reactive oxygen species (ROS) in pancreatic cancer cells, the supramolecular self-assembly approach selectively accumulates bioorthogonal reaction triggers within the targeted malignant cells, which subsequently facilitates the spatiotemporally controlled activation of the bioorthogonally caged PROTAC. This tumor-selective activation mechanism demonstrates enhanced degradation efficiency in pancreatic cancer cells compared to normal cells. In vivo studies reveal potent tumor growth inhibition with complete preservation of major organ histology, confirming the therapeutic index enhancement achieved through a controllable activation strategy. This biomimetic activation platform establishes a generalizable framework for safer PROTAC-based therapies by integrating tumor-specific microenvironmental cues with bioorthogonal reaction engineering.}, archive = {J_JACS}, author = {Qingxin Yao and Ziyang Wu and Jiaan Li and Xiaoqian Hu and Hanlin Xu and Xingyu Jiang and Yuan Gao}, doi = {10.1021/jacs.5c04857}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18208--18218}, shortjournal = {J. Am. Chem. Soc.}, title = {Reactive oxygen species-instructed supramolecular assemblies enable bioorthogonally activatable protein degradation for pancreatic cancer}, volume = {147}, year = {2025}, }
• (2025). Consecutive asymmetric transfer hydrogenation of c2-acylated quinolines and quinoxalines: A diastereodivergent synthesis of enantioenriched tetrahydroquinolines and tetrahydroquinoxalines bearing endo- and exocyclic chirality. JACS, 147(21), 18197--18207. (www)

  @article{ , abstract = {Consecutive asymmetric hydrogenation offers a direct and convenient approach to synthesizing complex C(sp 3 )-enriched products with multiple chirality. Herein, we report an asymmetric synthesis of chiral 1,2,3,4-tetrahydroquinolines (THQs) and tetrahydroquinoxalines bearing both endo - and exo cyclic vicinal chirality through the consecutive transfer hydrogenation of easily accessible C2-acylated quinolines and quinoxalines. The method features mild conditions, easy operation, broad substrate scope (42 examples), and excellent asymmetric control (generally >90% ee and 20/1 dr). The key to success is the use of a water-soluble chiral aminobenzimidazole Ir catalyst. Mechanistic experiments support that the reaction involves the sequential reduction of the carbonyl group and then the quinoline core, with the asymmetric control of each step dominated by the catalyst. Remarkably, a diastereodivergent synthesis of all four stereoisomers of a chiral THQ has been successfully implemented.}, archive = {J_JACS}, author = {Mangang Zhang and Tianyu Niu and Mingrong Liang and Feng Xu and Yongyi Du and Haokun Zhuang and Ren-Jie Song and Hua Yang and Qin Yin}, doi = {10.1021/jacs.5c04856}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18197--18207}, shortjournal = {J. Am. Chem. Soc.}, title = {Consecutive asymmetric transfer hydrogenation of c2-acylated quinolines and quinoxalines: A diastereodivergent synthesis of enantioenriched tetrahydroquinolines and tetrahydroquinoxalines bearing endo- and exocyclic chirality}, volume = {147}, year = {2025}, }
• (2025). Ammonia-assisted chemical vapor deposition growth of two-dimensional conjugated coordination polymer thin films. JACS, 147(21), 18190--18196. (www)

  @article{ , abstract = {As emerging electroactive materials, the controlled synthesis of highly ordered two-dimensional (2D) conjugated coordination polymer (c-CP) films ensuring the long-range π-electron delocalization is essential for advancing high-performance (opto-)electronics. Here, we demonstrate the growth of highly crystalline 2D c-CP thin films on inert substrates by chemical vapor deposition with the assistance of ammonia (NH 3 ) for the first time, leveraging its deprotonation effect on ligands and competing effect as additional coordinating species. The resulting Fe-HHB (HHB = hexahydroxybenzene) films exhibit large-area uniformity and a 2 order-of-magnitude increase in crystal grain size, which translates into significant improvements in electrical conductivity (from 0.002 to 3 S/cm), charge mobility, elastic modulus, and hardness. To verify the generality of this NH 3 -assisted synthesis, the contrast Cu-HHB and Cu-BHT (BHT = hexathiolbenzene) 2D c-CP thin films are also prepared and deliver significantly improved electrical conductivities from 51 to 113 and from 595 to 905 S/cm, respectively. The greatly improved crystallinity, combined with the high compatibility of the developed synthetic strategy with current device integration technologies, paves the way for developing c-CP-based electronics.}, archive = {J_JACS}, author = {Jinxin Liu and Shuai Fu and Yubin Fu and Yunxu Chen and Kian Tadayon and Mike Hambsch and Darius Pohl and Ye Yang and Alina Müller and Fengxiang Zhao and Stefan C. B. Mannsfeld and Lei Gao and Mischa Bonn and Xinliang Feng and Renhao Dong}, doi = {10.1021/jacs.5c04515}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18190--18196}, shortjournal = {J. Am. Chem. Soc.}, title = {Ammonia-assisted chemical vapor deposition growth of two-dimensional conjugated coordination polymer thin films}, volume = {147}, year = {2025}, }
• (2025). Spiro-linked planar core small molecule hole transport materials enabling high-performance inverted perovskite solar cells. JACS, 147(21), 18180--18189. (www)

  @article{ , abstract = {Small-molecule organic semiconductors have demonstrated significant potential for application in hole-transporting materials (HTMs) for perovskite solar cells (PSCs), thanks to their high reproducibility and convenient synthesis routes. Finely designed planar π–π stacking structures have emerged as one of the primary strategies for achieving high-performance small-molecule HTMs. In particular, the incorporation of a helical structure into HTM designs through a linearization approach has proven effective, leading to the development of novel materials with superior properties. In this study, the structure–property relationship of these small molecules has been systematically explored. The newly developed HTM, SPCF-MeTPA, based on a spiro[cyclopentane-1,9′-fluorene] core, features a rigid conjugated system with spiro-linked core. This design provides improved intermolecular charge extraction and transport, optimized energy levels, and effective surface passivation compared to SPTP-MeTPA, which has a nonplanar spatial arrangement. As a result, the champion device based on SPCF-MeTPA achieves efficiencies of 26.35% (certified 25.75%) and 24.55% for aperture areas of 0.07 and 1.01 cm 2 , respectively. Additionally, these devices demonstrate exceptional long-term stability, further highlighting the potential of SPCF-MeTPA as a high-performance HTM.}, archive = {J_JACS}, author = {Zhixin Liu and Jie Zeng and Deng Wang and Peide Zhu and Lida Wang and Yuqi Bao and Yintai Xu and Wenbo Peng and Siru He and Zhiwei Lei and Lihan Pang and Bo Jiang and Jiangfeng Wang and Zonglong Song and Yong Zhang and Xingzhu Wang and Lei Yan and Baomin Xu}, doi = {10.1021/jacs.5c04671}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18180--18189}, shortjournal = {J. Am. Chem. Soc.}, title = {Spiro-linked planar core small molecule hole transport materials enabling high-performance inverted perovskite solar cells}, volume = {147}, year = {2025}, }
• (2025). Recipe for flat bands in pyrochlore materials: A chemist’s perspective. JACS, 147(21), 18166--18179. (www)

  @article{ , abstract = {Materials in which atoms are arranged in a pyrochlore lattice have found renewed interest, as, at least theoretically, orbitals on that lattice can form flat bands. However, real materials often do not behave according to theoretical models, which is why there has been a dearth of pyrochlore materials exhibiting flat band physics. Here, we examine the conditions under which ideal “pyrochlore bands” can exist in real materials and how to have those close to the Fermi level. We find that the simple model used in the literature does not apply to the bands at the Fermi level in real pyrochlore materials. However, surprisingly, we find that certain oxide compounds that have oxygen orbitals inside the pyrochlore tetrahedra do exhibit near-ideal pyrochlore bands near the Fermi level. We explain this observation by a generalized tight-binding model, including the oxygen orbitals. We further classify all known pyrochlore materials based on their crystal structure, band structure, and chemical characteristics and propose materials to study in future experiments.}, archive = {J_JACS}, author = {Fatmagül Katmer and Milena Jovanovic and Jennifer Cano and Lukas Muechler and Leslie M. Schoop}, doi = {10.1021/jacs.5c04593}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18166--18179}, shortjournal = {J. Am. Chem. Soc.}, title = {Recipe for flat bands in pyrochlore materials: A chemist’s perspective}, volume = {147}, year = {2025}, }
• (2025). Heterointercalation in chevrel-phase sulfides: A model periodic solid for the investigation of chain electron transfer. JACS, 147(21), 18155--18165. (www)

  @article{ , abstract = {Modulation of electron density localization on periodic crystal solids through electron transfer from interstitial cations can directly influence the bonding configurations of small-molecule intermediates at the catalyst binding site. This study presents the microwave-assisted solid-state synthesis of four heterointercalant Chevrel-phase (CP) sulfides with varying metal cation intercalants with compositional and electronic structure investigations of the electron density redistribution as a result of intercalation. The heterointercalant CP sulfides, with the general formula Cu x M y Mo 6 S 8 (where M = Cr, Mn, Fe, Ni; x , y = 1.5–2.5), are presented here for the probe reaction of electrochemical CO 2 reduction. A change in product selectivity is observed toward the production of methanol at low overpotentials of −0.5 V vs reversible hydrogen electrode (RHE), as a result of the intercalant combination present within the CP interstitial cavity. Structural confirmation of all materials was examined through Rietveld refinement of the powder X-ray diffraction (PXRD) data, high-resolution transmission electron microscopy (HR-TEM), and selected-area electron diffraction (SAED). Electron transfer from the intercalated metal cations to the Mo 6 S 8 cluster was investigated via X-ray photoelectron spectroscopy (XPS) of the intercalated metal cations and the chalcogenide cluster. Electron transfer was further confirmed through X-ray absorption analysis (XAS) of the K-edges of Mo and intercalants. Intermediate studies of electrochemical reduction of formaldehyde to methanol resulted in a faradaic efficiency of ∼78% methanol production on Cu x Ni y Mo 6 S 8 . The results presented herein identify distinct principles for materials design that can be utilized in other compositional spaces within the broad families of periodic crystal solids.}, archive = {J_JACS}, author = {Konstantina G. Mason and Natalia Mosqueda and S. Avery Vigil and Paola N. Del Pozo-Gonzalez and Saxton Feiner and Kingston P. Robinson and Jenna M. Ynzunza and Ankita Kumari and Rose E. Smiley and Erika La Plante and George Agbeworvi and Ivan A. Moreno-Hernandez and Jesús M. Velázquez}, doi = {10.1021/jacs.5c04404}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18155--18165}, shortjournal = {J. Am. Chem. Soc.}, title = {Heterointercalation in chevrel-phase sulfides: A model periodic solid for the investigation of chain electron transfer}, volume = {147}, year = {2025}, }
• (2025). A broad-spectrum catalyst for aliphatic polymer breakdown. JACS, 147(21), 18145--18154. (www)

  @article{ , abstract = {Thermolysis of the well-defined aluminum fluoroalkoxide supported on silica (≡SiOAl(OC(CF 3 ) 3 ) 2 (O(Si≡) 2 ), 1 , 0.20 mmol Al g –1 ) at 200 °C forms a fluorinated amorphous silica–alumina (F-ASA) containing a distribution of Al(IV), Al(V), and Al(VI) sites that maintain relatively strong Lewis acidity. Small amounts of Brønsted sites are also present in F-ASA. Solid-state NMR studies show that a majority of the aluminum centers in F-ASA are not close to the Si–F groups that form during thermolysis. F-ASA is exceptionally reactive in cracking (or pyrolysis) reactions of neat polymer melts. Catalyst loadings as low as 2 wt % (0.017 mol % aluminum) efficiently break down isotactic polypropylene, high-density polyethylene, ethylene/1-octene copolymer, and postconsumer wastes. The major products of this reaction are hyperbranched liquid paraffins containing internal olefins and very small amounts of aromatics. Under continuous distillation of oils from the reaction mixtures, pyrolysis on 50 g reaction scales is feasible. F-ASA cokes and deactivates during this reaction but can be reactivated by calcination in air. These properties are complementary to other state-of-the-art catalysts for polymer breakdown, but unlike those catalysts F-ASA does not require an additional cofed reactant (e.g., H 2 , olefin, etc.) to drive the reaction.}, archive = {J_JACS}, author = {Jiaxin Gao and Frédéric A. Perras and Matthew P. Conley}, doi = {10.1021/jacs.5c04524}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18145--18154}, shortjournal = {J. Am. Chem. Soc.}, title = {A broad-spectrum catalyst for aliphatic polymer breakdown}, volume = {147}, year = {2025}, }
• (2025). Large temperature dependence of redox potential driven by semiclathrate hydrate formation for thermo-electrochemical conversion. JACS, 147(21), 18134--18144. (www)

  @article{ , abstract = {The temperature dependence of the redox potential (temperature coefficient) is a critical parameter for redox couples employed in thermoelectrochemical conversion devices, such as thermogalvanic cells and thermally regenerative electrochemical cycles (TRECs). We developed a novel strategy for boosting the temperature coefficient of ferro/ferricyanide through the formation/dissociation of a semiclathrate hydrate (SCH). The aqueous solution with ferro/ferricyanide and tetrabutylammonium fluoride (TBAF) showed SCH formation/dissociation by small temperature variations, which contributed to a huge temperature coefficient (−13.8 mV K –1 ) near ambient temperature. The large-temperature coefficient was attributed to a significant change in the TBAF concentration in the liquid phase caused by SCH formation/dissociation, resulting in the rearrangement of the ion pair of ferricyanide and cations. We introduced the electrolyte to a charging-free TREC device driven by a small temperature swing (9 K) and achieved the highest normalized power density (4.8 mW m –2 K –2 ). This electrolyte design strategy will pave the way for electrochemical energy harvesting from small temperature changes such as diurnal temperature variations. In addition, this study creates a new research field for semiclathrate hydrate chemistry.}, archive = {J_JACS}, author = {Yohei Matsui and Yuki Maeda}, doi = {10.1021/jacs.5c04430}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18134--18144}, shortjournal = {J. Am. Chem. Soc.}, title = {Large temperature dependence of redox potential driven by semiclathrate hydrate formation for thermo-electrochemical conversion}, volume = {147}, year = {2025}, }
• (2025). Phenalenyl chemistry revisited: Stable and bioactive multisubstituted phenalenyl radicals synthesized via a Protection–Oxidation–Protection strategy. JACS, 147(21), 18122--18133. (www)

  @article{ , abstract = {Phenalenyl chemistry has flourished for decades but currently faces bottlenecks related to synthetic challenges and stability issues. In this study, we introduced an iterative protection–oxidation–protection (POP) strategy to synthesize stabilized phenalenyl radicals (PRs) with multiple substitutions at the α-positions. The applicability of this POP strategy was verified using triisopropylsilylthyl and phenyl substituents to generate trisubstituted PR1 and hexasubstituted PR2 . In particular, both oxidation and dimerization were observed during the synthesis involving phenyl substituents. Both PR1 and PR2 were bench-stable, with half-lives in solution of up to 46 d and thermal decomposition temperatures of up to 300 °C. X-ray crystallographic analysis revealed that PR1 existed as a distinct 12-center-2-electron π-dimer, whereas PR2 existed as a monomer. The properties associated with monomer–dimer equilibrium both in the solid state and in solution were systematically investigated via variable-temperature spectroscopy, and the results revealed a small singlet–triplet energy gap and concentration-dependent absorption and electrochemical behaviors. Remarkably, both PR1 and PR2 formed biocompatible nanoparticles, with the latter capable of depleting reactive oxygen species in liver cells. This study thus demonstrated the applicability of the POP strategy for the construction of stable, functionalized PR derivatives with practical applications as spin functional materials.}, archive = {J_JACS}, author = {Miaoyue Tian and Lei Ye and Mingzhe Wang and Xiaoqi Tian and Zhe Sun}, doi = {10.1021/jacs.5c04413}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18122--18133}, shortjournal = {J. Am. Chem. Soc.}, title = {Phenalenyl chemistry revisited: Stable and bioactive multisubstituted phenalenyl radicals synthesized via a Protection–Oxidation–Protection strategy}, volume = {147}, year = {2025}, }
• (2025). Constructing a localized buffer interlayer to elevate high-rate CO2-to-c2+ electrosynthesis. JACS, 147(21), 18110--18121. (www)

  @article{ , abstract = {Catalytic surface and interface engineering for the electrosynthesis of multicarbon chemicals from CO 2 are widely investigated, while the selective regulation of mass transport for reactant CO 2 and intermediate CO remains rarely explored, which is a critical challenge limiting the C 2+ production rate. Here, we strategically construct a buffer interlayer with soluble ionic liquid (IL) additives between the aqueous electrolyte and the catalytic surface, which not only regulates the microenvironment of CO and CO 2 at different reaction stages but also stabilizes catalytic sites. The CO residence time is extended in the buffer interlayer ascribed to the attractive interactions via dipole–dipole interactions and hydrogen bonding. CO 2 and its transport are enhanced by the buffer reactions in the aqueous interlayer within the flow-through compact cell. Meanwhile, the utilization of ILs stabilizes active sites (Cu 2 O-derived Cu) by facilitating the regeneration of Cu 2 O through the applied potentials. Consequently, C 2+ products are synthesized at a high rate with a partial current density of 1.30 A/cm 2 for over 200 h. This concept is further scaled to a 100 cm 2 flow cell, exhibiting a carbon loss below 6%. Such a systematic investigation establishes a general construction strategy for the buffer interlayer and catalytic sites in electrolysis.}, archive = {J_JACS}, author = {Guobin Wen and Bohua Ren and Xin Wang and Lichao Tan and Silong Dong and Haoyang Xiong and Rui Gao and Dan Luo and Xiaoman Duan and Ning Zhu and Qianyi Ma and Aiping Yu and Zhongwei Chen}, doi = {10.1021/jacs.5c04129}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18110--18121}, shortjournal = {J. Am. Chem. Soc.}, title = {Constructing a localized buffer interlayer to elevate high-rate CO2-to-c2+ electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Spin manipulation engineering of photodynamic intermediates: Magnetic amplification of oxyradicals generation for enhanced antitumor phototherapeutic efficacy. JACS, 147(21), 18100--18109. (www)

  @article{ , abstract = {Improving the photosensitization efficiency represents a critical challenge in photodynamic therapy (PDT) research. While cyanines exhibit potential as photosensitizers (PSs) due to their large extinction coefficients and excellent biocompatibility, the inherent limitations in intersystem crossing severely affect therapeutic efficacy. Herein, we proposed a bottom-up magnetically enhanced photodynamic therapy (magneto-PDT) paradigm employing fluorobenzene-substituted pentamethine cyanine as type-I reactive oxygen species generators. Based on the radical pair mechanism and magnetic field effect, the notable difference in g-factors (Δg) between PSs and oxyradicals enabled magnetically responsive amplification of Cy5–3,4,5–3F-mediated hydroxyl radical (•OH) and superoxide anion radical (O 2 •– ) production, achieving maximum yield enhancements of 66.9 and 28.0% respectively at 500 mT. This magnetically augmented oxyradicals generation exhibited universal cytotoxicity superiority over conventional PDT protocols in various cancer cell models. Notably, the semi-inhibitory concentration (IC 50 ) of murine mammary carcinoma 4T1 cells demonstrated a remarkable reduction under both normoxic and hypoxic conditions, with the most pronounced decrease observed in normoxia from 0.91 μM (PDT alone) to 0.38 μM (magneto-PDT). The significantly magneto-enhanced therapeutic performance effectively inhibited orthotopic tumor growth. This magneto-PDT paradigm established a novel strategy for manipulating spin-dependent photosensitization processes in biological applications.}, archive = {J_JACS}, author = {Jiuyu Lu and Junying Ding and Zhuoran Xia and Zhuo Yang and Chengyuan Lv and Shenglin Zong and Jianfang Cao and Danhong Zhou and Saran Long and Wen Sun and Jianjun Du and Jiangli Fan and Xiaojun Peng}, doi = {10.1021/jacs.5c04111}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18100--18109}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin manipulation engineering of photodynamic intermediates: Magnetic amplification of oxyradicals generation for enhanced antitumor phototherapeutic efficacy}, volume = {147}, year = {2025}, }
• (2025). Mechanism of giant magnetic field effect in a red fluorescent protein. JACS, 147(21), 18088--18099. (www)

  @article{ , abstract = {Several fluorescent proteins, when expressed in E. coli , are sensitive to weak magnetic fields. We found that mScarlet3 fluorescence in E. coli reversibly decreased by 21% in the presence of a 60 mT magnetic field, the largest magnetic field effect (MFE) reported in any fluorescent protein. Purified mScarlet3 did not show an MFE, but the addition of flavin mononucleotide (FMN) and simultaneous illumination with blue and yellow light restored the MFE. Through extensive photophysical experiments, we developed a quantitative model of the giant MFE in mScarlet3-FMN mixtures. The key reaction step involved electron transfer from fully reduced FMNH 2 to triplet-state mScarlet3 to form a triplet spin-correlated radical pair. The magnetic field then controlled the branching ratio between singlet recombination vs triplet separation. Our quantitative model of the mScarlet3-FMN photocycle provides a framework for the design and optimization of magnetic-field-sensitive proteins, opening possibilities in fluorescent protein-based magnetometry, magnetic imaging, and magnetogenetic control.}, archive = {J_JACS}, author = {Katherine M. Xiang and Hana Lampson and Rebecca Frank Hayward and Andrew G. York and Maria Ingaramo and Adam E. Cohen}, doi = {10.1021/jacs.5c03997}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18088--18099}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanism of giant magnetic field effect in a red fluorescent protein}, volume = {147}, year = {2025}, }
• (2025). Decoding potassium homeostasis in cancer metastasis and drug resistance: Insights from a highly selective DNAzyme-based intracellular k+ sensor. JACS, 147(21), 18074--18087. (www)

  @article{ , abstract = {Potassium ions (K + ) within the tumor microenvironment, along with dysregulation of K + channels, play critical roles in supporting cancer cell survival and preventing their elimination. Directly monitoring changes in K + homeostasis within cancer cells is invaluable for understanding these processes. However, achieving high selectivity over other biological metal ions, a detection dynamic range that aligns with intracellular K + levels, and broad accessibility to research laboratories remain technically challenging for current K + imaging probes. In this study, we report the in vitro selection of the first K + -specific RNA-cleaving DNAzyme and the development of a K + -specific DNAzyme fluorescent sensor with exceptional selectivity, achieving over 1000-fold selectivity against Na + and more than 100-fold selectivity over other major biologically relevant metal ions. This sensor has an apparent dissociation constant (105 mM) that is close to the intracellular level of K + , and it has a broad detection range from 21 to 200 mM K + . Using this tool, we reveal a progressive decline in intracellular K + levels in breast cancer cells with more advanced progression states. Moreover, we demonstrate that elevated extracellular K + levels interfere with the efficacy of anticancer compounds like ML133 and Amiodarone, suggesting an underappreciated role of microenvironmental K + in chemoresistance. Notably, blocking the Kir2.1 channel activity restored treatment sensitivity, presenting a potential strategy to overcome chemoresistance in aggressive cancers. These findings underscore the role of K + homeostasis in tumor progression and support further exploration of ion-channel-targeted cancer therapies.}, archive = {J_JACS}, author = {Zhenglin Yang and Xiangli Shao and Yuting Wu and Aritra Roy and Elijah Garcia and Annie Farrell and Shreestika Pradhan and Weijie Guo and Heather Gan and Zeynep Korkmaz and Emily Adams and Yi Lu}, doi = {10.1021/jacs.5c03781}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18074--18087}, shortjournal = {J. Am. Chem. Soc.}, title = {Decoding potassium homeostasis in cancer metastasis and drug resistance: Insights from a highly selective DNAzyme-based intracellular k+ sensor}, volume = {147}, year = {2025}, }
• (2025). Stabilizing residual monomers within in situ polymerized electrolytes for high-voltage lithium metal batteries. JACS, 147(21), 18064--18073. (www)

  @article{ , abstract = {Poly(1,3-dioxolane) (PDOL)-based electrolyte has gained wide attention due to its high compatibility with the lithium metal anode, intimate contact with electrodes, and high ionic conductivity. However, its application in high-voltage batteries is limited because the residual DOL monomers are prone to oxidation at high voltage. Here, we report that LiDFOB-initiated in situ polymerization stabilizes these residual monomers, thus overcoming the oxidation-related limitations of PDOL-based electrolytes. This approach promotes the formation of a thermodynamically stable Li + –DOL–DFOB – solvation structure and DOL–PDOL clusters, reducing the oxidative decomposition of the residual DOL monomers and extending the electrochemical stability window up to 5.0 V vs Li + /Li. It also enhances ionic conductivity (4.39 mS cm –1 ), and facilitates the formation of a uniform, F-rich cathode-electrolyte interphase. Electrochemical tests and computational simulations reveal that the reduced Li + –PDOL interactions in the designed PDOL promote higher ionic mobility and electrochemical stability. Consequently, Li||LiCoO 2 cells using the designed PDOL exhibit remarkable cycling performance, maintaining 80% capacity retention over 760 cycles at a cut-off voltage of 4.35 V. These findings establish PDOL as a transformative electrolyte for high-voltage lithium metal batteries.}, archive = {J_JACS}, author = {Zejun Sun and Jinlin Yang and Yao Wu and Fanbin Meng and Yuxiang Niu and Hongfei Xu and Yupeng Zhu and Bolong Hong and Zhiyu Chen and Jinlong Zhu and Qian He and Gang Wu and Wei Chen}, doi = {10.1021/jacs.5c03911}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18064--18073}, shortjournal = {J. Am. Chem. Soc.}, title = {Stabilizing residual monomers within in situ polymerized electrolytes for high-voltage lithium metal batteries}, volume = {147}, year = {2025}, }
• (2025). 13C chemical shift of N-heterocyclic carbenes in coinage Metal(I) complexes and clusters: Trans-influence and Spin–Orbit coupling. JACS, 147(21), 18054--18063. (www)

  @article{ , abstract = {N-Heterocyclic carbenes (NHCs) are versatile ligands in organometallic chemistry, prized for their strong σ-donating and tunable electronic properties. They are used to stabilize a wide range of motifs, including clusters and nanoparticles, based in particular on coinage metals─Cu, Ag, and Au. Notably, the carbene 13 C NMR isotropic chemical shift (δ iso ) of NHC-coinage metal complexes varies significantly across these elements, reflecting the nuanced interplay of electronic and structural factors. Here, we study the carbene carbon chemical shift in NHC-Au(I)-X complexes (X = H, OH, halides, CN, N 3 , and neutral ligands such as pyridine and NHC) compared to the Cu and Ag congeners. Density functional theory calculations are used to analyze the chemical shielding tensor components, revealing that stronger σ-donor X-ligands lead to greater deshielding of δ iso through enhanced paramagnetic contributions and, for Au, spin–orbit contributions of comparable magnitude. Moreover, a correlation between the spin–orbit contribution to the chemical shift (σ so ) and the Au-carbene bond distance highlights the critical role of trans-influence in modulating spin–orbit coupling and the overall chemical shift. Analysis of σ so shows that stronger σ-donor ligands, associated with a greater trans-influence and elongated Au-carbene bond, lead to a higher-lying NHC-Au σ-bond and lower-lying π*-orbital, ultimately yielding greater deshielding and higher 13 C chemical shift. This work provides insight into how structural and electronic factors govern carbene chemical shifts in NHC-based Au complexes and clusters, establishing a direct link between NMR spectroscopic descriptors and electronic structure, thus opening avenues for developing structure–activity relationships in catalysis and materials science.}, archive = {J_JACS}, author = {Shahar Dery and Christian Ehinger and Jeremy Roudin and Yuya Kakiuchi and Domenico Gioffrè and Christophe Copéret}, doi = {10.1021/jacs.5c03929}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18054--18063}, shortjournal = {J. Am. Chem. Soc.}, title = {13C chemical shift of N-heterocyclic carbenes in coinage Metal(I) complexes and clusters: Trans-influence and Spin–Orbit coupling}, volume = {147}, year = {2025}, }
• (2025). Two-dimensional Metal–Organic framework with high-performance single-molecule magnets as nodes showing magnetic coercivity photomodulation. JACS, 147(21), 18044--18053. (www)

  @article{ , abstract = {Addressing the spatial organization of high-performance single-molecule magnets (SMMs) and achieving stimuli-responsive switching of their magnetic bistability are pivotal challenges in molecular memory technologies, paving the way for advanced opto-magnetic devices. Herein, we utilize the photosensitive ligand 4,4′-bipyridine (BPy) as a linker to incorporate typical pentagonal-bipyramidal SMMs as nodes into a two-dimensional metal-organic framework (MOF), formulated as {[Dy 1.5 (OPh) 2 Cl(BPy) 3 (THF) 1.5 ][(BPh 4 ) 1.5 ]·0.5THF} n ( 1 ). The precise synthesis facilitates axial coordination of PhO – and equatorial alignment of BPy, enforcing perpendicular orientations of the principal magnetic axes of Dy 3+ ions across all Kagomé layers. Compound 1 exhibits photochromic behavior upon exposure to ultraviolet irradiation at room temperature, driven by a photoinduced electron transfer process that generates radicals. The resulting 1uv displays overall faster relaxation dynamics compared to 1 , characterized by shorter relaxation times at identical temperatures within the 12–70 K range, a lower diverging temperature in field-cooled and zero-field-cooled curves (9 K for 1 vs. 6 K for 1uv ), and reduced energy barriers from 1048(17)/822(46) K for 1 to 1000(9)/641(34) K for 1uv . Notably, the coercive field decreases dramatically from 4500 Oe for 1 to 1300 Oe for 1uv at 2 K, while the hysteresis loop opening temperature decreases from 20 K for 1 to 14 K for 1uv . These photoinduced changes are due to the formation of photogenerated radicals and alterations in crystal packing. This work achieves an MOF that integrate high-performance SMM behavior with magnetic coercive photomodulation, providing a design paradigm for engineering advanced SMM-MOFs with tailored photomagnetic switching.}, archive = {J_JACS}, author = {Xiao-Qin Wang and Ya-Wei Geng and Zhimo Wang and Changjian Xie and Tian Han and Peng Cheng}, doi = {10.1021/jacs.5c03704}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18044--18053}, shortjournal = {J. Am. Chem. Soc.}, title = {Two-dimensional Metal–Organic framework with high-performance single-molecule magnets as nodes showing magnetic coercivity photomodulation}, volume = {147}, year = {2025}, }
• (2025). Constructing asymmetric defects pairs in electrocatalysts for efficient glycerol oxidation. JACS, 147(21), 18033--18043. (www)

  @article{ , abstract = {Disrupting the charge distribution equilibrium in catalysts is an effective strategy for the polarization and cleavage of small molecules during the electrocatalytic process. To achieve effective C–C bond cleavage in multicarbon molecules, such as glycerol, integrating the advantages of defect sites while creating spatially asymmetric sites that modulate the local electronic perturbations is both promising and challenging. In this study, spatially asymmetric defect pairs were engineered by partially refilling sulfur atoms into spinel CuCo 2 O x with a high oxygen vacancy density (H Vo -S). These oxygen defect-refilled S pairs (Vo-S) enhance the local charge transfer, reduce the energy barrier for glycerol adsorption, and create thermodynamically favorable conditions for the second C–C bond cleavage, whereas the high density of oxygen vacancies further amplifies the local electronic perturbations. Exploiting the spatial effects of asymmetric defect sites, H Vo -S demonstrated superior performance compared to H Vo without Vo refilling, achieving Faradaic efficiencies (FE) of 98.5% and 75.3% at 1.36 V vs RHE for formic acid in the glycerol oxidation reaction (GOR), respectively. Significantly, this strategy also promotes C–C bond cleavage during the electrooxidation of ethylene glycol and glucose, further confirming its broad applicability in activating C–C bonds in polyol substrates. This study elucidates the role of the spatial effects of localized asymmetric defect sites in the GOR process, providing new insights for the design of novel electrocatalysts aimed at promoting C–C bond cleavage in polyol molecules.}, archive = {J_JACS}, author = {Liyun Wu and Qilong Wu and Yun Han and Dongdong Zhang and Rongrong Zhang and Nan Song and Yiqing Fang and Haodong Liu and Mingyue Wang and Jun Chen and Aijun Du and KeKe Huang and Xiangdong Yao}, doi = {10.1021/jacs.5c03703}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18033--18043}, shortjournal = {J. Am. Chem. Soc.}, title = {Constructing asymmetric defects pairs in electrocatalysts for efficient glycerol oxidation}, volume = {147}, year = {2025}, }
• (2025). Ptychographic observation of lithium atoms in the irradiation-sensitive garnet-type solid electrolyte at sub-angstrom resolution. JACS, 147(21), 18025--18032. (www)

  @article{ , abstract = {Garnet-type solid electrolyte cubic Li 7 La 3 Zr 2 O 12 (c-LLZO) emerges as a promising candidate for establishing reliable and high-performance lithium-ion batteries. Its extreme sensitivity to electron irradiation poses a significant challenge in atomically resolving its structure using conventional transmission electron microscopy (TEM) techniques. We demonstrate that the combination of low-dose four-dimensional scanning TEM (4D-STEM) with multislice ptychographic retrieval methodology manages to achieve a sub-Angstrom resolution and the direct visualization of lithium atoms within c-LLZO. The distribution of lithium in depth direction is also obtained. This work provides atomic-scale insights into the distribution of light elements within irradiation-sensitive dense crystals, paving the way for investigating the microstructure–property relationship.}, archive = {J_JACS}, author = {Zeyu Wang and Xiangchen Hu and Yue Zhang and Xiaoyan Wu and Hongsheng Shi and Wei Liu and Yi Yu}, doi = {10.1021/jacs.5c03627}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18025--18032}, shortjournal = {J. Am. Chem. Soc.}, title = {Ptychographic observation of lithium atoms in the irradiation-sensitive garnet-type solid electrolyte at sub-angstrom resolution}, volume = {147}, year = {2025}, }
• (2025). Relaxation-based in vivo discrimination of oxidized and reduced states of a redox-switchable 19F MRI probe. JACS, 147(21), 18017--18024. (www)

  @article{ , abstract = {MRI assessment of the tissue redox state is important for revealing and understanding various pathologies, and redox-responsive imaging probes capable of generating discrete and quantifiable signals in both their reduced and oxidized forms can provide enhanced detection reliability. The small fluorinated, redox-active FeL1 chelate is a prototype of such agents. L1 forms stable and inert complexes with both Fe 2+ and Fe 3+ ions, and the redox potential of the Fe 3+ L1/Fe 2+ L1 couple (+240 mV vs NHE) is adapted to biological redox sensing. Fe 2+ L1 undergoes instantaneous oxidation in the presence of H 2 O 2 , and Fe 3+ L1 is reduced by cysteine, glutathione, and ascorbate. Fe 2+ L1 and Fe 3+ L1 have very different proton relaxivities (0.1 mM –1 s –1 and 2.83 mM –1 s –1 , respectively, 60 MHz, 298 K), as well as 19 F relaxation times ( T 1 = 71–130 ms; T 2 = 60–117 ms and T 1 = 2.43 ms; T 2 = 1.81 ms, respectively, 400 MHz, 298 K), in accordance with the different paramagnetic relaxation enhancement capacity of the two iron redox states. Upon application of specific MRI pulse sequences adapted to the relaxation rate (RARE for Fe 2+ L1 and UTE for Fe 3+ L1 , combined with appropriate acquisition parameters), both redox forms are detected in 19 F MR phantom images with good sensitivity and signal-to-noise ratios linearly dependent on probe concentration. Fe 2+ L1 and Fe 3+ L1 can be readily visualized and unambiguously discriminated based on their 19 F relaxation times in living mice, following intramuscular injection. The possibility of monitoring the redox switch in 1 H MRI as well is an additional advantage of this bioresponsive probe.}, archive = {J_JACS}, author = {Zoltán Garda and Frédéric Szeremeta and Csilla Noémi Tóth and Szilvia Bunda and Carlo Pifferi and Rudy Clémençon and Sandra Même and Gyula Tircsó and Éva Tóth}, doi = {10.1021/jacs.5c03244}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18017--18024}, shortjournal = {J. Am. Chem. Soc.}, title = {Relaxation-based in vivo discrimination of oxidized and reduced states of a redox-switchable 19F MRI probe}, volume = {147}, year = {2025}, }
• (2025). Construction of atomic-scale compressive strain for oxime electrosynthesis. JACS, 147(21), 18003--18016. (www)

  @article{ , abstract = {Tuning the surface strain is a powerful strategy to enhance the catalytic activity of metal nanocatalysts, yet an atomically precise catalyst with intramolecular strain to unlock the atomic-level strain-structure–activity relationship is still highly desired. Herein, we report the synthesis, structural anatomy, and catalytic performance toward cyclohexanone oxime electrosynthesis of an atomically precise Ag 16 Cu 18 (C≡C-C 6 H 11 ) 24 (Ag 16 Cu 18 ) nanocluster, which has a Cu 6 ring in the center. The Cu–Cu distance in the Cu 6 ring is only 1.616 Å in a single crystal, the shortest Cu–Cu bond in Cu nanomaterials to date. Furthermore, once Ag 16 Cu 18 was loaded onto carbon paper, the ultrashort Cu–Cu bond elongated to ∼2.40 Å, still showing strong intramolecular compressive strain. Ag 16 Cu 18 exhibited excellent catalytic activity toward oxime electrosynthesis, manifested by a maximal Faradaic efficiency, yield, and yield rate of cyclohexanone oxime reaching 47.4%, 95.4%, and 2.66 mmol·h –1 ·cm –2 at –0.35 V, respectively. In-situ attenuated total reflection surface-enhanced infrared spectroscopy revealed that the Cu sites adjacent to the Ag atoms primarily reduce NO and stabilize it at the *NH 2 OH stage, while the Cu sites with compressive strain provide H* for NO reduction and adsorb cyclohexanone to react with *NH 2 OH, forming cyclohexanone oxime simultaneously. Density functional theory calculations confirmed the presence of compressive strain in the Cu 6 ring, which facilitates H* formation and cyclohexanone adsorption, hence significantly contributing to oxime generation. This study not only reports a case of atomically precise clusters with intramolecular compressive strain but also provides an atomic-level understanding for employing bimetallic nanocluster-based catalysts toward the electrosynthesis of valuable organic molecules.}, archive = {J_JACS}, author = {Lubing Qin and Yuping Chen and Ziyi Liu and Mengyao Chen and Qing Tang and Zhenghua Tang}, doi = {10.1021/jacs.5c03600}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {18003--18016}, shortjournal = {J. Am. Chem. Soc.}, title = {Construction of atomic-scale compressive strain for oxime electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Dual-channel phosphorescence ratiometry and phosphorescence lifetime imaging of mitochondria-specific methionine sulfoxide reductase activity. JACS, 147(21), 17994--18002. (www)

  @article{ , abstract = {Methionine sulfoxide reductases (Msrs) are essential for preserving redox homeostasis in the nervous system, with dysregulation implicated in Alzheimer’s disease (AD). Conventional fluorescence-based assays for Msrs activity sensing are hampered by background interference, limited sensitivity, and inadequate quantification. This work introduces a novel supramolecular probe exhibiting redox-responsive dual-channel room-temperature phosphorescence (RTP) in aqueous media on a microsecond time scale. Upon reduction by Msrs, the probe transitions from its oxidized to reduced state, manifested by a red-shifted phosphorescence emission and extended lifetime in the microsecond range, which enables precise quantification of mitochondria-targeted Msrs activity via phosphorescence ratiometry and phosphorescence lifetime imaging (PLIM). The probe’s utility is demonstrated in visualizing neuronal Msrs activity and distribution within the mouse brain, which reveals a marked downregulation of Msrs activity in an AD model, highlighting the probe’s potential in elucidating redox-related pathological mechanisms underlying neurodegenerative disorders.}, archive = {J_JACS}, author = {Xuewei Wang and Chen Chen and Yang Tian and Qi-Wei Zhang}, doi = {10.1021/jacs.5c03235}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17994--18002}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual-channel phosphorescence ratiometry and phosphorescence lifetime imaging of mitochondria-specific methionine sulfoxide reductase activity}, volume = {147}, year = {2025}, }
• (2025). Balancing chemical and supramolecular stability in OEGylated supramolecular polymers for systemic drug delivery. JACS, 147(21), 17985--17993. (www)

  @article{ , abstract = {The chemical conjugation of poly(ethylene glycol) (PEG) to therapeutic agents, known as PEGylation, is a well-established strategy for enhancing drug solubility, chemical stability, and pharmacokinetics. Here, we report on a class of supramolecular polymeric prodrugs by utilizing oligo(ethylene glycol) (OEG) to modify the hydrophobic anticancer drug camptothecin (CPT). These OEGylated prodrugs, despite their low molecular weight, spontaneously self-assemble into therapeutic supramolecular polymers (SPs) with a tubular morphology, featuring a dense OEG coating on the surface. By designing biodegradable linkers with varying chemical stabilities, we investigated how the release kinetics of CPT influence the in vitro and in vivo performance of these SPs. Our findings demonstrate that self-assembling prodrugs (SAPDs) with a self-immolative disulfanyl-ethyl carbonate (etcSS) linker exhibit a faster drug release rate than those with a reducible disulfanyl butyrate (buSS) linker, leading to higher potency and significantly improved antitumor efficacy. Notably, two stable tubular SPs, Tubustecan ( TT ) 1E and TT 7E , outperformed irinotecan─a clinically approved CPT prodrug─in a colon cancer model, achieving enhanced tumor growth inhibition and prolonged animal survival. These results highlight the potential of supramolecular OEGylation as an important strategy for engineering drug-based supramolecular polymers and underscore the critical role of chemical stability vs supramolecular stability in optimizing supramolecular prodrug design.}, archive = {J_JACS}, author = {Weijie Zhang and Feihu Wang and Han Wang and Tian Xu and Hao Su and Honggang Cui}, doi = {10.1021/jacs.5c03253}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17985--17993}, shortjournal = {J. Am. Chem. Soc.}, title = {Balancing chemical and supramolecular stability in OEGylated supramolecular polymers for systemic drug delivery}, volume = {147}, year = {2025}, }
• (2025). Single-crystal Metal–Organic and covalent organic framework hybrids enable efficient photoelectrochemical CO2 reduction to ethanol. JACS, 147(21), 17975--17984. (www)

  @article{ , abstract = {Multicarbon alcohols produced through photochemical and electrochemical CO 2 reduction reactions (CO 2 RR) are promising alternatives to fossil fuels; however, their selectivity and efficiency remain low due to the high energy barrier for C–C coupling and the competition from hydrocarbon production. Here, we present a strategy to enhance ethanol efficiency and selectivity via cooperative catalysis in porous structures for photoelectrochemical (PEC) CO 2 RR. Using a coordination-templated strategy, we synthesized single crystals of MOF-COF (MOCOF) hybrids with metalloporphyrins, with their structures determined by single-crystal 3D electron diffraction. The porous frameworks featuring adjacent confined metalloporphyrins efficiently capture and cooperatively activate CO 2 , achieving outstanding PEC CO 2 -to-ethanol conversion. Particularly, the Pt-MOCOF delivers a Faradaic efficiency (FE) of 83.5% at −1.0 V with 91.7% carbon selectivity, surpassing state-of-the-art COF or MOF catalysts and ranking it among the top-performing catalysts. The catalyst system displays remarkable stability, maintaining 95% of its activity after 100 h of continuous operation. Experiments and theoretical calculations revealed that the cooperative catalyst enriches and stabilizes intermediates in the channels, guiding the reaction pathway toward ethanol production.}, archive = {J_JACS}, author = {Wenqiang Zhang and Zhiye Zhong and Xiaofei Wei and Yuting Zhang and Weili Ma and Dan Liu and Xing Han and Jinqiao Dong and Wei Gong and Fangna Dai and Yan Liu and Yanhang Ma and Yong Cui}, doi = {10.1021/jacs.5c03122}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17975--17984}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-crystal Metal–Organic and covalent organic framework hybrids enable efficient photoelectrochemical CO2 reduction to ethanol}, volume = {147}, year = {2025}, }
• (2025). Chirality-promoted chemical ligation and reverse transcription of acyclic threoninol nucleic acid. JACS, 147(21), 17967--17974. (www)

  @article{ , abstract = {The building blocks of current life on Earth are chiral compounds, such as 2’-deoxy- D -ribose of DNA and L -amino acids with homochirality, which play an important role in various biological reactions. We investigated the effect of chirality on the template-directed chemical synthesis of nucleic acids as a model for primitive replication of genetic materials in the absence of enzymes. The efficiency of the template-directed chemical ligation of two acyclic nucleic acids, achiral serinol nucleic acid (SNA) and chiral acyclic l -threoninol nucleic acid ( L - a TNA), induced by N -cyanoimidazole and a divalent metal cation, was evaluated. The chemical ligation of SNA fragments on an SNA template was much slower than the ligation of L - a TNA fragments on an L - a TNA template. Examination of L - a TNA and SNA heteroligation and the effects of chimeric template strands revealed the crucial importance of L - a TNA chirality, which induces helical propagation and fixes the local conformation of the reactive phosphate group for effective chemical ligation. DNA and RNA templates also enhanced the ligation of SNA and L - a TNA fragments. “Reverse transcription” from template RNA to L - a TNA was also demonstrated. Our findings show that scaffold chirality is crucial for chemical replication and reverse transcription in XNA-based systems. Furthermore, the reverse transcription from RNA to L - a TNA will find applications in XNA-based in vitro selection, the creation of artificial life, and nanotechnologies.}, archive = {J_JACS}, author = {Hikari Okita and Keiji Murayama and Hiroyuki Asanuma}, doi = {10.1021/jacs.5c03128}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17967--17974}, shortjournal = {J. Am. Chem. Soc.}, title = {Chirality-promoted chemical ligation and reverse transcription of acyclic threoninol nucleic acid}, volume = {147}, year = {2025}, }
• (2025). “Two-in-one” DPP building blocks for ambipolar conjugated polymers in flexible transistors. JACS, 147(21), 17954--17966. (www)

  @article{ , abstract = {Advancements in conjugated donor–acceptor (D–A) polymers with superior semiconducting performance and reliability are pivotal to the evolution of flexible electronics. However, the development of electron-accepting building blocks has lagged far behind that of electron-donating ones, hindering the progression of ambipolar and n-type semiconductor polymers―especially ambipolar types―and thereby limiting the construction of logic circuits and p–n heterojunctions. In this study, we introduce a new electron-accepting building block, 2Ar’Ar2DPP , meticulously engineered for semiconducting polymers tailored to flexible electronics applications. Synthesized through the modification of conventional diketopyrrolopyrrole (DPP), 2Ar’Ar2DPP ─including 2TPh2DPP and 3T2DPP ─incorporates structural innovations, merging a single DPP unit with two aromatic groups into a configuration featuring two DPP units and three aromatic groups. This modification enhances the electron-accepting ability and modulates intra- and intermolecular D–A interactions. 2TPh2DPP and 3T2DPP were investigated to explore their structure–property relationships. Specifically, 3T2DPP demonstrates improved backbone planarity, extended π-conjugation, and more efficient intramolecular D–A interactions. These features result in significantly lower LUMO levels and narrower band gaps compared to those of conventionally utilized thiophene-flanked DPP and even its dimer. Moreover, the change in the molecular structural symmetry of 3T2DPP induces a relatively large dipole moment, thereby enhancing intermolecular interactions. Consequently, polymers derived from 2Ar’Ar2DPP exhibit ambipolar semiconducting performance in flexible organic field-effect transistors, achieving hole and electron mobilities of up to 6.0 and 2.1 cm 2 V –1 s –1 , respectively, with good bending resistance. These preliminary results indicate that 2Ar’Ar2DPP holds significant promise for the future design of conjugated materials for flexible electronics.}, archive = {J_JACS}, author = {Bolun Huang and Pinyu Chen and Xinqiang Hua and Dongsheng Qiu and Tianqiang Cui and Jiulong Zhang and Shuxian Zhang and Cheng-Shan Yuan and Feng He and Xiangfeng Shao and Hao-Li Zhang and Zitong Liu}, doi = {10.1021/jacs.5c03046}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17954--17966}, shortjournal = {J. Am. Chem. Soc.}, title = {“Two-in-one” DPP building blocks for ambipolar conjugated polymers in flexible transistors}, volume = {147}, year = {2025}, }
• (2025). Colossal negative area compressibility in the ferroelastic framework cu(tcm). JACS, 147(21), 17946--17953. (www)

  @article{ , abstract = {Copper(I) tricyanomethanide, Cu(tcm), is a flexible framework material that exhibits the strongest negative area compressibility (NAC) effect ever observed─a remarkable property with potential applications in pressure sensors, artificial muscles, and shock-absorbing devices. Under increasing pressure, Cu(tcm) undergoes two sequential phase transitions (tetragonal → orthorhombic → monoclinic): It has an initial tetragonal structure ( I 4 1 md ) at ambient conditions, but this structure only persists within a narrow pressure range; at 0.12(3) GPa, a pressure-induced ferroelastic phase transition occurs, transforming Cu(tcm) into a low-symmetry orthorhombic structure ( Fdd 2). The orthorhombic phase has a NAC of −108(14) TPa –1 in the b–c plane between 0.12(3) and 0.93(8) GPa. The NAC behavior is associated with framework hinge motion in a flexible framework with “wine-rack” topology. At 0.93(8) GPa, Cu(tcm) undergoes a second phase transition and transforms into a layered monoclinic structure ( Cc ) with topologically interpenetrating honeycomb networks. The monoclinic phase of Cu(tcm) exhibits a slight negative linear compressibility (NLC) of −1.1(1) TPa –1 along the a axis and a zero area compressibility of K ac = K a + K c = 0.0(4) TPa –1 in the a – c plane over the pressure range of 0.93–2.63 GPa. In contrast to the orthorhombic phase, its mechanism is understood as the pressure-driven dampening of layer “rippling,” which acts to increase the cross-sectional area of the layer at higher hydrostatic pressures. These findings have implications for understanding the underlying mechanism of NAC phenomenon in framework materials.}, archive = {J_JACS}, author = {Muzi Chen and Hanna L. B. Boström and Dominik Daisenberger and Nicholas P. Funnell and Christopher J. Ridley and Mohamed Mezouar and Claudia Weidenthaler and Andrew B. Cairns}, doi = {10.1021/jacs.5c02999}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17946--17953}, shortjournal = {J. Am. Chem. Soc.}, title = {Colossal negative area compressibility in the ferroelastic framework cu(tcm)}, volume = {147}, year = {2025}, }
• (2025). Anti-biopassivated reticular micromotors for bladder cancer therapy. JACS, 147(21), 17936--17945. (www)

  @article{ , abstract = {The limited lifespan of enzyme-powered micro/nanomotors (MNMs) hinders their biomedical applications due to the easy deactivation in tumor microenvironments. In this study, by taking advantage of hydrogen bond-rich metal-organic frameworks (MOFs), we design anti-biopassivated urease-powered MOF motors (Ur-MOFtors) with sustained motility for bladder cancer therapy. Such reticular Ur-MOFtors exhibited an exceptionally long locomotion lifespan exceeding 90 min in highly concentrated urea, which was an 18-fold enhancement compared with urease-adsorbed MOFs, resulting in excellent anti-biopassivation of MOFtors. The underlying molecular mechanism of persistent motion involves hydrogen bonding interaction between the MOF skeleton and the catalytic product, as identified by in situ infrared spectroscopy and density functional theory. Based on the preserved enzymatic activity comparable to native urease, the self-propulsion pathway of Ur-MOFtors is driven by ionic self-diffusiophoresis with the positive chemotactic motion toward urea. Benefiting from the persistent motion of Ur-MOFtors in physiological urea, a rapid bladder cancer therapy was achieved with few instillation sessions and short treatment cycles during intravesical administration. This hydrogen bond-rich framework presents a promising anti-biopassivated approach to overcoming the short lifespan and easy deactivation of enzymatic motors for advanced therapeutic robotics.}, archive = {J_JACS}, author = {Jun Sun and Ran Chu and Xiaoqian Wu and Qian Yu and Wencheng Xiao and Hang Ao and Yuru Wang and Taikang Wu and Huangxian Ju and Jie Wu and Jianping Lei}, doi = {10.1021/jacs.5c02949}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17936--17945}, shortjournal = {J. Am. Chem. Soc.}, title = {Anti-biopassivated reticular micromotors for bladder cancer therapy}, volume = {147}, year = {2025}, }
• (2025). Odd–Even effects of linear alkyl-based organic spacers for efficient charge transport in two-dimensional Dion–Jacobson tin perovskites. JACS, 147(21), 17926--17935. (www)

  @article{ , abstract = {Two-dimensional (2D) tin (Sn 2+ )-based perovskites have emerged as promising p-type semiconducting materials for (opto)electronic devices due to their favorable balance of electrical performance and structural stability. While previous studies on 2D perovskites predominantly investigated Ruddlesden–Popper (RP) perovskites with monoammonium spacers, Dion–Jacobson (DJ) perovskites with diammonium spacers have recently sparked attention in the research community. The strong hydrogen bonds at both ends of the diammonium spacer, connecting neighboring inorganic octahedral layers, promote structural stability and efficient charge transport in DJ perovskites. This study systematically investigates a series of 2D DJ Sn 2+ perovskites, [H 3 N-(CH 2 ) m -(NH) 3 SnI 4 ] ( m = 3–8), to explore the influence from the length of spacer chains on lattice structures, film crystallinity, and charge transport properties. Our findings reveal that DJ perovskites with even-numbered chains ( m = 4, 6, 8) exhibit well-ordered layered structures, whereas those with odd-numbered chains ( m = 3, 5, 7) disrupt the formation of 2D structures. Furthermore, we reveal that the precursor stoichiometry can govern the phase evolution along with the role of spacer parity. Among the even-numbered 2D DJ Sn 2+ perovskites, 1,4-butanediammonium tin iodide (BDASnI 4 , m = 4) exhibits optimal lattice formation and superior charge transport properties. Moreover, the introduction of an additional self-assembly monolayer ([2-(3,6-diiodo-9H-carbazol-9-yl)ethyl]phosphonic acid, I-2PACz) between the dielectric and channel layers further enhances the interface quality and reduces the trap density. The optimized transistor exhibits significantly reduced hysteresis and boosted field-effect mobility up to 1.45 cm 2 V –1 s –1 .}, archive = {J_JACS}, author = {Wantae Park and Mingoo Kwon and Dong Hyeon Lee and Soohwan Yoo and Wonryeol Yang and Ji-Sang Park and Ao Liu and Youjin Reo and Huihui Zhu and Yong-Young Noh}, doi = {10.1021/jacs.5c02818}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17926--17935}, shortjournal = {J. Am. Chem. Soc.}, title = {Odd–Even effects of linear alkyl-based organic spacers for efficient charge transport in two-dimensional Dion–Jacobson tin perovskites}, volume = {147}, year = {2025}, }
• (2025). Pyrazolone-modified photosensitizers for precise cell membrane rupture to enhance cancer immunotherapy. JACS, 147(21), 17915--17925. (www)

  @article{ , abstract = {The advancement of immunotherapy aims to achieve complete tumor eradication. However, several critical challenges hinder the efficacy of conventional phototherapy-mediated immune responses, including insufficient immunogenicity and the presence of an immunosuppressive tumor microenvironment. Nonprogrammed cell death, as a highly immunogenic pathway, offers a promising strategy to enhance immune responses. Herein, a membrane-anchored photodynamic immunotherapy agent, PNBSe, was developed by conjugating a selenium-substituted benzophenothiazine photosensitizer with a pyrazolone group, enabling membrane targeting via pyrazolone–protein interactions. Upon light irradiation, PNBSe induced rapid and intense cell necrosis characterized by significant cell membrane rupture, organelle swelling, and content leakage. Further investigations demonstrated that PNBSe activated inflammatory signaling pathways, induced immunogenic cell death, and reshaped the immunosuppressive tumor microenvironment, ultimately promoting systemic antitumor immune responses in vivo. This membrane-anchored small molecule provides a novel perspective for promoting cancer photodynamic immunotherapy.}, archive = {J_JACS}, author = {Yingchao Chen and Tao Xiong and Mingrui Gu and Mingle Li and Xiaoqiang Chen and Lei Wang and Jiangli Fan and Xiaojun Peng}, doi = {10.1021/jacs.5c02764}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17915--17925}, shortjournal = {J. Am. Chem. Soc.}, title = {Pyrazolone-modified photosensitizers for precise cell membrane rupture to enhance cancer immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Engineering recombinant chimeric proteins that deliver therapies to the brain. JACS, 147(21), 17902--17914. (www)

  @article{ , abstract = {To engineer biotherapeutics that can specifically target glioma, a highly lethal and recurrent type of brain tumor, we created a class of recombinant chimeric proteins containing multiple functional modules, such as a blood–brain barrier (BBB)-penetrating domain and an immune checkpoint blockade (ICB) agent, PD-L1 nanobody, through fusion protein engineering. The recombinant proteins that could prolong circulation time, cross the BBB, target brain tumors, penetrate cell membranes, and release PD-L1 nanobody were demonstrated. Further, by covalently linking doxorubicin (DOX), an inducer of immunogenic cell death (ICD), to the recombinant proteins, we endow the recombinant protein-drug conjugates (RPDCs) with a combining capacity to induce ICD and block immune checkpoints in cancer cells, achieving significant inhibition of glioma growth and prolonging the survival time of orthotopic glioma-bearing mice by enhancing intratumoral dendritic cell maturation and T-cell activation. In addition, the RPDC also improves the intratumoral immune-suppressive microenvironment, reduces excess extracellular matrix, and alleviates tumor hypoxia. Our work not only offers a new opportunity for glioma treatment but also establishes the groundwork for the design of multifunctional and multitargeting protein-based therapeutics.}, archive = {J_JACS}, author = {Xuejian Zhang and Cheng Li and Weizhi Chen and Xiqun Jiang}, doi = {10.1021/jacs.5c02731}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17902--17914}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering recombinant chimeric proteins that deliver therapies to the brain}, volume = {147}, year = {2025}, }
• (2025). A chiral CdS magic-size cluster with enantiomerically-biased crystallization. JACS, 147(21), 17890--17901. (www)

  @article{ , abstract = {Despite the symmetric, achiral atomic lattices typically found in binary semiconductor nanocrystals, we show that during their early formation stages, especially in the magic-size cluster (MSC) regime, chirality can be present in these metastable, transient species, which are capable of further self-assembling into high-level chiral superstructures. Through a cation exchange process operating at room temperature, a structurally symmetrical copper sulfide cluster has been successfully converted into a pair of enantiomeric cadmium sulfide MSCs, formulated as Cd 28 S 17 I 22 (PEt 3 ) 12 (abbreviated as (+)/(−)-[Cd 28 S 17 ]). The atomic structures of these two MSCs were established by single-crystal X-ray crystallography. It is revealed that the [Cd 28 S 17 ] MSCs feature an antisupertetrahedron configuration which has never been observed in reported CdS structures. Remarkably, rather than crystallizing into a racemic mixture, (+)/(−)-[Cd 28 S 17 ] MSCs naturally crystallize out in an enantiomerically biased manner, sufficiently rendering distinctly opposite chiroptical responses. This behavior reflects genuine circular dichroism activity, which can be directly attributed to the chiral atomic structure of this well-known quantum photonic nanomaterial.}, archive = {J_JACS}, author = {Cheng Xu and Zhenyi Zhang and Zheng Zhou and Haixiang Han}, doi = {10.1021/jacs.5c02549}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17890--17901}, shortjournal = {J. Am. Chem. Soc.}, title = {A chiral CdS magic-size cluster with enantiomerically-biased crystallization}, volume = {147}, year = {2025}, }
• (2025). Planar chiral metallopolymers for electrochemically mediated enantioselective separations. JACS, 147(21), 17880--17889. (www)

  @article{ , abstract = {The molecular design of redox-responsive interactions can unlock new pathways for enantioselective separations. While chiral redox molecules are powerful platforms for molecular recognition, their implementation in enantioselective separations has remained elusive due to limitations in enantioselectivity and a lack of robust redox electrosorbents. Here, we design a redox-responsive polymer with planar chirality that can achieve exceptional enantioselectivity for the separation of biomolecules. Planar chirality is generated through the insertion of a substituent onto the cyclopentadienyl ring of an oxazoline-conjugated ferrocene with the stereochemical synthesis route guided by the point chirality at the oxazoline moiety. These planar chiral ferrocenes demonstrated significantly stronger enantioselective interactions than the equivalent ferrocenes with only point chirality. Electronic structure calculations revealed the key role of planar chirality, where the inserted functional groups can either coordinatively or antagonistically contribute to complexation, resulting in enhanced enantioselective interactions. Planar chiral metallopolymers were synthesized and evaluated for electrochemical enantioselective adsorption of N -Boc–proline, with over 99% enantiomeric excess achievable within seven theoretical stages in a multistage cascade. Planar chirality combined with redox electrochemistry offers a promising path for electrochemically mediated enantioselective separations.}, archive = {J_JACS}, author = {Jemin Jeon and Yuri Giovane Kappenberg and Ankit Kumar Gautam and Ching-Yu Chen and Johannes Elbert and Alexander V. Mironenko and Fabio Zazyki Galetto and Xiao Su}, doi = {10.1021/jacs.5c01571}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17880--17889}, shortjournal = {J. Am. Chem. Soc.}, title = {Planar chiral metallopolymers for electrochemically mediated enantioselective separations}, volume = {147}, year = {2025}, }
• (2025). Light-induced, lysine-targeting irreversible covalent inhibition of the human oxygen sensing hydroxylase factor inhibiting HIF (FIH). JACS, 147(21), 17871--17879. (www)

  @article{ , abstract = {Factor inhibiting hypoxia-inducible factor (FIH) is a JmjC domain 2-oxoglutarate (2OG) and Fe(II)-dependent oxygenase that catalyzes protein hydroxylations, including of specific asparagines in the C -terminal transcriptional activation domains of hypoxia-inducible factor alpha (HIF-α) isoforms. FIH is of medicinal interest due to its ability to alter metabolism and modulate the course of the HIF-mediated hypoxic response. We report the development of a light-induced, lysine (Lys106)-targeting irreversible covalent inhibitor of FIH. The approach is complementary to optogenetic methods for regulation of transcription. The covalently reacting inhibitor NBA-ZG-2291 was the result of structure-guided modification of the reported active site binding FIH inhibitor ZG-2291 with an appropriately positioned o -nitrobenzyl alcohol ( o -NBA) group. The results demonstrate that NBA-ZG-2291 forms a stable covalent bond in a light-dependent process with Lys106 of FIH, inactivating its hydroxylation activity and resulting in sustained upregulation of FIH-dependent HIF target genes. The light-controlled inhibitors targeting a lysine residue enable light and spatiotemporal control of FIH activity in a manner useful for dissecting the context-dependent physiological roles of FIH.}, archive = {J_JACS}, author = {Yue Wu and Zhihong Li and Samanpreet Kaur and Zewei Zhang and Jie Yue and Anthony Tumber and Haoshu Zhang and Zhe Song and Peiyao Yang and Ying Dong and Fulai Yang and Xiang Li and Christopher J. Schofield and Xiaojin Zhang}, doi = {10.1021/jacs.5c01935}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17871--17879}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-induced, lysine-targeting irreversible covalent inhibition of the human oxygen sensing hydroxylase factor inhibiting HIF (FIH)}, volume = {147}, year = {2025}, }
• (2025). Sulfite-based electrolyte chemistry with Ion–Dipole interactions and robust interphase achieves wide-temperature sodium-ion batteries. JACS, 147(21), 17860--17870. (www)

  @article{ , abstract = {Currently, ether- and carbonate-based electrolytes have been extensively studied for applications in harsh conditions; however, it is difficult to develop a suitable electrolyte system that is compatible with both high and low temperatures. Herein, for the first time, a cyclic sulfite-based electrolyte is formulated to successfully achieve the wide-temperature operation of sodium-ion batteries (SIBs) from −60 to 60 °C. By precisely modulating ion–dipole interactions, the dominant ion coordination states are screened directionally to accelerate the desolvation process and simultaneously maintain sufficient electrostatic constraints, laying the foundation for high- and low-temperature compatibility. And the coordinated anions and additives synergistically decompose to enable inorganic-rich interphases with robustness and favorable ion diffusion, extending the voltage window and temperature range. As a result, Na 3 V 2 (PO 4 ) 2 O 2 F demonstrates 58 mA h g –1 at −50 °C while stably cycling at 60 °C for 300 cycles with 80% capacity retention. Additionally, Na 3 V 2 (PO 4 ) 3 and NaFe 1/3 Ni 1/3 Mn 1/3 O 2 cathodes also exhibit discharge specific capacities of 50 and 65 mA h g –1 at −60 °C. Eventually, the Ah-class pouch cell displays 0.64 A h with 56% capacity retention at −40 °C. In short, the introduced electrolyte formulation enhances the wide temperature operation of SIBs, shedding light on the development of all-weather systems.}, archive = {J_JACS}, author = {Hao-Jie Liang and Wen-Yu Qian and Han-Hao Liu and Xiao-Tong Wang and Zhen-Yi Gu and Feilong Dong and Yating Deng and Yuan-Zheng Tang and Jingping Zhang and Jian Zhao and Xing-Long Wu}, doi = {10.1021/jacs.5c01864}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17860--17870}, shortjournal = {J. Am. Chem. Soc.}, title = {Sulfite-based electrolyte chemistry with Ion–Dipole interactions and robust interphase achieves wide-temperature sodium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Adsorption configuration and h* flux modulation enable electrocatalytic semihydrogenation of alkynes with group tolerance in a palladium membrane reactor. JACS, 147(21), 17849--17859. (www)

  @article{ , abstract = {Ineffective control of alkene adsorption on a palladium membrane (PM) and the flux of active hydrogen (H*) diffusing from the aqueous side to the organic side through the PM cause low selectivity and Faradaic efficiency (FE) of alkynes to alkenes in a PM reactor. Here, a PM with a phenylthiolate-modified palladium sulfide thin layer coupled with pulsed electrolysis is reported to enable alkyne-to-alkene electrosynthesis with up to 98% selectivity and 80% FE. Electrochemical in situ Raman spectra reveal weak alkene adsorption and specific σ-alkynyl adsorption rather than flat adsorption of alkynes on the modified PM, accounting for the high alkene selectivity and functional group tolerance. Pulsed electrolysis causes reduced H* generation and restricted H* diffusion to the organic side, which better balances the generation and utilization of H*, suppresses H 2 evolution, and improves the FE. The high alkene selectivity and FE in a wide potential and current range, over 50 examples of (deuterated) alkenes with functional group tolerance and deuterated drug applications ( d 2 - naftifine , d 2 - cinarizine , d 2 - bucinnazine , d 2 -artemisinin derivative , and d 2 -estradiol derivative ), and scalable electrosynthesis of deuterated styrene for deuterated polystyrene with improved thermal stability demonstrate potential utility.}, archive = {J_JACS}, author = {Huizhi Li and Qian Li and Shuoshuo Guo and Ying Gao and Bin Zhang and Cuibo Liu}, doi = {10.1021/jacs.5c01911}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17849--17859}, shortjournal = {J. Am. Chem. Soc.}, title = {Adsorption configuration and h* flux modulation enable electrocatalytic semihydrogenation of alkynes with group tolerance in a palladium membrane reactor}, volume = {147}, year = {2025}, }
• (2025). Simple and scalable introduction of single-atom mn on RuO2 electrocatalysts for oxygen evolution reaction with long-term activity and stability. JACS, 147(21), 17839--17848. (www)

  @article{ , abstract = {Electrochemical oxygen evolution reaction (OER) is the bottleneck for realizing renewable powered green hydrogen production through water splitting due to the challenges of electrode stability under harsh oxidative environments and electrolytes with extreme acidity and basicity. Here, we introduce a single-atom manganese-incorporated ruthenium oxide electrocatalyst via a facile impregnation approach for catalyzing the OER across a wide pH range, while solving the stability issues of RuO 2 . The modified catalyst maintains stability for over 1000 h, delivering a current density of 10 mA cm –2 at a 213 mV overpotential in acid (pH 0), 570 mV in potassium bicarbonate (pH 8.8), and 293 mV in alkaline media (pH 14), demonstrating exceptional durability under various conditions. When used as an anode for realistic water-splitting systems, Mn-modified RuO 2 performs at 1000 mA cm –2 with a voltage of 1.69 V (Nafion 212 membrane) for proton-exchange membrane water electrolysis, and 1.84 V (UTP 220 diaphragm) for alkaline water electrolysis, exhibiting low degradation and verifying its substantial potential for practical applications.}, archive = {J_JACS}, author = {Zhong-Hua Xue and Javeed Mahmood and Yuxuan Shang and Guanxing Li and Seok-Jin Kim and Yu Han and Cafer T. Yavuz}, doi = {10.1021/jacs.5c01886}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17839--17848}, shortjournal = {J. Am. Chem. Soc.}, title = {Simple and scalable introduction of single-atom mn on RuO2 electrocatalysts for oxygen evolution reaction with long-term activity and stability}, volume = {147}, year = {2025}, }
• (2025). Observation of water-induced synergistic acidic site from NMR-invisible al in zeolite via solid-state NMR spectroscopy. JACS, 147(21), 17829--17838. (www)

  @article{ , abstract = {Zeolites are highly sensitive to water, which significantly affects their acidity─a key factor in catalytic reactions. This study investigates the dynamic interactions between water and often overlooked active sites, specifically the “NMR-invisible” aluminum species (tricoordinated framework Al─FAL and cationic extra-framework Al─EFAL) in ultrastable Y (USY) zeolite under ambient conditions. Using solid-state NMR spectroscopy combined with theoretical calculations, we demonstrate that water readily undergoes dissociative adsorption on these “NMR-invisible” Al sites. This process transforms both FAL and EFAL into “NMR-visible” Al species. The formation of new Brønsted acid sites on tetra-, penta-, and hexa-coordinated FAL results in an increase of over 60% in the BAS concentration in the USY zeolite. The hydrolysis of EFAL cations leads to the formation of Brønsted/Lewis acid synergistic sites, significantly improving the catalytic activity of USY zeolite. This enhancement is evident in the improved conversion of diethyl ether to ethene in the presence of moisture.}, archive = {J_JACS}, author = {Xingxing Wang and Qiang Wang and Chao Wang and Yueying Chu and Min Hu and Feng Deng and Jihong Yu and Jun Xu}, doi = {10.1021/jacs.5c01756}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17829--17838}, shortjournal = {J. Am. Chem. Soc.}, title = {Observation of water-induced synergistic acidic site from NMR-invisible al in zeolite via solid-state NMR spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Ubiquitin azapeptide esters as next-generation activity-based probes for cysteine enzymes in the ubiquitin signal pathway. JACS, 147(21), 17817--17828. (www)

  @article{ , abstract = {Ubiquitination is a pivotal cellular process that controls protein homeostasis and regulates numerous biological functions. Its pathway operates through a cascade of enzyme reactions involving ubiquitin-activating (E1), ubiquitin-conjugating (E2), and ubiquitin-ligating (E3) enzymes and deubiquitinases (DUBs), many of which are cysteine enzymes. Activity-based ubiquitin probes were previously developed for profiling these enzymes. However, most conventional probes do not mimic natural enzyme–substrate interactions and involve chemical mechanisms different from enzyme catalysis. Their uses potentially affect the comprehensiveness of enzyme profiling results. The current study introduces a novel class of activity-based ubiquitin probes, ubiquitin azapeptide esters, designed to overcome these limitations. These probes incorporate an azaglycine ester at the ubiquitin C -terminus. They structurally mimic a ubiquitinated protein substrate and react with a cysteine enzyme via a mechanism like the enzyme catalysis. It was demonstrated that ubiquitin azapeptide esters are reactive toward a large variety of DUBs and several tested E1, E2, and E3 enzymes as well. Compared to a conventional probe, ubiquitin propargylamine, ubiquitin azapeptide esters generally provide superior labeling and profiling of active cysteine enzymes in the ubiquitination/deubiquitination cascade in both HEK293T cells and mouse tissue lysates. Activity-based protein profiling using these probes in mouse tissue lysates also revealed distinct patterns of labeled enzymes, confirming their potential in understanding the unique roles of these enzymes in different tissues.}, archive = {J_JACS}, author = {Saibal Chanda and Sandeep Atla and Xinlei Sheng and Satyanarayana Nyalata and Yugendar R. Alugubelli and Demonta D. Coleman and Wen Jiang and Rosana Lopes and Shaodong Guo and A. Joshua Wand and Yingming Zhao and Wenshe Ray Liu}, doi = {10.1021/jacs.5c01732}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17817--17828}, shortjournal = {J. Am. Chem. Soc.}, title = {Ubiquitin azapeptide esters as next-generation activity-based probes for cysteine enzymes in the ubiquitin signal pathway}, volume = {147}, year = {2025}, }
• (2025). Photobiocatalytic enantioselective benzylic C(sp3)–H acylation enabled by thiamine-dependent enzymes via intermolecular hydrogen atom transfer. JACS, 147(21), 17804--17816. (www)

  @article{ , abstract = {Hydrogen atom transfer (HAT) constitutes a powerful mechanism exploited in biology and chemistry to functionalize ubiquitous C(sp 3 )–H bonds in organic molecules. Despite its synthetic potential, achieving stereocontrol in chemical HAT-mediated C–H functionalization transformations remains challenging. By merging the radical reactivity of thiamine (ThDP)-dependent enzymes with chemical hydrogen atom transfer, we report here a photobiocatalytic strategy for the enantioselective C(sp 3 )–H acylation of an organic substrate, a transformation not found in nature nor currently attainable by chemical means. This method enables the direct functionalization of benzylic C(sp 3 )–H sites in a broad range of substrates to furnish valuable enantioenriched ketone motifs with good to high enantioselectivity (up to 96% ee). Mechanistic and spectroscopic studies support the involvement of radical species derived from the Breslow intermediate and C–H substrate, highlight the critical role of the photocatalyst and hydrogen atom abstraction reagents for productive catalysis, and reveal a specific enzyme/photocatalyst interaction favoring single electron transfer during catalysis. Further insights into how the enantioselectivity of the C–C bond-forming reaction is controlled by the enzyme and influenced by active site mutations were gained via molecular modeling. This study illustrates the productive integration of ThDP-mediated biocatalysis with chemical HAT, expanding the range of asymmetric C(sp 3 )–H functionalization transformations that can be accessed through biocatalysis.}, archive = {J_JACS}, author = {Yen-Chu Lu and Ronald D. Adukure and Satyajit Roy and Derek L. Chien and Matthew J. McGill and Sarthi Polara and G. Andrés Cisneros and Karl A. Scheidt and Rudi Fasan}, doi = {10.1021/jacs.5c01642}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17804--17816}, shortjournal = {J. Am. Chem. Soc.}, title = {Photobiocatalytic enantioselective benzylic C(sp3)–H acylation enabled by thiamine-dependent enzymes via intermolecular hydrogen atom transfer}, volume = {147}, year = {2025}, }
• (2025). A writhed möbius nanobelt derived from [7]Helicene. JACS, 147(21), 17795--17803. (www)

  @article{ , abstract = {A novel writhed Möbius nanobelt was synthesized using a helical building block derived from [7]helicene and a C-shaped building block derived from pyrene. These two building blocks were connected through nucleophilic aromatic substitution to form an oxanorbornene-containing macrocycle, which was then converted to the nanobelt by reductive aromatization and subsequent oxidation. The structure of the Möbius nanobelt was confirmed with X-ray crystallography. Both the nanobelt and its macrocyclic precursor exhibit C 2 symmetry, but this symmetry is only reflected by the 1 H NMR signals for the tetra(4- t -butylphenyl)dinaphthopyrene moiety in the nanobelt, not in its precursor. This difference is attributed to the distinct arrangements of the pendent 4- t -butylphenyl groups, caused by the crowdedness and restricted rotation of the C–C single bonds in the nanobelt. Theoretical calculations suggest that the nanobelt does not exhibit global ring currents but has localized aromatic ring currents. Additionally, when an enantiopure form of the [7]helicene derivative was used, the nanobelt was obtained in an enantiopure form, showing an absorption dissymmetry factor of 4 × 10 –3 .}, archive = {J_JACS}, author = {Liping Ye and Chenyu Hu and Daiyue Yang and Li Zhang and Xiao Chen and Lulin Qiao and Zhifeng Huang and Jun Yang and Qian Miao}, doi = {10.1021/jacs.5c01323}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17795--17803}, shortjournal = {J. Am. Chem. Soc.}, title = {A writhed möbius nanobelt derived from [7]Helicene}, volume = {147}, year = {2025}, }
• (2025). Single-particle correlated imaging reveals multiple chromophores in carbon dot fluorescence. JACS, 147(21), 17784--17794. (www)

  @article{ , abstract = {Carbon dots are remarkable nanomaterials with many applications, but the sources of their emission are still uncertain. Carbon dots exhibit complex behaviors such as excitation-dependent emission due to their heterogeneous composition and structure. Most studies have been carried out on the ensemble level, where sample heterogeneity remains hidden. Understanding the complex emission of carbon dots requires single-particle measurements. Here, we determined that for red-emitting carbon dots made from two bottom-up precursors, there is a significant population of dots with more than one emitting moiety. Polarization-resolved, single-dot emission microscopy revealed subpopulations of carbon dots based on their emission intensity and polarization. For the multichromophoric carbon dots, we found an average of about four emitters. Single-particle spectroscopy, acquired in parallel to the emission trajectories, and molecular dynamics simulations furthermore established that the countable chromophores in the carbon dots are chemically similar, considering the rather narrow room-temperature emission line width and the absence of significant spectral diffusion.}, archive = {J_JACS}, author = {Eric Gomez and Arshad Mehmood and Zhengyi Bian and Stephen A. Lee and Lawrence J. Tauzin and Subhasis Adhikari and Martin Gruebele and Benjamin G. Levine and Stephan Link}, doi = {10.1021/jacs.5c01367}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17784--17794}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-particle correlated imaging reveals multiple chromophores in carbon dot fluorescence}, volume = {147}, year = {2025}, }
• (2025). Regulating reversible untwisting and twisting motions in helical dynamic molecular crystals. JACS, 147(21), 17772--17783. (www)

  @article{ , abstract = {Dynamic molecular crystals with a desirable morphology and controllable responses to external stimuli are highly desired but remain challenging. Here, we present a new photoactive molecular crystal ( MCA ) featuring a naphthalene backbone linked with a vinyl structure and an asymmetric tail. It can undergo reversible head-to-tail [2 + 2] photodimerization under visible light illumination and heating. Helicoidally twisted crystalline fibers can be easily prepared by drop-casting an MCA ethanol solution onto a glass surface. The thread length and fiber width can be regulated by changing the solvent evaporation temperature. An MCA fiber untwists upon light irradiation and twists back under mild heating due to the dissociation of the metastable photodimer ( d - MCA ), enabling a highly reverse transformation. Crystallinity and overall helical morphology can be reserved well during the untwisting and twisting cycles, allowing multiple repetitions of the dynamic motions. Under interval light excitation and continuous heating, an MCA fiber can perform cyclical untwisting-twisting motions over 200 times for 5 h. The amount of photodimer significantly affects the photoresponse, resulting in fully reversible cycles, partial reverse twisting, or complete untwisting at different dimer fractions. We found that about 10% of d - MCA is enough to drive the circular movements. Higher photoproduct conversion makes the fibers prone to fatigue and lose the cyclic responses. Our results provide an excellent example for fabricating new dynamic organic crystals for soft robotics and photoactuators based on spiral twisting movements.}, archive = {J_JACS}, author = {Xiao-Dong Qiu and Lin Chen and Jia-Wang Hou and Hui-Yao Lin and Tian-Yi Xu and Fei Tong and He Tian and Da-Hui Qu}, doi = {10.1021/jacs.5c01145}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17772--17783}, shortjournal = {J. Am. Chem. Soc.}, title = {Regulating reversible untwisting and twisting motions in helical dynamic molecular crystals}, volume = {147}, year = {2025}, }
• (2025). Noncatalyzed intramolecular B–N and B–O cross-coupling of “Inert” carboranes lead to the formation of an unusual oxoborane, via reversible cluster C–B bond scission. JACS, 147(21), 17764--17771. (www)

  @article{ , abstract = {Polyhalogenated closo -12-vertex carborane anions are thought to be inert species incapable of participating in direct B– X substitution reactions. Here, we show that this is not true and that such species can be easily coaxed into intramolecular cross-coupling cyclizations without the need for a catalyst. When cage C-tethered O and N-heteroallylic anions are generated, a variety of cyclized products can be formed in high yield under mild conditions. Additionally, we show that even C-tethered neutral nucleophiles, such as the pyridine moiety, undergo facile B– X substitution chemistry and these reactions are not dependent on the countercation. Serendipitously, we also found that when these cyclizations are attempted with acetamide derivatives, an unprecedented cluster C–B bond scission reaction occurs, producing an unprecedented oxoborane stabilized by multicentered bonding. Amazingly this molecule can be protonated, leading to reformation of the C–B bond and cluster reorganization, and this process is reversible.}, archive = {J_JACS}, author = {Sergio O. Lovera and Aaron Gregory and Katherine Espinoza Morelos and Phillip Farias and Veronica Carta and Charles B. Musgrave, III and Vincent Lavallo}, doi = {10.1021/jacs.5c01106}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17764--17771}, shortjournal = {J. Am. Chem. Soc.}, title = {Noncatalyzed intramolecular B–N and B–O cross-coupling of “Inert” carboranes lead to the formation of an unusual oxoborane, via reversible cluster C–B bond scission}, volume = {147}, year = {2025}, }
• (2025). Homochiral versus racemic 2D covalent organic frameworks. JACS, 147(21), 17750--17763. (www)

  @article{ , abstract = {The synthesis of homochiral two-dimensional covalent organic frameworks (2D COFs) from chiral π-conjugated building blocks is challenging, as chiral units often lead to misaligned stacking interactions. In this work, we introduce helical chirality into 2D COFs using configurationally stable enantiopure and racemic [5]helicenes as linkers in the backbone of 2D [5]HeliCOFs as powders and films. Through condensation with 1,3,5-triformylbenzene (TFB) or 1,3,5-triformylphloroglucinol (TFP), our approach enables the efficient formation of a set of homochiral and racemic 2D [5]HeliCOFs . The resulting carbon-based crystalline and porous frameworks exhibit distinct structural features and different properties between homochiral and racemic counterparts. Propagation of helical chirality into the backbone of the crystalline frameworks leads to the observation of advanced chiroptical properties in the far-red visible spectrum, along with a less compact structure compared with the racemic frameworks. Homogeneous thin films of [5]HeliCOFs disclosed photoluminescent properties arising from the controlled growth of highly ordered π-conjugated lattices. The present study offers insight into general chiral framework formation and extends the Liebisch–Wallach rule to 2D COFs.}, archive = {J_JACS}, author = {José del Refugio Monroy and Tejas Deshpande and Joël Schlecht and Clara Douglas and Robbie Stirling and Niklas Grabicki and Glen J. Smales and Zdravko Kochovski and Filippo Giovanni Fabozzi and Stefan Hecht and Sascha Feldmann and Oliver Dumele}, doi = {10.1021/jacs.5c01004}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17750--17763}, shortjournal = {J. Am. Chem. Soc.}, title = {Homochiral versus racemic 2D covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Quantum coulombic interactions mediate free radical control in radical SAM Viperin/RSAD2. JACS, 147(21), 17739--17749. (www)

  @article{ , abstract = {There are thousands of radical S -adenosylmethionine (rSAM) enzymes capable of catalyzing over 80 distinct reactions, yet their use in biotechnological applications is limited, primarily due to a lack of understanding of how these enzymes control highly reactive radical intermediates. Here, we show that little-known quantum Coulombic interactions are, in part, responsible for free radical control in rSAM enzyme Viperin/RSAD2, one of the few radical SAM enzymes expressed in humans. Using molecular dynamics and high-level extensive multistate broken-symmetry quantum mechanical/molecular mechanics calculations (QM/MM), we elucidated both the mechanism and radical control in catalysis, identifying a key step characterized by the formation of an unusual metastable deprotonated ribose radical intermediate. This intermediate is thermodynamically stabilized by spin-charge exchange–correlation interactions─a quantum Coulombic effect. The magnitude of this stabilization is such that the radical displays acidity two to six p K a units lower than that of closed-shell ribose. Given the omnipresence of charges in biological systems, these interactions potentially represent a universal mechanism for stabilizing and controlling highly reactive radical intermediates across radical enzymes, opening new avenues for enzymatic engineering and biotechnological applications.}, archive = {J_JACS}, author = {M. Hossein Khalilian and Gino A. DiLabio}, doi = {10.1021/jacs.5c00572}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17739--17749}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantum coulombic interactions mediate free radical control in radical SAM Viperin/RSAD2}, volume = {147}, year = {2025}, }
• (2025). Complex iridate solid solutions for catalyzing oxygen evolution reaction: Comparison of elemental leaching and stability numbers. JACS, 147(21), 17725--17738. (www)

  @article{ , abstract = {As predicted by the Hume-Rothery rules, forming solid solutions of rutile IrO 2 with other metal oxides that have different crystal structures is thermodynamically challenging. Consequently, achieving high solubility of foreign elements in Ir-based solid-solution oxides has been significantly limited. We demonstrate that hexagonal-perovskite BaIrO 3 can serve as a flexible matrix oxide capable of incorporating a wide spectrum of (post)transition-metal cations with different electronic structures, ranging from d 0 to d 10 configurations. Among 12 cation solutes, Ta 5+ , Nb 5+ , and Zr 4+ are found to be stable without substantial leaching during the oxygen evolution reaction (OER) under acidic condition. Acceptor-type trivalent cations, including Sc 3+ , In 3+ , and Fe 3+ , are identified to leach out gradually from the particle surface while enhancing the OER catalytic activity. Both X-ray absorption spectroscopy and ab initio molecular dynamics simulations consistently show that the robust face-sharing [IrO 6 ] octahedral framework of the solid solutions remains unperturbed unless electrochemical leaching rapidly occurs. As a result, notably high S -numbers, on the order of 10 6 , are achievable at pH = 1. Although our work focuses on single-element incorporation, it is suggested that the solid-solution methodology is an effective strategy for developing stable, long-lasting OER catalysts with further reduced Ir usage for acidic water oxidation.}, archive = {J_JACS}, author = {Ki Hyun Park and Younghwan Lim and Hyung Bin Bae and Jun Seop Kim and Sangmyeong Lee and Dongho Kim and Sung-Yoon Chung}, doi = {10.1021/jacs.5c00380}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17725--17738}, shortjournal = {J. Am. Chem. Soc.}, title = {Complex iridate solid solutions for catalyzing oxygen evolution reaction: Comparison of elemental leaching and stability numbers}, volume = {147}, year = {2025}, }
• (2025). Supramolecular copolymerization of glycopeptide amphiphiles and amyloid peptides improves neuron survival. JACS, 147(21), 17710--17724. (www)

  @article{ , abstract = {Neurodegenerative diseases such as Alzheimer’s disease and amyotrophic lateral sclerosis are characterized by progressive neuronal loss and the accumulation of misfolded proteins including amyloid proteins. Current therapeutic options include the use of antibodies for these proteins, but novel chemical strategies need to be developed. The disaccharide trehalose has been widely reported to prevent misfolding and aggregation of proteins, and we therefore investigated the conjugation of this moiety to biocompatible peptide amphiphiles (TPAs) known to undergo supramolecular polymerization. Using X-ray scattering, circular dichroism, and infrared spectroscopy, we found that trehalose conjugation destabilized the internal β-sheet structures within the TPA supramolecular polymers as evidenced by a lower thermal transition. Thioflavin T fluorescence showed that these metastable TPA nanofibers suppressed A42 aggregation. Interestingly, we found that the suppression involved supramolecular copolymerization of TPA polymers with Aβ42, which effectively trapped the peptides within the filamentous structures. In vitro assays with human induced pluripotent stem cell-derived neurons demonstrated that these TPAs significantly improved neuron survival compared to other conditions. Our study highlights the potential of properly tuned supramolecular polymerizations of monomers to safely remove amyloidogenic proteins in neurodegeneration.}, archive = {J_JACS}, author = {Zijun Gao and Ruomeng Qiu and Dhwanit R. Dave and Palash Chandravanshi and Gisele P. Soares and Cara S. Smith and J. Alberto Ortega and Liam C. Palmer and Zaida Álvarez and Samuel I. Stupp}, doi = {10.1021/jacs.5c00105}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17710--17724}, shortjournal = {J. Am. Chem. Soc.}, title = {Supramolecular copolymerization of glycopeptide amphiphiles and amyloid peptides improves neuron survival}, volume = {147}, year = {2025}, }
• (2025). Real-time visualization of an elusive, strong reducing agent during tris(2,2'-bipyridyl)ruthenium(II) electro-oxidation in water. JACS, 147(21), 17701--17709. (www)

  @article{ , abstract = {Recently, liquid|liquid and liquid|gas interfaces have been implicated in driving unexpected chemistries, including dramatic rate enhancement and spontaneous redox reactions. Given such studies, new methods are necessary to observe and implicate such reactive species. Tris(2,2'-bipyridyl)ruthenium(II) ([Ru(bpy) 3 ] 2+ ) is a common luminophore for photoluminescence and electrochemiluminescence (ECL) studies. In this work, we demonstrate that the electro-oxidation of [Ru(bpy) 3 ] 2+ in water produces light without the addition of sacrificial coreactants. We have studied this by confining [Ru(bpy) 3 ] 2+ to an aqueous droplet adhered to both a tin-doped indium oxide electrode and, separately, a glassy carbon inlaid disc macroelectrode ( d = 3 mm). We also generalized the method to the observation of light at larger electrodes. The light intensity is higher in the absence of O 2 , diminishes when adding H 2 O 2 , and disappears in the presence of a well-behaved, one-electron oxidant (hexaammineruthenium(III)). Our results indicate that a powerful reducing agent is present during the electro-oxidation of [Ru(bpy) 3 ] 2+ . This reducing agent is at least energetic enough to create the excited state, [Ru(bpy) 3 ] 2+* , giving a minimum energy of ∼2 eV. Chemiluminescence persists as [Ru(bpy) 3 ] 3+ diffuses into solution, indicating that the strong reducing agent may exist natively in water and at low abundance. These observations have significant fundamental ramifications because they elucidate a new pathway for the [Ru(bpy) 3 ] 2+ ECL and allow real-time visualization of highly reactive species.}, archive = {J_JACS}, author = {Megan L. Hill and Brady R. Layman and Jeffrey E. Dick}, doi = {10.1021/jacs.4c18616}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17701--17709}, shortjournal = {J. Am. Chem. Soc.}, title = {Real-time visualization of an elusive, strong reducing agent during tris(2,2'-bipyridyl)ruthenium(II) electro-oxidation in water}, volume = {147}, year = {2025}, }
• (2025). Triple labeling resolves a GPCR intermediate state by using three-color single molecule FRET. JACS, 147(21), 17689--17700. (www)

  @article{ , abstract = {The correlation of individual conformational changes in dynamic protein complexes remains challenging as most structural methods rely on averaged information over a large number of molecules. Single molecule FRET is a powerful tool for monitoring such conformational changes. When performed using three distinct probes, it enables the correlation of domain movements by providing up to three simultaneous distance measurements with high temporal resolution. Nevertheless, a major challenge lies in the site-specific attachment of three probes to unique positions within the target protein. Here, we propose an orthogonal triple-labeling strategy that is not compromised by native, reactive amino acid functionalities. It combines genetic code expansion and bioorthogonal labeling of two different noncanonical amino acids with an enzymatic self-labeling SNAP tag. We demonstrate its application by establishment of a 3-color sensor on the human metabotropic glutamate receptor 2, a dimeric, multidomain G protein-coupled neuroreceptor, and describe a previously unknown conformational intermediate state using 3-color single molecule FRET.}, archive = {J_JACS}, author = {Léo Bonhomme and Ecenaz Bilgen and Caroline Clerté and Jean-Philippe Pin and Philippe Rondard and Emmanuel Margeat and Don C. Lamb and Robert B. Quast}, doi = {10.1021/jacs.4c18364}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17689--17700}, shortjournal = {J. Am. Chem. Soc.}, title = {Triple labeling resolves a GPCR intermediate state by using three-color single molecule FRET}, volume = {147}, year = {2025}, }
• (2025). Precise de novo design principle of antifreeze peptides. JACS, 147(21), 17682--17688. (www)

  @article{ , abstract = {De novo design of antifreeze peptides (AFPTs) represents a formidable challenge due to the unclarified active structure of AFPTs. Here, we describe a “Site to Distance” principle for de novo design of AFPTs, in terms of understanding their structure–activity relationships. The first step is to point E, identified as the most potent ice-binding site (IBS) possessing at least 4-fold binding energy than natural IBSs, into the candidate backbones. The second step, based on the IBS (E), is to judiciously adjust the distances of sites to match the favorable number of the ice crystal lattice to achieve the strongest ice-binding, relying on a newly established low-temperature AFPT structure prediction platform. The resultant AFPTs show a substantial reduction in single ice crystal growth rates, much superior to >100 natural or designed AFPTs, including all that have been reported. Cryopreservation of therapeutic cells further confirms the accuracy of this design principle.}, archive = {J_JACS}, author = {Xiangyu Zhang and Jing Yang and Yunqing Tian and Lei Zhang}, doi = {10.1021/jacs.4c18537}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17682--17688}, shortjournal = {J. Am. Chem. Soc.}, title = {Precise de novo design principle of antifreeze peptides}, volume = {147}, year = {2025}, }
• (2025). NMR structural characterization of SARS-CoV-2 ORF6 reveals an N-terminal membrane anchor. JACS, 147(21), 17668--17681. (www)

  @article{ , abstract = {SARS-CoV-2, the virus responsible for the COVID-19 pandemic, encodes several accessory proteins, among which ORF6, a potent interferon inhibitor, is recognized as one of the most cytotoxic. Here, we investigated the structure, oligomeric state, and membrane interactions of ORF6 using NMR spectroscopy and molecular dynamics simulations. Using chemical-shift-ROSETTA, we show that ORF6 in proteoliposomes adopts a straight α-helical structure with an extended, rigid N-terminal part and flexible C-terminal residues. Cross-linking experiments indicate that ORF6 forms oligomers within lipid bilayers, and paramagnetic spin labeling suggests an antiparallel arrangement in its multimers. The amphipathic ORF6 helix establishes multiple contacts with the membrane surface with its N-terminal residues acting as membrane anchors. Our work demonstrates that ORF6 is an integral monotopic membrane protein and provides key insights into its conformation and the importance of the N-terminal region for the interaction with the membrane.}, archive = {J_JACS}, author = {Martí Ninot-Pedrosa and Gyula Pálfy and Hafez Razmazma and Jackson Crowley and Marie-Laure Fogeron and Beate Bersch and Alexander Barnes and Bernhard Brutscher and Luca Monticelli and Anja Böckmann and Beat H. Meier and Lauriane Lecoq}, doi = {10.1021/jacs.4c17030}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17668--17681}, shortjournal = {J. Am. Chem. Soc.}, title = {NMR structural characterization of SARS-CoV-2 ORF6 reveals an N-terminal membrane anchor}, volume = {147}, year = {2025}, }
• (2025). Structure and synthesizability of Iron–Sulfur Metal–Organic frameworks. JACS, 147(21), 17651--17667. (www)

  @article{ , abstract = {Sulfur-based metal–organic frameworks (MOFs) and coordination polymers (CPs) are an emerging class of hybrid materials that have received growing attention due to their magnetic, conductive, and catalytic properties with potential applications in electrocatalysis and energy storage. In this work, we report a high-throughput virtual screening protocol to predict the synthesizability of candidate metal–sulfur MOFs/CPs by computing the thermodynamically stable structures resulting from a particular combination of metal cluster, linker, cation, and synthetic conditions. Free energies are computed by using all-atom classical mechanical thermodynamic integration. Low-free-energy structures are refined using ab initio density functional theory, and pair distribution functions and powder X-ray diffraction patterns are calculated to complement and guide experimental structure determination. We validate the computational approach by retrospective predictions of the stable structure produced by experimental syntheses, and a subsequent screen predicts Fe 4 S 4 -BDT–TPP as a new thermodynamically stable one-dimensional (1D) CP comprising a redox-active Fe 4 S 4 cluster, a 1,4-benzenedithiolate (BDT) linker, and a tetraphenylphosphonium (TPP) countercation. This material is experimentally synthesized, and the 1D chain structure of the crystal is confirmed using microcrystal electron diffraction. The computational screening pipeline is generically transferable to neutral and ionic MOFs/CPs comprising arbitrary metal clusters, linkers, cations, and synthetic conditions, and we make it freely available as an open source tool to guide and accelerate the discovery and engineering of novel porous materials.}, archive = {J_JACS}, author = {Jianming Mao and Ningxin Jiang and Andrea Darù and Alexander S. Filatov and Jessica E. Burch and Jan Hofmann and Simon M. Vornholt and Karena W. Chapman and John S. Anderson and Andrew L. Ferguson}, doi = {10.1021/jacs.4c16341}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17651--17667}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure and synthesizability of Iron–Sulfur Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Design guidelines to control rippled β-sheets versus pleated β-sheets in mixed-chirality peptides. JACS, 147(21), 17642--17650. (www)

  @article{ , abstract = {Decoding how amino acid sequences determine structure facilitates the design of functional proteins, advanced biomaterials, and selective, low-side-effect drugs. The rippled β-sheet, theorized by Pauling and Corey in 1953, has only recently begun to gain experimental support. However, research on rippled β-sheets remains limited, leaving gaps in our understanding of when and how they occur. To understand the relationship between sequences and rippled β-sheet formation propensities, we carried out molecular dynamics (MD) and density functional theory (DFT) simulations to predict the energetics for six systems of forming either a rippled or pleated β-sheets that are ordered either parallel or antiparallel. Notably, among these four possible structures of each system, the structure predicted to have the lowest energy agrees with the single case observed experimentally! To understand why this form is favored, we investigate the local structures of all six systems, with particular attention to the role of hydrogen bonds (H-bonds) in stabilization. In each system, the peptide consistently adopts a motif that allows it to form the maximum number of H-bonds between backbones, even when amidated, and composed of a single-component with mixed chirality or a cyclic peptide. We find that an achiral glycine–glycine bridge acts as a spacer between valine residues, effectively reducing steric hindrance between side chains. Furthermore, we conclude that the structures of cyclic peptides are stabilized by intramolecular H-bonds in an anhydrous environment. Our findings provide deeper insights into how sequences influence β-sheet conformations, enabling us to propose guidelines for the preferred structures of novel peptides.}, archive = {J_JACS}, author = {Hyeonju Lee and Amaruka Hazari and Jevgenij A. Raskatov and Hyungjun Kim and William A. Goddard, III}, doi = {10.1021/jacs.4c16425}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17642--17650}, shortjournal = {J. Am. Chem. Soc.}, title = {Design guidelines to control rippled β-sheets versus pleated β-sheets in mixed-chirality peptides}, volume = {147}, year = {2025}, }
• (2025). Pools of independently cycling inositol phosphates revealed by pulse labeling with 18O-water. JACS, 147(21), 17626--17641. (www)

  @article{ , abstract = {Inositol phosphates control many central processes in eukaryotic cells including nutrient availability, growth, and motility. Kinetic resolution of a key modulator of their signaling functions, the turnover of the phosphate groups on the inositol ring, has been hampered by slow uptake, high dilution, and constraining growth conditions in radioactive pulse-labeling approaches. Here, we demonstrate a rapid (seconds to minutes) and nonradioactive labeling strategy of inositol polyphosphates through 18 O-water in yeast, human cells, and amoeba, which can be applied in any media. In combination with capillary electrophoresis and mass spectrometry, 18 O-water labeling simultaneously dissects the in vivo phosphate group dynamics of a broad spectrum of even rare inositol phosphates. The good temporal resolution allowed us to discover vigorous phosphate group exchanges in some inositol polyphosphates and pyrophosphates, whereas others remain remarkably inert. We propose a model in which the biosynthetic pathway of inositol polyphosphates and pyrophosphates is organized in distinct, kinetically separated pools. While transfer of compounds between those pools is slow, each pool undergoes rapid internal phosphate cycling. This might enable the pools to perform distinct signaling functions while being metabolically connected.}, archive = {J_JACS}, author = {Geun-Don Kim and Guizhen Liu and Danye Qiu and Maria Giovanna De Leo and Navin Gopaldass and Jacques Hermes and Jens Timmer and Adolfo Saiardi and Andreas Mayer and Henning Jacob Jessen}, doi = {10.1021/jacs.4c16206}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17626--17641}, shortjournal = {J. Am. Chem. Soc.}, title = {Pools of independently cycling inositol phosphates revealed by pulse labeling with 18O-water}, volume = {147}, year = {2025}, }
• (2025). The conformational equilibria of a human GPCR compared between lipid vesicles and aqueous solutions by integrative 19F-NMR. JACS, 147(21), 17612--17625. (www)

  @article{ , abstract = {Endogenous phospholipids influence the conformational equilibria of G protein-coupled receptors, regulating their ability to bind drugs and form signaling complexes. However, most studies of GPCR–lipid interactions have been carried out in mixed micelles or lipid nanodiscs. Though useful, these membrane mimetics do not fully replicate the physical properties of native cellular membranes associated with large assemblies of lipids. We investigated the conformational equilibria of the human A 2A adenosine receptor (A 2A AR) in phospholipid vesicles using 19 F solid-state magic angle spinning NMR (SSNMR). By applying an optimized sample preparation workflow and experimental conditions, we were able to obtain 19 F-SSNMR spectra for both antagonist- and agonist-bound complexes with sensitivity and line widths closely comparable to those achieved using solution NMR. This facilitated a direct comparison of the A 2A AR conformational equilibria across detergent micelle, lipid nanodisc, and lipid vesicle preparations. While antagonist-bound A 2A AR showed similar conformational equilibria across all membrane and membrane mimetic systems, the conformational equilibria of agonist-bound A 2A AR exhibited differences among different environments. This suggests that the conformational equilibria of GPCRs may be influenced not only by specific receptor-lipid interactions but also by the membrane properties found in larger lipid assemblies.}, archive = {J_JACS}, author = {Arka Prabha Ray and Beining Jin and Matthew T. Eddy}, doi = {10.1021/jacs.4c15106}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17612--17625}, shortjournal = {J. Am. Chem. Soc.}, title = {The conformational equilibria of a human GPCR compared between lipid vesicles and aqueous solutions by integrative 19F-NMR}, volume = {147}, year = {2025}, }
• (2025). MACE-OFF: Short-range transferable machine learning force fields for organic molecules. JACS, 147(21), 17598--17611. (www)

  @article{ , abstract = {Classical empirical force fields have dominated biomolecular simulations for over 50 years. Although widely used in drug discovery, crystal structure prediction, and biomolecular dynamics, they generally lack the accuracy and transferability required for first-principles predictive modeling. In this paper, we introduce MACE-OFF, a series of short-range transferable force fields for organic molecules created using state-of-the-art machine learning technology and first-principles reference data computed with a high level of quantum mechanical theory. MACE-OFF demonstrates the remarkable capabilities of short-range models by accurately predicting a wide variety of gas- and condensed-phase properties of molecular systems. It produces accurate, easy-to-converge dihedral torsion scans of unseen molecules as well as reliable descriptions of molecular crystals and liquids, including quantum nuclear effects. We further demonstrate the capabilities of MACE-OFF by determining free energy surfaces in explicit solvent as well as the folding dynamics of peptides and nanosecond simulations of a fully solvated protein. These developments enable first-principles simulations of molecular systems for the broader chemistry community at high accuracy and relatively low computational cost.}, archive = {J_JACS}, author = {Dávid Péter Kovács and J. Harry Moore and Nicholas J. Browning and Ilyes Batatia and Joshua T. Horton and Yixuan Pu and Venkat Kapil and William C. Witt and Ioan-Bogdan Magdău and Daniel J. Cole and Gábor Csányi}, doi = {10.1021/jacs.4c07099}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17598--17611}, shortjournal = {J. Am. Chem. Soc.}, title = {MACE-OFF: Short-range transferable machine learning force fields for organic molecules}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of (−)-illisimonin a enabled by pattern recognition and olefin transposition. JACS, 147(21), 17592--17597. (www)

  @article{ , abstract = {We report an asymmetric total synthesis of (−)-illisimonin A, a sesquiterpene natural product with neurotrophic activity. Illisimonin A possesses a unique cage-like 5/5/5/5/5 pentacyclic scaffold containing a trans -pentalene and a norbornane, two highly strained and challenging structural motifs. It also contains seven contiguous fully substituted stereocenters, including three all-carbon quaternary centers, two of which are adjacent. Our synthesis exploits a pattern recognition strategy to identify a 5,6-fused bicyclic intermediate derived from ( S )-carvone in two steps as the starting point and leverages five sequential olefin transposition reactions to decorate the bicyclic carbocycle. Other key steps include a tandem Mukaiyama hydration-translactonization to form the γ-butyrolactone and an intramolecular aldol cyclization to close the cage and finally deliver (−)-illisimonin A in 16 steps.}, archive = {J_JACS}, author = {Bo Xu and Ziyao Zhang and Mingji Dai}, doi = {10.1021/jacs.5c05409}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17592--17597}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of (−)-illisimonin a enabled by pattern recognition and olefin transposition}, volume = {147}, year = {2025}, }
• (2025). Performance-enhancing asymmetric catalysis driven by achiral counterion design. JACS, 147(21), 17584--17591. (www)

  @article{ , abstract = {The development of highly enantioselective reactions often requires the adventitious discovery of a promising chiral catalyst and its resource-intensive optimization to high selectivity and generality. We report an approach less dependent on happenstance, whereby the performance of a single chiral ligand is enhanced not by modification of the architecturally complex chiral features but instead by an achiral counteranion. Critical to this strategy and its general application is the tactical development of N -aryl trifluoromethyl sulfonamide Brønsted acid donors and their ability to unlock the full enantioselectivity potential of a single chiral Brønsted basic ligand for the enantioselective addition of azide to nitroalkene.}, archive = {J_JACS}, author = {Zihang Deng and Jenna L. Payne and Mahesh Vishe and Julius E. L. Jan and Cody M. Funk and Jeffrey N. Johnston}, doi = {10.1021/jacs.5c05263}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17584--17591}, shortjournal = {J. Am. Chem. Soc.}, title = {Performance-enhancing asymmetric catalysis driven by achiral counterion design}, volume = {147}, year = {2025}, }
• (2025). High structural error rates in “Computation-ready” MOF databases discovered by checking metal oxidation states. JACS, 147(21), 17579--17583. (www)

  @article{ , abstract = {“Computation-ready” metal–organic framework (MOF) databases provide essential raw data for high-throughput computational screening (HTS) and machine-learning approaches to materials discovery. However, the structural fidelity of these databases remains largely unquantified. We introduce MOSAEC, an algorithm that detects chemically invalid structures based on metal oxidation states. MOSAEC was manually validated against 14,796 MOF structures from the popular CoRE database and found to flag erroneous structures with 96% accuracy. Examination of 14 leading experimental and hypothetical MOF databases containing >1.9 million structures reveals structural error rates exceeding 40% in most cases. Analysis of 8 recent HTS studies which highlighted top-performing candidates shows that 52% of these structures were chemically invalid.}, archive = {J_JACS}, author = {Andrew J. White and Marco Gibaldi and Jake Burner and R. Alex Mayo and Tom K. Woo}, doi = {10.1021/jacs.5c04914}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17579--17583}, shortjournal = {J. Am. Chem. Soc.}, title = {High structural error rates in “Computation-ready” MOF databases discovered by checking metal oxidation states}, volume = {147}, year = {2025}, }
• (2025). High-performance hypergolic fuels based on copper hydride clusters. JACS, 147(21), 17574--17578. (www)

  @article{ , abstract = {The development of novel high-performance hypergolic fuels is crucial for the advancement of the aerospace industry. Although hydride-containing compounds offer excellent combustion properties and a short ignition delay time, their inherent instability and strong reducing nature have hindered their widespread application. Herein, we report the synthesis and characterization of an energetic, atomically precise copper hydride cluster, Cu 11 H 3 (5N-dpf) 6 (OAc) 2 , denoted as Cu 11 H 3 . This cluster exhibits exceptional hypergolic performance and good stability. When paired with high-test peroxide (HTP, >90% H 2 O 2 ), Cu 11 H 3 demonstrates a short ignition delay time of 16 ms and achieves a high specific impulse of 254 s. Both experimental and theoretical studies suggest that the hydrides play a pivotal role in the ignition process through interactions with protons from H 2 O 2 , leading to hydrogen evolution and accelerated combustion. This research provides valuable insights for the design and development of novel, environmentally benign solid hypergolic fuels for propulsion applications.}, archive = {J_JACS}, author = {Chao Wang and Run-Meng Li and Zheng Duan and Guoqiang Sun and Xiao-Fei Liu and Shuang-Quan Zang}, doi = {10.1021/jacs.5c04736}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17574--17578}, shortjournal = {J. Am. Chem. Soc.}, title = {High-performance hypergolic fuels based on copper hydride clusters}, volume = {147}, year = {2025}, }
• (2025). Coverage-dependent selective conversion of methane into value-added ethane over noble-metal-free ni1-CeO2 photocatalyst. JACS, 147(21), 17566--17573. (www)

  @article{ , abstract = {Direct methane conversion to value-added chemicals under mild conditions presents a promising route toward net-zero carbon emissions. However, this process encounters significant challenges in efficiently activating inert C–H bonds and preventing excessive oxidation to CO 2 . Herein, we propose a coverage-dependent strategy that leverages the correlation between methane coverage and C–C coupling selectivity, thereby enhancing both the activity and selectivity. By tuning the Lewis acidity of a well-defined atomic 3d transition metal-modified ceria, from weak to moderate, it boosts methane adsorption capacity and promotes its dissociative activation. Additionally, incorporating a nickel cocatalyst improves the charge separation through efficient hole extraction. The optimal noble-metal-free catalyst (Ni 1 -CeO 2 ) delivers exceptional room-temperature performance, achieving a production rate of 243 μmol·g –1 ·h –1 with approximately 90% ethane selectivity over an ultralong test (>350 h), outperforming previously reported noble-metal-free catalysts. This work provides new insights into selectivity regulation via optimization of chemisorbed methane coverage and paves the way for the design of advanced noble-metal-free catalysts.}, archive = {J_JACS}, author = {Lei Luo and Rong Wang and Tieou Wang and Jiangnan Li and Yejun Xiao and Kun Qi and Xiangyang Guo and Zhaochi Feng and Junwang Tang and Fuxiang Zhang}, doi = {10.1021/jacs.5c04676}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17566--17573}, shortjournal = {J. Am. Chem. Soc.}, title = {Coverage-dependent selective conversion of methane into value-added ethane over noble-metal-free ni1-CeO2 photocatalyst}, volume = {147}, year = {2025}, }
• (2025). Specific interactions between HIV-1 env cytoplasmic tail and gag matrix domain probed by NMR. JACS, 147(21), 17561--17565. (www)

  @article{ , abstract = {HIV-1 envelope glycoprotein (Env) is a transmembrane protein that mediates membrane fusion during viral entry. Incorporation of a sufficient number of Envs during viral assembly is critical for viral infectivity. It has long been suggested that the interaction between Env and the matrix domain (MA) of the Gag polyprotein plays an important role in recruiting Envs to the site of viral assembly on the plasma membrane, but direct biochemical and structural evidence is lacking for such an interaction in the context of a membrane-like environment. Here, we report specific structural contacts between the cytoplasmic tail (CT) of the trimeric HIV-1 Env in bicelles and the trimeric MA. Using a combination of measurements of NMR chemical shift perturbation, intermolecular paramagnetic relaxation enhancements, and microscale thermophoresis, we found that, in DMPC-DHPC bicelles that mimic a lipid bilayer, the trimeric baseplate formed by the CT specifically interacted with the trimeric MA via mostly electrostatic interactions involving acidic residues of the CT and positively charged patches of the MA. Nonconservative substitution of these previously unrecognized acidic residues in Env resulted in drastically reduced viral infectivity. Our findings, together with early genetic and biochemical studies, indicate that specific interactions between the CT of Env and MA play a structural role during HIV-1 assembly.}, archive = {J_JACS}, author = {Manish Chaubey and Hailong Gao and Christy L. Lavine and Michael S. Seaman and Bing Chen and James J. Chou}, doi = {10.1021/jacs.5c04597}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17561--17565}, shortjournal = {J. Am. Chem. Soc.}, title = {Specific interactions between HIV-1 env cytoplasmic tail and gag matrix domain probed by NMR}, volume = {147}, year = {2025}, }
• (2025). 4,4′-hydrazobis(1-methylpyridinium) as a two-electron posolyte molecule for aqueous organic redox flow batteries. JACS, 147(21), 17555--17560. (www)

  @article{ , abstract = {Aqueous organic redox flow batteries (AORFBs) are a safe and sustainable solution for the storage of intermittent renewable energy. While several highly soluble two-electron organic molecule negolytes have been developed for AORFBs, most reported organic posolyte species exchange only one electron. Herein, readily available 4,4′-hydrazobis(1-methylpyridinium) dichloride (HydBPyMeCl) is described as a novel two-electron posolyte molecule for AORFBs. The synthesis of HydBPyMeCl was accomplished by a three-step process, yielding multiple grams of the compound. HydBPyMeCl exhibited a reversible two-electron transfer at high redox potential (+0.64 V vs Ag/AgCl reference electrode, pH = 0). When evaluated at 1 M concentration and low pH (2 M HCl) with V 3+ /V 2+ on the negative side, HydBPyMeCl showed high stability. A capacity retention of 99.997% per cycle (99.980% per day measured over 70 days) was achieved, coupled with a high volumetric specific capacity of 47.1 Ah/L (87.2% of capacity utilization at 80 mA/cm 2 ).}, archive = {J_JACS}, author = {Hélène Lebel and Dominic Rochefort and Calvine Lai and Thomas Boulanger and Alizée Debiais and Louis Hamlet and Meysam Maleki and Marc-Antoni Goulet}, doi = {10.1021/jacs.5c03524}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17555--17560}, shortjournal = {J. Am. Chem. Soc.}, title = {4,4′-hydrazobis(1-methylpyridinium) as a two-electron posolyte molecule for aqueous organic redox flow batteries}, volume = {147}, year = {2025}, }
• (2025). Enhancing the photoswitching properties of N-alkyl imines. JACS, 147(21), 17549--17554. (www)

  @article{ , abstract = {N -Alkyl imines are prevalent in dynamic-covalent chemistry and self-assembled structures, yet their E / Z photochromism is often overlooked due to the high-energy light required for isomerization. Here, we present a simple strategy to enhance their photoswitching properties, achieving switching wavelengths and photostationary state distributions comparable to azobenzene. Moreover, we demonstrate that these N -alkyl imines undergo photoisomerization in the condensed phase and exhibit isomer-dependent fluorescence. We anticipate that this study will inspire the design of photoresponsive architectures that operate directly at the dynamic-covalent bond, eliminating the need for dedicated photoswitchable motifs.}, archive = {J_JACS}, author = {Jiarong Wu and Lasse Kreimendahl and Jake L. Greenfield}, doi = {10.1021/jacs.5c02404}, journal = {Journal of the American Chemical Society}, month = {5}, number = {21}, pages = {17549--17554}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing the photoswitching properties of N-alkyl imines}, volume = {147}, year = {2025}, }
• (2025). Zr-catalyzed assembly of 1,1,1-triborylalkanes from alkenes and HBpin. JACS, 147(20), 17539--17548. (www)

  @article{ , abstract = {Multiboronated compounds play more and more significant roles in the chemical community, and 1,1,1-triborylalkanes have emerged as versatile building blocks in organic synthesis. However, efficient strategies for the assembly of such compounds are very rare. A general and atom-economical synthesis of 1,1,1-triborylalkanes from various alkenes with pinacolborane (HBpin) is reported for the first time. The success of this transformation relies on the use of the commercially available Schwartz reagent (Cp 2 ZrHCl) as a catalyst, enabling sequential dehydrogenative borylation and hydroboration. This reaction demonstrates excellent selectivity, high yields, and broad functional group tolerance. Mechanistic investigations reveal that the process begins with two consecutive dehydrogenative borylations catalyzed by zirconium, producing a 1,1-diborylalkene intermediate, which subsequently undergoes hydroboration with HBpin to afford 1,1,1-triborylalkanes. Notably, this approach allows for remote 1,1,1-triboration of internal alkenes.}, archive = {J_JACS}, author = {Kang Liu and Menghan Liang and Qiuling Song}, doi = {10.1021/jacs.5c05144}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17539--17548}, shortjournal = {J. Am. Chem. Soc.}, title = {Zr-catalyzed assembly of 1,1,1-triborylalkanes from alkenes and HBpin}, volume = {147}, year = {2025}, }
• (2025). Relaxation time of multipore nanofluidic memristors for neuromorphic applications. JACS, 147(20), 17529--17538. (www)

  @article{ , abstract = {Memristors have been positioned at the forefront of the purposes for carrying out neuromorphic computation. Their tunable conductance properties enable the imitation of synaptic behavior. Nanofluidic memristors made of multipore membranes have shown their memristic properties and are candidate devices for liquid neuromorphic systems. Such properties are visible through an inductive hysteresis in the current–voltage sweeps, which is then confirmed by the inductive characteristics in impedance spectroscopy measurements. The dynamic behavior of memristors is largely determined by a voltage-dependent relaxation time. Here, we obtain the kinetic relaxation time of a multipore nanofluidic memristor via its impedance spectra, modeling it and deriving a general equation for this time as a function of the applied voltage, fully correlated with the system’s internal parameters. We show that the behavior of this characteristic of memristors is comparable to that of natural neural systems. Hence, we open a way to study the mimic of neuron characteristics by searching for memristors with the same kinetic times.}, archive = {J_JACS}, author = {Gonzalo Rivera-Sierra and Patricio Ramirez and Juan Bisquert and Agustín Bou}, doi = {10.1021/jacs.5c04903}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17529--17538}, shortjournal = {J. Am. Chem. Soc.}, title = {Relaxation time of multipore nanofluidic memristors for neuromorphic applications}, volume = {147}, year = {2025}, }
• (2025). Proteome-wide covalent targeting of acidic residues with tunable N-aryl aziridines. JACS, 147(20), 17517--17528. (www)

  @article{ , abstract = {Carboxylate side chains in aspartic and glutamic acids play critical roles in protein structure and function due to their polarity and negative charge. These acidic residues, which are abundant in high-value drug targets, represent attractive yet underexplored hotspots for covalent inhibitor discovery. In this study, we introduce N -aryl aziridines as a systematically tunable, chemoselective scaffold for covalent targeting of carboxylates across the proteome. Using a library of N -pyridinium aziridine-based fragments combined with chemoproteomics-enabled target deconvolution, we identified lead hits for aspartates and glutamates in proteins such as mitochondrial carrier homologue 2 (MTCH2), RUN and FYVE domain-containing protein 1 (RUFY1), and delta(24)-sterol reductase (DHCR24). Modular build-and-couple synthetic logic enabled fragment evolution via Ni-catalyzed cross-coupling to access N -aryl aziridines with enhanced affinities for MTCH2 and RUFY1. Notably, N -aryl aziridine 5b selectively modified RUFY1 at E502, disrupting its interactions within the endosomal trafficking network and impairing receptor recycling. This work establishes N -aryl aziridines as versatile carboxylate-targeting covalent inhibitor scaffolds, broadening the scope of covalent ligand discovery.}, archive = {J_JACS}, author = {Nan Qiu and Hao Tan and Dany Pechalrieu and Daniel Abegg and Deepanshu Fnu and David C. Powers and Alexander Adibekian}, doi = {10.1021/jacs.5c04685}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17517--17528}, shortjournal = {J. Am. Chem. Soc.}, title = {Proteome-wide covalent targeting of acidic residues with tunable N-aryl aziridines}, volume = {147}, year = {2025}, }
• (2025). A catalytic asymmetric intramolecular [4 + 1]-cycloaddition for the total synthesis of terpene alkaloid natural products. JACS, 147(20), 17510--17516. (www)

  @article{ , abstract = {Intramolecular Diels–Alder reactions are privileged strategic disconnections in the synthesis of polycyclic natural products containing six-membered rings. The analogous [4 + 1]-cycloaddition may possess comparable utility in addressing [ n .3.0]-bicyclic frameworks. However, no viable methods suitable for natural product synthesis have been developed. Here, we report a nickel-catalyzed asymmetric intramolecular [4 + 1]-cycloaddition of a vinylidene and a 1,3-diene to form a [4.3.0]-azabicyclic product. The key vinylidene intermediate is generated reductively from a 1,1-dichloroalkene precursor, and DFT models suggest that addition to the 1,3-diene occurs by a stepwise sequence of [2 + 2]-cycloaddition, 1,3-migration, and reductive elimination. The cycloadduct features sterically differentiated tri- and tetrasubstituted alkenes that can be selectively functionalized to achieve divergent syntheses of 7- epi -incarvilline, hydroxyincarvilline, isoincarvilline, incarvilline, tecomanine, 5-hydroxyskytanthine, and tecostanine.}, archive = {J_JACS}, author = {Wen Xiu and Calvin D. Huffman and William A. Swann and Christina W. Li and Christopher Uyeda}, doi = {10.1021/jacs.5c04607}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17510--17516}, shortjournal = {J. Am. Chem. Soc.}, title = {A catalytic asymmetric intramolecular [4 + 1]-cycloaddition for the total synthesis of terpene alkaloid natural products}, volume = {147}, year = {2025}, }
• (2025). Investigating the conformational diversity of the TMR-3 aptamer. JACS, 147(20), 17497--17509. (www)

  @article{ , abstract = {Aptamers are a class of in vitro selected small RNA motifs that bind a small-molecule ligand with high affinity and specificity. They are promising candidates for the regulation of gene expression in vivo and can aid in further understanding the interaction of RNA with small molecules and conformational changes that may occur upon ligand binding. The TMR-3 aptamer was selected via systematic evolution of ligands by exponential enrichment (SELEX) and binds the fluorophores tetramethylrhodamine (TMR) and 5-carboxy-tetramethylrhodamine (5-TAMRA) with nanomolar affinity. The three-dimensional structure of the TMR-3 aptamer complex with 5-TAMRA was previously determined using liquid-state NMR. By combining the existing NMR restraints with long-range PELDOR distance and orientation information, a broad structural ensemble was generated. From this broad ensemble, a subset of structures was selected by globally fitting orientation-selective PELDOR data from multiple frequency bands. The subensemble represents the conformational variety resulting from the dynamics of the complex. The overall structure of the three-way junction, previously reported by NMR experiments, is retained in the ensemble of the bound state and we were additionally able to characterize the fluctuation of the different stems of the aptamer. Furthermore, in addition to the ligand-bound state we could access the unbound state of the TMR-3 aptamer which was previously uncharacterized. The unbound state of the aptamer is much more structurally diverse, compared to the ligand-bound state. A significant fraction of the ensemble of the unbound state strongly resembles the ligand-bound state, indicating that the ligand-bound state is preformed, which further suggests a conformational-capture ligand-binding mechanism. Apart from the conformations that resemble the ligand-bound state, distinct conformational states which are not present in the presence of the ligand, were successfully identified.}, archive = {J_JACS}, author = {Maximilian Gauger and Elke Duchardt-Ferner and Anna-Lena J. Halbritter and Thilo Hetzke and Snorri Th. Sigurdsson and Jens Wöhnert and Thomas F. Prisner}, doi = {10.1021/jacs.5c04576}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17497--17509}, shortjournal = {J. Am. Chem. Soc.}, title = {Investigating the conformational diversity of the TMR-3 aptamer}, volume = {147}, year = {2025}, }
• (2025). Lanthanide antenna amplifier multiplies the optical sensing efficiency in phototautomeric Metal–Organic frameworks. JACS, 147(20), 17486--17496. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) incorporating phototautomeric ligands have shown significant potential for new-generation optical sensing devices. It is challenging to enlarge the energy difference of tautomers, which is crucial for improving the sensing efficiency. Herein, we report a novel tactic to amplify the excited-state intramolecular proton transfer (ESIPT) effect via the “antenna effect” in lanthanide sensitization. Specifically, by leveraging the enol (E)–keto (K) phototautomerization process, we achieve precise manipulation of the energy gap between the lowest ligand triplet state and the Eu(III) emitting level through fine-tuning. As a result, the small wavelength shift (10 nm) between the E* and K* emissions is amplified into an approximately 65-fold intensity change in Eu(III) emission. This enhancement is accompanied by a significantly lowered limit of detection (LOD: 0.53 μg/L) and improved sensitivity (0.6955% RH –1 ) in real-time humidity monitoring across a broad linear detection range (0–95.0% RH). Computational simulations and single-crystal analyses demonstrate two key mechanisms: (1) the appropriate hydrophilic/hydrophobic distribution in the MOF cavity facilitates rapid hydration/dehydration and (2) H 2 O desorption/adsorption-dependent ESIPT switching governs the deactivation/activation of the Eu(III) 4f excited state. This work presents an optimization approach to enhance energy utilization in MOF-based optical sensing.}, archive = {J_JACS}, author = {Wei-Jie Zhang and Wen-Zhu Sun and Ji-Tong Xu and Bei-Qi Ou and Wan-Qing Zhou and Ling Chen and Jia-Wen Ye and Mei Pan}, doi = {10.1021/jacs.5c04171}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17486--17496}, shortjournal = {J. Am. Chem. Soc.}, title = {Lanthanide antenna amplifier multiplies the optical sensing efficiency in phototautomeric Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Designing high-mechanical-property organic polymeric crystals: Insights from stress dispersion and energy dissipation strategies. JACS, 147(20), 17477--17485. (www)

  @article{ , abstract = {Despite recent significant advancements in the applications of organic polymeric crystals (OPCs), a comprehensive understanding of the design principles for high-mechanical-property crystals remains somewhat elusive. Here, we investigate the mechanical properties of OPCs from the perspectives of stress dispersion and energy dissipation by examining crystals of a macrocycle and three analogous polymers with different solvent fillings, utilizing a novel research platform constructed via dative B–N bonds. Through a thorough mechanical study and investigation into the molecular mechanisms of these model topologies, it was demonstrated that structural expansion and solvent filling are effective pathways for enhancing the mechanical performance of the OPCs by employing stress dispersion and energy dissipation strategies. Overall, our research showcases precise control over the molecular topology of the OPC materials and elucidates specific pathways for stress dispersion and energy dissipation in modulating their mechanical performance, offering a broader design perspective for efficiently enhancing the mechanical properties of other crystalline polymers, such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs).}, archive = {J_JACS}, author = {Tianyu Shan and Liya Chen and Zhewen Guo and Ding Xiao and Mengbin Wang and Xuedong Xiao and Guangfeng Li and Feihe Huang}, doi = {10.1021/jacs.5c04397}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17477--17485}, shortjournal = {J. Am. Chem. Soc.}, title = {Designing high-mechanical-property organic polymeric crystals: Insights from stress dispersion and energy dissipation strategies}, volume = {147}, year = {2025}, }
• (2025). Amplification of asymmetry via structural transitions in supramolecular Polymer–Surfactant coassemblies. JACS, 147(20), 17468--17476. (www)

  @article{ , abstract = {Asymmetric structures are widespread in nature and essential for life and biointeractive materials. Although nature uniformly operates with homochirality, the hierarchical control of asymmetry in synthetic, water-soluble molecular systems is still underexplored. In this work, we present the amplification of helical asymmetry of benzene-1,3,5-tricarboxamide (BTA) supramolecular polymers by coassembly with homochiral nonionic surfactants. For these mixtures, a strong amplification of asymmetry was observed from the surfactant’s molecular chirality to a preferred helicity of the coassembled polymers. This amplification showed maxima at identical stoichiometric ratios for structurally distinct chiral surfactants, demonstrating the similarity of the coassembly mechanism. Notably, the surfactant-induced asymmetry was completely overridden by the introduction of stereogenic centers into the BTA structure, emphasizing the subtlety of the amplification process. Using a combination of spectroscopy and microscopy, we found that surfactants coassemble with the supramolecular polymers to change fiber morphology from racemic double helices to single helices with a preferred handedness. Furthermore, the coassemblies showed a unique combination of structures and dynamics. Our results elucidate the consequences of supramolecular polymer–surfactant coassembly, offering valuable insights into the resulting asymmetric structures.}, archive = {J_JACS}, author = {Freek V. de Graaf and Christian Zoister and Boris Schade and Tarek Hilal and Xianwen Lou and Stefan Wijker and Sandra M. C. Schoenmakers and Ghislaine Vantomme and Rainer Haag and Abhishek K. Singh and E. W. Meijer}, doi = {10.1021/jacs.5c04047}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17468--17476}, shortjournal = {J. Am. Chem. Soc.}, title = {Amplification of asymmetry via structural transitions in supramolecular Polymer–Surfactant coassemblies}, volume = {147}, year = {2025}, }
• (2025). Synthesis of ionizable lipids for gene delivery to the lung using an ugi four component reaction. JACS, 147(20), 17459--17467. (www)

  @article{ , abstract = {The development of efficient delivery systems for therapeutic agents with organ-specific targeting is critical for advancing targeted therapies for effective treatment. In this study, we present a novel approach utilizing a four-component reaction for the synthesis of a diverse library of lipids. These lipids exhibit a distinctive and remarkable tropism toward the lung, with a supplementary affinity toward the spleen. This work showcases the potential of this versatile synthetic strategy in tailoring lipid structures for enhanced organ-specific targeting, opening new avenues for the precise delivery of therapeutic payloads to specific tissues of interest. These findings hold significant promise for the development of advanced therapeutic interventions for pulmonary disorders.}, archive = {J_JACS}, author = {Jonas Renner and Namratha Turuvekere Vittala Murthy and Milan Gautam and Emily Bodi and Antony Jozic and Gaurav Sahay}, doi = {10.1021/jacs.5c04123}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17459--17467}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of ionizable lipids for gene delivery to the lung using an ugi four component reaction}, volume = {147}, year = {2025}, }
• (2025). Water-mediated interactions between glycans are weakly repulsive and unexpectedly long-ranged. JACS, 147(20), 17448--17458. (www)

  @article{ , abstract = {Glycans on the cell surface play an essential role in mediating cell–cell interactions and immune response. Despite their importance, the interactions between them have not been fully characterized. Here, we reveal, using all-atom molecular dynamics simulations and free energy calculations, that water-mediated interactions between a pair of N-glycans without a net charge are weakly repulsive with a range that exceeds their sizes. Unexpectedly, the effective glycan–glycan interactions decay logarithmically as the separation between them increases. Strikingly, this finding coincides exactly with the predicted interaction, which is entropic in origin, between two star polymers consisting of long flexible polymers grafted onto colloidal particles. The weak repulsive interaction, which extends beyond the size of a glycan, is sensitive to the relative orientation of the glycans. The effective long-range repulsive interaction vanishes if the charges on water are turned off, thus establishing that electrostatic interactions, arising in part due to the persistent hydrogen bonds between water and the glycans, are responsible for the interglycan repulsion.}, archive = {J_JACS}, author = {Sucheol Shin and Mauro L. Mugnai and D. Thirumalai}, doi = {10.1021/jacs.5c04126}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17448--17458}, shortjournal = {J. Am. Chem. Soc.}, title = {Water-mediated interactions between glycans are weakly repulsive and unexpectedly long-ranged}, volume = {147}, year = {2025}, }
• (2025). Metal-α-helix peptide frameworks. JACS, 147(20), 17433--17447. (www)

  @article{ , abstract = {Metal–peptide frameworks (MPFs) are a growing class of metal–organic frameworks with promising applications in metalloprotein mimicry, chiral separations, and catalysis. There are limited examples of MPFs, especially those with both secondary structure and natural amino acid side chains that coordinate to metal nodes, which are important for accurately mimicking metalloprotein active sites. Here, we design a robust and modular strategy based on short α-helical peptides (nine amino acids long) to form frameworks with many types of biomimetic metal sites. Peptides were designed to have Glu and His metal-binding residues, hydrophobic residues, and noncanonical helix-enforcing residues. With Co(II), it was shown that mutagenesis of a single amino acid near the metal-binding residues generates a diverse library of frameworks with varying metal node coordination geometries and compositions. Structures for 16 out of 20 variants were characterized by single-crystal X-ray diffraction, revealing how noncovalent interactions impact the metal primary sphere. In one case, a point mutation turns on reversible ligand-triggered conformational changes, demonstrating that this platform allows for dynamic behavior like that observed in metalloproteins. Furthermore, we show that frameworks readily assemble with Mn(II), Fe(II), Cu(II), and Zn(II) ions, highlighting the generality of this approach. The ease-of-synthesis, modularity, and crystallinity of these materials make this a highly accessible platform for studying and engineering biomimetic metal centers in porous materials.}, archive = {J_JACS}, author = {Ronnie Richardson-Matthews and Kateryna Velko and Bitan Bhunia and Sabari Ghosh and Julia Oktawiec and Joseph S. Brunzelle and Viet Thuc Dang and Andy I. Nguyen}, doi = {10.1021/jacs.5c04078}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17433--17447}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal-α-helix peptide frameworks}, volume = {147}, year = {2025}, }
• (2025). Proton-detected solid-state NMR for deciphering structural polymorphism and dynamic heterogeneity of cellular carbohydrates in pathogenic fungi. JACS, 147(20), 17416--17432. (www)

  @article{ , abstract = {Carbohydrate polymers in their cellular context display highly polymorphic structures and dynamics essential to their diverse functions, yet they are challenging to analyze biochemically. Proton-detection solid-state NMR spectroscopy offers high isotopic abundance and sensitivity, enabling the rapid and high-resolution structural characterization of biomolecules. Here, an array of 2D/3D 1 H-detection solid-state NMR techniques are tailored to investigate polysaccharides in fully protonated or partially deuterated cells of three prevalent pathogenic fungi: Rhizopus delemar , Aspergillus fumigatus , and Candida albicans , representing filamentous species and yeast forms. Selective detection of acetylated carbohydrates reveals 15 forms of N -acetylglucosamine units in R. delemar chitin, which coexists with chitosan, and associates with proteins only at limited sites. This is supported by distinct order parameters and effective correlation times of their motions, analyzed through relaxation measurements and model-free analysis. Five forms of α-1,3-glucan with distinct structural origins and dynamics were identified in A. fumigatus , important for this buffering polysaccharide to perform diverse roles of supporting wall mechanics and regenerating a soft matrix under antifungal stress. Eight α-1,2-mannan side chain variants in C. albicans were resolved, highlighting the crucial role of mannan side chains in maintaining interactions with other cell wall polymers to preserve structural integrity. These methodologies provide novel insights into the functional structures of key fungal polysaccharides and create new opportunities for exploring carbohydrate biosynthesis and modifications across diverse organisms.}, archive = {J_JACS}, author = {Jayasubba Reddy Yarava and Isha Gautam and Anand Jacob and Riqiang Fu and Tuo Wang}, doi = {10.1021/jacs.5c04054}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17416--17432}, shortjournal = {J. Am. Chem. Soc.}, title = {Proton-detected solid-state NMR for deciphering structural polymorphism and dynamic heterogeneity of cellular carbohydrates in pathogenic fungi}, volume = {147}, year = {2025}, }
• (2025). Metal-directed self-assembly of minimal heterochiral peptides into metallo-supramolecular β-helical tubules for artificial transmembrane water channels. JACS, 147(20), 17404--17415. (www)

  @article{ , abstract = {Transmembrane selective transport of metabolites controls essential biological functions. During the last two decades, artificial channels have been developed and cyclic peptides have emerged as ideal platforms for efficient ion, sugar, and nucleic acid channel translocation. Despite these tremendous developments, cyclic peptides have eluded selective water transport. Herein, we report the formation of narrow artificial β-helical tubules with diameters ranging from 2.80 to 3.25 Å that selectively control the water translocation, akin to natural aquaporin channels. The tubular assemblies resulted from the metal-driven folding and assembly of minimal heterochiral metal-binding 3-pyridyl-terminated peptides. The bent ultrashort peptide ligand coordinates with Ag + metal ions in a head-to-tail manner, which undergoes subsequent polymerization into a β-helical tubular structure stabilized by interstrand hydrogen bonds (H-bonds) between the β-strands and π–π staking interactions between terminal pyridyl moieties. Furthermore, sequence engineering of the heterochiral peptide and subsequent Ag + ion coordination of the tailored peptides enabled the formation of distinct synthetic double β-barrel and artificial β-helical tubular assemblies, with water molecules encapsulated in the hydrophilic core of the tubes. These water-encapsulated tubes were further explored as artificial water channels in lipid bilayers. Our findings suggest that such β-helical tubular channels achieve a single-channel permeability of 10 6 water molecules/second/channel, which is within 1-2 orders of magnitude lower than that of aquaporins, with a rather good ability to sterically reject ions and prevent proton transport. These assemblies present significant potential for engineering efficient membranes for water purification and separation sciences.}, archive = {J_JACS}, author = {Salil Pophali and Dan-Dan Su and Rudra Ata and Thangavel Vijayakanth and Shyamapada Nandi and Rahul Jain and Linda J. W. Shimon and Rajkumar Misra and Mihail Barboiu}, doi = {10.1021/jacs.5c03970}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17404--17415}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal-directed self-assembly of minimal heterochiral peptides into metallo-supramolecular β-helical tubules for artificial transmembrane water channels}, volume = {147}, year = {2025}, }
• (2025). Molecular cocrystal packing suppresses hopping-driven decoherence of excitonic spin qubits. JACS, 147(20), 17394--17403. (www)

  @article{ , abstract = {Molecular excitonic spins have garnered significant interest for quantum technologies because they can be initialized into addressable, multilevel quantum states through spin-selective intersystem crossing or singlet fission. However, excitonic spin coherence is difficult to maintain above liquid helium temperatures due to typical crystal packings, which promote decoherence through exciton hopping between magnetically inequivalent sites. Here, we engineer donor–acceptor cocrystals where molecular packing in isolated π-stacks of magnetically equivalent molecules suppresses hopping-induced decoherence. Pulse-electron paramagnetic resonance spectroscopy reveals that high-temperature spin coherence in this packing geometry is instead strongly influenced by mutual spin flip-flops between interacting excitons. Coherence anisotropy measurements indicate that spin–phonon coupling enhances the rate of spin flip-flops through dynamic reorientation of the zero field splitting tensor. As a result, coherence times decrease exponentially at elevated temperatures, with coherence times measurable up to 150 K. The combined results present generalized design strategies to preserve excitonic spin coherence at high temperatures.}, archive = {J_JACS}, author = {Jonathan R. Palmer and Samuel B. Tyndall and Georgia C. Mantel and Otis J. Buras and Ryan M. Young and Matthew D. Krzyaniak and Michael R. Wasielewski}, doi = {10.1021/jacs.5c03973}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17394--17403}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular cocrystal packing suppresses hopping-driven decoherence of excitonic spin qubits}, volume = {147}, year = {2025}, }
• (2025). High-resolution multicolor shortwave infrared dynamic in vivo imaging with chromenylium nonamethine dyes. JACS, 147(20), 17384--17393. (www)

  @article{ , abstract = {Imaging in the shortwave infrared (SWIR) region offers fast, high-resolution visualization of in vivo targets in a multiplexed manner. These methods require bright, bathochromically shifted fluorescent dyes with sufficient emission at SWIR wavelengths–ideally above 1500 nm for high-resolution deep tissue imaging. Polymethine dyes are a privileged class of contrast agents due to their excellent absorption and high degree of modularity. In this work, we push flavylium and chromenylium dyes further into the SWIR region through polymethine chain extension. This panel of nonamethine dyes boasts absorbances as red as 1149 nm and tail emission beyond 1500 nm. These dyes are the brightest organic fluorophores at their respective bandgaps to date, with ε max ∼ 10 5 M –1 cm –1 and Φ F up to 0.5%. Using two nonamethine dyes, Chrom9 and JuloFlav9 , we performed two-color all-SWIR multiplexed imaging (Excitation at 1060 and 1150 nm; Emission collection at >1500 nm), enhancing the depths and resolutions able to be obtained in multicolor SWIR imaging with small molecule contrast agents. Finally, we combine the nonamenthine dyes with other SWIR-emissive fluorophores and demonstrate five-color awake imaging in an unrestrained mouse, simultaneously pushing the multiplexing, resolution, and speed limits of in vivo optical imaging.}, archive = {J_JACS}, author = {Anthony L. Spearman and Eric Y. Lin and Emily B. Mobley and Andriy Chmyrov and Bernardo A. Arús and Daniel W. Turner and Cesar A. Garcia and Kyle Bui and Christopher Rowlands and Oliver T. Bruns and Ellen M. Sletten}, doi = {10.1021/jacs.5c03673}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17384--17393}, shortjournal = {J. Am. Chem. Soc.}, title = {High-resolution multicolor shortwave infrared dynamic in vivo imaging with chromenylium nonamethine dyes}, volume = {147}, year = {2025}, }
• (2025). Boosting cancer cell ferroptosis with carbon monoxide poisoned hemoglobin. JACS, 147(20), 17372--17383. (www)

  @article{ , abstract = {The peroxidase (POD)-like nanozymes, particularly those with atomic Fe–N x sites, have demonstrated exceptional catalytic potential in cancer cell ferroptosis. The biodegradable hemoglobin (Hb) is recognized as an Fe–N 5 POD-like nanozyme expected to replace the carbon-based ones, while its uncontrollable catalytic reaction remains a safety concern. Here, inspired by the carbon monoxide (CO) poisoned Hb, we develop a controllable and biodegradable catalytic nanoplatform DPHCO which integrates carboxyhemoglobin (HbCO) and platinum(IV) prodrug into −CH 2 SSCH 2 – bridged dendritic mesoporous organosilica nanoparticles (DMON). The Fe–N 5 site of HbCO could be temporarily deactivated during the blood circulation. In tumor tissue, the poisoned site will be in situ reactivated by the H 2 O 2 -driven valence modulation of heme iron, along with CO desorption. The reactivated Hb performs POD-like activity during the ferric–ferryl redox cycle, adhering to Michaelis–Menten kinetics and density function theory (DFT) calculation results. Both in vitro and in vivo data suggest that the reactivated Hb and released CO could induce lipid peroxidation and cancer cell ferroptosis, which is further boosted by cisplatin synergy. This gas modification and iron valence-driven modulation provide a feasible approach for toggling the “OFF/ON” activity of the catalytic site, which would inspire the development of nanozymes for precision oncotherapy.}, archive = {J_JACS}, author = {Meifang Wang and Wenying Zhang and Bin Liu and Binbin Ding and Kai Li and Ping’an Ma and Jun Lin}, doi = {10.1021/jacs.5c03831}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17372--17383}, shortjournal = {J. Am. Chem. Soc.}, title = {Boosting cancer cell ferroptosis with carbon monoxide poisoned hemoglobin}, volume = {147}, year = {2025}, }
• (2025). Self-regulating hydrogel with reversible optical activity in its gel-to-gel transformation. JACS, 147(20), 17361--17371. (www)

  @article{ , abstract = {This study reports a supramolecular gel system capable of dynamic gel-to-gel transformations and reversible inversion of optical activity between superhelical and single-helical structures without passing through a sol phase. Inspired by collagen-like adaptability, the system utilizes 4-pyridinylboronic acid and guanosine as building blocks. Hierarchical assembly is achieved through pH-responsive boronic ester formation and guanosine-mediated G-quadruplex stacking, enabling transitions between superhelices and single helices with opposite optical activity. The system employs three regulatory pathways: bidirectional pH modulation, monotonic pH increase, and monotonic pH decrease, demonstrating programmable and reversible control over chirality, morphology, and mechanical properties. In the autonomous pH regulation, we have created an out-of-equilibrium hydrogel system with controlled switching of optical activity. Unlike traditional gel–sol–gel systems, this gel maintains macroscopic stability during transformations. Our remarkable finding bridges the gap between static supramolecular assemblies and dynamic soft materials, offering a platform for designing functional, biomimetic systems. The combination of hierarchical organization, dynamic chirality control, and robust programmability positions this gel for applications in adaptive optics, responsive biomaterials, and programmable soft matter.}, archive = {J_JACS}, author = {Jingjing Li and Fang Yin and Jianhong Wang and Huachuan Du and Fan Xu and Stefan Meskers and Yudong Li and Stefan Wijker and Yu Peng and Riccardo Bellan and Ghislaine Vantomme and Jian Song and Chun-Sen Liu and E. W. Meijer}, doi = {10.1021/jacs.5c03844}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17361--17371}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-regulating hydrogel with reversible optical activity in its gel-to-gel transformation}, volume = {147}, year = {2025}, }
• (2025). Total chemical synthesis of glucagon glycoforms reveals the remarkable influence of natural glycosylation. JACS, 147(20), 17350--17360. (www)

  @article{ , abstract = {Glycosylation plays a critical role in modulating protein and peptide properties, yet the impact of recently discovered natural mucin-type O-glycosylation on therapeutic peptides like glucagon remains underexplored due to challenges in obtaining homogeneous research samples. Here, we address this challenge by developing a streamlined multistep synthesis–one purification protocol, enabling the production of 21 glucagon glycoforms with systematically varied glycosylation patterns. Investigation of these glycoforms revealed a remarkable impact of natural glycosylation on two properties critical for glucagon: solubility increased by over 870-fold, and fibrillation was completely inhibited, even under stringent conditions, while biological activity in elevating blood glucose levels was preserved. Computational analyses indicated that sialylated glycans disrupt intermolecular associations in the solid state, enhancing solubility, and shift secondary structures from β-sheets to α-helices, mitigating fibrillation. These findings suggest that glycosylation may have evolved as a natural mechanism to optimize undesirable properties, offering valuable insights for the development of therapeutics based on glucagon and other proteins and peptides with similar challenges.}, archive = {J_JACS}, author = {Yaohao Li and Xin Li and Ruihan Wang and Wenqiang Liu and Dan Liu and Zerun Song and Yajing Zhang and Chuang Zhang and Zhongping Tan}, doi = {10.1021/jacs.5c03757}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17350--17360}, shortjournal = {J. Am. Chem. Soc.}, title = {Total chemical synthesis of glucagon glycoforms reveals the remarkable influence of natural glycosylation}, volume = {147}, year = {2025}, }
• (2025). Inversed Benzene/Cyclohexene/Cyclohexane adsorption selectivities for one-step purification of cyclohexene and beyond. JACS, 147(20), 17342--17349. (www)

  @article{ , abstract = {Separation of benzene/cyclohexene/cyclohexane (Bz/Cye/Cya) mixtures, especially purification of Cye, is crucial but challenging in the petrochemical industry. Here, we report two new metal–organic frameworks with opposite adsorption selectivities for on-demand separation/purification of Bz/Cye/Cya mixtures. Although they possess similar frameworks and pore structures, their pore surfaces are functionalized by hydrophobic ethyl and hydrophilic hydroxymethyl groups, which interact conversely with Bz/Cye/Cya, giving a record-high Bz selectivity (129) and the first example of Cya/Cye/Bz selectivity (18.6), respectively. Equimolar ternary mixture breakthrough experiments showed that they could directly produce high-purity Cya (99.5%+, 0.39 mmol g –1 ) or Bz (99.5%+, 0.25 mmol g –1 ), and the tandem connection of two adsorbents enabled direct production of high-purity Cye (99.5%+, 0.37 mmol g –1 ) in a one-step adsorption process. Further, a bypass-tandem strategy is proposed to not only greatly improve Cye productivity (99.5%+, 0.57 mmol g –1 ) but also simultaneously produce high-purity Cya (99.5%+, 0.36 mmol g –1 ).}, archive = {J_JACS}, author = {Dong-Dong Zhou and Xi Feng and Ding-Yi Hu and Xiao-Tong Lu and Fang-Di Dong and Zi-Luo Fang and Rui-Biao Lin and Jie-Peng Zhang and Xiao-Ming Chen}, doi = {10.1021/jacs.5c03564}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17342--17349}, shortjournal = {J. Am. Chem. Soc.}, title = {Inversed Benzene/Cyclohexene/Cyclohexane adsorption selectivities for one-step purification of cyclohexene and beyond}, volume = {147}, year = {2025}, }
• (2025). Tuning second near-infrared fluorescence activation by regulating the excited-state charge transfer dynamics change ratio. JACS, 147(20), 17330--17341. (www)

  @article{ , abstract = {Second near-infrared (NIR-II) fluorescence imaging holds great promise for studying biopathological processes with high spatial resolution. However, developing activatable NIR-II fluorescent probes (AFPs) remains challenging due to insufficient signal activation in response to biomarkers and labor-intensive probe optimization. Here, we identify the excited-state charge transfer dynamics change ratios (δ) as a critical determinant of the fluorescence “turn-on” ratio of AFPs. We design a series of AFPs and their uncaged counterparts (uAFPs) and systematically analyze their photophysical characteristics and responsiveness. Comprehensive analyses including computational calculations, femtosecond transient absorption spectroscopy, steady-state fluorescence spectra, and fluorescence titration experiments verify a strong correlation between the theoretical and experimental δ values and the fluorescence “turn-on” ratios of activated AFPs. As a proof of concept, the optimal probe AFP2 indicated by δ enables early diagnosis of drug-induced liver injury and ultrasensitive detection of tiny metastatic foci (<2 mm) in mouse models, demonstrating superior sensitivity outperforming conventional methods. This study highlights the potential of δ as a predictor of probe responsiveness, which can streamline and accelerate the development and optimization of NIR-II AFPs for broader preclinical and translational applications.}, archive = {J_JACS}, author = {Linrong Chen and Meitang Peng and Yanni Ouyang and Jian Chen and Haoze Li and Min Wu and Rui Qu and Wenya Zhou and Chunfeng Zhang and Yuyan Jiang and Shidang Xu and Wei Wu and Xiqun Jiang and Xu Zhen}, doi = {10.1021/jacs.5c03763}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17330--17341}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning second near-infrared fluorescence activation by regulating the excited-state charge transfer dynamics change ratio}, volume = {147}, year = {2025}, }
• (2025). Photochemistry of Ni(II) tolyl chlorides supported by bidentate ligand frameworks. JACS, 147(20), 17315--17329. (www)

  @article{ , abstract = {Herein, we investigate the photoactivity of four Ni II tolyl chloride complexes supported by either the new bidentate [2.2]pyridinophane ( H N2) ligand or the traditional 4,4′-di- tert -butyl-2,2′-dipyridyl ( t Bu bpy) ligand. Despite a change in the ligand framework, we observe similar quantum yields for the photodegradation of all four Ni II complexes, while noting changes in their affinity for radical side reactivity and ability to stabilize the photogenerated mononuclear Ni I species. Furthermore, changing from an ortho -tolyl to a para -tolyl group affects the geometry of the complexes and makes the Ni center more susceptible to side reactivity. By leveraging the newly developed H N2 ligand, a bidentate ligand that hinders axial interactions with the Ni center, we limit the radical side reactivity. Time-dependent density functional theory (TDDFT) and complete active space self-consistent field (CASSCF) calculations predict that all four complexes have accessible MLCTs that excite an electron from a Ni-aryl bonding orbital into a Ni-aryl antibonding orbital, initiating photolysis. By decreasing this energy gap and stabilizing the tetrahedral triplet excited state, we increase quantum yields of photoexcitation. Importantly, we characterize the photogenerated mononuclear Ni I chloride species using X-band EPR spectroscopy and show that the H N2-supported Ni I complexes do not undergo the deleterious dimerization and tetramerization observed for the (bpy)Ni I Cl species. Overall, this study provides valuable insight into how the steric environment around the Ni center affects its photoactivity and demonstrates that such photoactivity is not unique to bipyridyl-supported Ni compounds.}, archive = {J_JACS}, author = {Luke P. Westawker and Bailey S. Bouley and Josh Vura-Weis and Liviu M. Mirica}, doi = {10.1021/jacs.5c03770}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17315--17329}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemistry of Ni(II) tolyl chlorides supported by bidentate ligand frameworks}, volume = {147}, year = {2025}, }
• (2025). Ketene conversion chemistry within mordenite zeolite: Pore-size-dependent reaction mechanism, product selectivity, and catalytic activity. JACS, 147(20), 17303--17314. (www)

  @article{ , abstract = {The oxide–zeolite bifunctional catalyst for ketene-bridged syngas conversion has gained great attention for addressing the selectivity challenge in light olefin production, where zeolite dominates the ketene conversion selectivity. However, the atomic-level mechanism underlying ketene-to-light olefin conversion within zeolite remains unclear. Herein, we focus on mordenite (MOR) zeolite and perform systematic first-principles calculations combined with microkinetic simulations to elucidate pore-type-dependent reaction networks for ketene-to-light olefin conversion. Our microkinetic results reveal that ketene conversion within MOR follows an autocatalytic process initiated by the Brønsted acid site, involving the generation and subsequent catalysis of reactive intermediates. Time-dependent dynamic evolution simulation shows that within the 12-membered-ring (12MR) pore, a thermodynamically stable five-membered-ring carbocation (FMR-CH 3 + ) self-evolves and acts as the active center to convert CH 2 CO to multihydrocarbons. Instead, in the 8-membered-ring side pocket (8MR), direct CH 3 + formation occurs via acetyl carbocation (CH 3 CO + ) decarbonylation, inducing CH 2 CO conversion with exclusive ethylene selectivity. The distinct reaction mechanisms and product selectivities are attributed to the thermodynamic and kinetic constraints of cyclic/long-chain intermediate formation imposed by the smaller 8MR pore. Despite its higher free energy barrier, 8MR is identified as the key active site for light olefin formation due to its lower dependence on ketene pressure. We also highlight the critical factors influencing both the selectivity and activity of light olefin formation, offering valuable insights for the optimization of MOR catalysts. This study provides a quantitative mechanistic understanding of ketene conversion, emphasizing the role of pore structure in shaping catalytic activity and product selectivity, which may facilitate the design of efficient zeolite-based catalysts.}, archive = {J_JACS}, author = {Danfeng Xiong and Zhuangzhuang Lai and Jianfu Chen and Haiyang Yuan and Haifeng Wang}, doi = {10.1021/jacs.5c03687}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17303--17314}, shortjournal = {J. Am. Chem. Soc.}, title = {Ketene conversion chemistry within mordenite zeolite: Pore-size-dependent reaction mechanism, product selectivity, and catalytic activity}, volume = {147}, year = {2025}, }
• (2025). Leveraging Protein–Ligand and DNA interactions to control hydrogel mechanics. JACS, 147(20), 17293--17302. (www)

  @article{ , abstract = {Biomacromolecules can serve as molecularly precise building blocks for hydrogel materials, dictating material properties that depend on the chemical identity and interactions of the individual components. Herein, we introduce biomolecular hydrogels where ligand-functionalized DNA sequences form the hydrogel backbone and multivalent protein–ligand interactions form supramolecular cross-links. In these hydrogels, we can independently leverage the programmable rigidity of DNA (i.e., single-stranded vs double-stranded DNA) and defined protein–ligand binding affinities spanning >10 orders of magnitude to modulate the gel stiffness, stress relaxation, and shear thinning. We learn that (1) double-stranded networks have stiffness values up to 3 orders of magnitude greater than single-stranded networks and exhibit thermoresponsiveness and (2) the protein–ligand binding affinities and dissociation rate constants determine the network topologies and stress relaxation rates of the hydrogels. Finally, the hydrogels exhibit cytocompatibility and cell-type-specific degradation, where cells can migrate through the gels via interactions between the gels and their ligand-binding receptors. Together, this work demonstrates that varying the local chemical interactions of the hydrogel backbone and the supramolecular binding affinity of dynamic cross-links leads to cytocompatible hydrogels with tunable viscoelastic properties for applications in drug delivery and tissue engineering.}, archive = {J_JACS}, author = {Namrata Ramani and Jeongmin Hwang and Alex J. Anderson and Jennifer Delgado and Laura Hernández-López and C. Adrian Figg and Peter H. Winegar and Chad A. Mirkin}, doi = {10.1021/jacs.5c03523}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17293--17302}, shortjournal = {J. Am. Chem. Soc.}, title = {Leveraging Protein–Ligand and DNA interactions to control hydrogel mechanics}, volume = {147}, year = {2025}, }
• (2025). Synthesis and characterization of cycloocta[1,2-a:6,5-a′]diindene as an octagon-containing nonalternant isomer of pentacyclic benzenoid aromatic hydrocarbons with hidden diradical character that induces dimerization. JACS, 147(20), 17281--17292. (www)

  @article{ , abstract = {Recently, the interest in nonbenzenoid hydrocarbons has resurged, focusing on the replacement of two benzenoid hexagons with a pentagon/heptagon pair, which has led to abundant azulenoid hydrocarbons. For ortho -fused benzenoid hydrocarbons with three or more rings, replacing the three hexagons with a set of two pentagons and one octagon is also possible. Following this concept, we designed pentacyclic cyclooctadiindenes 4 and 5 with a 5–8–5 tricyclic skeleton. Although the pronounced open-shell nature of 4 hampered its synthesis, five examples of cyclooctadiindenes 5 were synthesized and characterized as stable closed-shell molecules. A thin film of 5a exhibited p-type transistor behavior with a hole mobility of 0.63 × 10 –2 cm 2 /(V·s). Optoelectronic measurements clearly showed the nonalternant character of 5 . Heating or photoirradiation of a solution of 5 afforded a formal [6 + 4] cycloadduct. Theoretical calculations and mechanistic investigations revealed the occurrence of a stepwise formation of two C–C bonds, in which the hidden open-shell character of 5 emerges with the two molecules in close contact. Notably, in the dimeric π-complex 5 · 5 , the nonalternant character of 5 is alleviated. The increased spatial overlap of the frontier orbitals and the reduction of the energy gap facilitate the diradical-based bond formations. Our results demonstrate that the open-shell electronic structures of a π-stacked compound can be tuned even for monomer compounds with negligible open-shell character. This study will contribute to establishing design strategies for novel open-shell functional molecular materials based on closed-shell nonalternant hydrocarbons in the condensed state.}, archive = {J_JACS}, author = {Akihito Konishi and Haruka Tokuyama and Hinaki Kitamura and Seiya Tsuchida and Mitsuharu Suzuki and Ken-ichi Nakayama and Ryohei Kishi and Makoto Yasuda}, doi = {10.1021/jacs.5c03615}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17281--17292}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis and characterization of cycloocta[1,2-a:6,5-a′]diindene as an octagon-containing nonalternant isomer of pentacyclic benzenoid aromatic hydrocarbons with hidden diradical character that induces dimerization}, volume = {147}, year = {2025}, }
• (2025). Ni-doped perovskite for photocatalytic benzylic C–H amination. JACS, 147(20), 17273--17280. (www)

  @article{ , abstract = {Directly introducing aliphatic or aromatic amines into C(sp 3 )–H bonds remains a significant challenge in organic synthesis. One major difficulty is that C(sp 3 )–H activation is an oxidative process, whereas amines are generally more prone to oxidation than C–H bonds, making them difficult to use directly. Typically, protected amines are employed and then deprotected to realize amination, but this strategy limits the synthesis of tertiary amines, as protected secondary amines are often inactive in such reactions. Here, we present a mild photocatalytic method that overcomes these limitations by utilizing Ni-doped perovskite CsPbBr 3 nanocrystals (NCs) for benzylic C–H amination directly using unprotected aliphatic or aromatic amines. Perovskite enables highly selective C–H activation, while doped Ni(II) readily captures benzylic radicals via oxidative addition. XPS studies successfully validate such an oxidative addition step with a Ni(II)/Ni(III) configuration. Our methodology forges aromatic and aliphatic, cyclic and acyclic, and secondary and tertiary amines and provides a powerful tool for the late-stage functionalization of bioactive compounds and drug derivatives.}, archive = {J_JACS}, author = {Nhu Dang and Jovan San Martin and Melad Shaikh and Yong Yan}, doi = {10.1021/jacs.5c03588}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17273--17280}, shortjournal = {J. Am. Chem. Soc.}, title = {Ni-doped perovskite for photocatalytic benzylic C–H amination}, volume = {147}, year = {2025}, }
• (2025). Tuning the reaction chemistry for the sulfo-bromination of bismuth, leading to dual-tapered bi-sulfobromide platelet nanocrystals and their heterostructures. JACS, 147(20), 17260--17272. (www)

  @article{ , abstract = {The chemistry of sulfo-bromination of metals leading to dual-tapered 2D-shaped nanostructures is reported. This has been confined to the metal ion Bi(III), whose reduction followed by reionization in the presence of sulfide and bromide precursors leads to the desired bismuth sulfobromide nanocrystals. Initially Bi 19 S 27 Br 3 seed rods are taken, where Bi(0) nanocrystals are connected via a redox chemistry, conjugating with secondary metal ions. Then these 1D-shaped Bi 19 S 27 Br 3 –Bi(0) heterostructures are transformed to dual-tapered 2D-shaped Bi 19 S 27 Br 3 –Bi(0) nanostructures following a solution–liquid–solid (SLS) growth mechanism. The sulfo-bromination process is initially nucleated on the metal(0) sites but grown on the surface of the substrate seed rods. The size of Bi(0) equilibrates the tapering, whereby the length of the rods is gradually reduced and the width of the rods is slowly widened, leading to the dual-tapered 1D to 2D shape-transferred Bi-chalcohalide nanostructures. Extensive electron microscopic analysis and stepwise synthesis have been carried out to investigate the growth mechanism and to understand the tapering during the shape evolution processes. In addition, these materials of seed rods, intermediate and final nanostructures obtained are further explored as photocatalysts for HER and their activities are compared. The reaction chemistry discussed here enables the controlled incorporation of two anions with Bi(0) ionization, where one end of the nanostructure initiates nucleation, while the other end promotes growth. Overall, the reaction chemistry here provides a pathway for the solution-processed 2D SLS growth process, leading to shape-controlled metal chalcohalide nanostructures.}, archive = {J_JACS}, author = {Sanjib Shyamal and Avijit Patra and Naveen Goyal and Souvik Banerjee and Sumit Kumar Dutta and N. Ravishankar and Narayan Pradhan}, doi = {10.1021/jacs.5c03518}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17260--17272}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the reaction chemistry for the sulfo-bromination of bismuth, leading to dual-tapered bi-sulfobromide platelet nanocrystals and their heterostructures}, volume = {147}, year = {2025}, }
• (2025). A unified approach to chiral α-aryl ketones and aldehydes via ni-catalyzed asymmetric reductive cross-coupling. JACS, 147(20), 17251--17259. (www)

  @article{ , abstract = {We disclose a highly enantioselective protocol for the facile preparation of protected tertiary α-aryl ketones and aldehydes, enabled by chiral Ni/Biox-catalyzed reductive coupling of readily accessible α-iodoacetals and -ketals with (hetero)aryl halides. The generality of the method is demonstrated by its excellent performance across a broad range of (hetero)cyclic and acyclic carbonyl scaffolds. The reaction is thought to proceed through unactivated acetal/ketal α-carbon radicals, overcoming challenges related to the ancillary steric bulkiness of the acetal/ketal moieties and the lack of stabilizing and directing factors. Experimental and density functional theory (DFT) studies reveal a plausible radical chain mechanism and elucidate the observed enantioselectivity. This method avoids the postreaction epimerization issue often encountered in unprotected tertiary α-aryl ketones and aldehydes. Thus, it holds great promise for the rapid synthesis of a wide array of important natural products and drug molecules based on tertiary α-aryl ketones and aldehydes by leveraging earth-abundant nickel catalysts.}, archive = {J_JACS}, author = {Canbin Qiu and Lin Liu and Keyang Zhang and Shanshan Du and Yunrong Chen and Xiaotai Wang and Hegui Gong}, doi = {10.1021/jacs.5c03418}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17251--17259}, shortjournal = {J. Am. Chem. Soc.}, title = {A unified approach to chiral α-aryl ketones and aldehydes via ni-catalyzed asymmetric reductive cross-coupling}, volume = {147}, year = {2025}, }
• (2025). Electrifying redox-neutral palladium-catalyzed carbonylations: Multielectron transfer as a catalyst driving force. JACS, 147(20), 17239--17250. (www)

  @article{ , abstract = {Palladium-catalyzed bond-forming reactions such as carbonylations offer an efficient and versatile avenue to access products from often feedstock reagents. However, the use of catalysts also comes with a cost, as their need to be regenerated after each product-forming cycle requires balancing thermal operations. The latter can lead to high barriers even with catalysts as well as restrict their application to many products. We introduce herein an alternative approach to palladium catalyst design, where instead electrochemical potential can drive catalysis by continual two-electron cycling of the metal oxidation state. The power behind these redox steps offers a route to carry out carbonylation reactions, including the catalytic synthesis of high-energy aroyl halide electrophiles, at unprecedentedly mild ambient temperature and pressure. More generally, analysis suggests this catalyst functions by a distinct multi-electron exchange pathway, where two-electron reduction enables oxidative addition and two-electron oxidation drives product elimination. The combination creates a unique platform where both these reverse operations are favored in the same system and with electrochemical potential energy as the only added energy source.}, archive = {J_JACS}, author = {Pierre-Louis Lagueux-Tremblay and Kwan Ming Tam and Meijing Jiang and Bruce A. Arndtsen}, doi = {10.1021/jacs.5c03354}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17239--17250}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrifying redox-neutral palladium-catalyzed carbonylations: Multielectron transfer as a catalyst driving force}, volume = {147}, year = {2025}, }
• (2025). High-precision separation and refinement of fatty acid derivatives by Metal–Organic frameworks. JACS, 147(20), 17228--17238. (www)

  @article{ , abstract = {High-precision separation of fatty acid (FA) derivatives is essential for differentiating between structural variations such as E / Z isomerism and unsaturated bond (C═C) positions, which determine their properties and physiological functions. However, current separation and purification methods lack the necessary resolution, efficiency, and scalability. Herein, we report that metal–organic frameworks (MOFs) with configured nanopores enable the precise separation of long-chain FA derivatives. Two pillared-layer-type isoreticular MOFs featuring sub-nanometer channels were employed as adsorbents and stationary phases in liquid chromatography (LC). The MOF-packed LC columns demonstrated high-resolution separation of C18 fatty acid methyl esters (FAMEs), effectively distinguishing E / Z isomers and C═C positional isomers through a nanopore insertion-based recognition mechanism. Thermodynamic analysis and molecular dynamics simulations revealed an unprecedented recognition mechanism for C═C positional isomers, driven by specific multi-site interactions between the functional groups on the FAME chains and the regularly arranged organic ligands within the MOF nanopores. Moreover, MOFs enable the purification of fats and oils (triacylglycerols) by effectively separating them from associated process contaminants that may pose carcinogenic risks to humans. This approach facilitates the scalable and efficient refinement of edible oils, achieving contaminant elimination efficiencies exceeding 99%.}, archive = {J_JACS}, author = {Akihiro Torimoto and Daiki Ishibashi and Atsushi Yamashita and Takashi Uemura and Nobuhiko Hosono}, doi = {10.1021/jacs.5c03316}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17228--17238}, shortjournal = {J. Am. Chem. Soc.}, title = {High-precision separation and refinement of fatty acid derivatives by Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Asymmetric vicinal and remote hydroamination of olefins by employing a heck-reaction-derived hydride source. JACS, 147(20), 17217--17227. (www)

  @article{ , abstract = {Metal hydrides are reactive intermediates in numerous catalytic processes. In many catalytic processes, metal hydrides are formed, but their potential reactivity is often wasted by reaction with a base or an oxidant to permit catalyst turnover. In this report, the hydroamination of unactivated olefins is described by coupling a Heck reaction with a hydroamination reaction between aryl boronic acid, olefin, and a nitrene precursor dioxazolone. Initiated by a Heck reaction between the olefin and arylboroic acid, a rhodium hydride intermediate is generated and is retained for the hydroamination of a second equivalent of the olefin. Depending on the chain length of the alkyl group of the olefin, α- or β-amino amides were obtained in excellent regio- and enantioselectivity via direct or remote (migratory) hydroamination, respectively. The coupling system features a broad scope, mild conditions, and excellent enantioselectivity, and it also represents a rare example of asymmetric olefin hydroamination using a chiral rhodium(III) cyclopentadienyl catalyst. Mechanistic studies delineated the turnover-limiting and enantio-determining steps of this catalytic system.}, archive = {J_JACS}, author = {Ruijie Mi and Xuejing Yao and Youzhi Xu and Shunle Hu and Genping Huang and Xingwei Li}, doi = {10.1021/jacs.5c03076}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17217--17227}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric vicinal and remote hydroamination of olefins by employing a heck-reaction-derived hydride source}, volume = {147}, year = {2025}, }
• (2025). Catalytic atroposelective aza-grob fragmentation: An approach toward axially chiral biarylnitriles. JACS, 147(20), 17209--17216. (www)

  @article{ , abstract = {Grob fragmentation is a powerful synthetic tool for cleaving C–C bonds, which was particularly useful in the construction of seven- to nine-membered carbocycles or heterocycles. This reaction typically breaks one C–C bond and one C–X bond and forms two unsaturated functional groups. As no stereogenic centers are generated, catalytic asymmetric Grob fragmentation has remained unexplored. In this study, we have successfully developed a catalytic asymmetric aza-Grob fragmentation of α-keto oxime esters, achieving atroposelective C–C bond cleavage to construct axially chiral biarylnitriles. Single-crystal X-ray diffraction analysis of oxime esters elucidated the structure–reactivity relationship, highlighting the role of torsional strain. These studies also revealed the unique role of the 2-phenyl benzoyl group in controlling the substrate conformation, tuning reactivity, and stereoselectivity. The 1 H NMR titration experiments provided brief insights into the activation mode of the catalyst with the substrate, suggesting a multi-hydrogen-bonding interaction model.}, archive = {J_JACS}, author = {Lin Li and Linlin Ding and Xue Zhang and Chengnuo Zhang and Minyan Wang and Zhenhua Gu}, doi = {10.1021/jacs.5c02978}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17209--17216}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic atroposelective aza-grob fragmentation: An approach toward axially chiral biarylnitriles}, volume = {147}, year = {2025}, }
• (2025). Nanoscale flexing mechanism of a Metal–Organic framework determined by atomic force microscopy. JACS, 147(20), 17201--17208. (www)

  @article{ , abstract = {Flexible metal–organic frameworks (MOFs) are a unique set of compounds with applications in diverse areas. The nanoscale mechanism through which they flex is unproven. Herein, we use in situ atomic force microscopy to observe the crystal surface of Ga-MIL-53 MOF, [Ga(OH)(BDC)] ( 1 ) (BDC - 1, 4-benzenedicarboxylate) as it undergoes flexing transformations during the guest exchange between N,N-dimethylformamide (DMF) and ethanol (EtOH)-containing 1 . 1 ·0.96DMF undergoes a flexing expansion transformation on guest exchange to form 1 · x EtOH through the passage of wavefronts of cooperatively transforming, consecutive rows of unit cells parallel to the (011) plane, resulting in whole (011) layers of unit cells transforming by a layer-by-layer shear mechanism. The reverse process involves 1 · x EtOH undergoing a flexing contraction transformation on guest exchange to form 1 ·0.96DMF through a layer-by-layer shear mechanism involving layers of unit cells parallel to the (011̅) plane transforming in a cooperative manner. This proves a nanoscale mechanism through which a MOF can flex and the coexistence of phases with different degrees of expansion within a crystal, thus providing a missing link in the multilength scale understanding of MOF flexing transformations, which will support future design and application of flexible MOFs and other extended crystalline solids.}, archive = {J_JACS}, author = {Mollie Trueman and Rachel J. S. Pooley and A. R. Bonity J. Lutton-Gething and Avantika Hasija and George F. S. Whitehead and Sean J. O’Shea and Michael W. Anderson and Martin P. Attfield}, doi = {10.1021/jacs.5c02868}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17201--17208}, shortjournal = {J. Am. Chem. Soc.}, title = {Nanoscale flexing mechanism of a Metal–Organic framework determined by atomic force microscopy}, volume = {147}, year = {2025}, }
• (2025). Corrosion protection of rare earth for kilowatt-level alkaline seawater electrolyzer. JACS, 147(20), 17190--17200. (www)

  @article{ , abstract = {The competitive adsorption of Cl – caused by anode OH – consumption under high current density is an important factor restricting the development of an alkaline seawater electrolyzer (ASWE). Here, we propose a strategy for rare earth corrosion protection which utilizes oxygen friendly rare earths that do not participate in the reaction to adsorb OH – and maintain the surface environment for stable anodic catalysis in an ASWE. Differential electrochemical mass spectrometry (DEMS) and electrochemical quartz crystal microbalance (EQCM) were used to identify the causes of chlorine corrosion on the high current anode plate of traditional Ni mesh. In situ fluorescence spectra of N-ethoxycarbonylmethyl-6-methoxyquinolinium bromide (MQAE) labeled with a chloride ion fluorescence probe, a rotating ring disk electrode (RRDE), and a time-resolved absorption spectrum were used to test the recognition mechanism of rare earth. Eu 2 O 3 adsorbs OH – to maintain a high current pH environment and inhibits Cl – adsorption oxidation, thereby exhibiting stability for over 1000 h at 500 mA cm –2 current density. Furthermore, Eu 2 O 3 /FeNi 2 S 4 was assembled into a kilowatt-level ASWE in 17 chambers with a total area of 1081.5 cm 2 and operated stably for over 100 h at a current density of 500 mA cm –2 under industrial conditions of 80 °C and 30% KOH. Technical economic analysis (TEA) indicates that the rare earth corrosion protection strategy can enhance the service life of ASWE and reduce the cost of hydrogen production for profitable seawater hydrogen production, providing a new approach to solve the chlorine oxidation corrosion problem in an ASWE.}, archive = {J_JACS}, author = {Wei Shen and Yizhen Ye and Yang Hu and Huiying Wu and Qiujin Xia and Haodian Xie and Zijun Li and Nan Zhang and Li An and Rui Si and Pinxian Xi and Chun-Hua Yan}, doi = {10.1021/jacs.5c02876}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17190--17200}, shortjournal = {J. Am. Chem. Soc.}, title = {Corrosion protection of rare earth for kilowatt-level alkaline seawater electrolyzer}, volume = {147}, year = {2025}, }
• (2025). Non-stoichiometry governs the pathway from amorphous to crystalline calcium carbonate. JACS, 147(20), 17181--17189. (www)

  @article{ , abstract = {The controlled crystallization of calcium carbonate underlies the elaborate architectures of marine corals, the design of biomimetic materials, and the global carbon cycle. Despite its ubiquity, the chemical mechanisms that govern the crystallization of calcium carbonate from its amorphous precursor, amorphous calcium carbonate (ACC), remain elusive, largely due to the difficulty in resolving the structure and chemistry of this transient amorphous state. Here, we use time-lapse photography, image analysis, spatially resolved pH determination, in situ synchrotron pair distribution function (PDF) analysis, and dynamic nuclear polarization (DNP) solid-state nuclear magnetic resonance (NMR) spectroscopy to reveal pervasive compositional variability in ACC that underpins its metastability and crystallization. By evaluating the kinetics of the amorphous-to-crystalline transition across different solution chemistries, we demonstrate that ACC is non-stoichiometric and CO 3 -deficient. Counterions from the precursor (e.g., NO 3 – from Ca(NO 3 ) 2 ) substitute into the ACC network, displacing CO 3 ions and mediating both ACC stability and transformation. Crystallization proceeds through refinement of the stoichiometry toward CaCO 3 and uptake of free CO 3 2– anions. These findings are consistent across a wide range of concentrations and different carbonate sources, explaining the diverse behaviors observed for ACC and providing a chemical framework for controlling calcium carbonate crystallization.}, archive = {J_JACS}, author = {Michelle L. Beauvais and Bryan A. Sanchez Monserrate and Jiashan Mi and Aaron J. Rossini and John B. Parise and Karena W. Chapman}, doi = {10.1021/jacs.5c02800}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17181--17189}, shortjournal = {J. Am. Chem. Soc.}, title = {Non-stoichiometry governs the pathway from amorphous to crystalline calcium carbonate}, volume = {147}, year = {2025}, }
• (2025). Unraveling the nuclearity effect of atomically choreographed triatom cu3 clusters supported on zeolites. JACS, 147(20), 17170--17180. (www)

  @article{ , abstract = {A precise understanding of the structure–activity relationship of catalysts is crucial for catalysis research and is essential for rationalizing next-generation catalysts. As the size of catalysts decreases from nanometric to atomic dimensions, the focus on structure–activity relationship correlation has shifted from the “size effect” to the much more challenging “metal nuclearity effect”. However, precise synthesis and reliable characterization for structurally related solid atomic catalysts, such as single-, dual-, and triatom catalysts, still remain extremely challenging. Here, we present the controlled assembly of single-atomic Cu 1 , dual-atomic Cu 2 , and triatomic Cu 3 supported on zeolites through an innovative atomically choreographed approach. For the first time, we have directly visualized the atomic features of Cu 3 with respect to the zeolitic channels using double aberration-corrected scanning transmission electron microscopy (STEM). The structural and electronic properties of the catalysts have been characterized using synchrotron X-ray absorption spectroscopy, high-resolution synchrotron powder X-ray diffraction (PXRD), and density functional theory (DFT) calculations. We revealed the interplay among surface structures, adsorption configurations, catalytic reactivities (showing a significant 25-fold improvement), and product selectivity across structurally related species using a model methanol reforming reaction. We have successfully elucidated the relationship between the metal nuclearity effect and its activity and selectivity in a complex catalytic reaction. Our findings offer an unprecedented opportunity for the catalysis and materials community to finely manipulate the physicochemical properties of this category of solid atomic catalysts to achieve the desired reactivities and selectivities.}, archive = {J_JACS}, author = {Tianxiang Chen and Yunong Li and Ping-Luen Ho and Kwan Chee Leung and Jinjie Liu and Ching Kit Tommy Wun and Zehao Li and Chiu Chung Tang and Shogo Kawaguchi and Tai-Sing Wu and Yun-Liang Soo and Jun Yin and Shik Chi Edman Tsang and Tsz Woon Benedict Lo}, doi = {10.1021/jacs.5c02706}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17170--17180}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the nuclearity effect of atomically choreographed triatom cu3 clusters supported on zeolites}, volume = {147}, year = {2025}, }
• (2025). Catalyst-controlled site-selective and epimer-selective hydrogenations of thiostrepton. JACS, 147(20), 17161--17169. (www)

  @article{ , abstract = {The hydrogenation of the antibiotic thiostrepton with control over the site- and stereoselectivity of reduction is reported. Studies on model substrates designed to mimic aspects of the consecutive dimeric dehydroalanine (Dha) tail of thiostrepton first culminate in the development of an asymmetric hydrogenation method for a diverse set of bis(Dha) compounds. Monodentate phosphoramidite ligands (e.g., MonoPhos) are optimal and allow for selectivity of up to a 96:2:2:<1 ratio for doubly hydrogenated products. Subsequently, the protecting-group free, diastereomer-selective hydrogenation of the tail fragment of thiostrepton (Dha16 and Dha17) under mild conditions is presented with >80% selectivity for a single stereoisomer, relative to the sum of other detectable products. Opposite MonoPhos chirality results in alternative selectivity for the hydrogenated tail product, establishing ligand-controlled hydrogenation. The further study of ligands enabled hydrogenation of the internal dehydroalanine residue (Dha3), using sterically attenuated phosphoramidite ligands. Strikingly, ligand chirality dictates the stereochemical outcome at the sterically occluded Dha3, allowing for the synthesis of distinct stereoisomers, culminating in two distinct bis-hydrogenated isomers and two distinct tris-hydrogenated stereoisomers. Finally, hydrogenation with yet another phosphine ligand scaffold, a bidentate bisphosphine, results in the controlled formation of a single tetra-hydrogenated product. The structures and stereochemistry of the products are identified using multidimensional nuclear magnetic resonance methods, X-ray crystallography, and comparison to model substrates with confirmed absolute stereochemistry. The new thiostrepton derivatives are benchmarked for their antibiotic activity against representative antibiotic-resistant bacterial strains, revealing significant effects of Dha hydrogenation, and a number of new insights, most notably about the significance of Dha3 for antibiotic activity.}, archive = {J_JACS}, author = {Paul O. Peterson and Brandon Q. Mercado and Scott J. Miller}, doi = {10.1021/jacs.5c02720}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17161--17169}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalyst-controlled site-selective and epimer-selective hydrogenations of thiostrepton}, volume = {147}, year = {2025}, }
• (2025). Dynamic exciton polarons enabling dual-mode white-light emission with tunable color temperatures in 2D hybrid lead bromides. JACS, 147(20), 17152--17160. (www)

  @article{ , abstract = {White-light emission (WLE) with tunable chromaticity and correlated color temperature (CCT) is critical for lighting, display, and sensing applications. While recent two-dimensional (2D) lead halide perovskites have emerged as promising single-component WLE materials, their application is hindered by constrained and low CCT due to dominant localized exciton (LE) emission. Here, we report a dynamic exciton polaron mechanism in ⟨100⟩-oriented 2D lead bromides, (C n H 2 n +4 N 2 )PbBr 4 ( n = 5, 7, 9, 11), enabling intrinsic dual-mode WLE with widely tunable CCT. By combining ultrafast transient absorption spectroscopy and thermodynamic analyses, we reveal a double-well potential energy landscape driving the dynamic equilibrium between band-edge exciton (BE) and self-trapped LE states, and thus the formation of a dynamic exciton polaron. By elongating the ligand from n = 5 to 11, the self-trapping barrier decreases from 23.3 ± 1.3 to 10.1 ± 0.8 meV, and the trapping depth increases from 3.8 ± 0.4 to 14.7 ± 1.8 meV due to enhanced exciton–phonon coupling, which shifts the BE/LE emission ratio and tunes CCT from 21 000 K (bluish cold white) to 5100 K (reddish warm white). The dynamic exciton polaron with correlated BE and LE exhibits matched radiative lifetimes, ensuring stable dual-mode WLE without spectral distortion. Our work establishes that the dynamic exciton polaron, combined with ligand engineering, acts as a general principle for designing single-component multimode WLE materials with tailored chromatic properties, advancing their potential in efficient lighting and multifunctional optoelectronics.}, archive = {J_JACS}, author = {Yao Zhang and Yuhang Feng and Caiwei Zhang and Guohua He and Jinyang Yu and Haiming Zhu}, doi = {10.1021/jacs.5c02446}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17152--17160}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic exciton polarons enabling dual-mode white-light emission with tunable color temperatures in 2D hybrid lead bromides}, volume = {147}, year = {2025}, }
• (2025). Regulate ion transport in subnanochannel membranes by ion-pairing. JACS, 147(20), 17144--17151. (www)

  @article{ , abstract = {The ability of biological ion channels to respond to environmental stimuli, regulate ion permeation rates, and selectively transport specific ions is essential for sustaining physiological functions and holds immense potential for various practical applications. In this study, we report a highly selective ion separation membrane capable of responding to ionic stimuli, thereby regulating the permeation rate of the target ions. This membrane is constructed from two-dimensional MXene nanosheets functionalized with γ-poly(glutamic acid) (γ-PGA) molecules. Its biomimetic ion channel structure provides spatial confinements, as well as ion recognition and response sites. Remarkably, the membrane demonstrates the ability to respond to stimulus ions, achieving regulation of target ion permeation rates by over 2 orders of magnitude and achieving a K + /Mg 2+ selectivity exceeding 10. 3 Unlike traditional nanochannel membranes, where ion transport is predominantly driven by ion-channel interactions, this membrane operates through an ion–ion interaction-dominated mechanism. The introduction of stimulus ions dynamically alters ion-pair formation within the subnanochannels, thereby modulating the permeation rates of target ions. This study provides a fresh perspective on ion transport mechanisms in nanoconfined environments, reflecting conditions closer to those in real-world systems. It underscores the pivotal role of ion–ion interactions in regulating ion transport and offers valuable insights into the design of next-generation ion separation membranes with tailored responsiveness.}, archive = {J_JACS}, author = {Rongming Xu and Hang Yu and Jiachun Ren and Weiming Zhang and Yuan Kang and Zhuyuan Wang and Fan Feng and Xiaoli Xia and Jefferson Zhe Liu and Luming Peng and Xiwang Zhang and Bingcai Pan}, doi = {10.1021/jacs.5c02722}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17144--17151}, shortjournal = {J. Am. Chem. Soc.}, title = {Regulate ion transport in subnanochannel membranes by ion-pairing}, volume = {147}, year = {2025}, }
• (2025). Molecular and structural characterization of a chalcone di-C-methyltransferase RdCMT from rhododendron dauricum and its application in de novo biosynthesis of farrerol in pichia pastoris. JACS, 147(20), 17132--17143. (www)

  @article{ , abstract = {Methylation plays a crucial role in drug design and optimization. While numerous methyltransferases have been characterized from plants, C -methyltransferases, particularly those targeting phenolic skeletons, are rare. In this study, we identified a novel di- C -methyltransferase RdCMT from the medicinal plant Rhododendron dauricum . RdCMT catalyzes a sequential two-step 3′- C /5′- C -methylation of naringenin chalcone, leading to the biosynthesis of farrerol. RdCMT exhibited a strict substrate specificity for chalcones. Through combinatorial catalysis, a series of C -methylated flavonoids were synthesized. Moreover, farrerol was synthesized de novo in Nicotiana benthamiana and Pichia pastoris with yields of 0.4 mg/g (dry weight) and 149.0 mg/L, respectively. The structure of RdCMT was determined using cryo-electron microscopy (cryo-EM), revealing that residues R328 and G296 significantly influence the substrate specificity of RdCMT. This work not only introduces a potent biocatalyst for the preparation of C -methylated flavonoids but also offers insights into the catalytic mechanisms of C -methyltransferases.}, archive = {J_JACS}, author = {Meng Zhang and Yang-oujie Bao and Zonglin Dai and Zhilan Qian and Haishuang Yu and Jia-jing Zhou and Yi Chen and Zilong Wang and Kaituo Wang and Menghao Cai and Min Ye}, doi = {10.1021/jacs.5c02654}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17132--17143}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular and structural characterization of a chalcone di-C-methyltransferase RdCMT from rhododendron dauricum and its application in de novo biosynthesis of farrerol in pichia pastoris}, volume = {147}, year = {2025}, }
• (2025). Real-time recording the dynamic catalytic heterogeneity of enzymatic reactions using a nanopore. JACS, 147(20), 17121--17131. (www)

  @article{ , abstract = {Enzymatic reactions in cells control the diversity of biomolecular composition, structure, and function, by virtue of their dynamics and heterogeneity. Here, we describe the use of a protein nanopore to monitor, in real time, the action of Exonuclease I (Exo I) on its substrate (homogeneous and heterogeneous short single-stranded DNA, ssDNA) on a single-reactant molecule basis. The nanopore-based single-molecule measurement, combined with a transition kinetic analysis, determines the temporal dynamics and heterogeneous cleavage and release pathways of ssDNA by Exo I. The results demonstrate a stepwise cleavage that is sequence-dependent on short ssDNA molecules (<15 nt), which differs from the kinetic model based on bulk measurements. In addition, we show that damaged DNA irreversibly changes the enzymatic reaction processes by Exo I. Thus, nanopores might prove to be useful for studying multienzyme cascade reactions at the single-molecule level.}, archive = {J_JACS}, author = {Meng-Yin Li and Hongyan Niu and Jie Jiang and Xue-Yuan Wu and Yi-Lun Ying and Yi-Tao Long}, doi = {10.1021/jacs.5c02535}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17121--17131}, shortjournal = {J. Am. Chem. Soc.}, title = {Real-time recording the dynamic catalytic heterogeneity of enzymatic reactions using a nanopore}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic H2O2 production with >30% quantum efficiency via monovalent copper dynamics. JACS, 147(20), 17112--17120. (www)

  @article{ , abstract = {Photocatalytic O 2 reduction to H 2 O 2 is a green and promising technology with advantages in cost-effectiveness, sustainability, and environmental friendliness, but its efficiency is constrained by limited selectivity for the two-electron oxygen reduction reaction (ORR) pathway. Here, we anchored isolated Cu atoms with tunable oxidation states onto WO 3 as effective active centers to enhance photocatalytic H 2 O 2 production. Due to the charge compensation between single atoms and the support, the oxidation state of Cu species exhibited a loading-dependent transition between +2 and +1 valence. Experimental and theoretical analyses indicate that Cu(I) sites exhibit outstanding O 2 adsorption and activation capabilities, transforming the thermodynamically unfavorable hydrogenation of the *OOH intermediate (the rate-determining step in the two-electron ORR pathway) into an exothermic process, thereby significantly improving selectivity and efficiency. The Cu(I)-SA/WO 3 photocatalyst exhibited a H 2 O 2 production rate of 102 μmol h –1 under visible light irradiation, much higher than other reported photocatalysts. More importantly, it achieves an impressive apparent quantum efficiency of 30% at 420 nm, making a significant breakthrough in this field. This work provides novel perspectives for designing single-atom catalysts for efficient H 2 O 2 synthesis via electronic state modulation.}, archive = {J_JACS}, author = {Fan Yang and Chengyang Feng and Shouwei Zuo and Qingxiao Wang and Fen Wei and Miao Hu and Yuanfu Ren and Dongzhi Liu and Wan-Lu Li and Sibo Wang and Hassan S. Alqahtani and Yun Hau Ng and Huabin Zhang}, doi = {10.1021/jacs.5c02450}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17112--17120}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic H2O2 production with >30% quantum efficiency via monovalent copper dynamics}, volume = {147}, year = {2025}, }
• (2025). Inverted microdroplets (Microbubbles) induced interfacial water protonation to promote alkaline release of amine and reduce energy in CCS. JACS, 147(20), 17101--17111. (www)

  @article{ , abstract = {This study engineered a superacidic interface with a pronounced polar electric field within the amine-water system by inducing hydrogen bond charge transfer in interfacial water via inverted microdroplets (microbubbles), thereby stabilizing protons within the interfacial water layer. This mechanism enabled the continuous alkaline release of hindered amines (AMP-MIS), enhancing CO 2 absorption load capacity and reducing regeneration energy consumption. Nuclear magnetic resonance and potentiometric titration elucidated the product distribution, while Raman spectroscopy, pH analysis, and conductivity measurements confirmed proton stabilization. Theoretical calculations provided insights into the reaction mechanism. Pilot-scale testing revealed the AMP-MIS system achieved a 74.2% increase in CO 2 cyclic load capacity, surpassing the conventional 30 wt % MEA system, with regeneration energy reduced from 3.667 GJ/t CO 2 to 1.885 GJ/t CO 2 . This innovative strategy offers valuable guidance for advancing amine-based decarbonization technologies and reducing carbon emissions in the power industry, representing a pivotal step toward carbon neutrality.}, archive = {J_JACS}, author = {Yuewei Fan and Chen Lu and Haoyu Meng and Feng Zhang and Lei Li and Zhibing Zhang and Yi Chen}, doi = {10.1021/jacs.5c02240}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17101--17111}, shortjournal = {J. Am. Chem. Soc.}, title = {Inverted microdroplets (Microbubbles) induced interfacial water protonation to promote alkaline release of amine and reduce energy in CCS}, volume = {147}, year = {2025}, }
• (2025). Conformational plasticity in dsRNA-binding domains drives functional divergence in RNA recognition. JACS, 147(20), 17088--17100. (www)

  @article{ , abstract = {The functional specificity of proteins is often attributed to their sequence and structural homology while frequently neglecting the underlying conformational dynamics occurring at different time scales that can profoundly impact biological consequences. Using 15 N-CEST NMR and RDC-corrected metainference molecular dynamics simulations, here, we reveal differential substrate recognition mechanisms in two dsRNA-binding domain (dsRBD) paralogs, DRB2D1 and DRB3D1. Despite their nearly identical solution structures and conserved dsRNA interaction interfaces, DRB3D1 demonstrates structural plasticity that enables it to recognize conformationally flexible dsRNA, a feature notably absent in the more rigid DRB2D1. We present the pivotal role of intrinsic structural dynamics in driving functional divergence and provide insights into the mechanisms that govern specificity in dsRBD:dsRNA interactions. Importantly, our combined experimental and computational approach captures a cluster of intermediate conformations, complementing conventional methods to resolve the dominant ground state and sparsely populated excited states.}, archive = {J_JACS}, author = {Debadutta Patra and Jaydeep Paul and Upasana Rai and Aravind P. S. and Mandar V. Deshmukh}, doi = {10.1021/jacs.5c02057}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17088--17100}, shortjournal = {J. Am. Chem. Soc.}, title = {Conformational plasticity in dsRNA-binding domains drives functional divergence in RNA recognition}, volume = {147}, year = {2025}, }
• (2025). Three-dimensional atomic-level structure of an amorphous glucagon-like peptide-1 receptor agonist. JACS, 147(20), 17077--17087. (www)

  @article{ , abstract = {Amorphous formulations are increasingly used in the pharmaceutical industry due to their increased solubility, but their structural characterization at atomic-level resolution remains extremely challenging. Here, we characterize the complete atomic-level structure of an amorphous glucagon-like peptide-1 receptor (GLP-1R) agonist using chemical shift driven NMR crystallography. The structure is determined from measured chemical shift distributions for 17 of the 32 carbon atoms and 16 of the 31 hydrogen atoms in the molecule. The chemical shifts are able to provide a detailed picture of the atomic-level conformations and interactions, and we identify the structural motifs that play a major role in stabilization of the amorphous form. In particular, hydrogen bonding of the carboxylic acid proton is strongly promoted, although no carboxylic acid dimer is formed. Two orientations of the benzodioxole ring are promoted in the NMR structure, corresponding to a significant stabilization mechanism. Our observation that inclusion of water leads to stabilization of the carboxylic acid group might be used as a strategy in future formulations where hydrogen bonding between neighboring molecules may otherwise be hindered by sterics.}, archive = {J_JACS}, author = {Daria Torodii and Manuel Cordova and Jacob B. Holmes and Pinelopi Moutzouri and Tommaso Casalini and Sten O. Nilsson Lill and Arthur C. Pinon and Christopher S. Knee and Anna Svensk Ankarberg and Okky Dwichandra Putra and Staffan Schantz and Lyndon Emsley}, doi = {10.1021/jacs.5c01925}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17077--17087}, shortjournal = {J. Am. Chem. Soc.}, title = {Three-dimensional atomic-level structure of an amorphous glucagon-like peptide-1 receptor agonist}, volume = {147}, year = {2025}, }
• (2025). Direct observation of a fundamental arylium species using photoelectron spectroscopy: Singlet–Triplet gap in phenylium. JACS, 147(20), 17068--17076. (www)

  @article{ , abstract = {Reactive intermediates such as aryl cations play crucial roles in organic and astrochemical processes, yet their characterization remains a significant experimental challenge. The present study offers the first partially vibrationally resolved photoelectron spectrum of the phenyl radical (C 6 H 5 ), focusing on ionization thresholds to the lowest singlet and triplet states of its cation. Using synchrotron-based photoelectron spectroscopy, we directly determine the adiabatic ionization energy of the first triplet state of phenylium (C 6 H 5 + , IE ad (ã + ← X̃) = 9.300(10) eV), and use this as an anchor to derive the singlet-triplet energy gap (Δ E (S–T) = 1.043(32) eV) with assistance from advanced quantum chemical computations. These findings provide new constraints to thermochemical properties essential in arylium ground state determination (and thus essential for a better understanding of arylium chemistry), and establish a framework for future joint spectroscopic-computational studies of more complex arylium compounds.}, archive = {J_JACS}, author = {Megan R. Bentley and Ugo Jacovella and Jean-Christophe Loison and Myriam Drissi and Gustavo A. Garcia and Séverine Boyé-Péronne and Peter R. Franke and John F. Stanton and Bérenger Gans}, doi = {10.1021/jacs.5c01851}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17068--17076}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct observation of a fundamental arylium species using photoelectron spectroscopy: Singlet–Triplet gap in phenylium}, volume = {147}, year = {2025}, }
• (2025). Catalysis-assisted synthesis of two-dimensional conductive Metal–Organic framework films with controllable orientation. JACS, 147(20), 17058--17067. (www)

  @article{ , abstract = {The facile preparation of two-dimensional (2D) conductive metal–organic framework (MOF) films with controllable orientation and thickness greatly facilitates the further structure–property investigation and performance optimization in their applications. Here, we report a catalysis-assisted synthesis strategy to the rapid production of oriented films of catechol-based (Cu 3 (HHTP) 2 , Zn 3 (HHTP) 2 , and Cu 2 TBA) and diamine-based (Ni 3 (HITP) 2 ) 2D conductive MOFs with thicknesses adjustable from tens of nanometers to several micrometers. Relying on the utilization of a 0.3 nm Pt layer, which can be conveniently predecorated on a substrate surface via evaporating deposition or sputtering, as a catalyst for the aerobic oxidation of the redox-active ligands to trigger the formation of 2D conductive MOFs, this strategy is compatible with a majority of commonly used substrates and capable of producing patterned films with feature sizes ranging from micrometers to centimeters. Investigation on the growth kinetics of Cu 3 (HHTP) 2 indicates that the preferential growth along the c -axis or in the ab -basal plane of its crystallites can be flexibly tuned by the formation reaction kinetics to guide the evolution of films with the face-on or edge-on orientation. The chemiresistive device incorporating the face-on Cu 3 (HHTP) 2 film presents a high response (197%) and a fast respond speed (27 s) toward NH 3 (30 ppm) at room temperature, which are superior not only to its edge-on counterpart (90% and 69 s, correspondingly) but also to other reported Cu 3 (HHTP) 2 -based sensors.}, archive = {J_JACS}, author = {Min Song and Yixuan Wu and Jingjing Jia and Jiahao Peng and Yixiao Ren and Jingtian Cheng and Yulong Xu and Wuyan Liu and Shuilong Kang and Yuan Fang and Lizhen Huang and Long Chen and Lifeng Chi and Guang Lu}, doi = {10.1021/jacs.5c01881}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17058--17067}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalysis-assisted synthesis of two-dimensional conductive Metal–Organic framework films with controllable orientation}, volume = {147}, year = {2025}, }
• (2025). Regioselective dehydrogenation coupling via out-of-plane flipping on metal surfaces. JACS, 147(20), 17049--17057. (www)

  @article{ , abstract = {Selective dehydrogenation coupling plays a vital role in on-surface synthesis for achieving high-yield target nanostructures. Most dehydrogenation reactions are based on in-plane movement-induced reactant coupling, while the feasibility and selectivity of reactant cyclodehydrogenation through out-of-plane flipping have rarely been explored. Here, we report a regioselective dehydrogenation coupling reaction achieved through reactant flipping on two-dimensionally confined metal substrates. The yields of target reactants obtained by out-of-plane flipping of three benzofluoranthrene derivatives with different masses on the Au(111) surface are higher than 99%. By combining scanning tunneling microscope characterization and density functional theory calculations, we visualize the reaction process of reactant flipping and cyclization. By comparing the results on Au(111) with those on Ag(111) and Cu(111), we summarize that the main factors determining the out-of-plane flipping-induced cyclodehydrogenation reaction of benzofluoranthrene derivatives on a metal surface are their own mass and the interaction with the underlying substrate. Our work provides a new strategy for achieving regioselective surface dehydrogenation coupling reactions and offers a new research paradigm for the synthesis of conjugated carbon nanostructures.}, archive = {J_JACS}, author = {Yong Zhang and Jianchen Lu and Hangjing Zhou and Qingyan Li and Zilin Ruan and Yi Zhang and Gefei Niu and Boyu Fu and Shicheng Li and Yuhang Yang and Xin-Jing Zhao and Lei Gao and Yuan-Zhi Tan and Jinming Cai}, doi = {10.1021/jacs.5c01783}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17049--17057}, shortjournal = {J. Am. Chem. Soc.}, title = {Regioselective dehydrogenation coupling via out-of-plane flipping on metal surfaces}, volume = {147}, year = {2025}, }
• (2025). Simultaneous capture of N2O and CO2 from a N2O/N2/CO2/O2 mixture with a Ni(II)-pyrazolecarboxylate framework. JACS, 147(20), 17042--17048. (www)

  @article{ , abstract = {Nitrous oxide (N 2 O) is a potent greenhouse gas and a major contributor to ozone depletion. Its primary industrial emission source is tail gas from adipic acid production, which typically comprises a mixture of N 2 O, CO 2 , N 2 , and O 2 . Current technologies for the removal of N 2 O and CO 2 from tail gas are energy-intensive and operationally complex. Herein, for the first time, simultaneous capture of N 2 O and CO 2 from the quaternary mixture is achieved using a Ni(II)-pyrazolecarboxylate framework, BUT-167. This material demonstrated an exceptional adsorption capacity (135.8 cm 3 cm –3 at 40 kPa) and a high packing density (790 mg cm –3 ) for N 2 O, outperforming reported sorbents. Moreover, BUT-167 also exhibits a remarkable CO 2 adsorption capacity (101.5 cm 3 cm –3 at 4 kPa), achieving simultaneously high selectivity values of 257.6 for CO 2 /N 2 (4:96, v/v) and 135.7 for N 2 O/N 2 (40/60). Importantly, BUT-167 exhibits robust and outstanding dual-gas removal performance across multiple adsorption–desorption breakthrough cycles under both dry and humid conditions. The strong affinity toward CO 2 and N 2 O could be attributed to multiple hydrogen bonding interactions facilitated by its highly confined channel structure, as confirmed through single-crystal X-ray diffraction analysis.}, archive = {J_JACS}, author = {Xin Zhang and Muzi Li and Yan-long Zhao and Xiang-Yu Li and Yu Fang and Lin-Hua Xie and Jian-Rong Li}, doi = {10.1021/jacs.5c01676}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17042--17048}, shortjournal = {J. Am. Chem. Soc.}, title = {Simultaneous capture of N2O and CO2 from a N2O/N2/CO2/O2 mixture with a Ni(II)-pyrazolecarboxylate framework}, volume = {147}, year = {2025}, }
• (2025). Polyethyleneketones with controlled spacer units: Synthesis, characterization, and photodegradation. JACS, 147(20), 17034--17041. (www)

  @article{ , abstract = {In this study, a new synthetic method for structurally controlled polyethyleneketones, a photodegradable polyethylene-like polymer, has been developed. Telechelic Zn-polyethylene was prepared from α,ω-diene, diethylzinc, and ethylene, which was allowed to react with diacid chlorides to give polyethyleneketones with defined spacing between the neighboring ketone functionalities. The photodegradation of these polymers under UV light demonstrated a degradation rate dependency on the spacer units between the carbonyl groups. The ones with longer-spaced ketones (6–18 carbons) showed efficient degradation, while shorter-spaced ketones (3–5 carbons) exhibited a slower degradation process. Structural analysis by solid-state FT-IR and DSC suggested the existence of carbonyl–carbonyl interactions in the shorter-spaced polymers, which are presumed to interfere with photodegradation via the Norrish reaction.}, archive = {J_JACS}, author = {Matthias Nobis and Kohei Takahashi and Junya Uchida and Shintaro Nakagawa and Naoko Yoshie and Takashi Kato and Kyoko Nozaki}, doi = {10.1021/jacs.5c01664}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17034--17041}, shortjournal = {J. Am. Chem. Soc.}, title = {Polyethyleneketones with controlled spacer units: Synthesis, characterization, and photodegradation}, volume = {147}, year = {2025}, }
• (2025). Osmotic pressure induced morphological transformation of membranized coacervates. JACS, 147(20), 17022--17033. (www)

  @article{ , abstract = {The stimulus-response behavior of protocells under environmental osmotic pressure changes has long been a subject of scientific inquiry. Herein, we demonstrate a way to membranized coacervate microdroplets based on cholesterol anchoring of phospholipids, which provides enhanced stability, enabling morphological transformations instead of dissociation during subsequent osmotic pressure changes. In hypotonic environments, these membranized coacervates equilibrate osmotic pressure through transient internal vacuole formation, concomitant with a transmembrane substrate influx that triggers enzymatic reaction acceleration. By contrast, in a hypertonic environment, the membranized coacervate responds with bursting-like deformation that can then quickly recover due to the anchoring effect of cholesterol on phospholipids. Notably, it is found that such bursting-like deformation could even successfully induce endocytosis of Staphylococcus aureus by the membranized coacervates. Furthermore, through the integration of Coa@DMPC’s osmotic responsiveness, internal actin polymerization activated by the endocytic S. aureus is achieved. Not only our proposed method of phospholipid membranization of the coacervate could contribute a new model to mimic more complex bionic structures, but also the revealed morphological response behavior of the membranized coacervate under various osmotic pressure changes is expected to help explain the stress behaviors and emerging unique properties of cells in similar environments.}, archive = {J_JACS}, author = {Xin Qiao and Xiaoliang Wang and Haixu Chen and Yan Huang and Shangsong Li and Luxuan Li and Xin Huang}, doi = {10.1021/jacs.5c01581}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17022--17033}, shortjournal = {J. Am. Chem. Soc.}, title = {Osmotic pressure induced morphological transformation of membranized coacervates}, volume = {147}, year = {2025}, }
• (2025). Bioactive assembly cofactor-assisted ursolic acid helix for enhanced anticancer efficacy via in situ virus-like transition. JACS, 147(20), 17010--17021. (www)

  @article{ , abstract = {Natural bioactive pentacyclic triterpenoids, such as ursolic acid (UA), hold significant potential as anticancer agents. However, their clinical application is limited by their poor solubility and bioavailability. Herein, we developed a novel polypeptoid assembly cofactor-assisted nanoplatform designed to enhance UA’s therapeutic efficacy through in situ self-assembly within the tumor microenvironment (TME). Bioactive polypeptoid polyelectrolytes, inspired by natural molecular chaperones, were utilized as assembly cofactors to guide UA’s co-assembly into stimuli-responsive nanostructures. These polypeptoids provide precise control over the assembly process, improving stability and enabling reversible, pH-responsive transformations. Acid-responsive groups and the target molecule lactobionic acid further promote the specificity and efficacy of UA delivery. Under neutral conditions, the assemblies retain a helical fibrous structure, while in the acidic TME, they transform into virus-like clusters composed of assembly subunits, facilitating deeper tumor penetration. Once internalized, these nanoparticles escape into the cytoplasm and accumulate around the mitochondria, where the oxidation of thioether bonds triggers the release of UA and polypeptoids, causing mitochondrial damage and apoptosis. Some nanoparticles reassemble into fibrous structures intracellularly, extending their retention in tumor cells and potentially leading to mitochondria damage. Notably, the nanoplatform demonstrates excellent synergistic effects, achieving significantly higher therapeutic efficiency compared with individual components, including UA and polypeptoids. In vivo studies further confirmed the effectiveness, demonstrating significant tumor growth suppression and reduced metastasis. By integrating the therapeutic UA with bioactive polypeptoids under precise control, this synergistic platform represents a highly efficient and targeted approach to cancer therapy, offering a promising new opportunity for natural compounds for advanced nanomedicine.}, archive = {J_JACS}, author = {Min Lin and Dandan Liu and Yiyu Gong and Lilei Shu and Helin Wang and Guojing Zhang and Jiayi Li and Zixin Gao and Jing Sun and Xuesi Chen}, doi = {10.1021/jacs.5c01214}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17010--17021}, shortjournal = {J. Am. Chem. Soc.}, title = {Bioactive assembly cofactor-assisted ursolic acid helix for enhanced anticancer efficacy via in situ virus-like transition}, volume = {147}, year = {2025}, }
• (2025). Quantum tunneling fingerprints of chirality-induced symmetry preferences in methyl lactate dimer. JACS, 147(20), 17002--17009. (www)

  @article{ , abstract = {Methyl lactate, a chiral molecule with multiple functional groups, has played a pivotal role in advancing experimental and theoretical chiroptical methods. Leveraging conformer-specific jet-cooled rotational spectroscopy in tandem with extensive conformational searches and quantum chemical calculations, we investigated chirality self-recognition in the methyl lactate dimer. The experimental fingerprint-like spectral patterns, including methyl rotor tunneling splittings, allowed the definite identification of one heterochiral and two homochiral binary conformers from a large number of low-energy candidates. Nuclear spin statistics analyses and methyl internal rotor parameters reveal different nuclear tunneling dynamics in the homochiral versus heterochiral environments and highlight the associated chirality-driven symmetry preference in the observed conformers. The results provide comprehensive experimental data for benchmarking quantum chemical calculations of chiral properties and pave the way for the exploration of this prototypical dimer across different frequency ranges using other spectroscopic tools.}, archive = {J_JACS}, author = {Jiarui Ma and Aran Insausti and Wolfgang Jäger and Yunjie Xu}, doi = {10.1021/jacs.5c01184}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {17002--17009}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantum tunneling fingerprints of chirality-induced symmetry preferences in methyl lactate dimer}, volume = {147}, year = {2025}, }
• (2025). Oriented naphthalene-O-propylammonium-based (NOP)4AuBIIII8 (B = au, bi, sb) Ruddlesden–Popper two-dimensional gold double perovskite thin films featuring high charge-carrier mobility. JACS, 147(20), 16992--17001. (www)

  @article{ , abstract = {Two-dimensional perovskites show intriguing optoelectronic properties due to their anisotropic structure and multiple quantum well structure. Here, we report the first three gold-based Ruddlesden–Popper type two-dimensional double perovskites with a general formula (NOP) 4 Au I B III I 8 ( B = Au, Bi, Sb) employing naphthalene- O -propylammonium (NOP) as an organic cation. They were found to form highly crystalline thin films on various substrates, predominantly oriented in the [001] direction featuring continuous, crack-free film areas on the μm 2 scale. The thin films show strong optical absorption in the visible region, with band gap energies between 1.48 and 2.32 eV. Density functional theory calculations support the experimentally obtained band gap energies and predict high charge-carrier mobilities and effective charge separation. A comprehensive study with time-resolved microwave conductivity (TRMC) and optical-pump-THz-probe (OPTP) spectroscopy revealed high charge-carrier mobilities for lead-free two-dimensional perovskites of 4.0 ± 0.2 cm 2 (V s) −1 and charge-carrier lifetimes in the range of μs. Photoconductivity measurements under 1 sun illumination demonstrated the material’s application as a photodetector, showing a 2-fold increase in conductivity when exposed to light.}, archive = {J_JACS}, author = {Florian Wolf and Thanh Chau and Dan Han and Kieran B. Spooner and Marcello Righetto and Patrick Dörflinger and Shizhe Wang and Roman Guntermann and Rik Hooijer and David O. Scanlon and Hubert Ebert and Vladimir Dyakonov and Laura M. Herz and Thomas Bein}, doi = {10.1021/jacs.5c01102}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16992--17001}, shortjournal = {J. Am. Chem. Soc.}, title = {Oriented naphthalene-O-propylammonium-based (NOP)4AuBIIII8 (B = au, bi, sb) Ruddlesden–Popper two-dimensional gold double perovskite thin films featuring high charge-carrier mobility}, volume = {147}, year = {2025}, }
• (2025). Glycan-modified cellular nanosponges for enhanced treatment of cholera toxin-induced secretory diarrhea. JACS, 147(20), 16982--16991. (www)

  @article{ , abstract = {Cholera is a severe infectious disease caused by the Gram-negative bacterium Vibrio cholerae after colonization in the intestinal tract. Cholera toxin (CT), a key exotoxin protein, primarily causes acute secretory diarrhea and life-threatening complications in infected patients. Traditional approaches remain insufficient for effectively treating cholera, underscoring the need for innovative countermeasures to eliminate CT-caused symptoms. Here, we report a glycan-modified cellular nanosponge for the enhanced treatment of CT-induced secretory diarrhea. Specifically, intestinal epithelial cell membrane-camouflaged nanosponges are functionalized with a glycan receptor to promote their capability for CT neutralization, thereby competitively inhibiting CT entry into host cells. Moreover, an inhibitor is encapsulated into the cellular nanosponge to synergistically improve the therapeutic effect of diarrhea by blocking the excessive chloride ion efflux from the cystic fibrosis transmembrane conductance regulator (a crucial anion channel) on the membrane of CT-intoxicated epithelial cells. Upon oral administration, the biomimetic nanomedicine effectively eliminates CT-induced secretory diarrhea and intestinal injuries in mice. Overall, this study highlights the potential of glycan-modified cellular nanosponges as promising and broad-spectrum therapeutic agents against secretory diarrhea caused by bacterial exotoxins.}, archive = {J_JACS}, author = {Tianzhen Han and Wangyang Zhu and Rong Xu and Seok Theng Chiang and Xuefeng Jin and Xiaoshuai Shen and Chunxi Qian and Guangyu Yang and Rongxiu Li and Xiangzhao Ai}, doi = {10.1021/jacs.5c00955}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16982--16991}, shortjournal = {J. Am. Chem. Soc.}, title = {Glycan-modified cellular nanosponges for enhanced treatment of cholera toxin-induced secretory diarrhea}, volume = {147}, year = {2025}, }
• (2025). A robust single-molecule diode with high rectification ratio and integrability. JACS, 147(20), 16972--16981. (www)

  @article{ , abstract = {Advancements in molecular electronics focus on single molecules as key components to create stable and functional devices that meet the requirements of device miniaturization and molecular function exploration. However, as the pioneering concept of a molecular diode, all single-molecule rectifiers reported previously are limited by their modest rectification ratios, owing to electron transmission in the off-state, highlighting the imperative for performance enhancements. Here, we demonstrate a unique method capable of realizing a stable and reproducible high-performance single-molecule rectifier through the strategic application of an electric-field-catalyzed Fries rearrangement. This flexible reaction enables the exquisite control of reversible conductance switching between a structure with constructive quantum interference and a structure with destructive quantum interference, therefore leading to an exceptional rectification ratio of up to 5000 at a bias of 1.0 V, which ranks the highest among the rectifiers constructed by only one individual molecule. The stable operation of nearly 100 devices at high temperatures demonstrates reproducibility. Moreover, on-chip integration of different single-molecule rectifiers succeeds in achieving half-wave and bridge rectifications, thus facilitating efficient alternating current-to-direct current conversions. This convenient strategy of electric-field-catalyzed quantum interference switching potentially revolutionizes device efficiency and miniaturization in nanotechnology, laying an actual step toward future practical integrated molecular-scale electronic nanocircuits.}, archive = {J_JACS}, author = {Yilin Guo and Chen Yang and Shuyao Zhou and Kendall N. Houk and Xuefeng Guo}, doi = {10.1021/jacs.5c00566}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16972--16981}, shortjournal = {J. Am. Chem. Soc.}, title = {A robust single-molecule diode with high rectification ratio and integrability}, volume = {147}, year = {2025}, }
• (2025). Role of spectator species for amine-surface chemistry: Reactions of amines and alkenes on pt(111). JACS, 147(20), 16964--16971. (www)

  @article{ , abstract = {This study investigates the roles of ethylene and ethylidyne in the surface chemistry of N -methylaniline (NMA) on Pt(111). Using X-ray photoelectron spectroscopy, temperature-programmed desorption, and density functional theory calculations, we demonstrate that ethylidyne is not merely a passive spectator species but actively contributes to hydroamination. It facilitates C–N bond formation by transferring a methyl group to NMA, leading to the formation of N , N -dimethylaniline. Additionally, it stabilizes reaction intermediates and suppresses the decomposition of NMA. This works demonstrates, in contrast to the widely accepted notion, that ethylidyne is not just an inert spectator species; rather, it plays a dual role as both an active reaction partner and a stabilizer. In addition, the coadsorption of ethylene on an NMA-precovered surface shows a side reaction of ethylene with the decomposition products of NMA.}, archive = {J_JACS}, author = {Nils Brinkmann and Dave Austin and Bushra Ashraf and Duy Le and Talat S. Rahman and Katharina Al-Shamery}, doi = {10.1021/jacs.5c00567}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16964--16971}, shortjournal = {J. Am. Chem. Soc.}, title = {Role of spectator species for amine-surface chemistry: Reactions of amines and alkenes on pt(111)}, volume = {147}, year = {2025}, }
• (2025). Leveraging quantum chemistry and machine learning for the design of low-valent transition metal catalysts in nitrogen to ammonia conversion. JACS, 147(20), 16948--16963. (www)

  @article{ , abstract = {The conversion of N 2 to NH 3 under ambient conditions is a major goal in sustainable chemistry. Homogeneous catalysts, particularly those employing cyclic(alkyl)(amino)carbene (CAAC) ligands, have demonstrated promise in stabilizing low-valent Fe centers, yet industrial-level turnover numbers (TONs) and frequencies (TOFs) remain unmet. Here, we integrate quantum chemistry, molecular dynamics, and machine learning (ML) to uncover mechanistic features governing nitrogen reduction reaction (NRR) activity and guide catalyst design. Density functional theory (DFT) and ab initio molecular dynamics reveal that [Fe(CAAC) 2 ] leverages redox noninnocent CAAC ligands to stabilize Fe(I) ([Fe I (CAAC) 2 ·– ]), with strong antiferromagnetic coupling ( J Fe-CAAC = −1817 cm –1 ). Flexibility of bulky Dipp groups found to hinder N 2 binding, rationalizing experimental observations. The exothermic formation of [(CAAC(H)) 2 Fe] (Δ G = −4.5 kJ/mol) with in situ generated H 2 exposure rationalizes the lower TON observed via catalyst deactivation. ML models trained on quantum descriptors such as M–C bond lengths, spin density, and frontier orbital energies identify the M–C distance as a key predictor of reactivity. A composite free energy metric ( Δ G tot ) encompassing cis-trans isomerization ( Δ G 1 0 ), N 2 binding ( Δ G 2 0 ), and the first reduction step ( Δ G 3 0 ) enables ranking of candidate catalysts. Moreover, Ti and V complexes show the lowest Δ G tot (24–60 kJ/mol), while late transition and coinage metals exceed 120 kJ/mol, correlating with lower activity. By providing unprecedented insights into the interplay among ligand design, metal choice, and catalytic efficiency, this work lays a critical foundation for the rational design of homogeneous NRR catalysts, with implications for advancing sustainable ammonia production technologies.}, archive = {J_JACS}, author = {Chandrasekhar Nettem and Ankit Mondal and Gopalan Rajaraman}, doi = {10.1021/jacs.5c00099}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16948--16963}, shortjournal = {J. Am. Chem. Soc.}, title = {Leveraging quantum chemistry and machine learning for the design of low-valent transition metal catalysts in nitrogen to ammonia conversion}, volume = {147}, year = {2025}, }
• (2025). Atomic-level insights into cation-mediated mechanism in electrochemical nitrogen reduction. JACS, 147(20), 16935--16947. (www)

  @article{ , abstract = {The electrochemical nitrogen reduction reaction (NRR) provides a sustainable alternative to green ammonia synthesis. However, challenges persist due to limited accessibility of N 2 molecules at the electrode interface and competition from abundant protons at catalytic active sites, resulting in low N 2 coverage and compromised selectivity. In this work, we investigate the critical role of potassium cations (K + ) in modulating the interfacial environment, particularly focusing on how varying K + concentrations influence N 2 adsorption, *NH 3 desorption, and hydrogen transfer (HT) mechanisms under operating electrochemical conditions. Our results demonstrate that a highly concentrated K + electrode interface significantly enhances N 2 adsorption and *NH 3 desorption, collectively leading to improved NRR selectivity, in alignment with the experimental observations. We further uncover insights into HT kinetics, identifying two key steps: protonation (HT 1 ) and diffusion (HT 2 ). Among these, diffusion (HT 2 ) is the rate-limiting step, driven by hydrogen bond connectivity and proton shuttling strength within the cation-induced microenvironments. Specifically, at a low applied potential, a highly concentrated K + interface exhibits weak connectivity and sluggish proton shuttling, therefore limiting NRR efficiency. However, microkinetic modeling (MKM) analysis indicates that optimizing electrode potential and electrolyte compositions can overcome these limitations by promoting proton shuttling. Last but not least, we also provide a detailed map of the interplay among K + molarity, electrode potential, and NH 3 selectivity. Our work offers critical insights to guide the improvement of NRR efficiency through electrolyte and microenvironmental modulation.}, archive = {J_JACS}, author = {Lin Jiang and Xing Zhi and Xiaowan Bai and Yan Jiao}, doi = {10.1021/jacs.4c18622}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16935--16947}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic-level insights into cation-mediated mechanism in electrochemical nitrogen reduction}, volume = {147}, year = {2025}, }
• (2025). Direct synthesis of highly siliceous faujasite-type zeolite enabled by low charge density organic structure-directing agents. JACS, 147(20), 16922--16934. (www)

  @article{ , abstract = {Ultrastable Y (USY) zeolites (Faujasite-type, FAU ) with high SiO 2 /Al 2 O 3 ratios (SARs) have been widely applied in fluidized catalytic cracking and hydrocracking processes. However, their preparation typically involves labor-intensive post-treatments that inevitably introduce defects, extra-framework species, and compositional gradients. Herein, we report the direct synthesis of FAU -type zeolite with a record-high SAR up to 21.28, which shows superior catalytic performance in the catalytic cracking of cumene and straight-run diesel. This was achieved by using a highly siliceous initial gel and seed, together with low charge-density organic structure-directing agents (OSDAs) of tetramethylammonium (TMA + ) and tetrabutylammonium (TBA + ) cations, while minimizing the use of high charge-density inorganic Na + cations. Comprehensive NMR analyses, including two-dimensional (2D) heteronuclear correlation (HETCOR) experiments ( 1 H– 13 C, 1 H– 27 Al, 1 H– 29 Si), and synchrotron radiation X-ray diffraction-based Rietveld refinements, revealed that (1) TMA + and TBA + preferentially interact with Si species over Al species in the initial gel, promoting Si incorporation into the FAU structure’s long-range order; and (2) TMA + cations were tightly confined within the sodalite ( sod ) cages, while TBA + cations occupied the faujasite ( fau ) supercages, adopting folded butyl chain configurations. The encapsulation of low charge-density OSDA cations, coupled with the exclusion of high charge-density Na + cations, resulted in a highly siliceous Y zeolite with a SAR of 21.28. The synthesized Y zeolite exhibited improved durability and enhanced activity in cumene cracking and comparable selectivity for the target products [liquefied petroleum gas (LPG) and gasoline] while reducing coke formation by 28% in straight-run diesel catalytic cracking compared to conventional USY zeolites.}, archive = {J_JACS}, author = {Zhenrui Mi and Shaojie Li and Wei Liu and Jia Wang and Donghao Deng and Pusheng Liu and Peng Tian and Chuang Liu and Wenfu Yan and Kake Zhu and Zhendong Wang and Zhongmin Liu and Jihong Yu}, doi = {10.1021/jacs.4c18522}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16922--16934}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct synthesis of highly siliceous faujasite-type zeolite enabled by low charge density organic structure-directing agents}, volume = {147}, year = {2025}, }
• (2025). Top-down ion mobility mass spectrometry reveals a disease associated conformational ensemble of alpha-1-antitrypsin. JACS, 147(20), 16909--16921. (www)

  @article{ , abstract = {Mutants of members of the serpin superfamily can undergo nonamyloid aggregation to form polymeric chains that are associated with disease. This is typified by Z alpha-1-antitrypsin (Glu342Lys) that accumulates as polymers within hepatocytes to cause cirrhosis. We have used ion mobility mass spectrometry and electron-capture dissociation to directly observe and characterize novel intermediates formed during polymerization. Our data are congruent with an ensemble of conformations that are monomeric but maintained in a partially misfolded metastable state in which ∼12% of the molecule at the C-terminus is displaced. The application of these techniques to Z alpha-1-antitrypsin polymers isolated from human liver revealed a molecular species most consistent with a polymer mediated by an intermolecular C-terminal domain insertion. These findings establish a previously unobserved progression of pathogenic structural changes and thereby extend the mechanism of alpha-1-antitrypsin polymerization. They additionally demonstrate the strengths of native top-down ion mobility mass spectrometry in characterizing misfolding intermediates and proteins isolated from human tissue.}, archive = {J_JACS}, author = {Sarah Vickers and Ibrahim Aldobiyan and Sarah M. Lowen and James A. Irving and David A. Lomas and Konstantinos Thalassinos}, doi = {10.1021/jacs.4c18139}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16909--16921}, shortjournal = {J. Am. Chem. Soc.}, title = {Top-down ion mobility mass spectrometry reveals a disease associated conformational ensemble of alpha-1-antitrypsin}, volume = {147}, year = {2025}, }
• (2025). Iron-mediated nitrate reduction at ambient temperature for deaminative sulfonylation and fluorination of anilines. JACS, 147(20), 16901--16908. (www)

  @article{ , abstract = {Preparation of arylsulfonic acids and derivatives can be achieved under mild conditions from aryldiazonium salts, although conventional methods often require isolation or accumulation of these potentially hazardous intermediates. Herein, we present that iron nitrate reduction at 25 °C enables the in situ generation of diazonium salts, which allows direct deaminative chlorosulfonylation and fluorination from anilines via aryldiazonium salts as fleeting intermediates. Other sulfonic acid derivatives, such as sulfonamides, sulfonyl fluorides, and sulfonic acids, are readily accessible from this method.}, archive = {J_JACS}, author = {Tim Schulte and Deepak Behera and Davide Carboni and Annika Höppner and Felix Waldbach and Javier Mateos and Ahmet Altun and Markus Leutzsch and Moritz L. Krebs and Tobias Ritter}, doi = {10.1021/jacs.4c17981}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16901--16908}, shortjournal = {J. Am. Chem. Soc.}, title = {Iron-mediated nitrate reduction at ambient temperature for deaminative sulfonylation and fluorination of anilines}, volume = {147}, year = {2025}, }
• (2025). Intentional formation of persistent surface redox mediators by adsorption of polyconjugated carbonyl complexes to pd nanoparticles. JACS, 147(20), 16885--16900. (www)

  @article{ , abstract = {Adsorbing polyconjugated carbonyl and aromatic species to Pd nanoparticles forms persistent intermediates that mediate reactions between hydrogen and oxygen-derived species. These surface redox mediators form in situ and increase selectivities toward H 2 O 2 formation (∼65–85%) compared to unmodified Pd nanoparticles (∼45%). Infrared spectroscopy, temperature-programmed oxidation measurements, and ab initio calculations show that these species adsorb irreversibly to Pd surfaces and persist over extended periods of catalysis. Combined rates and kinetic isotope effect measurements and simulations suggest that carbonyl groups of bound organics react heterolytically with hydrogen to form partially hydrogenated oxygenated complexes. Subsequently, these organic species transfer proton–electron pairs to O 2 -derived surface species via pathways that favor H 2 O 2 over H 2 O formation on Pd nanoparticles. Computational and experimental measurements show redox pathways mediated by partially hydrogenated carbonyl species form H 2 O 2 with lower barriers than competing processes while also obstructing O–O bond dissociation during H 2 O formation. For example, adsorption and hydrogenation of hexaketocyclohexane on Pd forms species that react with oxygen with high H 2 O 2 selectivities (85 ± 8%) for 130 h on stream in flowing water without additional promoters or cosolvents. These paths resemble the anthraquinone auto-oxidation process (AAOP) used for industrial H 2 O 2 production. These surface-bound species form partially hydrogenated intermediates that mediate H 2 O 2 formation with high rates and selectivities, comparable to AAOP but on a single catalytic nanoparticle in pure water without organic solvents or multiunit reaction-separation chains. The molecular insights developed herein provide strategies to avoid organic solvents in selective processes and circumvent their associated process costs and environmental impacts.}, archive = {J_JACS}, author = {Jason S. Adams and Mayank Tanwar and Haoyu Chen and Sucharita Vijayaraghavan and Tomas Ricciardulli and Matthew Neurock and David W. Flaherty}, doi = {10.1021/jacs.4c15874}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16885--16900}, shortjournal = {J. Am. Chem. Soc.}, title = {Intentional formation of persistent surface redox mediators by adsorption of polyconjugated carbonyl complexes to pd nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Electric field’s dueling effects through dehydration and ion separation in driving NaCl nucleation at charged nanoconfined interfaces. JACS, 147(20), 16876--16884. (www)

  @article{ , abstract = {Investigating nucleation in charged nanoconfined environments under electric fields is crucial for many scientific and engineering applications. Here we study the nucleation of NaCl from aqueous solution near charged surfaces using machine-learning-augmented enhanced sampling molecular dynamics simulations. Our simulations successfully drive phase transitions between the liquid and solid phases of NaCl. The solid phase is stabilized under electric fields, particularly at an intermediate surface charge density. We examine which physical characteristics drive the nucleation of NaCl from aqueous solutions and find that the removal of solvent water from Cl – at the solid precursor surface plays a more critical role than the accumulation of ions. Our simulations reveal the competing effects of electric fields on nucleation processes: they facilitate the removal of water, promoting nucleation, but also promote the separation of ion pairs, thereby hindering nucleation. This work provides a framework for studying nucleation processes in nanoconfined environments under electric fields and provides physical insights for the design of electrochemistry materials.}, archive = {J_JACS}, author = {Ruiyu Wang and Pratyush Tiwary}, doi = {10.1021/jacs.4c16419}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16876--16884}, shortjournal = {J. Am. Chem. Soc.}, title = {Electric field’s dueling effects through dehydration and ion separation in driving NaCl nucleation at charged nanoconfined interfaces}, volume = {147}, year = {2025}, }
• (2025). Prediction of C2N-supported double-atom catalysts with Individual/Integrated descriptors for electrochemical and thermochemical CO2 reduction. JACS, 147(20), 16864--16875. (www)

  @article{ , abstract = {Electrochemical/thermochemical CO 2 reduction reactions (CO 2 RR) on double-atom catalysts (DACs) have emerged as a novel frontier in energy and environmental catalysis. However, the lack of investigation of the underlying structure–property relationship greatly limits the rational design and practical application of related catalysts. Herein, we carried out a comprehensive theoretical study on CO 2 RR catalyzed by a series of C 2 N-supported transition metals to shed light on this issue. We demonstrate that the activity of DAC can be obviously improved by judicious manipulation of metal type, and CoNi with the highest reactivity and excellent selectivity is identified as the most promising candidate for both electroreduction and thermoreduction processes. Then, based on systemically electronic and structural analysis, various quantitative structure–property relationships are established. The results reveal that key interaction and reaction properties of elementary steps can be quantitatively determined directly from individual descriptors, including key species, charge transfer, d-orbital center, bond length, spectroscopic signals, etc, while for total reaction, the integrated descriptors designed by a novel and effective three-step strategy have much better performance. The proposed ability of quantitative prediction of the catalytic property utilizing physically interpretable parameters can significantly broaden the applicability of catalytic descriptors for materials design, thus leading to indispensable guidelines for related DACs.}, archive = {J_JACS}, author = {Chuanyi Jia and Bo Li and Jing Yang and Shuang Jiang and Zhanyong Gu and Li Sun and Wenhui Zhong and Edward Sharman and Yi Luo and Jun Jiang}, doi = {10.1021/jacs.4c16377}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16864--16875}, shortjournal = {J. Am. Chem. Soc.}, title = {Prediction of C2N-supported double-atom catalysts with Individual/Integrated descriptors for electrochemical and thermochemical CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). Peptide recognition and mechanism of the radical S-adenosyl-l-methionine multiple cyclophane synthase ChlB. JACS, 147(20), 16850--16863. (www)

  @article{ , abstract = {Ribosomally synthesized and post-translationally modified peptides (RiPPs) represent a valuable class of natural products, often featuring macrocyclization, which enhances stability and rigidity to achieve specific conformations, frequently underlying antibiotic activity. ChlB is a metalloenzyme with two catalytic domains─a radical S -adenosyl- l -methionine (SAM) domain and an α-ketoglutarate-dependent oxygenase─that work in tandem to sequentially form three cyclophanes and introduce three hydroxyl groups into its substrate peptide, ChlA. Here, we present the crystal structure of the radical SAM domain of ChlB in complex with ChlA, revealing the mechanism underlying cyclophane formation. These structures also elucidate how the leader sequence of ChlA interacts with ChlB. By combining structural, in vitro, and in vivo approaches, we determined the precise sequence of the three cyclophane formations, interspersed with hydroxylation events. Our findings demonstrate a back-and-forth movement of the core peptide between the radical SAM domain and the oxygenase domain, which drives the stepwise modification process, leading to the fully modified peptide.}, archive = {J_JACS}, author = {Jérémie Ruel and Thi Quynh Ngoc Nguyen and Yohei Morishita and Anthony Usclat and Lydie Martin and Patricia Amara and Sylvie Kieffer-Jaquinod and Maria Cristina Stefanoiu and Eugenio de la Mora and Brandon I. Morinaka and Yvain Nicolet}, doi = {10.1021/jacs.4c16004}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16850--16863}, shortjournal = {J. Am. Chem. Soc.}, title = {Peptide recognition and mechanism of the radical S-adenosyl-l-methionine multiple cyclophane synthase ChlB}, volume = {147}, year = {2025}, }
• (2025). Molecular tweezers block the functional pore of a protein machine. JACS, 147(20), 16836--16849. (www)

  @article{ , abstract = {We present symmetric multivalent tweezers as the first class of supramolecular elements designed to cover and functionally block a protein pore. As a model, we chose the enzyme p97, a hexameric AAA-ATPase that unfolds or segregates substrate proteins by threading them through a pore and channel at the center of the symmetric p97 hexamer fueled by ATP hydrolysis. In a rational design approach, we developed a new class of p97 inhibitors, guided by molecular modeling. These dock onto lysine residues at the entry of the pore via appropriately positioned molecular tweezers. Ligand binding was accompanied by induction of fluorescence of the built-in binding sensitive luminophores which served as a sensor for affinity determination. We further confirmed specific interaction with p97 as well as concomitant inhibition of ATPase activity and protein substrate unfolding using an array of biophysical methods and state-of-the art biochemical assays. Specific binding was also validated by mutagenesis, demonstrating that inhibition of p97 function was mediated by blocking the pore entrance. Especially C 3 -symmetric multivalent tweezers potently inhibited ATPase activity and protein substrate processing consistent with the symmetry of the docking site. Our data independently confirm substrate threading as a mechanism for protein unfolding by p97 and highlight multivalent tweezers as a supramolecular strategy to target pores in various proteins. Since p97 and related protein machines are vital for protein quality control and cell survival, the new pore binders may open a new approach to combat diseases and be employed in drug discovery.}, archive = {J_JACS}, author = {Abbna Kirupakaran and Johannes van den Boom and Mike Blueggel and Christine Beuck and Felix Niemeyer and Matthias Hayduk and Jan Balszuweit and Peter Bayer and Jens Voskuhl and Hemmo Meyer and Thomas Schrader}, doi = {10.1021/jacs.4c15288}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16836--16849}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular tweezers block the functional pore of a protein machine}, volume = {147}, year = {2025}, }
• (2025). Measuring nanometer distances in proteins and rigid rulers between 19F and gd3+ by integration of 19F-ENDOR signal intensities. JACS, 147(20), 16826--16835. (www)

  @article{ , abstract = {19 F ENDOR is emerging as a powerful tool in structural biology for measuring distances in proteins labeled with 19 F and a paramagnetic tag. Due to spin–spin relaxation and line width limitations, it has been difficult to determine intertag distances larger than about 15 Å. Using a set of geometrically well-defined rulers and spin-labeled proteins, we show that 19 F–Gd 3+ distances up to 20 Å can be accessed by integrating the intensity of the ENDOR spectrum, with distances approaching 30 Å potentially in reach as well. This method is robust when the intensities are scaled to a known reference, and provides scope for nanometer-scale triangulation of the coordinates of a ligand in a protein–ligand complex.}, archive = {J_JACS}, author = {Martyna Judd and Mian Qi and Elwy H. Abdelkader and Haocheng Qianzhu and Anton Savitsky and Thomas Huber and Jeffrey R. Harmer and Adelheid Godt and Gottfried Otting and Nicholas Cox}, doi = {10.1021/jacs.4c13530}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16826--16835}, shortjournal = {J. Am. Chem. Soc.}, title = {Measuring nanometer distances in proteins and rigid rulers between 19F and gd3+ by integration of 19F-ENDOR signal intensities}, volume = {147}, year = {2025}, }
• (2025). Water-in-salt electrolyte stabilizes pyrazine radical: Suppression of its aggregation by interaction between pyrazine and Li(H2O)n+. JACS, 147(20), 16812--16825. (www)

  @article{ , abstract = {Stabilizing radical intermediates of redox-active organic molecules in aqueous media is crucial for advancing applications in energy storage, catalysis, and electrosynthesis. This study investigates the stabilization of protonated radical intermediates of pyrazine derivatives in water-in-salt electrolytes (WISEs) with 7–8 m LiTFSI. Strong interactions between pyrazine derivatives and Li + -coordinated water (Li(H 2 O) n + ) in WISEs prevent molecular aggregation and protect radical intermediates from disproportionation and oxygen-induced degradation. Voltammetric results show that higher concentrations of LiTFSI enhance both the stability and redox reversibility of dimethylpyrazine (DMP) radical intermediates, with protonation identified as a key stabilizing factor. Notably, these stabilizing effects were absent in solutions containing concentrated LiCl or LiNO 3 . Fourier-transform infrared (FTIR) spectroscopy and molecular dynamics (MD) simulations confirmed reduced DMP aggregation in LiTFSI-based electrolytes, driven by interactions with Li(H 2 O) n + , while no similar solvation structure modification occurred with LiNO 3 . The protonated radical intermediates in LiTFSI-based WISEs exhibited greater resistance to oxygen-induced degradation compared to conventional acidic solutions. Additionally, substitution of methyl or ethyl groups on the pyrazine ring destabilized the corresponding radical intermediates in LiTFSI-based WISEs, primarily due to the alkyl inductive effect, as evidenced by electrochemical and UV–visible absorption spectroscopy. Charge–discharge tests in an H-cell further demonstrated significantly improved Coulombic efficiency of pyrazine redox reactions in LiTFSI-based WISEs compared to acidic Salt-in-Water electrolytes, underscoring the importance of radical intermediate stabilization.}, archive = {J_JACS}, author = {Seeun Hong and Min Young Seo and Dongho Seo and Ki Min Nam and YongJoo Kim and Jinho Chang}, doi = {10.1021/jacs.4c09561}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16812--16825}, shortjournal = {J. Am. Chem. Soc.}, title = {Water-in-salt electrolyte stabilizes pyrazine radical: Suppression of its aggregation by interaction between pyrazine and Li(H2O)n+}, volume = {147}, year = {2025}, }
• (2025). A chemistry-informed generative deep learning approach for enhancing voltammetric neurochemical sensing in living mouse brain. JACS, 147(20), 16804--16811. (www)

  @article{ , abstract = {Exploring the time-resolved dynamics of neurochemicals is essential for deciphering neuronal functions, intercellular communication, and neurophysiological or pathological mechanisms. However, the complex interplay among neurochemicals between neurocytes, coupled with extensive chemical signal crosstalk, puts simultaneous sensing of multiple neurochemicals into a longstanding challenge. Herein, we report a chemistry-informed generative neural network (CIGNN) model to separate the Faradaic and the non-Faradaic components from voltammetric currents, minimizing their mutual interference and enhancing quantitative accuracy. With the assistance of generative deep learning, we successfully establish a new platform for in vivo neurochemical sensing, which is validated by simultaneously monitoring the dynamics of dopamine (DA), ascorbic acid (AA), and ionic strength in a neuroinflammation mouse model. We observe that the stimulation with KCl solution triggers a significant enhancement of AA efflux on the model mice (300 ± 50 μM) compared with that from the control mice (170 ± 20 μM), as well as a significant decrease of ion influx (55 ± 7 mM) compared with that from the control mice (120 ± 16 mM), while not evoking a significant change in the DA release from the model mice (2.8 ± 0.3 μM) versus that from the control mice (3.0 ± 0.5 μM). This work provides a robust tool for studying multineurochemical signaling and elucidating the molecular mechanisms underlying various brain activities.}, archive = {J_JACS}, author = {Shuxin Li and Yifei Xue and Zhining Sun and Huan Wei and Fei Wu and Lanqun Mao}, doi = {10.1021/jacs.5c05393}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16804--16811}, shortjournal = {J. Am. Chem. Soc.}, title = {A chemistry-informed generative deep learning approach for enhancing voltammetric neurochemical sensing in living mouse brain}, volume = {147}, year = {2025}, }
• (2025). Atomic-level electron crystallography of Metal–Organic frameworks via resin-peeled ultramicrotomy. JACS, 147(20), 16798--16803. (www)

  @article{ , abstract = {Electron crystallography offers the potential for ultra-high-resolution diffraction and imaging of materials. However, challenges remain, particularly regarding beam/mechanical sensitivity, severe electron multiple scattering, and the low contrast of light elements in fragile porous organic crystals that often cannot be thinned without compromising their crystallinity. Herein, we develop a method, named resin-peeled ultramicrotomy, to prepare high-crystalline lamella free of embedding resin. By applying crystalline lamellas for 3D electron diffraction, we improve data quality and achieve resolutions up to 0.39 Å. This improvement allows for single-crystal structure determinations of metal–organic frameworks (MOFs) with large unit cells and giant pores─previously unsolved by X-ray and electron diffraction─and resolves ordered/disordered positions of (hydro)oxyl bridging atoms. Moreover, resin-peeled ultramicrotomy enables thinning of 3D MOFs along multiple crystallographic orientations. The further combination with electron ptychography reveals the local structures of 3D MOFs with high resolution and contrast. This advancement opens new avenues for resolving atomic and local structures in soft functional materials.}, archive = {J_JACS}, author = {Zhiye Zhong and Enci Zhang and Pu Yan and Huaidong Jiang and Yanhang Ma}, doi = {10.1021/jacs.5c05117}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16798--16803}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic-level electron crystallography of Metal–Organic frameworks via resin-peeled ultramicrotomy}, volume = {147}, year = {2025}, }
• (2025). Ir-catalyzed, stereoselective total synthesis of (+)-rubriflordilactone a. JACS, 147(20), 16792--16797. (www)

  @article{ , abstract = {A stereocontrolled asymmetric total synthesis of the Schisandra nortriterpenoid (+)-rubriflordilactone A employing Krische’s Ir-catalyzed 2-(alkoxycarbonyl)allylation for late-stage γ-butenolide formation is described. Additional noteworthy aspects include the integration of Carreira’s Ir/amine dual-catalyzed allylation, Suzuki coupling, and Catellani reaction, resulting in the formation of an indane iodide. The alkylation of lactone 7 , followed by RCM, A-ring formation via condensation of the B-ring lactone with Bestmann ylide, and Morken’s Pt-catalyzed diboration/oxidation, facilitates the stereoselective formation of the ABCDEF ring system.}, archive = {J_JACS}, author = {Jun-Jie Liu and Zhi-Bin Ni and Lei Li and Kun Wei and Yu-Rong Yang}, doi = {10.1021/jacs.5c05000}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16792--16797}, shortjournal = {J. Am. Chem. Soc.}, title = {Ir-catalyzed, stereoselective total synthesis of (+)-rubriflordilactone a}, volume = {147}, year = {2025}, }
• (2025). Stabilizing catalytic performance in dry reforming of methane via surface-engineered intermetallic carbide nanoparticles. JACS, 147(20), 16786--16791. (www)

  @article{ , abstract = {Intermetallic Ni 3 ZnC 0.7 catalysts were synthesized and demonstrated for the stable low-temperature CO 2 reforming of methane. Annealing of silica-supported Ni 3 Zn nanoparticles with CO 2 /CH 4 formed an intermetallic ordered Ni 3 ZnC 0.7 phase with interstitial subsurface carbon atoms, and Ni δ- -Zn δ+ paired active sites. The intermetallic carbide exhibited exceptional 160 h stability with negligible deactivation, contrasted with severe deactivation in the monometallic Ni catalyst due to coking. The critical roles of carbon diffusion, local structural and electronic modulation, and intermetallic bonding in stabilizing the optimal surface structure in intermetallic carbide nanocatalysts were revealed through in situ XPS, HS-LEIS, XAS, neutron PDF analysis, and performance testing. The controlled synthesis of these intermetallic carbide nanoparticles provides insights into designing the next generation of high performing nanocatalysts.}, archive = {J_JACS}, author = {Olusola Johnson and Yang He and Jillian Richter and Isabella St. Pierre-Charles and Babu Joseph and John N. Kuhn}, doi = {10.1021/jacs.5c05049}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16786--16791}, shortjournal = {J. Am. Chem. Soc.}, title = {Stabilizing catalytic performance in dry reforming of methane via surface-engineered intermetallic carbide nanoparticles}, volume = {147}, year = {2025}, }
• (2025). 10-step, gram-scale total synthesis of (−)-bipinnatin j. JACS, 147(20), 16781--16785. (www)

  @article{ , abstract = {A concise, scalable total synthesis of (−)-bipinnatin J is disclosed. Commencing from inexpensive starting materials, this marine diterpenoid was fashioned through a convergent synthesis enabled by Ni-electrocatalytic decarboxylative cross–coupling taking advantage of succinate as an ethylene 2-carbon bridge, a unique halogen dance-Zweifel sequence to access a trisubstituted furan, a Ni-mediated 1,6-conjugate addition, and an asymmetric proton transfer.}, archive = {J_JACS}, author = {Anthony J. Rodriguez and Maithili S. Pokle and Griffin L. Barnes and Phil S. Baran}, doi = {10.1021/jacs.5c04761}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16781--16785}, shortjournal = {J. Am. Chem. Soc.}, title = {10-step, gram-scale total synthesis of (−)-bipinnatin j}, volume = {147}, year = {2025}, }
• (2025). Enantioselective synthesis of axially chiral alkylidenecyclobutanes via palladium-catalyzed N-tosylhydrazone-based carbene coupling. JACS, 147(20), 16773--16780. (www)

  @article{ , abstract = {The synthesis of axially chiral alkylidenecyclobutanes remains challenging due to the requirement of both an efficient asymmetric catalytic system and preservation of its inherent strained ring structure. We herein disclose an enantioselective carbene cross-coupling reaction of cyclobutanecarbaldehyde-derived N -tosylhydrazones with aryl bromides, enabled by palladium catalysis in combination with an elaborately modified sulfinamide phosphine ligand (Sadphos). This method demonstrates the feasibility of constructing axial chirality on a strained metal carbene intermediate precisely through a sequential process of enantiodetermined migratory insertion followed by central-to-axial-chirality-transfer β-H elimination. The reaction provides access to diverse alkylidenecyclobutanes featuring a heteroatom-substituted, tertiary and all-carbon quaternary stereocenter with excellent yields (up to 95%) and high enantioselectivities (up to 95% ee). Moreover, both enantiomers can be selectively obtained by choosing either cis- or trans- cyclobutane substrates in a stereospecific manner.}, archive = {J_JACS}, author = {Xiaoqin Ning and Tonglin Zhao and Yulei Zhu and Bo Liu and Xufei Yan and Ying Xia}, doi = {10.1021/jacs.5c04354}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16773--16780}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective synthesis of axially chiral alkylidenecyclobutanes via palladium-catalyzed N-tosylhydrazone-based carbene coupling}, volume = {147}, year = {2025}, }
• (2025). Zero- to one-dimensional transformation in a highly porous Metal–Organic framework to enhance physicochemical properties. JACS, 147(20), 16766--16772. (www)

  @article{ , abstract = {The dynamic behaviors of metal–organic frameworks (MOFs) continue to expand the accessible architectures and properties within this material class. However, the dynamic behaviors that can be studied in MOFs are limited to the transitions, preserving their high crystallinity. For this reason, their significant structural changes involving coordination bond breakage and rearrangement remain largely underexplored. Herein, we report a three-step single-crystal-to-single-crystal (SCSC) phase transition in a new cerium-based MOF, HKU-9 [Ce 2 PET(DMF) 2 (H 2 O) 2 ], transforming zero-dimensional (0D) secondary building units (SBUs) into one-dimensional (1D) chain SBUs in HKU-90 [Ce 2 (μ-H 2 O)PET(H 2 O) 2 ]. Single-crystal X-ray diffraction studies unambiguously delineate the structural evolution at each stage of this multistep transition, revealing multiple coordination bond dissociations/associations and a significant lattice contraction─all while preserving single-crystal integrity. This dimensional transformation endows HKU-90 with enhanced chemical stability (pH 1–10) and a record-high Brunauer–Emmett–Teller (BET) surface area of 2660 m 2 g –1 among reported Ce-based MOFs. Further, HKU-90 exhibits exceptional gas sorption performance, with one of the highest reported C 2 H 2 storage capacities (184 cc g –1 at 273 K, 1 bar) and outstanding C 2 H 2 /CO 2 selectivity (2.16) under these conditions. Notably, the formation of 1D chain SBUs, a structural motif found in many high-performance MOFs, highlights the potential of using the solid-state fusion of multinuclear metal clusters to tailor the properties of the framework.}, archive = {J_JACS}, author = {Enhui Jiang and Daisong Chen and Zhuoliang Ying and Jiaming Zhou and Artit Jarusarunchai and Xinyu Zhang and Chenxi Xiong and Keunhong Jeong and Dong-Myeong Shin and Jin Shang and Seungkyu Lee}, doi = {10.1021/jacs.5c03967}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16766--16772}, shortjournal = {J. Am. Chem. Soc.}, title = {Zero- to one-dimensional transformation in a highly porous Metal–Organic framework to enhance physicochemical properties}, volume = {147}, year = {2025}, }
• (2025). Ultraviolet photodissociation mass spectrometry captures the acyl chain length-dependent conformation dynamics of acyl carrier protein. JACS, 147(20), 16760--16765. (www)

  @article{ , abstract = {Capturing the acyl chain dependent conformation dynamics of acyl carrier protein (ACP) is critical for understanding the molecular mechanism of acyl chain stabilization and elongation, providing structural insights for ACP evolution. Herein, we utilize native mass spectrometry (nMS) and 193 nm ultraviolet photodissociation (UVPD) to systematically interrogate the structural details in activation and interactions of ACP with C4–C18 acyl chains. The unstable acyl-ACP intermediates can be isolated and subjected to high-sensitivity UVPD analysis individually without matrix interference. We find that the acyl chains mainly insert into ACP subpocket I until the chain length surpasses the cavity’s maximum capacity by 10 carbons. Then, the hydrophobic part of long acyl chains (>C10) bends into subpocket II. Notably, Phe50 and Ile62 play a critical role in regulating the size of the hydrophobic pocket, while Loop I and Thr64-Gln66 are essential for stabilizing long-chain acyl-ACPs. Our findings pave the way for ACP rational evolution to promote the biosynthesis of target fatty acids.}, archive = {J_JACS}, author = {Yuanzhi Xie and Zheyi Liu and Huiwen Qin and Heng Zhao and Weiqing Zhang and Chunlei Xiao and Xian Wang and Xueming Yang and Fangjun Wang}, doi = {10.1021/jacs.5c03426}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16760--16765}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultraviolet photodissociation mass spectrometry captures the acyl chain length-dependent conformation dynamics of acyl carrier protein}, volume = {147}, year = {2025}, }
• (2025). 3,6-anhydrogalactal as a single-addition monomer for chain-end functionalization of metathesis polymers. JACS, 147(20), 16754--16759. (www)

  @article{ , abstract = {Controlling the structure and reactivity of the chain-end group is a central objective in modern polymer chemistry. Here we introduce 3,6-anhydrogalactal as a single-addition monomer that enables efficient and versatile chain-end functionalization of metathesis polymers. Readily synthesized from biomass-derived galactal, 3,6-anhydrogalactal exhibits excellent single-addition reactivity, allowing precise chain-end modifications even when introduced simultaneously with the propagating monomer. Theoretical calculations provide mechanistic insights into the unique reactivities governing its single-addition behavior. Its broad functional group compatibility facilitates diverse applications, including block copolymer synthesis, polymer–polymer coupling, and bioconjugation, demonstrating significant potential for advancing polymer materials and bioconjugation strategies.}, archive = {J_JACS}, author = {Zefeng Zhou and Quan Pham and Gavin J. Giardino and Abhishek Chatterjee and Jia Niu}, doi = {10.1021/jacs.5c03379}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16754--16759}, shortjournal = {J. Am. Chem. Soc.}, title = {3,6-anhydrogalactal as a single-addition monomer for chain-end functionalization of metathesis polymers}, volume = {147}, year = {2025}, }
• (2025). Pd-catalyzed photoinduced interceptive decarboxylative allylation. JACS, 147(20), 16747--16753. (www)

  @article{ , abstract = {Herein, we describe a photoinduced Pd-catalyzed interceptive decarboxylative allylation of allyl esters. Our protocol provides a new gateway to enable atom pair swaps or a series of contractions and elongations, thus offering unconventional disconnections and a modular yet broadly applicable tool for rapidly and reliably accessing sp 3 architectures in drug discovery.}, archive = {J_JACS}, author = {Franz-Lucas Haut and Filip S. Meger and Tomás G. Santiago and Paula Fraňová and Daniel Kocsi and Joan V. Estornell and Marta Martínez-Belmonte and Jordi Benet-Buchholz and Ruben Martin}, doi = {10.1021/jacs.5c03044}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16747--16753}, shortjournal = {J. Am. Chem. Soc.}, title = {Pd-catalyzed photoinduced interceptive decarboxylative allylation}, volume = {147}, year = {2025}, }
• (2025). Synthesis of high-entropy alloy polyhedra using liquid metal dewetting. JACS, 147(20), 16742--16746. (www)

  @article{ , abstract = {High-entropy alloys (HEAs) are gaining extensive interest in materials science, and their facet engineering has long been a pursuit for materials design and advanced applications. However, limited by the poor compatibility of crystal face regulation in high-entropy scenarios with the existing extreme-condition synthetic techniques, the synthesis of HEA polyhedra is still scarce and challenging. Herein, we propose the strategy of liquid-metal-participating biphasic-modulated dewetting for self-confinement growth under near-equilibrium conditions. Owing to the surface energy anisotropy, HEAs could develop into the equilibrium shape with a polyhedral configuration, where liquid metal endows fast diffusion toward reaching the equilibrium shape. This strategy could also be extended to diverse HEA polyhedra with different chemical compositions and crystal structures with the formation mechanism elucidated through in situ transmission electron microscopy experiments and theoretical calculations. This work injects new vitality into the regulation of HEAs and expedites their facet engineering.}, archive = {J_JACS}, author = {Jingjing Liang and Guanghui Cao and Yile Zhang and Zeyuan Li and Xuhao Wan and Jiqing Jiao and Kaicong Yang and Li Xiao and Yuzheng Guo and Mengqi Zeng and Lei Fu}, doi = {10.1021/jacs.5c02254}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16742--16746}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of high-entropy alloy polyhedra using liquid metal dewetting}, volume = {147}, year = {2025}, }
• (2025). Dehomologative C–C borylation of aldehydes and alcohols via a rh-catalyzed Dehydroformylation–Borylation relay. JACS, 147(20), 16735--16741. (www)

  @article{ , abstract = {The dehomologative conversion of linear or α-methyl aldehydes to vinyl boronates is achieved via a one-pot sequence of rhodium-catalyzed transfer dehydroformylation and transfer borylation of the resulting alkenes. Similarly, allylic or aliphatic alcohols are converted to vinyl boronates through a sequence involving, respectively, rhodium-catalyzed isomerization or transfer dehydrogenation to aldehyde intermediates, followed by dehydroformylation–borylation. The vinyl boronates can be further hydrogenated to alkyl boronates using the same rhodium precatalyst, enabling all five catalytic steps with a single catalyst system.}, archive = {J_JACS}, author = {Kuhali Das and Nikodem Kuźnik and Paweł Dydio}, doi = {10.1021/jacs.5c02181}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16735--16741}, shortjournal = {J. Am. Chem. Soc.}, title = {Dehomologative C–C borylation of aldehydes and alcohols via a rh-catalyzed Dehydroformylation–Borylation relay}, volume = {147}, year = {2025}, }
• (2025). Phase engineering of 1T′-MoS2 via organic enwrapment. JACS, 147(20), 16729--16734. (www)

  @article{ , abstract = {Molybdenum disulfide (MoS 2 ) is a layered material known to show various phases. Most studies on it have focused on its semiconductor phase, but it is known to also have a metallic 1T′ phase. This 1T′ phase has also drawn attention as a quantum spin Hall phase, but the 1T′ phase is metastable, and methods for transforming or stabilizing it are still challenging. This Communication demonstrates a method for effectively transforming the monolayer or the topmost layer of multilayer semiconductor MoS 2 (the 1H or 2H phase) into the 1T′ phase via ultraviolet-ozone (UVO) treatment, followed by polymer enwrapment of the MoS 2 surface. UVO induces the transformation of the 1H (2H) phase into the 1T′ phase, but the generated phase is unstable. The enwrapment procedure with the polymer poly- l -lysine was found to be effective in transforming the 1H (2H) phase into the 1T′ phase and stabilizing it. Moreover, this procedure transformed only the topmost layer and generated a vertical 1T′/2H heterostructure in multilayer cases. This study shows the high potential of surface organic chemical procedures to control the phases in 2D transition metal dichalcogenides.}, archive = {J_JACS}, author = {Keigo Matsuyama and Limi Chen and Kohei Aso and Kaito Kanahashi and Kosuke Nagashio and Yoshifumi Oshima and Daisuke Kiriya}, doi = {10.1021/jacs.5c02099}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16729--16734}, shortjournal = {J. Am. Chem. Soc.}, title = {Phase engineering of 1T′-MoS2 via organic enwrapment}, volume = {147}, year = {2025}, }
• (2025). From reagent to catalyst: Dispersion-driven design of a general asymmetric transfer hydrogenation catalyst. JACS, 147(20), 16722--16728. (www)

  @article{ , abstract = {Even though chemists have long underappreciated the role of London dispersion in catalysis, its importance in determining a reaction course is now well recognized. Dispersion interactions have been shown to stabilize transition states and govern the stereoselectivity. In this context, the transfer hydrogenation of α,β-unsaturated aldehydes reported by our group via asymmetric counteranion-directed catalysis (ACDC) was revisited mechanistically. Previously, the use of an engineered Hantzsch ester featuring an isopropyl group was crucial for high enantioselectivity, suggesting London dispersion as an important stereocontrolling factor. Based on this hypothesis and the method’s drawbacks (commercially unavailable Hantzsch ester, limited substrate scope, high catalyst loadings), we designed a broadly applicable second-generation catalyst system by introducing dispersion energy donors into the catalyst instead of the Hantzsch ester reagent. With the help of computational analysis, noncovalent interactions contributing to stereocontrol in the two systems were elucidated.}, archive = {J_JACS}, author = {Wencke Leinung and Benjamin Mitschke and Markus Leutzsch and Vijay N. Wakchaure and Rajat Maji and Benjamin List}, doi = {10.1021/jacs.5c00641}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16722--16728}, shortjournal = {J. Am. Chem. Soc.}, title = {From reagent to catalyst: Dispersion-driven design of a general asymmetric transfer hydrogenation catalyst}, volume = {147}, year = {2025}, }
• (2025). Cage alkyl carbenes provide experimental evidence for isotope-controlled selectivity in competing tunneling reactions. JACS, 147(20), 16717--16721. (www)

  @article{ , abstract = {We report the synthesis and reactivity of adamantylidene ( 1 ) and pentacyclo[5.4.0.0 2,6 .0 3,10 .0 5,9 ]undecanylidene ( 2 ) under matrix isolation conditions. The latter previously unreported carbene is persistent under cryogenic conditions and has been characterized spectroscopically. The singlet carbenes were generated through irradiation of their corresponding diazirine precursors followed by trapping the products in argon or nitrogen matrices at 3.5 K. Analyses using IR and UV/vis spectroscopy together with density functional theory computations provide strong evidence for the successful preparation of these reactive species. Carbene 1 (Δ E ST = −3.0 kcal mol –1 ) undergoes a slow hitherto unreported but theoretically predicted quantum mechanical tunneling (QMT) C–H-bond insertion and ring-closure to 2,4-dehydroadamantane ( 4 ). In contrast, 2 (Δ E ST = −5.2 kcal mol –1 ) remains unchanged under cryogenic conditions but rearranges to homohypostrophene ( 9 ) upon λ = 627 nm irradiation. Attempts to prepare protoadamantylidene ( 3 ) (Δ E ST = −5.1 kcal mol –1 ) in a similar fashion did not allow the direct observation of the free carbene, but enabled follow-up QMT reactions, whose selectivities are determined by the 1 H and 2 H isotopologs, thereby demonstrating isotope-controlled selectivity (ICS).}, archive = {J_JACS}, author = {Akkad Danho and Bastian Bernhardt and Dennis Gerbig and Marija Alešković and Peter R. Schreiner}, doi = {10.1021/jacs.4c18129}, journal = {Journal of the American Chemical Society}, month = {5}, number = {20}, pages = {16717--16721}, shortjournal = {J. Am. Chem. Soc.}, title = {Cage alkyl carbenes provide experimental evidence for isotope-controlled selectivity in competing tunneling reactions}, volume = {147}, year = {2025}, }
• (2025). Correction to “Catalytic asymmetric oxidative coupling between C(sp3)–H bonds and carboxylic acids”. JACS, 147(19), 16716. (www)

  @article{ , archive = {J_JACS}, author = {Xian-Ming Liu and Fu Li and Tongkun Wang and Ling Dai and Yin Yang and Neng-Quan Jiang and Li-Yuan Xue and Jing-Yuan Liu and Xiao-Song Xue and Li-Jun Xiao and Qi-Lin Zhou}, doi = {10.1021/jacs.5c06157}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16716}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Catalytic asymmetric oxidative coupling between C(sp3)–H bonds and carboxylic acids”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Hexatopic vertex-directed approach to vinylene-linked covalent organic frameworks with heteroporous topologies”. JACS, 147(19), 16715. (www)

  @article{ , archive = {J_JACS}, author = {Zixing Zhang and Shuai Bi and Fancheng Meng and Xiaomeng Li and Mengqi Li and Kaiwen Mou and Dongqing Wu and Fan Zhang}, doi = {10.1021/jacs.5c05504}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16715}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Hexatopic vertex-directed approach to vinylene-linked covalent organic frameworks with heteroporous topologies”}, volume = {147}, year = {2025}, }
• (2025). Elucidating the iterative elongation mechanism in a type III polyketide synthase. JACS, 147(19), 16705--16714. (www)

  @article{ , abstract = {Type III polyketide synthases (PKSs) have a much simpler three-dimensional architecture compared with their type I and type II counterparts, yet they catalyze iterative polyketide elongation to generate a myriad of products in plants, fungi, and eubacteria. Despite this mechanistic complexity occurring within a single active site, the mechanism by which type III PKSs stabilize and direct their highly reactive keto and enolate intermediates has yet to be fully understood. Here, we report the synthesis and deployment of stable polyketone CoA analogues for each putative intermediate involved in the biphenyl synthase (BIS) mechanism together with three high-resolution crystal structures of each in complex with BIS from Malus domestica . This set of structures reveals key mechanistic features that control the number of iterative elongation steps and that shape the static architectural features responsible for organization of a water-mediated hydrogen bonding network necessary for termination of the elongation reaction by an intramolecular aldol cyclization and production of the 3,5-dihydroxybiphenyl BIS product. Elucidating these protein–substrate interactions provides a foundation for using polyketone CoA analogues to further unravel the control mechanisms of PKS catalysis and gain the insight necessary for predictive engineering of these enzymes.}, archive = {J_JACS}, author = {Rebecca N. Re and James J. La Clair and Joseph P. Noel and Michael D. Burkart}, doi = {10.1021/jacs.5c05635}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16705--16714}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating the iterative elongation mechanism in a type III polyketide synthase}, volume = {147}, year = {2025}, }
• (2025). Click chemistry-assisted rejuvenation of aging t cells sensitizes aged mice to tumor immunotherapy. JACS, 147(19), 16694--16704. (www)

  @article{ , abstract = {Enormous resources have been devoted to address the suboptimal response of tumor patients to immunotherapy. However, a crucial yet often overlooked factor in these effects is the strong correlation between the occurrence and development of tumors and the immune dysfunction associated with aging. Our study aims to rejuvenate aging T cells within tumor-draining lymph nodes (TdLNs) by using targeted delivery of rapamycin, a macrolide capable of mitigating aging-related decline in immune function, thereby enhancing the antitumor efficacy of immunotherapy in aged mice. The targeted delivery system relies on a bioorthogonal reaction that harnesses the click chemistry between the azide (N 3 ) groups artificially introduced onto TdLNs and the dibenzocyclooctyne (DBCO) groups attached to the rapamycin-loaded micelles administered intradermally. Experimental data demonstrate that this approach has effectively restored the functionality of impaired CD8 + T cells in aged mice, thereby enhancing the antitumor response to immune checkpoint blockade (ICB) therapy to levels comparable to those in young mice. This study presents a promising strategy to combat the resistance to immunotherapeutic approaches commonly encountered among elderly tumor patients.}, archive = {J_JACS}, author = {Xue-Feng Bai and Jun-Chi Ma and Cheng Zhang and Zhu Chen and Jinlian He and Si-Xue Cheng and Xian-Zheng Zhang}, doi = {10.1021/jacs.5c05312}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16694--16704}, shortjournal = {J. Am. Chem. Soc.}, title = {Click chemistry-assisted rejuvenation of aging t cells sensitizes aged mice to tumor immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Orientation-driven chirality funnels in chiral low-dimensional lead-halide perovskite heterostructures. JACS, 147(19), 16681--16693. (www)

  @article{ , abstract = {Chiral hybrid metal-halide perovskites show low-symmetry crystal structures, large Rashba splitting, spin-filtering, and strong chiroptical activity. Circular dichroism and circularly polarized photoluminescence have been investigated in chiral perovskites with increasingly distorted chiral structures. Here, we report the fabrication of chiral ( R / S )-EBAPbI 3 (EBA = α-ethylbenzylamine) single crystals, which possess highly distorted octahedral structures with a high angle variance value of ∼68 degree 2 . Using control in the fabrication conditions, we transfer chiral single crystals to thin films and achieve different crystal orientation preferences that induce tunable chiroptical properties to their heterostructures with PbI 2 nanodomains, which we characterize with in situ X-ray diffraction and grazing-incidence wide-angle X-ray scattering measurements. Using transient chiroptical spectroscopies, we resolve photoexcited charge carrier dynamics and chirality transfer processes in such heterostructures down to cryogenic temperatures. We observe rapid carrier transfer along the in-plane (002) facets in chiral perovskite phases to PbI 2 nanostructures within the initial few picoseconds, while carrier transfer along the out-of-plane (002) facets occurs at a slower rate. This fast transfer process leads to high photoluminescence intensities and large degrees of circular polarization in the emission from PbI 2 nanodomains at cryogenic temperatures. Our findings report a multidimensional chiral-achiral heterostructure which takes advantage of controllable chirality transfer and offers new routes for future spintronic and chiroptical applications.}, archive = {J_JACS}, author = {Shangpu Liu and Jonathan Zerhoch and Markus W. Heindl and Chaoran Zhang and Tim Kodalle and Kun Sun and Andrii Shcherbakov and Stanislav Bodnar and Milon Miah and Mohammad Gholipoor and Christian Jandl and Alexander Pöthig and Joachim Ballmann and Ian D. Sharp and Peter Müller-Buschbaum and Carolin M. Sutter-Fella and Ulrich W. Paetzold and Felix Deschler}, doi = {10.1021/jacs.5c05172}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16681--16693}, shortjournal = {J. Am. Chem. Soc.}, title = {Orientation-driven chirality funnels in chiral low-dimensional lead-halide perovskite heterostructures}, volume = {147}, year = {2025}, }
• (2025). Nonreciprocal circularly polarized lasing from organic achiral microcrystals. JACS, 147(19), 16674--16680. (www)

  @article{ , abstract = {Organic materials are particularly appealing for circularly polarized (CP) lasers due to their remarkable chiroptical activities and exceptional optical gain properties. However, conventional organic CP lasers based on chiral molecules or microstructures typically exhibit reciprocal behavior, which complicates material synthesis and device fabrication for practical applications. In this study, we present nonreciprocal CP lasing from achiral organic microcrystals through the coupling between fluorescence linear anisotropy ( f ) and linear birefringence (LB), known as f -LB effect. By carefully controlling the crystallization process, we prepared triclinic and orthorhombic polymorphs with distinct molecular packing arrangements, which unlock the precise manipulation of f -LB coupling for efficient polarization state conversion of photons. The triclinic crystals exhibited stronger f -LB effect owing to the suitable angle between the emission plane and birefringence axis, resulting in robust nonreciprocal CP luminescence. More importantly, this coupling was further amplified during lasing oscillation, ultimately enabling nonreciprocal CP lasing with a dissymmetry factor of ∼1.0. These findings provide a novel approach to exploring high-performance nonreciprocal CP lasers and offer new insights into chiral photonics and optoelectronics.}, archive = {J_JACS}, author = {Shiyang Ji and Yifan Zhou and Lin Xiong and Xinyu Liu and Tong Zhu and Xiuqin Zhan and Yongli Yan and Jiannian Yao and Kang Wang and Yong Sheng Zhao}, doi = {10.1021/jacs.5c05118}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16674--16680}, shortjournal = {J. Am. Chem. Soc.}, title = {Nonreciprocal circularly polarized lasing from organic achiral microcrystals}, volume = {147}, year = {2025}, }
• (2025). Rabies virus targeting NIR-II phototheranostics. JACS, 147(19), 16661--16673. (www)

  @article{ , abstract = {Rabies is a viral disease with an almost 100% fatality rate, primarily transmitted through bites from infected animals, with a long incubation period and no effective clinical treatments to date. Herein, we developed the first fluorescent nanotheranostic probe in the second near-infrared (NIR-II) window capable of efficiently crossing the blood–brain barrier (BBB), precisely targeting rabies virus (RABV), and enabling safe photodynamic therapy (PDT). This probe is based on a novel NIR-II organic polyacetylene fluorophore, DK, which self-assembles via a click reaction with a nanoparticle carrier, N3-PEG2000-R, that we synthesized with a high biocompatibility and BBB permeability. The probe surface is further modified with an aptamer that specifically binds to RABV glycoprotein (RVG), resulting in our final nanotheranostic probe, DK@RA-PEG . Upon intravenous injection into mice, it effectively crosses the BBB, localizes to the infection site, and binds to the RVG, allowing for real-time NIR-II fluorescence imaging. Additionally, it efficiently converts light energy into chemical energy without generating thermal effects, ensuring safe and effective PDT. This advanced nanotheranostic probe integrates precise targeting, deep-tissue imaging, and safe therapy, making it a promising candidate for future clinical applications in rabies treatment.}, archive = {J_JACS}, author = {Qihang Ding and Caiqian Wang and Haoran Wang and Chunbai Xiang and Zhao Wang and Yue Wang and Ling Zhao and Marc Vendrell and Jong Seung Kim}, doi = {10.1021/jacs.5c04975}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16661--16673}, shortjournal = {J. Am. Chem. Soc.}, title = {Rabies virus targeting NIR-II phototheranostics}, volume = {147}, year = {2025}, }
• (2025). Semiconducting polyaromatic covalent organic frameworks constructed through self-aldol condensation. JACS, 147(19), 16653--16660. (www)

  @article{ , abstract = {The construction of semiconducting covalent organic frameworks (COFs) via single-component self-polymerization is of broad interest in reticular chemistry. Herein, two semiconducting polyaromatic COFs with all-fused-ring conjugation structures were synthesized through the self-aldol condensation of indanone-based building blocks. The resulting COFs exhibit n -type semiconducting properties and exceptional stability under harsh acidic and alkaline conditions. The electrical conductivity and charge carrier mobility of the polyaromatic COFs reached up to 5.5 × 10 –3 S cm –1 and 0.62 cm 2 V –1 s –1 , which ranked as the highest values among n -type semiconducting COFs. The high crystallinity, intrinsic porosity, excellent conductivity, and abundant five-membered rings as active sites render these COFs as effective metal-free electrocatalysts toward oxygen reduction reaction (ORR). Notably, one of these COFs shows a half-wave potential of up to 0.77 V under alkaline conditions, which constitutes one of the highest values among the reported metal-free ORR electrocatalysts. In addition, owing to the strong robustness of the polyaromatic COFs, they also exhibit long-term catalytic durability. This study not only expands the diversity of semiconducting COFs but also establishes new paradigms for the development of high-performance metal-free electrocatalysts toward the ORR process.}, archive = {J_JACS}, author = {Xiaoyi Xu and Yaoqian Feng and Hongzheng Chen and Ning Huang}, doi = {10.1021/jacs.5c04944}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16653--16660}, shortjournal = {J. Am. Chem. Soc.}, title = {Semiconducting polyaromatic covalent organic frameworks constructed through self-aldol condensation}, volume = {147}, year = {2025}, }
• (2025). Tandem synthesis of N,O-containing heterocycles via nitrite upcycling at a trifunctional cobalt catalyst. JACS, 147(19), 16642--16652. (www)

  @article{ , abstract = {Biological reduction of nitrite (NO 2 – ) to nitric oxide (NO) by nitrite reductase (NIR) is a crucial step in the denitrification process of the global nitrogen cycle. To mitigate excess NO x pollutants from anthropogenic activity, developing catalytic processes for NO x conversion and utilization (NCU) is essential. This study presents a trifunctional cobalt catalyst supported by an acri PNP-ligand, mimicking the NIR reactivity. A Co(II) species catalyzes NO generation through NO 2 – deoxygenation with CO and concomitant 1 – e – oxidation, while the resulting Co(I)-carbonyl species activates benzyl halides, generating radicals that undergo C–N coupling with NO. The ( acri PNP)Co scaffold performs a triple function: deoxygenating nitrite, generating NO, and forming benzyl radicals. Comparing a nickel analogue, the open-shell reactivity of the Co system significantly enhances C–N coupling efficiency, achieving a turnover number of 5000 and a turnover frequency of ∼850 h –1 for oxime production. The oxime intermediate can then be converted into valuable N/ 15 N,O-containing bioactive heterocycles, advancing NCU technology.}, archive = {J_JACS}, author = {Jeewon Chun and Sudakar Padmanaban and Yunho Lee}, doi = {10.1021/jacs.5c04521}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16642--16652}, shortjournal = {J. Am. Chem. Soc.}, title = {Tandem synthesis of N,O-containing heterocycles via nitrite upcycling at a trifunctional cobalt catalyst}, volume = {147}, year = {2025}, }
• (2025). Facet-engineered copper electrocatalysts enable sustainable NADH regeneration with high efficiency. JACS, 147(19), 16630--16641. (www)

  @article{ , abstract = {Electrochemical regeneration of the nicotinamide cofactor (NADH) provides a sustainable approach to enzymatic reactions. However, the low productivity and selectivity of bioactive 1,4-NADH limit its broad applications. The hydrogenation of NAD + to 1,4-NADH at the electrode surface is strongly coupled to the conformation of adsorbed NAD*, the formation of adsorbed hydrogen (H ad ), and the H ad transfer to NAD*. Therefore, searching for materials with a suitable NAD* conformation, low H ad formation energy, and rapid NAD* hydrogenation becomes a key task for the research. In this study, the (111) facet of Cu was found to exhibit a higher 1,4-NADH selectivity of 86.4%, compared to 50.4% and 57.4% for (100) and (110) facets, respectively. Density functional theory (DFT) calculations revealed that the high selectivity of Cu(111) stemmed from the favorable conformation of adsorbed NAD* and the reduced hydrogenation barrier. Subsequently, a Cu nanowire electrode with a (111)-dominant surface and abundant grain boundaries, Cu gb (111), was constructed. Electrochemical kinetic analysis and DFT calculations demonstrated that the grain boundaries reduce the reaction barrier of H ad formation. A record-high 1,4-NADH productivity of 73.5 μmol h –1 cm –2 was achieved by Cu gb (111), while the 1,4-NADH selectivity was well-maintained at 84.7%. This study elucidates the effects of crystal facets and grain boundaries on regulating the selectivity and productivity of 1,4-NADH, providing a pathway for renewable energy-powered, high-efficiency green biomanufacturing.}, archive = {J_JACS}, author = {Shuo Sun and Yizhou Wu and Yunxuan Ding and Linqin Wang and Xing Cao and Licheng Sun}, doi = {10.1021/jacs.5c04431}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16630--16641}, shortjournal = {J. Am. Chem. Soc.}, title = {Facet-engineered copper electrocatalysts enable sustainable NADH regeneration with high efficiency}, volume = {147}, year = {2025}, }
• (2025). Monomeric two-coordinate beryllium imido and boryloxide complexes featuring Be–N and Be–O triple bonds. JACS, 147(19), 16620--16629. (www)

  @article{ , abstract = {The 2p elements possess a unique propensity to participate in multiple bonding. Realization of multiple bonding involving the 2s elements, however, is challenging and remains exceedingly rare. In this contribution, we present the syntheses, detailed characterization, and molecular structures of heteroleptic beryllium imido and boryloxide complexes of the type [(HCNDip) 2 YXBeAr(OEt 2 ) n ] m (Y,X = C,N or B,O; n = 0, 1; m = 1, 2; Dip = 2,6- i Pr 2 C 6 H 3 ) by salt metathesis and arene elimination approaches. Systematic adjustment of the steric demand of the aryl substituent resulted in the isolation of monomeric, two-coordinate beryllium imido and boryloxide complexes, (HCNDip) 2 CNBeTip ( 9 , Tip = 2,4,6- i Pr 3 C 6 H 2 ) and (HCNDip) 2 BOBeAr Dip ( 12 , Ar Dip = 2,6-Dip 2 C 6 H 3 ), containing virtually linear C–N–Be–C and B–O–Be–C arrangements and extremely short Be–N (1.434(2) Å, 1.437(3) Å) and Be–O (1.4035(14) Å) bonds, respectively. These were shown by in-depth computational electronic structure and bonding analyses to possess unprecedented triple bond character. The Be–O bond in 12 constitutes the first s-block metal–oxygen multiple bond.}, archive = {J_JACS}, author = {Christoph Helling and David J. D. Wilson and Cameron Jones}, doi = {10.1021/jacs.5c04320}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16620--16629}, shortjournal = {J. Am. Chem. Soc.}, title = {Monomeric two-coordinate beryllium imido and boryloxide complexes featuring Be–N and Be–O triple bonds}, volume = {147}, year = {2025}, }
• (2025). Intrinsic off-centering and light conduction band structure lead to high thermoelectric performance in N-type diamondoid AgInSe2. JACS, 147(19), 16611--16619. (www)

  @article{ , abstract = {Historically, the rocksalt crystal structure and its variants have long dominated the field of advanced thermoelectrics. Developing new structural thermoelectric materials is an interesting topic for the thermoelectric community. In this work, an n-type diamondoid compound, AgInSe 2 , was identified with extremely low thermal conductivity and very high carrier mobility. The intrinsic Ag off-centering behavior combined with the densely distributed twin boundaries and switched grain orientations significantly disrupts phonon transport and leads to the extremely low thermal conductivity of ∼0.19 W m –1 K –1 at 850 K in the Ag 0.98 In 1.02 Se 2 -0.03CdSe material. On the other hand, the light conduction band structure of AgInSe 2 leads to a small density-of-state effective mass of 0.1 m e and very high electron mobility of 700 cm 2 V –1 s –1 at room temperature. Combining this with the significant increase in carrier concentration induced by CdSe alloying, a record-high maximum ZT of 1.4 at 850 K and an average ZT of 0.8 are achieved in n-type Ag 0.98 In 1.02 Se 2 -0.03CdSe, which can be comparable to many typical rocksalt n-type thermoelectrics. Moreover, a maximum output power of ∼10 mW and an energy conversion efficiency of ∼5% were demonstrated in the AgInSe 2 -based single-leg device, highlighting the application potential of this novel n-type diamondoid thermoelectric.}, archive = {J_JACS}, author = {Jingyi Su and Yukun Liu and Yichen Li and Shulin Bai and Dezheng Gao and Pengpeng Chen and Zihao Zhao and Vinayak P. Dravid and Hongyao Xie and Li-Dong Zhao and Mercouri G. Kanatzidis}, doi = {10.1021/jacs.5c04294}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16611--16619}, shortjournal = {J. Am. Chem. Soc.}, title = {Intrinsic off-centering and light conduction band structure lead to high thermoelectric performance in N-type diamondoid AgInSe2}, volume = {147}, year = {2025}, }
• (2025). Quantum interference in a molecular analog of the crystalline silicon unit cell. JACS, 147(19), 16602--16610. (www)

  @article{ , abstract = {This manuscript describes the emergence of destructive σ-quantum interference (σ-DQI) in sila-adamantane, a molecule whose cluster core is isostructural with the crystalline silicon unit cell. To reveal these σ-DQI effects, we take a bridge-cutting approach where we conceptually pare sila-adamantane down to its bicyclic Si[3.3.1] and linear oligosilane forms. Scanning tunneling microscopy break-junction (STM-BJ) measurements reveal that conductance in single-molecule junctions of the tricyclic sila-adamantane is 2.7-times lower than their bicyclic Si[3.3.1] analog. The only structural difference between their cluster cores is a remote dimethylsilylene bridge that is present in sila-adamantane yet absent in Si[3.3.1]. Density functional theory calculations reveal that this dimethylsilylene enforces C 3 symmetry at the sila-diamondoid bridgeheads, allowing each electrode to couple into the three cluster bridge dimensions equally. Though each bridge alignment is sterically equivalent, they have profound electronic differences: when electrodes align with the long branches of sila-adamantane, strong σ-DQI interactions occur between frontier molecular orbitals that suppress electronic transmission across the molecular junction. We exploit these alignment-dependent σ-DQI effects to create new forms of stereoelectronic conductance switches, where a reversible mechanical stimulus controls which pathway through the diamondoid framework the electrodes align through. This represents the first example of dynamic modulation of σ-DQI and enables us to achieve switching ratios (average on/off ∼5.6) higher than previously reported σ-stereoelectronic switches. These studies reveal how the innate dimensionality and symmetry of crystalline silicon influence charge transport at its most fundamental level, and how these principles can be harnessed to control quantum interference in single-molecule electronics.}, archive = {J_JACS}, author = {Matthew O. Hight and Ashley E. Pimentel and Timothy C. Siu and Joshua Y. Wong and Jennifer Nguyen and Veronica Carta and Timothy A. Su}, doi = {10.1021/jacs.5c04272}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16602--16610}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantum interference in a molecular analog of the crystalline silicon unit cell}, volume = {147}, year = {2025}, }
• (2025). Atomic-precise active site surgery on carboranylthiolate-protected silver nanocluster catalysts. JACS, 147(19), 16593--16601. (www)

  @article{ , abstract = {Although significant progress has been made in precisely modulating the composition and structure of metal nanoclusters to tailor their properties, the well-controlled synthesis of metal nanoclusters with unsaturated coordination environments and highly active sites to enhance the catalytic performance remains remarkably challenging. Here, we propose an atomic-level surgical strategy involving the stepwise creation and manipulation of active metal sites on metal nanoclusters. A newly constructed Ag 17 P nanocluster, costabilized by carboranethiolate and phosphine ligands, features an Ag 13 icosahedral kernel capped by four tetrahedrally symmetrical silver atoms. Taking advantage of the phosphine ligands readily dissociating from the four peripheral silver atoms under solvent regulation, Ag 17 P could transform into Ag 17 with four exposed silver atoms. Furthermore, site-specific substitution could be accomplished in these open metal sites through a judicious choice of heterometal, resulting in an isostructural Cu-doping Ag 13 Cu 4 nanocluster. As a result, Ag 17 and Ag 13 Cu 4 with exposed metal sites showed improved catalytic activities in electrocatalytic nitrate reduction reaction (NO 3 RR) compared to Ag 17 P , and Ag 13 Cu 4 displayed superior performance with an optimal faradaic efficiency (FE) of 90.4 ± 0.2% for NH 3 production and a total FE of 99.6 ± 0.3%. This study not only offers a pathway for generating and manipulating open metal sites on metal nanoclusters but also provides new perspectives for the design and synthesis of efficient metal nanocluster-based catalytic materials.}, archive = {J_JACS}, author = {Jia-Hong Huang and Han Zhang and Zhao-Yang Wang and Jia-Hua Hu and Jing Li and Jinmeng Cai and Shuang-Quan Zang}, doi = {10.1021/jacs.5c03721}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16593--16601}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic-precise active site surgery on carboranylthiolate-protected silver nanocluster catalysts}, volume = {147}, year = {2025}, }
• (2025). Microscopic mechanical force-driven amorphization of Metal–Organic frameworks. JACS, 147(19), 16585--16592. (www)

  @article{ , abstract = {While metal–organic frameworks (MOFs) are renowned for their highly ordered crystalline structures, the amorphization of MOFs reveals new functional properties and creates opportunities for material innovation. In this study, we present a novel microscopic mechanical force-driven amorphization that occurs within a polycrystalline metal-azolate framework (MAF-5) membrane. We show that vapor flow during pervaporation across the membrane generates localized mechanical stresses that disrupt the ordered crystalline lattice. This mechanical amorphization is significantly influenced by the physical properties of the permeating organic solvents, underscoring the importance of solvent–framework interactions. Our findings unveil a previously unknown mechanical mechanism that drives MOF amorphization and provide essential insights into their mechanical tunability, facilitating the design of amorphous MOF membranes with customized properties for advanced applications.}, archive = {J_JACS}, author = {Ting Chen and He Li and Xiansong Shi and Yunchuan Pu and Nengxiu Zhu and Yidan Duan and Dongchen Shi and Wei Zhao and Joseph Imbrogno and Dan Zhao}, doi = {10.1021/jacs.5c04101}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16585--16592}, shortjournal = {J. Am. Chem. Soc.}, title = {Microscopic mechanical force-driven amorphization of Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Violations of coordination: Exploring metastable diborides via energetic transition metals. JACS, 147(19), 16578--16584. (www)

  @article{ , abstract = {The ideal aeronautical solid-state fuel should possess a high gravimetric heat of combustion (more energy for less weight) and a high volumetric heat of combustion (more room for mission-critical items). In this work, manganese diboride (MnB 2 ) demonstrates a high gravimetric heat of combustion of 39.26 kJ/g and the highest volumetric heat of combustion of any known fuel of 208.08 kJ/cm 3 . When compared to the currently used fuel in Space Shuttle rocket boosters and the Space Launch System, aluminum metal, MnB 2 represents a 26% increase in gravimetric heat of combustion and a 148% increase in volumetric heat of combustion. Surprisingly, the local topology of the inner coordination sphere controls energetic output. A model cluster system analyzed by density functional theory shows that the local environment can contribute to the bulk properties even without physical manifestations in the periodic structure. This high enthalpic performance comes from the metastability of MnB 2 and demonstrates that transition metals, typically shunned as solid-state fuels, can store potential energy from their high-temperature synthesis through ‘overcoordination’ and violation of their valence shell.}, archive = {J_JACS}, author = {Joseph T. Doane and Gregory M. John and Alma Kolakji and Abraham A. Rosenberg and Yiren Zhang and Alan A. Chen and Michael T. Yeung}, doi = {10.1021/jacs.5c04066}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16578--16584}, shortjournal = {J. Am. Chem. Soc.}, title = {Violations of coordination: Exploring metastable diborides via energetic transition metals}, volume = {147}, year = {2025}, }
• (2025). Enantiomeric ferroelectric chiral domains. JACS, 147(19), 16568--16577. (www)

  @article{ , abstract = {Chiral ferroelectric crystals with inherent chirality and spontaneous polarization have recently gained considerable interest. However, the chiral topological texture, which provides a promising platform for exploring exotic functionalities, has never been found in enantiomeric ferroelectric crystals. Here, we report a pair of enantiomeric molecular ferroelectrics, [RFAO][ReO 4 ] and [SFAO][ReO 4 ] (RFAO/SFAO = (4 R ,5 R /4 S ,5 S )-4-fluoro-1-azabicyclo[3.2.1]octane). The enantiomers crystallize in the chiral-polar point group 2 at room temperature and undergo two ferroelectric phase transitions with an Aizu notation of 222 F 2 at 350 K and 432 F 2 at 463 K, respectively. Such phase transitions enable them to show a multistep switchable second-harmonic generation circular dichroism (SHG-CD) effect from high to low to off (inactive) SHG-CD states. More importantly, we observed spiral chiral ferroelectric domains in the enantiomers. To the best of our knowledge, this is the first discovery of chiral domains in enantiomeric ferroelectric crystals. Our breakthrough findings give new sights into the interplay between polarization and chirality and will greatly stimulate further exploration of chiral ferroelectric crystals with switchable SHG-CD and chiral domains for next-generation electronic-photonic devices.}, archive = {J_JACS}, author = {Xian-Jiang Song and Yong Ai and Xiao-Gang Chen and Yan Qin and Yuan-Yuan Tang and Hui-Peng Lv and Peng-Fei Li and Hang Peng and Yan-Ran Weng and Huan-Huan Chen and Ren-Gen Xiong and Wei-Qiang Liao}, doi = {10.1021/jacs.5c04038}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16568--16577}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantiomeric ferroelectric chiral domains}, volume = {147}, year = {2025}, }
• (2025). DNA-based networks formed by coordination cross-linking of DNA with Metal–Organic polyhedra: From gels to aerogels to hydrogels. JACS, 147(19), 16560--16567. (www)

  @article{ , abstract = {Herein, we introduce a supramolecular method to form DNA-based networks by cross-linking DNA with Rh(II)-based metal–organic polyhedra (MOPs), which entails coordination of DNA to the exohedral Rh(II) axial sites of the MOP. The resultant highly connected networks can then be processed into gels, porous aerogels, or hydrogels, exhibiting properties suitable for pollutant removal and drug release.}, archive = {J_JACS}, author = {Laura Hernández-López and Akim Khobotov-Bakishev and Alba Cortés-Martínez and Eduard Garrido-Ribó and Partha Samanta and Sergio Royuela and Félix Zamora and Daniel Maspoch and Arnau Carné-Sánchez}, doi = {10.1021/jacs.5c03934}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16560--16567}, shortjournal = {J. Am. Chem. Soc.}, title = {DNA-based networks formed by coordination cross-linking of DNA with Metal–Organic polyhedra: From gels to aerogels to hydrogels}, volume = {147}, year = {2025}, }
• (2025). Cs2AgSbI6 nanocrystals: A new air-stable iodide double-perovskite (Elpasolite) semiconductor. JACS, 147(19), 16552--16559. (www)

  @article{ , abstract = {Three-dimensional (3D) iodide double perovskites (elpasolites) are extremely rare due to inherent instability issues. Here, we report the discovery of an air-stable iodide elpasolite semiconductor in the form of nanocrystals with the composition Cs 2 AgSbI 6 , synthesized via halide exchange from Cs 2 AgSbBr 6 nanocrystals. This composition, previously considered thermodynamically unstable based on computational predictions, shows a ∼1.8 eV optical gap with near-infrared photoluminescence. The nanocrystals are stable in air up to at least 140 °C. As one of only a few known examples of intermediate-bandgap 3D iodide double perovskites, Cs 2 AgSbI 6 represents a promising platform for further development of this family of materials as well as for fundamental and optoelectronic investigations.}, archive = {J_JACS}, author = {Faris Horani and Daniel R. Gamelin}, doi = {10.1021/jacs.5c03942}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16552--16559}, shortjournal = {J. Am. Chem. Soc.}, title = {Cs2AgSbI6 nanocrystals: A new air-stable iodide double-perovskite (Elpasolite) semiconductor}, volume = {147}, year = {2025}, }
• (2025). Chemical vapor deposition of “Stand-on” 2D single-crystal flakes. JACS, 147(19), 16545--16551. (www)

  @article{ , abstract = {Two-dimensional (2D) superconductors are highly valued for their reduced dimensionality and unique quantum properties. However, their susceptibility to oxidation and degradation, particularly during wet transfer processes, often leads to undesirable deterioration of their electrical properties. In this work, we present an innovative and facile synthesis strategy for producing ultrathin “stand-on” superconducting FeTe 1– x Se x nanosheets, enabling a highly efficient and damage-free transfer process. Low-temperature transport measurements confirm the superior superconducting performance of the transferred materials. Furthermore, by employing a convenient dry poly(dimethylsiloxane) (PDMS) stamping technique, we successfully fabricated high-quality 2D superlattices with precise angle control. Moreover, this synthesis strategy has been extended to various substrate and material systems, providing a versatile platform for studying high-performance integrated systems.}, archive = {J_JACS}, author = {Ya Deng and Jiefu Yang and Yao Wu and Chao Zhu and Dianyi Hu and Xiuxian Zhou and Wei Ma and Ruihuan Duan and Qundong Fu and Xiaowei Wang and Zheng Liu}, doi = {10.1021/jacs.5c03608}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16545--16551}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemical vapor deposition of “Stand-on” 2D single-crystal flakes}, volume = {147}, year = {2025}, }
• (2025). Metal doping of strongly confined halide perovskite nanocrystals under ambient conditions. JACS, 147(19), 16536--16544. (www)

  @article{ , abstract = {Halide perovskite nanocrystals are promising materials for optoelectronic applications. Metal doping provides an avenue to boost their performance further, e.g., by enhancing light emission, or to provide additional functionalities, such as nanoscale magnetism and polarization control. However, the synthesis of widely size-tunable nanocrystals with controlled doping levels has been inaccessible using traditional hot injection synthesis, preventing systematic studies on dopant effects toward device applications. Here, we report a versatile synthesis method for metal-doped perovskite nanocrystals with precise control over size and doping concentration under ambient conditions. Our room temperature approach results in fully size-tunable isovalent doping of CsPbX 3 nanocrystals (X = Cl, Br, I) with various transition metals M 2+ tested (M = Mn, Ni, Zn). This gives for the first time access to small, yet precisely doped quantum dots beyond the weak confinement regime reported so far. It also enables a comparative study of the photophysics across multiple size and dopant regimes, where we show dopant-induced localization to dominate over quantum confinement effects. This generalizable, facile synthesis method thus provides a toolbox for engineering perovskite nanocrystals toward light-emitting technologies under industrially relevant conditions.}, archive = {J_JACS}, author = {Zachary A. VanOrman and Mateo Cárdenes Wuttig and Antti-Pekka M. Reponen and Taek-Seung Kim and Claire E. Casaday and Dongtao Cui and Tejas Deshpande and Huygen J. Jöbsis and Pascal Schouwink and Emad Oveisi and Aurélien Bornet and Christian Reece and Sascha Feldmann}, doi = {10.1021/jacs.5c03629}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16536--16544}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal doping of strongly confined halide perovskite nanocrystals under ambient conditions}, volume = {147}, year = {2025}, }
• (2025). Tailoring mesopores on ultrathin hollow carbon nanoarchitecture with N2O2 coordinated ni single-atom catalysts for hydrogen evolution. JACS, 147(19), 16522--16535. (www)

  @article{ , abstract = {Single-atom catalysts (SACs) offer exceptional atomic utilization and catalytic efficiency, particularly in the hydrogen evolution reaction (HER), where effective mass transport and electronic structure control are critical. However, many SACs suffer from suboptimal hydrogen adsorption energies and limited synergy with the support matrix, which restrict their intrinsic activity and durability. Overcoming these limitations requires an integrated strategy that simultaneously optimizes both the atomic coordination environment and the support architecture. Here, we present a dual-template strategy for synthesizing ultrathin mesoporous hollow carbon (MHC) with tunable mesopores, which enhances ion transport and structural accessibility. Ni single atoms are stabilized within the MHC framework via a tailored N 2 O 2 coordination environment, which fine-tunes the electronic structure of Ni and facilitates efficient hydrogen adsorption and HER kinetics. This coordination environment and the hierarchical porous framework collectively enhance HER activity, significantly reducing the overpotential to 68 mV at 10 mA cm –2 and resulting in remarkable mass activity (5 A mg Ni –1 at 50 mV) and enhanced durability over 5000 cycles. Spectroscopic analyses and density functional theory calculations reveal that the N 2 O 2 coordination fine-tunes the electronic structure of Ni, promoting efficient hydrogen adsorption and evolution. These findings highlight the synergistic effects of atomic-level Ni dispersion and tailored support, offering a robust strategy for fabricating single-atom electrocatalysts for sustainable hydrogen production.}, archive = {J_JACS}, author = {Donggyun Kim and Ko-Eun Ryou and Godeung Park and Seonghyeon Jung and Jinhyeon Park and Minjun Kim and Jieun Jang and Myeongjun Song and Semi Kim and Juyeong Kim and Hyunsoo Lim and Yusuke Yamauchi and Hyosung An and Seong-Min Bak and Jeonghun Kim}, doi = {10.1021/jacs.5c03118}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16522--16535}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailoring mesopores on ultrathin hollow carbon nanoarchitecture with N2O2 coordinated ni single-atom catalysts for hydrogen evolution}, volume = {147}, year = {2025}, }
• (2025). Regulating amine substitution in fluorosulfonyl-based flame-retardant electrolytes for energy-dense lithium metal batteries. JACS, 147(19), 16506--16521. (www)

  @article{ , abstract = {Sulfone-based electrolytes offer unusually high anodic and thermal stability that in principle makes them promising candidates for fabricating energy-dense lithium metal batteries (LMBs). Their uses in practical batteries are currently limited by their inability to sustain long-term Li metal plating/stripping processes due to their high reactivity toward the Li metal. Here, we report on the design and synthesis of a unique family of fluorosulfonyl group-based (FSO 2 – ) molecules, modified with ethyl (FSE)/ N , N -dimethyl (FSNDM)/ N , N -diethyl (FSNDE)/ N -pyrrolidine (FSNP) end groups to create exceptionally stable single-salt single-solvent electrolytes. The flammability, solvation structure, ion transport, Li metal deposition kinetics, and high-voltage stability of the electrolytes are systematically studied. It is shown that the electrolytes are nonflammable, possess weak solvation characteristics, yet manifest high room-temperature ionic conductivities (1.6–6.1 mS cm –1 ) and low solution viscosities. In comparison to FSE, the FSNDM-, FSNDE-, and FSNP-based electrolytes exhibit an exceptionally reversible Coulombic efficiency for Li metal plating/stripping (>99.71% over 800 cycles) and exhibit typical oxidative stability at voltages exceeding 4.6 V. Deployed as electrolytes in Li metal batteries (20 μm Li anode and 3 g A h –1 electrolyte) with high-loading (18.5 mg cm –2 ) LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes, 329 cycles have been achieved before 80% capacity retention. Six Ah Li metal pouch cells based on the designed electrolytes also exhibit high stability and high energy density (496 W h kg –1 ) for over 150 cycles with at most 2.7% volume expansion. Our findings demonstrate that through an intentional molecular design, sulfone electrolytes provide a robust route toward nonflammable Li metal compatible electrolytes with practical high-voltage cathodes.}, archive = {J_JACS}, author = {Lan-Qing Wu and Zhe Li and Huamei Li and Jin-Yu Zhang and Yong Li and Shuang-Xin Ren and Zhen-Yu Fan and Xiao-Tian Wang and Kun Li and Zhen Liu and Jie Zhang and Ji-Chi Yang and Ya-Wen Li and Shou-Hang Bo and Qing Zhao}, doi = {10.1021/jacs.5c03606}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16506--16521}, shortjournal = {J. Am. Chem. Soc.}, title = {Regulating amine substitution in fluorosulfonyl-based flame-retardant electrolytes for energy-dense lithium metal batteries}, volume = {147}, year = {2025}, }
• (2025). Trilocked photodynamic senolytic inducer potentiating immunogenic senescent cell removal for liver fibrosis resolution. JACS, 147(19), 16494--16505. (www)

  @article{ , abstract = {Liver fibrosis is a major global health problem without effective therapies, and targeted elimination of senescent cells is beneficial for hepatic function and organism survival. We report a new trilocked photodynamic senolytic inducer (PDSI) strategy for liver fibrosis resolution using a type-I photodynamic agent for immunogenic clearance of senescent cells. We demonstrate that this trilocked PDSI not only facilitates efficient production of superoxide anions (O 2 •– ) in lysosomes of senescent cells for photodynamic therapy, but also permits NIR fluorescence and photoacoustic (NIRF/PA) imaging of senescent cells. Mechanistic investigation reveals that the trilocked PDSI elicited senescent cell clearance predominantly via the immunogenic necroptosis pathway. Moreover, this PDSI with a liver-targeting moiety enables high-contrast NIRF/PA imaging and effective liver fibrosis resolution in vivo. This liver-targeting PDSI exhibits remarkable immunogenic ablation of senescent cells, with enhancing dendritic cell maturation and cytotoxic T cell recruitment in liver fibrosis. Our study highlights the potential of trilocked type I PDSI for boosting immunity for senescent cell clearance and liver fibrosis treatment.}, archive = {J_JACS}, author = {Pei Lu and Huihui Zhou and Xiaoxiao Xu and Ying Long and Jian-Hui Jiang and Fenglin Wang}, doi = {10.1021/jacs.5c03498}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16494--16505}, shortjournal = {J. Am. Chem. Soc.}, title = {Trilocked photodynamic senolytic inducer potentiating immunogenic senescent cell removal for liver fibrosis resolution}, volume = {147}, year = {2025}, }
• (2025). Multivariate tuning of photosensitization in mixed-linker Metal–Organic frameworks for efficient CO2 reduction. JACS, 147(19), 16481--16493. (www)

  @article{ , abstract = {Photosensitization is a powerful approach for enhancing the photocatalyst performance by improving light absorption, energy transfer, and charge separation. However, achieving high efficiency requires precise control over photosensitizers, catalytic centers, and their interactions, which remain challenging in heterogeneous systems. Herein, we develop multivariate zirconium metal–organic frameworks (MOFs) with mixing linkers and tunable defects that enable unprecedented control over photosensitizers, catalytic centers, and their ratios, creating an efficient platform for CO 2 reduction. These MOFs integrate triphenylamine, phenoxazine, or phenothiazine-based linkers as photosensitizers and metal porphyrin linkers (metal = Fe, Co, Ni, and Zn) as CO 2 reduction catalytic centers. Furthermore, the defect tolerance of robust Zr 6 nodes allows for a systematic variation in linker ratios by introducing missing linker defects. By fine-tuning the photosensitizers, catalytic metal centers, and their ratios, we achieved an optimized photocatalyst with CO 2 -to-CO reduction rates of 247.8 μmol g cat. –1 h –1 , representing a 17-fold enhancement over homogeneous analogues. Transient spectra and density functional theory calculations reveal the critical role of the framework structure in promoting efficient intrareticular energy transfer and charge separation. This study highlights the unique advantage of MOF platforms in the multivariate tuning of photocatalysts, paving the way for advanced artificial photosynthetic systems.}, archive = {J_JACS}, author = {Ya Yin and Shijia Feng and Xinyu Xu and Yifan Liu and Youcong Li and Lei Gao and Xiaocheng Zhou and Jiahao Dong and Yulun Wu and Jian Su and Jing-Lin Zuo and Shuai Yuan and Jia Zhu}, doi = {10.1021/jacs.5c02940}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16481--16493}, shortjournal = {J. Am. Chem. Soc.}, title = {Multivariate tuning of photosensitization in mixed-linker Metal–Organic frameworks for efficient CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). Designing highly conductive anion exchange membranes: Tuning domain continuity with ABC block copolymer self-assembly. JACS, 147(19), 16471--16480. (www)

  @article{ , abstract = {Anion exchange membranes (AEMs) play a critical role in clean energy devices, and optimizing their performance requires a deeper understanding of morphology–performance relationships. This study investigates ABC triblock terpolymer AEMs to explore how domain continuity influences hydroxide conductivity, water uptake, and dimensional stability. High molecular weight ABC triblock terpolymers were synthesized through the controlled vinyl-addition polymerization of norbornene monomers functionalized with alkyl, benzyl, or bromobutyl substituents. Morphology was systematically varied across the series without significantly changing the molecular weight or ion exchange capacity (IEC) of the polymer by adjusting the alkyl/benzyl block length ratio. Solution-cast films exhibited either 2D-continuous lamellar or 3D- co -continuous network phase morphologies, with domain continuity largely retained after cationic functionalization. AEMs with 3D- co -continuous domains demonstrated superior performance, including enhanced dimensional stability and competitive hydroxide conductivities of up to 84 mS/cm at 25 °C and 131 mS/cm at 80 °C. This work highlights how the self-assembly of ABC triblock terpolymers can be leveraged to investigate morphology–performance relationships and achieve highly conductive, durable AEMs.}, archive = {J_JACS}, author = {Alexandra J. Macbeth and Danielle Markovich and Abigail L. Taylor and Ethan B. Flanagan and Julia E. Borowski and Jesse H. Hsu and Cheyenne R. Peltier and David A. Muller and Brett P. Fors and Kevin J. T. Noonan and Geoffrey W. Coates}, doi = {10.1021/jacs.5c03175}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16471--16480}, shortjournal = {J. Am. Chem. Soc.}, title = {Designing highly conductive anion exchange membranes: Tuning domain continuity with ABC block copolymer self-assembly}, volume = {147}, year = {2025}, }
• (2025). Erythromycin stress upregulates antiangiogenic metabolites in the gut bacterium aneurinibacillus aneurinilyticus. JACS, 147(19), 16459--16470. (www)

  @article{ , abstract = {The interplay among antibiotics, gut microbiota, and disease pathogenesis remains poorly understood, particularly in the context of rare gut bacteria. This study identifies a novel correlation between erythromycin-induced stress and the production of antiangiogenic metabolites in Aneurinibacillus aneurinilyticus , a human gut bacterium. We report the isolation and structural characterization of aneuristatin ( 1 ), a metabolite featuring a unique pyrrolo[1,2- a ]pyrazine scaffold, along with seven structurally related metabolites ( 2 – 8 ) from A. aneurinilyticus ATCC 12856 T . These metabolites were upregulated via the erythromycin-induced activation of the arnA biosynthetic gene. Aneuristatin ( 1 ) enhanced prolyl hydroxylase activity, promoting hypoxia-inducible factor-1α (HIF-1α) degradation and reducing downstream targets, including VEGF and EPO. It also exhibited antioxidant effects by reducing ROS levels under hypoxia. Additionally, it inhibited angiogenesis in HUVECs and zebrafish and effectively reduced inflammation, fibrosis, and angiogenesis in a mouse corneal injury model. Our study establishes a molecular basis for the potential of erythromycin-induced aneuristatin ( 1 ) to prevent or treat angiogenesis-related diseases such as cancer.}, archive = {J_JACS}, author = {Young Jun Ha and Su Jung Hwang and Subin Hong and Jonghwan Kim and Minji Kim and Gyu Sung Lee and Seung Hwan Lee and Hyemin Kim and Bum Soo Lee and Hye In An and Ki Hyun Kim and Wonsik Lee and Hyo-Jong Lee and Chung Sub Kim}, doi = {10.1021/jacs.5c03174}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16459--16470}, shortjournal = {J. Am. Chem. Soc.}, title = {Erythromycin stress upregulates antiangiogenic metabolites in the gut bacterium aneurinibacillus aneurinilyticus}, volume = {147}, year = {2025}, }
• (2025). Enhanced intermediates inter-migration on ag single-atom alloys for boosting multicarbon product selectivity in CO2 electroreduction. JACS, 147(19), 16450--16458. (www)

  @article{ , abstract = {Electrochemical CO 2 reduction reaction (CO 2 RR) to multicarbon (C 2+ ) products holds immense significance in promoting a closed carbon cycle and solving global energy problems, but it faces challenges of unsatisfactory selectivity. In this work, we constructed an Ag single-atom alloy cascade catalyst (AgCu-SAA) using an epoxide gelation approach, which enhanced the utilization efficiency of the CO intermediate through an inter-migration pathway. As a result, the C 2+ products’ Faradaic efficiency (FE) of 83.4% was achieved at a current density of 900 mA cm –2 . Moreover, the FE of the C 2+ products remained as high as 74.8% even at a high current density of 1100 mA cm –2 . In situ Raman spectra and density functional theory (DFT) calculations reveal that CO 2 is first converted to CO over the single-atom Ag site. Subsequently, the generated CO is directly transferred to the adjacent Cu site rather than desorbing into the electrolyte. This process avoids the inefficient migration of CO inter-mediates, thereby enhancing the selectivity for the formation of C 2+ products.}, archive = {J_JACS}, author = {Min Wang and Minghui Fang and Yingxuan Liu and Chunjun Chen and Yichi Zhang and Shuaiqiang Jia and Haihong Wu and Mingyuan He and Buxing Han}, doi = {10.1021/jacs.5c03057}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16450--16458}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced intermediates inter-migration on ag single-atom alloys for boosting multicarbon product selectivity in CO2 electroreduction}, volume = {147}, year = {2025}, }
• (2025). Branch-selective olefin hydroaminoalkylation from Ti(III)–Al bimetallic intermediates evidenced by EPR hyperfine spectroscopy and DFT calculations. JACS, 147(19), 16438--16449. (www)

  @article{ , abstract = {Regioselective hydroaminoalkylation of alkenes via α-C–H bond activation of alkylamines is an efficient process for the preparation of complex alkylamines minimizing stoichiometric waste. Herein, we report that a combination of Cp*TiMe 3 and AlMe 3 catalyzes the branch-selective hydroaminoalkylation of 1-alkenes, including styrene derivatives and 1,3-dienes, with N -methylaniline derivatives. Kinetic studies reveal that the active species are generated from in situ generated Cp*TiMe 2 (NMePh) and alkylaluminum. Continuous wave (CW) and pulse EPR spectroscopy show that multiple Ti(III) species, bearing amido and most probably alkyl ligands as well as an Al center, are formed, paralleling catalytic activity. Based on these findings complemented by DFT studies, we propose a reaction mechanism featuring d 1 Ti(III) three-membered azatitanacycle species with amidoaluminate anions as key reaction intermediates, where alkene insertion into the Ti–C bond of the three-membered metallacycle intermediate drives selectivity. This step favors the branched over the linear product, which may stem from differences in the spin delocalization from the metal to the alkene antibonding orbital for the corresponding transition states.}, archive = {J_JACS}, author = {Mariko Inoue and Julian Stropp and Anton Ashuiev and Yuya Kakiuchi and Pierre-Adrien Payard and Tokiya Teraishi and Mai Mizukami and Hayato Tsurugi and Daniel Klose and Christophe Copéret and Kazushi Mashima}, doi = {10.1021/jacs.5c02920}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16438--16449}, shortjournal = {J. Am. Chem. Soc.}, title = {Branch-selective olefin hydroaminoalkylation from Ti(III)–Al bimetallic intermediates evidenced by EPR hyperfine spectroscopy and DFT calculations}, volume = {147}, year = {2025}, }
• (2025). Click to stack: Shape-assisted self-assembly of unflattened macrocycles into waveguiding elastic crystals. JACS, 147(19), 16429--16437. (www)

  @article{ , abstract = {Designing molecular crystals for practical applications requires precise control over intermolecular interactions. We report a click-to-stack strategy to enable facile construction and systematic structural modification of tetraarene-fused cyclooctatetraenes. These saddle-shaped molecules self-assemble into one-dimensional columns with exceptional precision, driven solely by weak van der Waals interactions. Single-crystal X-ray crystallographic and computational studies revealed fully eclipsed π–π stacking, reinforced by the shape complementarity of the negatively curved molecular contour. With alkoxy groups tethered, the antiparallel alignment of coaxial cable-like assemblies produces centimeter-long voidless crystals that exhibit remarkable structural durability under mechanical stress. These glow stick-like elastic crystalline rods display optical waveguiding properties, demonstrating the practical utility of highly anisotropic molecular assemblies with structural uniformity and resilience.}, archive = {J_JACS}, author = {Hongsik Kim and Jung Bae Son and Myeongsu Jeong and Youmin Ahn and MinGyu Choi and Seungju Kang and Nam Ki Lee and Dongwhan Lee}, doi = {10.1021/jacs.5c02849}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16429--16437}, shortjournal = {J. Am. Chem. Soc.}, title = {Click to stack: Shape-assisted self-assembly of unflattened macrocycles into waveguiding elastic crystals}, volume = {147}, year = {2025}, }
• (2025). A light-responsive Metal–Organic framework with perchlorinated nanographene ligands. JACS, 147(19), 16420--16428. (www)

  @article{ , abstract = {Harnessing water as a sustainable electron source for artificial photosynthesis remains a significant challenge. This work presents Alice-MOF-1 , a novel zirconium metal–organic framework (MOF) incorporating hexatopic ligands with a perchlorinated hexa- peri -hexabenzocoronene (HBC) core, as a photocatalyst for CO 2 reduction using water as the terminal electron donor. Contortion of the ligand, induced by edge chlorination, minimizes π-stacking and enhances solubility, enabling direct MOF synthesis. The controlled arrangement of chromophores within Alice-MOF-1 is crucial for enabling the complex multielectron redox reactions. The unique ligand architecture within the MOF promotes symmetry-breaking charge transfer (SBCT), a mechanism observed in natural photosynthesis, leading to efficient charge separation with minimal energy loss. Femtosecond transient absorption spectroscopy and time-resolved electron paramagnetic resonance spectroscopy (EPR) confirm the formation of long-lived radical ions, providing direct evidence for efficient SBCT and negligible charge recombination. These findings demonstrate the power of MOF-based chromophore assemblies to mimic nature’s light-harvesting strategies for sustainable energy conversion.}, archive = {J_JACS}, author = {Xin Zheng and Nikita Gupta and Haiying He and Jasleen K. Bindra and Subharaj Hossain and Juan P. Vizuet and Atefeh Nadeali and Danial Zangeneh and Roushan Prakash Singh and Robert F. Klie and Brian P. Chaplin and Kenneth Brezinsky and Oleg G. Poluektov and Jens Niklas and Peter Zapol and Ksenija D. Glusac}, doi = {10.1021/jacs.5c02844}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16420--16428}, shortjournal = {J. Am. Chem. Soc.}, title = {A light-responsive Metal–Organic framework with perchlorinated nanographene ligands}, volume = {147}, year = {2025}, }
• (2025). Double-walled mesoporous hydrogen-bonded organic frameworks with high methane storage capacity. JACS, 147(19), 16412--16419. (www)

  @article{ , abstract = {The development of mesoporous hydrogen-bonded organic frameworks (HOFs) is critically important for various applications, yet it poses significant challenges. Herein, we present the synthesis and characterization of a robust mesoporous HOF, RP-H200, constructed through the orchestration of π–π stacking and hydrogen bonding interactions in a 2-fold interpenetrated framework. RP-H200 features a unique double-walled structure with a pore size of 3.6 nm, representing the largest pore size among reported HOFs to date. The framework exhibits a high surface area of 2313 m 2 g –1 , with aromatic surfaces dominating the mesoporous channels. The methane storage performance of RP-H200 reaches a high capacity of 0.31 g g –1 at 270 K/100 bar and 0.25 g g –1 at 296 K/100 bar. The combination of large permanent mesoporosity, excellent thermal stability, and high surface area in RP-H200 makes it a promising candidate for clean energy storage and other functions.}, archive = {J_JACS}, author = {Ruihua Zhang and Chun Tang and Shuliang Yang and Penghao Li and Han Han and Yong Wu and Guangcheng Wu and Xueze Zhao and Bai-Tong Liu and Sheng-Nan Lei and Bohan Tang and Enxu Liu and Yi-Kang Xing and Charlotte L. Stern and Christos D. Malliakas and J. Fraser Stoddart}, doi = {10.1021/jacs.5c02705}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16412--16419}, shortjournal = {J. Am. Chem. Soc.}, title = {Double-walled mesoporous hydrogen-bonded organic frameworks with high methane storage capacity}, volume = {147}, year = {2025}, }
• (2025). Photoswitchable fluorescent hydrazone for super-resolution cell membrane imaging. JACS, 147(19), 16404--16411. (www)

  @article{ , abstract = {Advancing the field of super-resolution microscopy will require the design and optimization of new molecular probes whose emission can be toggled “ON” and “OFF” using light. Recently, we reported on a hydrazone photochrome ( 1 ) whose emission can be photoswitched on demand, although its low brightness and UV light-dependent back isomerization limited its use in such applications. Here, we report on the optimization of this parent fluorophore by replacing its dimethylamine electron-donating group with conformationally more rigid groups, namely, azetidine ( 2 ), 3,3-difluoroazetidine ( 3 ), and julolidine ( 4 ). This structural change resulted in enhanced brightness (i.e., extinction coefficient multiplied by fluorescence quantum yield), specifically in 4 because of its rigidity and ED capability. Next, three electron push–pull hydrazones ( 5 – 7 ) were designed based on the scaffold of 4 , using cyano, nitro, or dicyanovinyl, respectively, as the electron-withdrawing groups, resulting in the progressive red-shifting of the photoswitching wavelengths into the visible region and further enhancement in brightness. Finally, fluorogenic probe 8 was developed based on parent compound 7 , which could be activated solely with visible light and used in the super-resolution imaging of fixed-cell and live-cell plasma membranes with average localization precisions of 17 and 25 nm, respectively.}, archive = {J_JACS}, author = {Qingkai Qi and Yunshu Liu and Vedang Puranik and Shefali Patra and Zdenek Svindrych and Xiayi Gong and Ziwei She and Yang Zhang and Ivan Aprahamian}, doi = {10.1021/jacs.5c02669}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16404--16411}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoswitchable fluorescent hydrazone for super-resolution cell membrane imaging}, volume = {147}, year = {2025}, }
• (2025). Transcription-coupled template reconfiguration of 8-oxoguanine for error-prone transcription revealed by time-resolved X-ray crystallography and molecular dynamics. JACS, 147(19), 16396--16403. (www)

  @article{ , abstract = {Oxidative DNA damage, particularly 8-oxoguanine (8OG), is a significant contributor to transcriptional errors that can alter the cellular phenotype and cell fate. While previous studies proposed that 8OG can use its anti-conformation or syn-conformation to form distinct base pairs with different substrates, it is not clear what conformation 8OG adopts during the template loading step and how different substrates induce transcription-coupled conformational changes of the 8OG template within the active site. Through a combined approach of time-resolved X-ray crystallography and molecular dynamics (MD) simulations, our study provides a comprehensive insight into these important questions. We found that the 8OG template behaves very differently for error-free and error-prone transcription. For error-free CTP incorporation, 8OG remains in anti-conformation during template loading, nucleotide binding, and incorporation steps. As for error-prone ATP incorporation, using time-resolved crystallography, we observed that the 8OG template initially adopts anti-conformation during template loading and the initial nucleotide binding step. However, it transitions to the syn-conformation to form a base pair with incoming ATP over the course of the reaction. Eventually, we observed a post-chemistry state where 8OG adopts the syn-conformation, base-paired with newly incorporated AMP. MD simulations further revealed that the 8OG template switches from an anti- to a syn-conformation by partially backtracking and subsequently reloading into the +1 site. These findings significantly contribute to our understanding of how RNA polymerase II navigates 8OG lesions during transcription, shedding light on transcription fidelity control and the lesion bypass of oxidative DNA damage.}, archive = {J_JACS}, author = {Juntaek Oh and Kirill A. Konovalov and Peini Hou and Jenny Chong and Xuhui Huang and Dong Wang}, doi = {10.1021/jacs.5c02687}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16396--16403}, shortjournal = {J. Am. Chem. Soc.}, title = {Transcription-coupled template reconfiguration of 8-oxoguanine for error-prone transcription revealed by time-resolved X-ray crystallography and molecular dynamics}, volume = {147}, year = {2025}, }
• (2025). Radical deamination of primary amines for initiation of controlled polymerization. JACS, 147(19), 16390--16395. (www)

  @article{ , abstract = {Selectively initiating controlled polymerizations using common functional groups is a powerful route to synthesizing advanced polymer architectures. Amines are one of the most common functional groups in small molecules, pharmaceuticals, and biomolecules, and thus are valuable substituents to use for initiating controlled polymerizations. In this study, we present the facile initiation of a controlled radical polymerization from the α-carbon of a primary amine via an electron donor–acceptor (EDA) complex-triggered radical deamination. Through this method, polymers were successfully grafted from a variety of amino acid derivatives. The resulting polymers had good matching between theoretical and experimental molar masses, narrow molar mass distributions ( Đ ∼ 1.1–1.2), and exceptional α-chain end fidelities. This method was trialed on a model dipeptide, demonstrating the viability of EDA-RAFT in the synthesis of peptide–polymer conjugates.}, archive = {J_JACS}, author = {Megan E. Driscoll and Bryce T. Nicholls and Brett P. Fors}, doi = {10.1021/jacs.5c02493}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16390--16395}, shortjournal = {J. Am. Chem. Soc.}, title = {Radical deamination of primary amines for initiation of controlled polymerization}, volume = {147}, year = {2025}, }
• (2025). Bioinspired methionine-selective desulfurization editing of peptides via the photocatalysis strategy. JACS, 147(19), 16379--16389. (www)

  @article{ , abstract = {S -Adenosylmethionine (SAM) frequently functions as a cofactor or precursor for enzymes, initiating an array of radical reactions in biological systems. In contrast with the conventional 5′-deoxyadenosyl (dAdo) radical pathway, which proceeds via homolytic cleavage of the S–C(5′) bond of SAM, the Dph2 enzyme provides an alternative 3-amino-3-carboxypropyl (ACP) radical pathway through breaking the S–C(γ) bond. Inspired by this distinctive bond cleavage mode, we have developed a chemically induced pathway to generate an ACP-type radical intermediate on methionine-based sulfonium. This strategy presents a novel desulfurization conjugation mode for methionine modification, diverging from previous approaches that conjugate onto the sulfur atom or the adjacent methyl group of methionine. The versatility of this strategy is demonstrated by the efficient functionalization of various peptides and peptide macrocyclizations. Density Functional Theory (DFT) calculations provide further insights into the mechanism of this desulfurization reaction, explaining the exceptional selectivity of homolytic cleavage of the S–C(γ) bond of methionine-based sulfonium. The successful implementation of this novel desulfurization strategy represents a substantial advancement in the understanding of sulfonium-based intramolecular radical substitution reactions and provides new opportunities for the functionalization of biomolecules, thereby fostering progress in interdisciplinary research.}, archive = {J_JACS}, author = {Yue Zhang and Huixin Yu and Feng Tang and Feng-Hua Zhang and Meihui Zhang and Jinhua Dong and Jianwei Zhao and Wei Huang and Bo Liu}, doi = {10.1021/jacs.5c02226}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16379--16389}, shortjournal = {J. Am. Chem. Soc.}, title = {Bioinspired methionine-selective desulfurization editing of peptides via the photocatalysis strategy}, volume = {147}, year = {2025}, }
• (2025). Self-adaptive release of stem cell-derived exosomes from a multifunctional hydrogel for accelerating MRSA-infected diabetic wound repair. JACS, 147(19), 16362--16378. (www)

  @article{ , abstract = {Chronic diabetic wounds are prone to severe skin necrosis and bacterial infections, with elevated reactive oxygen species (ROS) and persistent inflammation further hindering the healing process. Developing smart dressings with multifunctional therapeutic capabilities to simultaneously combat infections, reduce oxidative stress, alleviate inflammation, and promote tissue regeneration remains a significant challenge. Here, we introduce a self-adaptive yet multifunctional hydrogel (Exo-Gel) designed to accelerate methicillin-resistant Staphylococcus aureus (MRSA)-infected diabetic wound repair. Exo-Gel utilizes choline phosphate (CP) groups to both anchor stem cell-derived exosomes (Exo) via electrostatic interactions and disrupt bacterial membranes, providing inherent bacteriostatic effects. Additionally, ROS-responsive thioketal (TK) linkers enable the self-adaptive release of exosomes based on local ROS levels while also scavenging excess ROS. This synergistic system facilitates wound healing by modulating oxidative stress, reducing inflammation, promoting M2 macrophage polarization, and enhancing cell proliferation, myofibroblast migration, angiogenesis, and collagen deposition to accelerate tissue regeneration. In diabetic Sprague–Dawley rats with MRSA-infected full-thickness wounds, Exo-Gel achieved remarkable bacteriostatic activity and accelerated wound healing. Exo-Gel offers a cost-effective, multifunctional, and self-adaptive therapeutic strategy for managing chronic diabetic wounds, requiring no external components or operations, making it highly practical and translatable for clinical applications.}, archive = {J_JACS}, author = {Xiang Wang and Jiantong Dong and Jingjing Kang and Xujing Chen and Xiaoqin Hong and Jiaming Chen and Wei Du and Hong Cai and Dingbin Liu}, doi = {10.1021/jacs.5c02184}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16362--16378}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-adaptive release of stem cell-derived exosomes from a multifunctional hydrogel for accelerating MRSA-infected diabetic wound repair}, volume = {147}, year = {2025}, }
• (2025). Coordination chemistry toward advanced Zn–I2 batteries with four-electron I–/I0/I+ conversion. JACS, 147(19), 16350--16361. (www)

  @article{ , abstract = {Aqueous zinc–iodine (Zn–I 2 ) batteries with four-electron (4e) I – /I 0 /I + conversion (4eZIBs) offer high energy density but face significant challenges for application, including the polyiodide shuttle effect and I + hydrolysis for the I 2 cathodes and poor reversibility for the Zn anodes. Here, we report a coordination chemistry strategy to address these issues simultaneously by introducing hexamethylenetetramine (HMTA) as an electrolyte additive. In aqueous electrolytes, HMTA undergoes protonation to form positively charged nitrogen moieties that effectively precipitate the polyiodides and I + species (ICl 2 – ) to mitigate the polyiodides shuttle and I + hydrolysis. This strategy enables 4eZIBs to achieve a near-theoretical specific capacity of 425 mA h g –1 (based on the mass of iodine) and a Coulombic efficiency (CE) exceeding 99%. On the Zn anode, HMTA preferentially adsorbs onto its surface, inhibiting competitive water adsorption to suppress both Zn dendrite formation and hydrogen evolution. As a result, for the first time, we achieve durable 4eZIB performance in pouch-cell configurations with limited Zn supply. A 0.5 A h pouch cell with 15% Zn utilization exhibits a high energy density of 113.0 W h kg –1 (based on the mass of cathodes and anodes) and excellent cycling stability for over 1400 cycles, highlighting the potential of 4eZIBs for next-generation energy storage systems.}, archive = {J_JACS}, author = {Shao-Jian Zhang and Junnan Hao and Han Wu and Qianru Chen and Yiyang Hu and Xun Zhao and Shi-Zhang Qiao}, doi = {10.1021/jacs.5c02085}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16350--16361}, shortjournal = {J. Am. Chem. Soc.}, title = {Coordination chemistry toward advanced Zn–I2 batteries with four-electron I–/I0/I+ conversion}, volume = {147}, year = {2025}, }
• (2025). Deciphering Catalyst–Support interaction via doping for highly active and durable oxygen evolution catalysis. JACS, 147(19), 16340--16349. (www)

  @article{ , abstract = {The design of oxygen evolution reaction (OER) electrocatalysts demands a delicate balance between activity and stability. In this study, we present a rational design approach that leverages catalyst–support interactions to enhance both the intrinsic activity and durability of Ir-based catalysts. Our study reveals that while Mo doping energetically promotes the formation of high-valent Ir species, enhancing intrinsic catalytic activity, it also leads to a reduction in electrical conductivity. These findings emphasize that supporting doping can introduce both beneficial and limiting effects, highlighting the need for a carefully balanced design strategy to optimize the overall OER performance. Simultaneously, in situ analytical techniques and comparative evaluation reveal the crucial role of oxide supports in stabilizing the catalyst. These findings highlight the pivotal role of interface engineering in maintaining catalyst integrity and the need for support materials that balance dopant-driven electronic promotion with structural and electrochemical robustness. These interconnected degradation pathways highlight the need to move beyond a catalyst-centric view and instead adopt a system-level understanding of the stability. Our approach offers a strong foundation for the rational design and evaluation of high-performance OER electrocatalysts for electrochemical energy applications.}, archive = {J_JACS}, author = {Jinyeop Kim and Jinglong Guo and Nannan Shan and Jimun Yoo and Pedro Farinazzo Bergamo Dias Martins and Jongsu Noh and Moonjung Jung and Peter Zapol and Bongjin Simon Mun and Robert Klie and Pietro Papa Lopes and Nenad M. Markovic and Dong Young Chung}, doi = {10.1021/jacs.5c02001}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16340--16349}, shortjournal = {J. Am. Chem. Soc.}, title = {Deciphering Catalyst–Support interaction via doping for highly active and durable oxygen evolution catalysis}, volume = {147}, year = {2025}, }
• (2025). Rapid cathodic coloration in solution-processable electrochromic polymers of intrinsic microporosity. JACS, 147(19), 16331--16339. (www)

  @article{ , abstract = {This study describes four solution-processable polymers of intrinsic microporosity with rapid electrochemical switching in solid-state two-terminal devices. Conventional electrochromic polymers are often designed to be conformationally coplanar to maximize π-orbital overlap, which is presumed to increase electronic conductivity and electrochemical redox accessibility. However, this reduces the void space and polymer chain mobility needed to facilitate electrolyte ion penetration and exchange, which typically reduces switching speed. Here, we pursue a polymer design that incorporates spirobisindane units to intentionally install nonplanarity and create permanent void space in polymer thin films, which would typically be considered antithetical to electrochromic polymer design. The four n- type polymers we produce have four distinct chromophores that each host two electrochemically accessible reduced states, for a total of 12 distinct optical profiles. In complete electrochemical devices with a gel electrolyte, we achieve >90% optical contrast (Δ T %) with a 1-s switching time ( t 95 ). This rapid electrochromic switching is attributed to the large accessible surface areas (>250 m 2 g –1 ) of these polymers, as determined by CO 2 sorption isotherms and electrochemical impedance spectroscopy measurements. Additionally, high coloration efficiencies (CE) up to 450 cm 2 C – 1 are achieved with >95% retention over 200 cycles. Together, these findings highlight that electrochemical redox accessibility and porosity are not mutually exclusive and provide macromolecular structural design guidelines for the next generation of organic mixed ionic-electronic conductors.}, archive = {J_JACS}, author = {A M Mahmudul Hasan and Rupam Roy and Mohammad K. Shehab and Ani N. Davis and Kaitlin Slicker and Kent O. Kirlikovali and Robert M. Pankow and Omar K. Farha and Austin M. Evans}, doi = {10.1021/jacs.5c02014}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16331--16339}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid cathodic coloration in solution-processable electrochromic polymers of intrinsic microporosity}, volume = {147}, year = {2025}, }
• (2025). Water-assisted microwave synthesis of imide-linked covalent organic frameworks in minutes. JACS, 147(19), 16319--16330. (www)

  @article{ , abstract = {Solvothermal synthesis has been dominant for covalent organic frameworks (COFs) in the past decades. However, it requires high temperatures, harmful organic solvents, sealed pressurized reactors, and a long reaction time (from days to weeks). Herein, we report a solid-state strategy to synthesize imide-linked COFs rapidly. Utilizing water-assisted microwave synthesis, the process is remarkably fast, with one COF synthesized in merely 1 min. This method eliminates the need for toxic organic solvents and significantly shortens the reaction time. Using the water-assisted microwave method, we synthesized four previously reported COFs. The crystallinity and porosity of these COFs are comparable to or better than those made by the reported procedures. The generality of our synthetic method is shown in the preparation of three new imide-linked COFs. Finally, a microwave-synthesized COF@CNT composite acts as an excellent cathode material for lithium-ion batteries, showing a specific capacity of 154 mAh g –1 at an ultrahigh current density of 10 A g –1 (equivalent to 26 C), which can maintain a specific capacity of 128.59 mAh g –1 after 10,000 cycles. This excellent stability and durability under extreme operational conditions make the material highly suitable for applications requiring rapid charging and discharging. The speed, ease, and generality of this water-assisted microwave method, together with improved material quality, enable the rapid discovery of functional imide-linked COFs.}, archive = {J_JACS}, author = {Wei Zhao and Xingyang Wang and Mounib Bahri and Qiang Zhu and Boyu Li and Kun Wu and Zekun Wang and He Li and Xiansong Shi and Dongchen Shi and Chunqing Ji and Nigel D. Browning and Jianguo Sun and John Wang and Dan Zhao}, doi = {10.1021/jacs.5c01990}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16319--16330}, shortjournal = {J. Am. Chem. Soc.}, title = {Water-assisted microwave synthesis of imide-linked covalent organic frameworks in minutes}, volume = {147}, year = {2025}, }
• (2025). Colocalized raman and IR spectroscopies via vibrational-encoded fluorescence for comprehensive vibrational analysis. JACS, 147(19), 16309--16318. (www)

  @article{ , abstract = {Vibrational spectroscopy, including Raman scattering and infrared (IR) absorption, provides essential molecular fingerprint information, facilitating diverse applications, such as interfacial sensing, chemical analysis, and biomedical diagnostics. The complementary selection rules of Raman and IR spectroscopies offer distinct, yet mutually reinforcing, insights into molecular structure and dynamics. However, in dynamic or complex chemical environments, either technique alone is not capable of providing a complete and nuanced picture of molecular vibrations. Simultaneous detection of complementary vibrational modes within the same molecular group remains challenging due to wavelength discrepancies and sensitivity mismatches between Raman and IR spectroscopies. In this work, to address the gap between these spectroscopies, we developed an integrated approach based on vibrational-encoded fluorescence (VEF), in which the complementary vibrational information is respectively encoded into the different parts of fluorescence radiation: Stokes fluorescence carrying Raman information and anti-Stokes fluorescence reflecting IR information. This method employs a dual-resonant microsphere-on-mirror plasmonic structure to bridge the waveband gap, enabling the simultaneous detection of complete vibrational modes in the visible spectrum with ultrahigh sensitivity down to ∼100 molecules. Hyperspectral colocalization imaging demonstrates spatial correlations between the complementary vibrations. By careful calibration, the detection efficiency is improved by 8 orders of magnitude compared to unenhanced IR spectroscopy. This approach creates new opportunities for the precise identification of molecular vibrational information in complex chemical environments.}, archive = {J_JACS}, author = {Zhao-Dong Meng and Tai-Rui Wu and Li-Ling Zhou and En-Ming You and Zhi-Peng Dong and Xia-Guang Zhang and Gan-Yu Chen and De-Yin Wu and Jun Yi and Zhong-Qun Tian}, doi = {10.1021/jacs.5c01957}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16309--16318}, shortjournal = {J. Am. Chem. Soc.}, title = {Colocalized raman and IR spectroscopies via vibrational-encoded fluorescence for comprehensive vibrational analysis}, volume = {147}, year = {2025}, }
• (2025). Cathode–Anode synergy electrosynthesis of propanamide via a bipolar C–N coupling reaction. JACS, 147(19), 16301--16308. (www)

  @article{ , abstract = {Propanamide is a crucial synthetic intermediate in pharmaceuticals for the preparation of antibacterial and anticancer drugs. Conventional synthesis of propanamide involves the reaction of carboxylic acid derivatives with amines, which requires harsh reaction conditions, leading to an unfavorable environmental footprint. Here, we present a cathode–anode synergistic electrochemical strategy to transform nitrate and n-propanol into propanamide under ambient conditions, where both the cathode catalyst Co 3 O 4 /SiC and the anode catalyst Ti contribute distinctively to the electrochemical process. The CH 3 CH 2 CHO produced at the Ti anode can diffuse and react with the adsorbed intermediate *NH 2 OH on the surface of the cathode catalyst to form propanamide. The synergistic reactions at both electrodes collectively enhance the efficiency of the propanamide synthesis. This design enables efficient propanamide production in a flow cell at the gram scale with a remarkable yield of 986.13 μmol/(cm 2 ·h) at current densities of up to 650 mA/cm 2 . Our reports present a new option for environmentally friendly C–N bond synthesis, and the insights can be useful for the electrosynthesis of a wider scope of amides.}, archive = {J_JACS}, author = {Ming-Hao Guan and Hao-Nan Xu and Jin Liu and Xiao-Ya Zhou and Tao Wu and An-Hui Lu}, doi = {10.1021/jacs.5c01744}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16301--16308}, shortjournal = {J. Am. Chem. Soc.}, title = {Cathode–Anode synergy electrosynthesis of propanamide via a bipolar C–N coupling reaction}, volume = {147}, year = {2025}, }
• (2025). Avoidance of secondary carbocations, unusual deprotonation, and nonstatistical dynamic effects in the cyclization mechanism of tetraisoquinane. JACS, 147(19), 16293--16300. (www)

  @article{ , abstract = {The complexity and versatility of terpene cyclization reactions contribute to the wide variety of functions and properties that terpenoid compounds exhibit in nature. The management of reactive carbocations over the course of the reaction to ultimately arrive at a particular carbon fragment connectivity and stereochemistry is no small feat. Bacteria possess a variety of TSs that generate diverse polycyclic terpene skeletons; however, terpenoids in myxobacteria are especially rare. Here, we report the first mechanistic study of tetraisoquinene biosynthesis from TiqS, a diterpene synthase from Melittangium boletus . To understand formation of the unique 5/5/5/5-fused tetraisoquinane skeleton, we used the isolation and structural elucidation of nine minor metabolites, site-directed mutagenesis, stable isotope labeling experiments, and quantum chemical calculations to propose and support its mechanism. This study reveals a new mechanism of diterpene cyclization, expands our understanding of terpenoid biosynthesis, and enables the discovery of novel natural products in myxobacteria.}, archive = {J_JACS}, author = {Xiuting Wei and William DeSnoo and Zining Li and Wenbo Ning and Wang-Yeuk Kong and Jordan Nafie and Dean J. Tantillo and Jeffrey D. Rudolf}, doi = {10.1021/jacs.5c01828}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16293--16300}, shortjournal = {J. Am. Chem. Soc.}, title = {Avoidance of secondary carbocations, unusual deprotonation, and nonstatistical dynamic effects in the cyclization mechanism of tetraisoquinane}, volume = {147}, year = {2025}, }
• (2025). Shell thickness and heterogeneity dependence of triplet energy transfer between Core–Shell quantum dots and adsorbed molecules. JACS, 147(19), 16282--16292. (www)

  @article{ , abstract = {Quantum dot (QD)-sensitized triplet energy transfer (TET) has found promising applications in photon upconversion and photocatalysis. However, the underlying mechanism of TET in the QD-acceptor complex remains unclear despite the well-developed TET theory for the molecular donor–acceptor systems. Herein, the coupling strength of TET from CdSe/CdS core–shell QDs to 9-anthracene carboxylic acid (ACA) was studied by measuring the TET rate as a function of shell thickness with time-resolved photoluminescence. The change of TET-coupling strength with increasing shell thickness was further compared to those of electron and hole transfers from QDs so that we could test whether QD-sensitized TET is mediated by the charge transfer virtual state and can be considered as simultaneous electron and hole transfers as in molecular donor–acceptor systems. The measured coupling strength of TET from the CdSe/CdS QD decreases exponentially with the CdS shell thickness r : | V |( r ) = | V |(0)e –βr , with an exponential decay factor β of 0.19 Å –1 , which is smaller than the sum of the measured decay factors for electron transfer to methyl viologen (0.18 Å –1 ) and hole transfer to phenothiazine (0.29 Å –1 ) from the same QD. This inconsistency is explained by the broadening of QD shell thicknesses in the distance dependence study, which significantly modifies the TET-coupling strength and driving force, resulting in a shallower distance dependence of the TET rate constants. This study sheds light on the fundamental mechanisms of QD-sensitized TET reactions.}, archive = {J_JACS}, author = {Tao Jin and Zhendian Zhang and Sheng He and Alexey L. Kaledin and Zihao Xu and Yawei Liu and Peng Zhang and David N. Beratan and Tianquan Lian}, doi = {10.1021/jacs.5c01838}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16282--16292}, shortjournal = {J. Am. Chem. Soc.}, title = {Shell thickness and heterogeneity dependence of triplet energy transfer between Core–Shell quantum dots and adsorbed molecules}, volume = {147}, year = {2025}, }
• (2025). Dynamic kinetic asymmetric hydroacylation: Racemization by soft enolization. JACS, 147(19), 16270--16281. (www)

  @article{ , abstract = {We report a dynamic kinetic asymmetric transformation (DyKAT) of racemic aldehydes by Rh-catalyzed hydroacylation of acrylamides. This intermolecular hydroacylation generates 1,4-ketoamides with high enantio- and diastereoselectivity. DFT and experimental studies provide mechanistic insights and reveal an unexpected Rh-catalyzed pathway for aldehyde racemization. Our study represents a pioneering kinetic resolution by intermolecular hydroacylation and contributes to the growing field of stereoconvergent catalysis featuring C–C bond construction.}, archive = {J_JACS}, author = {Mengfei Xu and Stephanie A. Corio and Josephine M. Warnica and Erin L. Kuker and Alexander Lu and Jennifer S. Hirschi and Vy M. Dong}, doi = {10.1021/jacs.5c01753}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16270--16281}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic kinetic asymmetric hydroacylation: Racemization by soft enolization}, volume = {147}, year = {2025}, }
• (2025). Regulating the piezoelectricity of cyclic dipeptide-based supramolecular materials through co-assembly strategy. JACS, 147(19), 16255--16269. (www)

  @article{ , abstract = {Supramolecular co-assembly can modulate the architecture of molecular assemblies, thereby influencing their electromechanical properties. However, the relationship between supramolecular packing and electromechanical response of co-assemblies remains largely unexplored, posing a challenge in designing high-performance bioinspired piezoelectric materials. Herein, we combined experiments and theoretical calculations to systematically explore the regulation of supramolecular packing and electromechanical properties of cyclic l -aspartyl- l -aspartyl (cyclo-DD (LL))-based assemblies through co-assembling with pyridine derivatives. Crystal structures indicated that intermolecular hydrogen bonding between the carboxyl group of the cyclic dipeptide and the pyridine ring resulted in a markedly different molecular organizations and packing modes of co-assemblies. Density functional theory calculations revealed that increasing the molecular length of the pyridine derivatives enhanced the polarization effect and piezoelectric response of the cyclo-DD (LL)-based co-assemblies due to the reduced structural symmetry. Notably, the maximum piezoelectric coefficient of the cyclo-DD (LL)/4,4′-trimethylenedipyridine (TDP) co-assembly was predicted to be 140.8 pC/N, representing the highest value among peptide-based co-assemblies. Furthermore, cyclo-DD (LL)/TDP co-assembly based piezoelectric nanogenerator could generate stable open-circuit voltages over 3 V under an applied mechanical force of 50 N. For the first time, peptide-based co-assemblies were utilized as active piezoelectric materials to successfully power a display screen. Moreover, the effect of chirality on the piezoelectricity of cyclic dipeptide-based co-assemblies was investigated. This work presents an effective co-assembly strategy to manipulate the piezoelectric response of bioinspired cyclic dipeptide-based assemblies, advancing the development of high-performance piezoelectric molecular materials for sustainable energy harvesting systems.}, archive = {J_JACS}, author = {Xin Su and Shuaijie Liu and Xuewen Gong and Xiaoyu Tong and Lingling Li and Yehong Huo and Qingxi Liu and Yuehui Wang and Mei-Ling Tan and Qi Li and Shijin Zhang and Wei Ji}, doi = {10.1021/jacs.5c01672}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16255--16269}, shortjournal = {J. Am. Chem. Soc.}, title = {Regulating the piezoelectricity of cyclic dipeptide-based supramolecular materials through co-assembly strategy}, volume = {147}, year = {2025}, }
• (2025). Oxa-π, σ-methane rearrangement approach for epoxide synthesis. JACS, 147(19), 16248--16254. (www)

  @article{ , abstract = {Epoxides are significant chemicals that are utilized across various fields. Here, we describe an unprecedented photochemical rearrangement approach for synthesizing a diverse collection of epoxides enabled by energy transfer catalysis under visible light conditions. The process enables the easy preparation of α-amino-substituted epoxide derivatives with a broad substrate scope, functional group tolerance, and mild reaction conditions. Furthermore, this photorearrangement has also been applied in complex architectures, and the epoxides could be easily transferred to amino alcohol derivatives. Overall, this oxa-π, σ-methane rearrangement provides a complementary strategy to the existing methods of photochemical rearrangement through energy transfer catalysis.}, archive = {J_JACS}, author = {Qiu-Zhu Wang and Yu Zheng and Wen-Tao Wu and Huan-Ming Huang}, doi = {10.1021/jacs.5c01400}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16248--16254}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxa-π, σ-methane rearrangement approach for epoxide synthesis}, volume = {147}, year = {2025}, }
• (2025). Solvent-controlled enantioselective allylic C–H alkylation of 2,5-dihydrofuran via synergistic Palladium/Nickel catalysis. JACS, 147(19), 16237--16247. (www)

  @article{ , abstract = {Enantioenriched, substituted tetrahydrofuran skeletons extensively occur in natural products, bioactive targets, and organic frameworks. The rapid and diverse synthesis of these tetrahydrofuran molecules is highly desired yet challenging. Herein, we present a practical synthetic strategy for asymmetric allylic C–H bond functionalization of oxyheterocyclic alkenes by making use of the synergistic catalysis of achiral Pd complex and chiral N , N ′-dioxide-Ni(II) catalyst. Notably, the chemodivergent synthesis of allylic C–H alkylated products and hydroalkylated products was readily achieved in good outcomes via the regulation of solvents. Furthermore, the post-transformation of these functionalized 2,5-dihydrofurans provides an innovative synthetic route to access tetrahydrofuran skeleton compounds containing multiple stereocenters.}, archive = {J_JACS}, author = {Fule Wu and Hongkai Wang and Zhenwei Wu and Yangbin Liu and Xiaoming Feng}, doi = {10.1021/jacs.5c01228}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16237--16247}, shortjournal = {J. Am. Chem. Soc.}, title = {Solvent-controlled enantioselective allylic C–H alkylation of 2,5-dihydrofuran via synergistic Palladium/Nickel catalysis}, volume = {147}, year = {2025}, }
• (2025). Catalytic enantioselective chlorofunctionalizations of N-substituted amides using in situ generated HOCl as hydrogen bond source. JACS, 147(19), 16225--16236. (www)

  @article{ , abstract = {Asymmetric organocatalytic halocyclization represents a powerful method for the synthesis of valuable chiral haloheterocycles. However, its heavy dependence on substrates that contain hydrogen bond donors for enantiocontrol limits its broader application. Here we report a catalytic asymmetric chlorofunctionalization of olefinic amides that do not bear hydrogen bond donors, allowing for the efficient production of chlorooxazolidin-2-ones and chloroamino esters featuring quaternary stereocenters, achieved with high yields and excellent enantioselectivity. This catalytic protocol facilitates the synthesis of N -aryloxazolidin-2-ones and establishes a useful framework for synthesizing antibiotic analogues. Mechanistic studies indicate that trace amounts of water interact with the chlorinating agent to produce HOCl in situ, which acts as both a proton donor and a hypochlorite source, thereby promoting the asymmetric cyclization process. This strategy significantly broadens the potential of halocyclization for the development of a diverse array of functional molecules.}, archive = {J_JACS}, author = {Tengbo Ding and Liang Long and Mei-Jie Yuan and Wei Xu and Sze-Yung Wong and Hao Gao and Yong-Heng Wang and Ying-Yeung Yeung and Xiaojian Jiang}, doi = {10.1021/jacs.5c01224}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16225--16236}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic enantioselective chlorofunctionalizations of N-substituted amides using in situ generated HOCl as hydrogen bond source}, volume = {147}, year = {2025}, }
• (2025). Direct observation of C–F bond formation from isolable Palladium(IV) systems via an outer-sphere pathway. JACS, 147(19), 16217--16224. (www)

  @article{ , abstract = {Despite recent advancements in synthetic methods for palladium-catalyzed C–F couplings, the mechanistic understanding─particularly concerning high-valent palladium species─remains underexplored. In contrast to the commonly proposed inner-sphere mechanism, which involves C–F reductive elimination at a palladium(IV) center, the outer-sphere pathway is poorly understood, and little experimental evidence has been provided using well-defined, isolable high-valent Pd systems. In this study, we present the design and synthesis of a series of isolable and characterizable palladium(IV) alkyl systems. Their reactivity in C–F bond formation has been investigated and systematically compared. Through the isolation of intermediates, reactivity comparisons, kinetic studies, and DFT calculations, this work presents, for the first time, isolable palladium(IV) model systems that enable the direct observation of C–F bond formation via an outer-sphere pathway.}, archive = {J_JACS}, author = {Haobin Li and Rui Feng and Guo Wang and Yimeng Wang and Wenxi Liu and Shuai Guo}, doi = {10.1021/jacs.5c01147}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16217--16224}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct observation of C–F bond formation from isolable Palladium(IV) systems via an outer-sphere pathway}, volume = {147}, year = {2025}, }
• (2025). Polyethylene upcycling to liquid alkanes in molten salts under neat and external hydrogen source-free conditions. JACS, 147(19), 16207--16216. (www)

  @article{ , abstract = {Development of facile approaches to convert plastic waste into liquid fuels under neat conditions is highly desired but challenging, particularly without noble metal catalysts and an external hydrogen source. Herein, highly efficient and selective polyethylene-to-gasoline oil (branched C 6 –C 12 alkanes) conversion was achieved under mild conditions (<170 °C) using commercially available AlCl 3 -containing molten salts as reaction media and to provide catalytic sites (no extra solvents, additives, or hydrogen feeding). The high catalytic efficiency and selectivity was ensured by the abundant active Al sites with strong Lewis acidity (comparable to the Al type in acidic zeolite) and highly ionic nature of the molten salts to stabilize the carbenium intermediates. Dynamic genesis of the Al sites was elucidated via time-resolved Al K-edge soft X-ray and 27 Al NMR, confirming the tricoordinated Al 3+ as active sites and its coordination with the as-generated alkene/aromatic intermediates. The carbenium formation and polyethylene chain variation was illustrated by inelastic neutron scattering (INS) and an isotope-labeling experiment. Theoretical simulations further demonstrated the successive hydride abstraction, β-scission, isomerization, and internal hydrogen transfer reaction pathway with AlCl 3 as active sites. This facile catalytic system can further achieve the conversion of robust, densely assembled, and high molecular weight plastic model compounds to liquid alkane products in the diesel range.}, archive = {J_JACS}, author = {Liqi Qiu and Felipe Polo-Garzon and Luke L. Daemen and Min-Jae Kim and Jinghua Guo and Bobby G. Sumpter and Michael R. Koehler and Carlos Alberto Steren and Tao Wang and Logan T Kearney and Tomonori Saito and Zhenzhen Yang and Sheng Dai}, doi = {10.1021/jacs.5c01107}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16207--16216}, shortjournal = {J. Am. Chem. Soc.}, title = {Polyethylene upcycling to liquid alkanes in molten salts under neat and external hydrogen source-free conditions}, volume = {147}, year = {2025}, }
• (2025). Magnetic field-enhanced acidic CO2 electroreduction reaction on single nickel-site catalysts. JACS, 147(19), 16198--16206. (www)

  @article{ , abstract = {The synergistic integration of electrochemical reactions with an external magnetic field offers a powerful strategy for enhancing reaction performance. Herein, we introduce a flexible and continuously adjustable external magnetic field to enhance acidic CO 2 reduction reaction (CO 2 RR) performance. In an acidic electrolyte (pH = 0.91), the initial Faradaic efficiency (FE) of the CO 2 RR for CO is only 18%, which can be increased to 63.2% when a 2 T magnetic field is applied. More importantly, the introduction of this external magnetic field enables the continuous switching of CO 2 reduction products in a noncontact magnetic switching mode. Theoretical calculations demonstrate that the application of a magnetic field promotes CO 2 adsorption at Ni sites and inhibits the hydrogen evolution reaction (HER), ultimately enhancing CO 2 RR activity and selectivity. This work provides fresh insight into how an external magnetic field promotes CO 2 RR performance.}, archive = {J_JACS}, author = {Jia Song and Dayin He and Xianhui Ma and Peigen Liu and Wenxin Guo and Rongbo Sun and Feng Li and Zhicheng Zhong and Huang Zhou and Jun Tang and Jie Xu and Tongwei Wu and Lin Hu and Yuen Wu}, doi = {10.1021/jacs.5c00858}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16198--16206}, shortjournal = {J. Am. Chem. Soc.}, title = {Magnetic field-enhanced acidic CO2 electroreduction reaction on single nickel-site catalysts}, volume = {147}, year = {2025}, }
• (2025). Breaking supercapacitor symmetry enhances electrochemical carbon dioxide capture. JACS, 147(19), 16189--16197. (www)

  @article{ , abstract = {Electrochemical CO 2 capture using supercapacitors offers an energy-efficient approach for mitigating CO 2 emissions, but its performance is thought to be hindered by competing CO 2 capture and release processes at two identical porous carbon electrodes. To address this, we introduce an asymmetric supercapacitor-battery hybrid system with porous carbon and nonporous metallic zinc as the working and counter electrodes, respectively. The CO 2 capture capacity continuously increases as the charging rate decreases with a maximum capacity of 208 mmol CO2 kg −1 , surpassing that of an analogous symmetric supercapacitor. Our findings suggest that breaking device symmetry enhances CO 2 uptake in capacitive systems by suppressing competing processes, while the noncapacitive zinc counter electrode simplifies the mechanistic picture of capacitive CO 2 capture. Extending this approach, we develop asymmetric supercapacitors with two different porous carbon electrodes, demonstrating a 200% increase in CO 2 capture capacities at low charging rates. In summary, this study pioneers asymmetric systems for electrochemical CO 2 capture and establishes a general strategy to enhance both understanding and performance.}, archive = {J_JACS}, author = {Zhen Xu and Xinyu Liu and Grace Mapstone and Zeke Coady and Charles Seymour and Selina E. Wiesner and Svetlana Menkin and Alexander C. Forse}, doi = {10.1021/jacs.5c00999}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16189--16197}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking supercapacitor symmetry enhances electrochemical carbon dioxide capture}, volume = {147}, year = {2025}, }
• (2025). Atomically dispersed high-valent d0-metal breaks the Activity–Stability trade-off in proton exchange membrane water electrolysis. JACS, 147(19), 16179--16188. (www)

  @article{ , abstract = {Green hydrogen production via proton exchange membrane water electrolysis (PEMWE) faces economic feasibility challenges, primarily due to its reliance on noble metal catalysts. While cost-effective Ru-based catalysts show promise as alternatives to expensive Ir-based catalysts for an anodic oxygen evolution reaction, their long-term performance is compromised by overoxidation at high current densities. In addressing this challenge, we present a cooperative dual-site strategy for atomic-scale incorporation of high-valent d 0 -metal cations into RuO 2 . This synthesis results in uniformly distributed Ru–O–d 0 metal bonds, effectively reconciling the activity and stability trade-off. Leveraging these effects, our optimized Ta 1 /RuO 2 catalyst demonstrates exceptional performance, with a low overpotential of 164 ± 2 mV and stable operation for 1000 h at 100 mA cm –2 . In practical PEMWE systems, Ta 1 /RuO 2 achieves 1.58 V at 2 A cm –2 , surpassing the 2026 Department of Energy target, and maintains remarkable stability over 650 h at 500 mA cm –2 . This breakthrough offers a highly active and durable PEMWE system suitable for industrial-scale applications.}, archive = {J_JACS}, author = {Jaehyuk Shim and Kangjae Lee and Yunjae Yu and Hyeon Seok Lee and Heejong Shin and Kug-Seung Lee and Megalamane S. Bootharaju and Sanghwi Han and Gyu Seong Yi and Hyojoo Ko and Sihwa Lee and Jaeyune Ryu and Minho Kim and Byoung-Hoon Lee and Taeghwan Hyeon and Yung-Eun Sung}, doi = {10.1021/jacs.5c00936}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16179--16188}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomically dispersed high-valent d0-metal breaks the Activity–Stability trade-off in proton exchange membrane water electrolysis}, volume = {147}, year = {2025}, }
• (2025). Discrete brush polymers enhance 19F MRI performance through architectural precision. JACS, 147(19), 16171--16178. (www)

  @article{ , abstract = {The development of metal-free magnetic resonance imaging (MRI) agents demands precise control over molecular architecture to achieve optimal performance. Current fluorine-based contrast agents rely on maximizing fluorine content (>20 wt %) for sensitivity, requiring extensive solubilizing groups that lead to signal-diminishing aggregation. Here we show that discrete brush polymers ( Đ = 1.0) with precise backbone lengths and a single terminal fluorine group achieve superior imaging performance through architectural control rather than high fluorine content. This design prevents both intra- and intermolecular fluorine aggregation while maintaining high aqueous solubility, enabling sharper signals and higher sensitivity than conventional systems despite containing less than 7 wt % fluorine. Systematic investigation reveals how backbone length controls fluorine mobility and signal generation, establishing clear structure–property relationships previously obscured by molecular heterogeneity. This work demonstrates how precise architectural control can enhance functional performance beyond traditional approaches, providing new strategies for designing imaging materials.}, archive = {J_JACS}, author = {Nduka D. Ogbonna and Parikshit Guragain and Venkatesh Mayandi and Cyrus Sadrinia and Raman Danrad and Seetharama Jois and Jimmy Lawrence}, doi = {10.1021/jacs.5c00938}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16171--16178}, shortjournal = {J. Am. Chem. Soc.}, title = {Discrete brush polymers enhance 19F MRI performance through architectural precision}, volume = {147}, year = {2025}, }
• (2025). Groove-confined cobalt catalyst for low-temperature CO2 activation. JACS, 147(19), 16164--16170. (www)

  @article{ , abstract = {CO 2 activation is of great significance for resource utilization and environmental protection, but remains a major challenge. Here, we present a study of CO 2 activation and dissociation on a single crystal Co(101̅0) surface below 150 K via combined surface techniques and DFT calculations. Our study reveals that the groove site of the Co(101̅0) surface provides an ideal anchor for a surface-confined bent CO 2 , showing tridentate coordination with the surface. With this understanding, a cobalt nanocrystal catalyst containing groove sites was developed, high activity and high selectivity for conversion of CO 2 to CO by the reverse water–gas shift reaction were acquired. The nanocrystal catalyst with these groove sites appears to be much more active in comparison to the catalysts without such sites. This study provides key insights into the active sites and activation configuration for moderate-condition CO 2 activation and precise atomic-level design of confinement-controlled heterogeneous catalysts.}, archive = {J_JACS}, author = {Xiaowei Chang and Chengying Yu and Chen Yang and Huizhi Xie and Shucai Xia and Zihao Fang and Junhao Li and Sijia Zhang and Fangfang Liu and Tianjun Wang and Yuan Tan and Xingkun Chen and Song Shi and Qing Guo and Qian Xu and Jun Hu and Honghe Ding and Chuanqi Huang and Chuanyao Zhou and Junfa Zhu and Xueming Yang and Wenshao Yang}, doi = {10.1021/jacs.5c00807}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16164--16170}, shortjournal = {J. Am. Chem. Soc.}, title = {Groove-confined cobalt catalyst for low-temperature CO2 activation}, volume = {147}, year = {2025}, }
• (2025). Anchoring side chains to carbonate groups for reviving stable polycarbonate-based solid-state lithium metal batteries. JACS, 147(19), 16154--16163. (www)

  @article{ , abstract = {Polycarbonate-based electrolytes are ideal electrolytes for solid-state lithium metal batteries (LMBs) due to their wider electrochemical windows and considerable ionic conductivities compared with conventional solid polymer electrolytes. However, polycarbonates encounter severe interfacial side reactions with lithium metal, leading to the interfacial degradation of polymers. Herein, a spontaneously formed restricted conformation is designed via the in situ anchoring of side chains to suppress the interfacial degradation of polycarbonate-based electrolytes. The restricted conformation enables the side chains to shield and protect the degradable ester bonds of cyclic carbonates, suppressing contact and interfacial degradation between polycarbonates and lithium metal anodes. As a proof of concept, the protected polycarbonate-based electrolyte demonstrates a stable cycling capability of the Li/Li cell beyond 1000 h at a current density of 0.5 mA cm –2 , and the assembled LiNi 0.8 Co 0.1 Mn 0.1 O 2 /Li pouch cell also achieves similar improvement in cycling performance. This work indicates that the strategy of constructing restricted conformations via anchoring side chains is a feasible avenue for fabricating highly stable polycarbonate-based solid-state LMBs.}, archive = {J_JACS}, author = {Hantao Xu and Wei Deng and Jingyuan Yu and Lei Shi and Wenwei Zhang and Juncai Long and Chaobin He and Lin Xu}, doi = {10.1021/jacs.5c00760}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16154--16163}, shortjournal = {J. Am. Chem. Soc.}, title = {Anchoring side chains to carbonate groups for reviving stable polycarbonate-based solid-state lithium metal batteries}, volume = {147}, year = {2025}, }
• (2025). Enzyme- and DNAzyme-driven transient assembly of DNA-based phase-separated coacervate microdroplets. JACS, 147(19), 16141--16153. (www)

  @article{ , abstract = {An assembly of dissipative, transient, DNA-based microdroplet (MD) coacervates in the presence of auxiliary enzymes (endonucleases and nickases) or MD-embedded DNAzyme is introduced. Two pairs of different Y-shaped DNA core frameworks modified with toehold tethers are cross-linked by complementary toehold-functionalized duplexes, engineered to be cleaved by EcoRI or HindIII endonucleases, or cross-linked by palindromic strands that include pre-engineered Nt.BbvCI or Nb.BtsI nicking sites, demonstrating transient evolution/depletion of phase-separated MD coacervates. By mixing the pairs of endonuclease- or nickase-responsive MDs, programmed or gated transient formation/depletion of MD frameworks is presented. In addition, by cross-linking a pre-engineered Y-shaped core framework with a sequence-designed fuel strand, phase separation of MD coacervates with embedded Mg 2+ -DNAzyme units is introduced. The DNAzyme-catalyzed cleavage of a ribonucleobase-modified hairpin substrate, generating the waste product of the metabolite fragments, leads to the metabolite-driven separation of the cross-linked coacervates, resulting in the temporal evolution and depletion of the DNAzyme-functionalized MDs. By employing a light-responsive caged hairpin structure, the light-modulated fueled evolution and depletion of the DNAzyme-active MDs are presented. The enzyme- or DNAzyme-catalyzed transient evolution/depletion of the MD coacervates provides protocell frameworks mimicking dynamic transient processes of native cells. The possible application of MDs as functional carriers for the temporal, dose-controlled release of loads is addressed.}, archive = {J_JACS}, author = {Yunlong Qin and Yang Sung Sohn and Rachel Nechushtai and Fan Xia and Fujian Huang and Itamar Willner}, doi = {10.1021/jacs.5c00637}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16141--16153}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzyme- and DNAzyme-driven transient assembly of DNA-based phase-separated coacervate microdroplets}, volume = {147}, year = {2025}, }
• (2025). Coupling amorphization and compositional optimization of ternary metal phosphides toward high-performance electrocatalytic hydrogen production. JACS, 147(19), 16129--16140. (www)

  @article{ , abstract = {Amorphous materials, with abundant active sites and unique electronic configurations, have the potential to outperform their crystalline counterparts in high-performance catalysis for clean energy. However, their synthesis and compositional optimization remain underexplored due to the strict conditions required for their formation. Here, we report the synthesis of ternary platinum-nickel-phosphorus (PtNiP) amorphous nanoparticles (ANPs) within milliseconds by flash Joule heating, which features ultrafast cooling that enables the vitrification of metal precursors. Through compositional optimization, the Gibbs free energy of hydrogen adsorption for Pt 4 Ni 4 P 1 ANPs is optimized at 0.02 eV, an almost ideal value, even surpassing that of the benchmark metallic platinum catalyst. As a result, the PtNiP ANPs exhibited superior activity in electrocatalytic hydrogen evolution in acid electrolyte (η 10 ∼ 14 mV, Tafel slope ∼ 18 mV dec –1 , and mass activity 5× higher than state-of-the-art Pt/C). Life-cycle assessment and technoeconomic analysis suggest that, compared to existing processes, our approach enables notable reductions in greenhouse gas emission, energy consumption, and production cost for practical electrolyzer catalyst manufacturing.}, archive = {J_JACS}, author = {Bing Deng and Zhen-Yu Wu and Erkang Feng and Lu Ma and Zhe Wang and Jinhang Chen and Lucas Eddy and Alexander Lathem and Teng Wang and Weiyin Chen and Yi Cheng and Shichen Xu and Qiming Liu and Boris I. Yakobson and Haotian Wang and Yufeng Zhao and James M. Tour}, doi = {10.1021/jacs.5c00071}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16129--16140}, shortjournal = {J. Am. Chem. Soc.}, title = {Coupling amorphization and compositional optimization of ternary metal phosphides toward high-performance electrocatalytic hydrogen production}, volume = {147}, year = {2025}, }
• (2025). Dimensional control in phase-pure coevaporated quasi-2D Ruddlesden–Popper structures. JACS, 147(19), 16119--16128. (www)

  @article{ , abstract = {Fast, uncontrolled crystallization with several competing pathways makes solution-processing of phase-pure quasi-two-dimensional (quasi-2D) metal halide Ruddlesden–Popper thin films challenging. Typically, solution-processing results in the formation of different structural phases with varying dimensionality ranging from 2D, to quasi-2D, and 3D, introducing bandgap disorder and inhibiting charge transport. In this work, we eliminate interactions between precursor salts and solvents by using controlled thermal coevaporation to grow quasi-2D thin films that show high phase purity and narrow phase distribution. We study the structural landscape using synchrotron-based X-ray scattering and charge-carrier dynamics using ultrafast pump–probe spectroscopy. We then demonstrate a strategy to control the crystallographic phase of the film through phosphonic acid-based surface modification. We use density functional theory to study the interactions between propylphosphonic acid and the organic precursors and find that the interactions of loosely bound phosphonic acid molecules with evaporated precursors, followed by the migration of phosphonic acids through the deposited thin film, dictate the film structure between 2D and quasi-2D phases. These findings introduce new solvent-free methods for the fabrication of phase-pure quasi-2D Ruddlesden–Popper thin films and control phase selectivity across different dimensional (2D and quasi-2D) structures.}, archive = {J_JACS}, author = {Kunal Datta and Pranav Khadilkar and Honghu Zhang and Diana K. LaFollette and Esteban Rojas-Gatjens and Ruipeng Li and Guoxiang Hu and Juan-Pablo Correa-Baena}, doi = {10.1021/jacs.4c18641}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16119--16128}, shortjournal = {J. Am. Chem. Soc.}, title = {Dimensional control in phase-pure coevaporated quasi-2D Ruddlesden–Popper structures}, volume = {147}, year = {2025}, }
• (2025). Cation–Anion regulation engineering in a flame-retardant electrolyte toward safe na-ion batteries with appealing stability. JACS, 147(19), 16107--16118. (www)

  @article{ , abstract = {Great electrochemical stability and intrinsic safety are of critical significance in realizing large-scale applications of Na-ion batteries (NIBs). Unfortunately, the notorious decomposition of the electrolyte and undesirable side reactions on the cathode–electrolyte interphase (CEI) pose major obstacles to the practical implementation of NIBs. Besides, the flammability of traditional carbonate-based electrolytes raises increasing safety concerns about the batteries. Herein, a flame-retardant all-fluorinated electrolyte is proposed to achieve an anion-aggregated inner solvation shell by modulating cation–anion interactions through a low-coordination number cosolvent. The more electrochemically antioxidant fluorinated solvents and anion-dominated interfacial chemistry contribute to the construction of both mechanically and chemically stable F-rich CEI. Such thin, homogeneous interphase effectively inhibits the parasitic reaction, strengthens the interfacial stability, and enables fast Na + diffusion kinetics on the interface. When employing this electrolyte, the Na 0.95 Ni 0.4 Fe 0.15 Mn 0.3 Ti 0.15 O 2 (NFMT) cathode delivers remarkable discharge capacity up to 169.7 mAh g –1 , with stable cycling at 1C for 500 cycles. Impressively, NFMT//hard carbon pouch cells with such electrolyte also achieve a steady operation for 100 cycles at 0.5C with 86.8% capacity remaining. This study offers a practical reference for developing high-performance and flame-retardant electrolytes.}, archive = {J_JACS}, author = {Yi-Hu Feng and Chengye Lin and Hanwen Qin and Guang-Xu Wei and Chao Yang and Yongwei Tang and Xu Zhu and Shuai Sun and Tian-Ling Chen and Mengting Liu and Hong Zheng and Xiao Ji and Ya You and Peng-Fei Wang}, doi = {10.1021/jacs.4c18326}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16107--16118}, shortjournal = {J. Am. Chem. Soc.}, title = {Cation–Anion regulation engineering in a flame-retardant electrolyte toward safe na-ion batteries with appealing stability}, volume = {147}, year = {2025}, }
• (2025). Sorbent mediated electrocatalytic reduction of dilute CO2 to methane. JACS, 147(19), 16099--16106. (www)

  @article{ , abstract = {Efficient CO 2 utilization is a critical component of closing the anthropogenic carbon cycle. Most studies have focused on the use of pure streams of CO 2 . However, CO 2 is generally available only in dilute streams, which requires capture by sorbents followed by energy-intensive regeneration to release concentrated CO 2 . Direct utilization of sorbed-CO 2 avoids the costly regeneration step, and the sorbent-CO 2 interaction can kinetically activate CO 2 to tune its reactivity toward products that could otherwise be inaccessible with direct CO 2 reduction. We demonstrate that an N -heterocyclic carbene, 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (DPIy), quantitatively reacts with CO 2 from dilute streams (0.04 and 10%) to form the sorbent-CO 2 substrate 1,3-bis(2,6-diisopropylphenyl)imidazolium-2-carboxylate (DPICx). Electrocatalyst iron tetraphenylporphyrin chloride (Fe(TPP)Cl) typically reduces CO 2 to CO; however, with DPICx as the substrate, the eight-electron reduced product methane (CH 4 ) is produced with a high Faradaic efficiency (>85%) and regeneration of the sorbent DPIy. In addition to the overall energy and capital advantages of integrated CO 2 capture and conversion, this result illustrates how sorbents can serve a dual purpose for both CO 2 capture and chemical auxiliary purposes to access unique products. CO 2 has a spectrum of reactivity with different types of sorbents; thus, these studies demonstrate how sorbent-CO 2 interactions can be leveraged for integrated capture and utilization platforms to access a wider range of CO 2 -derived products.}, archive = {J_JACS}, author = {Jared S. Stanley and Hunter N. Pauker and Erin Kuker and Vy Dong and Robert J. Nielsen and Jenny Y. Yang}, doi = {10.1021/jacs.4c18303}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16099--16106}, shortjournal = {J. Am. Chem. Soc.}, title = {Sorbent mediated electrocatalytic reduction of dilute CO2 to methane}, volume = {147}, year = {2025}, }
• (2025). Redox-state-dependent structural changes within a prokaryotic 6–4 photolyase. JACS, 147(19), 16084--16098. (www)

  @article{ , abstract = {Photolyases repair UV damage to DNA by using absorbed blue light. Within the photolyase/cryptochrome superfamily (PCSf), a major subgroup consists of prokaryotic (6–4) photolyases. These enzymes rely on flavin adenine dinucleotide (FAD) as a catalytic cofactor, besides an ancillary antenna chromophore, and a [4Fe-4S] cluster with yet unknown function. For the prokaryotic 6–4 photolyase of Caulobacter crescentus , we investigated structural changes associated with its different redox states by damage-free crystallography using X-ray free-electron lasers. EPR and optical spectroscopy confirmed redox-dependent structural transitions, including the formation of an oxidized [4Fe-4S] 3+ cluster with the dynamic cleavage of a single iron–sulfur bond. Photoreduction to the catalytic FADH – state alters the flavin binding site at the proximal aromatic pair Y390/F394 that is part of the electron transport pathway. Upon oxidation, the observable structural transitions of the protein matrix around the [4Fe-4S] cluster may affect DNA binding and are consistent with the much-debated role of the iron–sulfur cluster in DNA-binding proteins for quenching electron holes.}, archive = {J_JACS}, author = {Po-Hsun Wang and Yuhei Hosokawa and Jessica C Soares and Hans-Joachim Emmerich and Valeri Fuchs and Nicolas Caramello and Sylvain Engilberge and Andrea Bologna and Christian Joshua Rosner and Mai Nakamura and Mohamed Watad and Fangjia Luo and Shigeki Owada and Takehiko Tosha and Jungmin Kang and Kensuke Tono and Yoshitaka Bessho and Eriko Nango and Antonio J. Pierik and Antoine Royant and Ming-Daw Tsai and Junpei Yamamoto and Manuel Maestre-Reyna and Lars-Oliver Essen}, doi = {10.1021/jacs.4c18116}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16084--16098}, shortjournal = {J. Am. Chem. Soc.}, title = {Redox-state-dependent structural changes within a prokaryotic 6–4 photolyase}, volume = {147}, year = {2025}, }
• (2025). The role of cu3+ in the oxygen evolution activity of copper oxides. JACS, 147(19), 16070--16083. (www)

  @article{ , abstract = {Cu-based oxides and hydroxides represent an important class of materials from a catalytic and corrosion perspective. In this study, we investigate the formation of bulk and surface Cu 3+ species that are stable under water oxidation catalysis in alkaline media. So far, no direct evidence existed for the presence of hydroxides (CuOOH) or oxides, which were primarily proposed by theory. This work directly places CuOOH in the oxygen evolution reaction (OER) Pourbaix stability region with a calculated free energy of −208.68 kJ/mol, necessitating a revision of known Cu–H 2 O phase diagrams. We also predict that the active sites of CuOOH for the OER are consistent with a bridge O* site between the two Cu 3+ atoms with onset at ≥1.6 V vs the reversible hydrogen electrode (RHE), aligning with experimentally observed Cu 2+/3+ oxidation waves in cyclic voltammetry of Fe-free and Fe-spiked copper in alkaline media. Trace amounts of Fe (2 μg/mL (ppm) to 5 μg/mL) in the solution measurably enhance the catalytic activity of the OER, likely due to the adsorption of Fe species that serve as the active sites . Importantly, modulation excitation X-ray absorption spectroscopy (ME-XAS) of a Cu thin-film electrode shows a distinct Cu 3+ fingerprint under OER conditions at 1.8 V vs RHE. Additionally, in situ Raman spectroscopy of polycrystalline Cu in 0.1 mol/L (M) KOH revealed features consistent with those calculated for CuOOH in addition to CuO. Overall, this work provides direct evidence of bulk electrochemical Cu 3+ species under OER conditions and expands our longstanding understanding of the oxidation mechanism and catalytic activity of copper.}, archive = {J_JACS}, author = {Pooja Basera and Yang Zhao and Angel T. Garcia-Esparza and Finn Babbe and Neha Bothra and John Vinson and Dimosthenis Sokaras and Junko Yano and Shannon W. Boettcher and Michal Bajdich}, doi = {10.1021/jacs.4c18147}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16070--16083}, shortjournal = {J. Am. Chem. Soc.}, title = {The role of cu3+ in the oxygen evolution activity of copper oxides}, volume = {147}, year = {2025}, }
• (2025). Microdroplet cascade catalysis for highly selective production of propylene glycol under ambient conditions. JACS, 147(19), 16060--16069. (www)

  @article{ , abstract = {Conventional propylene glycol (PG) production relies on an energy-intensive two-step thermocatalytic process, contributing significantly to CO 2 emissions. A sustainable alternative under ambient conditions remains elusive, hindered by challenges in selectivity and energy efficiency. Here, we present a cascade catalysis strategy for efficient and selective PG production within water microdroplets under ambient conditions. Propylene (CH 3 CH═CH 2 ) is converted to PG (CH 3 CH(OH)CH 2 OH) at the microdroplet/titanium silicalite-1 (TS-1) interface, driven by in situ generated hydrogen peroxide (H 2 O 2 ) via methyl viologen catalysis. This approach harnesses the water microdroplet interface to confine the reaction, enhancing catalytic activity and increasing selectivity. Our system achieves a PG production efficiency of 680 μM and a selectivity of 88%, while minimizing unwanted side products and energy demands. This innovative method offers a sustainable pathway for PG synthesis and highlights the transformative potential of water microdroplet technology in advancing green chemistry and industrial applications.}, archive = {J_JACS}, author = {Jianing Dong and Jiajia Xu and Zhao-Dong Meng and Zi-Ang Nan and Weixin Li and Richard N. Zare and Zhong-Qun Tian and Feng Ru Fan}, doi = {10.1021/jacs.4c17760}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16060--16069}, shortjournal = {J. Am. Chem. Soc.}, title = {Microdroplet cascade catalysis for highly selective production of propylene glycol under ambient conditions}, volume = {147}, year = {2025}, }
• (2025). Heterogeneous interfaces of Ni3Se4 nanoclusters decorated on a Ni3N surface enhance efficient and durable hydrogen evolution reactions in alkaline electrolyte. JACS, 147(19), 16047--16059. (www)

  @article{ , abstract = {Transition metal selenides (TMSes) have been identified as cost-efficient alternatives to platinum (Pt) for the alkaline hydrogen evolution reaction (HER) owing to their distinct electronic properties and excellent conductivity. However, they encounter challenges such as sluggish water dissociation and severe oxidative degradation, requiring further optimizations. In this study, we developed a dual-site heterogeneous catalyst, Ni 3 Se 4 –Ni 3 N, by decorating Ni 3 Se 4 nanoclusters on a Ni 3 N substrate. This catalyst design promoted significant interfacial electronic interactions, modulated electronic structures, and enhanced the adsorption of the intermediates. Various spectroscopic analyses and theoretical calculations revealed that the nitride surfaces improved water adsorption and dissociation, enriching the surface with adsorbed hydrogen (H*) atoms, while the Se sites facilitated hydrogen coupling and subsequent release of H 2 . Following a hydrogen spillover mechanism, the surface-adsorbed hydrogen atoms were transferred to nearby electron-dense selenide sites for H 2 formation and release. Consequently, the optimized catalyst demonstrated improved HER activity, requiring only an ∼60 mV overpotential at 10 mA cm –2 current density and maintained stability under higher potential conditions.}, archive = {J_JACS}, author = {Dessalew Dagnew Alemayehu and Meng-Che Tsai and Meng-Hsuan Tsai and Chueh-Cheng Yang and Chun-Chi Chang and Chia-Yu Chang and Endalkachew Asefa Moges and Keseven Lakshmanan and Yosef Nikodimos and Wei-Nien Su and Chia-Hsin Wang and Bing Joe Hwang}, doi = {10.1021/jacs.4c17747}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16047--16059}, shortjournal = {J. Am. Chem. Soc.}, title = {Heterogeneous interfaces of Ni3Se4 nanoclusters decorated on a Ni3N surface enhance efficient and durable hydrogen evolution reactions in alkaline electrolyte}, volume = {147}, year = {2025}, }
• (2025). Unraveling atomic-level mechanisms of structural transitions in lithium cobalt oxide under high-voltage conditions. JACS, 147(19), 16038--16046. (www)

  @article{ , abstract = {High-voltage cycling of layered cathode materials in lithium-ion batteries presents challenges related to structural instability. Deciphering atomic-scale structural degradation mechanisms is essential for improving their electrochemical performance at high voltages. This study utilized advanced electron microscopy and principal component analysis to detect subtle spinel-like structure induced by the migration of cobalt atoms within LiCoO 2 subjected to high-voltage cycling at charge voltages of 4.6 and 4.8 V. The formation of the spinel-like configuration was accompanied by the emergence of a densified O1 phase beneath thin spinel-like layer on the (003) facets during charging, along with an intriguing local O3- to P3-type oxygen stacking transition observed in LiCoO 2 charged to 4.8 V. Upon discharge, an enlarged and defective spinel phase preferentially formed on the non-(003) facets, and the migrated cobalt atoms cannot fully return to their original lattice sites, leading to the irreversible structural changes in LiCoO 2 . Long-term cycling revealed that the initial extended spinel phase underwent voltage-dependent evolution pathways, which contributed to accelerated capacity fading observed at the cutoff voltage of 4.8 V. Our findings provide new insights into the atomic-level structural transitions in LiCoO 2 under high-voltage conditions, offering guidance for the development of more structurally robust LiCoO 2 for high-voltage applications.}, archive = {J_JACS}, author = {Weiguang Lin and Wei Su and Ting Lin and Qiu Fang and Shiyu Wang and Jing Chen and Yuzhou He and Dongxiao Wang and Dongdong Xiao and Yingchun Lyu and Qinghua Zhang and Dong Su and Lin Gu}, doi = {10.1021/jacs.4c17362}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16038--16046}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling atomic-level mechanisms of structural transitions in lithium cobalt oxide under high-voltage conditions}, volume = {147}, year = {2025}, }
• (2025). Programmable coacervate droplets via reaction-coupled Liquid–Liquid phase separation (LLPS) and competitive inhibition. JACS, 147(19), 16027--16037. (www)

  @article{ , abstract = {Membraneless biomolecular condensates formed by liquid–liquid phase separation (LLPS) are crucial for many spatiotemporal biological functions. Designing synthetic mimics to emulate and understand LLPS is an active area of research, which has led to the development of coacervate droplets through elegant bioinspired designs. However, recent interest in this field has shifted toward designing programmable coacervates to impart spatiotemporal control over these liquid phases. Herein, we demonstrate the programming of LLPS in synthetic systems by employing concepts of competitive binding and reaction-coupled assembly involving dynamic covalent bonds. Our results utilize small building blocks that follow a simple coacervation mechanism, distinguishing this approach from previously reported programmable complex coacervates, which often rely on reaction-controlled generation of one of the components. We introduce these concepts using dynamic covalent bonds (boronate esters) and small chromophoric building blocks appended with terminal boronic acid groups. Upon reaction with substrates (monosaccharides), these building blocks form molecular structures resembling “sticker-and-spacer” designs for coacervation, leading to a reaction-driven, temporally controlled LLPS process. The differential reactivity of various monosaccharides, combined with the reversibility of dynamic bonds, enables competitive binding-driven control over the growth, inhibition, and dissolution of the coacervation process, offering new strategies for programmable LLPS that are reminiscent of protein-induced inhibition in biomolecular condensates. Detailed spectroscopic probing and kinetic analyses provide mechanistic insights into the reaction-coupled and autocatalytic growth processes, revealing the glucose-selective nature of this coacervation system. Finally, coupling dynamic covalent reactions with temporal pH modulation results in transient coacervation, which can be visualized by using confocal microscopy. We anticipate that this approach will pave the way for designing coacervate droplets with novel biorelevant emergent properties.}, archive = {J_JACS}, author = {Satyajit Patra and Bhawna Sharma and Subi J. George}, doi = {10.1021/jacs.4c17063}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16027--16037}, shortjournal = {J. Am. Chem. Soc.}, title = {Programmable coacervate droplets via reaction-coupled Liquid–Liquid phase separation (LLPS) and competitive inhibition}, volume = {147}, year = {2025}, }
• (2025). Dynamic competition between hubbard and superexchange interactions selectively localizes electrons and holes through polarons. JACS, 147(19), 16018--16026. (www)

  @article{ , abstract = {Controlling the effects of photoexcited polarons in transition metal oxides can enable the long time-scale charge separation necessary for renewable energy applications and controlling new quantum phases through dynamically tunable electron–phonon coupling. In previously studied transition metal oxides, polaron formation is facilitated by a photoexcited ligand-to-metal charge transfer (LMCT). When the polaron is formed, oxygen atoms move away from iron centers, which increases carrier localization at the metal center and decreases charge hopping. Studies of yttrium iron garnet and erbium iron oxide have suggested that strong electron and spin correlations can modulate photoexcited polaron formation. To understand the interplay between strong spin and electronic correlations in highly polar materials, we studied gadolinium iron oxide (GdFeO 3 ), which selectively forms photoexcited polarons through an Fe–O–Fe superexchange interaction. Excitation-wavelength-dependent transient extreme ultraviolet (XUV) spectroscopy selectively excites LMCT and metal-to-metal charge transfer (MMCT) transitions. The LMCT transition suppresses photoexcited polaron formation due to the balance between superexchange and Hubbard interactions, while MMCT transitions result in photoexcited polaron formation within 250 ± 40 fs. Ab initio theory demonstrates that electron and hole polarons localize on iron centers following MMCT. In addition to understanding how strong electronic and spin correlations can control strong electron–phonon coupling, these experiments separately measure electron and hole polaron interactions on neighboring metal centers for the first time, providing insight into a large range of charge-transfer and Mott–Hubbard insulators.}, archive = {J_JACS}, author = {Jocelyn L. Mendes and Hyun Jun Shin and Jae Yeon Seo and Nara Lee and Young Jai Choi and Joel B. Varley and Scott K. Cushing}, doi = {10.1021/jacs.4c16837}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16018--16026}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic competition between hubbard and superexchange interactions selectively localizes electrons and holes through polarons}, volume = {147}, year = {2025}, }
• (2025). Furan-derived lipid nanoparticles for transporting mRNA to the central nervous system. JACS, 147(19), 16007--16017. (www)

  @article{ , abstract = {Delivery of mRNA (mRNA) to the central nervous system (CNS) remains a significant challenge. Herein, we design a library of furan-derived lipids and, to our knowledge, for the first time, leverage the meningeal lymphatic vessels (MLVs) route to achieve efficient delivery of mRNA to the brain. These furan-derived lipids were engineered with different furan cores, functional groups, and tails. We found that tetrahydrofuran (THF)-derived lipid nanoparticles (LNPs) generally displayed exceptional mRNA delivery compared to their furan-based counterparts. Specifically, LNPs formulated with four-acetal-tail mono-THF-derived lipid F10T5 and four-acetal-tail di-THF-derived lipid F11T6 demonstrated significantly higher mRNA delivery efficiency to the brain compared with FDA-approved SM102 LNPs. The data revealed that these LNPs bypassed the blood-brain barrier (BBB) via the lymphatic pathway, traveling from deep cervical lymph nodes (dCLNs) to the meninges and subsequently entering brain cells. Collectively, this work provides valuable insights into engineering LNPs and exploring alternative approaches for the delivery of mRNA to the brain.}, archive = {J_JACS}, author = {Zhengwei Liu and Yuebao Zhang and Haoyuan Li and Kaiyuan Guo and Meng Tian and Dinglingge Cao and Diana D. Kang and Yonger Xue and Xucheng Hou and Chang Wang and Siyu Wang and Yichen Zhong and Changyue Yu and Binbin Deng and David W. McComb and Yizhou Dong}, doi = {10.1021/jacs.4c16326}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {16007--16017}, shortjournal = {J. Am. Chem. Soc.}, title = {Furan-derived lipid nanoparticles for transporting mRNA to the central nervous system}, volume = {147}, year = {2025}, }
• (2025). Faster amylin aggregation on fibrillar collagen i hastens diabetic progression through β-cell death and loss of function. JACS, 147(19), 15985--16006. (www)

  @article{ , abstract = {Amyloid deposition of the neuroendocrine peptide amylin in islet tissues is a hallmark of type 2 diabetes (T2DM), leading to β-cell toxicity through nutrient deprivation, membrane rupture, and apoptosis. Though accumulation of toxic amylin aggregates in islet matrices is well documented, the role of the islet extracellular matrix in mediating amylin aggregation and its pathological consequences remains elusive. Here, we address this question by probing amylin interaction with collagen I (Col)─whose expression in the islet tissue increases during diabetes progression. By combining multiple biophysical techniques, we show that hydrophobic, hydrophilic, and cation–π interactions regulate amylin binding to Col, with fibrillar Col driving faster amylin aggregation. Amylin-entangled Col matrices containing high amounts of amylin induce death and loss of function in INS1E β-cells. Together, our results illustrate how amylin incorporation in islet matrices through amylin–Col interactions drives T2DM progression by impacting β-cell viability and insulin secretion.}, archive = {J_JACS}, author = {Md Asrafuddoza Hazari and Gautam Kannan and Subrata Dasgupta and Musale Krushna Pavan and Akash Kumar Jha and Farhin Sultana and Soumya Ranjan Pujahari and Simran Singh and Sarbajeet Dutta and Sai Prasad Pydi and Sankhadeep Dutta and Hamim Zafar and Prasenjit Bhaumik and Ashutosh Kumar and Shamik Sen}, doi = {10.1021/jacs.4c15698}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {15985--16006}, shortjournal = {J. Am. Chem. Soc.}, title = {Faster amylin aggregation on fibrillar collagen i hastens diabetic progression through β-cell death and loss of function}, volume = {147}, year = {2025}, }
• (2025). Lipid scrambling pathways in the sec61 translocon complex. JACS, 147(19), 15970--15984. (www)

  @article{ , abstract = {Cellular homeostasis depends on the rapid, ATP-independent translocation of newly synthesized lipids across the endoplasmic reticulum (ER) membrane. Lipid translocation is facilitated by membrane proteins known as scramblases, a few of which have recently been identified in the ER. Our previous structure of the translocon-associated protein (TRAP) bound to the Sec61 translocation channel revealed local membrane thinning, suggesting that the Sec61/TRAP complex might be involved in lipid scrambling. Using complementary fluorescence spectroscopy assays, we detected nonselective scrambling by reconstituted translocon complexes. This activity was unaffected by Sec61 inhibitors that block its lateral gate, suggesting a second lipid scrambling pathway within the complex. Molecular dynamics simulations indicate that the trimeric TRAP subunit forms this alternative route, facilitating lipid translocation via a “credit card” mechanism, using a crevice lined with polar residues to shield lipid head groups from the hydrophobic membrane interior. Kinetic and thermodynamic analyses confirmed that local membrane thinning enhances scrambling efficiency and that both Sec61 and TRAP scramble phosphatidylcholine faster than phosphatidylethanolamine and phosphatidylserine, reflecting the intrinsic lipid flip–flop tendencies of these lipid species. As the Sec61 scrambling site lies in the lateral gate region, it is likely inaccessible during protein translocation, in line with our experiments on Sec61-inhibited samples. Hence, our findings suggest that the metazoan-specific trimeric TRAP bundle is a viable candidate for lipid scrambling activity that is insensitive to the functional state of the translocon.}, archive = {J_JACS}, author = {Matti Javanainen and Jan Šimek and Dale Tranter and Sarah O’Keefe and Sudeep Karki and Denys Biriukov and Radek Šachl and Ville O. Paavilainen}, doi = {10.1021/jacs.4c11142}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {15970--15984}, shortjournal = {J. Am. Chem. Soc.}, title = {Lipid scrambling pathways in the sec61 translocon complex}, volume = {147}, year = {2025}, }
• (2025). Convergent total synthesis of (−)-calidoustene. JACS, 147(19), 15963--15969. (www)

  @article{ , abstract = {The first total synthesis of the sesterterpenoid (−)-calidoustene has been accomplished, featuring a stereoselective Michael/aldol cascade to construct the trans -hydrindane backbone, a tandem Pummerer/Sakurai cyclization to establish the bicyclo[3.2.1]octane framework, a metallaphotoredox enone coupling followed by MHAT-initiated cyclization to forge the congested central C-ring, and late-stage functionalization via Cu-catalyzed desaturation and diimide reduction.}, archive = {J_JACS}, author = {Weidong Yao and Ziqi Liu and Hao Ling and Hongyu Wang and Hufeng Zheng and Shao-Hua Wang and Dao-Yong Zhu and Sheng-Yong Zhang and Xiaoming Chen}, doi = {10.1021/jacs.5c03983}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {15963--15969}, shortjournal = {J. Am. Chem. Soc.}, title = {Convergent total synthesis of (−)-calidoustene}, volume = {147}, year = {2025}, }
• (2025). Visible-light-induced [2 + 2] cyclization of alkynes with bromodifluoroacetylsilanes: Facile access to gem-difluorocyclobutenones. JACS, 147(19), 15955--15962. (www)

  @article{ , abstract = {Herein, we report a simple and efficient method for the synthesis of gem -difluorocyclobutenones from alkynes and bromodifluoroacetylsilanes, proceeding via a formal cyclization with in situ generated difluoroketene under visible-light-induced conditions. The reaction conditions are mild and exhibit a broad substrate scope, including both aromatic and aliphatic alkynes. Additionally, the reaction demonstrates good functional group tolerance, facile scalability, and the potential for diverse downstream transformations. Mechanistic studies suggest that bromodifluoroacetylsilanes act as photochemical precursors to difluoroketene.}, archive = {J_JACS}, author = {Gang Zhou and Yongpeng Li and Ying Liu and Xiaoqian He and Shanshan Liu and Xiao Shen}, doi = {10.1021/jacs.5c03504}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {15955--15962}, shortjournal = {J. Am. Chem. Soc.}, title = {Visible-light-induced [2 + 2] cyclization of alkynes with bromodifluoroacetylsilanes: Facile access to gem-difluorocyclobutenones}, volume = {147}, year = {2025}, }
• (2025). Rhodium-catalyzed [5 + 1 + 2] reaction of yne-vinylcyclopropenes and CO: The application of vinylcyclopropenes for higher-order cycloaddition. JACS, 147(19), 15947--15954. (www)

  @article{ , abstract = {Transition metal-catalyzed higher-order cycloadditions involving vinylcyclopropenes (VCPEs) have not been realized to synthesize challenging medium-sized rings, partially due to their poor stability and many competing side reactions. We report here a Rh-catalyzed [5 + 1 + 2] reaction of yne-VCPEs and CO for the synthesis of eight-membered carbocycles with trienone moiety, which so far can be accessed by only limited reactions. The key to this higher-order cycloaddition is that once C–C cleavage of VCPE (C 5 synthon) to form a six-membered metallacycle is initiated, CO (C 1 synthon) insertion happens before alkyne (C 2 synthon) insertion, attributing to the special reactivity of the sp 2 carbon in the vinylcyclopropene. Quantum chemical calculations have been applied to support this reaction pathway. The present [5 + 1 + 2] reaction has a broad scope, and the C 2 synthon can also be extended to alkenes and allene. Of the same importance, the present reaction can be catalyzed by either [Rh(CO) 2 Cl] 2 or a cheaper complex, RhCl 3 ·nH 2 O.}, archive = {J_JACS}, author = {Zhiqiang Huang and Zhi-Xiang Yu}, doi = {10.1021/jacs.5c02041}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {15947--15954}, shortjournal = {J. Am. Chem. Soc.}, title = {Rhodium-catalyzed [5 + 1 + 2] reaction of yne-vinylcyclopropenes and CO: The application of vinylcyclopropenes for higher-order cycloaddition}, volume = {147}, year = {2025}, }
• (2025). A highly efficient molecular Iron(II) photocatalyst for concurrent CO2 reduction and organic synthesis. JACS, 147(19), 15942--15946. (www)

  @article{ , abstract = {Molecular catalysts used for photocatalytic reduction of CO 2 heavily rely on photosensitizers to harvest light and then achieve photoinduced electron transfer to the catalytic center. However, a single earth-abundant molecular metal photocatalyst to independently execute CO 2 reduction remains a huge challenge. Herein, we report that a polypyridyl iron(II) molecular photocatalyst 1 , FePAbipyBn, exhibits outstanding activity for CO 2 reduction in the presence of 1,3-diethyl-2-phenyl-2,3-dihydro-1 H -benzo[d]imidazole (TON 3558 for CO production and selectivity >99%). More strikingly, molecular photocatalyst 1 takes advantage of unique photoredox properties to concurrently facilitate 2e – /2H + enamine oxidation and CO 2 reduction, resulting in value-added products of indoles and CO. This is an inaugural instance of a photoredox reaction for CO 2 reduction and organic synthesis using a molecular photocatalyst.}, archive = {J_JACS}, author = {Yan-Nan Jing and Hai-Xu Wang and Cheng Wang and Chen Ye and Chen-Ho Tung and Li-Zhu Wu}, doi = {10.1021/jacs.5c01698}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {15942--15946}, shortjournal = {J. Am. Chem. Soc.}, title = {A highly efficient molecular Iron(II) photocatalyst for concurrent CO2 reduction and organic synthesis}, volume = {147}, year = {2025}, }
• (2025). 2H quadrupolar coupling constant: A spectroscopic ruler for transition Metal–Hydride bond distances in molecular and surface sites. JACS, 147(19), 15936--15941. (www)

  @article{ , abstract = {Transition metal hydrides (TMHs) find numerous applications across fields from catalysis to H 2 storage. Yet, determining the structure of TMHs can remain a challenge, as hydrogen is difficult to detect by X-ray based or classical spectroscopic techniques. Considering that the deuterium isotope (D) is a quadrupolar nucleus ( I = 1) and that a quadrupolar coupling constant ( C Q ) depends on the distance between D and its bonding partner E ( d ED ), we evaluate this trend across molecularly defined transition metal deuterides (TMDs) through a systematic investigation across TM block elements using both computations and experiments. We show that the M–D bond distance ( d MD ) in [Å] correlates with the C Q values in [kHz] as d MD = 7.83( C Q + 28.7) −1/3 ─independently from the nature of the TM─with an accuracy >0.04–0.08 Å. Based on experimental C Q values measured by 2 H solid-state NMR, this simple correlation is then used to obtain the M–D bond distances in two silica-supported TMDs (M = Zr and Ir), notable heterogeneous catalysts representing early and late TMDs, where evaluating M–D bond distances by other means is very challenging. Considering the ease of measurement, this method is readily applicable to a large range of diamagnetic terminal M–Ds, from molecular to surface sites, making 2 H NMR a method of choice to measure TMD bond distances.}, archive = {J_JACS}, author = {Domenico Gioffrè and Cäcilie Müller and Scott R. Docherty and Alexander Yakimov and Christophe Copéret}, doi = {10.1021/jacs.5c01534}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {15936--15941}, shortjournal = {J. Am. Chem. Soc.}, title = {2H quadrupolar coupling constant: A spectroscopic ruler for transition Metal–Hydride bond distances in molecular and surface sites}, volume = {147}, year = {2025}, }
• (2025). Decarboxylative cross-acyl coupling of carboxylic acids with aldehydes enabled by Nickel/Photoredox catalysis. JACS, 147(19), 15929--15935. (www)

  @article{ , abstract = {We present a general method for accessing unsymmetrical alkyl–aryl and alkyl–alkyl ketones via nickel/photoredox-catalyzed decarboxylative cross-acyl coupling reactions between carboxylic acids and aldehydes without the need for an additional preactivation procedure. Specifically, by using the peroxide as both an oxidant and hydrogen atom transfer (HAT) reagent, we achieved the unprecedented combination of oxidative single electron transfer (SET) of carboxylates and HAT of aldehydes, in which the generated alkyl and acyl radicals were chemoselectively coupled by nickel catalysis. This method features a broad substrate scope with good functional group compatibility and offers new access to structurally diverse ketones.}, archive = {J_JACS}, author = {Xiao-Biao Yan and Ying-Qi Liu and Ning Wang and Tao Zhang and Danqing Li and Zhicai Wang and Yunzhi Lin and Kui Zhang}, doi = {10.1021/jacs.5c00372}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {15929--15935}, shortjournal = {J. Am. Chem. Soc.}, title = {Decarboxylative cross-acyl coupling of carboxylic acids with aldehydes enabled by Nickel/Photoredox catalysis}, volume = {147}, year = {2025}, }
• (2025). Coulomb field-driven Desorption/Ionization by femtosecond laser for mass spectrometry detection and imaging. JACS, 147(19), 15923--15928. (www)

  @article{ , abstract = {Surface-assisted laser desorption/ionization (SALDI) offers promising prospects for mass spectrometry detection and imaging of small biomolecules, as it addresses most of the matrix-related issues encountered in conventional matrix-assisted laser desorption/ionization (MALDI). Currently, nearly all of the fundamental aspects and applications of SALDI depend on nanosecond (ns) lasers, whereas few efforts have been made to integrate ultrafast femtosecond (fs) lasers with SALDI. Therefore, the intrinsic fundamental principle remains poorly understood. Herein, a novel surface-assisted femtosecond laser desorption/ionization mass spectrometry (fs-SALDI-MS) platform was developed, which significantly reduces analyte fragmentation and preserves molecular integrity. Spectral interferences from surface-assisted materials and alkali-metal adducts are absent in fs-SALDI mass spectra. Ion survival yields continuously increase with decreasing laser pulse widths from 5 ns to 600 fs, highlighting a gradual transition from thermal to nonthermal effects. A lower absolute limit of detection down to ∼3 amol for representative antifungal and psychotropic drugs and clearer visualization of ultratrace drug residues on latent fingerprints can be achieved, indicating that fs-SALDI results in gentler and more efficient detection/ionization processes than mainstream ns-SALDI. The biological applicability of this method was further validated through 10 μm-spatial-resolution lipid imaging of mouse brain sections. In short, a novel Coulomb field-driven desorption/ionization mechanism is proposed for fs-SALDI, opening new avenues for the development of emerging fs-SALDI techniques with superior analytical performance.}, archive = {J_JACS}, author = {Heng Zhang and Jingkai Luo and Qi Zhang and Yizhu Xu and Zhibin Yin and Wei Hang}, doi = {10.1021/jacs.4c18652}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {15923--15928}, shortjournal = {J. Am. Chem. Soc.}, title = {Coulomb field-driven Desorption/Ionization by femtosecond laser for mass spectrometry detection and imaging}, volume = {147}, year = {2025}, }
• (2025). Bilaterally substituted terphenyl molecules efficiently inhibit the interaction between a protein and a fully buried α-helix in the malaria parasite motor system. JACS, 147(19), 15917--15922. (www)

  @article{ , abstract = {Protein–protein interactions (PPI) frequently involve α-helices and are challenging targets for small-molecule drugs. Here we report the design, synthesis and evaluation of new PPI inhibitors based on a bilaterally substituted p-terphenyl scaffold. The side groups of this scaffold are projected in a broad spatial angle and reproduced the interactions of the myosin A (MyoA) α-helix wrapped by the Myosin Tail Interacting Protein (MTIP) in Plasmodium parasites causing malaria. Fluorescence, calorimetry, and NMR spectroscopy analyses revealed that the terphenyl molecules recognized the MyoA binding site within the MTIP and were capable of displacing the α-helix from its protein receptor and triggering comparable conformational changes in MTIP. The MTIP affinity of the best inhibitor was strikingly close to that exhibited by the MyoA helix. These data indicate that a small-molecule terphenyl compound can efficiently mimic a four-times heavier polypeptide. These molecules may serve as probes for PPIs involving deeply buried α-helices.}, archive = {J_JACS}, author = {Saurabh Loharch and Cristina Medina-Trillo and Daniel M. Sedgwick and Pablo Barrio and Santos Fustero and José Gallego}, doi = {10.1021/jacs.4c15031}, journal = {Journal of the American Chemical Society}, month = {5}, number = {19}, pages = {15917--15922}, shortjournal = {J. Am. Chem. Soc.}, title = {Bilaterally substituted terphenyl molecules efficiently inhibit the interaction between a protein and a fully buried α-helix in the malaria parasite motor system}, volume = {147}, year = {2025}, }
• (2025). Correction to “In-situ identification of zinc sites as potential-dependent selectivity switch over dual-atom catalysts for H2O2 electrosynthesis”. JACS, 147(18), 15916. (www)

  @article{ , archive = {J_JACS}, author = {Qizheng An and Xupeng Qin and Xuan Sun and Xu Zhang and Yuhao Zhang and Jianglong Guo and Jingjing Jiang and Jing Zhang and Baojie Li and Yaling Jiang and Hui Zhang and Xin Chen and Yuanli Li and Kun Zheng and Weiren Cheng and Dingsheng Wang and Qinghua Liu}, doi = {10.1021/jacs.5c06025}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15916}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “In-situ identification of zinc sites as potential-dependent selectivity switch over dual-atom catalysts for H2O2 electrosynthesis”}, volume = {147}, year = {2025}, }
• (2025). Correction to “A general method for selective recognition of monosaccharides and oligosaccharides in water”. JACS, 147(18), 15915. (www)

  @article{ , archive = {J_JACS}, author = {Roshan W. Gunasekara and Yan Zhao}, doi = {10.1021/jacs.5c03991}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15915}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “A general method for selective recognition of monosaccharides and oligosaccharides in water”}, volume = {147}, year = {2025}, }
• (2025). Permanent efferocytosis prevention by terminating MerTK recycle on tumor-associated macrophages for cancer immunotherapy. JACS, 147(18), 15901--15914. (www)

  @article{ , abstract = {Efferocytosis of apoptotic tumor cells by tumor-associated macrophages mediated through the phosphatidylserine (PtdSer)/MER proto-oncogene tyrosine kinase (MerTK) axis can exacerbate tumor immunosuppression, and conversely, prevention of efferocytosis via blocking PtdSer–MerTK association using prevalent antibodies represents a promising strategy for reversing tumor immunosuppression and boosting antitumor immunity. However, it remains unclear whether the antibody blockade can induce durable efferocytosis prevention and achieve sustained tumor growth inhibition. Here, we have shown that utilizing PtdSer and MerTK antibodies induced only a transient rather than a persistent efferocytosis prevention effect, and little enhancement was observed even after improving antibody enrichment in tumor sites. Further mechanistic studies suggested that degradation of anti -MerTK antibody and recycling of the MerTK receptor to the cell membrane would compromise the therapeutic benefits of antibody blockade. Based on these findings, we developed a CRISPR/Cas9 gene editing system deployed using Cas9 mRNA and MerTK sgRNA to permanently knock out MerTK, which achieved durable efferocytosis prevention, elicited persistent in situ vaccination immune responses via enhancing X-ray irradiation-induced immunogenic cell death, and led to sustained tumor suppression effects together with anti -PtdSer antibody and X-ray irradiation treatment in multiple B16 melanoma tumor models. Our findings provide a reliable gene-editing-mediated strategy for long-term modulating MerTK homeostasis and overcoming MerTK-dependent cancer immune evasion, generating adaptive antitumor immune responses for sustained cancer immunotherapy.}, archive = {J_JACS}, author = {Pei Huang and Yiwen Liu and Caiyan Zhao and Changrong Wang and Lirong Wang and Meng Luo and Weipeng Wang and Wenbo Shan and Xiaoqing Liu and Bingyu Li and Zhongliang Wang and Hongzhang Deng and Xiaoyuan Chen}, doi = {10.1021/jacs.5c05640}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15901--15914}, shortjournal = {J. Am. Chem. Soc.}, title = {Permanent efferocytosis prevention by terminating MerTK recycle on tumor-associated macrophages for cancer immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Stepwise self-assembly of multisegment mesoporous silica nanobamboos for enhanced thermal insulation. JACS, 147(18), 15890--15900. (www)

  @article{ , abstract = {Imitating the multinodal structures of plants and arthropods, precisely engineered multisegment nanostructures demonstrate enhanced synergistic properties and exceptional functionalities that surpass those of individual components. Utilizing micelle assemblies for constructing segments allows for precise structural control but requires management of interactions and assembly from molecular to mesoscopic levels, posing a significant challenge. In this paper, we present a stepwise self-assembly strategy to fabricate multisegment mesoporous silica (mSiO 2 ) nanobamboos. The nanobamboos are characterized by 16–25 shuttle-shaped mesoporous segments connected end-to-end in line, forming the main chains with an overall length of approximately 0.7–1.0 μm. Each individual segment is composed of 10–13 parallel layers, with an average layer thickness of ∼2.5 nm. The formation of this multisegment mesoporous nanobamboos, as proven by in situ testing, is initiated by the formation of shuttle-shaped segments from small bilayer micelle units, which then further assemble to form the nanobamboo. This stepwise self-assembly can be regulated from a kinetic perspective, thereby obtaining multisegment mesoporous nanostructures with varying lengths and branched morphologies. Due to multiple segments along with multilayer mesostructures, the nanobamboos can significantly restrict gas flow, resulting in a very low thermal conductivity (∼41.67 mW·m –1 ·K –1 ). By blending the multisegment mSiO 2 nanobamboos with cellulose nanofibers, mechanically stable, lightweight, and porous aerogels with an ultralow thermal conductivity (∼19.85 mW·m –1 ·K –1 ) can be obtained, verifying their potential in thermal insulation devices. The fabrication of this multisegment mesoporous nanobamboos enhances our understanding of micro-to-nanoscale assembling, establishing a foundation for precise control of complex structures.}, archive = {J_JACS}, author = {Xirui Huang and Tingting Ren and Runfeng Lin and Zirui Lv and Sixing Yin and Yifei Xu and Yupu Liu and Chin-Te Hung and Min Wang and Xiaomin Li and Tiancong Zhao and Dongyuan Zhao}, doi = {10.1021/jacs.5c05154}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15890--15900}, shortjournal = {J. Am. Chem. Soc.}, title = {Stepwise self-assembly of multisegment mesoporous silica nanobamboos for enhanced thermal insulation}, volume = {147}, year = {2025}, }
• (2025). Low-temperature nonoxidative dehydrogenation of short-chain alkanes over Copper(I) mordenite via chemical looping. JACS, 147(18), 15880--15889. (www)

  @article{ , abstract = {We report selective low-temperature non-oxidative dehydrogenation of ethane and propane to ethylene and propylene via chemical looping using copper(I)-containing mordenite as active material. Combining Cu K-edge X-ray absorption spectroscopy, in situ infrared spectroscopy (FTIR), H/D kinetic isotope effect measurements, and density functional theory calculations, we show that the active sites for the dehydrogenation reaction are copper(I) cations hosted in zeolite framework, and the rate-limiting step is activation of the first C–H bond of alkane. The stoichiometric reaction between the gas-phase alkane and copper(I) cationic site results in the formation of a stable copper(I)-alkene π-complex and gaseous hydrogen. Complete saturation of copper(I) sites with alkenes can be attained at 573 K with a selectivity close to 100%. The strong binding of alkenes to copper(I) sites promotes the dehydrogenation reaction, enabling the yield of alkene more than 100 times greater than the gas-phase thermodynamic limit. Copper(I)-alkene complexes can be decomposed in a separate step by contact with water at near-ambient temperature, releasing alkenes into the gas phase, and the material can be regenerated without detectable loss of activity.}, archive = {J_JACS}, author = {Mikalai A. Artsiusheuski and Jiawei Guo and Ambarish R. Kulkarni and Jeroen A. van Bokhoven and Vitaly L. Sushkevich}, doi = {10.1021/jacs.5c04229}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15880--15889}, shortjournal = {J. Am. Chem. Soc.}, title = {Low-temperature nonoxidative dehydrogenation of short-chain alkanes over Copper(I) mordenite via chemical looping}, volume = {147}, year = {2025}, }
• (2025). Isoleucine side chains as reporters of conformational freedom in protein folding studied by DNP-enhanced NMR. JACS, 147(18), 15867--15879. (www)

  @article{ , abstract = {Conformations of protein side chains are closely linked to protein function. DNP-enhanced solid-state NMR (ssNMR), which operates at cryogenic temperatures (<110 K), can be used to freeze-trap protein conformations, including the side chains. In the present study, we employed two-dimensional DNP-enhanced ssNMR to get detailed insights into backbone and side chain conformations of isoleucine. We used different amino acid selectively labeled model proteins for intrinsically disordered proteins (IDPs), denatured and well-folded proteins, and amyloid fibrils. 13 C chemical shifts are closely correlated with secondary structure elements and χ 1 and χ 2 angles in isoleucine side chains. Thus, line shape analysis by integration of representative peak areas in 2D spectra provides an accurate overview of the distribution of backbone and side chain conformations. For the well-folded proteins GABARAP and bovine PI3-kinase (PI3K) SH3 domain, most Ile chemical shifts in frozen solution are well resolved and similar to those observed in solution. However, line widths of individual Ile residues are directly linked to residual mobility, and line broadening or even signal splitting appears for those Ile residues, which are not part of well-defined secondary structure elements. For unfolded PI3K SH3 and the IDP α-synuclein (α-syn), all Ile side chains have full conformational freedom, and as a consequence, inhomogeneous line broadening dominates the cryogenic spectra. Moreover, we demonstrate that conformational ensembles of proteins strongly depend on solvent and buffer conditions. This allowed different unfolded structures for chemical and acidic pH denaturation of the PI3K SH3 domain to be distinguished. In amyloid fibrils of α-syn and PI3K SH3, chemical shifts typical for β-strand like secondary structure dominate the spectra, whereas Ile residues belonging to the fuzzy coat still add the IDP-type line shapes. Hence, DNP-enhanced ssNMR is a useful tool for investigating side chain facilitated protein functions and interactions.}, archive = {J_JACS}, author = {Leonardo Levorin and Nina Becker and Boran Uluca-Yazgi and Luis Gardon and Mirko Kraus and Marc Sevenich and Athina Apostolidis and Kai Schmitz and Neomi Rüter and Irina Apanasenko and Dieter Willbold and Wolfgang Hoyer and Philipp Neudecker and Lothar Gremer and Henrike Heise}, doi = {10.1021/jacs.5c04159}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15867--15879}, shortjournal = {J. Am. Chem. Soc.}, title = {Isoleucine side chains as reporters of conformational freedom in protein folding studied by DNP-enhanced NMR}, volume = {147}, year = {2025}, }
• (2025). Oxidative strong Metal–Support interaction stabilized single-atom catalysts for heterogeneous hydroformylation. JACS, 147(18), 15859--15866. (www)

  @article{ , abstract = {The strong metal–support interaction (SMSI) is one of the most important concepts in heterogeneous catalysis, which plays a crucial role in modifying catalytic performance. However, the study of SMSI on single-atom catalysts (SACs), which are considered to bridge homogeneous and heterogeneous catalysis, remains preliminary. Here, to the best of our knowledge, we first report the oxidative SMSIs on SACs and utilize them to enhance hydroformylation activity and stability. The surface-adsorbed Rh single atoms tend to be encapsulated by ZrO 2 supports after calcination in air and can be re-exposed after reduction in H 2 . The highest turnover frequency (TOF) of heterogeneous hydroformylation reaches 11,097 h –1 , surpassing previously reported SACs. The embedded Rh, generated through oxidative SMSI, also shows enhanced stability to resist metal leaching. Our work expands the conceptual boundaries of SMSIs and paves the way for the future design of highly active and stable heterogeneous hydroformylation catalysts.}, archive = {J_JACS}, author = {Boyang Liu and Muhan Li and Xiao Chen and Yifan Sun and Weixiang Wang and Zhangxinyu Fan and Xiaocheng Lan and Fei Wei and Binhang Yan and Qin Zhong and Tiefeng Wang}, doi = {10.1021/jacs.5c04086}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15859--15866}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxidative strong Metal–Support interaction stabilized single-atom catalysts for heterogeneous hydroformylation}, volume = {147}, year = {2025}, }
• (2025). Unveiling the biosynthetic logic of nosiheptide based on reconstitution of its bicyclic thiopeptide scaffold. JACS, 147(18), 15847--15858. (www)

  @article{ , abstract = {Thiopeptides, which share a macrocyclic framework characterized by a six-membered, nitrogen heterocycle central to multiple (thi)azol(in)es and dehydroamino acids, represent one of the most structurally complex groups of ribosomally synthesized and post-translationally modified peptides (RiPPs). Although post-translational modifications (PTMs) necessary for common framework formation were established, how bicyclic thiopeptides, which depend on additional specific enzyme activities to afford a side ring system, are formed remains poorly understood. Using the biosynthesis of nosiheptide as a model system, here, we report the first PTM logic to achieve a bicyclic thiopeptide based on in vivo and in vitro structural reconstitution. Eleven biosynthetic proteins are employed, processing the precursor peptide through the proper coordination of five PTM steps, of which three are common and two are specific: (1) formation of five thiazoles, (2) incorporation of an indolic moiety, (3) dehydration of five Ser/Thr residues, (4) indolic side ring closure, and (5) pyridine formation to establish the thiopeptide framework. Heterologous expression and biochemical characterization validated that the two macrocyclic ring systems are established in an interdependent and alternating manner. Distinct from tailoring PTMs, this study unveils a paradigm of a new PTM introduction for expanding the chemical and biological spaces during the establishment of the group-defining framework.}, archive = {J_JACS}, author = {Yijiao Xiong and Heng Guo and Wen Liu}, doi = {10.1021/jacs.5c03922}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15847--15858}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling the biosynthetic logic of nosiheptide based on reconstitution of its bicyclic thiopeptide scaffold}, volume = {147}, year = {2025}, }
• (2025). One-pot ‘Click’ synthesis of ring-in-rings complexes with customizable π-stacked dyads. JACS, 147(18), 15838--15846. (www)

  @article{ , abstract = {We report an efficient one-pot aqueous synthesis of ring-in-rings complexes featuring customizable π-stacked dyads. Conventional methods for such complexes often suffer from poor solubility and low yields due to irreversible kinetically controlled reactions. To overcome these limitations, we developed a strategy combining noncovalent preassembly with efficient dynamic covalent bonding to secure a ring-in-rings complex as the exclusive thermodynamic product. Through complexation with cucurbit[8]uril (CB[8]), a folded conformation was induced in an aldehyde-functionalized bis(phenylpyridinium) derivative, predisposing the reactive aldehyde groups to promote acylhydrazone condensation with aromatic dihydrazides. The method achieves high conversion and purity, enabling direct single-crystal growth without the need for purification. We successfully synthesized π-stacked dyads across diverse aromatic moieties, including five distinct single-crystal structures demonstrating dimeric cofacial stacking. Kinetic analysis reveals that CB[8] complexation increases the ceiling temperature of the condensation reaction, rendering the process both thermodynamically and kinetically favorable. The modular nature of this strategy allows for precise tuning of photophysical properties by simply altering the linker lengths and the central aromatic cores, providing a facile platform for exploring structure–function relationships in ring-in-rings complexes and beyond.}, archive = {J_JACS}, author = {Jia Liu and Xiujie Han and Ningxu Han and Bao Li and Yibin Sun and Ming Wang and Guanglu Wu}, doi = {10.1021/jacs.5c03926}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15838--15846}, shortjournal = {J. Am. Chem. Soc.}, title = {One-pot ‘Click’ synthesis of ring-in-rings complexes with customizable π-stacked dyads}, volume = {147}, year = {2025}, }
• (2025). Off-center distortions and resonant levels: A pathway to enhance power generation and thermoelectric cooling in PbSe crystals. JACS, 147(18), 15827--15837. (www)

  @article{ , abstract = {The scarcity of tellurium (Te) poses significant challenges to the widespread application of Bi 2 Te 3 -based thermoelectric systems. In this work, we investigated the potential of Te-free PbSe for thermoelectric applications by optimizing carrier mobility through crystal growth and a two-step strategy of light alloying and doping. First, Cd alloying was employed to reduce the lattice thermal conductivity ( κ lat ) of n-type PbSe through the off-center effect while preserving carrier mobility. Subsequent In doping enhanced the effective mass via the resonant level formation, achieving a high weighted mobility-to- κ lat ratio ( μ W / κ lat ∼338.4) and a large power factor of 36.7 μW cm –1 K –2 at 300 K in the Pb 0.9972 Se-0.008Cd-0.0008In crystal. Due to the reduced lattice thermal conductivity and largely promoted μ W / κ lat value, the optimized Pb 0.9972 Se-0.008Cd-0.0008In crystal exhibited a large ZT value of ∼0.5 at 300 K, a maximum ZT value of ∼1.3 at 673 K, and an average ZT value of ∼1.1 (300–773 K). Additionally, a thermoelectric generator based on the Pb 0.9972 Se-0.008Cd-0.0008In crystal achieves a power generation efficiency of 6.3%, while a 7-pair module (n-type Pb 0.9972 Se-0.008Cd-0.0008In crystal and p-type commercial Bi 0.4 Sb 1.6 Te 3 material) demonstrated a maximum cooling temperature difference (Δ T ) of 51.2 K ( T h = 353 K). This work establishes PbSe as a cost-effective, high-performance thermoelectric material for thermoelectric cooling and power generation.}, archive = {J_JACS}, author = {Siqi Wang and Shulin Bai and Pengpeng Chen and Shaoping Zhan and Yu Tian and Lei Wang and Dongrui Liu and Jiayi Peng and Yichen Li and Dezheng Gao and Tian Gao and Zhiyao Zhang and Zhan Si and Yuxiang Wei and Hongyao Xie and Xiang Gao and Yingcai Zhu and Yi Wen and Li-Dong Zhao}, doi = {10.1021/jacs.5c03732}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15827--15837}, shortjournal = {J. Am. Chem. Soc.}, title = {Off-center distortions and resonant levels: A pathway to enhance power generation and thermoelectric cooling in PbSe crystals}, volume = {147}, year = {2025}, }
• (2025). Synergizing catalysis with post-catalysis pseudo-iron release by building dynamic catalytic active sites in diatomic nanozymes for boosting cancer therapy. JACS, 147(18), 15814--15826. (www)

  @article{ , abstract = {Biomimetic nanozymes hold considerable promise for cancer therapy, but their therapeutic potential is often constrained by their limited catalytic activity. Here, we present a Ga/Zn diatomic nanozyme (Ga/Zn-NC) with a well-defined geometric structure and electronic configuration designed to emulate peroxidase and glutathione oxidase with exceptional catalytic activities, enabling cascade catalysis. We demonstrate that the formation of Ga–Zn metal bonding is essential for accelerating electron transfer and reducing the reaction energy barrier, thus enhancing the catalytic performance. Within the tumor microenvironment, the catalytic actions of Ga/Zn-NC induce oxidative damage and sensitize breast cancer cells to ferroptosis. Concurrently, the release of gallium from Ga/Zn-NC with “pseudo-iron” activity disrupts iron metabolism and activates a self-amplifying ferroptosis pathway, synergizing with the enzyme’s catalytic activity to potentiate ferroptosis and apoptosis, thereby achieving remarkable efficacy against tumors.}, archive = {J_JACS}, author = {Songjing Zhong and Zeyu Zhang and Zhuo Wang and Qinyu Zhao and Wenting Chen and Genglin Chen and Zhuoheng Jiang and Qian Cai and Likun Gong and Yuecheng Lai and Dingsheng Wang and Linlin Li}, doi = {10.1021/jacs.5c03804}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15814--15826}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergizing catalysis with post-catalysis pseudo-iron release by building dynamic catalytic active sites in diatomic nanozymes for boosting cancer therapy}, volume = {147}, year = {2025}, }
• (2025). A diffusion-based synthetic cell communication network enabled by a multitasking deoxyribonucleic acid nanomachine. JACS, 147(18), 15806--15813. (www)

  @article{ , abstract = {DNA-mediated synthetic cell communication enabling non-natural signaling and regulatory pathways is highly attractive but relies on direct cell contacts. Here, we report a diffusion-based synthetic cell communication capable of regulating migration behaviors of epithelial cell adhesion molecule (EpCAM)-overexpressed cancer cells in response to apoptosis events at distal sites. This synthetic cell communication network is enabled by a multitasking DNA nanomachine that not only mediates signal production, transmission, and regulation of cell migration but also amplifies signaling ligands in situ in response to specific receiver cells to overcome the signal attenuation during diffusion. Leveraging this diffusion-based synthetic cell communication network, we demonstrate the inhibition of cancer cell migrations in response to distal apoptosis events induced by an anticancer drug. Our system enriches current DNA nanotechnological tools for manipulating cellular interactions and function. It also directs a possible intervening strategy to reduce the invasiveness of cancer cells.}, archive = {J_JACS}, author = {Qianying Zhang and Jingyi Zheng and Yihan Wang and Shengshi Xu and Wenjing Wang and Junpeng Xu and Jian-Rong Zhang and Feng Li and Jun-Jie Zhu}, doi = {10.1021/jacs.5c03726}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15806--15813}, shortjournal = {J. Am. Chem. Soc.}, title = {A diffusion-based synthetic cell communication network enabled by a multitasking deoxyribonucleic acid nanomachine}, volume = {147}, year = {2025}, }
• (2025). Particle hopping and coalescence of supported au nanoparticles in harsh reactive environments. JACS, 147(18), 15796--15805. (www)

  @article{ , abstract = {Sintering of supported metal nanoparticles (NPs) is a general and important phenomenon in materials and catalysis science. A consensus view is that it takes place either via the Ostwald ripening (OR) or particle migration and coalescence (PMC) mechanism through the substrate, but how sintering occurs under high gas pressure and high temperature has not been addressed. Here, we perform millisecond-scale environmental kinetic Monte Carlo (EKMC) simulations combined with density functional theory (DFT) calculations to reveal a unique through-space sintering mechanism, particle hopping and coalescence (PHC). Under high CO pressure and high temperature, the coalescence of Au NPs takes place through NP hopping up from the anatase TiO 2 (101) substrate and mass transfer via the gas phase. When the sintered floating NP reaches a critical size, it spontaneously redeposits onto the substrate. This process is driven by the preference of interfacial Au atoms of small NPs to interact with CO rather than the substrate at a high CO chemical potential. The PHC mechanism implies that NP sintering and intersubstrate catalyst transfer may occur easier than expected during reactions and provides a distinct perspective to understand catalyst thermal deactivation under harsh operando conditions.}, archive = {J_JACS}, author = {Shuoqi Zhang and Yu Han and Xiao-Yan Li and Qingli Tang and Beien Zhu and Yi Gao}, doi = {10.1021/jacs.5c03633}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15796--15805}, shortjournal = {J. Am. Chem. Soc.}, title = {Particle hopping and coalescence of supported au nanoparticles in harsh reactive environments}, volume = {147}, year = {2025}, }
• (2025). Discovery of carbodiimide warheads to selectively and covalently target aspartic acid in KRASG12D. JACS, 147(18), 15787--15795. (www)

  @article{ , abstract = {Targeted covalent inhibitors are known to be successful therapeutics used in various indications. Covalent drugs typically target cysteine, as cysteine is well suited due to its high nucleophilicity. However, its low abundance in protein binding sites represents a major limitation. As a result, there is a need to covalently target additional nucleophilic amino acids. Recent literature has reported covalent inhibitors labeling aspartic acid in KRAS G12D . However, these compounds also covalently bind to KRAS G12C , indicating their cross-reactivity to cysteine along with aspartic acid. We report here carbodiimides as a novel reactive group to selectively target aspartic acid. Covalent inhibitors bearing a carbodiimide moiety are shown to covalently label KRAS G12D in biochemical and cellular assays. A high-resolution X-ray crystal structure was obtained, which illustrates the mechanism of the covalent bond formation with KRAS G12D . Carbodiimide warheads show selectivity toward KRAS G12D over other KRAS alleles and represent a new covalent warhead suitable for covalently binding to aspartic acid in a biochemical and cellular context.}, archive = {J_JACS}, author = {Ludovica S. Sirocchi and Maximilian Scharnweber and Sarah Oberndorfer and Gabriella Siszler and Krzysztof M. Zak and Klaus Rumpel and Ralph A. Neumüller and Birgit Wilding}, doi = {10.1021/jacs.5c03562}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15787--15795}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of carbodiimide warheads to selectively and covalently target aspartic acid in KRASG12D}, volume = {147}, year = {2025}, }
• (2025). Quantitative skeletal-charge engineering of anion-selective COF membrane for ultrahigh osmotic power output. JACS, 147(18), 15777--15786. (www)

  @article{ , abstract = {Osmotic energy contained in water bodies can generate abundant renewable electricity through reverse electrodialysis (RED) that relies on ion permselective membranes. Anion-permselective membrane RED offers a stable and sustainable energy output potential by maintaining a consistent driving force across the membrane, providing advantages in sustainability and versatility over cation-selective membranes. But significant challenges persist in developing anion-selective membranes that feature high selectivity and low impedance. Herein, this study presents the development of an anion-permselective osmotic power generation system using a free-standing chloride-selective covalent organic framework (COF) membrane. Inspired by biological chloride channels, the membrane is engineered with smooth, straight, and highly charged nanochannels for rapid chloride-anion transport. Its inner structure is stoichiometrically controlled to atomically distribute positive charges on the COF intraplane rings without introducing heterometal atoms or branch groups, enabling selective and efficient single-directional movement of anions. The RED device with this ionic-COF membrane achieves a remarkable output power density of 239.6 W m –2 , outperforming commercial benchmarks by 2 orders of magnitude, with low intermediate resistance under demanding gradients. Theoretical simulations corroborate that anion transport within ionic-COF membranes is governed by electrostatic interactions with the charged skeletons, thereby enhancing the anion selectivity and permeability. The findings highlight the potential of ionic-COF membranes for high-efficiency osmotic energy capture, demonstrating a substantial step toward sustainable and stable energy output from salinity gradients.}, archive = {J_JACS}, author = {Shuang Zheng and Xing Liu and Chunlei Wang and Zhaofeng Ouyang and Xiaohu Zhang and Shuai Bi and Guosheng Shi and Qing Xu and Joseph S. Francisco and Gaofeng Zeng}, doi = {10.1021/jacs.5c03492}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15777--15786}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantitative skeletal-charge engineering of anion-selective COF membrane for ultrahigh osmotic power output}, volume = {147}, year = {2025}, }
• (2025). Boosting the selectivity in oxygen electrocatalysis using chiral nanoparticles as electron-spin filters. JACS, 147(18), 15767--15776. (www)

  @article{ , abstract = {Controlling the electron spin of oxygen-containing intermediates is crucial for efficient oxygen electrocatalysis toward clean energy technologies such as fuel cells and water electrolysis. Current strategies for controlling the electron spins rely mainly on tuning the chemical structure of the oxygen electrocatalyst, which is often hardly achieved for metal and oxide electrocatalysts. The chiral-induced spin selectivity (CISS) effect, a significant discovery in chiral spintronics, represents an alternative approach for tuning the spin selectivity of oxygen electrocatalysts. Here we demonstrate the use of intrinsic chiral nanoparticles as electron-spin filters to tune the selectivity in oxygen electrocatalytic reactions. Chiral Au nanoparticles with a concave vortex cube structure were employed as the chiral substrate, exhibiting highly tunable optical chirality and intriguing CISS-like effect. As model systems, the catalytically active components such as Pt or Ni(OH) 2 are overgrown onto chiral Au nanoparticles to construct the chiral hybrid electrocatalysts. Remarkably, both cases show chirality-dependent tunable activities over oxygen reduction/evolution reactions, respectively. The insights gained from this work not only shed light on the underlying mechanisms dictating the CISS-enhanced oxygen electrocatalysis by chiral nanoparticles but also provide an important knowledge framework that guides the rational design of chiral electrocatalysts toward oxygen electrocatalysis.}, archive = {J_JACS}, author = {Zixu Wang and Jinling Wan and Xuehao Sun and Lichao Sun and Shengli Chen and Qingfeng Zhang}, doi = {10.1021/jacs.5c03394}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15767--15776}, shortjournal = {J. Am. Chem. Soc.}, title = {Boosting the selectivity in oxygen electrocatalysis using chiral nanoparticles as electron-spin filters}, volume = {147}, year = {2025}, }
• (2025). Catalytic metalloradical system for radical 1,6-C(sp3)–H amination with concurrent control of site-, chemo-, and enantio-selectivity. JACS, 147(18), 15755--15766. (www)

  @article{ , abstract = {A catalytic radical process has been developed via metalloradical catalysis (MRC) for 1,6-C(sp 3 )–H amination with concurrent control of site-, chemo-, and enantioselectivity. Supported by an optimal D 2 -symmetric chiral amidoporphyrin ligand, the Co(II)-based metalloradical system effectively catalyzes chemoselective amination of propargylic, allylic, and benzylic C–H bonds at 1,6- over 1,5-positions of alkoxysulfonyl azides, achieving high enantioselectivity. This Co(II)-catalyzed process, which operates at room temperature, is applicable to a broad range of alkoxysulfonyl azides with a high tolerance of functional groups, enabling the efficient construction of six-membered sulfamidates in high yields with excellent enantioselectivities. Comprehensive experimental investigations, complemented by computational studies, elucidate the stepwise radical mechanism underlying this transformation. The resulting six-membered cyclic sulfamidates from the enantioselective radical process can undergo stereospecific ring-opening reactions with various nucleophiles, affording γ-functionalized α-chiral amines in high yields while retaining the original enantiopurity. Since alkoxysulfonyl azides are readily synthesized from widely available alcohols through a nucleophilic azide transfer, this union of the radical and ionic processes constitutes a versatile 1,3-difunctionalization of alcohols.}, archive = {J_JACS}, author = {Yiling Zhu and Wan-Chen Cindy Lee and X. Peter Zhang}, doi = {10.1021/jacs.5c03259}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15755--15766}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic metalloradical system for radical 1,6-C(sp3)–H amination with concurrent control of site-, chemo-, and enantio-selectivity}, volume = {147}, year = {2025}, }
• (2025). Zeotype-confined frustrated lewis pair and its role in catalyzing hydrogenation. JACS, 147(18), 15747--15754. (www)

  @article{ , abstract = {Recent theoretical studies predicted that the frustrated Lewis pair (FLP) formed by carbonaceous species confined in zeolites/zeotypes can activate H–H and C–H bonds. However, there still lacks experimental evidence and understanding on the role of FLP in the hydrogenation reaction. Herein, we combined experiments and density functional theory (DFT) calculations to demonstrate that the Brønsted acid sites with weak acid strength can transfer H + to the confined carbonaceous species to form Si–O – –Al as a Lewis base and carbocation as a Lewis acid. They are electrostatically attracted and sterically repelled, thus, forming FLP sites. We present for the first time experimental evidence and a general principle about the formation of FLP sites inside zeotypes and investigated the effect of the topology and the acid strength on the FLP formation. FLP sites are active in ethylene hydrogenation, and their activity is inversely correlated with their parent Brønsted acid strength. FLP derived from weaker Brønsted acid sites promotes C 2 H 4 adsorption and H 2 activation, thus enhancing hydrogenation. This work not only provides mechanistic insights into the origin of olefin hydrogenation over metal-free zeolites/zeotypes but also offers guidance for further development of high-performance zeolite/zeotype-based catalysts and heterogeneous FLP catalysts.}, archive = {J_JACS}, author = {Mengyuan Li and Yihan Ye and Bing Bai and Cheng Liu and Hanlixin Wang and Zhaochao Xu and Jianping Xiao and Feng Jiao and Xiulian Pan and Xinhe Bao}, doi = {10.1021/jacs.5c03123}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15747--15754}, shortjournal = {J. Am. Chem. Soc.}, title = {Zeotype-confined frustrated lewis pair and its role in catalyzing hydrogenation}, volume = {147}, year = {2025}, }
• (2025). Light- and heat-responsive frustrated lewis pair enables on-demand fixation of ethylene. JACS, 147(18), 15740--15746. (www)

  @article{ , abstract = {Frustrated Lewis pairs (FLPs) have been widely utilized as useful reagents and catalysts for activation of small molecules (SMs) through thermally controlled equilibrium formation of FLP–SM adducts. Herein, we report a light- and heat-responsive FLP system for on-demand fixation of ethylene. The system realizes capture and release of ethylene orthogonally triggered by visible light and heat, demonstrating potential utility as a nonmetallic and environmentally benign method for separation and storage of ethylene. The applicability to other alkenes is also demonstrated. Mechanistic investigations clarify that the photoexcited FLP enables stepwise radical addition to ethylene, followed by skeletal rearrangement to afford the FLP–ethylene adduct, which undergoes thermally promoted, concerted retro -cycloaddition to release ethylene and the free FLP. As a synthetic application, nonequilibrium, selective cis -to- trans isomerization of cyclooctene is achieved through the capture and release of cyclooctene with the FLP. This work discloses unique photochemical reactivity and application of FLPs, leading to further expansion of FLP chemistry into chemical science.}, archive = {J_JACS}, author = {Taiki Yanagi and Jun Takaya}, doi = {10.1021/jacs.5c03130}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15740--15746}, shortjournal = {J. Am. Chem. Soc.}, title = {Light- and heat-responsive frustrated lewis pair enables on-demand fixation of ethylene}, volume = {147}, year = {2025}, }
• (2025). Developments of the mDZ-RhoBAST probe for super-resolution imaging of FTO demethylation in live cells. JACS, 147(18), 15732--15739. (www)

  @article{ , abstract = {Single-molecule localization microscopy (SMLM) provides precise, high-resolution visualization of target biomolecules in cellular imaging. Fluorescent light-up aptamers (FLAPs) offer a versatile approach for labeling RNA of interest in live cells by binding to fluorogens through adaptive recognition. Several FLAPs can generate blinking fluorescent signals in conjunction with fluorogens, enabling single-molecule imaging of RNA in living cells. An example of this is RhoBAST, which has been successfully used for single-molecule imaging of RNA due to its fast exchange kinetics with fluorogens. However, single-molecule imaging of RNA activities regulated by proteins in living cells presents a greater challenge. Here, we introduce mDZ-RhoBAST, a nucleic acid probe, to visualize the demethylation process by fat mass and obesity-associated protein (FTO) in living cells. This probe combines the 6mA-modified DNAzyme with the RhoBAST FLAP, activated by FTO, restoring the DNAzyme’s cleavage activity and releasing RhoBAST to bind the target fluorogen. Our approach achieved super-resolution imaging of the demethylation process of endogenous FTO, providing real-time insights into its demethylation processes in vivo .}, archive = {J_JACS}, author = {Xiaolu Zhou and Huihui Gao and Limin Xiang and Hui Liu and Xiang Zhou}, doi = {10.1021/jacs.5c03149}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15732--15739}, shortjournal = {J. Am. Chem. Soc.}, title = {Developments of the mDZ-RhoBAST probe for super-resolution imaging of FTO demethylation in live cells}, volume = {147}, year = {2025}, }
• (2025). Subcellular photocatalysis enables tumor-targeted inhibition of thioredoxin reductase i by Organogold(I) complexes. JACS, 147(18), 15719--15731. (www)

  @article{ , abstract = {Selective inhibition of TrxR1 over TrxR2 is a highly sought-after goal, because the two enzymes play distinct roles in cancer progression. However, achieving targeted inhibition is challenging due to their high homology and identical active site sequence. Herein we report a new subcellular photocatalysis approach for targeted inhibition by controllably activating organogold(I) prodrugs within the cytosol, the exclusive location of TrxR1. The NHC-Au(I)-alkynyl complexes are stable and evenly distributed in the cell; they can meanwhile be efficiently transformed into active NHC-Au(I)-L species (L = labile ligands) via a radical mechanism by photocatalysts released into the cytosol (from endosome/lysosome) upon light irradiation, leading to selective inhibition of TrxR1 without affecting TrxR2. This results in strong cytotoxicity to cancer cells with much higher selectivity than auranofin, a pan TrxR inhibitor that cannot discriminate TrxR1/2, along with potent antitumor activities in multiple zebrafish and mouse models. This subcellular prodrug activation may thus suggest a novel approach to precision targeting using the remarkable spatial control of photocatalysis.}, archive = {J_JACS}, author = {Moyi Liu and Haitao Liu and Yan Yang and Xiaolin Xiong and Taotao Zou}, doi = {10.1021/jacs.5c03186}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15719--15731}, shortjournal = {J. Am. Chem. Soc.}, title = {Subcellular photocatalysis enables tumor-targeted inhibition of thioredoxin reductase i by Organogold(I) complexes}, volume = {147}, year = {2025}, }
• (2025). Selective binding and light-driven release of fluorous PF6– and radioactive 99TcO4– anions for all-to-nothing Liquid–Liquid extraction. JACS, 147(18), 15707--15718. (www)

  @article{ , abstract = {The removal of anions from aqueous media using molecular receptors in liquid–liquid extraction is a long-standing strategy to clean up contaminated water sources. Therein, high selectivity is needed to remove specific ions from mixtures of other ions, and high affinity provides extractions at low concentrations. However, the high affinity creates a conundrum by impeding the release of the ions in any stripping steps needed for further processing. To circumvent this problem, light-responsive receptors have been proposed as candidates for turning off the binding, but they are currently untested in liquid–liquid extraction. We tested the feasibility of light-driven release using a cyanostar macrocycle. We demonstrate the selective extraction of PF 6 – anions over large excesses of competing anions (Cl – , NO 3 – , SO 4 2– ) followed by photodriven release for quantitative isolation of the target. Release relies on photoisomerization of the macrocycle’s five stilbenes generating distorted isomers to turn off binding. With modest reversibility, only a single-shot release was demonstrated, akin to photodriven uncaging. These methods were extended to the capture and photodriven release of ReO 4 – and radioactive 99 TcO 4 – anions at ∼90% efficiency. Extraction was demonstrated down to the highly dilute 4 ppb levels of the 99 TcO 4 – anion. This proof-of-concept demonstration verifies the use of a large change in affinity for the all-to-nothing capture and release of target anions between liquid phases.}, archive = {J_JACS}, author = {Nabarupa Bhattacharjee and Alketa Lutolli and Jeffrey D. Einkauf and Zhao Zhang and Amanda R. Morgan and Maren Pink and Santa Jansone-Popova and Amar H. Flood}, doi = {10.1021/jacs.5c03097}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15707--15718}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective binding and light-driven release of fluorous PF6– and radioactive 99TcO4– anions for all-to-nothing Liquid–Liquid extraction}, volume = {147}, year = {2025}, }
• (2025). Topologically engineered supramolecular cyclolipid nanoparticles: A custom-tailored delivery system for inhaled combination therapy. JACS, 147(18), 15693--15706. (www)

  @article{ , abstract = {Lipid nanoparticles (LNPs) have shown promising potential in the development of nucleic acid therapeutics and vaccines; however, unsatisfactory endosomal escape efficiency and physiological stability hinder their clinical applications. Herein, we design and synthesize a novel topologically engineered cyclodextrin-cored lipid (cyclolipid) featuring seven tertiary amine groups, seven secondary amine groups, and 14 hydrophobic alkyl tails to fabricate two-component supramolecular cyclolipid nanoparticles (CNPs). Benefiting from its cone-shaped structure, the cyclolipid facilitates the transition of endosomal membranes from the lamellar phase to the unstable hexagonal II phase, thereby promoting membrane destabilization and endosomal escape of CNPs. Additionally, the high density of ionizable sites enhances the binding capacity with RNA, while multiple hydrophobic alkyl chains strengthen the stability of CNPs, thus guaranteeing the in vivo circulation stability. Interestingly, the cavity of the cyclolipid enables the encapsulation of pirfenidone (PFD, an antifibrotic drug) through host–guest interactions, offering a promising strategy for synergistic therapy. Rationally optimizing the components and physicochemical properties of CNPs dramatically promotes mucus penetration capability, thereby enhancing their bioavailability in the lungs and avoiding unwanted side effects toward other organs. Leveraging their exceptional ability for achieving physiological stability, mucus penetration, and endosomal escape, siRNA targeting heat shock protein 47 (siHsp47) and PFD are codelivered by CNPs (CNPs@siHsp47/PFD) for the treatment of pulmonary fibrosis. CNPs@siHsp47/PFD synergistically alleviates pulmonary fibrosis, achieving therapeutic outcomes comparable to those of healthy mice, highlighting the outstanding potential of CNPs as the next-generation delivery platform for drug and gene combination therapy.}, archive = {J_JACS}, author = {Meiqi Cheng and Zheng Jiao and Jiaqi Lei and Mengyao Li and Kai Yang and Shaolong Qi and Xinyang Yu and Yangfan Wang and Li-Tang Yan and Guocan Yu}, doi = {10.1021/jacs.5c03033}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15693--15706}, shortjournal = {J. Am. Chem. Soc.}, title = {Topologically engineered supramolecular cyclolipid nanoparticles: A custom-tailored delivery system for inhaled combination therapy}, volume = {147}, year = {2025}, }
• (2025). Phase engineering of atomically dispersed fe-doped amorphous RuOx nanosheets via Amorphous–Amorphous transition for oxygen activation. JACS, 147(18), 15686--15692. (www)

  @article{ , abstract = {Amorphous nanomaterials with identical compositions can possess distinct atomic structures, which significantly influence their performance, underscoring the importance of phase engineering in amorphous nanomaterials. However, the high Gibbs free energy and complex structures associated with their disordered atomic arrangements pose a significant challenge to the phase engineering of amorphous nanomaterials. Herein, we achieved phase engineering of atomically dispersed Fe-doped amorphous RuO x nanosheets (A-Fe 1 /RuO x NSs) through amorphous–amorphous transition strategies. Specifically, as confirmed by X-ray absorption fine structure measurements, the Fe coordination environment in A-Fe 1 /RuO x NSs was regulated from FeO 4 tetrahedral to FeO 6 octahedral, driven by amorphous–amorphous transition, resulting in two distinct Ru–Fe pair configurations of A-Fe 1 /RuO x NSs: one with a connected tetrahedral FeO 4 -octahedral RuO 6 configuration and the other one with a connected octahedral FeO 6 -octahedral RuO 6 configuration. Density functional theory calculations demonstrated that the structure differences of the Ru–Fe pair efficiently regulated the adsorption mode of the O 2 molecules from top adsorption to bridge adsorption on an amorphous surface. Consequently, the A-Fe 1 /RuO x NSs with a connected tetrahedral FeO 4 -octahedral RuO 6 configuration exhibited an enhanced formation of superoxide radicals during oxidative dehydrogenation reactions, resulting in remarkable catalytic activity in the synthesis of indole, indole derivatives, and quinoline.}, archive = {J_JACS}, author = {Geng Wu and Peixin Cui and Bei Wu and Xiao Han and Haohui Hu and Jingjie Ge and Yanan Zhou and Xiaoping Gao and Daping He and Xun Hong}, doi = {10.1021/jacs.5c03066}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15686--15692}, shortjournal = {J. Am. Chem. Soc.}, title = {Phase engineering of atomically dispersed fe-doped amorphous RuOx nanosheets via Amorphous–Amorphous transition for oxygen activation}, volume = {147}, year = {2025}, }
• (2025). The heat-shock metabolite streptolactam d, produced by high-temperature culture of streptomyces sp. JA74, promotes thermotolerance via self-membrane stabilization. JACS, 147(18), 15676--15685. (www)

  @article{ , abstract = {A new streptolactam derivative featuring a 4-membered ring fused to a 6-membered ring in the macrolactam structure, streptolactam D ( 1 ), was isolated from the culture extract of thermotolerant Streptomyces sp. JA74. Production of compound 1 increased with high-temperature cultivation, and this type of compound was previously designated as a “heat-shock metabolite (HSM)” by our research group. The structure of 1 was determined by NMR and MS spectroscopic analyses, calculation of NMR and ECD spectra, and analysis of the biosynthetic gene cluster. Surprisingly, 1 promoted the growth of strain JA74 under high-temperature conditions and increased the growth limit temperature. Analysis of the mode of action using ultracentrifugation and scanning electron microscopy suggested that 1 localizes in the cell membrane and causes the cell to assume a short and thick morphology. Furthermore, 1 is predicted to maintain cell membrane fluidity and impart thermotolerance to strain JA74, similar to cholesterol and saturated fatty acids. These data suggest that 1 is produced to promote the survival of strain JA74 under high-temperature conditions.}, archive = {J_JACS}, author = {Shun Saito and Yurika Okumura and Sosuke Kataoka and Keisuke Fukaya and Daisuke Urabe and Midori A. Arai}, doi = {10.1021/jacs.5c03026}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15676--15685}, shortjournal = {J. Am. Chem. Soc.}, title = {The heat-shock metabolite streptolactam d, produced by high-temperature culture of streptomyces sp. JA74, promotes thermotolerance via self-membrane stabilization}, volume = {147}, year = {2025}, }
• (2025). Cu-catalyzed enantioselective carbene insertion into Ge–H and Si–H bonds enabled by SPSiBox with a tunable chiral pocket. JACS, 147(18), 15666--15675. (www)

  @article{ , abstract = {Here, we report the Cu-catalyzed asymmetric carbene insertion into both Ge–H and Si–H bonds with α-trifluoromethyl diazo compounds, enabled by a class of newly developed C 2 -symmetrical bisoxazoline ligands. This protocol provides an efficient method for the preparation of enantioenriched α-trifluoromethyl ogranogermanes and organosilanes, featuring a broad substrate scope, mild reaction conditions, excellent enantioselectivity, and low catalyst loading. The key to the tolerance of both Si–H and Ge–H bonds is the use of SPSiBox ligands bearing a flexible and tunable chiral pocket. Preliminary mechanistic studies and computational studies unveiled the origin of chiral induction with SPSiBox ligands, the mechanism of Cu-catalyzed Ge–H insertion. This method not only provides a new method for the construction of trifluoromethyl-containing chiral molecules but also opens a new avenue for the preparation of chiral Si- and Ge-containing functional molecules.}, archive = {J_JACS}, author = {Shi-Hao Chen and Shengye Zhang and Zi-Yang Chen and Yichen Wu and Peng Wang}, doi = {10.1021/jacs.5c02996}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15666--15675}, shortjournal = {J. Am. Chem. Soc.}, title = {Cu-catalyzed enantioselective carbene insertion into Ge–H and Si–H bonds enabled by SPSiBox with a tunable chiral pocket}, volume = {147}, year = {2025}, }
• (2025). Asymmetric CO–CHO coupling over pr single-atom alloy enables industrial-level electrosynthesis of ethylene. JACS, 147(18), 15654--15665. (www)

  @article{ , abstract = {The electrocatalytic conversion of carbon dioxide (CO 2 ) to ethylene (C 2 H 4 ) holds great promise for sustainable chemical synthesis, yet achieving industrially relevant production rates remains a significant challenge. Through computational screening, we have identified a praseodymium (Pr) single-atom alloy embedded in a copper (Cu) catalyst (Pr@Cu) that exhibits superior CO 2 activation and a remarkably low energy barrier for asymmetric *CO–*CHO coupling, primarily by facilitating the *CHO intermediate formation. Our optimized catalyst, Pr@Cu-2 (6 wt % Pr), achieves a C 2 H 4 Faradaic efficiency (FE) of 64.2% at −1.6 V versus the reversible hydrogen electrode (RHE) under a high current density of 1200 mA cm –2 in the CO 2 reduction reaction (CO 2 RR). Furthermore, when integrated into a 100 cm 2 membrane electrode assembly (MEA) electrolyzer, Pr@Cu-2 demonstrates robust performance, maintaining a continuous C 2 H 4 production rate of 21.3 mL min –1 at 20 A for over 200 h. This work provides fundamental insights into the role of Pr single-atom alloys in the CO 2 RR and highlights their potential for scalable C 2 H 4 electrosynthesis.}, archive = {J_JACS}, author = {Yanteng Xiao and Fuqing Yu and Chenfeng Xia and Deyu Zhu and Jiwen Chen and Nengji Liu and Yuye Zhao and Ruijuan Qi and Wei Guo and Bo You and Tao Yao and Yuanjie Pang and Ziyun Wang and Hongming Wang and Fei Song and Bao Yu Xia}, doi = {10.1021/jacs.5c02896}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15654--15665}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric CO–CHO coupling over pr single-atom alloy enables industrial-level electrosynthesis of ethylene}, volume = {147}, year = {2025}, }
• (2025). Making cells as a “Nirvana phoenix”: Precise coupling of precursors prior to ROS bursts for intracellular synthesis of quantum dots. JACS, 147(18), 15645--15653. (www)

  @article{ , abstract = {Rationally coupling natural biochemical reactions for live-cell synthesis of inorganic nanocrystals with fluorescence, such as quantum dots (QDs) especially near-infrared (NIR), holds significant potential for in situ labeling and bioimaging. However, the introduced exogenous reactants and intracellularly produced species, e.g., reactive oxygen species (ROS), often cause cell damage, decreasing the fluorescence of the QDs. Herein, we have found that cell-adaptable selenocystine ((Cys-Se) 2 ) can be reduced to biocompatible low-valence Se precursors, which could be subsequently hijacked by timely added Ag-glutathione (AgSG) to be transformed into NIR Ag 2 Se QDs. Such a comprehensive control strategy can inhibit the production of cytotoxic Se species and ROS bursts, significantly increasing the cell viability from 4 to 80% and enhancing the fluorescence of intracellularly synthesized Ag 2 Se QDs by over 8.7 times. Notably, the proliferative and in vivo tumorigenic capacities of the cells with strong NIR fluorescence-emitting functions could be maintained, enabling long-term tracking of cell division and disease progression. This work has provided new insights into fully excavating the potential of cells for the synthesis of inorganic nanocrystals by designing biocompatible precursors and also opened a new window for conventional synthetic biology from organic to inorganic.}, archive = {J_JACS}, author = {Juan Kong and An-An Liu and Xia Xu and Bo Tang and Yan-Yan Chen and Wei Zhao and Jianhong Jia and Ling-Ling Yang and Gongyu Li and Dai-Wen Pang}, doi = {10.1021/jacs.5c02861}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15645--15653}, shortjournal = {J. Am. Chem. Soc.}, title = {Making cells as a “Nirvana phoenix”: Precise coupling of precursors prior to ROS bursts for intracellular synthesis of quantum dots}, volume = {147}, year = {2025}, }
• (2025). Computer-generated, mechanistic networks assist in assigning the outcomes of complex multicomponent reactions. JACS, 147(18), 15636--15644. (www)

  @article{ , abstract = {The appeal of multicomponent reactions, MCRs, is that they can offer highly convergent, atom-economical access to diverse and complex molecules. Traditionally, such MCRs have been discovered “by serendipity” or “by analogy” but recently the first examples of MCRs designed by computers became known. The current work reports a situation between these extremes whereby the MCRs were initially designed by analogy to a known class but yielded unexpected results─at which point, mechanistic-network search performed by the computer was used to aid the assignment of the majority (though not all) of experimentally obtained products. The novel MCRs we report are of interest because they (i) have markedly different outcomes for substrates differing in relatively small structural detail; (ii) offer very high increase in substrate-to-product complexity; and (iii) enable access to photoactive scaffolds with potential applications as functional dyes. In a broader context, our results highlight a productive synergy between human and computer-driven analyses in synthetic chemistry.}, archive = {J_JACS}, author = {Maciej Krzeszewski and Olena Vakuliuk and Mariusz Tasior and Agnieszka Wołos and Rafał Roszak and Karol Molga and Mohammad B. Teimouri and Bartosz A. Grzybowski and Daniel T. Gryko}, doi = {10.1021/jacs.5c02846}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15636--15644}, shortjournal = {J. Am. Chem. Soc.}, title = {Computer-generated, mechanistic networks assist in assigning the outcomes of complex multicomponent reactions}, volume = {147}, year = {2025}, }
• (2025). Mechanochemical synthesis enables melting, glass formation and Glass–Ceramic conversion in a cadmium-based zeolitic imidazolate framework. JACS, 147(18), 15625--15635. (www)

  @article{ , abstract = {Metal-organic frameworks (MOFs) are versatile materials with tunable properties and broad applications. Here, we report the first cadmium-based zeolitic imidazolate framework (ZIF) glass, prepared by melt-quenching sub-micrometer-sized Cd(im) 2 particles (im – = imidazolate) obtained via mechanochemical synthesis. This route increases defect density and reduces crystallite domain size, lowering the melting temperature from 461 °C (for larger solution-synthesized microcrystals) to 455 °C, thereby mitigating thermal decomposition during melting. Crystalline Cd(im) 2 adopts a two-fold interpenetrated diamondoid ( dia-c ) topology, assembled from tetrahedral Cd 2+ centers and im – linkers. Rapid cooling of the Cd(im) 2 melt yields a monolithic glass with a glass transition temperature ( T g ) of 175 °C. Structural analysis confirms that short-range connectivity within individual networks is maintained, whereas interactions between the interpenetrated networks are disrupted in the glass. Upon reheating, partial recrystallization produces a single-component glass–ceramic with enhanced mechanical properties, an unprecedented behavior in melt-quenched ZIF glasses. Investigations of thermal parameters (cooling rates) and partial linker substitution reveal strategies for tuning the phase behavior of both glass and glass–ceramic. These findings extend ZIF glass systems to second-row transition metal ions and underscore mechanochemical synthesis as a tool for tailoring the thermal properties of MOFs. This dual-phase functionality, combining glassy and crystalline domains of identical composition within a single material, offers potential for applications in thermal energy storage, phase change memory, and optics.}, archive = {J_JACS}, author = {Wen-Long Xue and Alexander Klein and Mounir El Skafi and Jan-Benedikt Weiß and Felix Egger and Hui Ding and Suresh K. Vasa and Christian Liebscher and Mirijam Zobel and Rasmus Linser and Jin-Chong Tan and Sebastian Henke}, doi = {10.1021/jacs.5c02767}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15625--15635}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanochemical synthesis enables melting, glass formation and Glass–Ceramic conversion in a cadmium-based zeolitic imidazolate framework}, volume = {147}, year = {2025}, }
• (2025). Quantitative and multiplexing analysis of MicroRNAs by direct full-length sequencing in nanopores. JACS, 147(18), 15614--15624. (www)

  @article{ , abstract = {MicroRNAs (miRNAs) play important regulatory roles in biology. Direct sequencing of miRNAs in full-length can reveal comprehensive information on their sequences, abundance, and modifications, which, however, has yet to be achieved due to their extremely short length (∼22 nt). Herein, we developed Direct-miR-seq, a nanopore-based direct RNA sequencing (DRS) method that elongates miRNAs at both the 5′ and 3′ ends by ligating with custom nucleic acid adaptors to ensure full-length sequencing of miRNAs with high yield and accuracy. Compared to standard DRS, Direct-miR-seq enabled sequencing of the whole sequence of miRNAs, achieved a 26-fold sequencing yield, and exhibited reduced bias across miRNA species along with low sequencing error rates. We applied Direct-miR-seq to native RNA populations from cells and human serum to demonstrate its capability to selectively capture miRNAs of known sequences in complex RNA environments for revealing quantitative information in abundance and m6A modification at single-molecule and single-base resolution of ∼100 miRNA species in a single sequencing event. We envision that Direct-miR-seq may be translated toward a variety of biological and medical applications by sequencing miRNAs and other small RNAs.}, archive = {J_JACS}, author = {Chenzhi Shi and Donglei Yang and Xiaowei Ma and Yun Chen and Pengfei Hou and Li Pan and Min Li and Pengfei Wang}, doi = {10.1021/jacs.5c02808}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15614--15624}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantitative and multiplexing analysis of MicroRNAs by direct full-length sequencing in nanopores}, volume = {147}, year = {2025}, }
• (2025). Tail-assisted excited-state intramolecular proton transfer (ta-ESIPT) fluorophores: A universal ratiometric platform for hydration-sensitive biomolecular imaging and sensing. JACS, 147(18), 15602--15613. (www)

  @article{ , abstract = {Excited-state intramolecular proton transfer (ESIPT) fluorophores are valuable for ratiometric bioimaging due to their microenvironmental sensitivity, but traditional enol–keto systems suffer from poor biocompatibility and reduced efficiency in polar, protic environments. Here, we introduce a tail-assisted ESIPT ( ta -ESIPT) strategy in which proton transfer occurs from an amide donor to an amino nitrogen acceptor. This mechanism applies to biocompatible charge-transfer fluorophores, such as naphthalimide, coumarin, NBD, and acedan. ta -ESIPT fluorophores exhibit broad environmental stability and a hydration-gated response─proton transfer is inhibited in aqueous environments but restored in nonaqueous microenvironments, yielding ratiometric red-shifted emission. This property enables the precise visualization of biomolecular interactions. By conjugating ta -ESIPT fluorophores with protein ligands, we achieve precise, ratiometric imaging of targets like SNAP-tag, hCA, avidin, and HaloTag in live cells, with fluorescence signals that directly correlate with binding affinities. This correlation enables real-time monitoring of protein interactions and evaluation of inhibitors while minimizing nonspecific interference in the complex cellular environment, ensuring dynamic and accurate protein recognition.}, archive = {J_JACS}, author = {Qinglong Qiao and Chao Wang and Hanlixin Wang and Yiyan Ruan and Wenjuan Liu and Jie Chen and Zhimin Wu and Xiaogang Liu and Zhaochao Xu}, doi = {10.1021/jacs.5c02725}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15602--15613}, shortjournal = {J. Am. Chem. Soc.}, title = {Tail-assisted excited-state intramolecular proton transfer (ta-ESIPT) fluorophores: A universal ratiometric platform for hydration-sensitive biomolecular imaging and sensing}, volume = {147}, year = {2025}, }
• (2025). Core-substituted pyromellitic diimides: A versatile molecular scaffold for tunable triplet emission. JACS, 147(18), 15591--15601. (www)

  @article{ , abstract = {Arylene diimides represent a versatile class of n-type organic semiconductors, widely recognized for tunable photophysical properties, making them highly relevant across various optoelectronic applications. While their fluorescence can be finely modulated through core substitution, triplet-state emission has received comparatively little attention. This is particularly surprising given the growing field of ambient-organic triplet harvesting materials, such as thermally activated delayed fluorescence and phosphorescent systems, which would greatly benefit from structural modifications to the π-conjugated backbone and core substitution of arylene diimides to achieve the desired properties. Realizing tunable triplet states within a family of molecules is crucial for advancing organic triplet-based materials for applications in lighting, photocatalysis, and beyond. In this context, we present an unprecedented study demonstrating tunable triplet emission in pyromellitic diimides, the smallest member of the arylene diimide family, with an accessible emissive triplet state due to a narrow singlet–triplet energy gap. Herein, we report the synthesis of a series of core-substituted pyromellitic diimides (cPmDIs) using diverse synthetic strategies. Core substitution not only induces a wide spectrum of fluorescence colors but, notably, enables a wide-range phosphorescence spanning across the visible spectrum, depending on the core substituent. This article details the synthesis and photophysical and electrochemical characterization of a library of cPmDIs, supported by theory. Furthermore, we demonstrate the potential of this molecular design in achieving ambient-orange phosphorescence, as exemplified by the thiophenyl-cPmDI derivative, which exhibits triplet emission in the crystalline and film states by minimizing vibrational dissipation. In this regard, we envision that the present study represents a significant step toward the predictive structure–property design of ambient-organic phosphors and triplet harvesting materials.}, archive = {J_JACS}, author = {Sopan M. Wagalgave and Anju Ajayan Kongasseri and Utkarsh Singh and Ananya Anilkumar and Shagufi Naz Ansari and Swapan K. Pati and Subi J. George}, doi = {10.1021/jacs.5c02632}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15591--15601}, shortjournal = {J. Am. Chem. Soc.}, title = {Core-substituted pyromellitic diimides: A versatile molecular scaffold for tunable triplet emission}, volume = {147}, year = {2025}, }
• (2025). Fragmented ultrathin carbon buffed copper clusters for selective hydrogenation of N-heteroarenes under ambient pressure. JACS, 147(18), 15578--15590. (www)

  @article{ , abstract = {Selective hydrogenation of quinolines to 1,2,3,4-tetrahydroquinolines (py-THQ) realized by cost-effective catalysts holds great importance in the pharmaceutical and agrochemical industries but is challenging due to the high requirement of antipoisoning ability and selectivity. Herein, we propose a universal strategy for the preparation of ultrathin carbon-coated Cu nanoclusters inside the channels of MCM-41 by etching the carbonized template with oxygen-containing gas. The optimized catalyst (Cu/C@MCM-A) exhibits 100% quinoline conversion and 100% py-THQ selectivity at 80 °C and atmospheric pressure. This catalyst also maintained a nearly 100% py-THQ yield at 0.3 MPa for 100 h. In situ characterizations reveal that adjusting the oxygen content in the etching gas enables precise control of the carbon layer thickness and Cu particle size. Experimental results and DFT calculations confirm that the introduction of fragmented ultrathin carbon generates numerous Cu–C interfaces, which can prevent catalyst deactivation by poisoning and reduce the H 2 dissociation barrier by increasing local charge density. The synergy between Cu 0 and Cu + species ensures efficient and specific transformation. Moreover, Cu/C@MCM-A demonstrates highly selective hydrogenation activities toward other quinoline derivatives, as well as indole, naphthalene, and indene. This work unlocks a unique route for constructing carbon-confined metal clusters to achieve continuous production in selective hydrogenation.}, archive = {J_JACS}, author = {Yu Shu and Xiaomei Zhou and Jingnan Yang and Fujun Lan and Wenjiang Li and Zilu Zhang and Wei Li and Qingxin Guan and Shengqian Ma}, doi = {10.1021/jacs.5c02289}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15578--15590}, shortjournal = {J. Am. Chem. Soc.}, title = {Fragmented ultrathin carbon buffed copper clusters for selective hydrogenation of N-heteroarenes under ambient pressure}, volume = {147}, year = {2025}, }
• (2025). Phase-migrating Z-scheme charge transportation enables photoredox catalysis harnessing water as an electron source. JACS, 147(18), 15567--15577. (www)

  @article{ , abstract = {Z-schematic photocatalytic reactions are of considerable interest because of their potential for application to reductive molecular conversions to value-added chemicals using water as an electron source. However, most demonstrations of Z-scheme photocatalysis have been limited to overall water splitting. In particular, it has been basically impossible to couple the reduction of “water-insoluble compounds” with water oxidation by conventional Z-scheme systems in aqueous solution. In this work, an unconventional Z-scheme electron transportation system with a “phase-migrating” redox mediator is constructed that enables photocatalytic conversion of water-insoluble compounds by using water as an electron/proton source. In a dichloroethane (DCE)/water biphasic solution, a molecular Ir(III) complex acts as a photoredox catalyst for the reductive coupling of benzyl bromide by using ferrocene (Fc) as an electron donor in the DCE phase. On the other side, an aqueous dispersion of a Bi 4 TaO 8 Cl semiconductor loaded with a (Fe,Ru)O x cocatalyst photocatalyzed water oxidation using ferrocenium (Fc + ) as an electron acceptor. Because the partition coefficients of Fc + /Fc are significantly different, the Fc + and Fc generated by photoinduced electron transfer in each reaction could be selectively extracted to the opposite liquid phase. Spontaneous phase migration enables direction-selective electron transport across the organic/water interface that connects the reduction and oxidation reactions in the separated reaction phase. Eventually, photocatalytic reductive conversion of “water-insoluble” organic compounds using “water as the electron/proton source” was demonstrated through the step-by-step Z-scheme photocatalysis with the phase-migrating Fc + /Fc electron transportation.}, archive = {J_JACS}, author = {Ren Itagaki and Akinobu Nakada and Hajime Suzuki and Osamu Tomita and Ho-Chol Chang and Ryu Abe}, doi = {10.1021/jacs.5c02276}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15567--15577}, shortjournal = {J. Am. Chem. Soc.}, title = {Phase-migrating Z-scheme charge transportation enables photoredox catalysis harnessing water as an electron source}, volume = {147}, year = {2025}, }
• (2025). Proteomic ligandability maps of Phosphorus(V) stereoprobes identify covalent TLCD1 inhibitors. JACS, 147(18), 15554--15566. (www)

  @article{ , abstract = {Activity-based protein profiling (ABPP) of stereoisomerically defined sets of electrophilic compounds (‘stereoprobes’) offers a versatile way to discover covalent ligands for proteins in native biological systems. Here we report the synthesis and chemical proteomic characterization of stereoprobes bearing a P(V)-oxathiaphospholane (OTP) reactive group. ABPP experiments identified numerous proteins in human cancer cells that showed stereoselective reactivity with OTP stereoprobes, and we confirmed several of these liganding events with recombinant proteins. OTP stereoprobes engaging the poorly characterized transmembrane protein TLCD1 impaired the incorporation of monounsaturated fatty acids into phosphatidylethanolamine lipids in cells, a lipidomic phenotype that mirrored genetic disruption of this protein. Using AlphaFold2, we found that TLCD1 structurally resembles the ceramide synthase and fatty acid elongase families of coenzyme A-dependent lipid processing enzymes. This structural similarity included conservation of catalytic histidine residues, the mutation of which blocked the OTP stereoprobe reactivity and lipid remodeling activity of recombinant TLCD1. Taken together, these data indicate that TLCD1 acts as a lipid acyltransferase in cells, and that OTP stereoprobes function as inhibitors of this enzymatic activity. Our findings thus illuminate how the chemical proteomic analysis of electrophilic compounds can facilitate the functional annotation and chemical inhibition of a key lipid metabolic enzyme in human cells.}, archive = {J_JACS}, author = {Hayden A. Sharma and Michael Bielecki and Meredith A. Holm and Ty M. Thompson and Yue Yin and Jacob B. Cravatt and Timothy B. Ware and Alex Reed and Molhm Nassir and Tamara El-Hayek Ewing and Bruno Melillo and J. Fernando Bazan and Phil S. Baran and Benjamin F. Cravatt}, doi = {10.1021/jacs.5c01944}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15554--15566}, shortjournal = {J. Am. Chem. Soc.}, title = {Proteomic ligandability maps of Phosphorus(V) stereoprobes identify covalent TLCD1 inhibitors}, volume = {147}, year = {2025}, }
• (2025). Iron-catalyzed transfer hydroalumination of alkynes. JACS, 147(18), 15545--15553. (www)

  @article{ , abstract = {The limited availability of efficient synthetic methods for organoaluminum compounds constrains their broader applications. The transfer hydroalumination of alkynes emerges as a promising strategy for synthesizing alkenylaluminum species; however, achieving precise control of the selectivity remains a formidable challenge. Herein, we disclose a highly chemo-, regio-, and stereoselective transfer hydroalumination of alkynes, catalyzed by well-defined iron complexes, utilizing commercially available AlEt 3 as the hydroalumination reagent. The regioselectivity of the transfer hydroalumination reaction involving terminal alkynes can be effectively modulated by changing the 2,9-aryl substituents on the ligands with the observation of cis -α-selectivity not previously documented in the literature. Furthermore, we demonstrate unprecedented cis -β-selective transfer hydroalumination of simple unsymmetrical internal alkynes. This work not only broadens the scope of transfer hydroalumination reactions but also enhances the synthetic methodologies and diversity of organoaluminum compounds, highlighting the significant potential of iron catalysts in the development of organometallic reagents.}, archive = {J_JACS}, author = {Wen-Tao Li and Mu-Han Guan and Peng He and Ming-Yao Huang and Shou-Fei Zhu}, doi = {10.1021/jacs.5c02158}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15545--15553}, shortjournal = {J. Am. Chem. Soc.}, title = {Iron-catalyzed transfer hydroalumination of alkynes}, volume = {147}, year = {2025}, }
• (2025). Intermediate states enable keratin-like α-to-β transformations in strain-responsive synthetic polypeptides. JACS, 147(18), 15534--15544. (www)

  @article{ , abstract = {Nature’s fibrous proteins, such as α-keratin, achieve remarkable mechanical properties by undergoing strain-induced α-to-β conformational transitions. Inspired by these materials, we report a strategy for designing synthetic polypeptides that undergo similar transformations at elevated temperatures far exceeding keratin’s operational range. By employing helix-confined ring-opening polymerization (ROP) of N -carboxyanhydrides (NCAs) initiated by a short poly(γ-benzyl- l -glutamate) (PBLG) precursor, we synthesized poly( O -benzyl- l -serine) (PBLS) chains that adopt an α-helical structure yet transition into β-sheets upon heating. Compression molding at carefully chosen temperatures drives PBLS segments into an α-β intermediate state, characterized by relaxed intrachain hydrogen bonds and a hexagonal packing arrangement. Under mechanical strain, these intermediate states convert in situ into β-sheets, producing significant strain-hardening well below the spontaneous α-to-β temperature threshold. This approach extends to polypeptides bearing different side chains, such as poly( S -benzyl- l -cysteine), demonstrating robust mechanical reinforcement across a wide temperature window up to ∼ 200 °C. In situ synchrotron X-ray analysis confirms that chain alignment, β-sheet formation, and domain growth occur stepwise during deformation. By harnessing the intermediate states and the supramolecular cooperativity conferred by compression-molded films, our method provides a versatile platform for developing next-generation polypeptide materials with tunable mechanical resilience and responsiveness─surpassing the temperature limitations of natural fibrous proteins and enabling potential applications demanding broad-temperature mechanical adaptability.}, archive = {J_JACS}, author = {Tianjian Yang and Jianan Mao and Tianrui Xue and Siyu Wu and Ruipeng Li and Yingying Chen and Abrar A. Sitab and Jianjun Cheng and Yao Lin}, doi = {10.1021/jacs.5c02148}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15534--15544}, shortjournal = {J. Am. Chem. Soc.}, title = {Intermediate states enable keratin-like α-to-β transformations in strain-responsive synthetic polypeptides}, volume = {147}, year = {2025}, }
• (2025). Hydrogen incorporation selectively modulates the catalytic performance of pd nanozymes for cascade-catalytic tumor therapy. JACS, 147(18), 15519--15533. (www)

  @article{ , abstract = {Pd-based nanozymes have emerged as promising alternatives to natural enzymes, but their application is still constrained due to suboptimal activity and poor specificity. As efficient hydrogen storage nanomaterials, the specific implications of implanted hydrogen on the enzyme-mimicking activity of Pd-based nanomaterials remain largely uninvestigated. In this study, we discovered that hydrogenation process significantly enhances the enzyme-like activity of Pd-based nanomaterials, although reaction specificity varies in dependence on the synthetic route of Pd hydrides. Pd/H 2 nanocubes (NCs), which are synthesized by directly injecting hydrogen gas into a solution containing Pd NCs, exhibit a selective enhancement in antioxidative activity against cytotoxic hydrogen peroxide (H 2 O 2 ), superoxide anion (O 2 •– ), and hydroxyl radical ( • OH) due to the sustained release of bioreductive hydrogen. In contrast, stable Pd hydride NCs, which are prepared through the in situ catalytic decomposition of alternative sources of hydrogen atoms, exhibit a remarkable enhancement in exclusive H 2 O 2 activation pathways, specifically exhibiting peroxidase (POD)-like and catalase (CAT)-like activities. Multiple spectroscopic characterizations and density functional theory (DFT) calculations confirmed that this high catalytic activity and specificity of PdH NCs arise from lattice tensile strain and electronic structure change. Based on these findings, a PdH/glucose oxidase (GOx) nanocomplex was developed for cascade catalysis in tumor therapy. This work not only reveals that hydride formation can influence both the activity and selectivity of Pd nanozymes but also provides a viable strategy for the precise regulation of specific enzyme-like activity in hydrogen-loading nanozymes.}, archive = {J_JACS}, author = {Jiayu Ning and Xiafeng Zhu and Tengfei Hu and Chao Xia and Pengfei Hao and Jia Shi and Yijun Fang and Jiaying Xu and Duo Zhang and Khemayanto Hidayat and Liqiang Qin and Jianrong Zeng and Xiaomei Shen and Qianjun He and Yu Chong}, doi = {10.1021/jacs.5c02114}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15519--15533}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen incorporation selectively modulates the catalytic performance of pd nanozymes for cascade-catalytic tumor therapy}, volume = {147}, year = {2025}, }
• (2025). Stepwise epitaxial growth of Core–Shell organic crystals for advanced dual-emission optical applications. JACS, 147(18), 15510--15518. (www)

  @article{ , abstract = {Organic core–shell heterostructures (CSHs) offer a unique platform for integrating complementary properties of the core and shell materials, leading to an optimized multifunctional performance. However, the growth mechanism within CSHs remains unclear due to the poor crystallographic compatibility between different components and fast crystallization. This study elucidates the detailed process for fabricating organic crystalline CSHs with tunable morphologies through an in situ epitaxial growth approach, by employing IDF-TCNB (Cry DFNB ) and IDT-TCNB (Cry DTNB ) charge-transfer cocrystals. After the lattice matching in three dimensions is satisfied, the shell Cry DTNB epitaxially grows on the core Cry DFNB surface along specific crystallographic orientations, with the growth sequence determined by differences in attachment energy. The unique bilayer structure of the CSHs results in distinct dual-emission optical properties, including differentiated polarization, dual-band quasi-whispering gallery mode resonance, and dual-band optical waveguides. This work provides a new framework for the design and synthesis of organic CSHs with controlled structures and advanced photonic functionalities.}, archive = {J_JACS}, author = {Shuai Zhao and Jia-Xuan Zhang and Lei Wang and Chao-Fei Xu and Ying-Xin Ma and Xue-Dong Wang and Liang-Sheng Liao}, doi = {10.1021/jacs.5c01841}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15510--15518}, shortjournal = {J. Am. Chem. Soc.}, title = {Stepwise epitaxial growth of Core–Shell organic crystals for advanced dual-emission optical applications}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic and chemoselective H/D exchange at α-thio c(sp3)-H bonds. JACS, 147(18), 15499--15509. (www)

  @article{ , abstract = {Deuterated compounds used in drug discovery and live-cell imaging have recently gained the attention of various scientific fields. Although hydrogen–deuterium (H/D) exchange reactions are straightforward deuteration methods, achieving perfect chemoselectivity is challenging. We report the highly chemoselective deuteration of α-thio C(sp 3 )-H bonds using a thioxanthone or anthraquinone organic photocatalyst bearing an aromatic ketone skeleton and D 2 O as an inexpensive deuterium source under 390 nm irradiation. Notably, incorporation of deuterium at the α-positions of the O/N atoms, benzylic positions, and aromatic rings was not observed. The present chemoselectivity was accomplished via a single electron transfer mechanism between the photocatalyst and S-containing substrates, as proven by laser-induced time-resolved transient absorption spectroscopic measurements. Furthermore, the proposed deuteration method could be applied to various S-containing substrates, including pharmaceuticals and biologically active compounds with high regioselectivities. The available deuterated compounds as novel deuterated alkylation reagents for future drug discovery and materials for Raman imaging were also demonstrated.}, archive = {J_JACS}, author = {Riku Ogasahara and Miyu Mae and Yuki Itabashi and Kei Ohkubo and Keisuke Matsuura and Hyoga Shimizu and Kazuho Ban and Masaki Togami and Taro Udagawa and Hiroyoshi Fujioka and Mako Kamiya and Shuji Akai and Yoshinari Sawama}, doi = {10.1021/jacs.5c01894}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15499--15509}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic and chemoselective H/D exchange at α-thio c(sp3)-H bonds}, volume = {147}, year = {2025}, }
• (2025). Hydrophilic single-atom interface empowered pure formic acid fuel cells. JACS, 147(18), 15490--15498. (www)

  @article{ , abstract = {Single-atom catalysts (SACs), offering high mass activity and enhanced resistance to poisoning, are regarded as superior alternatives to traditional Pt/Pd nanocatalysts for direct formic acid fuel cells (DFAFCs). However, failure toward operation in concentrated formic acid (FA), which is critical for portable electronics, challenges their antipoisoning advantage and highlights a missing part in the understanding of the reaction. We herein demonstrate that the interfacial hydrophilicity of SACs is pivotal for high-performance DFAFCs, enabling, for the first time, stable operation with pure FA (>99%). By incorporating transition metal single atoms (Co, Fe, Ni, Ru) into Ir/NC catalysts, we engineered highly hydrophilic interfaces, as validated by molecular dynamics simulations and experimental studies. The optimized IrCo/NC anode exhibited a mass activity 342 times higher than that of nanoparticle-based catalysts and represented as the first SAC to achieve a higher peak power density (107.7 mW cm –2 ). A new reaction mechanism is revealed, where CO acts as a reactive intermediate rather than a poison. Further, in situ spectroscopy and isotope kinetic analyses identified water intermediate involvement in the rate-determining step, underscoring the critical role of hydrophilic interface engineering in DFAFC.}, archive = {J_JACS}, author = {Kai Wei and Mingzi Sun and Xiaoke Xi and Tongtong Yang and Meijian Tang and Kangcheng Wang and Siming Gao and Ruiguo Cao and Xian Wang and Bolong Huang and Junjie Ge}, doi = {10.1021/jacs.5c01842}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15490--15498}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrophilic single-atom interface empowered pure formic acid fuel cells}, volume = {147}, year = {2025}, }
• (2025). Photochemically enabled total syntheses of stemoamide alkaloids. JACS, 147(18), 15482--15489. (www)

  @article{ , abstract = {Photochemical transformations continue to serve as powerful synthetic tools for rapid chemical synthesis and diversification. Recent developments in photoredox and photochemical reactivity have captured the attention of researchers in a wide array of disciplines, where many new applications of these reactions have been reported. We disclose the use of photochemical synthetic strategies as a modern approach to natural product synthesis that leverages the inherent reactivity of radicals as a platform for constructing complex scaffolds. We demonstrate this in an iterative photochemical synthesis, offering novel synthetic tactics, mild conditions, and operationally simple synthetic procedures to construct three stemoamide alkaloids in the shortest sequences to date. The key disconnection involves the use of both the oxidative and reductive capabilities of an acridinium photoredox catalyst to forge the densely functionalized tetrahydrofuran ring via a polar radical crossover cycloaddition. The resultant butyrolactone serves as a handle for a radical polar crossover cycloaddition to construct a unique oxaspirocyclic butenolide. Finally, a late-stage heteroarene transmutation provides a linchpin intermediate used to access three stemoamide alkaloids. The efficiency of these syntheses exemplifies the power of this approach while also demonstrating a departure from traditional disconnections and shedding light on a new type of synthetic art.}, archive = {J_JACS}, author = {Nicholas R. Akkawi and David A. Nicewicz}, doi = {10.1021/jacs.5c01788}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15482--15489}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemically enabled total syntheses of stemoamide alkaloids}, volume = {147}, year = {2025}, }
• (2025). Residue-selective inhibitors discovery via covalent DNA-encoded chemical libraries with diverse warheads. JACS, 147(18), 15469--15481. (www)

  @article{ , abstract = {Covalent small molecule drugs have emerged as a crucial support in precision therapy due to their high selectivity and robust potency. Covalent DNA-encoded chemical library (CoDEL) technology is an advanced platform for covalent drug discovery. However, the application of CoDELs is constrained by a single-residue focus and limited warhead diversity. Here we report a method to identify residue-selective inhibitors using CoDELs with diverse warheads targeting multiple distinct residues. We systematically evaluated the reactivity of 17 warheads with 9 nucleophilic amino acids of FGFR2 and then constructed CoDELs comprising 24.8 million compounds. These CoDELs enabled the identification of active covalent inhibitors targeting cysteine, lysine, arginine, or glutamic acid. The lysine-targeting inhibitor engaged a novel reactive site. The arginine-targeting inhibitor demonstrated subtype selectivity and overcame drug resistance. The glutamic acid-targeting inhibitor validated the druggability of this unconventional covalent residue site. These findings suggest that our work could potentially expand the target space of covalent drugs and promote precision therapy by harnessing the power of the CoDELs.}, archive = {J_JACS}, author = {Xinyuan Wu and Jiayi Pan and Rufeng Fan and Yiwei Zhang and Chao Wang and Guoliang Wang and Jiaxiang Liu and Mengqing Cui and Jinfeng Yue and Rui Jin and Zhiqiang Duan and Mingyue Zheng and Lianghe Mei and Lu Zhou and Minjia Tan and Jing Ai and Xiaojie Lu}, doi = {10.1021/jacs.5c01712}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15469--15481}, shortjournal = {J. Am. Chem. Soc.}, title = {Residue-selective inhibitors discovery via covalent DNA-encoded chemical libraries with diverse warheads}, volume = {147}, year = {2025}, }
• (2025). Rapid synthesis of single-crystal covalent organic framework with controllable crystal habits. JACS, 147(18), 15459--15468. (www)

  @article{ , abstract = {Covalent organic frameworks (COFs) linked by poorly reversible covalent bonds lack dynamic formation and cleavage, so the synthesis of their single-crystal structures necessitates slow crystallization rates to mitigate defect formation. This, however, inherently restricts opportunities for facet-selective engineering beyond traditional compositional and topological controls. To address this fundamental limitation, we developed an acetal/CH 3 COOH protocol that paradoxically accelerated crystallization while enhancing structural perfection, reducing the synthesis time for 60 μm-sized single-crystal COF-300 to 1 h, while achieving crystal sizes of up to 120 μm within 48 h, and 300 μm after 30 days. Capitalizing on this accelerated synthesis platform, we systematically interrogated crystallization landscapes through multiparameter exploration─modulator chemoselectivity, catalyst dosages, temporal evolution, and reactive temperature─to decode possible growth mechanisms of single-crystal COFs. Based on these, the relationship between reaction conditions and the crystal size, size distribution, shape, and growth dynamics of single-crystal COFs was trained and predicted by a machine learning (ML) model.}, archive = {J_JACS}, author = {Wenqiang Gao and Ziao Chen and Jiaxin Hong and YinYue Zhang and Zhao Yang and Minghui Liu and Xinyu Wang and Shengcong Shang and Zewen You and Zhihao Shao and Jichen Dong and Yunlong Guo and Jianyi Chen and Yunqi Liu}, doi = {10.1021/jacs.5c01638}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15459--15468}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid synthesis of single-crystal covalent organic framework with controllable crystal habits}, volume = {147}, year = {2025}, }
• (2025). Perovskite catalysts for pure-water-fed anion-exchange-membrane electrolyzer anodes: Co-design of electrically conductive nanoparticle cores and active surfaces. JACS, 147(18), 15448--15458. (www)

  @article{ , abstract = {Anion-exchange-membrane water electrolyzers (AEMWEs) are a possible low-capital-expense, efficient, and scalable hydrogen-production technology with inexpensive hardware, earth-abundant catalysts, and pure water. However, pure-water-fed AEMWEs remain at an early stage of development and suffer from inferior performance compared with proton-exchange-membrane water electrolyzers (PEMWEs). One challenge is to develop effective non-platinum-group-metal (non-PGM) anode catalysts and electrodes in pure-water-fed AEMWEs. We show how LaNiO 3 -based perovskite oxides can be tuned by cosubstitution on both A- and B-sites to simultaneously maintain high metallic electrical conductivity along with a degree of surface reconstruction to expose a stable Co-based active catalyst. The optimized perovskite, Sr 0.1 La 0.9 Co 0.5 Ni 0.5 O 3 , yielded pure-water AEMWEs operating at 1.97 V at 2.0 A cm –2 at 70 °C with a pure-water feed, thus illustrating the utility of the catalyst design principles.}, archive = {J_JACS}, author = {Tingting Zhai and Hao Wang and Sarah R. Beaudoin and Ran Zhang and Minkyoung Kwak and Shujin Hou and Zhengxiao Guo and Shannon W. Boettcher}, doi = {10.1021/jacs.5c01621}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15448--15458}, shortjournal = {J. Am. Chem. Soc.}, title = {Perovskite catalysts for pure-water-fed anion-exchange-membrane electrolyzer anodes: Co-design of electrically conductive nanoparticle cores and active surfaces}, volume = {147}, year = {2025}, }
• (2025). Two-stage solvation of lithium polysulfides in working Lithium–Sulfur batteries. JACS, 147(18), 15435--15447. (www)

  @article{ , abstract = {Lithium–sulfur (Li–S) batteries are promising in achieving high energy density but inferior in cycling lifespan since Li polysulfides (LiPSs) corrode Li metal anode. Weakening the electrolyte solvating power (ESP) for LiPSs effectively mitigates anodic corrosion but inevitably retards cathodic reaction kinetics. Herein, the correlation between the ESP and the LiPS redox kinetics in weakly solvating electrolyte is unveiled for achieving high-performance Li–S batteries. The ESP exhibits a two-stage variation tendency as the weakly solvating solvent (WSS) content increases, where the transition depends on whether the WSS enters the LiPS inner solvation shell. Once the WSS directly coordinates with LiPSs, the LiPS charge-transfer kinetics deteriorate dramatically, with a rapid increase in activation polarization. To overcome the kinetic sluggishness, advanced electrocatalysts are introduced to endow Li–S batteries with reduced polarization and prolonged cycling lifespan. An ultrahigh energy density of 607 W h kg –1 is realized in 10 Ah-level pouch cells with a stable cycling lifespan. This work deepens the current understanding of LiPS solvation and kinetics, highlighting the significance of weakly solvating electrolytes toward high-energy-density and long-cycling Li–S batteries.}, archive = {J_JACS}, author = {Xi-Yao Li and Bo-Quan Li and Shuai Feng and Zheng Li and Liang Shen and Shu-Yu Sun and Zi-Xian Chen and Tian Jin and Xiang Chen and Meng Zhao and Xue-Qiang Zhang and Jia-Qi Huang and Qiang Zhang}, doi = {10.1021/jacs.5c01588}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15435--15447}, shortjournal = {J. Am. Chem. Soc.}, title = {Two-stage solvation of lithium polysulfides in working Lithium–Sulfur batteries}, volume = {147}, year = {2025}, }
• (2025). Nonmetal organic frameworks exhibit high proton conductivity. JACS, 147(18), 15429--15434. (www)

  @article{ , abstract = {Porous materials, such as metal–organic frameworks (MOFs) and porous organic salts, are promising materials for proton conduction. Recently, we developed a new subclass of porous materials, isoreticular nonmetal organic frameworks (N-MOFs), which can be designed using crystal structure prediction (CSP). Here, two porous, isostructural, and water-stable halide N-MOFs were prepared and found to show good proton conductivity of up to 1.1 × 10 –1 S cm –1 at 70 °C and 90% relative humidity. Changing the halides in these N-MOF materials affects the resulting proton conductivity, as observed in previous studies involving MOFs and lead halides. Although this is the first study of proton conductivity in N-MOFs, the bromide salt, TTBT.Br , shows a higher conductivity than most polycrystalline MOFs and porous organic salts, approaching that of Nafion.}, archive = {J_JACS}, author = {Megan O’Shaughnessy and Jungwoo Lim and Joseph Glover and Alex R. Neale and Graeme M. Day and Laurence J. Hardwick and Andrew I. Cooper}, doi = {10.1021/jacs.5c01336}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15429--15434}, shortjournal = {J. Am. Chem. Soc.}, title = {Nonmetal organic frameworks exhibit high proton conductivity}, volume = {147}, year = {2025}, }
• (2025). Thiocarboxylate and acid chloride mediated generation of nitric oxide from a Dinickel(II)-Bis(ONO) complex involving the formation of perthionitrite and O-nitrosyl carboxylate. JACS, 147(18), 15408--15428. (www)

  @article{ , abstract = {A detailed study for the generation of nitric oxide (NO) upon reaction of a binuclear Ni(II)-bis(ONO) complex with carboxylic acids (RCOOH, R = Me, Ph), thiols (RSH, R = Ph, p -F-C 6 H 4 ), benzeneselenol (PhSeH), thiocarboxylates (RC(O)S – , R = Me, Ph), thiocarboxylic acids (RC(O)SH, R = Me, Ph), and acid chlorides (RC(O)Cl, R = Me, Ph) has been presented. The reactions of the binuclear Ni(II)-bis(ONO) complex with thiols/selenols give access to unusual dinickel(II)-nitrito-thiolato/selenolato complexes, while the reactions with RC(O)S – , RC(O)SH, and RC(O)Cl offer new mechanistic insights into the generation of perthionitrite (SSNO – ) and O -nitrosyl carboxylates (RC(O)ONO), the well-known NO-carrying species in biology. Interestingly, while the reaction of the binuclear Ni(II)-bis(ONO) complex with RC(O)S – involved nucleophilic attack of the latter to the coordinated NO 2 – to generate SSNO – , the reaction with RC(O)Cl proceeds via the hitherto unknown nucleophilic attack of the coordinated NO 2 – to the carbonyl carbon of RC(O)Cl to generate RC(O)ONO, which, in turn, produces NO. The present comparative study thus demonstrates new reactions of metal-coordinated NO 2 – and detailed mechanistic investigations supported by molecular structure determinations and spectroscopic studies and establishes the hitherto unknown reaction of coordinated nitrite with RC(O)Cl to be a highly efficient method for the generation of NO in excellent yield.}, archive = {J_JACS}, author = {Kamal Hossain and Arindam Basak and Amit Majumdar}, doi = {10.1021/jacs.5c01529}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15408--15428}, shortjournal = {J. Am. Chem. Soc.}, title = {Thiocarboxylate and acid chloride mediated generation of nitric oxide from a Dinickel(II)-Bis(ONO) complex involving the formation of perthionitrite and O-nitrosyl carboxylate}, volume = {147}, year = {2025}, }
• (2025). Direct CO2 transformation to malate via bioelectrosynthesis upon engineered shewanella oneidensis. JACS, 147(18), 15397--15407. (www)

  @article{ , abstract = {Microbial electrosynthesis (MES) offers a sustainable and low-carbon approach for CO 2 valorization, with Shewanella oneidensis ( S. oneidensis ) MR-1 identified as an ideal microbe for MES. However, no prior research has demonstrated that S. oneidensis MR-1 can directly metabolize CO 2 into multicarbon (C 2+ ) products due to its inability to perform the intracellular formate assimilation pathway. Here, we provide initial proof-of-concept evidence of direct bioelectrochemical CO 2 reduction to the C 4 product of malate. Specifically, the transformation of CO 2 to malate attains a notable production concentration of 1.18 mmol·L –1 , marking the first instance of direct C 4 compound bioelectrosynthesis. Such remarkable CO 2 -to-C 4 conversion performances are attributed to the successful implementation of dual-plasmid systems in S. oneidensis MR-1, which facilitate the overexpression of the reductive glycine pathway (Plasmid I) for assimilating CO 2 -derived formate and the alternative malate biosynthetic pathway (Plasmid II) to channel metabolic intermediates toward the biosynthesis of malate. Advancing CO 2 valorization toward carbon-negative C 2+ bioproducts, our sophisticated dual-plasmid systems engineered in microbes can be further refined for scalable CO 2 bioelectrolysis with the objective of facilitating industrial applications.}, archive = {J_JACS}, author = {Yixin Li and Dong Xia and Yinuo Xie and Rong Dong and Mingfeng Cao and Qingbiao Li and Yuanpeng Wang}, doi = {10.1021/jacs.5c01494}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15397--15407}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct CO2 transformation to malate via bioelectrosynthesis upon engineered shewanella oneidensis}, volume = {147}, year = {2025}, }
• (2025). Chemoenzymatic site-specific lysine modification of nanobodies and subsequent bioconjugation via potassium acyltrifluoroborate (KAT) ligations. JACS, 147(18), 15389--15396. (www)

  @article{ , abstract = {Single chain camelid antigen binding domains, often called nanobodies, have emerged as powerful tools for diagnostics and therapy. Methods for their site-specific modification offer immense potential for enhancing their therapeutic applications, but established approaches, such as fusion proteins, have well-known limitations in the nanobody format. Here, we report a convenient and broadly applicable method for site-specifically functionalizing a single residue near the C-terminus of VHH nanobodies by employing lysine acylation using conjugating enzymes (LACE) to transfer short peptides bearing functional group handles for potassium acyltrifluoroborate (KAT) ligations onto a single lysine residue of the expressed nanobodies. This approach requires a LACE tag (4 residues or 11 residues) in the recombinant nanobodies and enables direct elaboration of the products via a rapid amide forming reaction. In this study, VHH nanobodies expressed in Escherichia coli could be efficiently modified through the transfer of specific chemical handles, enabling their conjugation to small molecules, nanobodies, and antibodies by chemoselective, amide-forming KAT ligations that operate at micromolar concentrations.}, archive = {J_JACS}, author = {Jinling Wang and Kateryna A. Tolmachova and Jeffrey W. Bode}, doi = {10.1021/jacs.5c01418}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15389--15396}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemoenzymatic site-specific lysine modification of nanobodies and subsequent bioconjugation via potassium acyltrifluoroborate (KAT) ligations}, volume = {147}, year = {2025}, }
• (2025). Fourteen-membered macrocyclic cobalt complex structure as a potential basis for durable and active non-platinum group metal catalysts for oxygen reduction and hydrogen evolution reactions. JACS, 147(18), 15377--15388. (www)

  @article{ , abstract = {Non-platinum group metal catalysts for the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) under acidic conditions were developed using a CoN 4 complex with a 14-membered-ring hexaazamacrocyclic ligand (Co-14MR). The carbon-supported Co-14MR catalyst (Co-14MR/C) showed higher ORR and HER activities than a conventional carbon-supported 16-membered-ring Co phthalocyanine (CoPc/C) catalyst. Heat treatment of Co-14MR/C at 600 °C further enhanced its ORR and HER activity through structural modification of the Co active center via deprotonation of ligand amine groups. Density functional theory calculations indicated that the structural modifications of Co-14MR induced by heat treatment adjusted the adsorption energies of important intermediates in the ORR and HER toward optimal values, resulting in enhanced catalytic activity. The Co-14MR/C catalysts also exhibited higher durability in the ORR and HER than CoPc/C and Fe-14MR/C catalysts. Structural analysis suggested that the short Co–N bond lengths and small distortion of the CoN 4 active site of the Co-14MR catalysts are the reasons for their high durability. These findings suggest that the Co-14MR structure is a promising design for non-platinum group metal catalysts for proton-exchange membrane fuel cells and water splitting.}, archive = {J_JACS}, author = {Zhiqing Feng and Junya Ohyama and Soutaro Honda and Yasushi Iwata and Keisuke Awaya and Masato Machida and Masayuki Tsushida and Ryota Goto and Takeo Ichihara and Makoto Moriya and Yuta Nabae}, doi = {10.1021/jacs.5c01306}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15377--15388}, shortjournal = {J. Am. Chem. Soc.}, title = {Fourteen-membered macrocyclic cobalt complex structure as a potential basis for durable and active non-platinum group metal catalysts for oxygen reduction and hydrogen evolution reactions}, volume = {147}, year = {2025}, }
• (2025). Hexaphenyl-1,2-diphosphonium dication [Ph3P–PPh3]2+: Superacid, superoxidant, or super reagent?. JACS, 147(18), 15369--15376. (www)

  @article{ , abstract = {The oxidation of triphenylphosphine by perfluorinated phenazinium F aluminate in difluorobenzene affords hexaaryl-1,2-diphosphonium dialuminate 1 . Dication 1 2+ is valence isoelectronic with elusive hexaphenylethane, where instead the formation of a mixture of the trityl radical and Gomberg’s dimer is favored. Quantum-chemical calculations in combination with Raman/IR spectroscopies rationalize the stability of the P–P bonded dimer in 1 2+ and suggest, akin to the halogens, facile homolytic as well as heterolytic scission. Thus, 1 2+ serves as a surrogate of both the triphenylphosphorandiylium dication (Ph 3 P 2+ ) and the triphenylphosphine radical monocation (Ph 3 P ·+ ). Treating 1 with dimethylaminopyridine (DMAP) or t Bu 3 P replaces triphenylphosphine under heterolytic P–P bond scission. Qualifying as a superoxidant ( E vs Fc/Fc + = +1.44 V), 1 oxidizes trimethylphosphine. Based on halide abstraction experiments ( – BF 4 , – PF 6 , – SbCl 6 , – SbF 6 ) as well as the deoxygenation of triethylphosphine oxide, triflate anions as well as toluic acid, 1 also features Lewis superacidity. The controlled hydrolysis affords Hendrickson’s reagent, which itself finds broad use as a dehydration agent. Formally, homolytic P–P bond scission occurs with diphenyldisulfide (PhSSPh) and the triple bonds in benzo- and acetonitrile. The irradiation by light cleaves the P–P bond homolytically and generates transient triphenylphosphine radical cations, which engage in H-atom abstraction as well as CH phosphoranylation.}, archive = {J_JACS}, author = {Fabian Dankert and Simon P. Muhm and Chandan Nandi and Sergi Danés and Sneha Mullassery and Petra Herbeck-Engel and Bernd Morgenstern and Robert Weiss and Pedro Salvador and Dominik Munz}, doi = {10.1021/jacs.5c01271}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15369--15376}, shortjournal = {J. Am. Chem. Soc.}, title = {Hexaphenyl-1,2-diphosphonium dication [Ph3P–PPh3]2+: Superacid, superoxidant, or super reagent?}, volume = {147}, year = {2025}, }
• (2025). Natural spy chaperone mimic: Tailored nanochaperone with Electrostatic–Hydrophobic synergy to enhance protein folding regulation. JACS, 147(18), 15357--15368. (www)

  @article{ , abstract = {Protein folding regulation is of great significance for maintaining protein structures and biological functions. This fundamental process is assisted by molecular chaperones, which act in inhibiting undesired protein aggregation and facilitating misfolded protein refolding. Inspired by the unique structure and ingenious mechanisms of natural Spy chaperones, we innovate a nanochaperone-guided protein folding strategy by rationally designed nanochaperones (nChaps) with customizable surface structures and properties. In this strategy, the nChaps with tunable charged surfaces can first rapidly capture different client proteins through long-range electrostatic attraction, similar to Spy. Subsequently, the captured proteins can be dynamically bound into the Spy-mimetic hydrophobic microdomains via short-range hydrophobic interactions. As a result, the client proteins are sequestered and stabilized in the chaperone-mimicking confined spaces on the surface of nChaps, thereby facilitating dynamic regulation of protein folding through an electrostatic-hydrophobic synergy mechanism. Moreover, benefiting from the adjustable charge and multiple hydrophobic microdomains, this biomimetic nChap potentiates protein stability at harsh temperatures and long-term storage, which is hardly achieved by natural Spy. Additionally, this strategy is applicable to 9 different proteins with varying isoelectric points and molecular weights, showing superior generality than Spy. Therefore, this work provides new perspectives in developing an advanced strategy for enhanced protein folding regulation.}, archive = {J_JACS}, author = {Shuyue Zhao and Shu Quan and Wei He and Linlin Xu and Haodong Hu and Zixuan Ma and Rujiang Ma and Fan Huang and Linqi Shi}, doi = {10.1021/jacs.5c01133}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15357--15368}, shortjournal = {J. Am. Chem. Soc.}, title = {Natural spy chaperone mimic: Tailored nanochaperone with Electrostatic–Hydrophobic synergy to enhance protein folding regulation}, volume = {147}, year = {2025}, }
• (2025). Insight into the catalytic nature of lithiophilicity for high-energy-density lithium metal batteries. JACS, 147(18), 15344--15356. (www)

  @article{ , abstract = {Designing dendrite-free lithium (Li) metal anodes for high-performance batteries requires a fundamental understanding of the substrate’s lithiophilicity. Here, we systematically explore the electrochemical nucleation behavior of Li on various transition-metal substrates and uncover a substrate-dependent nucleation barrier that follows an inverted volcano-shaped curve, determined by the d-band center (ε d ) of these metals. Density functional theory calculations reveal that an optimal ε d balances Li-atom adsorption and migration during Li nucleation, minimizing the nucleation barrier. To this end, we propose and validate the catalytic nature of lithiophilicity across diverse transition metal compounds. As a proof-of-concept, we modulate the electronic structure of CoP by incorporating Ni 2 P, which downshifts the ε d of CoP through electron redistribution at the CoP/Ni 2 P heterointerface, thereby optimizing Li-atom adsorption and migration for enhanced lithiophilicity. This leads to the well-designed CoP/Ni 2 P heterointerface-rich framework that enables selective bottom nucleation and effectively suppresses dendrite formation. The resulting framework demonstrates exceptional cycling stability, achieving 99.1% Coulombic efficiency over 450 cycles and 90.2% capacity retention after 100 cycles in a Li||LiFePO 4 pouch cell. This work revolutionizes our understanding of the catalytic nature of lithiophilicity and offers a pioneering approach for designing next-generation anodes for high-energy-density Li metal batteries.}, archive = {J_JACS}, author = {Yuan Wang and Guanglei Liu and Haohui Qiao and Jian Tan and Sizhe Li and Mingxin Ye and Jianfeng Shen}, doi = {10.1021/jacs.5c01017}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15344--15356}, shortjournal = {J. Am. Chem. Soc.}, title = {Insight into the catalytic nature of lithiophilicity for high-energy-density lithium metal batteries}, volume = {147}, year = {2025}, }
• (2025). Narrow-bandgap Iridium(III)-C3N5 nanocomplex as an oxygen self-sufficient piezo-sonosensitizer for hypoxic tumor sonodynamic immunotherapy. JACS, 147(18), 15329--15343. (www)

  @article{ , abstract = {Low immunogenicity and insufficient infiltration of immune cells are the main factors affecting the therapeutic efficacy of melanoma immunotherapy. Ultrasound-triggered sonodynamic therapy (SDT) based on piezoelectric materials has attracted substantial attention due to its high efficiency of piezoelectric catalytic generation of reactive oxygen species (ROS) to induce immunogenic cell death (ICD). However, the hypoxic environment in solid tumors hinders the infiltration of immune cells and limits the SDT effect. Herein, we construct a novel Ir-C 3 N 5 nanocomplex that uses nitrogen-rich carbon nitride (C 3 N 5 ) nanosheets as nanoligands and Ir(tpy)Cl 3 as a precursor. The newly formed Ir-C 3 N 5 nanocomplex exhibits a narrowed band gap and an enlarged dipole moment, resulting in a better electron–hole pair separation and band bending, contributing to the ROS burst upon ultrasonic activation. In addition, Ir(III) enables the C 3 N 5 nanosheets to catalyze the degradation of H 2 O 2 to O 2 , alleviating tumor hypoxia and reinforcing SDT efficacy. Mechanistically, due to the generation of ROS by piezoelectric catalysis, Ir-C 3 N 5 can target lysosomes to trigger autophagy inhibition caused by lysosome rupture and to evoke pyroptosis. More importantly, the cleaved caspase-1/GSDMD-N pyroptosis pathway activated by Ir-C 3 N 5 was associated with ICD, effectively initiating the innate and adaptive immunity of the body for suppressing tumor metastasis and relapse.}, archive = {J_JACS}, author = {Xianbo Wu and Jinzhe Liang and Jun Shu and Zeqi Li and Tiantian Yin and Xiting Zhang and Hui Chao}, doi = {10.1021/jacs.5c00843}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15329--15343}, shortjournal = {J. Am. Chem. Soc.}, title = {Narrow-bandgap Iridium(III)-C3N5 nanocomplex as an oxygen self-sufficient piezo-sonosensitizer for hypoxic tumor sonodynamic immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Transfer learning-enabled ligand prediction for ni-catalyzed atroposelective Suzuki–Miyaura cross-coupling based on mechanistic similarity: Leveraging pd knowledge for ni discovery. JACS, 147(18), 15318--15328. (www)

  @article{ , abstract = {The rational design of novel molecular catalysts often confronts challenges due to complex structure–performance relationships. Emerging data-driven approaches provide revolutionary solutions, yet the application of machine learning to new catalyst development inevitably faces a low-data regime with limited effective structure–performance modelings available. In this study, we present a transfer learning strategy to facilitate knowledge transfer from well-documented Pd catalysis to a novel, underexplored Ni system. By synergistically modeling extensive Pd catalysis data with limited Ni/Sadphos data, our approach accurately predicted novel Sadphos ligands, enabling the first atroposelective Ni-catalyzed Suzuki–Miyaura cross-coupling reaction. The synthetic utility of the machine learning-predicted ligand was further demonstrated in its broad synthetic scope, gram-scale synthesis, and precise control of dual axial chiralities in ternaphthalene through the sequential coupling under Ni and Pd catalysis. Additionally, density functional theory calculations were employed to reveal the reaction mechanism and stereochemical model of this new Ni catalyst, validating the proposed mechanistic connection between Ni and Pd. This work demonstrates how machine learning models can effectively leverage mechanistic connectivity, applying extensive structure–performance relationship data from the literature to predict new catalysts, providing a novel strategy for the rational design of molecular catalysts from a few-shot learning perspective.}, archive = {J_JACS}, author = {Xin-Yuan Xu and Li-Gao Liu and Li-Cheng Xu and Shuo-Qing Zhang and Xin Hong}, doi = {10.1021/jacs.5c00838}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15318--15328}, shortjournal = {J. Am. Chem. Soc.}, title = {Transfer learning-enabled ligand prediction for ni-catalyzed atroposelective Suzuki–Miyaura cross-coupling based on mechanistic similarity: Leveraging pd knowledge for ni discovery}, volume = {147}, year = {2025}, }
• (2025). Photocatalyst-dependent enantioselectivity in the light-driven deracemization of cyclic α-aryl ketones. JACS, 147(18), 15307--15317. (www)

  @article{ , abstract = {We report a photoredox-enabled deracemization of cyclic α-aryl ketones that occurs with high stereoselectivity and yield and proceeds by mechanistically distinct proton transfer reactions. This reaction is jointly mediated by a visible-light photocatalyst and a chiral phosphate base cocatalyst under blue light irradiation. Notably, the extent of deracemization for this reaction exhibits an unexpected dependence on the identity of the photocatalyst and the concentration of a chiral base cocatalyst, wherein the extent of deracemization can be increased by employing photocatalysts with more positive ground-state reduction potentials, raising the concentration of the chiral base cocatalyst, or by a combination of these factors. This effect is attributed to two competing processes, back-electron transfer and deprotonation, which consume the same reaction intermediate, and we propose a kinetic model that rationalizes this behavior. We also demonstrate that the redox properties of the photocatalyst impact the stereoselectivity of the product-forming step, which is the dominant stereoselective step in this transformation. Together, these mechanistic insights facilitate a deeper understanding of the complexity of light-driven deracemization reactions involving reversible electron transfer and suggest approaches by which the stereoselectivity of these processes may be increased.}, archive = {J_JACS}, author = {Justin Y. Wang and Eris Villalona and Robert R. Knowles}, doi = {10.1021/jacs.5c00847}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15307--15317}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalyst-dependent enantioselectivity in the light-driven deracemization of cyclic α-aryl ketones}, volume = {147}, year = {2025}, }
• (2025). Catalytic activity of an ensemble of sites for CO2 hydrogenation to methanol on a ZrO2-on-cu inverse catalyst. JACS, 147(18), 15294--15306. (www)

  @article{ , abstract = {The significant increase in CO 2 emissions from heavy fossil fuel utilization has raised serious concerns, highlighting the need for effective methods to convert CO 2 into value-added chemicals. Here, we report a computational investigation on the catalytic activity of ZrO 2 -on-Cu inverse catalysts for CO 2 hydrogenation to methanol, considering highly dispersed ZrO 2 trimers on Cu (111). Such clusters present a large ensemble of formate-containing configurations, Zr 3 O n (OH) m (OCHO) l , making the evaluation of the catalytic activity very challenging. We found that the sites on the various catalyst configurations exhibit markedly different activities for formate hydrogenation, despite their similar free energy and composition. To understand these differences in reactivity, we examined the structural and electronic nature of the low free-energy catalyst configurations and identified that the energy of the lowest unoccupied orbital of the reacting formate, modified by its binding with the catalytic site, is a descriptor for the reaction energy of the formate hydrogenation step. From there, we screened an ensemble of catalyst structures using this descriptor to predict highly active metastable catalyst configurations and computed the reaction pathways and transition states for formate hydrogenation. From this investigation, we distinguished reactive from nonreactive sites and formate species on the ZrO 2 /Cu inverse catalyst based on structural and electronic features. We showed that rare metastable configurations control the activity. Additionally, an efficient method for examining the reactivity of a large number of coexisting catalyst structures was developed.}, archive = {J_JACS}, author = {Zihan Yang and Simran Kumari and Anastassia N. Alexandrova and Philippe Sautet}, doi = {10.1021/jacs.5c00848}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15294--15306}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic activity of an ensemble of sites for CO2 hydrogenation to methanol on a ZrO2-on-cu inverse catalyst}, volume = {147}, year = {2025}, }
• (2025). Selective C–H borylation of polyaromatic compounds enabled by metal-arene π-complexation. JACS, 147(18), 15281--15293. (www)

  @article{ , abstract = {The undirected Ir-catalyzed C–H borylation usually occurs preferentially at the least hindered and more acidic C–H bond of the aromatic ring. In the case of polyaromatic compounds possessing multiple unbiased and sterically accessible C–H bonds, the site selectivity for the nondirected C–H borylation is low. Here, we report the dramatic effect exerted by the π-complexation of a chromium tricarbonyl unit on the aromatic ring in the context of Ir-catalyzed C–H borylation. Competition experiments demonstrate that the C–H bonds of an aromatic ring bound to the chromium tricarbonyl unit react on average two orders in magnitude faster toward the C–H borylation than the unbound arenes. This enables an unprecedented C–H borylation with high site selectivity of the aromatic ring π-complexed with a chromium tripod in a series of organic polyaromatic compounds. Besides, the drastic enhancement of the reactivity of C–H bonds induced by the chromium tripod allows the C–H borylation to occur at room temperature with the substrate as a limiting reagent. The DFT studies indicate that the oxidative addition of the C–H bonds has lower activation barriers when the arenes are complexed with a chromium tricarbonyl unit, explaining the observed exceptional site selectivity. This study will further spearhead the development of nondirected C–H borylation with a bimetallic system to harness the effect of the noncovalent metal-arene π-type interactions on the reactivity and the selectivity of the C–H functionalization.}, archive = {J_JACS}, author = {Anup Mandal and Clemens Maurer and Christoph Plett and Kavin Raj Kumar Chandramohan and Ruben Fleischer and Gregor Schnakenburg and Stefan Grimme and Ala Bunescu}, doi = {10.1021/jacs.5c00774}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15281--15293}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective C–H borylation of polyaromatic compounds enabled by metal-arene π-complexation}, volume = {147}, year = {2025}, }
• (2025). ESylites: Synthetic probes for visualization and topographic mapping of single excitatory synapses. JACS, 147(18), 15261--15280. (www)

  @article{ , abstract = {The spatiotemporal organization of the postsynaptic density (PSD) is a fundamental determinant of synaptic transmission, information processing, and storage in the brain. The major bottleneck that prevents the direct and precise representation of the nanometer-scaled organization of excitatory glutamatergic synapses is the size of antibodies, nanobodies, and the genetically encoded fluorescent tags. Here, we introduce small, high affinity synthetic probes for simplified, high contrast visualization of excitatory synapses without the limitations of larger biomolecules. In vitro binding quantification together with microscopy-based evaluation identified eSylites, a series of fluorescent bivalent peptides comprising a dye, linker, and sequence composition that show remarkable cellular target selectivity. Applied on primary neurons or brain slices at nanomolar concentrations, eSylites specifically report PSD-95, the key orchestrator of glutamate receptor nanodomains juxtaposed to the presynaptic glutamate release sites that mediate fast synaptic transmission. The eSylite design minimizes a spatial dye offset and thereby enables visualization of PSD-95 with improved localization precision and further time-resolved discrimination. In particular, we find that individual dendritic spines can contain separate nanodomains enriched for either PSD-95 or its closest homologues, PSD-93 or SAP102. Collectively, these data establish eSylites as a broadly applicable tool for simplified excitatory synapse visualization, as well as a high-end microscopy compatible probe for resolving the PSD organization with unprecedented resolution.}, archive = {J_JACS}, author = {Christiane Huhn and Sheng-Yang Ho and Clemens Schulte and Vladimir Khayenko and Katherina Hemmen and Thomas-Otavio Peulen and Anna-Lena Wiessler and Sebastian Bothe and Aritra Bej and Ivan Talucci and Lars Schönemann and Christian Werner and Hermann Schindelin and Kristian Strømgaard and Carmen Villmann and Katrin G. Heinze and Martin Hruska and Johannes W. Hell and Hans M. Maric}, doi = {10.1021/jacs.5c00772}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15261--15280}, shortjournal = {J. Am. Chem. Soc.}, title = {ESylites: Synthetic probes for visualization and topographic mapping of single excitatory synapses}, volume = {147}, year = {2025}, }
• (2025). Microsolvation of charged sites in vacuo: Are native protein structures retained when charge-backbone interactions are suppressed?. JACS, 147(18), 15253--15260. (www)

  @article{ , abstract = {Native mass spectrometry (nMS) is increasingly used to study proteins and their complexes, providing insights into their stoichiometry, topology, and binding affinities. While noncovalent interactions are thought to largely remain intact after desolvation, protein conformation is highly charge-dependent. Increased Coulomb repulsion typically promotes unfolding and charged surface residues engage in interactions with the protein backbone, disrupting hydrogen bonds and distorting secondary structures. However, the relative contributions of these factors to protein unfolding are not well understood. This study investigates how microsolvation of charged sites using crown ethers affects native-like α-helical structures in the gas phase. Using gas-phase fluorescence spectroscopy and ion mobility-mass spectrometry (IM-MS), we find that crown ethers that bind to lysine side chains promote more compact helical conformations, although the charge state still dictates overall compaction. Crown ether variants with different cavity sizes and electron-rich groups showed similar effects, indicating effective occupation of ammonium cations via hydrogen bonding without attenuating charge–charge interactions. These results suggest that while microsolvation can prevent interactions between charged sites and the protein backbone, it has minimal impact on the overall structure compared to Coulomb repulsion. Comparison with solution-phase data reveals significant helical stretching in the gas phase despite microsolvation, further emphasizing the role of Coulomb repulsion in determining biomolecular structure. This work highlights the value of gas-phase fluorescence spectroscopy as a complementary technique to IM-MS for detecting subtle structural changes.}, archive = {J_JACS}, author = {Lukas R. Benzenberg and Elena Giaretta and Ri Wu and Despoina Svingou and Renato Zenobi}, doi = {10.1021/jacs.5c00740}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15253--15260}, shortjournal = {J. Am. Chem. Soc.}, title = {Microsolvation of charged sites in vacuo: Are native protein structures retained when charge-backbone interactions are suppressed?}, volume = {147}, year = {2025}, }
• (2025). Encoding and expressing the handedness of a möbius π system in a totemic architecture. JACS, 147(18), 15242--15252. (www)

  @article{ , abstract = {The efficient control of the chirality of Möbius π systems remains a challenging task that hinders the development of such molecules into information processing systems. Achieving such control through a redox process would thus open new opportunities. In this context, redox behaviors of Ni(II) and Pd(II) complexes of a Möbius aromatic [28]hexaphyrin doubly linked to an α-cyclodextrin have been investigated. This totemic architecture embedding three types of chirality elements generates two pseudoenantiomers after coordination with either metal. These isomeric pairs possess marked and opposite chiroptical signatures resulting from the P and M configurations of the Möbius π systems. Chemical oxidation to 26-π systems led to behaviors reminiscent to The Oak and the Reeds fable, due to a N3C coordination sphere of Ni(II) being more robust than that of Pd(II). Oxidized Ni(II) complexes ( the Oak ) maintain a Möbius-type conformation at the expense of the π-systems, which undergo an interruption due to inevitable water insertion. In contrast, oxidation of Pd(II) complexes ( the Reeds ) converts the Möbius aromatic systems into Hückel (rectangular) aromatic ones that are maintained in the chiral environment provided by the linking pattern with the cyclodextrin. This constitutes an effective chiral instructing site, as reduction back to their original Möbius configuration occurs with high stereoselectivity. Such a reversible shape-shifting process corresponds to a chiral memory phenomenon where the handedness of a cyclic π system is encoded in a scaffold and expressed upon changing an electronic state. For both metals, spectroelectrochemical studies ultimately revealed robust ON-OFF chiroptical switches, which is unprecedented with Möbius π-systems.}, archive = {J_JACS}, author = {Syamasrit Dash and Arnaud Fihey and Ludovic Favereau and Corinne Lagrost and Rajaa Benchouaia and Sébastien Blanchard and Mickaël Ménand and Stéphane Le Gac}, doi = {10.1021/jacs.5c00524}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15242--15252}, shortjournal = {J. Am. Chem. Soc.}, title = {Encoding and expressing the handedness of a möbius π system in a totemic architecture}, volume = {147}, year = {2025}, }
• (2025). Creation of artificial subcellular organelles using compartmentalized escherichia coli bodies for artificial metalloenzyme-mediated abiotic catalysis in eukaryotic cells. JACS, 147(18), 15229--15241. (www)

  @article{ , abstract = {Artificial metalloenzymes (ArMs) stand out as excellent tools mediating intracellular abiotic transformations due to their multifaceted advantages, including their adaptability through directed evolution and availability as whole-cell catalysts. However, the applications of ArMs as exogenous agents in eukaryotic systems remain challenging due to issues with protein purification and delivery, metalloenzyme stability, and complex catalyst preparation. In this article, we present a method inspired by nature’s endosymbiotic process, enabling the direct use of ArMs residing within the bacterial cells that express them as whole-cell-based catalytic platforms in eukaryotic cells. This approach utilizes HaloTag-SNAPTag fusion protein as the ArM scaffold, which undergoes liquid–liquid phase separation to form sanctuaries in Escherichia coli for different ArMs created from the same fusion protein. Such compartmentalized E. coli are then sterilized and granted cell permeability with polymer decoration so that they may enter eukaryotic cells and work as artificial subcellular organelles, mediating abiotic transformations using those well-protected ArMs residing within. We further demonstrate the potential of this strategy in therapeutic applications in proof-of-concept demonstrations, by showing that these encapsulated ArMs can be viable options for intracellular bacterial pathogen elimination and cancer therapy through prodrug activation in live cells and animals. Likely, this strategy will suggest a different pathway for expanding ArM applications in chemical biology and biomedicine.}, archive = {J_JACS}, author = {Tong Wu and Yating Fei and Yingjiao Deng and Xianhui Chen and Yuli Duan and Ying Liu and Yugang Bai}, doi = {10.1021/jacs.5c00473}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15229--15241}, shortjournal = {J. Am. Chem. Soc.}, title = {Creation of artificial subcellular organelles using compartmentalized escherichia coli bodies for artificial metalloenzyme-mediated abiotic catalysis in eukaryotic cells}, volume = {147}, year = {2025}, }
• (2025). Oxoisoaporphine alkaloid Iridium(III) derivative: An immunogenic cell death inducer that engages the autophagy-dependent regulator cathepsin d. JACS, 147(18), 15216--15228. (www)

  @article{ , abstract = {Autophagy has been recognized as one of the pathways for eliciting immunogenic cell death (ICD). However, the specific molecular target responsible for autophagy-mediated ICD has not yet been elucidated. Here, we report that an oxoisoaporphine alkaloid-modified iridium(III) complex ( 2a ) displays autophagy-inducing ICD activity. Through unbiased thermal proteome profiling (TPP), this new complex was found to interact with the lysosomal protease cathepsin D (Cat D). Subsequent cellular and biochemical assays─including the cellular thermal shift assay, isothermal dose-response assay, enzymatic assays, and molecular docking─confirmed that 2a binds to and inhibits Cat D. Further pathway analysis demonstrated that 2a triggers autophagy-dependent ICD via the LKB1-AMPK-ULK1 signaling pathway by inhibiting Cat D. Several other autophagy-dependent ICD inducers were tested and likewise found to inhibit Cat D. In contrast, an earlier reported analogue of 2a , complex 1a , was found to bind and destabilize binding immunoglobulin protein (BiP) and promote its ICD activity through an endoplasmic reticulum stress response. We believe that the findings reported here will enhance the understanding of the novel mechanisms of ICD agents and pave the way for the design of new ICD inducers with high specificity and efficacy.}, archive = {J_JACS}, author = {Yuan Lu and Feng-Yang Wang and Matthew S. Levine and Hai-Rong Shi and Yuan Wang and Xiaolin Xiong and Liang-Mei Yang and Ya-Qian Shi and Taotao Zou and Jonathan L. Sessler and Hong Liang and Ke-Bin Huang}, doi = {10.1021/jacs.5c00255}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15216--15228}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxoisoaporphine alkaloid Iridium(III) derivative: An immunogenic cell death inducer that engages the autophagy-dependent regulator cathepsin d}, volume = {147}, year = {2025}, }
• (2025). Design and evolution of a phosphorescent protein via the proximal encoding of lanthanide and the antenna chromophore. JACS, 147(18), 15205--15215. (www)

  @article{ , abstract = {Genetically encoded phosphorescent proteins with extended luminescence lifetimes provide an orthogonal channel for biological imaging and detection. While conventional fluorescent proteins typically exhibit nanosecond-scale lifetimes, the development of proteins with longer lifetimes enables time-resolved detection and enhanced signal-to-noise ratios. Here, we designed a novel phosphorescent protein system by incorporating photosensitizing unnatural amino acids (UAAs) proximal to the metal center of a lanthanide binding protein (LanM). Through systematic optimization of the incorporation sites, we achieved considerable enhancement in lanthanide phosphorescence compared with that of the wild-type LanM protein. The subsequent directed evolution of LanM and chemical evolution of UAA yielded variants with an additional muti-fold increase in signal intensity. This iterative optimization strategy generated phosphorescent proteins with extended lifetimes of up to 500 μs and significantly increased brightness. Using this phosphorescence protein platform, a europium sensor with a signal-to-noise ratio of more than 100 for 200 nM Eu(III) and a detection limit of less than 10 nM was developed. In addition, a protease sensor was further designed by inserting a cleavage site into a loop of the phosphorescent protein, achieving remarkable signal-to-noise ratios at nanomolar concentrations. Finally, this phosphorescent protein was fused to the affibody and further used for immunofluorescence imaging. These applications demonstrated a novel platform for developing genetically encoded sensors with enhanced detection sensitivity through time-resolved measurements.}, archive = {J_JACS}, author = {Jinyu Wang and Xingfeng Liu and Kaitong Li and Tao Shi and Qianqian Xu and Tiantian Peng and Qingjun Huang and Ziqi Gao and Hongqi Zhou and Wei Lu and Jie Wang}, doi = {10.1021/jacs.5c00199}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15205--15215}, shortjournal = {J. Am. Chem. Soc.}, title = {Design and evolution of a phosphorescent protein via the proximal encoding of lanthanide and the antenna chromophore}, volume = {147}, year = {2025}, }
• (2025). An experimental and theoretical investigation into [2π + 2π] cycloaddition reactions catalyzed by a cationic Cobalt(I) complex containing a strong-field PCNHCP pincer ligand. JACS, 147(18), 15195--15204. (www)

  @article{ , abstract = {In the past decade, metal-catalyzed [2π + 2π] cycloaddition reactions have gained significant momentum for the synthesis of substituted cyclobutanes and bicyclo[3.2.0]-heptanes. To date, earth-abundant metals that contain redox non-innocent (radical)-type ligands are most commonly used in these cycloaddition reactions, whereby the redox non-innocent ligand plays a crucial role in stabilizing the oxidation and spin-state of the metal center. Classical π-accepting ligands, however, are inactive for these transformations. Here, we report efficient [2π + 2π] cycloaddition reactions that are catalyzed by a cobalt(I) complex containing a traditional π-accepting but redox innocent PC NHC P pincer ligand. Mechanistic and computational investigations revealed a classical Co(I)–Co(III) redox cycle on the singlet spin manifold, where oxidative cyclization is the rate-limiting step. Overall, the herein developed methodology exhibits a wide substrate scope and low catalyst loadings (<1 mol %) and is compatible with a variety of functional groups while occurring under mild conditions (40–60 °C, N 2 ) with short reaction times.}, archive = {J_JACS}, author = {Tofayel Sheikh Mohammad and Yi Jin and Sakthi Raje and Katarzyna Młodzikowska-Pieńko and Zhi-Xiang Yu and Graham de Ruiter}, doi = {10.1021/jacs.5c00018}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15195--15204}, shortjournal = {J. Am. Chem. Soc.}, title = {An experimental and theoretical investigation into [2π + 2π] cycloaddition reactions catalyzed by a cationic Cobalt(I) complex containing a strong-field PCNHCP pincer ligand}, volume = {147}, year = {2025}, }
• (2025). Capturing the conformational heterogeneity of HSPB1 chaperone oligomers at atomic resolution. JACS, 147(18), 15181--15194. (www)

  @article{ , abstract = {Small heat shock proteins (sHSPs), including HSPB1, are essential regulators of cellular proteostasis that interact with unfolded and partially folded proteins to prevent aberrant misfolding and aggregation. These proteins fulfill a similar role in biological condensates, where they interact with intrinsically disordered proteins to modulate their liquid–liquid and liquid-to-solid phase transitions. Characterizing the sHSP structure, dynamics, and client interactions is challenging due to their partially disordered nature, their tendency to form polydisperse oligomers, and their diverse range of clients. In this work, we leverage various biophysical methods, including fast 1 H-based magic angle spinning (MAS) NMR spectroscopy, molecular dynamics (MD) simulations, and modeling, to shed new light on the structure and dynamics of HSPB1 oligomers. Using split-intein-mediated segmental labeling, we provide unambiguous evidence that in the oligomer context, the N-terminal domain (NTD) of HSPB1 is rigid and adopts an ensemble of heterogeneous conformations, the α-Crystallin domain (ACD) forms dimers and experiences multiple distinct local environments, while the C-terminal domain (CTD) remains highly dynamic. Our computational models suggest that the NTDs participate in extensive NTD–NTD and NTD–ACD interactions and are sequestered within the oligomer interior. We further demonstrate that HSPB1 higher order oligomers disassemble into smaller oligomeric species in the presence of a client protein and that an accessible NTD is essential for HSPB1 partitioning into condensates and interactions with client proteins. Our integrated approach provides a high-resolution view of the complex oligomeric landscape of HSPB1 and sheds light on the elusive network of interactions that underlies the function of HSPB1 in biological condensates.}, archive = {J_JACS}, author = {Raymond F. Berkeley and Alexander P. Plonski and Tien M. Phan and Kristof Grohe and Lukas Becker and Sebastian Wegner and Mark A. Herzik, Jr. and Jeetain Mittal and Galia T. Debelouchina}, doi = {10.1021/jacs.4c18668}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15181--15194}, shortjournal = {J. Am. Chem. Soc.}, title = {Capturing the conformational heterogeneity of HSPB1 chaperone oligomers at atomic resolution}, volume = {147}, year = {2025}, }
• (2025). Protein dynamics affect o2-stability of group b [FeFe]-hydrogenase from thermosediminibacter oceani. JACS, 147(18), 15170--15180. (www)

  @article{ , abstract = {In the pursuit of sustainable “green” energy generation, [FeFe]-hydrogenases have attracted significant attention due to their ability to catalyze hydrogen production. However, the sensitivity of these enzymes to O 2 is a major obstacle for their application as biocatalysts in energy conversion technologies. In the search for an O 2 -stable [FeFe]-hydrogenase, we identified the hydrogenase ToHydA from Thermosediminibacter oceani that belongs to the rarely characterized Group B (M2a) [FeFe]-hydrogenases. Our findings demonstrate that ToHydA exhibits remarkable O 2 -stability, even under prolonged O 2 exposure. By characterizing site-directed mutagenesis variants, we found that the highly conserved proton-transporting active site cysteine residue protects the H-cluster from O 2 -induced degradation by forming the H inact state. The additional cysteine residue in the TSCCCP motif of ToHydA, a feature unique to Group B (M2a) [FeFe]-hydrogenases, enhances the flexibility of that motif and facilitates the formation of the H inact state. Moreover, ToHydA possesses unique features, including the formation of an unusual H inact resting state that distinguishes the enzyme from other [FeFe]-hydrogenases. Our atomistic molecular dynamics simulations reveal a previously unrecognized cluster of hydrophobic residues centered around the proton-transporting cysteine-bearing loop. This structural feature appears to be a common molecular characteristic in hydrogenases that form the O 2 -protected H inact state. By exploiting these molecular features of ToHydA, future research can aim to rationally design hydrogenases that combine high catalytic activity with enhanced O 2 -stability to develop more efficient and durable catalysts.}, archive = {J_JACS}, author = {Subhasri Ghosh and Chandan K. Das and Sarmila Uddin and Sven T. Stripp and Vera Engelbrecht and Martin Winkler and Silke Leimkühler and Claudia Brocks and Jifu Duan and Lars V. Schäfer and Thomas Happe}, doi = {10.1021/jacs.4c18483}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15170--15180}, shortjournal = {J. Am. Chem. Soc.}, title = {Protein dynamics affect o2-stability of group b [FeFe]-hydrogenase from thermosediminibacter oceani}, volume = {147}, year = {2025}, }
• (2025). Magnetic properties tuning via broad range site deficiency in square net material UCuxBi2. JACS, 147(18), 15157--15169. (www)

  @article{ , abstract = {HfCuSi 2 -type pnictogen compounds have recently been shown to be a versatile platform for designing materials with topologically nontrivial band structures. However, these phases require strict control over the electron count to tune the Fermi level, which can only be achieved in compositions with A 2+ M 2+ Pn 2 and A 3+ M + Pn 2 (A = lanthanides, M = transition metals, Pn = pnictogens P–Bi) charge distribution. While such lanthanide compounds have been thoroughly studied as candidate magnetic topological materials, their heavy element analogs with uranium and bismuth remain largely underexplored. In this report, we present the synthesis of UCu x Bi 2 single crystals and study their magnetic properties. Detailed structural analysis revealed that flux-grown crystals always form as a site-deficient UCu x Bi 2 composition, where x varies between 0.20 and 0.64. Magnetic property measurements revealed a dependence of the magnetic coupling on the Cu site deficiency, linearly changing the Néel temperature from 51 K for UCu 0.60 Bi 2 to 118 K for UCu 0.30 Bi 2 . Moreover, higher Cu concentration promotes a metamagnetic transition in highly magnetically anisotropic UCu 0.60 Bi 2 single crystals. We show that DFT calculations can successfully model site deficiency in the UCu x Sb 2 and UCu x Bi 2 systems. This work paves the way toward using the site deficiency to tune the Fermi level in more ubiquitous A 3+ M 2+ x Pn 2 phases, which previously have not been considered topological candidate materials due to unfavorable electron count.}, archive = {J_JACS}, author = {Hope A. Long and Daniel Duong and Joanna Blawat and Gregory Morrison and Yan Wu and Huibo Cao and Nabaraj Pokhrel and David S. Parker and John Singleton and Rongying Jin and Vladislav V. Klepov}, doi = {10.1021/jacs.4c18438}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15157--15169}, shortjournal = {J. Am. Chem. Soc.}, title = {Magnetic properties tuning via broad range site deficiency in square net material UCuxBi2}, volume = {147}, year = {2025}, }
• (2025). Heterometallic aluminum Metal–Organic frameworks. JACS, 147(18), 15146--15156. (www)

  @article{ , abstract = {From spinel gemstone (MgAl 2 O 4 ) to layered double hydroxides, nature has long relied on combinations between charge-complementary metal ions such as divalent metal ions (M 2+ ) and Al 3+ to create diverse valuable materials. However, for metal–organic frameworks (MOFs), heterometallic combinations such as Mg–Al are conspicuously absent. Here, we report a breakthrough in the synthesis of heterometallic Al-MOFs containing M 2+ /Al 3+ trimeric clusters (M = Mg, Mn, Co, Ni). The synergistic effect between M(II) chlorides and aluminum lactate plays a critical role in the cooperative crystallization of M 2+ and Al 3+ into pore-space-partitioned MOFs (partitioned acs topology) with fast crystallization kinetics (about 3 h). New M 2+ /Al 3+ MOFs exhibit highly tunable porosity and extraordinarily high uptakes for CO 2 and small hydrocarbon molecules (112 cm 3 /g for CO 2 , 176 cm 3 /g for C 2 H 2 , 156 cm 3 /g for C 2 H 4 , and 163 cm 3 /g for C 2 H 6 ) at 298 K and 1 bar. The high uptake capacity coupled with high selectivity (up to 8.5 for C 2 H 2 /CO 2 , 10.8 for C 2 H 2 /C 2 H 4 ) gives rise to efficient separations of either C 2 H 2 /CO 2 or C 2 H 2 /C 2 H 4 gas mixtures, as confirmed by experimental breakthrough experiments.}, archive = {J_JACS}, author = {Wei Wang and Yichong Chen and Xianhui Bu and Pingyun Feng}, doi = {10.1021/jacs.4c18251}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15146--15156}, shortjournal = {J. Am. Chem. Soc.}, title = {Heterometallic aluminum Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Amorphous-nanocrystalline fluorinated halide electrolytes with high ionic conductivity and high-voltage stability. JACS, 147(18), 15136--15145. (www)

  @article{ , abstract = {All-solid-state sodium-ion batteries (ASSSIBs) offer a cost-effective, scalable alternative to rechargeable lithium-ion batteries, but their advancement requires solid electrolytes with high ionic conductivity, wide electrochemical stability, and robust interfacial compatibility. Here, a fluorine-doped halide solid electrolyte (2NaF–ZrCl 4 , 2-NFZC) featuring an amorphous-nanocrystalline structure with high ionic conductivity (2.35 × 10 –4 S cm –1 at 25 °C) and good high-voltage stability is presented. Fluorine doping in 2-NFZC promotes Zr–F bonding with limited Na–F interaction, which facilitates fast Na-ion transport through disordered regions and the NaF/amorphous phase interface. Paired with a NaNi 1/3 Fe 1/3 Mn 1/3 O 2 cathode, a Na 15 Sn 4 anode, and a Na 3 PS 4 anode interlayer, the all-solid-state cell with the 2-NFZC electrolyte demonstrates a discharged capacity of 137.1 mAh g –1 , 81.1% capacity retention over 600 cycles, and suppressed interfacial side reactions. These findings highlight the potential of fluorine doping in designing advanced solid electrolytes for high-performance all-solid-state Na-ion batteries.}, archive = {J_JACS}, author = {Lihai Zhou and Sidong Zhang and Weiping Li and Bing Li and Nicholas S. Grundish and Pengfei Ren and Xuefeng Wang and Nan Wu and Weidong Zhou and Yutao Li}, doi = {10.1021/jacs.4c18090}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15136--15145}, shortjournal = {J. Am. Chem. Soc.}, title = {Amorphous-nanocrystalline fluorinated halide electrolytes with high ionic conductivity and high-voltage stability}, volume = {147}, year = {2025}, }
• (2025). Controlling glycan folding with ionic functional groups. JACS, 147(18), 15126--15135. (www)

  @article{ , abstract = {Glycans are intrinsically flexible molecules that can adopt many conformations. These molecules often carry ionic functional groups that influence glycan’s conformational preferences, dynamics, and aggregation tendencies. Inspired by these mechanisms, we have engineered a glycan sequence whose secondary structure can be precisely manipulated by using ionic groups. We strategically incorporated ionic substituents into a glycan sequence adopting a hairpin conformation. Complementary ionic groups stabilized the closed conformers, while ionic repulsions shifted the populations toward the open forms. External stimuli, such as pH variations or enzyme addition, enabled us to dynamically control the hairpin’s opening and closing. Additionally, changes in protonation states led to glycan aggregation, suggesting opportunities for the creation of responsive glycan-based materials.}, archive = {J_JACS}, author = {Nishu Yadav and Ana Poveda and Yadiel Vázquez Mena and Martin Rosenthal and Yu Ogawa and Jesús Jiménez-Barbero and Martina Delbianco}, doi = {10.1021/jacs.4c17992}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15126--15135}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlling glycan folding with ionic functional groups}, volume = {147}, year = {2025}, }
• (2025). Strategic modulation of polarity and viscosity sensitivity of bimane molecular rotor-based fluorophores for imaging α-synuclein. JACS, 147(18), 15115--15125. (www)

  @article{ , abstract = {Molecular rotor-based fluorophores (RBFs) that are target-selective and sensitive to both polarity and viscosity are valuable for diverse biological applications. Here, we have designed next-generation RBFs based on the underexplored bimane fluorophore either through a change in aryl substitution or varying π-linkages between the rotatable electron donors and acceptors to produce red-shifted fluorescence emissions with large Stokes shifts. RBFs exhibit a twisted intramolecular charge transfer mechanism that enables control of polarity and viscosity sensitivity as well as target selectivity. These features enable their application in (1) turn-on fluorescent detection of α-synuclein (αS) fibrils, a hallmark of Parkinson’s disease, including amplified fibrils from patient samples; (2) monitoring early misfolding and oligomer formation during αS aggregation; and (3) selective imaging of αS condensates formed by liquid–liquid phase separation. In all three cases, we show that our probes have high levels of selectivity for αS compared to other aggregating proteins. These properties enable one to study the interplay of αS and tau in amyloid aggregation and the mechanisms underlying neurodegenerative disorders.}, archive = {J_JACS}, author = {Yarra Venkatesh and Karthik B. Narayan and Tobias Baumgart and E. James Petersson}, doi = {10.1021/jacs.4c17933}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15115--15125}, shortjournal = {J. Am. Chem. Soc.}, title = {Strategic modulation of polarity and viscosity sensitivity of bimane molecular rotor-based fluorophores for imaging α-synuclein}, volume = {147}, year = {2025}, }
• (2025). Uncovering the molecular landscape of tetracycline family natural products through bacterial genome mining. JACS, 147(18), 15100--15114. (www)

  @article{ , abstract = {Tetracycline (TC) family natural products have attracted significant attention due to their diverse chemical structures and important role in drug development. As one of the most successful classes of drugs, TC antibiotics have been used clinically for over 70 years and remain crucial in treating infections. Despite their importance, systematic exploration of novel TC natural products has been limited, leaving the molecular landscape of the TC family poorly understood and hindering further development of these compounds for therapeutic applications. Here, we developed a targeted strategy to identify TC biosynthetic gene clusters (BGCs) based on specific cyclase signatures involved in assembling the TC scaffold. This led to the discovery of 82 representative BGCs with the potential to produce structurally diverse TCs. Among them, we uncovered three groups of novel natural products─misiomycins, varsomycins, and hibarimicins J–L─and identified their biosynthetic pathways. These compounds display distinctive structural features, with misiomycin A and hibarimicin L among the most highly modified TCs identified to date. Misiomycin A biosynthesis involves extensive glycosylation, while biosynthesis of varsomycin A, featuring a unique six-membered lactone ring structure, requires the coordinated action of two TC BGCs. The biosynthesis of hibarimicins J–L, derived from TC monomer dimerization, undergoes complex oxidative modifications involving seven oxygenases. Several TCs exhibited potent activity against drug-resistant Gram-positive pathogens. Our work further expands the structural diversity within the TC family and underscores the potential of these BGCs for generating new TC structures, providing valuable insights for the discovery and development of novel TC-based therapeutics.}, archive = {J_JACS}, author = {Haiyan Wang and Lijun Wang and Dong Li and Keqiang Fan and Yingzhe Yang and Haolan Cao and Jianing Sun and Jinwei Ren and Yao Liu and Lijun Xiang and Weishu Li and Minghui Pan and Huitao Hu and Yihua Chen and Zhengren Xu and Ying Huang and Weishan Wang and Guohui Pan}, doi = {10.1021/jacs.4c17551}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15100--15114}, shortjournal = {J. Am. Chem. Soc.}, title = {Uncovering the molecular landscape of tetracycline family natural products through bacterial genome mining}, volume = {147}, year = {2025}, }
• (2025). Molybdenum cofactor model reveals remarkable redox activity at both molybdenum and the pyranopterin dithiolene ligand. JACS, 147(18), 15088--15099. (www)

  @article{ , abstract = {The molybdenum (Moco) and tungsten (Tuco) cofactors are uniquely found in pyranopterin dithiolene (PDT) molybdenum and tungsten enzymes, yet the roles of this electronically complex PDT ligand in the catalytic cycles of these enzymes has yet to be revealed. After more than a decade of effort, we have synthesized and characterized a model compound containing a reduced PDT ligand coordinated to a diamagnetic d 2 low-spin Mo(4+) ion, mimicking the MoO(PDT) structure common to most Mo enzyme active sites. A combination of 1D and 2D NMR spectroscopies, augmented by molecular geometry optimization computations, confirms that both R,R- and S,S- diastereomers coexist in the synthetic final product. Redox processes at both the Mo ion and the pyranopterin are detected by cyclic voltammetry. The two-electron oxidant DCIP oxidizes the pterin component of the ligand in methanol, whereas no reaction occurs in aprotic acetonitrile. Addition of 1 equiv of the one-electron oxidant Fc + stoichiometrically oxidizes the Mo(4+) ion to the paramagnetic d 1 Mo(5+) species, a result supported by electron paramagnetic resonance (EPR) spectroscopy. However, the addition of more than 1 equiv of Fc + results in oxidation of the reduced pyranopterin to yield a Mo(4+) complex of the oxidized pyranopterin dithiolene ligand, a result supported by both the cyclic voltammetry and electronic absorption titrations. The concrete examples from these model studies suggest how the unique electronic structure of the PDT ligand in Moco and Tuco may enable variable redox reactivity in enzymatic catalysis, highlighting its role as a complex noninnocent biological ligand.}, archive = {J_JACS}, author = {Jinming Liu and Angelina Rogatch and Benjamin R. Williams and Chelsea Freer and Chiara Zuccoli and Jing Yang and Martin L. Kirk and Sharon J. Nieter Burgmayer}, doi = {10.1021/jacs.4c17577}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15088--15099}, shortjournal = {J. Am. Chem. Soc.}, title = {Molybdenum cofactor model reveals remarkable redox activity at both molybdenum and the pyranopterin dithiolene ligand}, volume = {147}, year = {2025}, }
• (2025). Formation of ground-state intermediate during electronic relaxation of pyrimidine nucleobases. JACS, 147(18), 15077--15087. (www)

  @article{ , abstract = {Ultrafast electronic relaxation of nucleobases from the 1 ππ* state to the ground electronic state (S 0 ) is crucial for the photostability of DNA and RNA. However, it has been suggested that electronic relaxation of pyrimidine nucleobases, nucleosides, and nucleotides in an aqueous environment generates an electronically excited intermediate state with a lifetime of tens to hundreds of picoseconds with a relatively high quantum yield (QY) of 0.2–0.5. The generation of such a long-lived excited state seems to be inconsistent with the photostability of these molecules. A recent extreme ultraviolet time-resolved photoelectron spectroscopy study by Miura et al. [ J. Am. Chem. Soc. 2023 , 145 (6), 3369] reinvestigated this problem and revealed that the accurately determined QY for long-lived excited states is much too low to allow an electronically excited reaction intermediate to exist. In the present study, we investigated the nature of the reaction intermediate using ultraviolet and infrared transient absorption spectroscopy, along with quantum chemical calculations to show that the intermediate is in the S 0 state, and its infrared spectrum is compatible with a metastable twisted C═C species theoretically predicted by Park et al. [ J. Phys. Chem. Lett. 2022 , 13 (30), 7072].}, archive = {J_JACS}, author = {Yuki Obara and Srijon Ghosh and Alexander Humeniuk and Shota Kamibashira and Shunsuke Adachi and Toshinori Suzuki}, doi = {10.1021/jacs.4c17415}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15077--15087}, shortjournal = {J. Am. Chem. Soc.}, title = {Formation of ground-state intermediate during electronic relaxation of pyrimidine nucleobases}, volume = {147}, year = {2025}, }
• (2025). Molecular dynamics simulations of native protein charging in electrosprayed droplets with experimentally relevant compositions. JACS, 147(18), 15066--15076. (www)

  @article{ , abstract = {Electrospray ionization-mass spectrometry (ESI-MS) has been widely used to study proteins given its preservation of native-protein structure when transitioning to the gas-phase. Understanding the influence of experimental factors on ESI can provide insight into the resulting charge states, as well as the degree to which “native” structure is maintained. Experimentally, it is challenging to characterize nanometer-scale electrosprayed droplets; however, molecular dynamics (MD) simulations pose an attractive solution by providing a molecular perspective of protein-ion formation. By resolving many approximations used in past MD simulations of ESI, we demonstrate the capability of simulating electrosprayed droplets with experimentally relevant droplet compositions and behavior. This is accomplished by modeling proton transfers between all titratable molecules in simulated droplets under atmospheric conditions; thus, enabling simulated droplets containing ammonium acetate that form experimentally observed (de)protonated protein ions. Application of the proposed protocol to several native proteins in positive- and negative-ion mode ESI produced simulated weighted averages of charge-state distributions that differed by 0.14 compared to experimental values. Our simulations suggest that changes in residue basicity during the transition to the gas-phase play a significant role in moderating protein charging during native-ESI and can explain many experimentally observed trends. Ionic protein structures produced via the simulated model maintained, on average, 73% of their native contacts into the gas phase relative to solution-phase structures. While applied towards native proteins here, novel insights into effects of the transition to gas-phase enable a deeper understanding of the ESI process itself and thus, are informative regardless of analyte.}, archive = {J_JACS}, author = {Michael S. Cordes and Elyssia S. Gallagher}, doi = {10.1021/jacs.4c17382}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15066--15076}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular dynamics simulations of native protein charging in electrosprayed droplets with experimentally relevant compositions}, volume = {147}, year = {2025}, }
• (2025). Nanopores with an engineered selective entropic gate detect proteins at nanomolar concentration in complex biological sample. JACS, 147(18), 15050--15065. (www)

  @article{ , abstract = {Biological nanopores enable the electrical detection of biomolecules, making them ideal sensors for use in health-monitoring devices. Proteins are widely recognized as biomarkers for various diseases, but they present a unique challenge due to their vast diversity and concentration range in biological samples. Here, inspired by the nuclear pore complex, we incorporated a layer of disordered polypeptides into the biological nanopore YaxAB. This polypeptide mesh formed an entropic gate, significantly reducing the entry of proteins from a highly concentrated mixture, including blood. The introduction of a specific recognition element within the disordered polypeptides allowed targeted proteins to penetrate through the nanopores, where they were recognized by specific current signatures. This biosensing approach allowed for the recognition of nanomolar proteins directly from blood samples without prior sample preparation. This work paves the way for the next generation of nanopore sensors for the real-time detection of proteins in blood.}, archive = {J_JACS}, author = {Sabine Straathof and Giovanni Di Muccio and Giovanni Maglia}, doi = {10.1021/jacs.4c17147}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15050--15065}, shortjournal = {J. Am. Chem. Soc.}, title = {Nanopores with an engineered selective entropic gate detect proteins at nanomolar concentration in complex biological sample}, volume = {147}, year = {2025}, }
• (2025). Enantioselective Cobalt(III)-catalyzed [4 + 1] annulation of benzamides: Cyclopropenes as one-carbon synthons. JACS, 147(18), 15041--15049. (www)

  @article{ , abstract = {A chiral cyclopentadienyl cobalt(III)-catalyzed enantioselective [4 + 1] annulation of N -chlorobenzamides with cyclopropenes is reported. The cobalt catalyst engages in the C–H activation as well as promotes the C–C bond cleavage of the cyclopropene, rendering it as a one-carbon unit for the annulation. The reaction efficiently constructs biologically relevant chiral isoindolinones with selectivities of up to 99:1 er and >20:1 E / Z ratios. The cobalt(III) catalyst displays a unique orthogonal reactivity profile delivering [4 + 1] annulation products, whereas its rhodium(III) homologue engages in the more classical [4 + 2] annulation pattern. Computational studies reveal the origin of these reactivity divergences.}, archive = {J_JACS}, author = {Lenin Kumar Verdhi and Matthew D. Wodrich and Nicolai Cramer}, doi = {10.1021/jacs.4c16953}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15041--15049}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective Cobalt(III)-catalyzed [4 + 1] annulation of benzamides: Cyclopropenes as one-carbon synthons}, volume = {147}, year = {2025}, }
• (2025). Ampere-hour-scale quasi-solid-state Zinc–Air batteries with a wide operating temperature range (−50 to 60 °C). JACS, 147(18), 15029--15040. (www)

  @article{ , abstract = {Quasi-solid-state Zn–air batteries typically exhibit limited rate capability (<10 mA cm –2 ), primarily due to sluggish oxygen electrocatalysis and unstable electrochemical interfaces. Herein, we report a realistic quasi-solid-state Zn–air battery featuring multiactive sites' MnFeCoNiRu high-entropy alloys uniformly anchored in carbon nanofibers (MnFeCoNiRu/CNF) as the air cathode and a poly(acrylamide- co -acrylic acid) organohydrogel as an antifreezing conductor electrolyte. The proposed (MnFeCoNiRu/CNF) exhibits superb bifunctional activity (Δ E = 0.64 V) and stability (>10,000 cycles) toward a reversible oxygen reaction, outperforming commercial Pt/C and RuO 2 , which is mainly due to MnFeCoNiRu/CNF possessing different active sites in oxygen reactions, as evidenced by in situ Raman spectroscopy and density functional theory. Furthermore, a poly(acrylamide- co -acrylic acid) organohydrogel with its multiple intermolecular hydrogen bond network modified by the addition of dimethyl sulfoxide reveals strength at a freezing temperature (−50 °C) with high chemical/mechanical robustness. A high capacity of 7.15 Ah and an energy density of 110 Wh kg cell –1 are normally measured in a quasi-solid-state Zn–air battery with a cycle test under 500 mA and 250/500 mAh conditions. Quasi-solid-state Zn–air batteries operate effectively at rates of 5–2000 mA over a wide temperature range from −50 to 60 °C.}, archive = {J_JACS}, author = {Tengteng Gu and Yunqi Jia and Linjie Zhang and Linwei Zhao and Jiadong Shen and Liuzhang Ouyang and Min Zhu and Jun Liu}, doi = {10.1021/jacs.4c16807}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15029--15040}, shortjournal = {J. Am. Chem. Soc.}, title = {Ampere-hour-scale quasi-solid-state Zinc–Air batteries with a wide operating temperature range (−50 to 60 °C)}, volume = {147}, year = {2025}, }
• (2025). Cathode electrolyte interphase regulation for high-performance Lithium–Organic batteries. JACS, 147(18), 15019--15028. (www)

  @article{ , abstract = {Organic cathode materials (OCMs) have garnered significant attention due to their high capacity and environmental friendliness. However, their practical application is severely limited by their strong interaction with conventional liquid electrolytes, leading to serious dissolution. To address this issue, we introduced a series of lithium fluorocarboxylates (LFCs) with a low conjugation effect and high energies of the highest occupied molecular orbital (HOMO) into the electrolyte, forming a favorable cathode electrolyte interphase (CEI) layer on the surface of the OCMs. This mitigates the direct interaction between the electrolyte and electrode materials, resolving the dissolution problem and achieving excellent cycling stability. Theoretical calculations and spectroscopic analyses indicate that the introduction of LFCs results in more fluorine-containing anions participating in the solvation structure, which further decompose to form a uniform, dense, and robust CEI layer during discharge–charge cycles. Notably, when the L3FC with strong adsorption to carbonyl materials is introduced, the resulting CEI layer provides excellent interfacial kinetics and effectively protects the cathode from electrolyte erosion. In this electrolyte, the pyrene-4,5,9,10-tetraone (PTO) cathode exhibits outstanding electrochemical performance, with a discharge capacity of 232 mA h g –1 at a rate of 5C and capacity retention rate of 72% after 1000 cycles at 2C. This study proposes the construction of an excellent CEI layer tailored for OCMs by regulating the electrolyte composition to alleviate dissolution of electrode materials in the electrolyte, thereby significantly enhancing electrochemical performance.}, archive = {J_JACS}, author = {Zhuo Yang and Yong Lu and Shuo Xu and Xiaomeng Liu and Long Shang and Zhenhua Yan and Kai Zhang and Jun Chen}, doi = {10.1021/jacs.4c16492}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15019--15028}, shortjournal = {J. Am. Chem. Soc.}, title = {Cathode electrolyte interphase regulation for high-performance Lithium–Organic batteries}, volume = {147}, year = {2025}, }
• (2025). Debate of nucleophilic versus electrophilic oxidative aldehyde deformylation by mononuclear nonheme Iron(III)-peroxo and Iron(IV)-oxo complexes. JACS, 147(18), 15006--15018. (www)

  @article{ , abstract = {High-valent iron(IV)-oxo species are fleeting intermediates that perform vital reactions in enzymatic catalysis. In contrast, heme and nonheme iron(III)-peroxo intermediates usually act as nucleophiles and are converted to high-valent iron-oxo intermediates for electrophilic oxidation reactions. Herein, we report a study on aldehyde deformylation reactions of 2-phenylpropionaldehyde (2-PPA) and its derivatives by iron(III)-peroxo complexes bearing tetramethylated cyclam (TMC) analogues, including [Fe III (O 2 )(12-TMC)] + ( 1 ), [Fe III (O 2 )(13-TMC)] + ( 2 ), and [Fe III (O 2 )(14-TMC)] + ( 3 ). Reactivity studies by employing deuterated substrates, such as α-[D 1 ]-2-phenylpropionaldehyde and aldehyde-[D]-2-phenylpropionaldehyde, demonstrate that deformylation of 2-PPA by the nonheme iron(III)-peroxo complexes occurs via abstraction of the stronger aldehyde C–H atom, rather than the expected nucleophilic attack or weaker α-C–H atom abstraction reactions. Interestingly, the preference for aldehyde C–H atom abstraction is retained during the deformylation of 2-PPA by iron(IV)-oxo complexes, i.e., [Fe IV (O)(13-TMC)] 2+ ( 4 ) and [Fe IV (O)(N4Py)] 2+ ( 5 ). DFT calculations reproduce the experimental trends in reactivity and reveal that the peroxide O–O bond is cleaved to form an iron(III)-dioxyl species that conducts aldehyde C–H bond abstraction; this chemoselectivity is achieved through stabilizing noncovalent interactions between the oxidants and the aromatic ring of the substrate that positions the aldehyde in close proximity to the Fe III –O 2 /Fe IV ═O cores. These new experimental and theoretical findings together with the previous demonstrations of the ability of 1 – 3 in hydrogen atom transfer, oxygen atom transfer, and cis -dihydroxylation reactions highlight that iron(III)-peroxo cores are not inherently nucleophiles and can have more important functions in chemical and biological oxidation reactions, rather than acting as transient species en route to high-valent metal–oxo intermediates.}, archive = {J_JACS}, author = {Wenjuan Zhu and Dongru Sun and Anran Zhou and Shoujun Wang and Yi Zhang and Henrik P. H. Wong and Akhilesh Kumar and Xiaoyan Lu and Peng Wu and Sayanta Sekhar Nag and Yong Wang and Kallol Ray and Sam P. de Visser and Wonwoo Nam}, doi = {10.1021/jacs.4c16522}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {15006--15018}, shortjournal = {J. Am. Chem. Soc.}, title = {Debate of nucleophilic versus electrophilic oxidative aldehyde deformylation by mononuclear nonheme Iron(III)-peroxo and Iron(IV)-oxo complexes}, volume = {147}, year = {2025}, }
• (2025). Enhanced catalytic activity via rapid two-electron transfer in low-spin Fe(II) complex and spin-state dependent proton reduction pathways. JACS, 147(18), 14997--15005. (www)

  @article{ , abstract = {The growing interest in green hydrogen gas production has brought significant attention to the development of efficient proton reduction catalysts. A comprehensive understanding of proton and electron transfer processes within catalyst complexes is crucial for developing efficient catalysts. While the proton transfer process is influenced by the Brønsted acid used, electron transfer is an intrinsic property determined by the molecular orbitals and spin states of complexes. Complexes that rapidly transfer electrons are associated with high catalytic performance. In this study, we present a first example of low-spin Fe II complex that utilizes the π* orbital of ligand for rapid two-electron transfer, resulting in exceptional catalytic performance for hydrogen gas evolution. The consecutive two-electron transfer rate was measured at 33.24 s –1 , and in combination with proton transfer, the catalyst achieved an extraordinarily high turnover frequency (TOF) of 224,643 s –1 for hydrogen gas production. Conversely, a high-spin Fe(II) complex produced hydrogen gas at a relatively low TOF of 8848 s –1 . These comparative experiments confirmed that the observed high catalytic efficiency is unique to the low-spin Fe II complex, attributed to its distinct electron transfer mechanism.}, archive = {J_JACS}, author = {Jueun Lee and Donguk Heo and Wonjung Lee and Junhyeok Seo}, doi = {10.1021/jacs.4c16429}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14997--15005}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced catalytic activity via rapid two-electron transfer in low-spin Fe(II) complex and spin-state dependent proton reduction pathways}, volume = {147}, year = {2025}, }
• (2025). Enzyme enhancement through computational stability design targeting NMR-determined catalytic hotspots. JACS, 147(18), 14978--14996. (www)

  @article{ , abstract = {Enzymes are the quintessential green catalysts, but realizing their full potential for biotechnology typically requires improvement of their biomolecular properties. Catalysis enhancement, however, is often accompanied by impaired stability. Here, we show how the interplay between activity and stability in enzyme optimization can be efficiently addressed by coupling two recently proposed methodologies for guiding directed evolution. We first identify catalytic hotspots from chemical shift perturbations induced by transition-state-analogue binding and then use computational/phylogenetic design (FuncLib) to predict stabilizing combinations of mutations at sets of such hotspots. We test this approach on a previously designed de novo Kemp eliminase, which is already highly optimized in terms of both activity and stability. Most tested variants displayed substantially increased denaturation temperatures and purification yields. Notably, our most efficient engineered variant shows a ∼3-fold enhancement in activity ( k cat ∼ 1700 s –1 , k cat / K M ∼ 4.3 × 10 5 M –1 s –1 ) from an already heavily optimized starting variant, resulting in the most proficient proton-abstraction Kemp eliminase designed to date, with a catalytic efficiency on a par with naturally occurring enzymes. Molecular simulations pinpoint the origin of this catalytic enhancement as being due to the progressive elimination of a catalytically inefficient substrate conformation that is present in the original design. Remarkably, interaction network analysis identifies a significant fraction of catalytic hotspots, thus providing a computational tool which we show to be useful even for natural-enzyme engineering. Overall, our work showcases the power of dynamically guided enzyme engineering as a design principle for obtaining novel biocatalysts with tailored physicochemical properties, toward even anthropogenic reactions.}, archive = {J_JACS}, author = {Luis I. Gutierrez-Rus and Eva Vos and David Pantoja-Uceda and Gyula Hoffka and Jose Gutierrez-Cardenas and Mariano Ortega-Muñoz and Valeria A. Risso and Maria Angeles Jimenez and Shina C. L. Kamerlin and Jose M. Sanchez-Ruiz}, doi = {10.1021/jacs.4c09428}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14978--14996}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzyme enhancement through computational stability design targeting NMR-determined catalytic hotspots}, volume = {147}, year = {2025}, }
• (2025). A crystalline annelated pyridin-1-ylidene and its isomerization into a pyridin-3-ylidene. JACS, 147(18), 14972--14977. (www)

  @article{ , abstract = {An isolable ring-fused pyridinylidene (a so-called Hammick intermediate) was synthesized from a benzo[ h ]isoquinolinium salt, and its structure in the solid state was determined. The isolation of this first-of-its-kind pyridine-derived aromatic N-heterocyclic carbene was made possible due to the presence of an adamantyl group on nitrogen, forcing the nitrogen to be planar and enhancing both π-donation and steric protection, and to its unique polycyclic structure, which displays an intramolecular C–H···C carbene interaction. Additionally, an example of isomerization of a carbene into another carbene, namely, a benzo[ h ]isoquinolin-1-ylidene into a benzo[ h ]isoquinolin-3-ylidene, is reported.}, archive = {J_JACS}, author = {Jan Lorkowski and Levan Gojiashvili and Patrick Yorkgitis and Delphine Pichon and Jakub Talcik and Milan Gembicky and Thierry Roisnel and Olivier Baslé and Rodolphe Jazzar and Marc Mauduit and Guy Bertrand}, doi = {10.1021/jacs.5c05642}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14972--14977}, shortjournal = {J. Am. Chem. Soc.}, title = {A crystalline annelated pyridin-1-ylidene and its isomerization into a pyridin-3-ylidene}, volume = {147}, year = {2025}, }
• (2025). Electrochemical oxidation of methane to methylamine. JACS, 147(18), 14966--14971. (www)

  @article{ , abstract = {The electrochemical methane (CH 4 ) oxidation reaction under ambient conditions is a promising approach for natural gas utilization. However, the highly stable nature of CH 4 restrains efficient cleavage of the C–H bond without overoxidation. To this end, we proposed a coupled oxidative strategy for converting CH 4 to value-added products via NH 2 intermediates. The ammonia-oxidation-driven anodic reaction facilitates the formation of NH 2 species and activates CH 4 through nucleophilic attack to achieve C–N bond formation. Further the generated methylamine could be protected from overoxidation in the ammonia-based anolyte. Under such conditions, a methylamine productivity of 3.8 mmol g –1 cat h –1 at 1.55 V vs a reversible hydrogen electrode is reported. This work provides new insights into electrocatalytic C–N coupling based on the ammonia oxidation reaction, which could extend to other alkane or alkene conversions.}, archive = {J_JACS}, author = {Qiang Song and Wanping Xu and Xin Zeng and Tianqi Zhang and Jungmi Hong and Patrick J. Cullen}, doi = {10.1021/jacs.5c04802}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14966--14971}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical oxidation of methane to methylamine}, volume = {147}, year = {2025}, }
• (2025). Manipulating the isomerization of a tris-azobenzene cage by anion binding. JACS, 147(18), 14960--14965. (www)

  @article{ , abstract = {Here, we report a C 3 -symmetric tris-azobenzene cage 1 comprising azobenzene cores and bis(urea) units. This system demonstrates efficient reversible photoisomerization and unprecedented anion-mediated switching modes. Specifically, the phosphate anion induces a concerted ZZZ → EEE isomerization with prolonged thermal relaxation ( t 1/2 = 37.5 h at 298 K). In contrast, the bulky benzene-1,3,5-tricarboxylate anion enforces a stepwise pathway ( ZZZ → EZZ → EEZ → EEE ) with rapid thermal relaxation ( t 1/2 = 54.4, 44.5, and 12.9 min for each step). This study represents the first demonstration of selective control over stepwise and concerted multi-azobenzene switch, mimicking biological adaptability through environmental changes.}, archive = {J_JACS}, author = {Huibin Shan and Wei Zhao and Ji Wang and Yougang Yao and Hongwei Ma and Kanglei Liu and Xiao-Juan Yang and Biao Wu}, doi = {10.1021/jacs.5c04399}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14960--14965}, shortjournal = {J. Am. Chem. Soc.}, title = {Manipulating the isomerization of a tris-azobenzene cage by anion binding}, volume = {147}, year = {2025}, }
• (2025). Ruthenium-catalyzed enantioselective alkylation of sulfenamides: A general approach for the synthesis of drug relevant S-methyl and S-cyclopropyl sulfoximines. JACS, 147(18), 14954--14959. (www)

  @article{ , abstract = {Sulfoximines are increasingly utilized in pharmaceuticals and agrochemicals with all sulfoximine clinical candidates incorporating either an S -methyl or an S -cyclopropyl substituent. Here, we report on a general and efficient sequence for the asymmetric synthesis of both of these sulfoximine substitution patterns. The asymmetric synthesis of sulfilimine intermediates by the first Ru-catalyzed enantioselective alkylation of sulfenamides enables the first examples of enantioselective S -alkylation with monosubstituted diazo compounds. The reaction proceeds at ≤1 mol % Ru-catalyst loading, and for tert -butyl diazoacetate, high yields and ≥98:2 er are achieved for an exceedingly broad range of sulfenamides, including with S -(hetero)aryl, -alkenyl, -methyl, -benzyl, -branched alkyl, and - tert -butyl substituents and for sterically and electronically diverse N -acyl groups. Sulfenamides derived from densely functionalized advanced drug intermediates also alkylated with 99:1 er. After oxidation of an N -pivaloyl S - tert -butyl acetate substituted sulfilimine to the corresponding sulfoximine, treatment with trifluoracetic acid in an aprotic solvent resulted in decarboxylation to the S -methyl N -pivaloyl sulfoximine, while aqueous HCl resulted in both decarboxylation and cleavage of the N -acyl group to give the S -methyl NH sulfoximine. Alternatively, sulfoximine alkylation with dibromoethane followed by acid-mediated decarboxylation provided the S -cyclopropyl sulfoximine. The efficient asymmetric synthesis of the preclinical candidate LTGO-33 and the formal asymmetric synthesis of the phase II clinical candidate ART0380 demonstrate the utility of the disclosed approach.}, archive = {J_JACS}, author = {Zachary W. Boyer and Na Yeon Kwon and Jonathan A. Ellman}, doi = {10.1021/jacs.5c03841}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14954--14959}, shortjournal = {J. Am. Chem. Soc.}, title = {Ruthenium-catalyzed enantioselective alkylation of sulfenamides: A general approach for the synthesis of drug relevant S-methyl and S-cyclopropyl sulfoximines}, volume = {147}, year = {2025}, }
• (2025). Direct enantioselective allylic alkylation of α-amino esters to quaternary glutamates via strategic pyridoxal catalyst design. JACS, 147(18), 14945--14953. (www)

  @article{ , abstract = {The difficulty for N-unprotected α-substituted glycinates as α-C nucleophiles originates from both competing N nucleophilic interference and steric hindrance of the α substituent, which makes direct asymmetric α-C alkylation of N-unprotected α-substituted glycinates with Morita–Baylis–Hillman (MBH) adducts especially challenging. Given the wide utilization of α-quaternary chiral glutamic acid derivatives in therapeutic studies, we took advantage of biomimetic carbonyl catalysis to achieve their efficient synthesis. A bifunctional centrally chiral pyridoxal, featured with an expanded catalytic cavity and reduced steric hindrance around the aldehyde group, was designed and synthesized. In this work, we describe the novel centrally chiral pyridoxal enabled direct asymmetric α-C alkylation of N-unprotected α-substituted glycinates with MBH acetates. A broad range of α-quaternary chiral glutamic acid derivatives with multiple modifications were produced with high reactivity and excellent stereocontrol.}, archive = {J_JACS}, author = {Zhengjun Shi and Tianhao Wu and Longjie Huang and Siqi Liu and Xiao Xiao and Baoguo Zhao}, doi = {10.1021/jacs.5c02644}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14945--14953}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct enantioselective allylic alkylation of α-amino esters to quaternary glutamates via strategic pyridoxal catalyst design}, volume = {147}, year = {2025}, }
• (2025). Catalyst-controlled regiodivergent synthesis of bicyclo[2.1.1]hexanes via photochemical strain-release cycloadditions. JACS, 147(18), 14936--14944. (www)

  @article{ , abstract = {Bicyclo[2.1.1]hexane is an emerging scaffold in various pharmaceutical settings, but the scarcity of approaches to target different regioisomers from a common starting material prevents targeting a broader range of chemical space. Herein, we demonstrate a new design for the photocatalyst-controlled regiodivergent synthesis of this scaffold. Of particular interest is that the synthesis of two distinct substitution patterns was achieved under photochemical conditions with catalyst control. This was possible due to the activating group, N -methylimidazole, not only playing an important role in guiding divergent pathways but also enabling transformation to various functional groups. Transient absorption spectroscopy discerned between the regiodivergent mechanisms, as assignable bands consistent with electron transfer and energy transfer processes were distinctively observed, depending on the identity of the photocatalyst.}, archive = {J_JACS}, author = {Yu-Che Chang and María Martín and Kingsley Bortey and Quentin Lefebvre and Thomas Fessard and Christophe Salome and Ricardo Javier Vázquez and M. Kevin Brown}, doi = {10.1021/jacs.5c02425}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14936--14944}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalyst-controlled regiodivergent synthesis of bicyclo[2.1.1]hexanes via photochemical strain-release cycloadditions}, volume = {147}, year = {2025}, }
• (2025). “Clicked” hydrazone photoswitches. JACS, 147(18), 14930--14935. (www)

  @article{ , abstract = {The length of the linker connecting a photoswitch to a material significantly influences the latter’s properties, with “zero-length” linkers being ideal for optimal photomodulation. The 1,2,3-triazole formed through the “click” reaction between an azide and an alkyne has been used as such a linking motif in various areas of research spanning from materials to biological chemistry. However, its effect, as well as that of its regioisomers, on the photoswitching properties has not been fully elucidated. Here, we report on a series of triazole-containing hydrazone photoswitches, investigating how the connectivity (1,4 vs 1,5) between the triazole and the switch affects the photoswitching properties. The structure–property analysis and DFT/TD-DFT calculations show that the switching efficiency of N-connected 1,4-triazole hydrazones is lower than their C-connected counterparts, while the 1,5-triazole hydrazone exhibits an overall better photoswitching efficiency.}, archive = {J_JACS}, author = {Daniil Sosnin and Mohammad Izadyar and Syed Ali Abbas Abedi and Xiaogang Liu and Ivan Aprahamian}, doi = {10.1021/jacs.5c02183}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14930--14935}, shortjournal = {J. Am. Chem. Soc.}, title = {“Clicked” hydrazone photoswitches}, volume = {147}, year = {2025}, }
• (2025). Photoelectrochemical imaging of charge separation between MoS2 triangles and insulating SiO2 support. JACS, 147(18), 14924--14929. (www)

  @article{ , abstract = {The role of the insulating support in photocatalysis is poorly understood. Using high-resolution photo-scanning electrochemical microscopy (photo-SECM), we observed significant spatial charge separation in few-layer-thick molybdenum disulfide (MoS 2 ) triangles attached to a SiO 2 substrate. Spatially resolved surface photovoltage (SPV) measurements revealed that photogenerated holes migrate from MoS 2 to the SiO 2 surface and travel laterally over distances exceeding 2 μm, driven by the built-in electric field of ∼1.7 kV/cm. In thicker and less uniform flakes, the charge separation is dominated by internal driving forces within MoS 2 , without significant contribution from SiO 2 . These findings underscore the importance of insulator–semiconductor interactions for effective charge separation, suggesting a new strategy for optimizing photocatalytic systems.}, archive = {J_JACS}, author = {Ziyuan Wang and Qing Huang and Chenwei Ni and Tianyu Bo and Fengtao Fan and Michael V. Mirkin}, doi = {10.1021/jacs.5c02136}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14924--14929}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoelectrochemical imaging of charge separation between MoS2 triangles and insulating SiO2 support}, volume = {147}, year = {2025}, }
• (2025). Copper-catalyzed C–B(sp3) bond formation through the intermediacy of Cu–B(sp3) complex. JACS, 147(18), 14915--14923. (www)

  @article{ , abstract = {The vast majority of transition metal (TM) catalyzed borylative transformations rely on TM–B(sp 2 ) complexes. Contrastingly, the chemistry of TM–B(sp 3 ) species and their potential in catalytic borylation remain surprisingly underdeveloped, due probably to the lack of suitable boron(sp 3 ) reagents. Herein, we employ our recently developed sp 2 -sp 3 diboron reagent to successfully enable a copper-catalyzed hydroboration of allenes for C–B(sp 3 ) bond formation. A comprehensive mechanistic study, including the isolation and structural characterization of a Cu–B(sp 3 ) complex, substantiates the presence of a Cu–B(sp 3 ) intermediate in the catalytic cycle.}, archive = {J_JACS}, author = {Zhanqiang Ye and Chun Yin Kwok and Sze Lam Lam and Linlin Wu and Hairong Lyu}, doi = {10.1021/jacs.5c00974}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14915--14923}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper-catalyzed C–B(sp3) bond formation through the intermediacy of Cu–B(sp3) complex}, volume = {147}, year = {2025}, }
• (2025). Aryl acid-alcohol cross-coupling: C(sp3)–C(sp2) bond formation from nontraditional precursors. JACS, 147(18), 14905--14914. (www)

  @article{ , abstract = {Alcohols and aryl carboxylic acids are among the most commercially abundant, synthetically versatile, and operationally convenient building blocks in organic chemistry. Despite their widespread availability, the direct formation of C(sp 3 )–C(sp 2 ) bonds from these functional groups remains a challenge. Recently, our group developed robust protocols to harness alcohols as alkyl radical precursors, but the activation of aryl acids remains relatively unexplored. Herein, we describe the merger of N-heterocyclic carbene (NHC)-mediated deoxygenation and nickel-mediated decarbonylation of aryl acids toward C(sp 3 )–C(sp 2 ) bond formation. The utility of this method is demonstrated through the synthesis of a diverse range of aryl–alkyl cross-coupled products and the late-stage functionalization of complex molecules, including drugs, natural products, and biomolecules.}, archive = {J_JACS}, author = {Eva Lin and Johnny Z. Wang and Edna Mao and Stephanie Tsang and Kurtis M. Carsch and Cesar N. Prieto Kullmer and Ryan E. McNamee and Jeffrey R. Long and Chi “Chip” Le and David W.C. MacMillan}, doi = {10.1021/jacs.4c15827}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14905--14914}, shortjournal = {J. Am. Chem. Soc.}, title = {Aryl acid-alcohol cross-coupling: C(sp3)–C(sp2) bond formation from nontraditional precursors}, volume = {147}, year = {2025}, }
• (2025). A foundational shift in models for enzyme function. JACS, 147(18), 14884--14904. (www)

  @article{ , abstract = {This Perspective addresses the unresolved, and still hotly contested, question of how enzymes transition from stable enzyme–substrate (ES) complexes to successful, femtosecond barrier crossings. By extending Marcus theory to enzyme-catalyzed reactions, we argue that environmental reorganization of the protein scaffold, together with associated water molecules, achieves the intersection of reactant and product potential energy surfaces. After discussing the experimentally demonstrated importance of reduced activation enthalpy in enzyme-catalyzed transformations, we describe new methodologies that measure the temperature dependence of (i) time-averaged hydrogen/deuterium exchange into backbone amides and (ii) time-dependent Stokes shifts to longer emission wavelengths in appended chromophores at the protein/water interface. These methods not only identify specific pathways for the transfer of thermal energy from solvent to the reacting bonds of bound substrates but also suggest that collective thermally activated protein restructuring must occur very rapidly (on the ns–ps time scale) over long distances. Based on these findings, we introduce a comprehensive model for how barrier crossing takes place from the ES complex. This exploits the structural preorganization inherent in protein folding and subsequent conformational sampling, which optimally positions essential catalytic components within ES ground states and correctly places reactive bonds in the substrate(s) relative to embedded energy transfer networks connecting the protein surface to the active site. The existence of these anisotropic energy distribution pathways introduces a new dimension into the ongoing quest for improved de novo enzyme design.}, archive = {J_JACS}, author = {Judith P. Klinman and Susan M. Miller and Nigel G. J. Richards}, doi = {10.1021/jacs.5c02388}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14884--14904}, shortjournal = {J. Am. Chem. Soc.}, title = {A foundational shift in models for enzyme function}, volume = {147}, year = {2025}, }
• (2025). Recent advances in solid-state batteries. JACS, 147(18), 14881--14883. (www)

  @article{ , archive = {J_JACS}, author = {Kelsey B. Hatzell and Linda F. Nazar}, doi = {10.1021/jacs.5c06058}, journal = {Journal of the American Chemical Society}, month = {5}, number = {18}, pages = {14881--14883}, shortjournal = {J. Am. Chem. Soc.}, title = {Recent advances in solid-state batteries}, volume = {147}, year = {2025}, }
• (2025). Correction to “Unusual phospholipids from morganella morganii linked to depression”. JACS, 147(17), 14879--14880. (www)

  @article{ , archive = {J_JACS}, author = {Sunghee Bang and Yern-Hyerk Shin and Sung-Moo Park and Lei Deng and R. Thomas Williamson and Daniel B. Graham and Ramnik J. Xavier and Jon Clardy}, doi = {10.1021/jacs.5c05127}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14879--14880}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Unusual phospholipids from morganella morganii linked to depression”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Nontraditional fragment couplings of alcohols and carboxylic acids: C(sp3)–C(sp3) cross-coupling via radical sorting”. JACS, 147(17), 14878. (www)

  @article{ , archive = {J_JACS}, author = {Holt A. Sakai and David W. C. MacMillan}, doi = {10.1021/jacs.5c05046}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14878}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Nontraditional fragment couplings of alcohols and carboxylic acids: C(sp3)–C(sp3) cross-coupling via radical sorting”}, volume = {147}, year = {2025}, }
• (2025). Lattice hydrogen involved electrocatalytic nitrate reduction to hydroxylamine. JACS, 147(17), 14869--14877. (www)

  @article{ , abstract = {Electrocatalytic nitrate reduction to hydroxylamine (ENRH) provides a sustainable strategy for NH 2 OH synthesis under ambient conditions. At present, active hydrogen (*H) derived from water dissociation has been widely used as a H-source for nitrate hydrogenation, bringing a big challenge for ENRH. On the one hand, insufficient *H would lead to the accumulation of nitrite. On the other hand, sufficient *H with high reduction ability would induce over-hydrogenation of hydroxylamine to ammonia. To overcome this challenge, herein, we propose to utilize lattice hydrogen (H lat ) with an appropriate reduction ability as the H-source for ENRH. We design and construct a Cu-MnO 2 H x electrocatalyst, in which the Cu-triggered Jahn–Teller distortion of [MnO 6 ] octahedron significantly increases the number of H lat . The Faradaic efficiency and yield of NH 2 OH are as high as 91.1% and 396.6 mmol g cat. –1 h –1 over Cu-MnO 2 H x , outperforming most of the reported catalysts. The combined results of isotopic tracking experiments and theoretical calculations prove the enrichment and buffer functions of H lat , which can provide an abundant H-source for nitrate’s selective reduction to hydroxylamine.}, archive = {J_JACS}, author = {Chengying Guo and Minghao Guo and Yuhan Zhang and Shuhe Han and Yifu Yu}, doi = {10.1021/jacs.5c04863}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14869--14877}, shortjournal = {J. Am. Chem. Soc.}, title = {Lattice hydrogen involved electrocatalytic nitrate reduction to hydroxylamine}, volume = {147}, year = {2025}, }
• (2025). Tuning interlayer couplings and stabilizing 2D perovskite lattices through intercalation chemistry. JACS, 147(17), 14856--14868. (www)

  @article{ , abstract = {Two-dimensional (2D) organic–inorganic hybrid lead halide perovskites are promising semiconductors for optoelectronics, spintronics, and ferroelectrics due to their versatile structural and physical properties enabled by a variety of organic spacer cations. While previous research has focused on new spacer cations for templating 2D perovskite structures and influencing their properties, the intercalation of functional molecules within the organic layers has been less explored. Here, we demonstrate the intercalation of iodine within the organic sublattice as an effective tool to tune interlayer electronic interactions and stabilize 2D perovskite structures that would otherwise not form. We synthesized and determined the single-crystal structures of seven new iodine-intercalated 2D perovskites with varying spacer cations and inorganic compositions. The intercalated iodine bridges neighboring inorganic layers via halogen bonding with the apical iodides, leading to interlayer vibrational and electronic couplings. The iodine intercalation enhances the lattice rigidity, which decreases phonon–phonon scattering and exciton–phonon coupling. Adjusting the inorganic composition further tunes the electronic band structures, because iodine’s frontier orbitals contribute differently to the band edge states, leading to varied band alignments and photoluminescence quenching behaviors. Moreover, a decreased anisotropic emission polarization is observed after iodine intercalation due to the decreased in-plane confinement of the excitons. Our results demonstrate iodine intercalation as a powerful tool for tuning the structural and optoelectronic properties of 2D perovskites.}, archive = {J_JACS}, author = {Tianhao Zhang and Mingyuan Li and Xinyu Li and Xiaofan Jiang and Yu Tao and Shixuan Zheng and Jiazhen Gu and Nanlong Zheng and Guangsheng Bai and Meng Zhang and Chen Li and Yan Guan and Bingwu Wang and Yongping Fu}, doi = {10.1021/jacs.5c04810}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14856--14868}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning interlayer couplings and stabilizing 2D perovskite lattices through intercalation chemistry}, volume = {147}, year = {2025}, }
• (2025). N-heterocyclic carbene polymer-stabilized au nanowires for selective and stable reduction of CO2. JACS, 147(17), 14845--14855. (www)

  @article{ , abstract = {The structural stability of nanocatalysts during electrochemical CO 2 reduction (CO 2 RR) is crucial for practical applications. However, highly active nanocatalysts often reconstruct under reductive conditions, requiring stabilization strategies to maintain activity. Here, we demonstrate that the N -heterocyclic carbene (NHC) polymer stabilizes Au nanowire (NW) catalysts for selective CO 2 reduction to CO over a broad potential range, enabling coupling with Cu NWs for one-step tandem conversion of CO 2 to C 2 H 4 . By combining the hydrophobicity of the polystyrene chain and the strong binding of NHC to Au, the polymer stabilizes Au NWs and promotes CO 2 RR to CO with excellent selectivity (>90%) across −0.4 V to −1.0 V (vs RHE), a significantly broader range than unmodified Au NWs (−0.5 V to −0.7 V). Stable CO 2 RR at negative potentials yields a high j CO of 142 A/g Au at −1.0 V. In situ ATR-IR analysis indicates that the NHC polymer regulates the water microenvironment and suppresses hydrogen evolution at high overpotential. Moreover, NHC-Au NWs maintain excellent stability during 10 h of CO 2 RR testing, preserving the NW morphology and catalytic performance, while unmodified NWs degrade into nanoparticles with reduced activity and selectivity. NHC-Au NWs can be coupled with Cu NWs in a flow cell to catalyze CO 2 RR to C 2 H 4 with 58% efficiency and a partial current density of 70 mA/cm 2 (overall C 2 product efficiency of 65%). This study presents an adaptable strategy to enhance the catalyst microenvironment, ensure stability, and enable efficient tandem CO 2 conversion into value-added hydrocarbons.}, archive = {J_JACS}, author = {Yuliang Chen and Kecheng Wei and Hanyi Duan and Haobo Sun and Ziyan Yu and Ahsan Zohaib and Pengcheng Zhu and Jie He and Shouheng Sun}, doi = {10.1021/jacs.5c04742}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14845--14855}, shortjournal = {J. Am. Chem. Soc.}, title = {N-heterocyclic carbene polymer-stabilized au nanowires for selective and stable reduction of CO2}, volume = {147}, year = {2025}, }
• (2025). NHC-mediated radical acylation catalyzed by thiamine- and flavin-dependent enzymes. JACS, 147(17), 14837--14844. (www)

  @article{ , abstract = {Cross-coupling reactions between short-lifetime radicals are challenging reactions in organic chemistry. Here, we report the development of an N -heterocyclic carbene (NHC)-mediated radical coupling reaction based on the catalytic machinery of thiamine- and flavin-dependent enzymes. Through a series of enzyme screenings, we found that acetolactate synthase from Thermobispora bispora (TbALS) and its engineered variants exhibit promising catalytic activity toward abiotic radical acylation reactions of α-bromo carbonyl compounds. Notably, the TbALS variant has higher catalytic activity for small nonaromatic substrates despite forming less stable radical intermediates. Furthermore, the catalytic system of TbALS can be applied to photocatalytic reactions utilizing the photoredox properties of FAD. Nonbenzylic alkyl radicals generated from N -acyloxyphthalimides are efficiently converted into the corresponding dialkyl ketones under irradiation of a blue LED. These findings highlight the utility of thiamine- and flavin-dependent enzymes for achieving selective cross-coupling reactions of short-lifetime radicals.}, archive = {J_JACS}, author = {Shunsuke Kato and Shuto Fujisawa and Yuto Adachi and Mitsuhiro Bandai and Yutaro Mori and Seiji Mori and Tomokazu Shirai and Takashi Hayashi}, doi = {10.1021/jacs.5c04484}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14837--14844}, shortjournal = {J. Am. Chem. Soc.}, title = {NHC-mediated radical acylation catalyzed by thiamine- and flavin-dependent enzymes}, volume = {147}, year = {2025}, }
• (2025). Inhibiting glycolysis and disrupting the mitochondrial HK2–VDAC1 Protein–Protein interaction using a bifunctional lonidamine-conjugated metal probe for combating triple-negative breast cancer. JACS, 147(17), 14824--14836. (www)

  @article{ , abstract = {Triple-negative breast cancer (TNBC) relies primarily on aerobic glycolysis for energy and rapid cancer cell proliferation. Hexokinase 2 (HK2), a key enzyme regulating glycolysis, is overexpressed in TNBC, promoting tumor cell proliferation and apoptosis resistance by interacting with the mitochondrial membrane’s voltage-dependent anion channel 1 (VDAC1). However, the development of bioactive molecules for effectively disrupting the HK2–VDAC1 interaction remains challenging. Herein, we have modified londamine (LND) with an iridium(III) complex to create bifunctional far-red probe 1 . This complex not only has the ability to distinguish TNBC cells from normal cells by probing HK2 in mitochondria, but also significantly enhances antitumor activity by inhibiting mitochondrial glycolysis and effectively disrupting the HK2–VDAC1 interaction. This led to increased Bax–VDAC1 interaction, opening of the mitochondrial permeability transition pores (MPTPs), and generation of ROS, ultimately leading to mitochondrial dysfunction and enhanced cancer cell apoptosis. Probe 1 also demonstrated stronger antiproliferative activity than LND alone in a TNBC mouse model by targeting the HK2–VDAC1 interaction without causing overt toxicity. This work showcases the potential of probe 1 as an effective therapeutic agent for TNBC by inhibiting the mitochondrial HK2–VDAC1 interaction.}, archive = {J_JACS}, author = {Ling Wang and Lingtan Kong and Ding-Qi Zhang and Liuqi Ye and Sang-cuo Nao and Daniel Shiu-Hin Chan and Xueying Li and Yutong Peng and Lijun Yang and Chun-Yuen Wong and Vincent Kam Wai Wong and Wanhe Wang and Hui Chao and Chung-Hang Leung}, doi = {10.1021/jacs.5c04233}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14824--14836}, shortjournal = {J. Am. Chem. Soc.}, title = {Inhibiting glycolysis and disrupting the mitochondrial HK2–VDAC1 Protein–Protein interaction using a bifunctional lonidamine-conjugated metal probe for combating triple-negative breast cancer}, volume = {147}, year = {2025}, }
• (2025). Manipulating electron structure through dual-interface engineering of 3C-SiC photoanode for enhanced solar water splitting. JACS, 147(17), 14815--14823. (www)

  @article{ , abstract = {Interface engineering is crucial for enhancing the efficiency of semiconductor-based solar energy devices. In this work, we report a novel dual-interface engineering strategy by designing a Ni(OH) 2 /Co 3 O 4 /3C-SiC photoanode that achieves remarkable enhancements in photoelectrochemical (PEC) water splitting performance. The optimized photoanode delivers a photocurrent density of 1.68 mA cm –2 at 1.23 V vs the reversible hydrogen electrode (RHE), representing an 8-fold increase compared to pristine 3C-SiC, along with excellent operational stability. In this architecture, Co 3 O 4 serves as a highly efficient hole-extraction layer and forms a p–n junction with 3C-SiC, enhancing the separation of photogenerated electron–hole pairs. At the Ni(OH) 2 /Co 3 O 4 interface, the formation of Ni–O–Co bonds facilitates rapid charge transfer and accelerates oxygen evolution reaction (OER) kinetics. The microwave photoconductivity decay (μ-PCD) measurements confirm a prolonged minority carrier lifetime, demonstrating the critical role of electronic structure modulation in improving charge separation and reducing recombination. Using advanced synchrotron radiation and X-ray absorption spectroscopy, we unveil critical modifications to the interfacial electronic structure induced by the dual-interface engineering and their roles in enhancing PEC performance. These findings establish a clear relationship between electronic structure modulation, charge carrier dynamics, and PEC performance, providing new insights into interface design strategies for highly efficient solar-driven water splitting systems.}, archive = {J_JACS}, author = {Hui Zeng and Satoru Yoshioka and Weimin Wang and Zhongyuan Han and Ivan G. Ivanov and Hongwei Liang and Vanya Darakchieva and Jianwu Sun}, doi = {10.1021/jacs.5c04005}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14815--14823}, shortjournal = {J. Am. Chem. Soc.}, title = {Manipulating electron structure through dual-interface engineering of 3C-SiC photoanode for enhanced solar water splitting}, volume = {147}, year = {2025}, }
• (2025). Bilayer Metal–Organic framework altermagnets with electrically tunable spin-split valleys. JACS, 147(17), 14806--14814. (www)

  @article{ , abstract = {Bilayer altermagnets featuring layer-mediated spin-valley locking hold significant promise in spintronics and valleytronics. In this study, we perform a comprehensive symmetry analysis of bilayer altermagnets and identify seven spin point group candidates with spin-valley-layer coupling, including 2 2, 2 2 2 2 1 2, 2 4̅, 1 4 2 2 2 2, 2 4̅ 2 2 1 m , 1 3 2 2, and 1 6 2 2 2 2. Focusing on the platform of bilayer metal–organic frameworks, we theoretically design materials with S 4 symmetry through chemical modification, achieving spin-splitting in the valence band. Furthermore, the spin valleys from different layers exhibit tunable responses to external static gate electric fields, enabling precise control of spin-splitting. Our findings presented a framework that integrates spin, valley, and layer degrees of freedom in bilayer altermagnets, paving the way for nanoscale spintronics and valleytronics applications.}, archive = {J_JACS}, author = {Yixuan Che and Haifeng Lv and Xiaojun Wu and Jinlong Yang}, doi = {10.1021/jacs.5c04106}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14806--14814}, shortjournal = {J. Am. Chem. Soc.}, title = {Bilayer Metal–Organic framework altermagnets with electrically tunable spin-split valleys}, volume = {147}, year = {2025}, }
• (2025). Nickel-catalyzed asymmetric synthesis of ambiphilic secondary phosphine oxides. JACS, 147(17), 14797--14805. (www)

  @article{ , abstract = {The synthesis of ambiphilic compounds, which possess both strong nucleophilic and electrophilic functional groups, presents a significant challenge due to their propensity to self-react, forming oligomers or polymers. We have successfully achieved the nickel-catalyzed asymmetric synthesis of ambiphilic P -stereogenic alkenyl secondary phosphine oxides from a tailored primary phosphine oxide by leveraging their controversial stability and reactivity. This method demonstrates remarkable tolerance toward a wide range of unactivated alkynes, including those derived from natural products and medicinally relevant molecules, thus providing a universal synthon for P -stereogenic phosphines with high enantioselectivity and regioselectivity. The ambiphilic product exhibits interesting orthogonal reactivities with both nucleophiles and electrophiles and can be easily converted to a variety of medicinally relevant P -stereogenic compounds.}, archive = {J_JACS}, author = {Wei-Han Wang and Si-Yu Zhang and Yu-Xiang Zhang and Yin-Qi Wang and Qing-Wei Zhang}, doi = {10.1021/jacs.5c03897}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14797--14805}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-catalyzed asymmetric synthesis of ambiphilic secondary phosphine oxides}, volume = {147}, year = {2025}, }
• (2025). Synergistic LMCT and ni catalysis for methylative cross-coupling using tert-butanol: Modulating radical pathways via selective bond homolysis. JACS, 147(17), 14785--14796. (www)

  @article{ , abstract = {Ligand-to-metal charge transfer (LMCT) excitation has emerged as a potent strategy for the selective generation of heteroatom-centered radicals, yet its full potential in modulating open-shell radical pathways remains underexplored. Here, we present a photocatalytic methylative cross-coupling reaction that capitalizes on the synergistic interplay between LMCT and Ni catalysis, enabling the use of tert -butanol as an efficient and benign methylating reagent. The electron-deficient ligand 2,6-ditrifluoromethyl benzoate facilitates Ce(IV)-mediated bond scission of tert -butanol, generating a methyl radical that is subsequently captured by the Ni catalytic cycle to form C–CH 3 bonds. Under mild reaction conditions, this strategy affords efficient methylation of sp 3 carbons adjacent to carbonyls and sp 2 centers, demonstrating broad functional group tolerance and applicability in late-stage functionalization of bioactive molecules. Additionally, trideuteromethylative coupling can be facilely achieved using commercial tert -butanol- d 10 . This approach circumvents the need for traditional tert -butoxy radical precursors, such as peroxides, while strategically modulating the radical pathway to favor β-scission and suppress unwanted tert -butoxy radical formation in solution. Mechanistic studies reveal that the benzoate ligand plays a crucial role in enabling LMCT excitation and facilitating methyl radical generation, supporting a concerted Ce–OR and β-C–C bond homolysis mechanism, further evidenced by the modulation of regioselectivity in alkoxy radical-mediated β-scission.}, archive = {J_JACS}, author = {Lingfei Duan and Yunzhi Lin and Qing An and Zhiwei Zuo}, doi = {10.1021/jacs.5c03711}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14785--14796}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic LMCT and ni catalysis for methylative cross-coupling using tert-butanol: Modulating radical pathways via selective bond homolysis}, volume = {147}, year = {2025}, }
• (2025). Singlet carbenes are stereoinductive main group ambiphiles. JACS, 147(17), 14777--14784. (www)

  @article{ , abstract = {Stereogenic units are a critical source of molecular complexity, but their stereoselective formation via main group ambiphiles─which are suitable for derivatizing a wide scope of functionalities─is largely unexplored. Herein, using chiral cyclic (alkyl)(amino)carbenes ( Chi CAACs), we study stereoinduction during the oxidative addition of E–H σ-bonds (E = C, N, O, Si, P). Through computational modeling, the relationship between stereochemical outcome and mechanism is elucidated, providing insight into when and why Chi CAACs exhibit excellent stereoselectivities. Altogether, these results demonstrate the potential for chiral main group ambiphiles to generate stereogenic units in a highly controlled manner opening avenues for applying “metal-like” reactivity in metal-free asymmetric syntheses.}, archive = {J_JACS}, author = {Jan Lorkowski and Patrick Yorkgitis and Fanny Morvan and Jennifer Morvan and Nicolas Vanthuyne and Thierry Roisnel and Milan Gembicky and Guy Bertrand and Marc Mauduit and Rodolphe Jazzar}, doi = {10.1021/jacs.5c03845}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14777--14784}, shortjournal = {J. Am. Chem. Soc.}, title = {Singlet carbenes are stereoinductive main group ambiphiles}, volume = {147}, year = {2025}, }
• (2025). Neutral all-metal σ-aromaticity in a rhombic cluster. JACS, 147(17), 14769--14776. (www)

  @article{ , abstract = {Aromaticity is a cornerstone concept in chemistry, playing a crucial role in understanding molecular stability and reactivity. Traditionally, aromaticity has been primarily associated with cyclic planar conjugated organic molecules composed solely of carbon, but it has recently expanded to include metal-containing systems. However, metal-only aromatics remain extremely scarce. Here, we present the first neutral all-metal aromatic cluster with a rhombic geometry. X-ray crystallography reveals that the rhombic Al 2 Pd 2 core is stabilized by an innovative double-layer N–P ligand framework, featuring essentially the same Al–Pd bond lengths (2.4706(4) and 2.4636(4) Å) and two planar tetracoordinate Al centers. Quantum chemical calculations provide compelling evidence for the two-electron σ-aromaticity in this molecule. Further research on the reactivity of the σ-aromatic Al 2 Pd 2 cluster reveals that it can accept lone-pair electron coordination and act as a two-electron reducing agent. This study not only extends the concept of aromaticity to neutral all-metal rhombic systems but also opens new horizons for the synthesis and exploration of novel all-metal aromatic clusters.}, archive = {J_JACS}, author = {Pengfei Chen and Yafei Li and Jing Ma and Jun Zhu and Jin Xie and Miquel Solà and Congqing Zhu and Qin Zhu}, doi = {10.1021/jacs.5c03828}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14769--14776}, shortjournal = {J. Am. Chem. Soc.}, title = {Neutral all-metal σ-aromaticity in a rhombic cluster}, volume = {147}, year = {2025}, }
• (2025). Mechanistic insights into copper-catalyzed asymmetric cyanation of allylic C–H bonds. JACS, 147(17), 14756--14768. (www)

  @article{ , abstract = {Direct C–H bond functionalization has emerged as one of the most powerful and practical strategies for the modification of drug molecules. We have recently disclosed a Cu/NFAS (NFAS = N -fluoroalkyl sufonamide) catalytic system that exhibits high site-, regio-, and enantioselectivity for the direct cyanation of allylic C–H bonds. Here, we present a mechanistic investigation of this catalyst system, including the elucidation of side reactions involved in the transformation. This work focuses on an in-depth analysis of the catalytic cycle based on kinetic studies by NMR spectroscopy and characterization of the catalyst speciation by EPR and UV–vis spectroscopy. These studies indicate that a fraction of NFAS is sacrificed to the side reactions of the Cu(II)-bounded N -centered radical (Cu(II)–NCR) species for the generation of silylated sulfonamides and (CN) 2 . The data also show a great dependence of the reaction yield and selectivity (hydrogen atom abstraction or HAA over side reactions) on the structure of the Cu(II)–NCR species. Kinetic studies and DFT calculations further reveal that oxidation of the CuCN species by NFAS, HAA process, and cyanation of Cu(II)–NCRs with TMSCN have comparable energy barriers, which collectively determine the rate of the overall C–H cyanation reaction.}, archive = {J_JACS}, author = {Jiayuan Li and Tilong Yang and Pinhong Chen and Farshad Shiri and Hairong Guan and Zhenyang Lin and Guosheng Liu}, doi = {10.1021/jacs.5c03680}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14756--14768}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic insights into copper-catalyzed asymmetric cyanation of allylic C–H bonds}, volume = {147}, year = {2025}, }
• (2025). Unsupervised machine learning prediction of a novel 1:3 intermetallic phase with the synthesis of TbIr3 (PuNi3-type) as experimental validation. JACS, 147(17), 14739--14755. (www)

  @article{ , abstract = {Crystal structure classification of binary intermetallic structures with 1:3 stoichiometry was done with machine learning algorithms. The data set included 97 features and a total of 2366 reported compounds adopting six different structure types. An unsupervised learning method based on principal component analysis (PCA) followed by clustering using the K-means method was applied to cluster compounds belonging to different structure types. With the recommendation engine, we predicted the expansion of the clusters and then identified the cluster/structure-type overlap. The PuNi 3 -type was among the clearly segregated structure types according to the unsupervised model, and a novel representative, TbIr 3 , was selected for experimental validation, adopting this structure. The final supervised machine learning predictions were done with partial least squares discriminant analysis (PLS-DA), support vector machine (SVM), and XGBoost, confidently predicting that the novel TbIr 3 belongs to the PuNi 3 -type with accuracies of 96.6, 99.8, and 99.9% respectively. Successful crystal structure segregation was attributed to a novel set of descriptors comprising both compositional and structural features. Given that the predicted PuNi 3 -type of the TbIr 3 phase could be controversial due to the extensive study of the Tb–Ir phase diagram and the reports of the TbIr 3 in two different structure types, we conducted two independent experimental structural validations to confirm the existence of TbIr 3 in the PuNi 3 -type structure. Subsequent theoretical validation explained that Ir–Ir contacts are the primary stability factor of TbIr 3 in the PuNi 3 -type structure compared to other structure types.}, archive = {J_JACS}, author = {Siddha Sankalpa Sethi and Arnab Dutta and Emil I. Jaffal and Nishant Yadav and Danila Shiryaev and Brian Hoang and Anirudh Machathi and Sangjoon Lee and Karabi Das and Partha Pratim Jana and Anton O. Oliynyk}, doi = {10.1021/jacs.5c03510}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14739--14755}, shortjournal = {J. Am. Chem. Soc.}, title = {Unsupervised machine learning prediction of a novel 1:3 intermetallic phase with the synthesis of TbIr3 (PuNi3-type) as experimental validation}, volume = {147}, year = {2025}, }
• (2025). Mechanical transitions in crystals: The low-temperature thermosalient transition of a mesogenic polyphenyl. JACS, 147(17), 14731--14738. (www)

  @article{ , abstract = {Thermosalient transitions are a subset of single-crystal-to-single-crystal (SCSC) transitions, in which the change of lattice parameters is highly anisotropic and very fast. As a result, crystals at the transition undergo macroscopic dynamical effects (hopping, jumping, and shattering). These transitions feature a conversion of heat to mechanical energy that can be exploited in the realization of advanced materials. Most thermosalient transitions are observed at temperatures higher than room temperature. Examples of low-temperature thermosalient transitions are rare. We describe a new example of a low-temperature thermosalient transition in a sexiphenyl compound. At about −40 °C, the parent single crystal (phase I) shatters into single crystal fragments of the new phase (phase II). The two phases have been studied by single-crystal X-ray analysis using a synchrotron source, variable-temperature Raman spectroscopy, and computational analysis of lattice normal vibration modes. A mechanism of the transition is proposed. We confirm colossal thermal expansion coefficients and supercells as reliable features of thermosalient transitions and add as a third feature a low-frequency principal optical vibration of the crystal lattice prompting the transition. Based on this, a roadmap for the automated prediction of thermosalient transitions in molecular crystals is also outlined.}, archive = {J_JACS}, author = {Emmanuele Parisi and Emanuela Santagata and Przemysław Kula and Jakub Herman and Sakuntala Gupta and Elena Simone and Salvatore Zarrella and Timothy M. Korter and Roberto Centore}, doi = {10.1021/jacs.5c03448}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14731--14738}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanical transitions in crystals: The low-temperature thermosalient transition of a mesogenic polyphenyl}, volume = {147}, year = {2025}, }
• (2025). Electrostatic stimulation of monopolar electrodes. JACS, 147(17), 14725--14730. (www)

  @article{ , abstract = {Changes in the electrostatic potential within an aqueous acidic solution induced by the passage of current between the Au disk of a stationary Au|Au ring disk electrode or stimulating electrode, SE, and a distant counter electrode made it possible to stimulate the reduction of selenous acid, H 2 SeO 3 , to elemental selenium at the concentric Au ring polarized at a fixed potential, just positive to its otherwise expected onset. This effect was ascribed to variations in the surface overpotential, η s , and, thus, in the rates of H 2 SeO 3 reduction along the ring, which we define, hereafter, as a monopolar electrode, ME. The stimulation efficiency could be accurately determined from a coulometric analysis of the peak for Se oxidation observed by subsequently scanning the ring linearly toward positive potentials to yield H 2 SeO 3 . Excellent quantitative agreement was obtained between the current flowing through the ME, I ME , and E ME o , as a function of I SE , and theoretical simulations employing COMSOL using parameters extracted from independent measurements performed under otherwise identical experimental conditions. This novel tactic is expected to open new prospects for gaining insight into surface diffusion and other interfacial dynamics phenomena, as well as local modifications in the microstructure of electrodes, such as etching.}, archive = {J_JACS}, author = {Arvind Singh Heer and Harlan Mantelli and Qi Han and Nicholas Georgescu and Daniel Scherson}, doi = {10.1021/jacs.5c03256}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14725--14730}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrostatic stimulation of monopolar electrodes}, volume = {147}, year = {2025}, }
• (2025). Manipulating aromaticity to redirect topochemical polymerization pathways. JACS, 147(17), 14715--14724. (www)

  @article{ , abstract = {Topochemical polymerization (TCP) represents an essential route to create regio- and stereoregular polymers through solid-state transformations. Herein, we present an innovative strategy for controlling topochemical polymerization pathways by tailoring the terminal group aromaticity in the para -azaquinodimethane (AQM) ring system. Substituting phenyl groups with less aromatic furyl units extends significant spin density delocalization across the conjugated core upon thermal activation, inducing significant diradicaloid characters at furyl positions and enabling unconventional reactivities in both solution and solid states. Thermal treatment in toluene yields a unique cyclophane dimer formed via furyl-methine C–C coupling, confirmed by X-ray crystallography, while solid-state reactions produce polymers formed via both intercolumnar furyl-methine coupling and intracolumnar methine–methine coupling. The spin-center-directed mechanism underlying these transformations is validated through theoretical modeling and isotopic labeling experiments. This study highlights the prowess of aromaticity modulation in functional pro-aromatic systems, which enables the synthesis of polymers with main chain structures that are otherwise difficult to access.}, archive = {J_JACS}, author = {Qingsong Zhang and Zhipeng Pei and Ah-Young Song and Miao Qi and Rebecca Shu Hui Khoo and Chongqing Yang and Tao Xia and Chen Zhou and Haiyan Mao and Zhiyuan Huang and Shiqi Lai and Yunfei Wang and Liang Z. Tan and Jeffrey A. Reimer and Jian Zhang and Michelle L. Coote and Yi Liu}, doi = {10.1021/jacs.5c03077}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14715--14724}, shortjournal = {J. Am. Chem. Soc.}, title = {Manipulating aromaticity to redirect topochemical polymerization pathways}, volume = {147}, year = {2025}, }
• (2025). Activating lattice oxygen in perovskite ferrite for efficient and stable photothermal dry reforming of methane. JACS, 147(17), 14705--14714. (www)

  @article{ , abstract = {Lattice oxygen (LO)-mediated photothermal dry reforming of methane (DRM) presents a promising approach to syngas production. However, realizing high DRM efficiency and durability remains challenging due to the difficulty in activating LOs in catalysts. Herein, we demonstrate that partially substituting Fe sites in perovskite ferrite (LaFeO 3 ) by Mn triggers LOs, bestowing the catalyst with superior activity and stability for photothermal DRM after modification with Ru. The Mn exchange induces a charge transfer from La to Mn, which combined with the incoming photoexcited electrons reconstructs the perovskite’s electronic structure, weakening the La–O–Mn bonds and facilitating the LO migration. Meanwhile, photogenerated holes migrate to surface LOs, further enhancing their reactivity to mediate DRM. Under light irradiation, the catalyst exhibits an outstanding syngas production rate (H 2 : 42.89 mol g Ru –1 h –1 , CO: 54.92 mol g Ru –1 h –1 ) while stably operating over 150 h. It also achieves a methane turnover frequency of 0.9 s –1 and a light-to-chemical energy efficiency of 15.3%, setting a benchmark for light-driven DRM performance. This work underscores the significance of exact site doping in metal oxides to fine-tune LO activity, providing valuable guidance for fabricating efficient catalysts for solar-powered redox reactions proceeded via the light-supported Mars–van Krevelen mechanism.}, archive = {J_JACS}, author = {Jilong Li and Jiwu Zhao and Sibo Wang and Kang-Shun Peng and Bo Su and Kunlong Liu and Sung-Fu Hung and Meirong Huang and Guigang Zhang and Huabin Zhang and Xinchen Wang}, doi = {10.1021/jacs.5c03098}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14705--14714}, shortjournal = {J. Am. Chem. Soc.}, title = {Activating lattice oxygen in perovskite ferrite for efficient and stable photothermal dry reforming of methane}, volume = {147}, year = {2025}, }
• (2025). Hexafluoroisopropanol solvent effects on enantioselectivity of dirhodium tetracarboxylate-catalyzed cyclopropanation. JACS, 147(17), 14694--14704. (www)

  @article{ , abstract = {In recent years, additives that modulate both reactivity and selectivity in rhodium-catalyzed reactions of aryldiazoacetates have become increasingly prominent. 1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) has been shown to have a profound effect on rhodium carbene reactivity and selectivity, especially on enabling carbene cyclopropanation in the presence of various nucleophilic poisons. HFIP also has a variable influence on the enantioselectivity of the reactions catalyzed by chiral dirhodium tetracarboxylates, and this study examines the fundamental properties of the rhodium carbene/HFIP system through experimentation, density functional theory (DFT), and molecular dynamics (MD) simulations. These studies revealed that the C 4 -symmetric bowl-shaped catalysts, which have been previously considered to be relatively rigid, experience far greater flexibility in this hydrogen bonding media, resulting in distortion of the bowl-shaped catalysts. These studies explain why even though a majority of the catalysts have a drop in enantioselectivity in HFIP, some catalysts, such as Rh 2 (TCPTAD) 4 , lead to a switch in enantioselectivity, whereas others, such as Rh 2 (NTTL) 4 , lead to a considerably enhanced enantioselectivity.}, archive = {J_JACS}, author = {Turki M. Alturaifi and Kristin Shimabukuro and Jack C. Sharland and Binh Khanh Mai and Evan A. Weingarten and Mithun C. Madhusudhanan and Djamaladdin G. Musaev and Peng Liu and Huw M. L. Davies}, doi = {10.1021/jacs.5c03007}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14694--14704}, shortjournal = {J. Am. Chem. Soc.}, title = {Hexafluoroisopropanol solvent effects on enantioselectivity of dirhodium tetracarboxylate-catalyzed cyclopropanation}, volume = {147}, year = {2025}, }
• (2025). Ferromagnetic Eu2SiO4 compound with a record low-field magnetocaloric effect and excellent thermal conductivity near liquid helium temperature. JACS, 147(17), 14684--14693. (www)

  @article{ , abstract = {Researchers in the field of magnetic refrigeration have recently been chronically committed to the development of magnetic refrigeration materials with a large magnetocaloric effect (MCE) at low magnetic fields. In practice, a brilliant magnetic refrigeration material should not only exhibit a large MCE but also have excellent thermal properties. Therefore, pursuing such an ideal combination in materials becomes a necessity to realize the application of magnetic refrigeration. In this work, a good combination of MCE and thermal properties is presented in the ferromagnetic Eu 2 SiO 4 compound. The maximum magnetic entropy change (−Δ S M max ) reaches an impressive value of 21.6 J·kg –1 ·K –1 under a magnetic field change of 0–1 T, creating a new record for materials in the liquid helium temperature range. Heat capacity data show that the peak value of specific heat reaches 107.9 J·kg –1 ·K –1 near the liquid helium temperature. In addition, this compound exhibits excellent thermal conductivity, with a considerable value of 1.52 W·m –1 ·K –1 at 4.2 K, which surpasses most oxides and is comparable to that of the commercial regenerative material HoCu 2 . Remarkable magnetocaloric parameters and thermal properties enable Eu 2 SiO 4 to be a promising cryogenic magnetic refrigerant. The magnetic refrigeration experiments further prove it to be a brilliant magnetic refrigerant operating in the liquid helium temperature range.}, archive = {J_JACS}, author = {Zhaojun Mo and Jiaxin Jiang and Lu Tian and Huicai Xie and Yan Li and Xinqi Zheng and Lei Zhang and Xinqiang Gao and Zhenxing Li and Guodong Liu and Lingwei Li and Jun Shen}, doi = {10.1021/jacs.5c02997}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14684--14693}, shortjournal = {J. Am. Chem. Soc.}, title = {Ferromagnetic Eu2SiO4 compound with a record low-field magnetocaloric effect and excellent thermal conductivity near liquid helium temperature}, volume = {147}, year = {2025}, }
• (2025). Electric-field-induced giant resonant enhancement of second harmonic generation in two-dimensional hybrid perovskite. JACS, 147(17), 14677--14683. (www)

  @article{ , abstract = {For the advancement of optical information technology, nonlinear optical systems with tunable and reconfigurable functionality are essential. Electric-field-induced second harmonic generation (EFISH) is a promising approach, enabling electrical control over nonlinear light-matter interactions. However, efficient, simple, and highly adaptable EFISH materials or systems have yet to be reported. In this study, we demonstrate that two-dimensional (2D) organic–inorganic hybrid perovskites (OIHPs) exhibit a remarkable EFISH performance with significant tunability. The second harmonic generation is dramatically enhanced at excitonic resonance, increasing by more than 2 orders of magnitude when a 70 kV/cm electric field is applied. In addition, this efficient EFISH is observed even in nonpolar and nonchiral 2D-OIHPs. This study opens up the broader potential of low-dimensional OIHPs as nonlinear optical materials, leading to the development of tunable and dynamic nonlinear optical systems with simple and versatile material designs.}, archive = {J_JACS}, author = {Daichi Okada and Fumito Araoka}, doi = {10.1021/jacs.5c02956}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14677--14683}, shortjournal = {J. Am. Chem. Soc.}, title = {Electric-field-induced giant resonant enhancement of second harmonic generation in two-dimensional hybrid perovskite}, volume = {147}, year = {2025}, }
• (2025). Decoding the competing effects of dynamic solvation structures on nuclear magnetic resonance chemical shifts of battery electrolytes via machine learning. JACS, 147(17), 14667--14676. (www)

  @article{ , abstract = {Understanding the solvation structure of electrolytes is critical for optimizing the electrochemical performance of rechargeable batteries as it directly influences properties such as ionic conductivity, viscosity, and electrochemical stability. The highly complex structures and strong interactions in high-concentration electrolytes make accurate modeling and interpretation of their “structure–property” relationships even more challenging with spectroscopic methods. In this study, we present a machine learning-based approach to predict dynamic 7 Li NMR chemical shifts in LiFSI/DME electrolyte solutions. Additionally, we provide a comprehensive structural analysis to interpret the observed chemical shift behavior in experiments, particularly the abrupt changes in 7 Li chemical shifts at high concentrations. Using advanced modeling techniques, we quantitatively establish the relationship between the molecular structure and NMR spectrum, offering critical insights into solvation structure assignments. Our findings reveal the coexistence of two competing local solvation structures that shift in dominance as electrolyte concentration approaches the concentrated limit, leading to an anomalous reversal of 7 Li NMR chemical shift in the experiment. This work provides a detailed molecular-level understanding of the intricate solvation structures probed by NMR spectroscopy, leading the way for an enhanced electrolyte design.}, archive = {J_JACS}, author = {Qi You and Yan Sun and Feng Wang and Jun Cheng and Fujie Tang}, doi = {10.1021/jacs.5c02710}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14667--14676}, shortjournal = {J. Am. Chem. Soc.}, title = {Decoding the competing effects of dynamic solvation structures on nuclear magnetic resonance chemical shifts of battery electrolytes via machine learning}, volume = {147}, year = {2025}, }
• (2025). Cu-facet selective sulfur chemistry for ultrastable Sodium–Sulfur batteries. JACS, 147(17), 14659--14666. (www)

  @article{ , abstract = {Sodium–sulfur batteries face significant challenges due to the high solubility of sodium polysulfides and the resulting shuttle effect, which compromise cycling stability and efficiency. This study introduces the Cu(111) facet-selective reactivity of sulfur redox, which promotes the formation of a stable intermediate, NaCu 5 S 3 , enabling efficient sulfur conversion, rapid ionic transport, and a fully solid–solid reaction pathway. The system achieves exceptional performance, retaining a specific capacity of 602 mAh g –1 over 800 cycles at 0.5 A g –1 and delivering 463 mAh g –1 at a high current density of 5 A g –1 in ether-based electrolytes, representing the highest rate capability reported for cathodes with sulfur content ≥ 60 wt %. Comparative studies with Cu(100), Cu(110), and aluminum substrates highlight the unique reactivity of Cu(111). Density functional theory calculations further reveal the structural and electronic interactions between copper and sodium polysulfides, clarifying the facet-dependent mechanisms. This work establishes facet engineering as a promising approach to modulating sulfur redox pathways and improving the electrochemical reversibility in metal–sulfur batteries.}, archive = {J_JACS}, author = {Xin Xu and Shiying Ren and Huan Li and Shi-Zhang Qiao}, doi = {10.1021/jacs.5c02751}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14659--14666}, shortjournal = {J. Am. Chem. Soc.}, title = {Cu-facet selective sulfur chemistry for ultrastable Sodium–Sulfur batteries}, volume = {147}, year = {2025}, }
• (2025). Design of twisted two-dimensional heterostructures and performance regulation descriptor for electrocatalytic ammonia production from nitric oxide. JACS, 147(17), 14647--14658. (www)

  @article{ , abstract = {The electrocatalytic reduction of nitric oxide (NO) to ammonia (NH 3 ) represents an attractive alternative for valorizing waste NO streams (NORR). However, discovering efficient catalysts for NO-to-NH 3 conversion remains challenging. We have designed metal-intercalated twisted graphene-BN heterostructures, in which metal atoms act as electron-transfer bridges. The twisted configuration facilitates cross-interface charge transfer, redistributing electrons from the graphene–metal interface to the metal–BN interface and BN surface. This electronic modulation enables boron atom adjacent to the metal center in BN to serve as active sites, promoting strong chemisorption and enhanced activation of NO. After high-throughput screening of the stability and NO capture ability of various transition metal-intercalated twisted heterostructures, we have investigated systematically the NORR pathways across 30 candidates. The results show that the rBN-Ti-Gθ and rBN-V-Gθ heterostructures exhibit exceptional NO-to-NH 3 catalytic performance under optimized twisting conditions. Additionally, using sure independence screening and sparsifying operator (SISSO) for model training, we propose a descriptor and establish a relationship between the twist angle and catalytic activity. This study bridges the gap in applying twisted heterostructures to NORR electrocatalysis and provides new insights and strategies for designing high-performance NORR catalysts.}, archive = {J_JACS}, author = {Xingxing Wen and Oleg V. Prezhdo and Lai Xu}, doi = {10.1021/jacs.5c02696}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14647--14658}, shortjournal = {J. Am. Chem. Soc.}, title = {Design of twisted two-dimensional heterostructures and performance regulation descriptor for electrocatalytic ammonia production from nitric oxide}, volume = {147}, year = {2025}, }
• (2025). Unlocking phase purity of sodium iron sulfate for low-cost and high-performance sodium-ion batteries. JACS, 147(17), 14635--14646. (www)

  @article{ , abstract = {The alluaudite-type sulfate Na 2 Fe 2 (SO 4 ) 3 has gained significant attention as a promising cathode material for sodium-ion batteries (SIBs). However, the inevitable formation of impurities during synthesis and the irreversible structural distortion caused by Fe–Na exchange during electrochemical reactions severely hinder its electrochemical performance. Herein, we tackle these challenges by engineering an enlarged Fe–Fe distance in the lattice through partial PO 4 3– substitution. This strategic modification significantly alleviates the Coulombic repulsion between Fe ions and effectively prevents Fe-migration during the electrochemical reaction. Moreover, the unique ion state within the structure ensures enhanced ion/electron transport kinetics, minimal volume change, and a stable framework conducive to long cycling life. Notably, the novel Fe-fully occupied phase-pure Na 2.5 Fe 2 (SO 4 ) 2.5 (PO 4 ) 0.5 [also denoted as Na 5 Fe 4 (SO 4 ) 5 (PO 4 )] electrode delivers a record-high discharge capacity of 112 mA h g –1 at 0.2C, coupled with exceptional cycling stability with 88.8% capacity retention over 10,000 cycles at 10C. Additionally, the enhanced adsorption energy of Na 2.5 Fe 2 (SO 4 ) 2.5 (PO 4 ) 0.5 cathode toward H 2 O contributes to its outstanding air stability in humid atmosphere. This finding offers valuable insights for the development of advanced, low-cost materials for SIBs.}, archive = {J_JACS}, author = {Changyu Liu and Kean Chen and Fumin Li and Along Zhao and Ping Liu and Zhongxue Chen and Yongjin Fang and Yuliang Cao}, doi = {10.1021/jacs.5c02485}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14635--14646}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking phase purity of sodium iron sulfate for low-cost and high-performance sodium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Deracemization of C(sp3)–H arylated carbonyl compounds via asymmetric ion-pairing photoredox catalysis. JACS, 147(17), 14625--14634. (www)

  @article{ , abstract = {Deracemization of C(sp 3 )–H arylated carbonyl compounds faces limitations in terms of substrate scope. Through the photoactivation of the aryl group and the stereocontrol of the generated arene radical cation via asymmetric ion-pairing catalysis, we are able to achieve deracemization of carbonyl compounds arylated at both enolizable and unenolizable stereocenters. A diverse range of α-, β-, and γ-aryl ketones and esters, including natural products and medicinal derivatives, can be effectively converted into their enantiomers with high enantioselectivity. Mechanistic investigations through combined experimental and computational studies suggest that the reaction involves single-electron oxidation of electron-rich aryl groups, followed by a kinetic resolution of the resulting radical cation intermediates by the chiral phosphate anion. Deprotonation is identified as the stereodetermining step, while stereoselective back electron transfer and triplet-state quenching of 3 Mes-Acr 1 + * may also affect the enantioselectivity at the photostationary state.}, archive = {J_JACS}, author = {Chenxi Wen and Zhengke Huang and Sheng-Ye Zhang and Zhimin Li and Bolong Chai and Zheng Huang and Qi-Kai Kang}, doi = {10.1021/jacs.5c02235}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14625--14634}, shortjournal = {J. Am. Chem. Soc.}, title = {Deracemization of C(sp3)–H arylated carbonyl compounds via asymmetric ion-pairing photoredox catalysis}, volume = {147}, year = {2025}, }
• (2025). Boosting reaction kinetics with viscous nanowire dispersions. JACS, 147(17), 14614--14624. (www)

  @article{ , abstract = {Higher viscosity typically slows chemical reactions by restricting molecular movement, while stirring accelerates reactions by enhancing reactant diffusion and collisions. However, in this study, we reveal that reaction rates in nanowire dispersions─with microscopic viscosity ∼300 times that of decane, can be enhanced by over an order of magnitude. Counterintuitively, stirring slows the reaction with higher stirring rates causing even greater deceleration. This phenomenon is observed in both photo- and thermally activated cyclic reactions. Molecular dynamics simulations and confocal laser scanning microscopy suggest that aliphatic chains grafted onto nanowires interact with anisotropic molecules, increasing their local concentrations near the nanowires. Notably, azobenzene photoisomerization is completely inhibited in the nanowire dispersion, despite completing within 30 s in the absence of nanowires. We propose that the aliphatic chains align reactive molecules directionally, while the confined space prevents bulky cis -isomer formation. These findings show that nanowires not only harvest and orient reactive molecules but also exclude bulky products, significantly enhancing the reaction kinetics in confined systems.}, archive = {J_JACS}, author = {Jurong Dong and Hongkun Cao and Zhiwei Yang and Zongze Zhang and Zhijie Yang and Lingxiang Jiang and Jingjing Wei}, doi = {10.1021/jacs.5c02034}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14614--14624}, shortjournal = {J. Am. Chem. Soc.}, title = {Boosting reaction kinetics with viscous nanowire dispersions}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic synthesis of substituted 2-aryl morpholines via diastereoselective annulation. JACS, 147(17), 14605--14613. (www)

  @article{ , abstract = {Morpholines are prevalent in medicinal chemistry due to their favorable pharmacokinetic properties and widespread presence in FDA-approved drugs. Existing methods for morpholine synthesis often require prefunctionalized or protected reagents, limiting their versatility and efficiency. Here, we present a photocatalytic, diastereoselective annulation strategy for the synthesis of morpholines directly from readily available starting materials. This method employs a visible-light-activated photocatalyst, Lewis acid, and Brønsted acid to achieve high yields and stereoselectivity. It also provides access to diverse substitution patterns, including challenging tri- and tetra-substituted morpholines. Mechanistic studies reveal that the reaction proceeds through the formation of a radical cation intermediate, with triflic acid playing critical roles in protonating the substrate, preserving the photocatalyst, and preventing product oxidation. Beyond morpholines, this strategy is extended to piperidines, pyrrolidines, and other privileged nitrogen heterocycles. Our findings provide a modular approach for constructing complex, medicinally valuable scaffolds, advancing both synthetic and medicinal chemistry.}, archive = {J_JACS}, author = {Tiffany A. Brisco and Simon De Kreijger and Vaishnavi N. Nair and Ludovic Troian-Gautier and Uttam K. Tambar}, doi = {10.1021/jacs.5c01832}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14605--14613}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic synthesis of substituted 2-aryl morpholines via diastereoselective annulation}, volume = {147}, year = {2025}, }
• (2025). Light-boosted osmotic energy conversion and ion pumping through a graphdiyne oxide-based membrane. JACS, 147(17), 14595--14604. (www)

  @article{ , abstract = {Two-dimensional (2D) membranes with engineered light-responsive ion transport dynamics have been explored to construct efficient nanofluidic platforms that show great potential in osmotic and solar-osmotic energy conversion. However, the power density is still limited by poor responsivity and the inevitable trade-off effect between ion selectivity and flux. Here, we observed light-pumping ion transport behavior in graphdiyne oxide (GDYO) with a unique carbon hybrid skeleton that provides sensitive photoelectric responsivity and high-speed cation pathways. Molecular dynamics simulations verify that the coexistent interaction effects between cations and the negatively charged sites in GDYO (i.e., oxygen-containing groups and electron-rich acetylenic bonds) could significantly promote cation transmembrane transport via an absorption-acceleration mechanism. Furthermore, the GDYO-based system, possessing a coupled photon-electron-ion transport behavior due to its inherent semiconductor properties, could subtly realize unidirectional ion movement, consuming luminous energy either from low concentration to high concentration or vice versa, flexibly promoting the osmotic power density by ∼195% to 11.91 W m –2 .}, archive = {J_JACS}, author = {Qingchen Wang and Zidi Yan and Yuhao Hu and Qixiang Zhang and Xiang-Yu Kong and Yongchao Qian and Haoyang Ling and Zhe-Hua Zhang and Tingyang Li and Xin Li and Lei Kang and Linsen Yang and Lei Jiang and Zhen Zhang and Liping Wen}, doi = {10.1021/jacs.5c01960}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14595--14604}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-boosted osmotic energy conversion and ion pumping through a graphdiyne oxide-based membrane}, volume = {147}, year = {2025}, }
• (2025). Hierarchical engineering of single-crystalline mesoporous Metal–Organic frameworks with hollow structures. JACS, 147(17), 14585--14594. (www)

  @article{ , abstract = {Although the superiority of hierarchical structure has driven extensive demand for applications, establishing hierarchy in a long-range-ordered single crystal remains a formidable challenge due to the inherent competition and contradiction between single crystallinity and controllable hierarchical structure. Herein, we demonstrate a growth and dissociation kinetics cooperative strategy for synthesizing a family of hollow single-crystalline mesoporous metal–organic frameworks (meso-MOFs) with hierarchical structures. The approach employs a dual-template method, integrating both hard and soft templates. By adjusting the HCl/CH 3 COOH ratio, the reaction system’s pH can be tuned to regulate the dissociation kinetics of the acid-sensitive seeds serving as hard templates for the formation of hollow structure, while simultaneously modifying the concentration of the dual acids to control the growth kinetics of meso-MOF shells. The competition between maintaining a single crystallinity and achieving a well-defined hierarchical structure can be effectively balanced. Driven by the two interfacial kinetics, we successfully obtained the octahedral meso-MOF nanoparticles that not only exhibit a well-defined hollow structure with precisely controllable hollow size (∼81–1120 nm) and tunable wall thickness (∼28.6–61.3 nm) but also retain their single-crystal integrity. Specifically, the dissociation kinetics of seeds governed the formation of hollow structures, while the growth kinetics of single-crystalline meso-MOF shells ensured uniform coverage and structural integrity. Based on this strategy, we further developed a series of novel hollow meso-MOFs with hierarchical nanostructures, including hollow open-capsule meso-MOFs, 2D hollow meso-MOFs, hollow interlayer-structured meso-MOFs, macro-meso-micro trimodal porous MOFs, and so on.}, archive = {J_JACS}, author = {Zirui Lv and Minchao Liu and Yi Yang and Tianhao Chen and Wenyu Yang and Yijin Wang and Zaiwang Zhao and Kun Lan and Tiancong Zhao and Qiaowei Li and Xiaomin Li and Dongyuan Zhao}, doi = {10.1021/jacs.5c01415}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14585--14594}, shortjournal = {J. Am. Chem. Soc.}, title = {Hierarchical engineering of single-crystalline mesoporous Metal–Organic frameworks with hollow structures}, volume = {147}, year = {2025}, }
• (2025). Access to enantiopure spiropyridines enabled by enantio-relay double [2 + 2 + 2] cycloaddition and kinetic resolution [2 + 2 + 2] cycloaddition of alkynes and nitriles. JACS, 147(17), 14574--14584. (www)

  @article{ , abstract = {The synthesis of enantiopure and structurally unique spiro-type molecules is of utmost significance in catalysis, synthetic chemistry, and related fields. We present here a general solution, a nickel-catalyzed [2 + 2 + 2] cycloaddition, for accessing enantioenriched spiropyridines from readily available nitriles and alkynes in a single synthetic step, including (1) enantio-relay double [2 + 2 + 2] cycloaddition of malononitriles with alkynes and (2) kinetic resolution [2 + 2 + 2] cycloaddition of racemic pyridine-containing nitriles with alkynes. Both strategies feature a broad substrate scope and exclusive regioselectivities, and are scalable to multigram. Remarkably, the double [2 + 2 + 2] cycloaddition integrates enantio-induction by desymmetrizing dinitriles during the initial catalytic cycle with additional enantio-enhancement during the second cycloaddition (enantio-relay), yielding excellent enantioselectivities (>99% ee for all examined examples). Furthermore, the highly efficient kinetic resolution strategy enables the achievement of exceptionally high enantioselectivities without compromising yields ( s > 200 for most examples), overcoming the general challenges of kinetic resolution toward yield and enantioselectivity. The ability to construct previously inaccessible spiro structures lays the groundwork for advancing spiropyridine derivatives, especially the multinitrogen-containing compounds as potential ligands. Due to the perpendicular molecular orientation and inherent rigidity of the architectures obtained, we anticipate significant promise of the presented synthetic approaches for enhancing efforts in synthesis and catalysis.}, archive = {J_JACS}, author = {Li-Gang Bai and Yu-Qing Zheng and Han-Nan Chen and Jinhui Cai and Wen-Bo Liu}, doi = {10.1021/jacs.5c01653}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14574--14584}, shortjournal = {J. Am. Chem. Soc.}, title = {Access to enantiopure spiropyridines enabled by enantio-relay double [2 + 2 + 2] cycloaddition and kinetic resolution [2 + 2 + 2] cycloaddition of alkynes and nitriles}, volume = {147}, year = {2025}, }
• (2025). Harnessing the deubiquitinase USP1 for targeted protein stabilization. JACS, 147(17), 14564--14573. (www)

  @article{ , abstract = {Deubiquitinase-targeting chimera (DUBTAC) has emerged as a promising technology for targeted protein stabilization (TPS) by harnessing deubiquitinases (DUBs) to remove polyubiquitin chains from target proteins. Despite the presence of over 100 human DUBs, only OTUB1 and USP7 have been utilized in the development of DUBTAC. Hence, there is an urgent need to harness additional DUBs to expand the DUBTAC arsenal. In this work, we demonstrate for the first time that the USP1 deubiquitinase, which is overexpressed in several human cancers, can be leveraged for TPS. We report the development of novel USP1-recruiting DUBTACs by utilizing a noncovalent small-molecule inhibitor of USP1. First, we generated a USP1-based CFTR DUBTAC, MS5310, which effectively stabilized CFTR and is more potent than previously reported CFTR DUBTACs. Next, we developed first-in-class USP1-recruiting UTX DUBTACs, including MS7131, from a small-molecule inhibitor of UTX and JMJD3. Notably, MS7131 effectively stabilized the tumor suppressor UTX in a concentration- and time-dependent manner, while sparing the oncoprotein JMJD3, despite it retaining potent inhibition of JMJD3. Furthermore, UTX stabilization induced by MS7131 was dependent on the engagement of both USP1 and UTX. Consequently, MS7131, but not the parent USP1 inhibitor or UTX inhibitor, effectively reduced histone H3 lysine 27 trimethylation and significantly suppressed the proliferation and clonogenicity of cancer cells. Overall, this study highlights that USP1 can be harnessed for DUBTAC development. Moreover, we developed a valuable chemical tool, MS7131, for the investigation of UTX’s distinct functions. This advancement paves the way for leveraging DUBTACs in the treatment of related diseases.}, archive = {J_JACS}, author = {Chao Qian and Zhen Wang and Yan Xiong and Dingpeng Zhang and Yue Zhong and Hiroyuki Inuzuka and Yihang Qi and Ling Xie and Xian Chen and Wenyi Wei and Jian Jin}, doi = {10.1021/jacs.5c01662}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14564--14573}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing the deubiquitinase USP1 for targeted protein stabilization}, volume = {147}, year = {2025}, }
• (2025). Single-ion polymer-in-salt electrolytes enabling percolating ionic nanoaggregates for ambient-temperature solid-state batteries. JACS, 147(17), 14554--14563. (www)

  @article{ , abstract = {Solid polymer electrolytes (SPEs) with high ion conduction and interfacial stability are crucial for advancing high-performance solid-state batteries. While tuning electrolytes with weak solvation structures shows promise in enhancing interfacial stability, it remains challenging to concurrently achieve high Li + conductivity. Herein, we introduce a single-ion polymer-in-salt (SIP-in-salt) electrolyte, which not only provides additional charge carriers and enhanced salt compatibility via an ionic polymer backbone but also forms nanometric percolating ionic aggregates ( p -AGGs) at high salt concentrations. Unlike state-of-the-art weak solvation structures, p -AGGs are found to be homogeneous, interconnected, and possess enhanced Li + -anion dissociation, allowing structural diffusion over reduced distances and continuous Li + transport pathways. The SIP-in-salt electrolyte enables a 100-fold improvement in Li + conductivity compared to traditional polymer-in-salt electrolytes, lowering the operational temperature of SPE-based solid-state batteries to 25 °C. This work demonstrates a promising strategy for advancing SPEs by tuning ionic solvation structures, paving the way for next-generation high-performance batteries.}, archive = {J_JACS}, author = {Huaijiao Wang and Peng Wen and Yixuan Liu and Shantao Han and Zexi Zhang and Yifei Xu and Mao Chen and Xinrong Lin}, doi = {10.1021/jacs.5c01574}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14554--14563}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-ion polymer-in-salt electrolytes enabling percolating ionic nanoaggregates for ambient-temperature solid-state batteries}, volume = {147}, year = {2025}, }
• (2025). Revolutionizing ammonia synthesis: FeCoNiAlSi high-entropy alloy catalyst for low-pressure, low-temperature applications. JACS, 147(17), 14541--14553. (www)

  @article{ , abstract = {The Haber-Bosch (HB) process, critical for global ammonia production, is hindered by its high energy consumption and operational demands, requiring extreme pressures and temperatures. Developing catalysts that reduce these demands while maintaining practical efficiency is essential for achieving sustainable ammonia synthesis. Here, we investigate the FeCoNi(AlSi) 0.76 high-entropy alloy (HEA) as a catalyst for the HB process using quantum mechanics (QM) and kinetic Monte Carlo (kMC) simulations. Mechanistic analysis revealed significantly lower reaction barriers compared to pure Fe, and kMC simulations predict an NH 3 turnover frequency (TOF) that is 65 times higher than pure Fe under industrial conditions. Under reduced pressure (21 atm) and moderate temperature condition (673 K), the HEA retained half the NH 3 production rate of pure Fe at extreme industrial conditions, revealing its potential to reduce energy and pressure requirements. This study demonstrates the promise of HEAs in enabling more energy-efficient and sustainable ammonia production technologies.}, archive = {J_JACS}, author = {Yidi Shen and Luca Sementa and Duane D. Johnson and Alessandro Fortunelli and Qi An and William A. Goddard, III}, doi = {10.1021/jacs.5c00606}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14541--14553}, shortjournal = {J. Am. Chem. Soc.}, title = {Revolutionizing ammonia synthesis: FeCoNiAlSi high-entropy alloy catalyst for low-pressure, low-temperature applications}, volume = {147}, year = {2025}, }
• (2025). Mild-condition conversion of methane to acetic acid over MoS2–Confined Rh–Fe sites. JACS, 147(17), 14530--14540. (www)

  @article{ , abstract = {The oriented conversion of CH 4 to CH 3 COOH at low temperature, even room temperature, is both scientifically significant and industrially applicable for CH 4 utilization, yet it is extremely challenging due to the difficulties associated with efficient CH 4 activation and controllable C–C coupling. In this study, we for the first time achieve the room-temperature conversion of CH 4 to CH 3 COOH using molecular O 2 and CO over MoS 2 -confined Rh–Fe sites, which delivers an unprecedented CH 3 COOH selectivity of 90.3% and a productivity of 26.2 μmol g cat. –1 h –1 at 25 °C. Furthermore, the productivity of CH 3 COOH can be enhanced to 105.6 μmol g cat. –1 h –1 at 80 °C, while maintaining a high selectivity of 95.6%. Comprehensive experimental and theoretical investigation reveal the critical role of Rh–Fe synergy in the selective formation of CH 3 COOH. The confined Fe sites in MoS 2 enable the activation of O 2 to generate highly reactive Fe═O center for CH 4 dissociation to CH 3 species at room temperature, which then readily couple with adsorbed CO on adjacent Rh sites to form the key CH 3 CO intermediate for CH 3 COOH production. The unique structure of Rh–Fe sites offers synergistic catalytic properties that effectively balance C–H activation and C–C coupling, successfully addressing the trade-off between activity and selectivity in the carbonylation of CH 4 to CH 3 COOH under mild conditions.}, archive = {J_JACS}, author = {Jun Mao and Huan Liu and Yanan Li and Meng Gao and Yunlong Zhang and Yao Song and Mo Zhang and Guilan Xu and Wu Zhou and Liang Yu and Xiaoju Cui and Dehui Deng}, doi = {10.1021/jacs.5c01515}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14530--14540}, shortjournal = {J. Am. Chem. Soc.}, title = {Mild-condition conversion of methane to acetic acid over MoS2–Confined Rh–Fe sites}, volume = {147}, year = {2025}, }
• (2025). NMR-based measurements of site-specific electrostatic potentials of histone tails in nucleosome core particles. JACS, 147(17), 14519--14529. (www)

  @article{ , abstract = {Electrostatics play a dominant role in guiding many biological processes. This is especially the case in the context of chromatin, where charge interactions modulate diverse activities such as DNA repair, transcription, replication, condensation, and phase separation. Using NMR experiments quantifying solvent paramagnetic relaxation enhancements of backbone amide and side chain methyl protons in the presence of paramagnetic cosolutes and focusing on the nucleosome core particle (NCP), we report near surface electrostatic potentials of tail residues of each of the four histone components of the NCP. These are all negative, despite sequences comprising a high density of positively charged amino acids, emphasizing the strong contribution of the negatively charged DNA with which the tails interact. Changes in electrostatic potentials of as much as 60 mV between isolated histone tails and tails in the context of the NCP are calculated. Notably, the tail potentials can vary significantly from each other, with enrichment in glycine residues correlating with less negative values, highlighting differences in the interactions with DNA.}, archive = {J_JACS}, author = {Nicolas Bolik-Coulon and Philip Rößler and Lewis E. Kay}, doi = {10.1021/jacs.5c01567}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14519--14529}, shortjournal = {J. Am. Chem. Soc.}, title = {NMR-based measurements of site-specific electrostatic potentials of histone tails in nucleosome core particles}, volume = {147}, year = {2025}, }
• (2025). Bimetallic synergy in oxygen reduction: How tailored Metal–Metal interactions amplify cooperative catalysis. JACS, 147(17), 14504--14518. (www)

  @article{ , abstract = {Bimetallic cooperative catalysis, inspired by cytochrome c oxidase and multicopper oxidase, plays a crucial role in the development of four-electron oxygen reduction catalysts. The distance between metals is a crucial factor affecting the cooperative effect, but its precise influence on bimetallic cooperativity in selective oxygen reduction catalysis still awaits an in-depth understanding. Herein, we employ a series of dicopper complexes with varying linkers to systematically adjust the Cu···Cu distance for electrocatalytic oxygen reduction. Structure–activity relationship analyses reveal that catalysts with a shorter dicopper center exhibited significantly higher four-electron selectivity (approaching 100% for BPMPDCu 2 and BPMANCu 2 ) than that with a longer distance (below 80% for 6-HPACu 2 ) in an aqueous solution (pH 7.0). Notably, the catalytic activity of BPMPDCu 2 is 11 times and 237 times faster than those of 6-HPACu 2 and BPMANCu 2 , respectively, which does not correlate directly with their Cu···Cu distances. Further investigations into low-valent LCu I 2 intermediates, supported by DFT calculations, indicate that the oxygen binding process is the rate-determining step under electrocatalytic conditions and is sensitive to the Cu I ···Cu I distance. The closest BPMANCu I 2 characterized by strong Cu I –Cu I interactions and the more distant 6-HPACu I 2 with its separated dicopper sites both hinder effective O 2 binding. In contrast, BPMPDCu I 2 maintains an optimal Cu···Cu distance that facilitates O 2 binding and ensures robust bimetallic cooperativity throughout the catalytic cycle. This work underscores the significance of metal–metal distance regulation in bimetallic cooperatively selective oxygen reduction and provides valuable insights for the rational design of high-performance oxygen reduction catalysts.}, archive = {J_JACS}, author = {Qi-Fa Chen and Yao Xiao and Kai Hua and Hong-Tao Zhang and Ming-Tian Zhang}, doi = {10.1021/jacs.5c01406}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14504--14518}, shortjournal = {J. Am. Chem. Soc.}, title = {Bimetallic synergy in oxygen reduction: How tailored Metal–Metal interactions amplify cooperative catalysis}, volume = {147}, year = {2025}, }
• (2025). Atomic force microscopy strategies for capturing guest-induced structural transitions in single flexible Metal–Organic framework particles. JACS, 147(17), 14491--14503. (www)

  @article{ , abstract = {Flexible metal–organic frameworks (MOFs) exhibit stepped adsorption isotherms due to structural transitions between narrow-pore (np) and large-pore (lp) states. This characteristic stepwise uptake at a certain pressure results in adsorptive high working capacities, making these materials highly effective for energy-efficient gas storage and separation processes. The transition pressure, which is key to enhancing separation efficiency, can be tuned by varying the particle size of flexible MOFs. However, a comprehensive understanding of size-dependent effects has been limited due to particle size distribution in samples. Conventional adsorption measurements provide only averaged isotherms for powder samples, and analyzing the size effect at the single-particle level requires experimental techniques that can capture transition behavior of individual particles separately. This study utilized atomic force microscopy coupled with thermodynamic analysis to investigate guest-induced structural transitions. Force application to a MOF particle triggered a structural change from the lp to np state, generating force profiles that were analyzed to uncover the underlying transition mechanisms and calculate transition pressures using free energy analysis. The evaluation revealed distinct transition mechanisms for two flexible MOFs: ELM-12 exhibited a step-by-step mechanism, while DUT-8(Ni) displayed an all-at-once transition. Force profile analysis enabled precise determination of the free energy changes and transition pressures for individual particles. This approach provided detailed insights into the transition mechanisms and their impact on overall adsorption isotherms, offering a novel perspective on how single-particle behavior influences bulk material performance.}, archive = {J_JACS}, author = {Homare Arima and Shotaro Hiraide and Hiroyuki Nagano and Leila Abylgazina and Irena Senkovska and Günter K. Auernhammer and Andreas Fery and Stefan Kaskel and Satoshi Watanabe}, doi = {10.1021/jacs.5c01377}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14491--14503}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic force microscopy strategies for capturing guest-induced structural transitions in single flexible Metal–Organic framework particles}, volume = {147}, year = {2025}, }
• (2025). Broadly applicable Copper(I)-catalyzed alkyne semihydrogenation and hydrogenation of α,β-unsaturated amides enabled by bifunctional iminopyridine ligands. JACS, 147(17), 14481--14490. (www)

  @article{ , abstract = {A highly active bifunctional catalyst consisting of a copper(I)/N-heterocyclic carbene complex and a basic 2-iminopyridine subunit allows for copper hydride chemistry under low H 2 pressure, achieving efficient catalysis reaching 1 bar (balloon pressure). The bifunctional catalyst tolerates a remarkable variety of functional groups in catalytic alkyne semihydrogenations. Furthermore, this catalyst design gives rise to a high reactivity that allows for the catalytic hydrogenation of α,β-unsaturated amides (a substrate class hitherto unreactive in copper hydride catalysis) at a low H 2 pressure for the first time. In this manner, late-stage modification and isotope labeling of α,β-unsaturated amides, common subunits in biologically active compounds, can be realized through catalytic hydrogenation using a first-row transition metal catalyst based on abundant copper. Preliminary mechanistic experiments indicate that the bifunctional catalyst operates via an iminopyridine-mediated proximity effect. We hypothesize that the coordination of an alcohol as a proton source on the copper(I) complex facilitates the overall reactions through a rapid proto-decupration step.}, archive = {J_JACS}, author = {Mahadeb Gorai and Jonas H. Franzen and Philipp Rotering and Tobias Rüffer and Fabian Dielmann and Johannes F. Teichert}, doi = {10.1021/jacs.5c01339}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14481--14490}, shortjournal = {J. Am. Chem. Soc.}, title = {Broadly applicable Copper(I)-catalyzed alkyne semihydrogenation and hydrogenation of α,β-unsaturated amides enabled by bifunctional iminopyridine ligands}, volume = {147}, year = {2025}, }
• (2025). Retinal to retinal energy transfer in a bistable microbial rhodopsin dimer. JACS, 147(17), 14468--14480. (www)

  @article{ , abstract = {Neorhodopsin (NeoR) is a newly discovered fungal bistable rhodopsin that reversibly photoswitches between UV- and near-IR absorbing states denoted NeoR 367 and NeoR 690 , respectively. NeoR 367 represents a deprotonated retinal Schiff base (RSB), while NeoR 690 represents a protonated RSB. Cryo-EM studies indicate that NeoR forms homodimers with 29 Å center-to-center distance between the retinal chromophores. UV excitation of NeoR 367 takes place to an optically allowed S3 state of 1B u + symmetry, which rapidly converts to a low-lying optically forbidden S1 state of 2A g – symmetry in 39 fs, followed by a multiexponential decay to the ground state on the 1–100 ps time scale. A theoretically predicted nπ* (S2) state does not get populated in any appreciable transient concentration during the excited-state relaxation cascade. We observe an intradimer retinal to retinal excitation energy transfer (EET) process from the NeoR 367 S1 state to NeoR 690 , in competition with photoproduct formation. To quantitatively assess the EET mechanism and rate, we experimentally addressed and modeled the EET process under varying NeoR 367 -NeoR 690 photoequilibrium conditions and determined the EET rate at (200 ps) −1 . The NeoR 367 S1 state shows a weak stimulated emission band in the near-IR around 700 nm, which may result from mixing with an intramolecular charge-transfer (ICT) state, enhancing the transition dipole moment of the S1–S0 transition and possibly facilitating the EET process. We suggest that EET may bear general relevance to the function of bistable multiwavelength rhodopsin oligomers.}, archive = {J_JACS}, author = {Ivo H. M. van Stokkum and Jakub Dostal and Thanh Nhut Do and Lifei Fu and Gregor Madej and Christine Ziegler and Peter Hegemann and Miroslav Kloz and Matthias Broser and John T. M. Kennis}, doi = {10.1021/jacs.5c01276}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14468--14480}, shortjournal = {J. Am. Chem. Soc.}, title = {Retinal to retinal energy transfer in a bistable microbial rhodopsin dimer}, volume = {147}, year = {2025}, }
• (2025). Similar but different: Structural and spectroscopic characterization of series of neodymium, europium, americium, and curium coordination complexes. JACS, 147(17), 14455--14467. (www)

  @article{ , abstract = {Series of curium, americium, europium, and neodymium complexes with five different polyoxometalate (POM) ligands were structurally and spectroscopically characterized: Na x Cs y H z [M(XW 11 O 39 ) 2 ]· n H 2 O, where M = Nd 3+ , Eu 3+ , Am 3+ , or Cm 3+ and X = B 3+ , Ga 3+ , Si 4+ , Ge 4+ , or P 5+ . This first “serial approach” on transplutonium chemistry was allowed by minimizing the amount of f-element needed per synthesis down to ∼10 μg. This offers a unique opportunity to contrast structural and spectroscopic properties of trivalent actinide with those of lanthanide compounds under identical conditions. The results showcase that although actinide(III) and lanthanide(III) can make isostructural complexes, their solid-state coordination chemistries deviate significantly. The curium and americium compounds were found to be more uniform than their europium and neodymium counterparts, respectively. The particular symmetry of the Cm-POMs also enables the observation of rarely seen emission bands, which hints at vibronic coupling or new emissive pathways. Additionally, the Cm-POM and Eu-POM complexes were characterized via steady-state and time-resolved excitation and emission spectroscopy in solutions containing five different counterions (Li + , Na + , K + , Rb + , or Cs + ), representing 50 combinations of alkali/[M III (XW 11 ) 2 ] n − complexes. The Cm-POMs respond to the alkali counterions by improving symmetry from Li + to Cs + , while the Eu-POMs do the opposite. The luminescence lifetimes of the Cm-POMs also depart from the ideal Kimura equation. This study provides a rare, and perhaps the most comprehensive, experimental data set comparing heavy actinides and lanthanides via single crystal XRD plus, solution-state, solid-state, and time-resolved emission spectroscopy and demonstrates that lanthanides are only a coarse approximation for actinide elements.}, archive = {J_JACS}, author = {Ian Colliard and Gauthier J.-P. Deblonde}, doi = {10.1021/jacs.5c00861}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14455--14467}, shortjournal = {J. Am. Chem. Soc.}, title = {Similar but different: Structural and spectroscopic characterization of series of neodymium, europium, americium, and curium coordination complexes}, volume = {147}, year = {2025}, }
• (2025). Short-range magnetic correlations and thermally assisted spin tunnelling in distorted diamond lattices RTaO4 (R = tb and dy). JACS, 147(17), 14442--14454. (www)

  @article{ , abstract = {Rare earth-based frustrated systems provide an excellent platform to study novel magnetic phenomena owing to their localized moment and unquenched orbital momentum. Here, we present a comprehensive investigation of crystallographic and thermodynamic properties of TbTaO 4 and DyTaO 4 , wherein the magnetic ions form a distorted diamond structure. The former exhibits a crossover from short-ranged magnetic correlations to long-ranged antiferromagnetic ordering at ∼2.2 K, while the latter manifests only short-ranged magnetic correlations down to 1.8 K. Interestingly, a field-induced frequency dependence is observed in AC susceptibility in both cases, similar to that observed in spin ice systems. Analysis using the Casimir–duPre plot and Arrhenius law confirms that the origin behind this spin relaxation is thermal in nature, with activation energy close to the first excited crystal electric field gap. Our studies suggest that the observed frequency-dependent behavior is not only limited to spin ice materials, but it is a generic phenomenon in a broader class of rare earth-based frustrated magnetic systems.}, archive = {J_JACS}, author = {Jogendra Kumar and K. Mukherjee}, doi = {10.1021/jacs.5c00872}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14442--14454}, shortjournal = {J. Am. Chem. Soc.}, title = {Short-range magnetic correlations and thermally assisted spin tunnelling in distorted diamond lattices RTaO4 (R = tb and dy)}, volume = {147}, year = {2025}, }
• (2025). Pd-catalyzed counter-steric site- and chemoselective glycosylation: Total synthesis of fridamycin a and himalomycin b. JACS, 147(17), 14432--14441. (www)

  @article{ , abstract = {Here, we report a de novo synthetic strategy toward fridamycin-type glycoside natural products. A salient feature of the method is highlighted by the Pd-catalyzed asymmetric hydroalkoxylation of fridamycin A methyl ester with alkoxyallene, which enables site- and chemoselective introduction of 2,3,6-trideoxyglycosysides to various hydroxyl positions in a highly controlled manner. A unique advantage of this method is demonstrated by the total synthesis of himalomycin B and a C 4 ′- epi derivative of the proposed structure of amicenomycin B.}, archive = {J_JACS}, author = {Jihun Kang and Seungsoo Moon and Young Ho Rhee}, doi = {10.1021/jacs.5c00855}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14432--14441}, shortjournal = {J. Am. Chem. Soc.}, title = {Pd-catalyzed counter-steric site- and chemoselective glycosylation: Total synthesis of fridamycin a and himalomycin b}, volume = {147}, year = {2025}, }
• (2025). Mechanistic investigations into the olefination of oximes and hydrazones support intermediate ruthenium nitrides. JACS, 147(17), 14422--14431. (www)

  @article{ , abstract = {The olefination of oximes and hydrazones with ruthenium alkylidenes has recently been developed by matching substrate/metal orbital energy and polarization. We herein report detailed mechanistic investigations showing that the reaction pathway is distinct from previously established olefin–olefin metathesis reactions. The ruthenium alkylidene-mediated metathesis of olefins and hydrazones or oximes proceeds via a pathway that form intermediate ruthenium nitrides, which undergo subsequent bimolecular extrusion of molecular nitrogen. Detailed insights into the controlling features of this transformation presented herein are key to the development of future catalytic protocols for the olefination of oximes and hydrazones.}, archive = {J_JACS}, author = {Jacob R. Ludwig and John J. Kiernicki and Daniel J. Nasrallah and Troy E. Zehnder and Matthias Zeller and Nathaniel K. Szymczak and Corinna S. Schindler}, doi = {10.1021/jacs.5c00787}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14422--14431}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic investigations into the olefination of oximes and hydrazones support intermediate ruthenium nitrides}, volume = {147}, year = {2025}, }
• (2025). Rapid acquisition of 103Rh solid-state NMR spectra by 31P detection and sideband selective methods. JACS, 147(17), 14411--14421. (www)

  @article{ , abstract = {103 Rh solid-state nuclear magnetic resonance (SSNMR) spectroscopy is potentially a powerful method for investigating the molecular and electronic structure of rhodium compounds. However, 103 Rh is a difficult nucleus to study by NMR spectroscopy because of its small gyromagnetic ratio, broad chemical shift range, and long spin–lattice relaxation times ( T 1 ). While there are many prior reports demonstrating acquisition of 103 Rh solution NMR spectra, there are few examples of 103 Rh SSNMR spectra in the literature. Here, we utilize the large 31 P- 103 Rh scalar couplings ( J -couplings) to efficiently acquire 31 P-detected high-resolution 103 Rh SSNMR spectra. 31 P{ 103 Rh} J -resolved NMR experiments were used to measure 31 P- 103 Rh J -couplings. Sideband selective SSNMR techniques originally developed for wide-line 195 Pt SSNMR experiments were then used to rapidly acquire 103 Rh SSNMR spectra. Notably, we were able to acquire MAS 103 Rh SSNMR spectra in experiment times on the order of 30 min to a few hours and from only a few mg of materials. The sideband selective experiments offer significant time savings as compared to existing direct detection methods, which require days of acquisition to obtain a directly detected MAS spectrum, or yield low-resolution static powder patterns. Numerical fits of the SSNMR spectra provide 103 Rh chemical shift tensor parameters, with the experimental spectra agreeing well with the DFT-calculated spectra.}, archive = {J_JACS}, author = {Benjamin A. Atterberry and Piotr Paluch and Andrew R. Lamkins and Wenyu Huang and Aaron J. Rossini}, doi = {10.1021/jacs.5c00784}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14411--14421}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid acquisition of 103Rh solid-state NMR spectra by 31P detection and sideband selective methods}, volume = {147}, year = {2025}, }
• (2025). Altered mode of structural changes in solid solutions leading to dual modulation: Spin transition temperatures and steps. JACS, 147(17), 14401--14410. (www)

  @article{ , abstract = {The development of high-density information storage materials requires precise control of electron spin states. Multistep spin-crossover (SCO) materials with multiple stable spin states are prime candidates for this purpose. However, accurate control of the dynamic SCO behavior, including the dual dynamic modulation of the spin transition temperature ( T c ) and transition steps, has been a significant hurdle. In this study, we propose a new two-dimensional SCO solid solution system, [Fe III (H 0.5 L I ) 2–2 x (H 0.5 L Cl ) 2 x ]·H 2 O , where H 0.5 L X ( L X for short) denotes 5- X -2-hydroxybenzylidene-hydrazinecarbothioamide, with X being I or Cl and x ranging from 0 to 1. The proposed system exhibits a unique nonmonotonic variation in T c with x , obtaining a minimum at x = 0.7, allowing fine-tuning of T c across a 66 K range and control over transition steps from two steps to one step, accomplishing dual modulation. Single-crystal diffraction analysis and periodic density functional theory (DFT) calculations demonstrate that the doped ligand L Cl modulates the Fe III N 2 O 2 S 2 ligand field with increasing doped L Cl ligands during the HS → LS transition in solid solutions, enabling dual dynamic modulation of the T c and the number of transition steps from two steps to one step through dynamic variation in the structural contraction modes (from b - and c -axis contraction to a -axis contraction). This study motivates the synthetic control of dynamic SCO solid solutions through the altered mode of structural contraction as a complementary route to adjust their SCO behavior.}, archive = {J_JACS}, author = {Ying-Ying Wu and Guang-Yan Xu and Zi-Han Yan and Xiao-Yong Zhou and Feng-Lei Yang and Jing-Wei Dai and Shu-Qi Wu and Zhao-Yang Li and Osamu Sato}, doi = {10.1021/jacs.5c00712}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14401--14410}, shortjournal = {J. Am. Chem. Soc.}, title = {Altered mode of structural changes in solid solutions leading to dual modulation: Spin transition temperatures and steps}, volume = {147}, year = {2025}, }
• (2025). A pulsed tandem electrocatalysis strategy for CO2 reduction. JACS, 147(17), 14388--14400. (www)

  @article{ , abstract = {Electroreduction of CO 2 to value-added C 2 products remains hindered by sluggish C–C coupling kinetics and competing side reactions. Inspired by the tandem catalytic mechanisms of multienzyme systems, we designed a dual-site single-atom nanozyme (DSAN) comprising FeN 4 and FeO 4 sites (FeN 4 –FeO 4 ). Density functional theory (DFT) calculations under constant potential reveal that the FeN 4 site functions as a CO generator, while the FeO 4 site facilitates CO migration, C–C coupling, and subsequent C 2 product formation. To further optimize the catalytic efficiency, we introduced a pulsed electrocatalysis strategy by alternating between zero potential and −0.7 V. This approach dynamically modulates active-site functions: at −0.70 V, CO 2 adsorption and *CH 3 CH 2 OH formation are facilitated, while at 0 V, CO migration and C–C coupling are enhanced due to the spin-state transitions during potential switching. Additionally, the zero potential suppresses excessive hydrogenation of key intermediates, thereby improving CH 3 CH 2 OH selectivity. These findings highlight the synergistic strategy integrating tandem catalysis and pulsed potential control, offering a novel and effective approach for CO 2 -to-C 2 conversion using SAN catalysts.}, archive = {J_JACS}, author = {Hao Sun and Jing-Yao Liu}, doi = {10.1021/jacs.5c00633}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14388--14400}, shortjournal = {J. Am. Chem. Soc.}, title = {A pulsed tandem electrocatalysis strategy for CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). From hydrogel to crystal: A molecular design strategy that chemically modifies racemic gel-forming peptides to furnish crystalline fibrils stabilized by parallel rippled β-sheets. JACS, 147(17), 14377--14387. (www)

  @article{ , abstract = {Rippled β-sheets are an underutilized secondary structural motif that hold promise in the rational design of peptide hydrogel materials with unique and desirable properties. Fully capitalizing on the design potential of this structural element, however, requires a high-resolution molecular understanding of the interactions they form within the supramolecular assemblies comprising the material – which are absent in all reports to date. Herein, we develop a molecular design strategy to modulate the phase state of β-hairpin peptides prone to form fibrillar gels into ones that assemble into crystal lattices, making high-resolution structural analysis possible. Truncating, cyclizing and Cα-methylating enantiomeric gel-forming peptides affords mirror-image macrocyclic peptides. Crystallography reveals that the enantiomeric macrocycles coassemble to form racemic fibril-like assemblies of unprecedented structure. Extended arrays of sheet-rich fibrils contain alternating blocks of enantiopure β-hairpins that assemble to form both canonical pleated β-sheets as well as stereocomplexed rippled β-sheets. This structure illuminates new molecular interactions to leverage in the design of next generation peptide hydrogels and provides the first crystallographic evidence of a parallel rippled β-sheet.}, archive = {J_JACS}, author = {Tuan D. Samdin and Jacek Lubkowski and Caleb F. Anderson and Joel P. Schneider}, doi = {10.1021/jacs.5c00671}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14377--14387}, shortjournal = {J. Am. Chem. Soc.}, title = {From hydrogel to crystal: A molecular design strategy that chemically modifies racemic gel-forming peptides to furnish crystalline fibrils stabilized by parallel rippled β-sheets}, volume = {147}, year = {2025}, }
• (2025). Irreversible oxygen redox enables lithium extraction from ternary lithium-ion battery cathodes in water. JACS, 147(17), 14369--14376. (www)

  @article{ , abstract = {Developing a low-cost and environmentally friendly method for lithium extraction is essential for the efficient recycling of spent lithium-ion battery (LIB) cathodes. Current technologies, such as solvent extraction/precipitation and electrochemical processes, rely on anion- or cation-rich extraction agents and necessitate further purification, leading to high energy consumption and waste pollution. Here, we demonstrate that applying mechanical treatment on ternary LIB cathodes enables water to extract lithium from the cathode materials under mild conditions, achieving Li extraction efficiencies of 99.4% for LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811), 98.9% for LiNi 0.9 Co 0.075 Al 0.025 O 2 (NCA), and 97.1% for LiNi 0.9 Mn 0.05 Co 0.05 O 2 (NMC955) at 150 °C. This process involves an irreversible oxygen redox reaction, resulting in the structural transformation to metal hydroxide species. Further experiments revealed that mechanical treatment leads to the formation of oxygen holes (O 2−δ ), which are subsequently oxidized into O 2 gas through O–O dimerization during the hydrothermal process, creating oxygen vacancies. These vacant sites then act as channels for the release of surrounding Li + ions, followed by the OH – refilling process. Unlike previous methods, this work avoids the use of additional leaching reagents and produces high-quality end products, such as transition metal hydroxides and analytical-grade Li 2 CO 3 . Moreover, our proposed lithium extraction strategy further enables the recovered materials to be seamlessly reintegrated into the production of fresh cathode materials, providing valuable insights into the sustainable recycling of LIB cathodes.}, archive = {J_JACS}, author = {Chao Wu and Qi Zhang and Haoyan Meng and Bo Wu and Yiming Zhang and Junhua Li and Ying Tang and Anqi Zou and Jiliang Zhu and Caozheng Diao and Feng Gao and Zhi Gen Yu and Junmin Xue and Shibo Xi and Xiaopeng Wang and Jiagang Wu}, doi = {10.1021/jacs.5c00452}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14369--14376}, shortjournal = {J. Am. Chem. Soc.}, title = {Irreversible oxygen redox enables lithium extraction from ternary lithium-ion battery cathodes in water}, volume = {147}, year = {2025}, }
• (2025). In situ time-resolved X-ray absorption spectroscopy unveils partial re-oxidation of tellurium cluster for prolonged lifespan in hydrogen evolution. JACS, 147(17), 14359--14368. (www)

  @article{ , abstract = {Efficient and long-lasting electrocatalysts are one of the key factors in determining their large-scale commercial viability. Although the fundamentals of deactivation and regeneration of electrocatalysts are crucial for understanding and sustaining durable activity, little has been conducted on metalloids compared to metal-derived ones. Herein, by virtue of in situ seconds-resolved X-ray absorption spectroscopy, we discovered the chemical evolution during the deactivation-regeneration cycles of tellurium clusters supported by nitrogen-doped carbon (termed Te-ACs@NC) as a high-performance electrocatalyst in the hydrogen evolution reaction (HER). Through in situ electrochemical reduction, Te-ACs@NC, which had been deactivated due to surface phase transitions in a previous HER process, was reactivated and regenerated for the next run, where partially oxidized Te was found, surprisingly, to perform better than its nonoxidized state. After 10 consecutive deactivation-regeneration cycles over 480 h, the Te-ACs@NC retained 85% of its initial catalytic activity. Theoretical studies suggest that local oxidation modulates the electronic distribution within individual Te clusters to optimize the adsorption energy of water molecules and reduce dissociation energy. This study provides fundamental insights into the rarely explored metalloid cluster catalysts during deactivation and regeneration and will assist in the future design and development of supported catalysts with high activity and long durability.}, archive = {J_JACS}, author = {Kanglei Pang and Chang Long and Yu Zhang and Miao Zhang and Jian Chang and Yong-Lei Wang and Hao Zhang and Rongying Liu and Sadaf Saeedi Garakani and Özlem Uguz Neli and Jiayin Yuan}, doi = {10.1021/jacs.5c00167}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14359--14368}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ time-resolved X-ray absorption spectroscopy unveils partial re-oxidation of tellurium cluster for prolonged lifespan in hydrogen evolution}, volume = {147}, year = {2025}, }
• (2025). Linking solvation equilibrium thermodynamics to electrolyte transport kinetics for lithium batteries. JACS, 147(17), 14348--14358. (www)

  @article{ , abstract = {Correlating the solvation structure and thermodynamic properties with transport properties serves as the foundation for electrolyte design. While various physicochemical properties, such as relative solvating power, solvation energy, and spectroscopies have been used to study ion solvation, fundamental investigations in thermodynamic properties of solvation equilibrium across broad temperature ranges are not available. In this work, we combined temperature-resolved Infrared and Raman spectroscopies to systematically pinpoint the dynamic evolution of Li + -solvent and Li + -anion local coordination in typical ether and carbonate electrolytes from −60 to 60 °C. We identified a trend of temperature-driven equilibrium among electrolyte components. As the temperature increases, solvent-separated ion pairs (SSIP) are prone to converting to contact ion pairs (CIP), and CIP reverts to SSIP reversibly as the temperature decreases. By quantifying the temperature-responsive mean coordination number and solvate species concentrations, we reveal a preferential CIP association in carbonates compared to that in ethers. Gibbs free energy changes in diverse electrolytes exhibit a strong correlation with their respective Li + transference number. The thermodynamic properties of solvation equilibrium offer new descriptors for quantifying dynamic solvation structure, and the solvation-property knowledge gained from these model electrolytes can serve as a benchmark reference for a broad spectrum of battery electrolytes.}, archive = {J_JACS}, author = {Jianwei Lai and Yanjun Guo and Hao-En Lai and Francisco A. Ospina-Acevedo and Weixi Tian and Dacheng Kuai and Dongliang Chen and Perla B. Balbuena and Feifei Shi}, doi = {10.1021/jacs.5c00106}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14348--14358}, shortjournal = {J. Am. Chem. Soc.}, title = {Linking solvation equilibrium thermodynamics to electrolyte transport kinetics for lithium batteries}, volume = {147}, year = {2025}, }
• (2025). Liquid–Liquid phase separation-mediated cellular-scale compartmentalization of hydrogel covalent cross-linking promotes microtubule-based mechanosensing. JACS, 147(17), 14336--14347. (www)

  @article{ , abstract = {Controlled liquid–liquid phase separation (LLPS) plays an important role in the formation of a heterogeneously structured extracellular matrix (ECM) consisting of densely cross-linked stiff structures compartmentalized in a loosely cross-linked matrix. Moreover, the mechanical cues presented by the cellular-scale structural heterogeneity of the ECM facilitate the mechanotransduction of cells and subsequent cellular development. Therefore, developing ECM-mimetic hydrogels with compartmentalized structural heterogeneity as inductive cell carriers is highly desirable but challenging. Inspired by the ECM formation process, we capitalized on the temperature-assisted LLPS of a custom-designed temperature-responsive macromer (TRM) to concentrate and compartmentalize the TRM in the dense phase of the phase-separated precursor solution while keeping the gelatin comacromer complex in the dilute phase. The subsequent cross-linking produces the cellular (micron)-scale microdomains with dense covalent cross-linking interspersed in the loosely cross-linked cell-adaptable interdomain hydrogel matrix. The obtained ECM-mimetic heterogeneous hydrogel, which is solely cross-linked by covalent bonds, promotes extensive spreading, microtubule-based mechanotransduction, and autophagic flux of encapsulated human mesenchymal stem cells (hMSCs), thereby enhancing osteogenesis and bone regeneration. Our findings not only provide valuable guidance for the fabrication of ECM-mimetic biomaterials via LLPS-mediated assembly but also shed light on the mechanobiological mechanism underlying the regulation of cellular development by mechanical cues of the ECM.}, archive = {J_JACS}, author = {Jianyang Zhao and Yuan Hu and Hao Li and Caikun Liu and Zhiqiang Nie and Zekun Chen and Qiangjun Ling and Zhuo Li and Pengchao Zhao and Bin Song and Kunyu Zhang and Liming Bian}, doi = {10.1021/jacs.5c00079}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14336--14347}, shortjournal = {J. Am. Chem. Soc.}, title = {Liquid–Liquid phase separation-mediated cellular-scale compartmentalization of hydrogel covalent cross-linking promotes microtubule-based mechanosensing}, volume = {147}, year = {2025}, }
• (2025). Highly active and air-stable iron phosphide catalyst for reductive amination of carbonyl compounds enabled by Metal–Support synergy. JACS, 147(17), 14326--14335. (www)

  @article{ , abstract = {Iron has long been recognized as an ideal catalytic material for sustainable chemistry. However, conventional iron catalysts employed in liquid-phase hydrogenation reactions suffer from poor activity and air instability, severely restricting their wide applicability in practical use. Herein, we present the development of highly active and air-stable iron phosphide nanocrystal immobilized on zirconia (Fe 2 P NC/ZrO 2 ) for the reductive amination of aldehydes and ketones. The Fe 2 P NC/ZrO 2 catalyst demonstrated broad substrate applicability, high recyclability, and scalability in both gram-scale and continuous-flow processes. This catalyst leverages the synergistic metal–support effect of Fe 2 P NCs and ZrO 2 support, leading to activity 313 times higher than that of conventional iron nanoparticle catalysts. In-depth mechanistic studies elucidated that the distinctive interplay between Fe 2 P and ZrO 2 significantly accelerates ammonolysis of Schiff bases, a key step for boosting reaction efficiency. This study sets a new benchmark for iron-based catalysis, offering a robust alternative to precious metals, thereby contributing significantly to sustainable chemical manufacturing and green organic synthesis.}, archive = {J_JACS}, author = {Tomohiro Tsuda and Hiroya Ishikawa and Min Sheng and Motoaki Hirayama and Satoshi Suganuma and Ryota Osuga and Kiyotaka Nakajima and Junko N. Kondo and Sho Yamaguchi and Tomoo Mizugaki and Takato Mitsudome}, doi = {10.1021/jacs.4c18611}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14326--14335}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly active and air-stable iron phosphide catalyst for reductive amination of carbonyl compounds enabled by Metal–Support synergy}, volume = {147}, year = {2025}, }
• (2025). Mechanical and covalent tailoring of copper catenanes for selective aqueous nitrate-to-ammonia electrocatalysis. JACS, 147(17), 14316--14325. (www)

  @article{ , abstract = {Electrocatalytic nitrate reduction reaction (NO 3 RR) for the selective generation of ammonia (NH 3 ) enables the removal of deleterious nitrate pollutants while simultaneously upcycling them into a value-added fertilizer. The development of nonprecious metal-derived catalysts such as those featuring copper (Cu) as earth-abundant alternatives for the state-of-the-art precious metal catalysts is of urgent need yet suffering from the activity–selectivity–durability trilemma. Rational design of molecular Cu complexes with well-defined coordination structures permitting systematic structure–activity relationship (SAR) investigations is key to addressing the challenge. Here, a series of molecular Cu(I) complexes with [2]catenane ligands are developed as NO 3 RR electrocatalysts for the first time. By engineering multiple cationic ammoniums on the catenane backbone, acceptance of the anionic nitrate substrate as well as the release of the cationic ammonium product are promoted, thereby facilitating a higher Faradaic efficiency and product selectivity toward ammonia via an 8e – pathway. Of note, the mutual Coulombic repulsion between the multiply charged ligands is overcome by the mechanical interlocking such that the catalyst integrity can be maintained under practical conditions. This report highlights the promise of employing mechanically interlocked ligands as a platform for customizing metal complexes as catalysts for redox processes involving multiple proton-coupled electron transfer steps.}, archive = {J_JACS}, author = {Yulin Deng and Xiaoyong Mo and Samuel Kin-Man Lai and Shu-Chih Haw and Ho Yu Au-Yeung and Edmund C. M. Tse}, doi = {10.1021/jacs.4c18547}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14316--14325}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanical and covalent tailoring of copper catenanes for selective aqueous nitrate-to-ammonia electrocatalysis}, volume = {147}, year = {2025}, }
• (2025). Temperature dependence of proton coverage and the total potential at fused Silica:Water interfaces from phase-resolved nonlinear optics. JACS, 147(17), 14308--14315. (www)

  @article{ , abstract = {We study the temperature and ionic strength dependence of interfacial amphoterism via phase- and amplitude-resolved SHG measurements at the fused silica:water interface, finding that the total interfacial potential becomes increasingly negative when raising the temperature from 20 to 60 °C. The interfacial structure, reported by calibrated measurements of the second-order nonlinear susceptibility of the interface, remains largely temperature invariant. Our approach is presented in form of a blueprint for second harmonic generation (SHG) amplitude and phase measurements at buried aqueous interfaces using an affordable Y-crystal-based oscillator. A Galilean beam expander addresses the signal vs local oscillator mismatch, while a beam block eliminates otherwise interfering front reflections from the flat optical windows used here. The results show nearly linear voltage increases with temperature that rise faster at low vs high ionic strength and are consistent with temperature-dependent equilibrium constants governing the amphoteric silica:water interface. Proton surface coverages at pH 2.5, 6, and 11 increase with temperature as the surface becomes more negatively charged, reaching up to 10 13 protons cm –2 at 60 °C. These findings aid interfacial model development, benchmark atomistic simulations, explore temperature-dependent Hofmeister effects, and enhance understanding of interfacial electrocatalysis.}, archive = {J_JACS}, author = {Amani O. Alghamdi and Nicole M. Gonzalez and Franz M. Geiger}, doi = {10.1021/jacs.4c18310}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14308--14315}, shortjournal = {J. Am. Chem. Soc.}, title = {Temperature dependence of proton coverage and the total potential at fused Silica:Water interfaces from phase-resolved nonlinear optics}, volume = {147}, year = {2025}, }
• (2025). Photochemical generation and cycloadditions of strained cycloalkynes. JACS, 147(17), 14299--14307. (www)

  @article{ , abstract = {Strained cycloalkynes and their utilization have enabled prospective and tactical strategies for synthetic and medicinal chemistry, chemical biology, materials science, and allied fields. However, their full potential remains largely underexplored due to the limited availability of efficient sp 3 -rich cycloalkyne precursors with high synthetic efficiency and structural complexity. Herein, we describe an intuitive and modular photochemical approach to liberate cycloalkyne analogs from cyclic diacyl peroxides, without external reagents. This disclosed platform hinges on the leverage of cycloalkynes to realize two distinct classes of strain-promoted cycloadditions for the straightforward construction of diverse polycyclic scaffolds without the production of any side product except nitrogen and CO 2 . Moreover, high functional group tolerance, biorelevant molecules compatibility, scalability, and late-stage functionalization of bioactive molecules demonstrate the synthetic utility of the presented methods. These features enrich synthetic strategies for assembling cycloalkenyl-containing polycyclic scaffolds with structural diversity, offering new opportunities for click chemistry and bioorthogonal reactions.}, archive = {J_JACS}, author = {Congyin Wei and Kang Fu and Zhiyou Yu and Ziye Zhan and Denghu Chang and Lei Shi}, doi = {10.1021/jacs.4c18057}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14299--14307}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemical generation and cycloadditions of strained cycloalkynes}, volume = {147}, year = {2025}, }
• (2025). Mechanistic insights into molecular copper hydride catalysis: The kinetic stability of CuH monomers toward aggregation is a critical parameter for catalyst performance. JACS, 147(17), 14280--14298. (www)

  @article{ , abstract = {The activity of molecular copper hydride (CuH) complexes toward the selective insertion of unsaturated hydrocarbons under mild conditions has contributed significantly to versatile methodologies for upgrading these feedstocks. However, these catalysts are particularly susceptible to deleterious aggregation, leading to the depletion of active CuH species. Little is known about the mechanisms of CuH aggregation, how it influences overall catalyst performance, and how it can be controlled. We address these challenges with mechanistic studies on a model reaction of unactivated alkene hydroboration catalyzed by (IPr*CPh 3 )CuH (LCuH). We report a comprehensive mechanistic investigation of this system, identifying an aggregation pathway that continuously depletes catalytically active LCuH to form inactive CuH clusters during turnover. Deactivation of LCuH is controlled primarily by the competition between the kinetics of the initial LCuH dimerization step and that of alkene insertion into LCuH. We therefore propose that a comprehensive understanding of CuH catalyst performance must account for the kinetics of the initial LCuH dimerization step, revising a previously explored thermodynamic understanding of CuH aggregation, where the concentration of active species is controlled by equilibria established between CuH clusters and monomers. With a series of (NHC)CuH congeners (NHC = N -heterocyclic carbene), we demonstrate that ostensibly minor structural modifications to the ligand peripheries can drastically affect the LCuH dimerization kinetics, while maintaining reactivity toward on-cycle alkene insertion. We employed a computational approach based on molecular dynamics simulations to provide an in-depth understanding of how specific structural ligand modifications can substantially increase the kinetic stability of monomeric CuH catalysts. Our combined experimental and computational studies suggest strategies for rational ligand design that can be broadly applied to molecular catalyst systems that are susceptible to deactivation via aggregation pathways.}, archive = {J_JACS}, author = {David E. Ryan and Jack T. Fuller, III and Evan A. Patrick and Jeremy D. Erickson and Amy L. Speelman and Timothy G. Carroll and Gregory K. Schenter and Bojana Ginovska and Simone Raugei and R. Morris Bullock and Ba L. Tran}, doi = {10.1021/jacs.4c17955}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14280--14298}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic insights into molecular copper hydride catalysis: The kinetic stability of CuH monomers toward aggregation is a critical parameter for catalyst performance}, volume = {147}, year = {2025}, }
• (2025). Molecularly thin nanosheet films as water dissociation reaction catalysts enhanced by strong electric fields in bipolar membranes. JACS, 147(17), 14270--14279. (www)

  @article{ , abstract = {Bipolar membranes (BPMs) are interesting materials for the development of next-generation electrochemical energy conversion and separations processes. One of the key challenges in optimizing BPM performance is enhancing the rate of the water dissociation (WD) reaction. While electric field effects, specifically the second Wien effect, have been demonstrated to enhance the rate of WD reaction, making BPMs with low overpotentials for WD using primary electric field effects has been difficult to achieve. In this study, we constructed an abrupt interfacial structure between the anion exchange membrane (AEM) and cation exchange membrane (CEM) of BPMs to maximize the intensity of local electric field. A film of densely tiled, molecularly thin titanium oxide nanosheets was deposited as the interfacial layer to create an abrupt interface for studying extreme electric field effects. Although BPMs with titanium oxide nanosheet films exhibited higher WD reaction resistance compared to thicker catalyst layers composed of nanoparticles at low current density, they showed superior performance at higher current densities, where strong electric fields were present, and an apparent WD overpotential of 0.25 V at 300 mA cm –2 was extracted from electrochemical impedance measurements. These results highlight the potential of optimizing BPM performance by maximizing the second Wien effect through the utilization of two-dimensionally assembled nanosheet films.}, archive = {J_JACS}, author = {Eisuke Yamamoto and Tianyue Gao and Langqiu Xiao and Kelly Kopera and Sariah Marth and Heemin Park and Chulsung Bae and Minoru Osada and Thomas E. Mallouk}, doi = {10.1021/jacs.4c17830}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14270--14279}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecularly thin nanosheet films as water dissociation reaction catalysts enhanced by strong electric fields in bipolar membranes}, volume = {147}, year = {2025}, }
• (2025). NMR-based rational drug design of G:G mismatch DNA binding ligand trapping transient complex via disruption of a key allosteric interaction. JACS, 147(17), 14254--14269. (www)

  @article{ , abstract = {Small molecules that bind to mismatched DNA have been applied in various fields, including nanotechnology, bioimaging, and therapeutics. However, the intrinsic dynamic nature of mismatched DNA complicates the prediction of structural changes upon ligand binding, hindering rational ligand design. In this study, NMR was used for structure-based drug design, with a focus on the G:G mismatch binder ND and the structural dynamics of the DNA- ND complex. Through comprehensive NMR analysis with isotope labeling, two complex structures, the transient and stable complexes, were successfully determined. The nucleobase flip-outs and the distortion of the phosphate backbone of the complex structures were characterized by residual dipolar coupling (RDC) and 31 P NMR, respectively. The RDC-refined stable complex structure suggested that the ligand linker–nucleobase interaction allosterically regulates a structural transition. This interaction was experimentally validated by 1 H– 15 N HSQC spectra using a 15 N-labeled ligand. Disruption of this key allosteric interaction facilitated the design of a new ligand, sND , that traps the transient complex structure. In conclusion, comprehensive NMR analysis using a weak binder aids in designing nucleic acid-binding ligands based on transient complex structures.}, archive = {J_JACS}, author = {Shuhei Sakurabayashi and Kyoko Furuita and Takeshi Yamada and Noriaki Sugiura and Makoto Nomura and Takanori Nakane and Akihiro Kawamoto and Genji Kurisu and Yohei Miyanoiri and Toshimichi Fujiwara and Kazuhiko Nakatani and Chojiro Kojima}, doi = {10.1021/jacs.4c17538}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14254--14269}, shortjournal = {J. Am. Chem. Soc.}, title = {NMR-based rational drug design of G:G mismatch DNA binding ligand trapping transient complex via disruption of a key allosteric interaction}, volume = {147}, year = {2025}, }
• (2025). Hydride ion conductors with polyanionic complex anions. JACS, 147(17), 14244--14253. (www)

  @article{ , abstract = {Hydride ion (H – )-conducting solid-state materials have lately received great attention for advanced electrochemical energy storage/conversion systems, including hydride ion-based batteries, electrolysis, and fuel cells. However, the highly reactive nature of hydride ions has posed challenges in diversifying anion systems, which are crucial for designing their effective transport. This study reports perovskite-type hydride ion conductors, Sr 1– y Na y LiH 3– x – y (BH 4 ) x (0 ≤ x ≤ 1 and 0 ≤ y ≤ 0.1), employing polyanionic borohydride (BH 4 – ) as the anions in the structure. Structural characterization indicates that single-phase hydride ion conductors, in which H – and BH 4 – coexist in the cubic perovskite structure, are stabilized at the low- x region. In addition, incorporating H – vacancies (an increase in y ) enhances the disorder of H – and BH 4 – , improving hydride ion conductivity by 3 orders of magnitude. Neutron powder diffraction analysis reveals that the polyanionic BH 4 – interacts asymmetrically with the cations (Sr 2+ and Na + ), thereby facilitating hydride ion conduction through pathways where these interactions are weaker. This unusual structure allows for a high hydride ion conductivity of over 10 –4 S cm –1 at 100 °C. The current study suggests that many complex anions can be promising candidates as novel anion systems for hydride ion conductors.}, archive = {J_JACS}, author = {Taehyun Kim and Taeseung Kim and Taegyoung Lee and Ye-Eun Park and Jeonghyun Kim and Seoungjae Kang and Hyerim Kim and Seokjae Hong and Naoki Matsui and Hyungsub Kim and Sangryun Kim}, doi = {10.1021/jacs.4c17532}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14244--14253}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydride ion conductors with polyanionic complex anions}, volume = {147}, year = {2025}, }
• (2025). Steric complementarity drives strong co-assembly of short peptide stereoisomers. JACS, 147(17), 14231--14243. (www)

  @article{ , abstract = {Steric complementarity plays an essential role in maintaining protein architecture and recognition. In supramolecular chemistry and material science, however, it remains a major challenge to precisely control steric complementarity and associated interactions across different length scales for the construction of higher-order peptide and protein nanostructures and nanomaterials. Through coassembly of designed aromatic short peptide stereoisomers, we here incorporate specific π–π stacking interactions into facial complementarity between peptide strands within a β-sheet in a controllable manner. The high steric complementarity between aromatic side chains leads to strong coassembly capabilities of these peptide stereoisomers and dramatic changes in supramolecular morphology and size. We also unravel suprastructural handedness codes for their coassemblies and relate them to the side chain geometric complementarity and distribution on the two faces of the β-sheet. This work not only highlights the importance of steric complementarity in peptide folding but also provides a paradigm for the fabrication of intricate peptide β-sheet assemblies via steric complementarity at the subsheet level.}, archive = {J_JACS}, author = {Hao Qi and Kai Qi and Yan Wang and Xinfeng Ju and Yuchun Han and Stephen M. King and Sarah E. Rogers and Yilin Wang and Feng Zhou and Jian R. Lu and Hai Xu and Xuzhi Hu}, doi = {10.1021/jacs.4c17497}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14231--14243}, shortjournal = {J. Am. Chem. Soc.}, title = {Steric complementarity drives strong co-assembly of short peptide stereoisomers}, volume = {147}, year = {2025}, }
• (2025). Synthesis and sodium-ion storage of triazole-substituted graphdiyne. JACS, 147(17), 14219--14230. (www)

  @article{ , abstract = {Sodium-ion batteries (SIBs) have developed rapidly in recent years, confronting low capacity and poor cycling stability issues for anode material. Herein, triazole-substituted graphdiyne (TzlGDY) was designed to tune the sodium-ion insertion sequence, and an effective diyne-radical Na-storage mechanism was discovered. The distinctive diyne-ditriazole architecture actualizes a preferential Na + –N complexation, then π-bond homolysis of diyne is induced by Na + to generate two radicals at two end carbons of diyne, and thereby two radicals capture two additional Na + by Na + –radical coupling. This Na + –N complexation followed by the Na + –radical coupling mechanism more effectively enhances capacity compared with the reported cation−π mechanism. Furthermore, other ditriazole-N atoms chelate two more Na + . The triazole-filled nanopores and full-carbon backbone in TzlGDY effectively stabilize diyne radicals and enhance the Na + -transport kinetics. As a result, TzlGDY’s anode presented almost no capacity decay over 12,000 cycles at 5 A g –1 with a final capacity of 251.7 mAh g –1 . Moreover, the TzlGDY||NVP full cell delivered a high specific capacity of 114 mAh g –1 at 0.2C with a capacity retention of 81.8% and an average CE of 99.6% after 150 cycles. Our results demonstrate the diyne-radical mechanism is a new concept of energy storage and open up a new route for efficiently regulating anode materials in SIBs.}, archive = {J_JACS}, author = {Yang Kong and Yujie Wang and Yurui Xue and Lu Qi and Wenlong Yang and Guoxing Li and Taifeng Liu and Yuliang Li}, doi = {10.1021/jacs.4c17376}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14219--14230}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis and sodium-ion storage of triazole-substituted graphdiyne}, volume = {147}, year = {2025}, }
• (2025). Electrocatalytic oxidation of ammonia by (Salen)ruthenium(III) ammine complexes: Direct evidence for a Ruthenium(VI) nitrido active intermediate. JACS, 147(17), 14211--14218. (www)

  @article{ , abstract = {The electrocatalytic oxidation of ammonia using molecular catalysts has attracted much attention recently due to its potential for fuel cell applications. In this study, we report the electrocatalytic ammonia oxidation (AO) by [Ru III (salchda)(NH 3 )(CH 3 CN)] + ( RuNH 3 , salchda = N,N ′-bis(salicylidene)- o -cyclohexyldiamine dianion) and its bromo derivative. Controlled potential electrolysis at 0.65 V versus Fc +/0 for 3.2 h of a solution of RuNH 3 and NH 3 in CH 3 CN produced N 2 with a TON of 26 and Faradaic efficiency (FE) close to 100%. The TON was increased to 79 and 147 when electrolysis was carried out at 0.7 and 0.80 V vs Fc +/0 , respectively, with FE maintained at >99%, which are the highest among molecular ruthenium catalysts. An active intermediate was detected and shown to be the corresponding ruthenium(VI) nitrido complex [Ru VI (salchda)(N)] + ( RuN ) by direct comparison with an authentic sample of RuN , which we have previously synthesized and fully characterized. Direct kinetic studies on the oxidation of NH 3 to N 2 have also been carried out and the results are consistent with parallel electrophilic attack of NH 3 by RuN and bimolecular N···N coupling of RuN to produce N 2 . DFT calculations have also been performed to support the proposed mechanism.}, archive = {J_JACS}, author = {Jianhui Xie and Tingting Yang and Longzhu Hong and Hui Li and Bing Li and Zhenguo Guo and Yingying Liu and Tai-Chu Lau}, doi = {10.1021/jacs.4c16902}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14211--14218}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrocatalytic oxidation of ammonia by (Salen)ruthenium(III) ammine complexes: Direct evidence for a Ruthenium(VI) nitrido active intermediate}, volume = {147}, year = {2025}, }
• (2025). Bright and ultralong organic phosphorescence via sulfonic acid functionalization for high-contrast real-time light-writing display. JACS, 147(17), 14198--14210. (www)

  @article{ , abstract = {It is challenging to achieve room-temperature phosphorescence (RTP) in pure organics with both high efficiency and long lifetime. While much effort has been placed on discovering efficient phosphor skeletons, the importance of phosphor functionalization in enhancing the RTP performance has not received adequate attention. Herein, we demonstrate that functionalization of phosphors with sulfonic acid can ensure both bright and ultralong RTP, outperforming other substituents. The unique trigonal pyramidal structure of sulfonic acid group allows for more effective ( n , π *) transitions to enhance intersystem crossing efficiency. Its highly polarized S–O bonds render strengthened hydrogen bonding interactions and a narrower confinement within the poly(vinyl alcohol) (PVA) matrix, to minimize the nonradiative dissipation. Furthermore, its excellent water solubility contributes to the outstanding transparency of PVA film (over 97%), yielding high-quality optical imaging with a high contrast ratio of 48.0 and a low blurriness of 0.24. Moreover, full-color phosphorescence with exceptional performance ( Φ P, max = 37.2%, τ P, max = 2.09 s) is achieved from different sulfonic acids, validating the effectiveness and universality of this strategy. By leveraging these advantages, real-time light-writing displays with sharp imaging, high sensitivity, and exceptional rewritability are demonstrated. This work not only contributes to the substituent engineering in the molecular design of phosphors but also opens new opportunities for RTP materials in the next-generation intelligent optoelectronic materials.}, archive = {J_JACS}, author = {Xin Li and Wenlang Li and Ziqi Deng and Xinwen Ou and Feng Gao and Shan He and Xiao Li and Zijie Qiu and Ryan T. K. Kwok and Jianwei Sun and David L. Phillips and Jacky W. Y. Lam and Zhihong Guo and Ben Zhong Tang}, doi = {10.1021/jacs.4c17142}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14198--14210}, shortjournal = {J. Am. Chem. Soc.}, title = {Bright and ultralong organic phosphorescence via sulfonic acid functionalization for high-contrast real-time light-writing display}, volume = {147}, year = {2025}, }
• (2025). High enantioselectivity in adsorption of chiral molecules on the surface of chiral terbium phosphate nanocrystals. JACS, 147(17), 14191--14197. (www)

  @article{ , abstract = {The enantioselective adsorption (and catalysis) of molecules on chiral surfaces has been a topic of interest, in particular with respect to models describing homochirality in the evolution of life. While such adsorption on single crystal surfaces has been studied using various traditional surface science techniques, similar studies on powders have been less successful. Here we show that studying enantioselective adsorption on the particular system of intrinsically chiral TbPO 4 ·H 2 O nanocrystals (chiral space group) is highly useful and obeys some simple rules. The advantages of this system are the ability to produce such nanocrystals with 100% enantiomeric purity with virtually no ligands, due to strong autocatalytic effects in their enantioselective nucleation, and the prevalence of one type of surface type (100) in the formed nanocrystals. We show that particular chiral molecules such as tartaric and aspartic acids exhibit significant enantioselectivity in adsorption, while similar ones, like glutamic acid, show none. We demonstrate that at least three functional groups are required to define enantioselective adsorption, and in addition, there should be matching of distances between these groups and the corresponding surface adsorption sites (Tb 3+ sites in our case).}, archive = {J_JACS}, author = {Abdullah Idrees and Bar Reuven and Gil Markovich}, doi = {10.1021/jacs.4c16883}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14191--14197}, shortjournal = {J. Am. Chem. Soc.}, title = {High enantioselectivity in adsorption of chiral molecules on the surface of chiral terbium phosphate nanocrystals}, volume = {147}, year = {2025}, }
• (2025). Multiplicity of regulatory subunit conformations defines structural ensemble of reset protein kinase a holoenzyme. JACS, 147(17), 14174--14190. (www)

  @article{ , abstract = {How protein kinase A (PKA) is reset to a basal state following 3′5′-cyclic adenosine monophosphate (cAMP)-mediated activation is unknown. Here we describe the mechanism of cAMP-PKA type I signal termination leading to a reset of PKA by holoenzyme formation through the obligatory action of phosphodiesterases (PDEs). We report a catalytic subunit (Cα)-assisted mechanism for the reset of type I PKA and describe for the first time multiple structures of the reset PKA holoenzyme (RIα 2 :Cα 2 ) that capture an ensemble of multiple conformational end-states through integrative electron microscopy and structural mass spectrometry approaches. Together these complementary methods highlight the large conformational dynamics of the regulatory subunit (RIα) within the tetrameric reset PKA holoenzyme. The cAMP-free reset PKA holoenzyme adopts multiple distinct conformations of RIα with contributions from the N-terminal linker and CNB-B dynamics. Our findings highlight the interplay between RIα, Cα, and PDEs (PDE8) in cAMP-PKA signalosomes to offer a new paradigm for PDE-mediated regulation of cAMP-PKA signaling.}, archive = {J_JACS}, author = {Varun Venkatakrishnan and Tatiana N. Laremore and Theresa S.C. Buckley and Jean-Paul Armache and Ganesh S. Anand}, doi = {10.1021/jacs.4c16269}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14174--14190}, shortjournal = {J. Am. Chem. Soc.}, title = {Multiplicity of regulatory subunit conformations defines structural ensemble of reset protein kinase a holoenzyme}, volume = {147}, year = {2025}, }
• (2025). The role of boron reagents in determining the site-selectivity of pyridine(dicarbene) cobalt-catalyzed C–H borylation of fluorinated arenes. JACS, 147(17), 14163--14173. (www)

  @article{ , abstract = {The origin of the meta - and ortho -to-fluorine site-selectivity in the C(sp 2 )–H borylation of fluorinated arenes with B 2 Pin 2 and HBPin promoted by pyridine(dicarbene)cobalt catalysts has been investigated. In situ generation of the cobalt(I)-boryl complex and treatment with three representative fluoroarenes established meta -selective C(sp 2 )–H oxidative addition to form predominantly the meta isomers of the corresponding cobalt(I)-aryl complexes. Attempts to observe or isolate the four-coordinate cobalt(I)-boryl complex yielded the cobalt-hydride dimer, [( iPr ACNC)CoH] 2 , borohydride ( iPr ACNC)CoH 2 BPin , or diboryl hydride, ( iPr ACNC)CoH(BPin) 2 depending on the amounts of B 2 Pin 2 and HBPin present. The phosphite derivatives ( iPr ACNC)CoH(P(O i Pr) 3 ) and ( iPr ACNC)CoBPin(P(O i Pr) 3 ) were prepared and crystallographically characterized. In the catalytic borylation of 1,3-difluorobenzene, ortho -to-fluorine cobalt(I)-aryl and borohydride complexes were identified as resting states despite meta -to-fluorine borylation being the major product of catalysis. Deuterium kinetic isotope effects support irreversible but not turnover-limiting C(sp 2 )–H oxidative addition. Stoichiometric borylation of isolated cobalt(I)-aryl intermediates with B 2 Pin 2 established that the meta- cobalt(I)-aryl was more reactive than the ortho- isomer and accounts for the observed cobalt(I)-aryl resting states. All cobalt(I)-aryl compounds reacted more quickly with HBPin. While ortho -cobalt(I)-aryl compounds yielded arylboronate products with high site-selectivity, meta -cobalt-aryl counterparts yielded a mixture of arylboronate isomers and free arene. Deuterium labeling experiments with DBPin confirmed that HBPin mediates reversible C(sp 2 )–H oxidative addition. Thus, the overall site-selectivity arises from two reinforcing effects: ( i ) kinetically meta- selective oxidative addition and ( ii ) faster reaction of the meta -cobalt-aryl isomer with B 2 Pin 2 . As B 2 Pin 2 is converted to HBPin, C(sp 2 )–H reductive elimination competes against borylation of the meta -cobalt-aryl isomer, resulting in increased ortho -selective borylation.}, archive = {J_JACS}, author = {Haozheng Li and Hanna H. Cramer and Jose B. Roque and Carlota Odena and Alex M. Shimozono and Paul J. Chirik}, doi = {10.1021/jacs.4c15596}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14163--14173}, shortjournal = {J. Am. Chem. Soc.}, title = {The role of boron reagents in determining the site-selectivity of pyridine(dicarbene) cobalt-catalyzed C–H borylation of fluorinated arenes}, volume = {147}, year = {2025}, }
• (2025). Terminal vanadium hydride through oxidative C–H cleavage and its application in reduction of o2. JACS, 147(17), 14154--14162. (www)

  @article{ , abstract = {We reported the synthesis and characterization of a novel vanadium hydride complex {[ Dipp N 2 NCH 2 C 6 H 4 ]VH} 2 {K} 2 ( 2 ) obtained through intramolecular C aryl -H oxidative addition with an in situ-generated low-valent vanadium intermediate. This vanadium hydride exhibits strong reducing properties and is capable of activating O 2 through a 4-electron reduction process. Simultaneously, it forms dioxovanadate complex 5 with a regenerated Csp 2 -H bond and oxovanadium complex 6 . Feasible mechanisms for the formation of 5 and 6 were proposed based on the deuterium-labeled experiments and DFT calculations.}, archive = {J_JACS}, author = {Lei Zheng and Yun-Shu Cui and Dong-Ping Chen and Geng-Mu Li and Feng Liu and Dan-Dan Zhai and Zhang-Jie Shi}, doi = {10.1021/jacs.4c14758}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14154--14162}, shortjournal = {J. Am. Chem. Soc.}, title = {Terminal vanadium hydride through oxidative C–H cleavage and its application in reduction of o2}, volume = {147}, year = {2025}, }
• (2025). Photo-switchable supramolecular interactions regulate k+ transmembrane transport and cancer cell apoptosis. JACS, 147(17), 14139--14153. (www)

  @article{ , abstract = {Natural channel proteins (NCPs) have numerous ion transport modes, but it remains a big challenge to replicate this trait by artificial ion transport systems. Herein, we present an azobenzene-incorporated single-chain random heteropolymers (RHPs)-derived biomimetic K + channel P3 , which can switch between three ion transport states (“ON,” “Partially OFF,” and “Totally OFF”) in both liposomes and cancer cells. The conformational adjustments of P3 activated by light-modulating two groups of supramolecular interactions ((1) hydrogen bonding and π–π interactions; (2) host–guest interactions) realize these switches, resembling the protein mechanisms that govern activity. Underlying molecular mechanisms are the photoisomerization of azobenzene moieties in P3 and their complexation with β-cyclodextrin (β-CD), enabling the exploit of a “one stone (azobenzene moiety), two birds (supramolecular interactions)” strategy. Mechanistic investigations demonstrate that P3 -induced substantial K + efflux (a 50% drop within just 4 min) causes endoplasmic reticulum (ER) stress, intriguing Ca 2+ sparks, enhanced reactive oxygen species (ROS), and finally severe mitochondria-dependent apoptosis. This NCP-like channel ( P3 ) is expected to provide new opportunities for a deeper understanding of the internal mechanisms of NCPs, as well as for treating cancer and other diseases.}, archive = {J_JACS}, author = {Cong Li and Yaqi Wu and Sheng Bao and Hui Li and Zhengwei Xu and Jing Yan and Xiaoxuan Yu and Lei He and Tianlong Zhang and Wang Liu and Shida Hou and Yang Zhang and Jiayun Xu and Tengfei Yan and Tingting Wang and Yi Yan and Junqiu Liu}, doi = {10.1021/jacs.4c14583}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14139--14153}, shortjournal = {J. Am. Chem. Soc.}, title = {Photo-switchable supramolecular interactions regulate k+ transmembrane transport and cancer cell apoptosis}, volume = {147}, year = {2025}, }
• (2025). Selective deuteration reveals the importance of multiple branching pathways in α-pinene autoxidation. JACS, 147(17), 14131--14138. (www)

  @article{ , abstract = {The oxidation of monoterpenes is one of the largest single sources of atmospheric secondary organic aerosol (SOA) significantly impacting the climate and air quality. Still, the autoxidation mechanisms converting these volatile precursors to low-volatility condensable products remain elusive even for the most abundant monoterpene α-pinene. We studied the ozonolysis of α-pinene by combining advanced isotopic labeling and state-of-the-art chemical ionization mass spectrometry supported by quantum chemical calculations. We reacted a full set of eight selectively deuterated α-pinene analogues separately in a flow reactor to probe the oxidation mechanisms on a molecular level. We found that surprisingly few carbon atoms participate in the autoxidation process when forming even the most oxygenated products. Additionally, prompt pinonic acid formation has likely been greatly overestimated, whereas the α-pinene-derived dioxirane appears more stable than previously thought. Importantly, we reveal that oxidation models should include multiple branching pathways rather than simple linear autoxidation progression from less to more oxygenated species. Correct modeling of the oxidation is crucial to enable accurate predictions in the changing climate and atmospheric conditions.}, archive = {J_JACS}, author = {Melissa Meder and Frans Graeffe and Yuanyuan Luo and Jingyi Luo and Siddharth Iyer and Rashid Valiev and Runlong Cai and Matti Rissanen and Theo Kurtén and Jonathan G. Varelas and Franz M. Geiger and Regan J. Thomson and Mikael Ehn}, doi = {10.1021/jacs.4c14462}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14131--14138}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective deuteration reveals the importance of multiple branching pathways in α-pinene autoxidation}, volume = {147}, year = {2025}, }
• (2025). Electric-double-layer mechanism of surface oxophilicity in regulating the alkaline hydrogen electrocatalytic kinetics. JACS, 147(17), 14122--14130. (www)

  @article{ , abstract = {Regulating the surface oxophilicity of the electrocatalyst is known as an efficient strategy to mitigate the order-of-magnitude kinetic slowdown of hydrogen electrocatalysis in a base, which is of great scientific and technological significance. So far, its mechanistic origin remains mainly ascribed to the bifunctional or electronic effects that revolve around the catalyst–intermediate interactions and is under extensive debate. In addition, the understanding from the perspective of interfacial electric-double-layer (EDL) structures, which should also strongly depend on the electrode property, is still lacking. Here, by decorating a Pt electrode with Mo, Ru, Rh, and Au metal atoms to tune surface oxophilicity and systematically combining electrochemical activity tests, in situ surface-enhanced infrared absorption spectroscopy, density functional theory calculation, and ab initio molecular dynamics simulation, we found that there exist consistent volcano-type relationships between *OH adsorption strength and alkaline hydrogen evolution activity, the stretching/bending vibration information on interfacial water, and the potential of zero charge (PZC) of the electrode. This demonstrates that the origin of surface oxophilicity in impacting the alkaline hydrogen electrocatalytic activity lies in its modification toward the electrode PZC, which thereby dictates the electric field strength, rigidity, and hydrogen bonding network structure in EDL and ultimately governs the interfacial proton transfer kinetics. These findings emphasize the importance of focusing on electrocatalytic interface structures to understand electrode property-dependent reaction kinetics.}, archive = {J_JACS}, author = {Yaling Jiang and Peimeng Qiu and Qinghua Liu and Peng Li and Shengli Chen}, doi = {10.1021/jacs.4c14511}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14122--14130}, shortjournal = {J. Am. Chem. Soc.}, title = {Electric-double-layer mechanism of surface oxophilicity in regulating the alkaline hydrogen electrocatalytic kinetics}, volume = {147}, year = {2025}, }
• (2025). Heterobimetallic complexes that point to when bond dissociation energies deviate from computational expectations. JACS, 147(17), 14105--14121. (www)

  @article{ , abstract = {Measurement of the formal, gas-phase, d 8 –d 10 bond dissociation energy across a series of structurally homologous heterobimetallic complexes of Pd(II) with Cu(I), Ag(I), Au(I), and Zn(II), themselves models for the transition states for transmetalation in Sonogashira and Negishi couplings, finds large discrepancies relative to predictions by a commonly used dispersion-corrected density-functional theory method, DFT-D3(BJ), but not in all cases . Control studies on the threshold collision-induced dissociation (T-CID) of electrosprayed molecular ions, as well as the deconvolution of the bond energy from the experimentally measured energy-resolved cross sections, indicate that the experimentally determined bond dissociation energies are most likely correct, which raises the question of why the computational methods, while sometimes agreeing acceptably with experiment, can also sometimes disagree egregiously. While initial attempts to characterize the discrepancy focused on the metal–metal interaction, the most likely origin of the discrepancy appears to be an uneven treatment of nonbonded interactions, among them medium-ranged correlation effects and London dispersion, between the ligands on the two metal centers. The contribution of these effects to the formal bond dissociation energy is large enough to be chemically significant, but it appears to depend on the nature of the interacting groups, specifically the hybridization at carbon, and, more importantly, their relative orientation. Whereas face-to-face aryl–aryl interactions seem to be modeled well by PBE-D3(BJ), a representative DFT-D3 method, alkyl-aryl, and edge-to-face aryl–aryl interactions appear to be overestimated. The consequences for structure and stability in organic and organometallic molecules are discussed, especially with regard to relative energies of conformers and interconverting valence isomers.}, archive = {J_JACS}, author = {Raphael Bissig and Raphael Oeschger and Peter Chen}, doi = {10.1021/jacs.4c14399}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14105--14121}, shortjournal = {J. Am. Chem. Soc.}, title = {Heterobimetallic complexes that point to when bond dissociation energies deviate from computational expectations}, volume = {147}, year = {2025}, }
• (2025). Tests of the DFT ladder for the fulminic acid challenge. JACS, 147(17), 14088--14104. (www)

  @article{ , abstract = {Properties of the historically pivotal fulminic acid (HCNO) molecule have been computed with a panoply of 473 density functionals of all varieties, providing a snapshot of the performance of contemporary density functional theory (DFT) for a challenging chemical system. Exhaustive tabulations and statistical analyses have been carried out for geometric parameters, vibrational frequencies, barriers to linearity, and the HCN–O dissociation energy. As the DFT ladder is climbed, confusion rather than consensus ensues regarding the details of the distinctive, extremely flat H–C–N bending potential of fulminic acid and whether the equilibrium structure is linear or bent. While high-ranking DFT functionals produce the smallest errors for the HCN + O( 3 P ) → HCNO reaction energy, lower rungs emerge as the best performers for many of the bond distances and harmonic vibrational frequencies. This research shows that the current DFT zoo of approximations does not constitute a transparent ladder of increasingly accurate methods that consistently converges on definitive predictions for various properties of HCNO. Additional analyses are performed on the side effects of popular dispersion corrections on the covalently bonded properties and thermochemistry of HCNO.}, archive = {J_JACS}, author = {Ashley M. Allen and Laura N. Olive Dornshuld and Patricia A. Gonzalez Franco and Wesley D. Allen and Henry F. Schaefer, III}, doi = {10.1021/jacs.4c13823}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14088--14104}, shortjournal = {J. Am. Chem. Soc.}, title = {Tests of the DFT ladder for the fulminic acid challenge}, volume = {147}, year = {2025}, }
• (2025). Stereoselective total synthesis of nimbolide. JACS, 147(17), 14083--14087. (www)

  @article{ , abstract = {A stereoselective total synthesis of nimbolide has been achieved in a convergent, 11-step sequence from α-methyl-( R )-carvone. The strategy relied on a stereoselective palladium-catalyzed borylative Heck cyclization where the A-ring of the nimbolide core was constructed while simultaneously performing oxidation at C(28). Selective manipulations delivered a fully decorated decalin moiety on large scale. Then, a stereoretentive etherification reaction brought together two fragments and forged the critical C–O bond with high selectivity. Finally, a regioselective radical cyclization and late-stage lactonization completed the total synthesis of nimbolide.}, archive = {J_JACS}, author = {David B. Ryffel and Peter C. Ryffel and Matteo Martinelli and Vineet R. Pillai and David Sarlah}, doi = {10.1021/jacs.5c04899}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14083--14087}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereoselective total synthesis of nimbolide}, volume = {147}, year = {2025}, }
• (2025). Isomeric separation of c6 alkanes via organic solvent reverse osmosis with covalent organic framework membranes. JACS, 147(17), 14077--14082. (www)

  @article{ , abstract = {Membrane separation represents cutting-edge technology for the isomeric separation of C6 alkanes in the petrochemical sector. However, it remains challenging to design membranes with sub-0.1 nm resolution that can effectively discriminate between C6 alkane isomers. In this study, we report a molecularly selective, ultramicroporous covalent organic framework (COF) membrane featuring an accessible pore size of ∼4.5 Å for the isomeric separation of C6 alkanes. High permeance of 2.56 kg m –2 h –1 bar –1 together with a high selectivity of 70.9 are achieved for a binary separation of linear n -hexane ( n HEX) and branched 2,3-dimethylbutane (23DMB) through organic solvent reverse osmosis (OSRO). Notably, the research octane number (RON) of a five-component C6 alkane mixture can be effectively improved from 67.7 to 92.8 through a continuous separation using the COF membrane. The exceptional performance of the COF membrane suggests a new design of next-generation molecularly selective membranes toward efficient isomeric separation.}, archive = {J_JACS}, author = {Hao Yang and Haoyuan Zhang and Zhengxuan Ji and Dongchen Shi and Chunqing Ji and Kexin Yu and Chengjun Kang and Dan Zhao}, doi = {10.1021/jacs.5c04063}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14077--14082}, shortjournal = {J. Am. Chem. Soc.}, title = {Isomeric separation of c6 alkanes via organic solvent reverse osmosis with covalent organic framework membranes}, volume = {147}, year = {2025}, }
• (2025). Enantioselective formation of isoxazolidines via brønsted-base catalyzed (3 + 2) annulation of cyclopropanes with nitrosoarenes. JACS, 147(17), 14071--14076. (www)

  @article{ , abstract = {Enantioselective transformations of donor–acceptor cyclopropanes have opened a new chemical space for the construction of enantioenriched molecules. This work presents the first catalytic enantioselective synthesis of isoxazolidines─a privileged key-structure in organic and medicinal chemistry─through a Brønsted-base catalyzed (3 + 2) annulation of donor–acceptor cyclopropanes with nitrosoarenes. The reaction concept is general, scalable to gram-scale, and enables the reaction between cyclopropanes, substituted with ketones, aldehydes, esters, thioesters, or sulfones, and nitrosoarenes with different substitution patterns, yielding isoxazolidines in generally excellent yields (up to 98%) and enantioselectivities (up to 97% ee). For the (3 + 2) annulation of β-cyclopropyl ketones with nitrosobenzenes, a Hammett study was conducted to elucidate the role of substituents on enantioselectivity. The isoxazolidines can undergo different transformations, such as oxidative cleavage of the N -PMP-group or N–O bond cleavage by LiAlH 4 , where the two cyano groups are key-functionalities, as this reaction also provided the simultaneous didecyanation and reduction of the carbonyl, affording attractive 5-amino-1,3-diols, a scaffold present in drugs like atorvastatin. Finally, a mechanistic model is proposed to account for the stereochemical outcome of the (3 + 2) annulation.}, archive = {J_JACS}, author = {Erlaitz Basabe Obregón and Leire Villaescusa and José Trujillo-Sierra and Roberta Mastroddi and Karl Anker Jørgensen}, doi = {10.1021/jacs.5c04032}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14071--14076}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective formation of isoxazolidines via brønsted-base catalyzed (3 + 2) annulation of cyclopropanes with nitrosoarenes}, volume = {147}, year = {2025}, }
• (2025). Asymmetric cobalt catalysis for the construction of quaternary stereogenic centers with fluorine atoms. JACS, 147(17), 14065--14070. (www)

  @article{ , abstract = {The advancement of robust synthetic methodologies for generating fluorinated quaternary carbon chiral centers is highly sought after in the fields of organic and medicinal chemistry. This study successfully provides such compounds through cobalt-catalyzed asymmetric Negishi coupling reactions of α-bromo-α-fluoro ketones with aryl/alkenyl zinc reagents. The adjustment of chiral unsymmetric N , N , N -tridentate (CUT) ligands played a key role in improving reactivity and selectivity in the cobalt catalysis, preventing the formation of hydrodebromination byproducts, and accommodating sterically hindered substrates and heterocycles. Control and kinetic experiments reveal that transmetalation serves as the rate-limiting step, a mechanistic characteristic that sets the newly developed asymmetric cobalt-catalyzed cross-couplings apart from previous methodologies.}, archive = {J_JACS}, author = {Jingyi Wang and Jin Yang and Jian He and Zhan Lu}, doi = {10.1021/jacs.5c03944}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14065--14070}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric cobalt catalysis for the construction of quaternary stereogenic centers with fluorine atoms}, volume = {147}, year = {2025}, }
• (2025). Cobalt-catalyzed syntheses of esters and carboxylic acids from alkenes promoted by light. JACS, 147(17), 14060--14064. (www)

  @article{ , abstract = {Alkoxy- and hydroxycarbonylations of alkenes are widely useful transformations for the preparation of esters and carboxylic acids, respectively. Catalytic systems using earth-abundant, first-row metals hold significant promise in increasing the scope and sustainability of these processes, but general methods remain virtually undeveloped. Herein, we report alkene alkoxycarbonylations and hydroxycarbonylations catalyzed by unmodified, inexpensive cobalt carbonyl under mild conditions and under low pressure promoted by light. These reactions display a broad substrate scope with respect to the alkene and alcohol components, with alkoxycarbonylations proceeding efficiently with 1 equiv of both partners, enabling coupling of complex substrates. A successful alkoxycarbonylation was performed even in the absence of solvent, displaying a remarkably low E factor for the hydrocarbonylation process.}, archive = {J_JACS}, author = {Mason S. Faculak and Michael R. Rodriguez and Erik J. Alexanian}, doi = {10.1021/jacs.5c03769}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14060--14064}, shortjournal = {J. Am. Chem. Soc.}, title = {Cobalt-catalyzed syntheses of esters and carboxylic acids from alkenes promoted by light}, volume = {147}, year = {2025}, }
• (2025). Ordered graphane nanoribbons synthesized via high-pressure Diels–Alder polymerization of 2,2′-bipyrazine. JACS, 147(17), 14054--14059. (www)

  @article{ , abstract = {Graphane shares the same two-dimensional honeycomb structure of graphene, but its saturated carbon skeleton gives rise to a bandgap and therefore provides more possibilities for the development of novel carbon-based semiconductors. However, the hydrogenation of graphene usually leads to disordered and incompletely hydrogenated graphane, and the precise synthesis of graphane with a specific configuration is still very challenging. Here, we synthesized a crystalline graphane nanoribbon (GANR) via pressure-induced polymerization of 2,2′-bipyrazine (BPZ). By performing Rietveld refinement of in situ neutron diffraction data, nuclear magnetic resonance spectroscopy, infrared spectra, and theoretical calculation, we found that BPZ experienced Diels–Alder polymerization between the π···π stacked aromatic rings and formed extended boat-GANR structures with exceptional long-range order. The unreacted −C═N– groups bridge the two ends of the boat and are ready for further functionalization. The GANR has a bandgap of 2.25 eV, with booming photoelectric response ( I ON / I OFF = 18.8). Our work highlights that high-pressure topochemical polymerization is a promising method for the precise synthesis of graphane with specific structure and desired properties.}, archive = {J_JACS}, author = {Fang Li and Xingyu Tang and Yunfan Fei and Jie Zhang and Jie Liu and Puyi Lang and Guangwei Che and Zilin Zhao and Yuqing Zheng and Yuan Fang and Chen Li and Dexiang Gao and Xiao Dong and Takanori Hattori and Jun Abe and Ho-kwang Mao and Haiyan Zheng and Kuo Li}, doi = {10.1021/jacs.5c03116}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14054--14059}, shortjournal = {J. Am. Chem. Soc.}, title = {Ordered graphane nanoribbons synthesized via high-pressure Diels–Alder polymerization of 2,2′-bipyrazine}, volume = {147}, year = {2025}, }
• (2025). Synergistic photoenzymatic anti-markovnikov hydroarylation of olefins via heteroaryl radical intermediates. JACS, 147(17), 14048--14053. (www)

  @article{ , abstract = {Heteroaromatic alkylations are indispensable reactions for synthesizing biologically active molecules. The anti-Markovnikov hydroarylation of olefins using heteroaryl halides furnishes the product as a single regioisomer; however, catalytic variants are ineffective at controlling the stereochemical outcome of these reactions. Here, we report a synergistic photoenzymatic hydroarylation of olefins using flavin-dependent “ene”-reductases with ruthenium photoredox catalysts. Enzyme homologues were identified, which provide access to both product enantiomers in greater than 80% yield with up to 99:1 er. This method is effective for styrenyl- and unactivated alkenes, highlighting the generality of this approach. The highest yielding system involves a carboxylated photocatalyst with increased affinity for the enzyme. This work expands the types of radical intermediates that enzymes can use for stereoselective intermolecular coupling reactions.}, archive = {J_JACS}, author = {Prasun Mukherjee and Zayed Alassad and Todd K. Hyster}, doi = {10.1021/jacs.5c01066}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14048--14053}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic photoenzymatic anti-markovnikov hydroarylation of olefins via heteroaryl radical intermediates}, volume = {147}, year = {2025}, }
• (2025). The Nicotine–Tryptophan dimer: Probing the principal interaction of nicotine with the nicotinic acetylcholine receptor (nAChR), the binding pocket in the human brain. JACS, 147(17), 14043--14047. (www)

  @article{ , abstract = {To elucidate the principal interaction of nicotine (NIC) with the binding pocket of nicotinic acetylcholine receptor (nAChR), a simplified model complex comprising of N′-methyl-indolyl-2-propanamide (MIPA) and NIC was studied using infrared spectroscopy and theoretical calculations. MIPA serves as a surrogate for the tryptophan 156 residue of the α-subunit of nAChR, which was previously identified to stabilize NIC binding in a model binding pocket. The MIPA–NIC interaction stabilizes the bioactive N -methylpyrrolidinium protomer of NIC (Pyrro-H + , 60% population) that stimulates nAChR over the inactive pyridinium protomer (Pyri-H + , 40% population) via the interaction of Trp with the indole side chain of MIPA. The observed selectivity of NIC’s pyrrolidine protonation site in its complex with MIPA originates from its stabilization via cooperative interactions between the amide and indole functional groups. This work illustrates the importance of fundamental interactions at the molecular level in describing biological activity between an agonist and the binding pocket of the nAChR.}, archive = {J_JACS}, author = {Yuika Okura and Madisen N. Hallsten and Garrett D. Santis and Keisuke Hirata and Masaaki Fujii and Shun-Ichi Ishiuchi and Sotiris S. Xantheas}, doi = {10.1021/jacs.5c00880}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14043--14047}, shortjournal = {J. Am. Chem. Soc.}, title = {The Nicotine–Tryptophan dimer: Probing the principal interaction of nicotine with the nicotinic acetylcholine receptor (nAChR), the binding pocket in the human brain}, volume = {147}, year = {2025}, }
• (2025). Slow electron spin relaxation at ambient temperatures with copper coordinated by a rigid macrocyclic ligand. JACS, 147(17), 14036--14042. (www)

  @article{ , abstract = {Paramagnetic transition metal complexes can serve as quantum bits, storing phase information through unpaired electrons. Despite their promise, these systems often require low temperatures and tend to rapidly decohere. Recent efforts have sought to improve longitudinal relaxation ( T 1 ), which provides an upper limit for phase coherence ( T m ), by investigating existing literature compounds with reduced vibrational coupling and orbital angular momentum. However, synthetic strategies for improving T 1 through novel ligand design have remained scant. Here, we disclose the synthesis of a new modular macrocyclic ligand framework with four nitrogen donors (N 4 ) derived from phenanthroline that supports room-temperature coherent Cu(II) spin centers. The optimized complex more than doubles the T 1 over the next best Cu(II)-N 4 compound and exhibits a room temperature coherence time ( T m ) of 0.28 μs, close to previously reported values. This performance enhancement arises from a tight binding site with short Cu–N distances, resulting in a stronger ligand field and reduced thermal accessibility of symmetric vibrational modes. This work demonstrates a practical approach to enabling spin coherence at room temperature, a factor critical to accessing relevant quantum bits and biological sensors, through a designer macrocyclic ligand platform.}, archive = {J_JACS}, author = {Matthew R. Espinosa and Fernando Guerrero and Nathanael P. Kazmierczak and Paul H. Oyala and Alexandria Hong and Ryan G. Hadt and Theodor Agapie}, doi = {10.1021/jacs.5c00803}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14036--14042}, shortjournal = {J. Am. Chem. Soc.}, title = {Slow electron spin relaxation at ambient temperatures with copper coordinated by a rigid macrocyclic ligand}, volume = {147}, year = {2025}, }
• (2025). Generation and reactivity of a high-spin Iron(IV)-oxo complex that is stable at ambient temperatures. JACS, 147(17), 14031--14035. (www)

  @article{ , abstract = {Nature operates a variety of challenging oxidation reactions through intermediates bearing tetravalent iron centers bound to a terminal oxo ligand. The high-spin ( S = 2) electronic configuration is believed to be particularly important in C–H activation reactions mediated by iron(IV)-oxo species. Coordination environments that promote high-spin ground states obviate the need for spin-state crossing to access this state and can promote rapid oxidation reactivity. As a result, however, synthetic iron(IV)-oxo species with S = 2 ground states tend to exhibit poor thermal stabilities, which has hampered a broader elucidation of their reactivity profiles. In this work, we report the synthesis of a remarkably stable high-spin iron(IV)-oxo complex that localizes the Fe═O unit within a rigid organic macrocycle. This design results in essentially unlimited stability at ambient temperatures and a half-life of 21 h at 70 °C in CH 3 CN, endowing this compound with the highest thermal stability for a high-spin Fe IV ═O complex reported to date. The ligand’s steric profile shuts down intermolecular reactivity with potential O atom acceptors and hydrocarbons bearing weak C–H bonds, but proton-coupled electron transfer reactivity with 2,4,6-tri- tert -butylphenol (TTBP) occurs readily at room temperature despite its steric bulk.}, archive = {J_JACS}, author = {Christopher D. Hastings and Lucy S. X. Huffman and William W. Brennessel and Brandon R. Barnett}, doi = {10.1021/jacs.5c00503}, journal = {Journal of the American Chemical Society}, month = {4}, number = {17}, pages = {14031--14035}, shortjournal = {J. Am. Chem. Soc.}, title = {Generation and reactivity of a high-spin Iron(IV)-oxo complex that is stable at ambient temperatures}, volume = {147}, year = {2025}, }
• (2025). Retraction of “Room temperature metallic conductivity in a Metal–Organic framework induced by oxidation”. JACS, 147(16), 14030. (www)

  @article{ , archive = {J_JACS}, author = {Andrew J. Clough and Nicholas M. Orchanian and Jonathan M. Skelton and Abbey J. Neer and Sebastian A. Howard and Courtney A. Downes and Louis F. J. Piper and Aron Walsh and Brent C. Melot and Smaranda C. Marinescu}, doi = {10.1021/jacs.5c00681}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {14030}, shortjournal = {J. Am. Chem. Soc.}, title = {Retraction of “Room temperature metallic conductivity in a Metal–Organic framework induced by oxidation”}, volume = {147}, year = {2025}, }
• (2025). Correction to “In situ probing the anion-widened anodic electric double layer for enhanced faradaic efficiency of chlorine-involved reactions”. JACS, 147(16), 14029. (www)

  @article{ , archive = {J_JACS}, author = {Mingming Yan and Rong Yang and Cuibo Liu and Ying Gao and Bin Zhang}, doi = {10.1021/jacs.5c05221}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {14029}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “In situ probing the anion-widened anodic electric double layer for enhanced faradaic efficiency of chlorine-involved reactions”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Engaging alkenes in metallaphotoredox: A triple catalytic, radical sorting approach to olefin-alcohol cross-coupling”. JACS, 147(16), 14028. (www)

  @article{ , archive = {J_JACS}, author = {Qinyan Cai and Iona M. McWhinnie and Nathan W. Dow and Amy Y. Chan and David W. C. MacMillan}, doi = {10.1021/jacs.5c05132}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {14028}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Engaging alkenes in metallaphotoredox: A triple catalytic, radical sorting approach to olefin-alcohol cross-coupling”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Synthesis of cationic cyclic oligo(disulfide)s via cyclo-depolymerization: A redox-responsive and potent antibacterial reagent”. JACS, 147(16), 14026--14027. (www)

  @article{ , archive = {J_JACS}, author = {Jia Guo and Siqi Zhang and Yaqi Tao and Wei Zheng and Hao Cheng and Hao Li and Zhibo Wang and Yangqing Gou and Jun Zhu and Linxian Li and Yun Liu and Matthew L. Becker and Wen Tang}, doi = {10.1021/jacs.5c04719}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {14026--14027}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Synthesis of cationic cyclic oligo(disulfide)s via cyclo-depolymerization: A redox-responsive and potent antibacterial reagent”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Stability frontiers in the AM6X6 kagome metals: The LnNb6Sn6 (Ln:Ce–Lu,Y) family and density-wave transition in LuNb6Sn6”. JACS, 147(16), 14024--14025. (www)

  @article{ , archive = {J_JACS}, author = {Brenden R. Ortiz and William R. Meier and Ganesh Pokharel and Juan Chamorro and Fazhi Yang and Shirin Mozaffari and Alex Thaler and Steven J. Gomez Alvarado and Heda Zhang and David S. Parker and German D. Samolyuk and Joseph A. M. Paddison and Jiaqiang Yan and Feng Ye and Suchismita Sarker and Stephen D. Wilson and Hu Miao and David Mandrus and Michael A. McGuire}, doi = {10.1021/jacs.5c04409}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {14024--14025}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Stability frontiers in the AM6X6 kagome metals: The LnNb6Sn6 (Ln:Ce–Lu,Y) family and density-wave transition in LuNb6Sn6”}, volume = {147}, year = {2025}, }
• (2025). Triplet sensitization photon upconversion using near-infrared indirect-bandgap AgBiS2 nanocrystals. JACS, 147(16), 14015--14023. (www)

  @article{ , abstract = {Colloidal semiconductor nanocrystals (NCs) have recently emerged as ideal triplet sensitizers owing to their diverse material composition and spectral tunability. However, the NCs that can efficiently sensitize near-infrared-to-visible photon upconversion remain largely limited to toxic lead-based NCs. Here, we present a new lead-free, near-infrared, indirect-bandgap sensitizer based on AgBiS 2 NCs, enabling near-infrared-to-yellow upconversion with a quantum yield reaching 10.5% (normalized to 100%). The key to success is the precise stoichiometry control of AgBiS 2 NCs, which provides the essential surface states for both radiative recombination and triplet energy transfer. Ultrafast transient absorption spectroscopy verifies the efficient triplet energy transfer mechanism mediated by surface states. Our work presents a new eco-friendly material system for efficient triplet fusion near-infrared photon upconversion.}, archive = {J_JACS}, author = {Kin Ting Chang and Wenfei Liang and Shaokuan Gong and Pang Ho Yeung and Jianning Feng and Xihan Chen and Haipeng Lu}, doi = {10.1021/jacs.5c04015}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {14015--14023}, shortjournal = {J. Am. Chem. Soc.}, title = {Triplet sensitization photon upconversion using near-infrared indirect-bandgap AgBiS2 nanocrystals}, volume = {147}, year = {2025}, }
• (2025). Electrocatalytic ethylene glycol to long-chain c3+ α-hydroxycarboxylic acids via cross-coupling with primary alcohols. JACS, 147(16), 14004--14014. (www)

  @article{ , abstract = {Electrocatalytic conversion of ethylene glycol (EG) into α-hydroxycarboxylic acids (α-HCAs) holds great importance for advancing sustainable chemical development since EG is widely accessible in polyethylene terephthalate (PET) plastic and biomass. Herein, we report the direct electrocatalytic cross-coupling of EG and primary C 1 –C 4 alcohol, producing carbon-chain-propagated C 3 –C 6 α-HCAs over a gold (Au) catalyst. Taking EG and methanol (MeOH) cross-coupling to lactic acid (LA) as an example, experimental evidence shows that stabilization of the aldehyde intermediates (glycolaldehyde and formaldehyde from EG and MeOH, respectively) without overoxidation is important for the following cross-coupling via aldol condensation and thus LA formation. Based on this understanding, we systematically modulate the catalyst and reaction conditions, achieving a high LA productivity of 268.1 μmol cm –2 h –1 with a Faradaic efficiency of 28.7% at a constant current of 100 mA cm –2 . The carbon-chain propagation strategy shows generality for EG cross-coupling with C 1 –C 4 primary alcohols, successfully producing C 3 –C 6 α-HCAs. As a proof of concept, a postconsumer PET bottle is converted to LA with a good productivity of 224.5 μmol cm –2 in a 2 h electrolysis. This work demonstrates the possibility of the electrocatalytic strategy to convert EG into long-chain compounds via C–C bond cross-coupling, representing a crucial step toward building a sustainable society.}, archive = {J_JACS}, author = {Qiujin Shi and Yu-Quan Zhu and Xiang Liu and Bo-Jun Yuan and Wengio Tang and Xi Wang and Ruo-Pu Li and Haohong Duan}, doi = {10.1021/jacs.5c04034}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {14004--14014}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrocatalytic ethylene glycol to long-chain c3+ α-hydroxycarboxylic acids via cross-coupling with primary alcohols}, volume = {147}, year = {2025}, }
• (2025). Layer-by-layer interdigitated CuS/Au2S heteronanoplates by selectively blocking the pathway of cation exchange reaction. JACS, 147(16), 13993--14003. (www)

  @article{ , abstract = {Cation exchange reactions (CERs), recognized as a promising postsynthetic modification strategy, have garnered significant interest for generating thermodynamically unfavorable structural features, such as heterointerfaces. The formation of these heterointerfaces, which exhibit physicochemical properties distinct from those of their individual components, relies on precise control over the diffusion pathways of externally introduced cations as they migrate from the surface into the crystal interior. However, achieving regiospecific modulation of cation diffusion to rationally design heterointerfaces remains a formidable challenge. Herein, we synthesized layer-by-layer interdigitated {CuS/Au 2 S}@IrS 2 heteronanoplates (L-Au 2 S HNPs), in which Au 2 S and CuS are alternately stacked at the atomic scale, using Cu 1.81 S@IrS 2 nanoplates (CSIS NPs) as a starting template. This distinct structural arrangement was realized through a two-step CER with Au cations and a phase transformation process from Cu 2– x S to CuS. Experimental results indicate that S–S bonds within phase-converted CuS crystals act as diffusion barriers during subsequent CER, restricting the migration of Au cations into specific CuS layers. Furthermore, theoretical calculations suggest that the expansion of the anion sublattice within channels containing diffused Au cations induces compressive strain in adjacent CuS layers, thereby impeding further Au incorporation. Expanding this synthetic strategy to construct atomic-layer-level stacked heteronanostructures across a broader range of materials could unlock new opportunities for developing advanced materials with unprecedented optical and catalytic properties.}, archive = {J_JACS}, author = {Suin Jo and Taekyung Kim and Chi Ho Lee and Eunsoo Lee and Haneul Jin and Sang Uck Lee and Kwangyeol Lee and Hionsuck Baik and Jongsik Park}, doi = {10.1021/jacs.5c03707}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13993--14003}, shortjournal = {J. Am. Chem. Soc.}, title = {Layer-by-layer interdigitated CuS/Au2S heteronanoplates by selectively blocking the pathway of cation exchange reaction}, volume = {147}, year = {2025}, }
• (2025). Regiodivergent hydroamidation of alkenes via cobalt-hydride catalysis. JACS, 147(16), 13983--13992. (www)

  @article{ , abstract = {Regiodivergent hydroamin(d)ation of alkenes presents a valuable strategy for the synthesis of diverse amines or amides from a common set of starting materials, yet achieving controlled regioselectivity remains a significant challenge. In this work, we present a cobalt-catalyzed regiodivergent hydroamidation of alkenes, enabling enantioselective ipso - and migratory hydroamidation of heterocyclic alkenes. The ability to finely tune various reaction parameters allows for a seamless switch in regioselectivity. Notably, ipso - and migratory selectivity are governed by the choice of cobalt catalyst anions. Mechanistic studies reveal a neutral Co–H species mediating ipso -hydroamidation and a cationic Co–H intermediate promoting migratory hydroamidation. This protocol exhibits a broad substrate scope, high functional group tolerance, and provides an efficient pathway for synthetizing structurally diverse amides.}, archive = {J_JACS}, author = {Bingxue Liu and Qianqian Lu and Xiao Hu and Dandan Li and Zheyuan Xu and Xi Lu and Yao Fu and Qiang Liu}, doi = {10.1021/jacs.5c03484}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13983--13992}, shortjournal = {J. Am. Chem. Soc.}, title = {Regiodivergent hydroamidation of alkenes via cobalt-hydride catalysis}, volume = {147}, year = {2025}, }
• (2025). After 75 years, an alternative to edman degradation: A mechanistic and efficiency study of a base-induced method for N-terminal peptide sequencing. JACS, 147(16), 13973--13982. (www)

  @article{ , abstract = {The sequencing of peptides via N-terminal amino acid removal is a classic reaction termed Edman degradation. This method involves repeated treatment of the N-terminal amino group of a peptide with phenyl isothiocyanate (PITC), followed by treatment with trifluoroacetic acid. Spurred by the need for an alternative non-acid-based chemistry for next-generation protein sequencing technologies, we developed a base-induced N-terminal degradation method. Several N-terminal derivatization reagents carrying supernucleophiles were tested. After rounds of iterative designs, compound DR3 , with a N -hydroxysuccinimide as a leaving group and hydrazinecarboxamide as the supernucleophile, demonstrated the highest yield for the peptide derivatization step and the most efficient elimination of the N-terminal amino acid in just 1% of a hydroxide salt. The method successfully removed all 20 amino acids at the N-terminus in high yield. The technique demonstrates compatibility with oligonucleic acids, which differs from Edman degradation due to their inherent sensitivity to acidic environments. To demonstrate the practical application of our approach, we sequenced amino acids sequentially from a peptide, effectively determining the sequence of an unknown peptide. Notably, our methodology was successfully applied to mixtures of peptides derived from protein samples, where a significant fraction of the peptides derivatized with DR3 underwent elimination of their N-terminal amino acid upon addition of base. Overall, although our method does not outperform Edman degradation in efficiency, it serves as a valuable alternative in cases where base-induced cleavage is advantageous, particularly for preserving acid-sensitive functionalities.}, archive = {J_JACS}, author = {Harnimarta Deol and Ava Raeisbahrami and Phuoc H.T. Ngo and Jagannath Swaminathan and Ophelia Papoulas and Edward M. Marcotte and Eric V. Anslyn}, doi = {10.1021/jacs.5c03385}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13973--13982}, shortjournal = {J. Am. Chem. Soc.}, title = {After 75 years, an alternative to edman degradation: A mechanistic and efficiency study of a base-induced method for N-terminal peptide sequencing}, volume = {147}, year = {2025}, }
• (2025). A bimolecular Diels–Alder reaction mediated by inclusion in a polar bis-calix[4]pyrrole octa-imine cage. JACS, 147(16), 13962--13972. (www)

  @article{ , abstract = {We describe using a dynamically self-assembled octa-imine cage as a molecular flask to accelerate a bimolecular Diels–Alder reaction. We investigate the cage’s binding properties using 1 H NMR spectroscopic titrations, ITC experiments, and X-ray crystallography. We detect and characterize the formation of the ternary complex (Michaelis) in solution. A detailed kinetic analysis of the reaction data supports that the cage’s acceleration is provided by including the two reactants, resulting in an effective molarity (EM) of ∼40 M. Exo -selectivity and shift of the reaction’s chemical equilibrium are also encountered in the cage’s confined space. Our results mimic enzymes’ ability to bind two substrates in a polar cavity, using directional interactions, and accelerate their stereoselective reaction, with the potential for cavity engineering to enable other reactions.}, archive = {J_JACS}, author = {Jiaming Huang and Pablo Ballester}, doi = {10.1021/jacs.5c03361}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13962--13972}, shortjournal = {J. Am. Chem. Soc.}, title = {A bimolecular Diels–Alder reaction mediated by inclusion in a polar bis-calix[4]pyrrole octa-imine cage}, volume = {147}, year = {2025}, }
• (2025). Giant near-infrared induced polarization change via a long-lived hidden phase of a valence tautomeric complex. JACS, 147(16), 13953--13961. (www)

  @article{ , abstract = {Light-induced polarization change has attracted significant attention due to its rapid response and nondestructive nature, positioning it as a promising candidate for next-generation molecular storage devices and energy harvesting. However, achieving substantial photoconversion that results in giant polarization changes via a hidden phase under near-infrared light irradiation remains a formidable challenge. In this study, we successfully synthesized a novel [CrCo] complex with an enantiopure ligand. Unlike previously reported Co valence tautomeric (VT) complexes, this complex exhibits light-induced VT (LIVT) with nearly complete photoconversion ratio upon irradiation with a 1340 nm laser. Additionally, the molecules pack in the P 2 1 polar space group with an optimized arrangement, leading to a giant NIR-induced polarization change (1.71 μC cm –2 ), which surpasses that of other nonferroelectric crystals. Importantly, electric measurements and single-crystal X-ray analysis after irradiation revealed that the induced polarization change is related to not only the directional electron transfer but also the displacement of anions, which render a distinct hidden metastable phase compared to the thermally approachable one. Moreover, pyroelectric measurement was first used to characterize relaxation kinetics after light irradiation.}, archive = {J_JACS}, author = {Wenwei Zheng and Shu-Qi Wu and Qirui Shui and Shinji Kanegawa and Sheng-Qun Su and Osamu Sato}, doi = {10.1021/jacs.5c02909}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13953--13961}, shortjournal = {J. Am. Chem. Soc.}, title = {Giant near-infrared induced polarization change via a long-lived hidden phase of a valence tautomeric complex}, volume = {147}, year = {2025}, }
• (2025). Rational control of ionic conduction of encapsulated ionic liquid by fluorination of isoreticular Metal–Organic frameworks. JACS, 147(16), 13948--13952. (www)

  @article{ , abstract = {Hybrid materials have attracted much attention in solid-state conductors because of their great advantage in various combinations of components. In this study, the control of ionic conductivity of ionic liquid (IL), which is encapsulated in micropores of metal–organic frameworks (MOFs), has been realized by the chemical modification of the ligands of MOFs for the first time. When IL, 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide ((EMI)(TFSA)), is encapsulated into the pores with a 50% volumetric filling level, it shows the highest ionic conductivity when encapsulated in the fluorous MOF among the three isoreticular zinc-based microporous MOFs; the ionic diffusivity is 1 order of magnitude higher than that of (EMI)(TFSA)-encapsulated non-fluorous MOF. Computational simulations indicate that the mobility of (EMI)(TFSA) in a non-fluorous framework is significantly restricted due to abundant C–H···F interactions, whereas the introduction of fluorine atoms on the ligands suppresses the C–H···F interactions, thereby showing the highest ionic conductivity. On the other hand, the ion migration of encapsulated (EMI)(TFSA) is not greatly affected by the fluorination of the ligands at a 100% filling level, because the possible different IL distributions with a 50% filling level are largely eliminated for the fully occupied (EMI)(TFSA).}, archive = {J_JACS}, author = {Tuo Di and Yukihiro Yoshida and Hiroshi Kitagawa}, doi = {10.1021/jacs.5c02879}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13948--13952}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational control of ionic conduction of encapsulated ionic liquid by fluorination of isoreticular Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Exploring the balance between faradaic and non-faradaic processes in organic chemical reactions at plasma-liquid interfaces. JACS, 147(16), 13937--13947. (www)

  @article{ , abstract = {Electrochemistry can enable sustainable chemical manufacturing but is limited by the reactions possible with conventional metal electrodes. Plasma electrochemistry, which replaces a conventional solid electrode with plasma in electrochemical cells, opens new avenues for chemical synthesis by combining Faradaic and non-Faradaic processes at the plasma-liquid interface. To understand how plasma electrochemistry differs from conventional electrochemistry, we investigated plasma reactions with acrylonitrile, an industrially relevant molecule used as the precursor in the well-characterized electrosynthesis of adiponitrile. We demonstrate that non-Faradaic processes dominate plasma-driven chemistry through systematic variation of plasma polarity, current, and reactant concentration, combined with comprehensive quantitative analysis of solid, liquid, and gas products. Most notably, we observed no adiponitrile formation (the desired electrochemical product), while total product yields exceeded the theoretical charge-transfer maximum by up to 32-fold. Substantial polyacrylonitrile formation occurred under all conditions, a product not typically seen in conventional electrochemistry. The plasma anode produced consistently higher yields than the plasma cathode, generating hydrogen and propionitrile at 21 and 2 times the charge-transfer maximum, respectively. Electron scavenger experiments confirmed these transformations occurred primarily through non-Faradaic processes rather than charge transfer. These results demonstrate that plasma electrochemistry with acrylonitrile is primarily driven by non-Faradaic processes at plasma-electrolyte interfaces, providing fundamental insights for harnessing these interactions in chemical synthesis.}, archive = {J_JACS}, author = {Casey K. Bloomquist and Daniel Naumov and Ahrin Yang and Ricardo Mathison and Benjamin D. Herzog and William J. Tenn, III and Miguel A. Modestino and Eray S. Aydil}, doi = {10.1021/jacs.5c02740}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13937--13947}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploring the balance between faradaic and non-faradaic processes in organic chemical reactions at plasma-liquid interfaces}, volume = {147}, year = {2025}, }
• (2025). Homonuclear/Heteronuclear bimetallic conjugated coordination polymers with customized oxygen evolution pathway. JACS, 147(16), 13928--13936. (www)

  @article{ , abstract = {The reasons for the generally superior performance of synergistic effects in bimetallic catalysts in the oxygen evolution reaction (OER) are not fully understood, largely due to the complexity of catalyst structures and the challenges associated with synthesizing long-range atomic ordering catalysts. In this study, we present a series of two-dimensional (2D) conjugated bimetallic coordination polymers (c-CPs) involving Co or Ni with unambiguous and nearly identical geometry structures for the electrocatalysis of OER, which are highly suitable for discussions on structure–property correlations. The heteronuclear CoNi-PI unexpectedly alters the OER catalytic mechanisms from adsorbate evolution mechanism those observed in homonuclear CoCo-PI and NiNi-PI to the kinetically faster oxide path mechanism, exhibiting high stability and an ultralow overpotential of 282 mV even at 100 mA cm –2 with a Tafel slope of approximately 42 mV dec –1 . This study presents an extremely rare crystalline heteronuclear bimetallic catalyst with excellent catalytic properties, promising significant influences in catalyst development research.}, archive = {J_JACS}, author = {Yuhao Weng and Lizhi Sun and Hao Jia and Wenjuan Shang and Jie-Jie Chen and Barun Dhara and Yong Chen and Fei Huang and Shu Han and Hangjuan He and Baipeng Yin and Chuang Zhang and Ben Liu and Zhongxin Chen and Jingsong You and Daigo Miyajima and Cheng Zhang}, doi = {10.1021/jacs.5c02700}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13928--13936}, shortjournal = {J. Am. Chem. Soc.}, title = {Homonuclear/Heteronuclear bimetallic conjugated coordination polymers with customized oxygen evolution pathway}, volume = {147}, year = {2025}, }
• (2025). Involving carbene or not? mechanism of Corey–Winter reaction. JACS, 147(16), 13915--13927. (www)

  @article{ , abstract = {The mechanism of the Corey–Winter reaction is unclear, even though this reaction, discovered more than 60 years ago, has evolved as an indispensable method of synthesizing olefins from diols. We report a computational study of the mechanism of the Corey–Winter reaction, ruling out three well-known pathways of this reaction and proposing a new pathway consistent with the experimental observations. This new pathway starts from nucleophilic addition of phosphite to the carbon (not the sulfur) atom of the cyclic thionocarbonates. This step is followed by the intramolecular addition of S to P, generating thiaphosphirane intermediates. Elimination of phosphorothioates then takes place, giving oxygen-heterocyclic carbenes (OHCs). Finally, the cycloreversion of the OHCs gives carbon dioxide and the target olefin products. Calculations support that the OHC intermediates are involved in the Corey–Winter reaction. In addition, the Woodward–Hoffmann orbital correlation and electron flow pattern for the cycloreversion process of the OHCs to olefins and carbon dioxide have been revised. Moreover, why diazaphospholidine can accelerate the Corey–Winter reaction has been rationalized in this study by multivariable linear regression analysis.}, archive = {J_JACS}, author = {Pan Zhang and Zhi-Xiang Yu}, doi = {10.1021/jacs.5c02629}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13915--13927}, shortjournal = {J. Am. Chem. Soc.}, title = {Involving carbene or not? mechanism of Corey–Winter reaction}, volume = {147}, year = {2025}, }
• (2025). Heterogeneous-interface-induced charge redistribution toward fe-based polyanion cathode for advanced sodium-ion batteries. JACS, 147(16), 13905--13914. (www)

  @article{ , abstract = {Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 (NFPP) is gradually developing into one of the most commercially prospective cathode materials for sodium-ion batteries. However, the inactive phase maricite-NaFePO 4 (m-NFP) normally tends to be formed during the synthesis process of NFPP, as well as the intrinsic poor electronic conductivity, which impacts the realization of high Na-storage performance. Herein, for the first time, we have constructed a heterostructure in Fe-based polyanionic cathode materials by fine-tuning the stoichiometric ratio of the Na site; the inactive phase m-NFP is fully transformed to the active Na 2 FeP 2 O 7 or NFPP. In NFPP-NFPO heterogeneous composites, density functional theory calculations reveal that the charge redistribution occurs at the heterogeneous interface, leading to stronger and more uniform interactions that can strengthen the structural stability and enhance the charge transport kinetics. Benefiting from the heterogeneous intergrowth structure and the formation of the electrochemically active phase, a high discharge specific capacity, ultralong cycle life (71.4% capacity retention after 10,000 cycles at 50 C), ultrafast rate capability (60.2 mAh g –1 at 200 C), and impressive high-temperature tolerance have been achieved. This work achieves heterogeneous composites by manipulation of the phase composition, providing a new approach for designing high-performance polyanionic cathodes for sodium-ion batteries.}, archive = {J_JACS}, author = {Ze-Lin Hao and Jin-Zhi Guo and Miao Du and Xin-Ru Zhang and Yong-Li Heng and Zhen-Yi Gu and Xiao-Tong Wang and Xin-Xin Zhao and Ning Yu and Zi-Hang Xue and Shuo-Hang Zheng and Bao Li and Xing-Long Wu}, doi = {10.1021/jacs.5c02480}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13905--13914}, shortjournal = {J. Am. Chem. Soc.}, title = {Heterogeneous-interface-induced charge redistribution toward fe-based polyanion cathode for advanced sodium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Oxetane cleavage pathways in the excited state: Photochemical kinetic resolution as an approach to enantiopure oxetanes. JACS, 147(16), 13893--13904. (www)

  @article{ , abstract = {Chiral spirocyclic oxetanes [2-oxo-spiro(3 H -indole-3,2′-oxetanes)] were subjected to irradiation in the presence of a chiral thioxanthone catalyst (5 mol %) at λ = 398 nm. An efficient kinetic resolution was observed, which led to an enrichment of one oxetane enantiomer as the major enantiomer (15 examples, 37−50% yield, 93−99% ee ). The minor enantiomer underwent decomposition, and the decomposition products were carefully analyzed. They arise from a photocycloreversion (retro-Paternò–Büchi reaction) into a carbonyl component and an olefin. The cycloreversion offers two cleavage pathways depending on whether a C−O bond scission or a C−C bond scission occurs at the spirocyclic carbon atom. The course of this reaction was elucidated by a suite of mechanistic, spectroscopic, and quantum chemical methods. In the absence of a catalyst, cleavage occurs exclusively by initial C−O bond scission, leading to formaldehyde and a tetrasubstituted olefin as cleavage products. Time-resolved spectroscopy on the femtosecond/picosecond time scale, synthetic experiments, and calculations suggest the reaction to occur from the first excited singlet state (S 1 ). In the presence of a sensitizer, triplet states are populated, and the first excited triplet state (T 1 ) is responsible for cleavage into an isatin and a 1,1-diarylethene by an initial C−C bond scission. The kinetic resolution is explained by the chiral catalyst recruiting predominantly one enantiomer of the spirocyclic oxindole. A two-point hydrogen-bonding interaction is responsible for the recognition of this enantiomer, as corroborated by NMR titration studies and quantum chemical calculations. Transient absorption studies on the nanosecond/microsecond time scale allowed for observing the quenching of the catalyst triplet by either one of the two oxetane enantiomers with a slight preference for the minor enantiomer. In a competing situation with both enantiomers present, energy transfer to the major enantiomer is suppressed initially by the better-binding minor enantiomer and─as the reaction progresses─by oxindole fragmentation products blocking the binding site of the catalyst.}, archive = {J_JACS}, author = {Niklas Pflaum and Mike Pauls and Ajeet Kumar and Roger Jan Kutta and Patrick Nuernberger and Jürgen Hauer and Christoph Bannwarth and Thorsten Bach}, doi = {10.1021/jacs.5c02483}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13893--13904}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxetane cleavage pathways in the excited state: Photochemical kinetic resolution as an approach to enantiopure oxetanes}, volume = {147}, year = {2025}, }
• (2025). Photoinduced formation of oxygen vacancies on mo-incorporated WO3 for direct oxidation of benzene to phenol by air. JACS, 147(16), 13885--13892. (www)

  @article{ , abstract = {Photocatalysts with abundant oxygen vacancies (OVs) exhibit enhanced activity for the direct oxidation of benzene to phenol with O 2 , owing to their superior O 2 activation and charge separation properties. However, OVs on metal oxide surfaces such as WO 3 are susceptible to healing by oxygen-containing reactants or intermediates, leading to their irreversible deactivation. Herein, we demonstrate that incorporating Mo into the WO 3 lattice effectively lowers the energy barrier for OV formation, promoting the dynamic formation of more abundant photoinduced OVs in situ on the surface during the photocatalytic reaction. These Mo-promoted photoinduced OVs are found to ensure the long-term sustainability of sufficient OVs under working conditions, enhancing photocatalytic performance and particularly its durability in the aerobic oxidation of benzene to phenol. These findings provide a straightforward strategy to overcome the issue of OV healing, enabling the sustainable operation of OV-rich photocatalysts for a range of emerging applications, even in O 2 -involved redox reactions.}, archive = {J_JACS}, author = {Zhenzhen Yu and Dexi Yu and Xiaoyi Wang and Meirong Huang and Yidong Hou and Wei Lin and Masakazu Anpo and Jimmy C. Yu and Jinshui Zhang and Xinchen Wang}, doi = {10.1021/jacs.5c02086}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13885--13892}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoinduced formation of oxygen vacancies on mo-incorporated WO3 for direct oxidation of benzene to phenol by air}, volume = {147}, year = {2025}, }
• (2025). Tripodal silanolate ligands expand [MoX3] chemistry beyond its traditional borders. JACS, 147(16), 13871--13884. (www)

  @article{ , abstract = {Homodimeric complexes [X 3 Mo≡MoX 3 ] are commonplace, but in no case is the corresponding monomeric [MoX 3 ] species known; conversely, none of the very rare monomeric complexes [MoX 3 ] has the respective homodimeric analogue. This mutual exclusivity ends with the present study; on top, an entirely unprecedented class of heterodimers of type [X 3 Mo≡MoY 3 ] is reported. Key to success was the use of tripodal silanolates as ancillary ligands; the fence formed by properly chosen peripheral substituents shields the sensitive Mo(+3) center; homodimerization of the resulting [MoX 3 ] complexes is then kinetically strongly disfavored, though possible. The monomers are able to cleave N 2 O and convert gem -dihalides into metal alkylidynes; they exist in different binding modes, in which the basal phenyl ring of the ligand backbone is either completely unengaged with the central metal or tightly bound to it, depending on whether the ligand sphere is complemented by solvent molecules or not. If the latter are sufficiently labile, a surprisingly facile heterodimerization of the d 3 electron fragments will ensue; the resulting products [X 3 Mo≡MoY 3 ] incorporate the intact Cummins complex [( t Bu)(Ar)N] 3 Mo (Ar = 3,5-dimethylphenyl) as one of their constituents, which is famous for not engaging in metal–metal triple bonding otherwise. Heterodimerization was also observed with simple tert -butoxide ligands. The new type of heterodimers features unusually long yet robust Mo≡Mo bonds, which are notably polarized according to DFT. However, there is no direct correlation between the extreme Mo≡Mo bond lengths and the strikingly deshielded 95 Mo NMR signals, since ligand-based orbitals can also markedly affect the shielding tensor.}, archive = {J_JACS}, author = {Daniel Rütter and Nils Nöthling and Markus Leutzsch and Alexander A. Auer and Alois Fürstner}, doi = {10.1021/jacs.5c02178}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13871--13884}, shortjournal = {J. Am. Chem. Soc.}, title = {Tripodal silanolate ligands expand [MoX3] chemistry beyond its traditional borders}, volume = {147}, year = {2025}, }
• (2025). Ligand shell thickness of colloidal nanocrystals: A comparison of small-angle neutron and X-ray scattering. JACS, 147(16), 13859--13870. (www)

  @article{ , abstract = {Colloidal nanocrystals (NCs) are coated by an organic ligand shell that imparts colloidal stability, mediates self-assembly, and impacts functional properties. Despite the variety of methods to chemically characterize ligands, common structural characterization techniques like small-angle X-ray scattering (SAXS) and electron microscopy selectively resolve the NC core and can only indirectly infer the structure of ligands. Small-angle neutron scattering (SANS) can directly characterize the ligand shell structure of colloidal NCs, enabled by the unique sensitivity of SANS to organic molecules. In this work, we compare and contrast the information about the NC ligand shell gained directly through SANS and indirectly through SAXS. Monodisperse oleyl-capped PbS NCs were synthesized with varying core sizes (4.8 – 7.4 nm diameter) and solvents (toluene, n -hexane, cyclohexane). We then performed SANS to extract the ligand shell thickness and composition, SAXS to infer the ligand structure from NC interactions, and grazing-incidence SAXS to compare interparticle distances in self-assembled PbS NC superlattices. We observe with SANS that ligands extend up to 15% farther away from the NC surface with increasing core size over the size range studied, attributed to curvature effects that are not captured by the inferred structure from SAXS. We also see that the ligand shell thickness varies with solvent identity due to differences in how solvent molecules penetrate the ligand shell. In a detailed comparison, we demonstrate that SANS, SAXS, and GISAXS reveal distinct but complementary information about the ligand shell, enabling the holistic characterization of the structure–property relationships of NCs from colloid to self-assembled superlattice.}, archive = {J_JACS}, author = {Eliza K. Price and Guilherme Bejar and Jimin Kwag and Niamh Brown and Lilin He and William A. Tisdale}, doi = {10.1021/jacs.5c02070}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13859--13870}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand shell thickness of colloidal nanocrystals: A comparison of small-angle neutron and X-ray scattering}, volume = {147}, year = {2025}, }
• (2025). Enzyme-mediated dynamic combinatorial chemistry enables large-scale synthesis of δ-cyclodextrin. JACS, 147(16), 13851--13858. (www)

  @article{ , abstract = {α-, β-, and γ-cyclodextrins (CDs) are macrocycles formed from six, seven, and eight α-1,4-linked d -glucopyranose units and are industrially produced on ton scales for use as hosts for bioactive guests in foods, cosmetics, and pharmaceuticals. Large-ring cyclodextrins, with more than eight glucose units, have been known for decades but never isolated in more than milligram quantities. We report a scalable method to synthesize δ-CD, formed from nine glucose units, in high yield (>40%), high purity (>95% purity without chromatography), and unprecedented quantities (multigram scale). We exploit a superchaotropic dodecaborate template, B 12 Cl 12 2– , to direct the selective synthesis of δ-CD from within an enzyme-mediated dynamic combinatorial library of interconverting cyclodextrins. Our single-step reaction uses a recyclable template, cheap starting materials, and a commercial ‘food-grade’ enzyme and can thus give access to large quantities of δ-CD. This work will enable the first large-scale investigations of the properties and applications of this little-known larger CD.}, archive = {J_JACS}, author = {Kasper H. Hansen and Andreas Erichsen and Dennis Larsen and Sophie R. Beeren}, doi = {10.1021/jacs.5c02055}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13851--13858}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzyme-mediated dynamic combinatorial chemistry enables large-scale synthesis of δ-cyclodextrin}, volume = {147}, year = {2025}, }
• (2025). Ultrasound-energized OX40L-expressing biohybrid for multidimensional mobilization of sustained t cell-mediated antitumor immunity and potent sono-immunotherapy. JACS, 147(16), 13833--13850. (www)

  @article{ , abstract = {Harnessing immunostimulation to reinvigorate antitumor effector immune cells represents a promising strategy for tumor eradication. However, achieving durable clinical outcomes necessitates multidimensional activation to sustain robust immune responses. Here, we present an ultrasound-empowered living biohybrid that strategically mobilizes T-cell-mediated immunity for potent tumor sono-immunotherapy. Through synthetic biology, we engineer bacteria to express a fusion protein encoding the costimulatory OX40 ligand (OX40L), and further functionalize them with a high-performance polymer sonosensitizer tethered via a reactive oxygen species-cleavable linker. Upon ultrasound irradiation, the sono-activated nanocargoes detach from the bacterial surface, facilitating cellular entry and exposing immune-stimulating OX40L. The potent sonodynamic effects, coupled with the native immunogenicity of bacteria, promotes tumor-associated antigen release, fosters a proinflammatory microenvironment, and drives dendritic cell maturation, thereby priming cytotoxic T-cell activation. The OX40L expressed by the engineered bacteria amplifies and sustains T-cell activity, orchestrating a robust and durable antitumor response. This cascade-amplified immune activation effectively suppresses tumor growth, induces long-lasting immune memory, and provides protection against tumor metastasis and recurrence, significantly enhancing survival outcomes. By integrating ultrasound-energized nanoadjuvants with costimulatory immune boosters, this hybrid living biotherapeutic platform offers a versatile and powerful strategy for multidimensional immune activation, advancing the frontier of cancer sono-immunotherapy.}, archive = {J_JACS}, author = {Mengyun Liang and Xiaoying Kang and Hanwen Liu and Lu Zhang and Tianjiao Wang and Mengjie Ye and Wen Li and Ji Qi}, doi = {10.1021/jacs.5c02025}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13833--13850}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrasound-energized OX40L-expressing biohybrid for multidimensional mobilization of sustained t cell-mediated antitumor immunity and potent sono-immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Sulfenylcarbene-mediated carbon atom insertion for the late-stage functionalization of N-heterocycles. JACS, 147(16), 13824--13832. (www)

  @article{ , abstract = {Late-stage functionalization (LSF) is a crucial strategy in drug discovery, allowing the modification of complex molecules, including pharmaceuticals, to enhance chemical diversity in drug libraries. We harness the chemoselectivity of sulfenylcarbenes, which selectively react with alkenes even in the presence of more reactive functional groups such as alcohols, carboxylic acids, and amines. This reactivity allows sulfenylcarbenes to insert a single carbon atom bearing diverse functional groups, transforming pyrroles, indoles, and imidazoles into synthetically challenging pyridines, quinolines, and pyrimidines, respectively. Sulfenylcarbene precursors are easily synthesized in two steps from commercially available reagents. Our metal-free LSF approach employs benchtop-stable sulfenylcarbene precursors and enables late-stage modification of natural products, amino acids, pharmaceuticals, and C -glycosides. Mechanistic studies and density functional theory (DFT) calculations were conducted to investigate the regio- and chemoselectivity outcomes.}, archive = {J_JACS}, author = {Prakash Kafle and Deacon Herndon and Indrajeet Sharma}, doi = {10.1021/jacs.5c02012}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13824--13832}, shortjournal = {J. Am. Chem. Soc.}, title = {Sulfenylcarbene-mediated carbon atom insertion for the late-stage functionalization of N-heterocycles}, volume = {147}, year = {2025}, }
• (2025). Anisotropy of Spin–Lattice relaxation time (T1) for oxo-Vanadium(IV) and nitrido Chromium(V) porphyrins. JACS, 147(16), 13815--13823. (www)

  @article{ , abstract = {Designing molecular complexes as qubits requires understanding properties that contribute to long electron spin–lattice relaxation times. Spin–lattice relaxation was measured as a function of temperature and position in the spectrum for vanadyl tetraphenylporphyrin (VOTPP) in titanyl tetraphenylporphyin (TiOTPP) and zinc tetraphenylporphyrin (ZnTPP) hosts and for nitrido chromium(V) TPP in TiOTPP. T 1 also was measured for the vanadyl complexes of octaethylporphyrin (OEP) and tetratolylporphyrin (TTP) in ZnOEP or ZnTTP, respectively. T 1 anisotropy is defined as the ratio of T 1 when the magnetic field is along the VO or CrN bond (the z axis) to T 1 when the magnetic field is in the porphyrin plane. For these vanadyl and Cr(V) porphyrins, T 1 anisotropy increases rapidly between about 60 and 140 K and is strongly dependent on the host lattice, ranging from the unusually large maxima of 36 for VOTPP in TiOTPP and 28 for CrNTPP in TiOTPP to 3.8 for VOTPP in ZnTPP and 3.3 for VOOEP in ZnOEP. Empirical modeling of the temperature dependence of T 1 showed that phonons with energies of 170 to 225 cm –1 made substantially larger contributions to relaxation in the perpendicular plane than along the z axis and that the magnitudes of these contributions were strongly dependent on the host lattice. These results demonstrate that optimizing molecules as qubits requires consideration of interaction with the host lattice in addition to molecular properties.}, archive = {J_JACS}, author = {Sandra S. Eaton and Tsutomu Yamabayashi and Yoji Horii and Masahiro Yamashita and Gareth R. Eaton}, doi = {10.1021/jacs.5c01962}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13815--13823}, shortjournal = {J. Am. Chem. Soc.}, title = {Anisotropy of Spin–Lattice relaxation time (T1) for oxo-Vanadium(IV) and nitrido Chromium(V) porphyrins}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of (+)-hazuntiphylline, (−)-anhydrohazuntiphyllidine, and (−)-hazuntiphyllidine. JACS, 147(16), 13808--13814. (www)

  @article{ , abstract = {The first total synthesis of the bisindole alkaloids (+)-hazuntiphylline, (−)-anhydrohazuntiphyllidine, and (−)-hazuntiphyllidine is described. We envisioned an efficient synthetic strategy based on a plausible biosynthetic hypothesis for the rapid assembly of these complex alkaloids via successive methylenation of an oxidized variant of the natural product (−)-mehranine. Our concise synthesis of these alkaloids required the development of completely stereoselective double alkylation sequences of transiently formed C3-enamines and precise timing for hydration of intricate intermediates. Whereas homodimerization of a C3-methylene mehranine-derivative exclusively gave (−)-3- epi -anhydrohazuntiphyllidine, an alternative alkylation cascade was developed to afford the natural products (−)-anhydrohazuntiphyllidine and (+)-hazuntiphylline. Insights gained in these studies concerning the intermediacy of hydrated intermediates enabled a completely stereoselective synthesis of (−)-hazuntiphyllidine, the most complex member of the Hazunta alkaloids. We discuss our hypothesis for the rapid assembly of these intriguing alkaloids, including our completely controlled access to both the natural and epimeric C3-quaternary stereochemistry of anhydrohazuntiphyllidine, and analysis of plausible biosynthetic intermediates including a sensitive methylenebisdesmethylmehranine-derivative, highlighting divergent pathways to each natural alkaloid based on the order of C–C and C–N bond formation and the hydration of putative intermediates.}, archive = {J_JACS}, author = {Robert-Cristian Raclea and Marius Mewald and Kolby L. White and Mohammad Movassaghi}, doi = {10.1021/jacs.5c01932}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13808--13814}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of (+)-hazuntiphylline, (−)-anhydrohazuntiphyllidine, and (−)-hazuntiphyllidine}, volume = {147}, year = {2025}, }
• (2025). Large hyperfine coupling arising from pseudo-2S ground states in a series of Lutetium(II) metallocene complexes. JACS, 147(16), 13799--13807. (www)

  @article{ , abstract = {The synthesis of molecules with strong coupling between electronic and nuclear spins represents an important challenge in molecular quantum information science. Here, we report the synthesis and characterization of the divalent lutetium metallocene complexes Lu(Cp Me 5 )(Cp i Pr 5 ) (Cp Me 5 = pentamethylcyclopentadienyl; Cp i Pr 5 = pentaisopropylcyclopentadienyl), Lu(Cp i Pr 4 Et ) 2 (Cp i Pr 4 Et = ethyltetraisopropylcyclopentadienyl), and Lu(Cp i Pr 4 ) 2 (Cp i Pr 4 = tetraisopropylcyclopentadienyl). The molecular structures of these complexes, as determined through single-crystal X-ray diffraction, feature a common bent sandwich geometry, with average Cp–Lu–Cp angles ranging from 159.9° to 152.6°. Analysis of continuous-wave electron paramagnetic resonance (EPR) spectra for the complexes reveals nearly isotropic g tensors with only a slight deviation from that of a free electron. Moreover, an extremely large splitting of the eight-line spectra indicates the presence of strong hyperfine coupling, and simulations provide isotropic hyperfine coupling constants of A iso = 4.38, 4.30, and 4.17 GHz across the series, where the value of A iso is found to decrease as the Cp–Lu–Cp angle becomes more acute. Notably, these values are the largest yet observed for any lanthanide complex. Moreover, EPR and computational analysis show that the large values of A iso stem from large s-orbital character─up to 41.2%─in the corresponding singly occupied molecular orbitals. To our knowledge, this degree of s-character in a molecular orbital is the largest yet reported for an open-shell isolable complex. These results outline a general strategy toward the isolation of paramagnetic molecules with strong hyperfine coupling and highly isotropic doublet electronic ground states.}, archive = {J_JACS}, author = {Danh X. Ngo and K. Randall McClain and Jakub Hrubý and Yannick J. Franzke and Krishnendu Kundu and Hyunchul Kwon and Colin A. Gould and Benjamin G. Harvey and Stephen Hill and Jeffrey R. Long}, doi = {10.1021/jacs.5c01947}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13799--13807}, shortjournal = {J. Am. Chem. Soc.}, title = {Large hyperfine coupling arising from pseudo-2S ground states in a series of Lutetium(II) metallocene complexes}, volume = {147}, year = {2025}, }
• (2025). Unraveling the unique behavior of atomically dispersed pt on zeolite fe-DeAlBEA for catalyzing propane dehydrogenation with cofed hydrogen. JACS, 147(16), 13784--13798. (www)

  @article{ , abstract = {Propene, used on a large scale to manufacture polypropylene and several commodity chemicals, is increasingly produced by catalytic propane dehydrogenation (PDH). Atomically dispersed Pt has emerged as a promising candidate catalyst for PDH; however, stabilizing atomically dispersed Pt at high temperatures is challenging. Here, we demonstrate the use of dealuminated zeolite beta with a high Fe content as a host for stabilizing isolated Pt, which is anchored strongly to the zeolite support by Pt–Fe bonds. The isolated Pt–Fe sites exhibit promising PDH performance, including a high apparent forward rate coefficient for propene formation (404.8–26.4 mol propene/mol Pt·bar·s) and a high selectivity (≥96%) at 823 K in the presence of H 2 . Kinetics data characterizing the rate of PDH with a range of Pt loadings show that atomically dispersed Pt catalyzes propene formation at rates independent of H 2 partial pressure, whereas metallic Pt clusters, formed at high Pt loadings, catalyze the reaction with a slightly negative dependence on H 2 partial pressure. The shift in Pt speciation with Pt loading, confirmed by infrared spectroscopy of adsorbed CO, X-ray absorption spectroscopy, and high-angle angular dark field scanning transmission electron microscopy, suggests that the observed change in kinetics with Pt dispersion is a consequence of a change in the reaction mechanism.}, archive = {J_JACS}, author = {Afnan Alghannam and Alexander J. Pattison and Sonali Das and Chaochao Dun and Peter Ercius and Jeffrey J. Urban and Bruce C. Gates and Alexis T. Bell}, doi = {10.1021/jacs.5c01730}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13784--13798}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the unique behavior of atomically dispersed pt on zeolite fe-DeAlBEA for catalyzing propane dehydrogenation with cofed hydrogen}, volume = {147}, year = {2025}, }
• (2025). Sub-4 nm ru-RuO2 schottky nanojunction as a catalyst for durable acidic water oxidation. JACS, 147(16), 13775--13783. (www)

  @article{ , abstract = {RuO 2 with high intrinsic activity for water oxidation is a promising alternative to IrO 2 in proton exchange membrane (PEM) electrolyzer, but it suffers from long-term stability issues due to overoxidation. Here, we report a sub-4 nm Ru-RuO 2 Schottky nanojunction (Ru-RuO 2 –SN) prepared by a microwave reaction that exhibits high activity and long-term stability in both three-electrode systems and PEM devices. The lattice strain and charge transfer induced by the metal-oxide SN increase the work function of the Ru-RuO 2 –SN, optimize the local electronic structure, and reduce the desorption energy of the metal site to the oxygen-containing intermediates; as a result, it leads to the oxide path mechanism (OPM) and inhibits the excessive oxidation of surface ruthenium. The Ru-RuO 2 –SN requires only 165 mV overpotential to obtain 10 mA·cm –2 with 1400 h stability without obvious activity degradation, achieving a stability number (6.7 × 10 6 ) matching iridium-based catalysts. In a PEM electrolyzer with Ru-RuO 2 –SN as an anode catalyst, only 1.6 V is needed to reach 1.0 A·cm –2 and it shows long-term stability at 100 mA·cm –2 for 1100 h and at 500 mA·cm –2 for 100 h. The reaction mechanism for the high stability of Ru-RuO 2 –SN was analyzed by density functional theory calculations. This work reports a durable, pure Ru-based water-oxidation catalyst and provides a new perspective for the development of efficient Ru-based catalysts.}, archive = {J_JACS}, author = {Yuxiang Song and Wanghui Zhao and Zhi Wang and Weili Shi and Feiyang Zhang and Zhuoming Wei and Xin Cui and Yihan Zhu and Tao Wang and Licheng Sun and Biaobiao Zhang}, doi = {10.1021/jacs.5c01876}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13775--13783}, shortjournal = {J. Am. Chem. Soc.}, title = {Sub-4 nm ru-RuO2 schottky nanojunction as a catalyst for durable acidic water oxidation}, volume = {147}, year = {2025}, }
• (2025). Biomimetic total synthesis and paired omics identify an intermolecular Diels–Alder reaction as the key step in lugdunomycin biosynthesis. JACS, 147(16), 13764--13774. (www)

  @article{ , abstract = {Microbial natural products are the basis of the majority of clinical drugs, where the discovery of truly novel structural scaffolds to fill the discovery pipelines is a prerequisite. Lugdunomycin is a highly rearranged angucycline polyketide produced by Streptomyces sp. QL37, with an enigmatic biosynthetic pathway. Here we show that lugdunomycin is formed by a rare intermolecular Diels–Alder reaction, with elmonin as a masked diene and iso -maleimycin as a dienophile. Genomics, mutational analysis, and heterologous expression revealed that the biosynthesis of the substrates is encoded by distinct biosynthetic gene clusters (BGCs), whereby elmonin is specified by an angucycline BGC, while the biosynthesis of iso -maleimycin is encoded by a BGC for a β-lactone-like compound. Biomimetic total synthesis of lugdunomycin showed that the Diels–Alder reaction leads to the production of a diastereomer of lugdunomycin as the main product in vitro. The diastereomeric ratio of the in vitro Diels–Alder reaction shifted toward lugdunomycin in the presence of proteinaceous material, suggesting that the in vivo Diels–Alder reaction is templated. Alphafold modeling and experimental data suggest that GarL could potentially function as a Diels–Alder template in lugdunomycin biosynthesis. The requirement of distinct biosynthetic pathways and complex chemical reactions indicates the challenges we face in discovering new chemical space.}, archive = {J_JACS}, author = {Michiel T. Uiterweerd and Isabel Nuñez Santiago and Ana V. Cunha and Remco W. A. Havenith and Chao Du and Le Zhang and Helga U. van der Heul and Somayah S. Elsayed and Adriaan J. Minnaard and Gilles P. van Wezel}, doi = {10.1021/jacs.5c01883}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13764--13774}, shortjournal = {J. Am. Chem. Soc.}, title = {Biomimetic total synthesis and paired omics identify an intermolecular Diels–Alder reaction as the key step in lugdunomycin biosynthesis}, volume = {147}, year = {2025}, }
• (2025). USP28-based deubiquitinase-targeting chimeras for cancer treatment. JACS, 147(16), 13754--13763. (www)

  @article{ , abstract = {Deubiquitinase-targeting chimeras (DUBTACs) are an emerging class of therapeutics that can stabilize tumor suppressors by hijacking a deubiquitinase (DUB), thereby offering a strategic pivot from conventional approaches to target tumor suppressors. However, only OTUB1 and USP7 have been harnessed for DUBTAC development to date. Here, we show for the first time that USP28 can be leveraged for developing DUBTACs. Utilizing a USP28 noncovalent ligand, we crafted USP28-recruiting DUBTACs that effectively stabilized the ΔF508-CFTR mutant protein, with comparable effectiveness to the previously reported OTUB1- and USP7-recruiting CFTR DUBTACs. Furthermore, we developed USP28-recruiting cGAS DUBTACs that effectively stabilized cGAS, elevated the cGAS-STING signaling pathway, and elicited an antiproliferative effect. We also developed first-in-class PPARγ DUBTACs to target cancer metabolism pathways. Our lead PPARγ DUBTACs effectively stabilized PPARγ and suppressed cancer cell proliferation, thus providing a new potential anticancer therapeutic approach. Hence, this work advances the targeted protein stabilization field.}, archive = {J_JACS}, author = {Zhen Wang and Chao Qian and Yan Xiong and Dingpeng Zhang and Hiroyuki Inuzuka and Yue Zhong and Ling Xie and Xian Chen and Jian Jin and Wenyi Wei}, doi = {10.1021/jacs.5c01889}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13754--13763}, shortjournal = {J. Am. Chem. Soc.}, title = {USP28-based deubiquitinase-targeting chimeras for cancer treatment}, volume = {147}, year = {2025}, }
• (2025). Minimally protected and stereoselective O-glycosylation of carboxylic acid allows rapid access to α-1-O- and 2-O-acyl glycosides. JACS, 147(16), 13744--13753. (www)

  @article{ , abstract = {We herein reported a catalytic, minimally protected, and highly α-stereoselective glycosylation protocol using carboxylic acid as an acceptor and glycosyl 8-alkynyl-1-naphthoate as a donor, enabling efficient access to unprotected α-1- O - and 2- O -acyl glycosides. This method demonstrates excellent functional compatibility and scope generality, allowing for the glycosylation of a wide range of complex carboxylic acids. Notably, we successfully synthesized two natural products, α-penta- O -galloyl- d -glucopyranose and nyctanthesin A, using this protocol. Mechanistic studies highlighted the crucial role of the 1- O ester functionality in ensuring chemoselectivity and the important contribution of the 2- O functionality in facilitating the reaction.}, archive = {J_JACS}, author = {Bangxing Hao and Rongxia Li and Panpan Wang and Yingjie Wang and Xiaolong Li and Peifan Xu and Qian Zhang and Xinhao Zhu and Xiaojuan Zhang and Yugen Zhu}, doi = {10.1021/jacs.5c01845}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13744--13753}, shortjournal = {J. Am. Chem. Soc.}, title = {Minimally protected and stereoselective O-glycosylation of carboxylic acid allows rapid access to α-1-O- and 2-O-acyl glycosides}, volume = {147}, year = {2025}, }
• (2025). Designer catalyst-enabled regiodivergent histone acetylation. JACS, 147(16), 13732--13743. (www)

  @article{ , abstract = {The “histone code,” defined by the combinatorial patterns of post-translational modifications (PTMs) on histones, plays a pivotal role in chromatin structure and gene expression. Tools for the regioselective introduction of histone PTMs in living cells are critical for dissecting the functions of these epigenetic marks. Here, we report the design and development of three regioselective catalysts that acetylate distinct lysine residues (K43, K108, and K120) on histone H2B. Using a combination of molecular dynamics simulations of catalyst-nucleosome complexes and systematic experimental optimization of catalyst structures, we identified key design principles for achieving regioselectivity. Specifically, excluding highly reactive off-target lysine residues from the catalyst effective region (CER) while maintaining proximity to a target lysine residue proved crucial. Biochemical and cellular analyses of the catalytic histone acetylation revealed that each lysine acetylation elicited unique effects on the binding affinity and activity of nucleosome-interacting molecules, as well as on transcriptional programs and cellular phenotypes. These findings establish a framework for designing regioselective histone acetylation catalysts and advance our understanding of the regulatory mechanisms underlying histone PTMs.}, archive = {J_JACS}, author = {Tamiko Nozaki and Mayu Onoda and Misuzu Habazaki and Yuma Takeuchi and Hisashi Ishida and Yuko Sato and Tomoya Kujirai and Kayo Hanada and Kenzo Yamatsugu and Hitoshi Kurumizaka and Hiroshi Kimura and Hidetoshi Kono and Shigehiro A. Kawashima and Motomu Kanai}, doi = {10.1021/jacs.5c01699}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13732--13743}, shortjournal = {J. Am. Chem. Soc.}, title = {Designer catalyst-enabled regiodivergent histone acetylation}, volume = {147}, year = {2025}, }
• (2025). Environmentally benign and long cycling mn-ion full batteries enabled by hydrated eutectic electrolytes and polycarbonyl conjugated organic anodes. JACS, 147(16), 13721--13731. (www)

  @article{ , abstract = {Aqueous rechargeable manganese (Mn)-ion batteries have recently emerged as a promising candidate for multivalent ion rechargeable batteries. However, challenges remain, particularly in expanding the electrolyte’s voltage window and identifying compatible anode materials. Herein, we introduce a Mn-ion full battery comprising a nickel hexacyanoferrate (NiHCF) cathode, a perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) anode, and a novel hydrated eutectic electrolyte formulated from Mn(ClO 4 ) 2 ·6H 2 O and acetamide. This electrolyte composition, optimized for molar ratio, provides a stable solvation structure that suppresses water reactivity and supports high ionic conductivity, as confirmed by spectroscopic and molecular dynamics analyses. The PTCDI anode facilitates highly reversible Mn 2+ storage via a unique enolization redox reaction, delivering exceptional rate capability and cycling stability. As a result, the NiHCF||PTCDI full battery achieves a 1.2 V plateau, excellent rate performance (up to 5.0 A g –1 ), and long cycling life with 95.6% capacity retention over 1200 cycles at 1.0 A g –1 . This study proposes a feasible strategy for the construction of environment-friendly, long-life and low-cost aqueous Mn-ion full batteries, offering a sustainable and high-performance solution for future energy storage applications.}, archive = {J_JACS}, author = {Tengfei Dai and Binze Yang and Jie Wei and Xinmei Song and Pengbo Zhang and Yuzhu Liu and Sheng Wen and Huan Li and Tianchen Yu and Zuoxiu Tie and Huapeng Sun and Yichao Yan and Zhong Jin}, doi = {10.1021/jacs.5c01639}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13721--13731}, shortjournal = {J. Am. Chem. Soc.}, title = {Environmentally benign and long cycling mn-ion full batteries enabled by hydrated eutectic electrolytes and polycarbonyl conjugated organic anodes}, volume = {147}, year = {2025}, }
• (2025). Aqueous-phase synthesis of cyclic trinuclear cluster-based Metal–Organic frameworks. JACS, 147(16), 13711--13720. (www)

  @article{ , abstract = {The synthesis of metal–organic frameworks (MOFs) often involves high-boiling-point organic solvents, which can have extensive environmental impact and limit their large-scale applications. Here, we present a one-pot aqueous-phase approach for the rapid preparation of 33 trinuclear-copper-cluster-based MOFs ( 1 to 33 ) with different pyrazoles under ultrasonic irradiation. To address the water-solubility challenge of organic linkers, we employ aromatic amines/aldehydes and pyrazole aldehydes/amines to in situ generate imine-based pyrazoles. This linker dismantling strategy enables the formation of low-concentration pyrazoles, which are essential for the assembly of trinuclear-copper-cluster-based MOFs in the aqueous phase. The use of preassembled trinuclear gold complexes instead of aromatic amines affords an Au–Cu-based MOF ( 34 ) of alternating gold and copper clusters, a rare example of MOFs with mixed yet precise arrangement of metal compositions. Additionally, the direct addition of pyruvic acid to the reaction mixture results in the facile synthesis of a carboxylic-acid-functionalized MOF ( 35 ), eliminating the need for preinstallation or postmodification steps in traditional MOF synthesis. Furthermore, we demonstrate 11-AA as an efficient photocatalyst for cross-dehydrogenative coupling (CDC) reactions, exploiting the synergetic effect of substrate activation on the copper sites and subsequent coupling initiated by the photosensitive organic linkers. This work offers a simple solution for making MOFs with minimal environmental impact; it also opens up possibilities for developing multifunctional MOFs for diverse applications.}, archive = {J_JACS}, author = {Kun Wu and Wei Zhao and Ling Huang and Wen-Ting Zeng and Qiang Zhu and Hao-Bo Wang and Qin-Hong Wang and Xiansong Shi and He Li and Weigang Lu and Guo-Hong Ning and Dan Zhao and Dan Li}, doi = {10.1021/jacs.5c01434}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13711--13720}, shortjournal = {J. Am. Chem. Soc.}, title = {Aqueous-phase synthesis of cyclic trinuclear cluster-based Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Observation of the assembly of the nascent mineral core at the nucleation site of human mitochondrial ferritin. JACS, 147(16), 13699--13710. (www)

  @article{ , abstract = {Ferritins play a crucial role in iron homeostasis and detoxification in organisms from all kingdoms of life. They are composed of 24 α-helical subunits arranged around an interior cavity where an iron-containing mineral core can be reversibly stored. Despite decades of study, leading to significant progress in defining the routes of Fe 2+ uptake and the mechanism of its subsequent oxidation to Fe 3+ at diiron catalytic sites termed ferroxidase centers, the process of core synthesis from the product of ferroxidase center activity remains poorly understood. In large part, this is due to the lack of high-resolution structural data on ferritin cores anchored to their nucleation sites on the inner surface of the protein. Mitochondrial ferritins are atypical of those found in higher eukaryotes in that they are homopolymers in which all subunits contain both a ferroxidase center and a presumed but undefined core nucleation site. Here, in conjunction with a novel method for producing iron-enriched ferritin crystals, we exploit these unusual features to structurally characterize both the nucleation site of mitochondrial ferritin and a pentanuclear, ferrihydrite-like iron-oxo cluster formed there. Kinetic data for wild-type and variant proteins confirmed the functional importance of this site, indicating a critical role for E61 in the transfer of Fe 3+ from the ferroxidase center to the nascent mineral core.}, archive = {J_JACS}, author = {Justin M. Bradley and Zinnia Bugg and Geoffrey R. Moore and Andrew M. Hemmings and Nick E. Le Brun}, doi = {10.1021/jacs.5c01337}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13699--13710}, shortjournal = {J. Am. Chem. Soc.}, title = {Observation of the assembly of the nascent mineral core at the nucleation site of human mitochondrial ferritin}, volume = {147}, year = {2025}, }
• (2025). Pyridine(diimine) chromium η,1η3-metallacycles as precatalysts for alkene-diene [2 + 2] cycloaddition. JACS, 147(16), 13688--13698. (www)

  @article{ , abstract = {The synthesis, characterization, and catalytic cycloaddition reactivity of aryl-substituted pyridine(diimine) (PDI) chromium ether complexes and alkene-diene derived metallacycles are described. The reduction of either (PDI)CrCl 2 or (PDI)CrCl 3 with sodium and catalytic amounts of naphthalene furnished the corresponding chromium THF or diethyl ether complexes. Exposure of the reduced chromium compounds to a mixture of butadiene and ethylene induced rapid oxidative cyclization and yielded isolable, thermally stable chromium η, 1 η 3 trans -metallacycles. In the presence of pure butadiene, oxidative cyclization was also observed, and a η, 1 η 3 diene–diene chromacycloheptane with vinyl substitution was isolated and crystallographically characterized. Reductive C(sp 3 )–C(sp 3 ) elimination of the resulting vinylcyclobutane products was promoted by either one-electron oxidation or irradiation with visible light in the presence of diene or coordinating solvents such as THF. Under thermal catalytic conditions, the chromacycles converted butadiene and ethylene to a mixture of vinylcyclobutane arising from [2 + 2] cycloaddition and cis -1,4-hexadiene resulting from competitive hydrovinylation. Visible light irradiation at ambient temperature enabled selective catalytic [2 + 2] cycloaddition. Isotopic labeling studies with 13 C-labeled ethylene established that the alkene–diene chromacycle is thermodynamically preferred over the diene–diene alternative and that both oxidative cyclization and reductive coupling steps are reversible. Visible light accelerated the reductive coupling step, while subsequent product displacement from the metal center occurs in the presence of excess diene.}, archive = {J_JACS}, author = {Hanna H. Cramer and Matthew V. Pecoraro and Paul J. Chirik}, doi = {10.1021/jacs.5c01182}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13688--13698}, shortjournal = {J. Am. Chem. Soc.}, title = {Pyridine(diimine) chromium η,1η3-metallacycles as precatalysts for alkene-diene [2 + 2] cycloaddition}, volume = {147}, year = {2025}, }
• (2025). Enhanced binding site identification in Protein–Ligand complexes with a combined blind docking and dipolar electron paramagnetic resonance approach. JACS, 147(16), 13677--13687. (www)

  @article{ , abstract = {Understanding protein–drug complex structures is crucial for elucidating therapeutic mechanisms and side effects. Blind docking facilitates site identification but is hindered by computational complexity and imprecise scoring, causing ambiguity. Dipolar electron paramagnetic resonance (EPR) provides spin–spin distances but struggles to determine relative positions within complexes. We present a novel approach combining GPU-accelerated blind docking with EPR distance constraints to enhance binding site detection. Our algorithm uses a single EPR distance distribution to filter and validate docking results. Ligand poses from blind docking are clustered, filtered by expected distances, and refined through focused docking. To illustrate our approach, we investigated human serum albumin binding with porphyrin-based photosensitizers used in photodynamic therapy. Combining docking and EPR, we identified possible binding sites, demonstrating that EPR data significantly reduce possible configurations and provide experimentally validated information. This strategy produces a detailed map of photoligand binding sites, revealing that binding may occur away from standard albumin sites and often involves multiple locations. Furthermore, it overcomes key limitations of fluorescence-based methods, which are prone to misinterpretation in albumin studies due to non one-to-one donor–acceptor relationships. By resolving ambiguities in both blind docking and EPR, our framework provides a versatile platform for investigating EPR-active ligands.}, archive = {J_JACS}, author = {Mikhail Kolokolov and Natalya Sannikova and Sergei Dementev and Roman Podarov and Kseniya Zhdanova and Natal’ya Bragina and Alexey Chubarov and Matvey Fedin and Olesya Krumkacheva}, doi = {10.1021/jacs.5c01274}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13677--13687}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced binding site identification in Protein–Ligand complexes with a combined blind docking and dipolar electron paramagnetic resonance approach}, volume = {147}, year = {2025}, }
• (2025). Three-dimensional covalent organic frameworks with jcg topology based on a trinodal strategy. JACS, 147(16), 13667--13676. (www)

  @article{ , abstract = {The development of three-dimensional (3D) covalent organic frameworks (COFs) holds significant promise for various applications, but the conventional uninodal or binodal design strategies limit their structural diversity. In this work, we present a novel trinodal strategy for the synthesis of 3D COFs featuring both microporous and mesoporous nanochannels. Using powder X-ray diffraction (PXRD), computational simulations, and high-resolution transmission electron microscopy (HR-TEM), we demonstrate that employing an 8-c building block with reduced symmetry, which can be considered as 4- and 3-connected subunits, along with planar 4-c building blocks, results in an unprecedented [4 + 3 + 4]-c jcg net. This structure features rare saddle-shaped eight-membered rings and mirror-symmetrical chains. Furthermore, the incorporation of chromophore pyrene and redox-active triphenylamine components, coupled with structural conjugation, imparts tunable photophysical and electronic properties to these COFs, making them promising candidates for photocatalytic H 2 O 2 production. This work highlights the potential of the trinodal strategy in creating intricate COF architectures and enhances their applicability in heterogeneous photocatalysis.}, archive = {J_JACS}, author = {Haorui Zheng and Jie Ji and Yusran Yusran and Jianhong Chang and Fengqian Chen and Zitao Wang and Jinquan Suo and Jie Zhang and Hui Li and Dan Zhao and Valentin Valtchev and Shilun Qiu and Qianrong Fang}, doi = {10.1021/jacs.5c00961}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13667--13676}, shortjournal = {J. Am. Chem. Soc.}, title = {Three-dimensional covalent organic frameworks with jcg topology based on a trinodal strategy}, volume = {147}, year = {2025}, }
• (2025). Enantioselective ortho-C–H addition of aromatic amines to alkenes by bulky chiral anilido-oxazoline scandium complexes. JACS, 147(16), 13658--13666. (www)

  @article{ , abstract = {The enantioselective C–H addition of anilines to alkenes represents an ideal protocol for the synthesis of chiral aromatic amines in terms of step- and atom-economy. However, this field remains predominantly unexplored. Herein, a series of newly designed bulky chiral anilido-oxazoline ligand precursors were synthesized, and the corresponding rare-earth metal alkyl complexes were obtained successfully. The resultant scandium complexes exhibit high regioselectivity for the ortho -C–H addition of tertiary anilines to unactivated alkenes, providing a wide range of chiral alkylated anilines in high yields (up to 98% yield) with excellent enantioselectivity (up to 98% ee). Moreover, the addition products can be easily converted into biorelevant derivatives and pharmacophore-containing skeletons.}, archive = {J_JACS}, author = {Qianlin Sun and Xiangli Feng and Xintong Wang and Haowen Shi and Jianhong Su and Mingxuan Wang and Gen Luo and Xin Xu}, doi = {10.1021/jacs.5c00986}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13658--13666}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective ortho-C–H addition of aromatic amines to alkenes by bulky chiral anilido-oxazoline scandium complexes}, volume = {147}, year = {2025}, }
• (2025). Multi-state redox and light-driven switching of pseudorotaxanation and cation shuttling. JACS, 147(16), 13649--13657. (www)

  @article{ , abstract = {The modulation of molecular recognition underpins numerous wide-ranging applications and has inspired the development of a myriad of switchable receptors, in particular photo- or redox-responsive hosts. Herein, we report a highly versatile three-state cation receptor family and switch system based on an overcrowded alkene strapped with crown ethers, which can be switched by both redox and light stimuli, thereby combining the advantages of both approaches. Specifically, the neutral switches can be quantitatively converted between anti- and syn- folded receptor geometries by irradiation, leading to the discovery of a significant increase or decrease in cation binding affinity, which was exploited to shuttle the pseudorotaxane-forming dibenzylammonium guest between the switchable crown ethers of slightly different sizes. Alternatively, two-electron oxidation to the orthogonal, dicationic, nonvolatile state completely turns off cation binding to the host, thereby ejecting the guest. Upon reduction, the metastable syn- folded state is first formed, which then thermally relaxes, resulting in a unique, autonomous, and cation-dependent multistate switching cascade.}, archive = {J_JACS}, author = {Robert Hein and Yohan Gisbert and Ben L. Feringa}, doi = {10.1021/jacs.5c00997}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13649--13657}, shortjournal = {J. Am. Chem. Soc.}, title = {Multi-state redox and light-driven switching of pseudorotaxanation and cation shuttling}, volume = {147}, year = {2025}, }
• (2025). Piezoelectric transition in a nonpyroelectric gyroidal Metal–Organic framework. JACS, 147(16), 13642--13648. (www)

  @article{ , abstract = {Among the thirty-two crystallographic point groups, 432 is the only one that lacks an inversion center but does not exhibit piezoelectricity. A gyroidal structure belongs to point group 432 and shows characteristic physical properties attributed to its distinctive strong isotropic network. Here, we investigate a gyroidal cobalt oxalate metal–organic framework (MOF) with disordered orientations of SO 4 tetrahedra. Synchrotron X-ray diffraction experiments using a single crystal reveal a cubic-to-cubic structural phase transition at T S = 120 K. This transition involves a change in the point group from nonpiezoelectric 432 to piezoelectric 23. The symmetry change arises from the ordering of distorted SO 4 molecules, leading to a three-dimensional helical arrangement of electric dipole moments. Furthermore, pyroelectric current measurements using polycrystalline pellet samples reveal that electric polarization emerges below T S depending on the magnitude of the pelletizing pressure, demonstrating piezoelectricity. The gyroidal MOF offers an opportunity to explore unique dielectric properties induced by the helical ordering of molecules and structural flexibility.}, archive = {J_JACS}, author = {Shunsuke Kitou and Hajime Ishikawa and Yusuke Tokunaga and Masato Ueno and Hiroshi Sawa and Yuiga Nakamura and Yuto Kinoshita and Tatsuya Miyamoto and Hiroshi Okamoto and Koichi Kindo and Taka-hisa Arima}, doi = {10.1021/jacs.5c00886}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13642--13648}, shortjournal = {J. Am. Chem. Soc.}, title = {Piezoelectric transition in a nonpyroelectric gyroidal Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Modeling the superlattice phase diagram of transition metal intercalation in bilayer 2H-TaS2. JACS, 147(16), 13629--13641. (www)

  @article{ , abstract = {Van-der-Waals hosts intercalated with transition-metal (TM) ions exhibit a range of magnetic properties strongly influenced by the structural order of the intercalants. However, predictive computational models for the intercalant ordering phase diagram are lacking, complicating experimental pursuits to target key structural phases. Here we use density functional theory (DFT) to construct a pairwise lattice model and Monte Carlo to determine its associated thermodynamic phase diagram. To circumvent the complexities of modeling magnetic effects, we use the diamagnetic ions Zn 2+ and Sc 3+ as computationally accessible proxies for divalent and trivalent species of interest (Fe 2+ , Co 2+ , V 3+ and Cr 3+ ), which provide insights into the thermodynamic phase diagram well above the paramagnetic transition temperature. We find that electrostatic coupling between intercalants is almost entirely screened, so the pairwise lattice model represents a coarse-grained charge density reorganization. The resulting phase diagram reveals that entropically favored √3 × √3 ordering and coexisting locally ordered √3 × √3 and 2 × 2 domains persist across a range of temperatures and stoichiometries. This occurs even at quarter-filling of interstitial sites (corresponding to bulk stoichiometries of M 0.25 TaS 2 ; M = intercalant) where there are experimental reports of 2 × 2 and √3 × √3 coexistence but a thermodynamic preference for long-range 2 × 2 order is often assumed. Accompanying Raman spectra revealing quenching-induced √3 × √3 order in 2H -V 0.25 NbS 2 supports that deficient √3 × √3 domains may dominate 2 × 2 at high temperatures in a range of TM-intercalated transition metal dichalcogenides.}, archive = {J_JACS}, author = {Isaac M. Craig and B. Junsuh Kim and Shannon S. Fender and Philipp Letman and Sadie M. Asker and David T. Limmer and D. Kwabena Bediako and Sinéad M. Griffin}, doi = {10.1021/jacs.5c00925}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13629--13641}, shortjournal = {J. Am. Chem. Soc.}, title = {Modeling the superlattice phase diagram of transition metal intercalation in bilayer 2H-TaS2}, volume = {147}, year = {2025}, }
• (2025). Regulating enol-to-keto tautomerization of pillararene-based conjugated macrocycle polymers for H2O2 photosynthesis. JACS, 147(16), 13618--13628. (www)

  @article{ , abstract = {Porous organic polymers have emerged as promising materials for energy conversion, pollutant adsorption, and heterogeneous catalysis because of their tunable pore structures and high surface areas. However, most porous organic polymers are still limited by insufficient conjugation and inefficient electron–hole separation, hindering the tunability of their photoelectric properties and overall functionality. By integrating macrocyclic compounds as a new building block, which feature electron-rich cavities and rigid ring structures, into the polymer network, the resulting conjugated macrocycle polymers are expected to provide an innovative approach to enrich the photoelectric functionalities of porous organic polymers. Herein, an enaminone-based pillararene photocatalyst, TpAP[5], is constructed by covalently linking functionalized pillar[5]arene to conjugated macrocycle polymers through Schiff base condensation for efficient photocatalytic reactions. This material demonstrates exceptional performance in the photocatalytic production of hydrogen peroxide, achieving a rate of 2343 μmol g –1 h –1 . In-depth investigations reveal that the incorporation of pillararenes enables synergistic catalysis of water oxidation and oxygen reduction reactions and significantly enhances catalyst stability by regulating molecular tautomerization. This work opens new avenues for designing high-performance multifunctional conjugated macrocycle polymers with significant potential for clean energy conversion.}, archive = {J_JACS}, author = {Zhuo-Qin Wang and Meng-Hao Li and Shuang Liang and Yuxiang Kong and Chunyu Wang and Lu Li and Ji-Jing Xu and Ying-Wei Yang}, doi = {10.1021/jacs.5c00768}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13618--13628}, shortjournal = {J. Am. Chem. Soc.}, title = {Regulating enol-to-keto tautomerization of pillararene-based conjugated macrocycle polymers for H2O2 photosynthesis}, volume = {147}, year = {2025}, }
• (2025). Single-atom saturation: A fundamental principle for single-atom-site catalyst design. JACS, 147(16), 13610--13617. (www)

  @article{ , abstract = {Single-atom alloys (SAAs), with twin advantages of alloys and single-atom catalysts, have emerged as an innovative class of electrocatalysts. This uniqueness is expected to achieve unattainable catalytic performance but simultaneously gives rise to the absence of guidelines for designing desired SAAs. Herein, we proposed a fundamental principle, single-atom saturation ( S SA ), to quantify the binding strength of different intermediates on SAAs, enabling the rapid and qualitative evaluation of the catalytic activity across various reactions. S SA is rationalized by combining the variation of electronic structure ( d electron occupancy saturation) and geometrical structure (coordination saturation) of the single guest atom as well as the effect of the host atom type and the intermediate adsorption configuration. Based on the insights given by S SA , Pd 1 Cu(111), Ru 1 Cu(111), Ir 1 Ag(111), Pt 1 Ag(111), and Pt 1 Cu(111) are predicted to possess excellent activity for CO 2 reduction, N 2 reduction, O 2 evolution, O 2 reduction, and H 2 evolution reactions, respectively, most of which are supported by reported experiments. Moreover, S SA is also applicable to nitrogen-doped graphene-supported single-atom catalysts (SACs) with ultrahigh accuracy. In general, single-atom saturation is a concise, interpretable, and universal descriptor that deciphers the structure–activity relation of SAAs across various reactions, where the insights revealed also offer a simple and fundamental principle for the design of excellent single-atom-site catalysts.}, archive = {J_JACS}, author = {Chunjin Ren and Yu Cui and Qiang Li and Chongyi Ling and Jinlan Wang}, doi = {10.1021/jacs.5c00643}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13610--13617}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-atom saturation: A fundamental principle for single-atom-site catalyst design}, volume = {147}, year = {2025}, }
• (2025). Fusion of four aromatic rings via an atom-mutual-embedding strategy to form a tetrahexacyclic system. JACS, 147(16), 13601--13609. (www)

  @article{ , abstract = {Skeletal manipulation of aromatic compounds has emerged as a potent tool in synthetic chemistry, but simultaneous multiring manipulation remains largely unexplored due to the inherent complexities of ring and site selectivity. Herein, we report an unprecedented multiring skeletal manipulation that fuses four 5-membered aromatic rings, comprising two organic and two metal-containing aromatic systems, into a novel metal-bridged 6/6/6/6-membered ring scaffold. The sequential ring fusion is accomplished through an atom-mutual-embedding strategy; this strategy entails the stepwise insertion of two nitrogen atoms into separate metal–carbon bonds and simultaneously integrates a metal atom as a bridge across two isoxazole moieties. The presence of a central metal atom is crucial for ensuring precise substrate alignment and enhancing both the ring and site specificity. The resulting tetrahexacyclic products exhibit remarkable stability and superior near-infrared (NIR) functional properties, surpassing those of the precursor compounds. This work not only establishes a conceptual foundation for designing versatile substrate molecules amenable to intricate editing but also contributes to the rational and performance-targeted manipulation of molecular architectures.}, archive = {J_JACS}, author = {Fei-Hu Cui and Le-Han Gao and Kaidong Ruan and Fei Li and Meng Meng and Kexin Ma and Zhengyu Lu and Jiawei Fei and Huayu Tian and Liu Leo Liu and Yu-Mei Lin and Haiping Xia}, doi = {10.1021/jacs.5c00697}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13601--13609}, shortjournal = {J. Am. Chem. Soc.}, title = {Fusion of four aromatic rings via an atom-mutual-embedding strategy to form a tetrahexacyclic system}, volume = {147}, year = {2025}, }
• (2025). Superhydrophobic molecular selector for efficient separation of ethane over ethylene under dry and humid conditions. JACS, 147(16), 13592--13600. (www)

  @article{ , abstract = {Exploring humidity-resistant, ethane-selective adsorbents for the one-step purification of polymer-grade (>99.95%) ethylene from ethane-ethylene mixtures is of great importance, yet remains a significant challenge. To address this challenge, we present a novel strategy for constructing a “superhydrophobic molecular selector” (SMS) based on a porous organic cage (POC), which features a superhydrophobic outer surface and an inner cavity with multiple ethane-selective functional sites. The resulting SMS-POC-1 demonstrates excellent C 2 H 6 adsorption capacity (97 cm 3 g –1 at 298 K) and C 2 H 6 /C 2 H 4 selectivity ( S ads = 2.40 at 298 K), offering a superior trade-off between ethane adsorption capacity and C 2 H 6 /C 2 H 4 adsorption selectivity among all C 2 H 6 -selective adsorbents. Especially, breakthrough experiments demonstrate that SMS-POC-1 efficiently produces polymer-grade C 2 H 4 from C 2 H 6 /C 2 H 4 mixtures at 60% relative humidity (RH), making it the highest-selectivity adsorbent reported to date that can stably operate in a humid environment. The combination of experimental results and theoretical calculations reveals that the coexistence of a superhydrophobic outer surface and synergistic C–H···π interactions and hydrogen-bonding sites accounts for the high C 2 H 6 /C 2 H 4 separation performance under humid conditions for SMS-POC-1. Our work thus not only demonstrates a general strategy for guiding the design of humidity-resistant adsorption-separation materials but also presents a promising candidate for potential applications in hydrocarbon separation.}, archive = {J_JACS}, author = {Mao Yi and Shan Wang and Shenfang Li and Shuo Zhang and Yilian Liu and Laiyu Zhang and Zifeng You and Xiongli Liu and Lin Li and Junhua Wang and Hao Wang and Qiao Zhao and Baiyan Li and Xian-He Bu}, doi = {10.1021/jacs.5c00658}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13592--13600}, shortjournal = {J. Am. Chem. Soc.}, title = {Superhydrophobic molecular selector for efficient separation of ethane over ethylene under dry and humid conditions}, volume = {147}, year = {2025}, }
• (2025). Membrane charge drives the aggregation of TDP-43 pathological fragments. JACS, 147(16), 13577--13591. (www)

  @article{ , abstract = {TDP-43 protein is an RNA-binding protein linked to amyotrophic lateral sclerosis, frontotemporal dementia, and Alzheimer disease. While normally a protein that shuttles between the nucleus and cytoplasm, TDP-43 has recently been found also in extracellular vesicles. These are an important medium for cell–cell communication that allows the transfer of lipids, proteins, and genetic material among cells. An increasing concern in neurodegenerative diseases, however, is the possibility that extracellular vesicles can also provide an effective way to spread misfolded proteins that could “infect” other cells according to a “prion-like” mechanism. To characterize the interaction of TDP-43 with lipid membranes, we carried out a systematic biophysical study using a TDP-43 fragment lacking the first 84 N-terminal residues, called M85, and synthetic model phospholipid membranes. We utilized standard techniques, such as fluorescence and microscopy, complemented by neutron reflectivity measurements. Our results show that lipid charge affects the modality by which M85 interacts with membranes: a higher negative charge induces the protein to bind to the bilayer surface, promoting protein aggregation and decreasing lipid bilayer damage that this interaction causes. Thus, we speculate that the M85-lipid membrane interaction could play an important and previously undefined role in TDP-43-related neurodegenerative diseases.}, archive = {J_JACS}, author = {Giacomo Corucci and Devkee M. Vadukul and Nicolò Paracini and Valérie Laux and Krishna C. Batchu and Francesco A. Aprile and Annalisa Pastore}, doi = {10.1021/jacs.5c00594}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13577--13591}, shortjournal = {J. Am. Chem. Soc.}, title = {Membrane charge drives the aggregation of TDP-43 pathological fragments}, volume = {147}, year = {2025}, }
• (2025). Stereogenic P(V) synthesis via catalytic continuous substitutions. JACS, 147(16), 13566--13576. (www)

  @article{ , abstract = {Phosphorus(V) stereocenters that are fully substituted by heteroatoms play important roles in bioactive molecules and organocatalysts. Existing methods to achieve such motifs rely almost entirely on resolution or diastereocontrol, and prefunctionalized substrates are usually required to generate specific P(V) stereocenters. In contrast, related catalytic methods are rare, and no generally applicable method is described. Here, we report a modular strategy to access a broad variety of stereogenic-at-phosphorus skeletons, including ProTide analogs, alkoxylphosphoramidates, phosphates, phosphorothioates, and phosphonamidates, through designed enantioselective continuous substitutions of simple P(V) precursors. The nucleophilic substitution sequence readily determined the stereoconfiguration of the products. Concise synthesis of ProTide analogs and drug molecules demonstrated the practical value of the protocol. Experimental and computational studies unveiled a unique π–π stacking effect and chalcogen bonding interaction between the catalyst and substrate as the origin of stereoselectivity.}, archive = {J_JACS}, author = {Gao-Liang Zheng and Yuchen Zhang and Jing-Ming Zhang and Liang Chen and Xiao-Song Xue and Zhi-Tao He}, doi = {10.1021/jacs.5c00591}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13566--13576}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereogenic P(V) synthesis via catalytic continuous substitutions}, volume = {147}, year = {2025}, }
• (2025). Highly efficient charge transfer between water and two-dimensional materials with polar bonds. JACS, 147(16), 13556--13565. (www)

  @article{ , abstract = {Charge transfer at solid–liquid interfaces is pivotal in biochemical processes, catalysis, and electrochemical devices. However, understanding the charge transfer mechanism at the nanoscale solid–liquid interface remains highly challenging. Here, we conduct ab initio molecular dynamics simulations to investigate interfacial charge transfer between water and the two most common two-dimensional materials: graphene with nonpolar C–C bonds and hexagonal boron nitride (hBN) with polar B–N bonds. It is counterintuitive to find that the charge transfer between water and hBN is approximately 1 order of magnitude higher than that between water and graphene despite the fact that graphene is semiconducting and hBN is insulating. Our further analyses attribute this phenomenon to a higher tendency of water molecules to point a hydrogen atom toward the hBN surface compared to the graphene surface, although they have similar crystallographic structures. This single hydrogen-down water configuration on the hBN surface prompts electron delocalization from hBN and facilitates electron migration to water. Moreover, the polar B–N bonds in hBN result in a strong orbital overlap between nitrogen atoms and hydrogen atoms of water. A similar charge transfer enhancement is also observed between water and two-dimensional gallium nitride (GaN) and aluminum nitride (AlN), which also own polar bonds, and a positive correlation between the charge transfer and the bond polarity is demonstrated. Further simulations indicate that the friction coefficient of water on graphene and hBN surfaces positively correlates with the amount of charge transfer. These findings suggest that materials with polar bonds like hBN can serve as promising materials for biochemical sensors and energy conversion devices.}, archive = {J_JACS}, author = {Yuwei Cao and Chenchen Zhou and Wanqi Zhou and Chun Shen and Bao Jin and Tianbao Ma and Hu Qiu and Wanlin Guo}, doi = {10.1021/jacs.5c00480}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13556--13565}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly efficient charge transfer between water and two-dimensional materials with polar bonds}, volume = {147}, year = {2025}, }
• (2025). Dynamic DNA-based nanoadjuvants for TLR9 clustering and innate immune activation in dendritic cells. JACS, 147(16), 13545--13555. (www)

  @article{ , abstract = {The regulation of toll-like receptor (TLR) clustering is a pivotal strategy for enhancing innate immune responses, but the development of methods to precisely control receptor assembly remains challenging. Herein, we present a dynamic, DNA-based nanoadjuvant that triggers TLR9 clustering for potent innate immune activation in dendritic cells (DCs) via in situ assembly in lysosomes. This nanoadjuvant integrates CpG oligonucleotides (TLR9 ligands) and cytosine-rich DNA sequences (acid-responsive sequences) into a polymeric nanoframework via a cascade hybridization chain reaction. Upon lysosomal internalization, the nanoadjuvants form large-sized aggregates through cytosine protonation-induced i-motif formation, a process driven by the acidic lysosomal environment. This assembly consumes lysosomal protons, thus reducing lysosomal acidity and attenuating hydrolase activity, leading to enhanced intralysosomal retention of nanoadjuvants. Moreover, the nanoadjuvant aggregates promote CpG ODN contact with the lysosomal membrane, thereby facilitating prolonged ligand–receptor interactions and efficient TLR9 clustering. Consequently, the nanoadjuvant aggregates induce efficient DC maturation, secretion of cytokines, and T-cell proliferation, culminating in robust antitumor immunity both in vitro and in vivo. Our approach offers a novel strategy to manipulate receptor assembly using an environmentally stimulus-responsive system, holding significant promise for vaccine adjuvants and cancer immunotherapy.}, archive = {J_JACS}, author = {Zhaoyue Lv and Xiaocui Guo and Rui Zhang and Yao Yao and Lanqi Shao and Siqi Li and Chunying Chen and Dayong Yang and Ying Liu}, doi = {10.1021/jacs.5c00481}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13545--13555}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic DNA-based nanoadjuvants for TLR9 clustering and innate immune activation in dendritic cells}, volume = {147}, year = {2025}, }
• (2025). Hydrodealkenylative C(sp3)–C(sp2) bond fragmentation using Isayama–Mukaiyama peroxidation. JACS, 147(16), 13531--13544. (www)

  @article{ , abstract = {Advancements in radical capture strategies have expanded the range of products accessible from alkenes through dealkenylative synthesis. These methods, however, are still limited, as they rely on ozonolysis to generate the key peroxide intermediates from alkenes. Ozonolysis has several limitations. It is not compatible with alkenes containing electron-rich aromatics. It is also inapplicable to certain alkene substitution patterns in the context of dealkenylative synthesis. Additionally, it struggles with sterically hindered alkenes, internal nucleophiles and electrophiles, and allylic alcohols. In this paper, using Isayama–Mukaiyama peroxidation (IMP), we address the limitations of ozonolysis to rescue previously inaccessible alkene substrates and broaden the applicability of dealkenylative functionalization. In particular, we apply IMP in hydrodealkenylation and describe a novel radical hydrogenation condition─employing catalytic [Fe III ], catalytic benzenethiol, and γ-terpinene in refluxing methanol─to resolve β-scission issues associated with IMP-generated alkyl silylperoxides.}, archive = {J_JACS}, author = {Jeremy H. Dworkin and Zhuoxi M. Chen and Kathleen C. Cheasty and Aris V. Rubio and Ohyun Kwon}, doi = {10.1021/jacs.5c00540}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13531--13544}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrodealkenylative C(sp3)–C(sp2) bond fragmentation using Isayama–Mukaiyama peroxidation}, volume = {147}, year = {2025}, }
• (2025). Harnessing mechanochemistry for direct synthesis of imine-based Metal–Organic frameworks. JACS, 147(16), 13522--13530. (www)

  @article{ , abstract = {The growth of metal–organic frameworks (MOFs) is most frequently accessed by the direct assembly of metal cations and multitopic ready-to-connect ligands under solvothermal conditions. However, such nonambient conditions are expected to impose a synthetic challenge to incorporate degradable ligands into MOFs. This explains why imine-based MOFs are scarce as the imine motif is usually prone to decompose through hydrolysis. This work not only showcases mechanochemistry as an ambient, sustainable, and high-yield strategy for synthesizing a variety of imine-based MOFs but also achieves the integration of ligand synthesis and MOF growth into a single tandem step. Thus, this work provides straightforward access to imine-based MOFs, a subfamily of historically challenging MOF materials.}, archive = {J_JACS}, author = {Zhuorigebatu Tegudeer and Luke C. Davenport and Martin E. Kordesch and Wen-Yang Gao}, doi = {10.1021/jacs.5c00460}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13522--13530}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing mechanochemistry for direct synthesis of imine-based Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Rapid fluorochromic sensing of tertiary amines and opioids via dual-emissive ground and excited charge-transfer states. JACS, 147(16), 13512--13521. (www)

  @article{ , abstract = {The recognition and differentiation of organic amines are crucial for applications in drug analysis, food spoilage, biomedical assays, and clinical diagnostics. Existing luminescence-based recognition methods for amines predominantly rely on fluorescence quenching, limiting the scope of sensitive and selective detection. Here, we present a fluorochromic approach for rapidly distinguishing different organic amines based on their unique excited-state and ground-state interactions with a naphthalimide derivative under ultraviolet light. Our findings reveal that the photoluminescence quantum yield and emission color are significantly influenced by the substituent group and the molecular flexibility of the amine. Specifically, primary amines, together with other common lone-pair donors, such as alcohol, ether, thiol, thioether, and phosphine, did not exhibit photoluminescence changes, while secondary amines exhibited only weak emission. For tertiary amines, however, bright green photoluminescence activation was rapidly produced for molecules containing at least one methyl group; red-shifted yellow emission was observed for ones with bulkier side groups other than methyl; and for conformationally locked bicycloamines, no emission was observed. In addition, this fluorochromic process of the naphthalimide derivative not only depends on tertiary amine substituent groups but also shows distinctly different ground- and excited-state photoluminescence dynamics in time-resolved spectroscopy. Based on these differences, a qualitative method is developed for visual recognition of natural and synthetic opioids, including heroin, fentanyl, and metonitazene, which is more facile and rapid compared to current methods such as the Marquis reagent kit, and could facilitate onsite testing, real-time monitoring, and streamlined workflows in both laboratory and field settings.}, archive = {J_JACS}, author = {Aoyuan Cheng and Xuewen Gu and Chengze Yang and Mei Liu and Baicheng Zhang and Hongping Liu and Xiaoyu Chen and Airong Feng and Pieter E. S. Smith and Jun Jiang and Yi Luo and Wenhuan Huang and Guoqing Zhang}, doi = {10.1021/jacs.5c00425}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13512--13521}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid fluorochromic sensing of tertiary amines and opioids via dual-emissive ground and excited charge-transfer states}, volume = {147}, year = {2025}, }
• (2025). Role of site-specific iron in fe-doped nickel hydroxide toward water oxidation revealed by spatially resolved imaging at the single-particle level. JACS, 147(16), 13502--13511. (www)

  @article{ , abstract = {Water electrolysis driven by renewable electricity is limited by the slow-kinetic oxygen evolution reaction (OER). NiFe-based hydroxides are considered promising non-noble electrocatalysts toward the OER but require profound insight into the role of site-specific iron incorporation. Herein, we determined the critical role of edge sites on single-crystalline NiFe-based hydroxide toward the OER using spatially resolved in situ single-particle imaging techniques. The potential-driven incorporation of Fe into the specific edge or plane sites was achieved on two-dimensional (2D) Ni layer double hydroxide (LDH) single crystals. The spatially resolved scanning electrochemical cell microscopy imaging illustrated that Fe-doped edge sites dominated the activity of the OER rather than Fe-doped plane sites. In situ Raman spectroscopy imaging of single particles was used to monitor the evolution of edge and plane sites, revealing that the incorporation of Fe impeded the oxidation of Ni. Moreover, spatially resolved 18 O-isotope-labeling experiments demonstrated that Fe doping hindered the oxygen exchange between Ni LDH and the electrolyte, inducing the switch of partial active sites from Ni to Fe. Combined with theoretical calculations, the Fe–O bridge –Ni sites contributed to the enhanced OER activity on Ni LDH with Fe doping at the edge, whereas the O hollow (NiNiFe) sites induced by the infiltration of Fe into the plane were detrimental to the OER performance. This work provides direct spectroscopic evidence for understanding the specific sites at the single-particle level and guides the rational design of optimal electrocatalysts.}, archive = {J_JACS}, author = {Jie Wei and Jing Zhu and Rong Jin and Yan Liu and Guiliang Liu and Ming-Hui Fan and Mingkai Liu and Dechen Jiang and Jie Zeng}, doi = {10.1021/jacs.5c00438}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13502--13511}, shortjournal = {J. Am. Chem. Soc.}, title = {Role of site-specific iron in fe-doped nickel hydroxide toward water oxidation revealed by spatially resolved imaging at the single-particle level}, volume = {147}, year = {2025}, }
• (2025). Amplifying the reactivity of anionic Mn(I)–H catalysts via the cation effect: Mechanistic investigation and application to the hydrogenation of α-trisubstituted carboxylic esters. JACS, 147(16), 13491--13501. (www)

  @article{ , abstract = {Despite significant advancements in ester hydrogenation using homogeneous metal catalysts over the past two decades, the catalytic hydrogenation of sterically hindered α-trisubstituted carboxylic esters remains a formidable challenge. Herein, we present a class of imidazole-based NNP-pincer manganese (Mn) catalysts capable of efficiently hydrogenating α-trisubstituted carboxylic esters to their corresponding β-trisubstituted primary alcohols, which are widely applied in the pharmaceutical and fine-chemical industry. Under catalytic conditions, the imidazole moiety is deprotonated by t BuOK to generate a highly reactive anionic Mn–H species with a potassium countercation. Mechanistic studies reveal that the potassium cation in this anionic Mn–H intermediate interacts synergistically with the substrate’s carbonyl group and the alkoxide group during hydrogen activation. This cation effect significantly lowers the energy barriers for both hydride transfer and heterolytic H 2 cleavage, thereby enhancing catalytic activity. Leveraging this potent anionic Mn–H catalyst, we achieved the hydrogenation of a diverse array of α-trisubstituted carboxylates (80 examples) under mild conditions.}, archive = {J_JACS}, author = {Haobo Yang and Shihan Liu and Hao Dong and Hui Huang and Yujie Wang and Wei Hao and Yu Lan and Qiang Liu}, doi = {10.1021/jacs.5c00362}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13491--13501}, shortjournal = {J. Am. Chem. Soc.}, title = {Amplifying the reactivity of anionic Mn(I)–H catalysts via the cation effect: Mechanistic investigation and application to the hydrogenation of α-trisubstituted carboxylic esters}, volume = {147}, year = {2025}, }
• (2025). Bidirectional intramolecular singlet and triplet energy transfer in tetracene-ultrasmall gold nanocluster dyads: An evaluation of the triplet behavior of gold nanoclusters. JACS, 147(16), 13483--13490. (www)

  @article{ , abstract = {A series of tetracene (Tc)-alkanethiol-functionalized gold nanoclusters (Au m : m = 25, 38) dyads with varying alkyl chain lengths ( n = 5, 11) (denoted as Tc-C n -Au m ) were synthesized to investigate the excited-state dynamics through the triplet excited state of these gold nanoclusters. Transient absorption measurements revealed bidirectional intramolecular energy transfer processes, including the initial singlet–singlet energy transfer (S-SEnT) from Tc to Au 25 , followed by the subsequent triplet–triplet energy transfer (T-TEnT) from Au 25 to Tc in Tc-C n -Au 25 ( n = 5, 11), with nearly similar rate constants regardless of the alkyl chain length ( n ). In the case of Tc-C 5 -Au 38 , intramolecular S-SEnT from Tc to Au 38 was similarly observed; however, T-TEnT from Au 38 to Tc was not detected. The differences in excited-state dynamics between Tc-C 5 -Au 25 and Tc-C 5 -Au 38 can be attributed to variations in the triplet energies of Au m . These results clearly demonstrate the triplet character of Au 25 and Au 38 .}, archive = {J_JACS}, author = {Hayato Sakai and Sunao Hiramatsu and Aoi Akiyama and Yuichi Negishi and Taku Hasobe}, doi = {10.1021/jacs.5c00337}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13483--13490}, shortjournal = {J. Am. Chem. Soc.}, title = {Bidirectional intramolecular singlet and triplet energy transfer in tetracene-ultrasmall gold nanocluster dyads: An evaluation of the triplet behavior of gold nanoclusters}, volume = {147}, year = {2025}, }
• (2025). Unraveling side reactions in paired CO2 electrolysis at operando conditions: A case study of ethylene glycol oxidation. JACS, 147(16), 13471--13482. (www)

  @article{ , abstract = {Replacing the oxygen evolution reaction (OER) in CO 2 electrolysis with an energetically and economically favorable alternative is very promising. Yet, understanding paired organic oxidation in the environment for CO 2 reduction is particularly challenging, as monitoring multiple side reactions is problematic. Herein, we examined the oxidation of ethylene glycol (EG), one of the simplest polyols, as a model reaction on a series of nickel oxyhydroxide model catalysts (β-NiM x OOH, M = Ni, Co, Fe, and Cu). Using in situ techniques, including surface-enhanced infrared absorption spectroscopy (SEIRAS) and differential electrochemical mass spectrometry (DEMS), together with various ex situ approaches, we obtained the potential-resolved and quantitative information on various side reactions comprising the OER, overoxidation to CO/CO 2 , catalyst dissolution, and CO 2 evolution from electrolyte decarbonation. Many factors including impurity cations, pH, and potential can substantially influence the product distribution and side reactions. Such influences are nearly identical for both the electrocatalytic and chemical–electrochemical oxidation pathways. The optimized system can achieve stable and high Faradaic efficiencies of formate (∼100%), glycolaldehyde (∼86%), and glycolate (∼66%), respectively. Importantly, paired electrolysis can easily suffer from higher energy consumption than the conventional counterpart, provided side reactions are unregulated. Yet the modulated one consumed 21.1% less energy even when product separation was considered. This work reveals the unique side reactions in paired CO 2 electrolysis, opening up opportunities for designing efficient systems for real-life applications.}, archive = {J_JACS}, author = {Xiaoyi Jiang and Kai Zhao and Haozhou Feng and Le Ke and Xiude Wang and Yuchen Liu and Lingjiao Li and Pengfei Sun and Zhou Chen and Yifei Sun and Zhiping Wang and Lin Yu and Ning Yan}, doi = {10.1021/jacs.5c00325}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13471--13482}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling side reactions in paired CO2 electrolysis at operando conditions: A case study of ethylene glycol oxidation}, volume = {147}, year = {2025}, }
• (2025). Electrochemical benzylic C–H carboxylation. JACS, 147(16), 13461--13470. (www)

  @article{ , abstract = {Direct benzylic C–H carboxylation stands as a high atom economy, efficient, and convenient route for the synthesis of valuable benzylic carboxylic acids, which are of great significance in many pharmaceuticals and bioactive molecules. However, the inherent inertness of both benzylic C–H bonds and carbon dioxide presents a great challenge for further transformations. Herein, we report our efforts to overcome this obstacle via halide-promoted linear paired electrolysis to generate various benzylic carboxylic acids. Remarkably, this process is transition-metal- and base-free, making it environmentally benign and cost-effective. Besides, it is suitable for constructing a wide range of primary, secondary, and tertiary benzylic carboxylic acids under mild reaction conditions, demonstrating broad substrate scopes and good functional group tolerance. Furthermore, our protocol enables the direct synthesis of some drug molecules, including Flurbiprofen, Ibuprofen, and Naproxen, and facilitates the late-stage modification of complex compounds, showcasing the practical application in synthetic chemistry and underscores its potential to advance the synthesis of benzylic carboxylic acids and related compounds.}, archive = {J_JACS}, author = {Weimei Zeng and Chengyi Peng and Youai Qiu}, doi = {10.1021/jacs.5c00259}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13461--13470}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical benzylic C–H carboxylation}, volume = {147}, year = {2025}, }
• (2025). Biomimetic parallel vein-like two-dimensional supramolecular layers containing embedded one-dimensional conduits driven by cation−π interaction and hydrogen bonding to promote photocatalytic hydrogen evolution. JACS, 147(16), 13447--13460. (www)

  @article{ , abstract = {Two-dimensional supramolecular assemblies (2DSAs) with well-defined nanostructures have emerged as promising candidates for diverse applications, particularly in photocatalysis. However, it still remains a significant challenge to simultaneously achieve effective electron transport and multiple active sites in 2DSA, even though this is crucial for enhancing photocatalytic performance. This reason can be attributed to the lack of a suitable structural paradigm that enables both effective intermolecular orbital overlap and increased substrate contact. Inspired by the parallel venation of monocotyledons that can facilitate substrate transfer, we overcome the limitation, in this study, by integrating parallel-arranged one-dimensional (1D) conduits with edge-on packing motifs to construct biomimetic, parallel vein-like two-dimensional supramolecular layers (PV-2DSLs) through the hierarchical self-assembly of cationically modified, rigid multiarmed monomers. The resulting PV-2DSLs exhibit a long-range aromatic cation−π stacking that can facilitate electron transport. Importantly, the unique structural feature of these PV-2DSLs is the orderly and parallel embedding of 1D conduits within the 2D plane, which is significantly different from the conventional channels formed by the vertical stacking of 2D porous materials. These conduits promote multielectron transfer pathways, leading to enhanced charge separation and carrier transport when coupled with long-range aromatic cation−π stacking. As a consequence, these PV-2DSLs exhibit long excited state lifetime, leading to significantly improved hydrogen production rates up to 3.5 mmol g –1 h –1 , which is approximately 17.5 times higher than that of the counterpart without 1D conduits (0.2 mmol g –1 h –1 ).}, archive = {J_JACS}, author = {Ju-An Zhang and Xuedong Xiao and Jinyi Wang and Shuai Luo and Yi Lu and Yan-Yu Pang and Wei Tian}, doi = {10.1021/jacs.5c00204}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13447--13460}, shortjournal = {J. Am. Chem. Soc.}, title = {Biomimetic parallel vein-like two-dimensional supramolecular layers containing embedded one-dimensional conduits driven by cation−π interaction and hydrogen bonding to promote photocatalytic hydrogen evolution}, volume = {147}, year = {2025}, }
• (2025). Advancing mn-based li-ion battery cathodes via a partially cation-disordered zigzag-type Li–Nb–Mn–O framework. JACS, 147(16), 13437--13446. (www)

  @article{ , abstract = {Mn-based Li-ion battery cathodes encompass a great variety of materials structures. Decades of research effort have proven that developing a Mn-based structure featuring a high redox activity, stable cycling, and cost-effectiveness is a longstanding challenge. Motivated by such a need and inspired by the structural diversity of Mn-based cathodes, we develop a partially cation-disordered lithium niobium manganese oxide with a zigzag structure, filling the knowledge gap between zigzag-ordered and fully disordered Li–Mn-based oxides. Electrochemically, the partially disordered cathode greatly unlocks the redox activity of the zigzag lattice and maintains the cycling stability. Mechanism-wise, the partial disordering suppresses the disproportionation reaction of Mn(III) and facilitates a disordered λ-MnO 2 –tetragonal cation-disordered rock salt structural transformation. The work suggests the substantial opportunity of using partial disordering as the key strategy to revive locked-up redox activities and realize new energy storage mechanisms, for the pursuit of high-performance cost-effective battery materials.}, archive = {J_JACS}, author = {You Wang and Wonu Choe and Yong Ding and Rui Liu and Dennis Nordlund and Dongchang Chen}, doi = {10.1021/jacs.5c00139}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13437--13446}, shortjournal = {J. Am. Chem. Soc.}, title = {Advancing mn-based li-ion battery cathodes via a partially cation-disordered zigzag-type Li–Nb–Mn–O framework}, volume = {147}, year = {2025}, }
• (2025). Enzyme-mimic activities of RuCo bimetallic nanosheets for inflammatory bowel disease treatment. JACS, 147(16), 13424--13436. (www)

  @article{ , abstract = {The presence of abnormal levels of reactive oxygen species (ROS) is a recognized pathological feature of inflammatory bowel disease (IBD). Therefore, the development of orally administered antioxidants with high antioxidative capacity and gastric acid tolerance for the treatment of IBD is of great significance. Here, we present the design and synthesis of a bimetallic ruthenium–cobalt (RuCo) nanosheet for the treatment of IBD. The Ru–Co atoms within the nanosheet structure exhibit significant electron transfer properties owing to their electronegativity feature. Density functional theory calculations indicate that the RuCo nanosheets have higher d-band centers than the corresponding Ru and Co metal monoliths, which increases the catalytic activity. Such RuCo nanosheets exhibit superoxide dismutase and catalase-like cascade enzyme activities and show robust stability in gastric fluid over a 4 h period when exposed to simulated gastric fluid, ensuring desirable retention of antioxidative activity. Cellular and animal studies show that RuCo nanosheets are capable of effectively reducing oxidative stress, preventing inflammatory responses triggered by an abnormal increase in ROS at intestinal sites, and thus protecting cells from inflammatory damages. This research presents a gastric-acid-stabilized antioxidative nanocatalytic platform for the efficient treatment of inflammatory diseases of the digestive system.}, archive = {J_JACS}, author = {Zhixin Chen and Ya-Xuan Zhu and Yanling You and Min Ge and Yihan Chen and Han Lin and Jianlin Shi}, doi = {10.1021/jacs.5c00100}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13424--13436}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzyme-mimic activities of RuCo bimetallic nanosheets for inflammatory bowel disease treatment}, volume = {147}, year = {2025}, }
• (2025). Regioselective hydroaminoalkylation with silylated alkenes for β-amino acid synthesis. JACS, 147(16), 13415--13423. (www)

  @article{ , abstract = {Catalyst and substrate steric and electronic features that influence regioselectivity in hydroaminoalkylation were leveraged to develop a synthetic approach for the selective synthesis of β-amino acids. An in situ generated tantalum-ureate catalyst was used to prepare 18 γ-silylated amines in up to 93% yield from internal silylated alkenes. β-Amino silane regioisomer production was rarely observed, making this work one of the few examples of highly regioselective hydroaminoalkylation with unsymmetric internal alkenes. These γ-amino silanes were converted to γ-amino alcohols with a modified Tamao–Fleming oxidation strategy followed by two additional steps to prepare β-amino acids, including a key fragment of the anticancer drug candidate Ipatasertib.}, archive = {J_JACS}, author = {Maxwell J. Thompson and Daveen Yang and Jacqueline B. M. Higgins and Laurel L. Schafer}, doi = {10.1021/jacs.4c18706}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13415--13423}, shortjournal = {J. Am. Chem. Soc.}, title = {Regioselective hydroaminoalkylation with silylated alkenes for β-amino acid synthesis}, volume = {147}, year = {2025}, }
• (2025). Single catalyst with dynamic ligands enabled synthesis of olefin block copolymers. JACS, 147(16), 13405--13414. (www)

  @article{ , abstract = {Olefin block copolymers (OBCs) are among the most advanced classes of polyolefins, produced in large quantities as part of the approximately 200 million tons of polyolefins produced annually. However, current OBCs manufacturing relies on a complex, costly, two-catalyst process that requires hazardous chain shuttling agents. A more efficient approach using a single catalyst for the synthesis of the OBCs is highly desirable but remains significantly challenging. Traditional olefin copolymerization catalysts typically grow a single polymer chain and are incapable of generating block structures as they fail to incorporate α-olefins with the necessary precision. To achieve block copolymerization, the catalyst must simultaneously accomplish two seemingly contradictory tasks, efficiently and inefficiently incorporating α-olefins into the polymer chain. Here, we introduce a new approach for synthesizing OBCs using a single catalyst. By coupling this catalyst with a regulating agent, we enabled a one-step synthesis of OBCs with tunable hard/soft block ratios and high melting temperatures (∼120 °C). This method offers significant advantages, featuring its operational simplicity, elimination of chain shuttling agents, separate comonomer addition, or adjustments in reaction conditions. Mechanistic studies suggest that alkyl chains act as temporary ligands, dynamically influencing the catalyst’s polymerization behavior. This dynamic process allows the catalyst to alternate between efficient and inefficient α-olefin incorporators, thereby facilitating the synthesis of OBCs.}, archive = {J_JACS}, author = {Lanfei Lu and Yu Li and Chenxiaoning Meng and Kunyu Liu and Yue Yu and Hui Chen and Guoming Liu and Yang Wang}, doi = {10.1021/jacs.4c18606}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13405--13414}, shortjournal = {J. Am. Chem. Soc.}, title = {Single catalyst with dynamic ligands enabled synthesis of olefin block copolymers}, volume = {147}, year = {2025}, }
• (2025). (GGAA)3-based TF-PROTACs enable targeted degradation of ETV6 to inhibit ewing sarcoma growth. JACS, 147(16), 13396--13404. (www)

  @article{ , abstract = {Ewing sarcoma is a rare pediatric cancer primarily driven by the EWS::FLI1 oncofusion transcription factor. Despite being an ideal drug target, EWS::FLI1 has proven challenging to inhibit with conventional approaches. Recent studies identified ETV6 as a vulnerability in Ewing sarcoma, where it competes with EWS::FLI1 at short GGAA repeats to restrain EWS::FLI1 function. However, no therapies targeting ETV6 have been developed. In this study, we report the discovery of a unique (GGAA) 3 DNA oligonucleotide that specifically binds to ETV6 but not EWS::FLI1. We developed (GGAA) 3 -based TF-PROTACs, termed d(GGAA) 3 s, by coupling (GGAA) 3 with VHL ligands. d(GGAA) 3 s effectively degraded endogenous ETV6 but not EWS::FLI1 proteins in Ewing sarcoma cells, thus suppressing Ewing sarcoma growth. Mechanistically, d(GGAA) 3 s enhanced oncogenic EWS::FLI1 transcriptional activity, inducing cellular stress and cell death. Additionally, d(GGAA) 3 s sensitized Ewing sarcoma cells to standard chemotherapy, suggesting their potential use in combination therapies. Beyond Ewing sarcoma, d(GGAA) 3 s also targeted ETV6-fusion proteins found in breast cancer, broadening their potential clinical applications. In summary, d(GGAA) 3 s represent a nucleotide-based approach for degrading ETV6, inhibiting Ewing sarcoma growth and targeting ETV6-dependent cancers. This strategy offers a promising therapeutic avenue for Ewing sarcoma and other malignancies involving ETV6 fusions.}, archive = {J_JACS}, author = {Zhichuan Zhu and He Chen and Xing Qiu and H. Umit Kaniskan and Ling Xie and Xian Chen and Jian Jin and Pengda Liu}, doi = {10.1021/jacs.4c18484}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13396--13404}, shortjournal = {J. Am. Chem. Soc.}, title = {(GGAA)3-based TF-PROTACs enable targeted degradation of ETV6 to inhibit ewing sarcoma growth}, volume = {147}, year = {2025}, }
• (2025). Integrating cryo-electron microscopy and molecular dynamics simulations to investigate membrane binding of influenza virus fusion peptides. JACS, 147(16), 13385--13395. (www)

  @article{ , abstract = {We propose an approach for determining the positioning of membrane-active peptides within a lipid bilayer. It is based on a combination of cryogenic electron microscopy (cryo-EM) with molecular dynamics (MD) simulations. Cryo-EM image intensity profiles across peptide-containing liposome membranes are analyzed by comparing them to synthetic images that are derived from MD trajectories of peptide-membrane systems representing different assumed binding modes. These simulated profiles serve as baseline models, which are then used to classify experimentally obtained images into respective categories. The approach was applied to influenza virus fusion peptides, providing evidence for predominantly transmembrane binding in pure POPC membranes and a transition toward surface-bound configurations upon the addition of cholesterol.}, archive = {J_JACS}, author = {Piotr Setny and Paulina Borkowska and Remigiusz Worch}, doi = {10.1021/jacs.4c18441}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13385--13395}, shortjournal = {J. Am. Chem. Soc.}, title = {Integrating cryo-electron microscopy and molecular dynamics simulations to investigate membrane binding of influenza virus fusion peptides}, volume = {147}, year = {2025}, }
• (2025). Versatile solid-state medical superglue precursors of α-lipoic acid. JACS, 147(16), 13377--13384. (www)

  @article{ , abstract = {α-Lipoic acid ( αLA ) is an attractive building block for medical adhesives. However, due to poor water solubility of αLA and high hydrophobicity of poly(αLA), elevated temperatures, organic solvents, or complex preparations are typically required to obtain and deliver αLA -based adhesives to biological tissue. Here, we report αLA -based powder and low-viscosity liquid superglues that polymerize and bond rapidly upon contact with wet tissue. A monomeric mixture of αLA, sodium lipoate, and an activated ester of lipoic acid was used to formulate the versatile adhesives. Stress–strain measurements of the wet adhesives confirmed the high flexibility of the adhesive. Moreover, a small molecule regenerative drug was successfully incorporated into and released from the adhesive without altering the physical and adhesive properties. In vitro and in vivo studies of the developed adhesives confirmed their cell and tissue compatibility, biodegradability, and potential for sustained drug delivery. Moreover, due to the inherent ionic nature of the adhesives, they demonstrated high electric conductivity and sensitivity to deformation, allowing for the development of a tissue-adherent strain sensor.}, archive = {J_JACS}, author = {Subhajit Pal and Erika E. Salzman and Dominic Ramirez and Hannah Chen and Cynthia A. Perez and Katelyn Dale and Sujoy K. Ghosh and Liwei Lin and Phillip B. Messersmith}, doi = {10.1021/jacs.4c18448}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13377--13384}, shortjournal = {J. Am. Chem. Soc.}, title = {Versatile solid-state medical superglue precursors of α-lipoic acid}, volume = {147}, year = {2025}, }
• (2025). Hydrogen controls the heavy atom roaming in transient negative ion. JACS, 147(16), 13370--13376. (www)

  @article{ , abstract = {Bromine and hydrogen play unusual roles as mobile atom and dissociation dynamics moderator, respectively, during roaming in the 3-bromo-4H-1,2,4-triazole anion. The present study of the reactivity of 3-bromo-1H-1,2,4-triazole and 3-bromo-4H-1,2,4-triazole with low-energy electrons reveals the effect of the hydrogen position on the reaction dynamics. We report energy-dependent ion yields for both molecules showing significant differences. Quantum chemical calculations reveal that heavy Br atom migration is energetically more favored than H atom migration in the case of the H atom adjacent to Br. This is enabled by the energetically favorable formation of a noncovalent complex of Br – around the triazole ring. Recently, such complexes have been reported for several other biologically relevant molecules. In the present work, we demonstrate that the position of hydrogen on the ring influences the character of the lowest resonant state and, consequently, the Br – roaming and dissociation dynamics, particularly the neutral release of hydrogen bromide.}, archive = {J_JACS}, author = {Smith Pataraprasitpon and Thomas F. M. Luxford and Roman Čurík and Jaroslav Kočišek and Dariusz G. Piekarski}, doi = {10.1021/jacs.4c18446}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13370--13376}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen controls the heavy atom roaming in transient negative ion}, volume = {147}, year = {2025}, }
• (2025). Redox-active ligands permit multielectron o2 homolysis and O-atom transfer at exceptionally high-valent vanadyl complexes. JACS, 147(16), 13356--13369. (www)

  @article{ , abstract = {A five-coordinate chlorovanadium species supported by two redox-active N -phenyl aminophenol ligands was prepared. Experimental and computational data support formulation of this complex as [( Ph ap)( Ph isq)V IV Cl], containing one dianionic [ Ph ap] 2– amidophenolate and one monoanionic [ Ph isq] •– iminosemiquinonate radical. Exposure of [( Ph ap)( Ph isq)V IV Cl] to O 2 readily cleaves the O═O bond to generate [( Ph isq)( Ph ibq)V IV (O)Cl], containing an [ Ph ibq] iminobenzoquinone, so the 2e – oxidation is entirely ligand centered. [( Ph isq)( Ph ibq)V IV (O)Cl] is reduced by net H 2 abstraction from 9,10-dihydroanthracene, or in reactions with main-group nucleophiles, such as PPh 3 and Me 2 S, which form a new bond to oxygen and regenerate [( Ph ap)( Ph isq)V IV Cl]. Accordingly, the dioxygenase-type O 2 activation and O-atom transfer cycling are a direct consequence of ligand redox noninnocence and covalency in the vanadium─aminophenol bonding. The reactions with O–atom donor and acceptor substrates establish a V≡O BDE of 73 ± 14 kcal mol –1 in [( Ph isq)( Ph ibq)V IV (O)Cl]. Reported V≡O BDEs in redox-innocent vanadyl complexes typically fall in the range of 120–170 kcal mol –1 . Unlike later 3d metals, where M═O species are typically high energy and activated by, for instance, occupancy of M–O π* antibonding MOs, the exceptionally weak V≡O bond in [( Ph isq)( Ph ibq)V IV -(O)Cl] reflects stabilization of the reduced product. Thus, this research highlights an alternative pathway to generating strong oxidants that are not strong outer-sphere electron acceptors, with implications for the design of early metal catalysts for aerobic oxidations of weak O–atom acceptors or strong X–H bonds.}, archive = {J_JACS}, author = {Andrew G. Hill and Mariah C. Castillo and John Bacsa and Kaitlyn S. Otte and Jake D. Soper}, doi = {10.1021/jacs.4c18305}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13356--13369}, shortjournal = {J. Am. Chem. Soc.}, title = {Redox-active ligands permit multielectron o2 homolysis and O-atom transfer at exceptionally high-valent vanadyl complexes}, volume = {147}, year = {2025}, }
• (2025). Mesoporous single-crystalline particles as robust and efficient acidic oxygen evolution catalysts. JACS, 147(16), 13345--13355. (www)

  @article{ , abstract = {The scarcity of iridium (Ir) limits its widespread use in acidic oxygen evolution reaction (OER). Herein, mesoporous single-crystalline spinel Co 3 O 4 with atomically dispersed low-valence-state Ir has been developed to enable Ir’s efficient and stable utilization. The surface Pourbaix diagram suggests that under acidic OER conditions, O* fully covers both Co 3 O 4 (111) and (110) surfaces, passivating Co sites but enhancing Co 3 O 4 ’s structural stability, a benefit further improved by Ir doping. Mesopores offer numerous loading sites for Ir single atoms (13.8 wt %), which activate the originally O*-passivated Co 3 O 4 (111) surface by creating high-intrinsic-activity Co–Ir bridge sites; meanwhile, Ir and Co leaching rates are reduced to about 1/4 and 1/5, respectively, compared to conventional Ir/Co 3 O 4 catalysts. Our catalyst exhibits a low η 10 of 248 mV for over 100 h, showcasing its potential in water electrolysis.}, archive = {J_JACS}, author = {Yong Wang and Yunpu Qin and Sijia Liu and Yongzhi Zhao and Luan Liu and Di Zhang and Shangqing Zhao and Jianfang Liu and Jie Wang and Yadong Liu and Haoyang Wu and Baorui Jia and Xuanhui Qu and Hao Li and Mingli Qin}, doi = {10.1021/jacs.4c18390}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13345--13355}, shortjournal = {J. Am. Chem. Soc.}, title = {Mesoporous single-crystalline particles as robust and efficient acidic oxygen evolution catalysts}, volume = {147}, year = {2025}, }
• (2025). Rational design of PROTAC linkers featuring ferrocene as a molecular hinge to enable dynamic conformational changes. JACS, 147(16), 13328--13344. (www)

  @article{ , abstract = {Proteolysis Targeting Chimeras (PROTACs) are bifunctional molecules that induce ubiquitination and degradation of a target protein via recruitment to an E3 ligase. The linker influences many steps of the PROTAC mode of action, from cellular permeability to ternary complex formation and target degradation. Much interest has therefore been devoted to linker design to fine-tune molecular and mechanistic properties of PROTACs. In this study, we present FerroTACs, a novel PROTAC design strategy incorporating ferrocene as the linker chemotype. We exemplify the approach across three different PROTAC systems: VHL-VHL (homo-PROTACs), VHL-CRBN, and VHL-BETs. We find that ferrocene’s unique organometallic structure, featuring freely rotating cyclopentadienyl rings around a central Fe(II) ion, acts as a molecular hinge enabling structural adjustment to the environment that results in properties alteration, i.e., chameleonicity. Conformational analyses via NMR spectroscopy support ferrocene’s role in fostering intramolecular interactions that result in a more folded state in an apolar environment. This property promotes compact conformations, improving cellular permeability and reducing efflux liabilities. Cellular assays demonstrate that FerroTACs exhibit robust target degradation and cell permeability profiles, en-par or enhanced compared to benchmark PROTACs CM11 , 14a , and MZ1 . These findings highlight ferrocene’s potential as a new linker design strategy, offering a versatile platform to install and control molecular chameleonicity into next-generation PROTACs.}, archive = {J_JACS}, author = {Alessandra Salerno and Lianne H. E. Wieske and Claudia J. Diehl and Alessio Ciulli}, doi = {10.1021/jacs.4c18354}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13328--13344}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design of PROTAC linkers featuring ferrocene as a molecular hinge to enable dynamic conformational changes}, volume = {147}, year = {2025}, }
• (2025). Cyclometallated Co(III) complexes with lowest-energy charge transfer excited states accessible with visible light. JACS, 147(16), 13315--13327. (www)

  @article{ , abstract = {The Co(III) complexes, cis -[Co(ppy) 2 (L)]PF 6 , where ppy = 2-phenylpyridine and L = bpy (2,2′-bipyridine; 1 ), phen (1,10-phenanthroline; 2 ), and DAP (1,12-diazaperylene; 3 ), are reported and their photophysical properties were investigated to evaluate their potential as sensitizers for applications that include solar energy conversion schemes and photoredox catalysis. Calculations show that cyclometallation in the cis -[Co(ppy) 2 (L)]PF 6 series affords strong Co(dπ)/ppy(π) orbital interactions that result in a Co/ppy(π*) highest occupied molecular orbital (HOMO) and a lowest unoccupied molecular orbital (LUMO) localized on the diimine ligand, L(π*). Complexes 1–3 exhibit relatively invariant oxidation potentials, whereas the reduction event is dependent on the identity of the diimine ligand, L, consistent with the theoretical predictions. For 3 a broad Co/ppy(π*) → L(π*) metal/ligand-to-ligand charge transfer (ML-LCT) absorption band is observed in CH 3 CN with a maxima at 507 nm, extending beyond 600 nm. Upon excitation of the 1 ML-LCT transition, transient absorption features consistent with the population of a 3 ML-LCT excited state with lifetimes, τ, of 3.0 ps, 4.6 and 42 ps for 1 , 2 and 3 in CH 3 CN respectively are observed. Upon irradiation with 505 nm, 3 is able to reduce methyl viologen (MV 2+ ), an electron acceptor commonly in photocatalytic schemes. To our knowledge, 3 represents the first heteroleptic molecular Co(III) complex that combines cyclometallation with a diimine ligand with lowest-lying metal-to-ligand charge transfer excited states able to undergo photoinduced charge transfer with low-energy green light. As such, the structural design of 3 represents an important step toward d 6 photosensitizers based on earth abundant metals.}, archive = {J_JACS}, author = {Spencer T. Burton and Gyunhee Lee and Curtis E. Moore and Christo S. Sevov and Claudia Turro}, doi = {10.1021/jacs.4c18299}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13315--13327}, shortjournal = {J. Am. Chem. Soc.}, title = {Cyclometallated Co(III) complexes with lowest-energy charge transfer excited states accessible with visible light}, volume = {147}, year = {2025}, }
• (2025). Magnetite nanodiscs activate mechanotransductive calcium signaling in diverse cell types. JACS, 147(16), 13303--13314. (www)

  @article{ , abstract = {Remote magnetomechanical stimulation using magnetic nanomaterials has emerged as a robust and minimally invasive technique for modulating neuronal activity. However, despite the presence of machinery to convert mechanical force into biochemical signals in many types of cells, magnetomechanical stimulation of non-neuronal tissue remains largely unexplored. Here, we demonstrate that in the presence of weak magnetic fields (12–56 mT) with frequencies 5–125 Hz, magnetite nanodiscs (MNDs) activate ubiquitous mechano-sensitive calcium signaling pathways, including transmembrane calcium entry, the release of intracellular calcium reserves, and store-operated calcium signaling. MNDs mediate calcium transients in cells with disparate calcium signaling machinery, such as cardiomyocytes and hippocampal astrocytes. The characteristics of these calcium responses depend on the protein machinery available in each cell type. These findings expand the reach of cellular modulation strategies using magnetic nanoparticles to non-neuronal cells and thereby open new applications probing endocrine, immune, and circulatory functions and related disorders with remote magnetic approaches.}, archive = {J_JACS}, author = {Jacob L. Beckham and Ye Ji Kim and Emmanuel Vargas Paniagua and Noah Kent and Keisuke Nagao and Sharmelee Selvaraji and Florian Koehler and Elian Malkin and Xavier Smith and Anthony Tabet and Sehoon Kang and Polina Anikeeva}, doi = {10.1021/jacs.4c18227}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13303--13314}, shortjournal = {J. Am. Chem. Soc.}, title = {Magnetite nanodiscs activate mechanotransductive calcium signaling in diverse cell types}, volume = {147}, year = {2025}, }
• (2025). Proteomimetic strategy for the modulation of intrinsically disordered protein MYC. JACS, 147(16), 13296--13302. (www)

  @article{ , abstract = {The difficulty in developing specific ligands for protein receptors is directly correlated to the presence of unique binding sites on the protein surface. Conformationally dynamic proteins increase the level of difficulty in ligand design, and the challenge is further exacerbated for proteins that are intrinsically disordered. Intrinsically disordered proteins (or IDPs) do not adopt a fixed three-dimensional shape until they bind their target; an absence of organized binding sites underscores the difficulty in developing synthetic ligands for these proteins. We hypothesized that one avenue for the development of binders for a disordered region would be to trap one of its thermodynamically accessible conformations in a receptor. Here, we show the application of this approach to MYC, which represents a critical therapeutic target but has not yielded small-molecule inhibitors due to its conformationally dynamic nature. MYC adopts a helical configuration when it binds to its cellular partner MAX. We rationally designed a proteomimetic scaffold to trap this conformation. We show that MYC can be directly engaged in both biochemical and cellular assays. Overall, this work demonstrates a general method to capture and trap intrinsically disordered proteins with a propensity to adopt α-helical conformations.}, archive = {J_JACS}, author = {Thu Nguyen and Seong Ho Hong and Paramjit S. Arora}, doi = {10.1021/jacs.4c18144}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13296--13302}, shortjournal = {J. Am. Chem. Soc.}, title = {Proteomimetic strategy for the modulation of intrinsically disordered protein MYC}, volume = {147}, year = {2025}, }
• (2025). In situ identification of spin magnetic effect on oxygen evolution reaction unveiled by X-ray emission spectroscopy. JACS, 147(16), 13286--13295. (www)

  @article{ , abstract = {Manipulating the spin ordering of the oxygen evolution reaction (OER) catalysts through magnetization has recently emerged as a promising strategy to enhance performance. Despite numerous experiments elaborating on the spin magnetic effect for improved OER, the origin of this phenomenon remains largely unexplored, primarily due to the difficulty in directly distinguishing the spin states of electrocatalysts during chemical reactions at the atomic level. X-ray emission spectroscopy (XES), which provides information sensitive to the spin states of specific elements in a complex, may serve as a promising technique to differentiate the onset of OER catalytic activities from the influence of spin states. In this work, we employ the in situ XES technique, along with X-ray absorption spectroscopy (XAS), to investigate the interplay between atomic/electronic structures, spin states, and OER catalytic activities of the CoFe 2 O 4 (CFO) catalyst under an external magnetic field. This enhancement is due to the spin magnetic effect that facilitates spin-selective electron transfer from adsorbed OH – reactants, which strongly depends on the spin configurations of the tetrahedral-( T d ) and octahedral-( O h ) sites of both Fe and Co ions. Our result contributes to a comprehensive understanding of magnetic field-assisted electrocatalysis at the atomic level and paves the way for designing highly efficient OER catalysts.}, archive = {J_JACS}, author = {Chih-Ying Huang and Hsin-An Chen and Wei-Xuan Lin and Kuan-Hung Chen and Yu-Chang Lin and Tai-Sing Wu and Chia-Che Chang and Chih-Wen Pao and Wei-Tsung Chuang and Jyh-Chyuan Jan and Yu-Cheng Shao and Nozomu Hiraoka and Jau-Wern Chiou and Pai-Chia Kuo and Jessie Shiue and Deepak Vishnu S. K and Raman Sankar and Zih-Wei Cyue and Way-Faung Pong and Chun-Wei Chen}, doi = {10.1021/jacs.4c18149}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13286--13295}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ identification of spin magnetic effect on oxygen evolution reaction unveiled by X-ray emission spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Cyclic bifunctional reagents enabling a strain-release-driven formal [3 + 2] cycloaddition of 2H-azirines by cascade energy transfer. JACS, 147(16), 13276--13285. (www)

  @article{ , abstract = {The energy transfer (EnT)-catalyzed ring opening and further decarboxylation of isoxazole-5(4 H )-ones enables the in situ generation of strained 2 H -azirines. Subsequent selective C(sp 2 )–C(sp 3 ) bond cleavage of the azirine intermediate allows a formal [3 + 2] cycloaddition with a wide range of electrophiles, unlocking access to valuable pyrroline-type moieties. Mechanistic experiments in combination with density functional theory (DFT) calculations revealed the unique nature of the EnT-cascade process for the generation and ring opening of the three-membered aza-cycle while providing insight into the regio- and diastereoselectivity of the annulation. This mild and straightforward method ensures the rapid construction of highly substituted cyclic imines, which can be easily converted into pyrrolidines, fused oxaziridines, and biologically relevant β-amino acid precursors.}, archive = {J_JACS}, author = {Alessia Petti and Mathis J. Karrasch and Preeti Chahar and Felix H. Wessels and Niklas Hölter and Florian Boser and Constantin G. Daniliuc and Frank Glorius}, doi = {10.1021/jacs.4c18080}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13276--13285}, shortjournal = {J. Am. Chem. Soc.}, title = {Cyclic bifunctional reagents enabling a strain-release-driven formal [3 + 2] cycloaddition of 2H-azirines by cascade energy transfer}, volume = {147}, year = {2025}, }
• (2025). Rapid access to small molecule conformational ensembles in organic solvents enabled by graph neural network-based implicit solvent model. JACS, 147(16), 13264--13275. (www)

  @article{ , abstract = {Understanding and manipulating the conformational behavior of a molecule in different solvent environments is of great interest in the fields of drug discovery and organic synthesis. Molecular dynamics (MD) simulations with solvent molecules explicitly present are the gold standard to compute such conformational ensembles (within the accuracy of the underlying force field), complementing experimental findings and supporting their interpretation. However, conventional methods often face challenges related to computational cost (explicit solvent) or accuracy (implicit solvent). Here, we showcase how our graph neural network (GNN)-based implicit solvent (GNNIS) approach can be used to rapidly compute small molecule conformational ensembles in 39 common organic solvents reproducing explicit-solvent simulations with high accuracy. We validate this approach using nuclear magnetic resonance (NMR) measurements, thus identifying the conformers contributing most to the experimental observable. The method allows the time required to accurately predict conformational ensembles to be reduced from days to minutes while achieving results within one k B T of the experimental values.}, archive = {J_JACS}, author = {Paul Katzberger and Lea M. Hauswirth and Antonia S. Kuhn and Gregory A. Landrum and Sereina Riniker}, doi = {10.1021/jacs.4c17622}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13264--13275}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid access to small molecule conformational ensembles in organic solvents enabled by graph neural network-based implicit solvent model}, volume = {147}, year = {2025}, }
• (2025). High-throughput extracellular vesicle isolation using plate-based size exclusion chromatography and automation. JACS, 147(16), 13258--13263. (www)

  @article{ , abstract = {Extracellular vesicles (EVs) are natural, cell-derived nanoparticles released into biofluids, such as plasma, and hold great potential as a new class of biomarkers. However, the utility of analyzing EVs in clinical samples has been hampered by a lack of suitable EV isolation methods that can be performed reproducibly in a scalable manner. The current method of choice for isolating EVs, size exclusion chromatography (SEC), is performed manually one column at a time, and thus does not have the throughput for isolating EVs from clinical samples. In this work, we adapt SEC to a plate-based format to increase its throughput. We show that SEC can be performed using plates containing frits packed with resin, where each well of a 24-well plate can be used for a different sample. By measuring EV markers CD63 and CD81, as well as Albumin as a representative free protein, we optimize the separation of EVs from free proteins in the 24-well format. We also demonstrate that performing SEC in these plates can be automated using liquid handling platforms with the use of custom adapters. We quantify the high reproducibility of this automated platform and then apply the platform to analyze the tetraspanins CD63 and CD81 across individuals. Our work represents a solution to the long-standing challenge in the EV biomarker field of reproducible high-throughput EV isolation from plasma and other biofluids. We envision that the automated methods we have developed will scale SEC to hundreds of samples per day, enabling the use of EVs for biomarker discovery and diagnostics.}, archive = {J_JACS}, author = {Tal Gilboa and Dmitry Ter-Ovanesyan and Clarissa May Babila and Sara Whiteman and Shad Morton and David Kalish and Jamie Johnston and David Tesin and Matthew Davies and Jenny M. Tam and George M. Church and David R. Walt}, doi = {10.1021/jacs.4c17948}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13258--13263}, shortjournal = {J. Am. Chem. Soc.}, title = {High-throughput extracellular vesicle isolation using plate-based size exclusion chromatography and automation}, volume = {147}, year = {2025}, }
• (2025). Quantum mechanical behavior of hydrogen bonds enables supramolecular structure in a weak Acid–Base monoprotic complex. JACS, 147(16), 13251--13257. (www)

  @article{ , abstract = {The unconventional supramolecular chemistry between perfluoro- tert -butanol (PFTB), as an acid, and 1-methylimidazole (MIM), as a base, is presented. Supramolecular chemistry occurs in MIM-PFTB mixtures with a base-to-acid molar ratio of 1:2, or higher, and coincides with the formation of strong hydrogen bonds (SHBs) in which the acidic hydrogen atoms are quantum mechanically delocalized. Evidence for the SHB and the hydrogen atom sharing is obtained from IR and 1 H NMR spectroscopies and X-ray crystallography. First-principles simulations incorporating both electronic and nuclear quantum effects verify the presence of the SHBs and demonstrate that the broad IR absorption band centered at 2400 cm –1 and the large downfield 1 H NMR of the complexes are a consequence of the hydrogen atom sharing between the acid and the base. The supramolecular behavior reported for PFTB-MIM has not been previously observed in other monoprotic acid–base mixtures forming either conventional or SHBs. Hence, MIM-PFTB mixtures depart from the behavior typically exhibited by other liquid mixtures, demonstrating that electronic and nuclear quantum effects play an important role in driving the unconventional supramolecular chemistry observed in MIM-PFTB samples.}, archive = {J_JACS}, author = {Anit Gurung and Rui Zhang and Lu Wang and Daniel G. Kuroda}, doi = {10.1021/jacs.4c17870}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13251--13257}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantum mechanical behavior of hydrogen bonds enables supramolecular structure in a weak Acid–Base monoprotic complex}, volume = {147}, year = {2025}, }
• (2025). Reversible interconversion of nitrate and nitrite catalyzed by periplasmic nitrate reductase from campylobacter jejuni. JACS, 147(16), 13243--13250. (www)

  @article{ , abstract = {The periplasmic nitrate reductase catalytic subunit (NapA) belongs to the DMSO reductase (DMSOR) family of the molybdenum cofactor (Moco) containing enzymes and catalyzes nitrate reduction to nitrite. Some members of the DMSOR family (e.g., DMSO reductase, formate dehydrogenase, nitrite oxidoreductase, and arsenate reductase) catalyze the reversible interconversion of the substrate and product with varying efficiency. Here, we demonstrate that NapA not only can reduce nitrate to nitrite but also can also oxidize nitrite to nitrate. At least three mechanisms involving the oxygen atom transfer (OAT) process have been proposed for NapA-catalyzed nitrate reduction. NapA can also oxidize nitrite via an OAT process. However, there is no experimental evidence for any of these OAT processes using isolated pure enzymes so far. Here, we provide the first experimental evidence for OAT reactions in both forward (i.e., nitrate reduction) and backward (i.e., nitrite oxidation) reactions catalyzed by NapA using isotope labeling, mass spectrometry, and NMR experiments. Finally, we propose a mechanistic scheme supported by experiment and computation consistent with atom transfer as the rate-limiting step.}, archive = {J_JACS}, author = {Nitai C. Giri and Lahiru Wedasingha and Nicholas Manicke and Maciej Szaleniec and Partha Basu}, doi = {10.1021/jacs.4c17874}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13243--13250}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible interconversion of nitrate and nitrite catalyzed by periplasmic nitrate reductase from campylobacter jejuni}, volume = {147}, year = {2025}, }
• (2025). Porphyrin-engineered 125I-nanoseeds as a prototype for immunogenic brachytherapy. JACS, 147(16), 13229--13242. (www)

  @article{ , abstract = {Internal radiotherapy holds a greater potential than external radiotherapy for precisely destroying tumors and minimizing side effects. 125 I seeds are routinely used as radioactive sources in clinical brachytherapy for patients with various types of cancers. However, 125 I seeds are losing ground to flashier cancer therapies, mainly due to their limited therapeutic efficacy, uneven dose distribution, and negligible antitumor immune response. Here, we present porphyrin-engineered 125 I-nanoseeds as a prototype for immunogenic brachytherapy. 125 I-nanoseeds were rationally designed as a core–shell structure, in which Au@Ag cores enhance the energy deposition of photons to produce more ·OH, while porphyrin shells transfer the energy of Auger electrons to generate 1 O 2 . Benefiting from improving energy utilization efficiency, 125 I-nanoseeds can efficiently produce ·OH and 1 O 2 in tumors, enhancing antitumor efficacy and inducing immunogenic cell death in both murine tumor models and human tumor tissues. When combined with checkpoint blockade immunotherapy, 125 I-nanoseeds elicit a systemic immune response in tumor-bearing mice, inhibiting both distant and metastatic tumors. This work demonstrates that porphyrin-engineered 125 I-nanoseeds can synergize brachytherapy and dynamic therapy, resulting in enhanced antitumor efficacy and antitumor immune response compared to those of clinical 125 I seeds, which is expected to improve the applied prospect of clinical brachytherapy.}, archive = {J_JACS}, author = {Zhiyu Tu and Ziyang Sang and Yang Xu and Weiqiu Liang and Simiao Qiao and Qi Sun and Kongchang Feng and Ziren Kong and Hao Wang and Zhibo Liu}, doi = {10.1021/jacs.4c17573}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13229--13242}, shortjournal = {J. Am. Chem. Soc.}, title = {Porphyrin-engineered 125I-nanoseeds as a prototype for immunogenic brachytherapy}, volume = {147}, year = {2025}, }
• (2025). Space charge, modulating the catalytic activity of single-atom metal catalysts. JACS, 147(16), 13220--13228. (www)

  @article{ , abstract = {Potential-induced electrode charging is a prerequisite to initiate electrochemical reactions at the electrode–electrolyte interface. The ‘interface space charge’ could dramatically alter the reaction environment and the charge density of the active site, both of which potentially affect the electrochemical activity. However, our understanding of the electrocatalytic role of space charge has been limited. Here, we separately modulate the amount of space charge (characterized by the areal density, σ) with maintaining the electrochemical potential for the oxygen reduction reaction (ORR) at the same level, by exploiting the unique structural feature of MeNC. We reveal that changes in σ control the ORR activity, which is computationally explained by the inductive polarization of the charge density at the active sites, affecting their turnover rates. To guide catalyst design including the space charge effect, we develop a new descriptor, explaining the activity trend in various metal centers and pH conditions using a single volcano. These findings offer fresh insights into the role of space charge in electrocatalysis, providing a new framework for optimizing catalyst design and performance.}, archive = {J_JACS}, author = {Hansol Choi and Seung-Jae Shin and Geunsu Bae and Junsic Cho and Man Ho Han and Moulay Tahar Sougrati and Frédéric Jaouen and Kug-Seung Lee and Hyung-Suk Oh and Hyungjun Kim and Chang Hyuck Choi}, doi = {10.1021/jacs.4c17413}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13220--13228}, shortjournal = {J. Am. Chem. Soc.}, title = {Space charge, modulating the catalytic activity of single-atom metal catalysts}, volume = {147}, year = {2025}, }
• (2025). Oxide support inert in its interaction with metal but active in its interaction with oxide and vice versa. JACS, 147(16), 13210--13219. (www)

  @article{ , abstract = {Supported metal or oxide nanostructures catalyze many industrial reactions, where the interaction of metal or oxide overlayer with its support can have a substantial influence on catalytic performance. In this work, we show that small Pt species can be well stabilized on CeO 2 under both H 2 -containing and O 2 -containing atmospheres but sintering happens on SiO 2 , indicating that CeO 2 is active whereas SiO 2 is inert in Pt–support interaction. On the other hand, Co oxide (CoO x ) supported on SiO 2 can maintain a low-valence Co 2+ state both in air and during CO 2 hydrogenation to CO, indicating a strong interaction of CoO x with SiO 2 . However, the CoO x overlayer has a weak interaction with CeO 2 and is easily reduced to metallic Co during the CO 2 hydrogenation reaction producing CH 4 . Thus, SiO 2 is active, but CeO 2 is inert for CoO x –support interaction, which is counter to the common sense from the Pt/oxide systems. Systematic studies in stability behaviors of Pt and CoO x nanocatalysts supported on various oxides show that the reducibility of the oxide supports can be used to describe the catalyst–support interaction. Oxide supports with high reducibility or low metal–oxygen bond strength interact strongly with Pt and other metals, showing high metalphilicity. Conversely, oxide supports with low reducibility or high metal–oxygen bond strength have strong interaction with CoO x and other oxides, having high oxidephilicity.}, archive = {J_JACS}, author = {Cui Dong and Rongtan Li and Zhenping Qu and Yamei Fan and Jianyang Wang and Xiangze Du and Chengxiang Liu and Xiaohui Feng and Yanxiao Ning and Rentao Mu and Qiang Fu and Xinhe Bao}, doi = {10.1021/jacs.4c17075}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13210--13219}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxide support inert in its interaction with metal but active in its interaction with oxide and vice versa}, volume = {147}, year = {2025}, }
• (2025). NMR2-based drug discovery pipeline presented on the oncogenic protein KRAS. JACS, 147(16), 13200--13209. (www)

  @article{ , abstract = {Fragment-based drug discovery has emerged as a powerful approach for developing therapeutics against challenging targets, including the GTPase KRAS. Here, we report an NMR-based screening campaign employing state-of-the-art techniques to evaluate a library of 890 fragments against the oncogenic KRAS G12V mutant bound to GMP-PNP. Further HSQC titration experiments identified hits with low millimolar affinities binding within the SI/SII switch region, which forms the binding interface for the effector proteins. To elucidate the binding modes, we applied NMR molecular replacement ( N MR 2 ) structure calculations, bypassing the need for a conventional protein resonance assignment. Traditionally, N MR 2 relies on isotope-filtered nuclear Overhauser effect spectroscopy experiments requiring double-labeled [ 13 C, 15 N]-protein. We introduce a cost-efficient alternative using a relaxation-based filter that eliminates isotope labeling while preserving structural accuracy. Validation against standard isotopically labeled workflows confirmed the equivalence of the derived protein–ligand structures. This approach enabled the determination of 12 N MR 2 KRAS–fragment complex structures, providing critical insights into structure–activity relationships to guide ligand optimization. These results demonstrate the streamlined integration of N MR 2 into a fragment-based drug discovery pipeline composed of screening, binding characterization, and rapid structural elucidation with or without isotopic labeling.}, archive = {J_JACS}, author = {Matthias Bütikofer and Felix Torres and Harindranath Kadavath and Nina Gämperli and Marie Jose Abi Saad and Daniel Zindel and Nicolas Coudevylle and Roland Riek and Julien Orts}, doi = {10.1021/jacs.4c16762}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13200--13209}, shortjournal = {J. Am. Chem. Soc.}, title = {NMR2-based drug discovery pipeline presented on the oncogenic protein KRAS}, volume = {147}, year = {2025}, }
• (2025). Light-driven deracemization by a designed photoenzyme. JACS, 147(16), 13190--13199. (www)

  @article{ , abstract = {The creation of enzymes with abiological abilities offers exciting opportunities to access new-to-nature biocatalysis beyond that found in nature. Here, we repurpose a novel protein scaffold, CTB10, as an artificial photoenzyme through genetic code expansion. It enables catalytic deracemization of cyclopropane, a process that remains inaccessible to traditional biocatalysis due to its thermodynamically unfavorable nature. Following structural optimization through directed evolution, a broad substrate scope with high enantioselectivities is achieved. Furthermore, the crystal structure of the CTB10-based photoenzyme–substrate complex well demonstrates how the catalytic chiral cavity is sculpted to promote efficient and selective light-enabled deracemization. Therefore, this study unlocks the potential for achieving challenging deracemization through biocatalysis.}, archive = {J_JACS}, author = {Min Li and Yan Zhang and Kai Fu and Zhiwei Deng and Zhenbo Yuan and Zhengshan Luo and Yijian Rao}, doi = {10.1021/jacs.4c16521}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13190--13199}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-driven deracemization by a designed photoenzyme}, volume = {147}, year = {2025}, }
• (2025). Organelle-specific quantum thermometry using fluorescent nanodiamonds: Insights into cellular metabolic thermodynamics. JACS, 147(16), 13180--13189. (www)

  @article{ , abstract = {Intracellular thermometry is a powerful method for studying biological thermodynamics across various physiological contexts. In this study, we present an organelle-specific quantum thermometry utilizing nitrogen-vacancy (NV) centers in fluorescent nanodiamonds (FNDs) to obtain precise temperature measurements at the subcellular level. By conjugating antibodies, FNDs were selectively targeted to mitochondria, nuclei, and cell membranes in living fibroblasts, enabling real-time monitoring of temperature changes during adenosine triphosphate (ATP) synthesis and inhibition. The system integrates advanced bioconjugation and quantum sensing methodologies, thereby overcoming challenges, such as photobleaching and limited spatial resolution. Notably, mitochondria-targeted FNDs revealed significant temperature increases, revealing mitochondria as the primary site of thermogenesis during ATP inhibition. These findings establish a robust framework for investigating metabolic thermodynamics and offer a powerful tool for exploring the thermal regulation of cellular processes.}, archive = {J_JACS}, author = {Yoobeen Lee and Kiho Kim and Dohun Kim and Jin Seok Lee}, doi = {10.1021/jacs.4c16365}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13180--13189}, shortjournal = {J. Am. Chem. Soc.}, title = {Organelle-specific quantum thermometry using fluorescent nanodiamonds: Insights into cellular metabolic thermodynamics}, volume = {147}, year = {2025}, }
• (2025). Evidence for a unifying NiI/NiIII mechanism in light-mediated cross-coupling catalysis. JACS, 147(16), 13169--13179. (www)

  @article{ , abstract = {Advances in nickel catalysis have significantly broadened the synthetic chemists’ toolbox, particularly through methodologies leveraging paramagnetic nickel species via photoredox catalysis or electrochemistry. Key to these reactions is the oxidation state modulation of nickel via single-electron transfer events. Recent mechanistic studies indicate that C(sp 2 )–heteroatom bond formations proceed through Ni I /Ni III cycles. Related C(sp 2 )–C(sp 3 ) cross-couplings operate via the photocatalytic generation of C-centered radicals and a catalytic cycle that involves Ni 0 , Ni I , and Ni III species. Here, we show that light-mediated nickel-catalyzed C(sp 2 )–C(sp 3 ) bond formations can be carried out without using exogenous photoredox catalysts but with a photoactive ligand. In a pursuit of expanding the scope of C(sp 2 )–heteroatom couplings using donor–acceptor ligands, we identified a photoactive nickel complex capable of catalyzing cross-couplings between aryl halides and benzyltrifluoroborate salts. Mechanistic investigations provide evidence that transmetalation between a photochemically generated Ni I species and the organoboron compound is the key catalytic step in a Ni I /Ni III catalytic cycle under these conditions.}, archive = {J_JACS}, author = {Lucia Anghileri and Haralds Baunis and Aleksander R. Bena and Christos Giannoudis and John H. Burke and Susanne Reischauer and Christoph Merschjann and Rachel F. Wallick and Tarek Al Said and Callum E. Adams and Gianluca Simionato and Sergey Kovalenko and Luca Dell’Amico and Renske M. van der Veen and Bartholomäus Pieber}, doi = {10.1021/jacs.4c16050}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13169--13179}, shortjournal = {J. Am. Chem. Soc.}, title = {Evidence for a unifying NiI/NiIII mechanism in light-mediated cross-coupling catalysis}, volume = {147}, year = {2025}, }
• (2025). Driving electrochemical organic hydrogenations on metal catalysts by tailoring hydrogen surface coverages. JACS, 147(16), 13158--13168. (www)

  @article{ , abstract = {Electrochemical hydrogenation, powered by renewable electricity, represents a promising sustainable approach for organic synthesis and the valorization of biomass-derived chemicals. Traditional strategies often rely on alkaline conditions to mitigate the competing hydrogen evolution reaction, posing challenges in sourcing hydrogen atoms for hydrogenation, which can be addressed through localized water dissociation on the electrode surface. In this study, we present a computationally guided design of electrochemical hydrogenation catalysts by optimizing hydrogen coverage density and binding strength on the electrode. Our theoretical investigations identify Cu, Au, and Ag − metals with moderate hydrogen coverage − as promising catalysts for electrochemical hydrogenations in alkaline media. These predictions are experimentally validated using a model organic substrate (acetophenone), achieving yields and faradaic efficiencies of up to 90%. Additionally, Cu, a nonprecious metal, is demonstrated to selectively hydrogenate a wide range of unsaturated compounds, including C═O, C═C, C≡C, and C≡N bonds, at low potentials with moderate to excellent conversion rates and chemoselectivities. This work highlights the potential of tailoring hydrogen coverage on electrode surfaces to rationally design nonprecious metal electrocatalysts for efficient organic hydrogenations. The insights gained here are expected to inform the development of more effective catalysts for organic hydrogenations and other industrially relevant chemical transformations.}, archive = {J_JACS}, author = {Anna Ciotti and Motiar Rahaman and Celine Wing See Yeung and Tengfei Li and Erwin Reisner and Max García-Melchor}, doi = {10.1021/jacs.4c15821}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13158--13168}, shortjournal = {J. Am. Chem. Soc.}, title = {Driving electrochemical organic hydrogenations on metal catalysts by tailoring hydrogen surface coverages}, volume = {147}, year = {2025}, }
• (2025). Decoding order and disorder in proteins by NMR spectroscopy. JACS, 147(16), 13146--13157. (www)

  @article{ , abstract = {Proteins often have a complex architecture, consisting of both globular ordered domains and intrinsically disordered regions (IDRs). These multidomain proteins pose challenges for traditional structural biology techniques. One major difficulty arises from the dynamic and flexible nature of IDRs, which lack a stable three-dimensional structure. Indeed, this feature further complicates the application of traditional structural biology techniques. Characterizing these systems is typically simplified by isolating individual domains, which can provide valuable insights into the structure and function of specific regions. However, this approach overlooks the interactions and regulatory mechanisms that occur between domains. To capture the full functional and structural complexity of multidomain proteins, it is crucial to study larger constructs. In this study, we focused on the CREB binding protein (CBP), a pivotal protein involved in numerous cellular processes. CBP is characterized by its modular structure, featuring alternating globular domains and IDRs. We specifically examined the TAZ4 construct, encompassing the TAZ2 globular domain and the ID4 flexible linker region. To characterize this multidomain system, we designed NMR experiments that take advantage of the dynamic differences between the two domains to obtain 2D and 3D spectra enabling the selection of the signals based on their nuclear relaxation properties. These experiments allowed the sequence-specific assignment of the TAZ4 construct to be extended revealing a crosstalk between the disordered region and the globular domain.}, archive = {J_JACS}, author = {Lorenzo Bracaglia and Silvia Oliveti and Isabella C. Felli and Roberta Pierattelli}, doi = {10.1021/jacs.4c14959}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13146--13157}, shortjournal = {J. Am. Chem. Soc.}, title = {Decoding order and disorder in proteins by NMR spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Local ionic conditions modulate the aggregation propensity and influence the structural polymorphism of α-synuclein. JACS, 147(16), 13131--13145. (www)

  @article{ , abstract = {Parkinson’s disease (PD) is linked to the aggregation of the intrinsically disordered protein α-synuclein (aSyn), but the precise triggers and mechanisms driving this process remain unclear. Local environmental factors, such as ion concentrations, can influence aSyn’s conformational ensemble and its tendency to aggregate. In this study, we explore how physiologically relevant ions, mainly Ca 2+ and Na + , affect aSyn aggregation, monomer structural dynamics, and fibril polymorphism. ThT fluorescence assays show that all ions speed up aggregation, with Ca 2+ having the strongest effect. Using heteronuclear single quantum correlation nuclear magnetic resonance ( 1 H– 15 N HSQC NMR) spectroscopy, we validate that Ca 2+ binds at the C-terminus while Na + interacts nonspecifically across the sequence. Small-angle neutron scattering (SANS) and hydrogen–deuterium exchange mass spectrometry (HDX-MS) show that Na + leads to more extended aSyn structures, while Ca 2+ results in moderate extension. Molecular dynamics (MD) simulations support this, showing Na + increases extension between the NAC region and C-terminus, whereas Ca 2+ biases the ensemble toward a moderately elongated structure. MD also shows that Ca 2+ increases water persistence times in the hydration shell, indicating that aSyn aggregation propensity is due to a combination of conformational bias of the monomer and solvent mobility. Atomic force microscopy (AFM) points toward the formation of distinct fibril polymorphs under different ionic conditions, suggesting ion-induced monomer changes contribute to the diversity of fibril structures. These findings underscore the pivotal influence of the local ionic milieu in shaping the structure and aggregation propensity of aSyn, offering insights into the molecular underpinnings of PD and potential therapeutic strategies targeting aSyn dynamics.}, archive = {J_JACS}, author = {Maria Zacharopoulou and Neeleema Seetaloo and James Ross and Amberley D. Stephens and Giuliana Fusco and Thomas M. McCoy and Wenyue Dai and Ioanna Mela and Ana Fernandez-Villegas and Anne Martel and Alexander F. Routh and Alfonso De Simone and Jonathan J. Phillips and Gabriele S. Kaminski Schierle}, doi = {10.1021/jacs.4c13473}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13131--13145}, shortjournal = {J. Am. Chem. Soc.}, title = {Local ionic conditions modulate the aggregation propensity and influence the structural polymorphism of α-synuclein}, volume = {147}, year = {2025}, }
• (2025). Direct observation of alkyl group transmetalation from boron to copper: Impact of structure modification and the critical role of Copper–Oxygen preassociation in stereospecificity. JACS, 147(16), 13126--13130. (www)

  @article{ , abstract = {Mechanistic investigations of prospective intermediates in copper-catalyzed cross-coupling reactions with alkyllithium-activated alkylboronic esters are described. Complexes between (NHC)copper and the borate salts were characterized by X-ray crystallography and NMR, and the rate of intramolecular transmetalation of an alkyl group from boron to copper was measured. Derived activation parameters were correlated with those determined by DFT analysis and give insight into the mechanism of stereospecific transmetalation.}, archive = {J_JACS}, author = {Hao Liang and James P. Morken}, doi = {10.1021/jacs.5c03197}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13126--13130}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct observation of alkyl group transmetalation from boron to copper: Impact of structure modification and the critical role of Copper–Oxygen preassociation in stereospecificity}, volume = {147}, year = {2025}, }
• (2025). Rh-catalyzed enantioselective aryl C–H bond cyclopropylation. JACS, 147(16), 13120--13125. (www)

  @article{ , abstract = {Herein, we disclose the discovery and development of a site-, regio-, diastereo-, and enantioselective aryl C–H bond cyclopropylation using diazomethyl hypervalent iodine reagents, styrenes, and paddlewheel dirhodium carboxylate catalysts. A key aspect of this work was the catalytic generation of a chiral Rh(II) carbene through an electrophilic aromatic substitution with chiral Rh(II) carbynoids. The strategy allows the construction of cyclopropane rings using aryl C–H bonds from aromatic feedstocks and drug molecules and promises to reach an unexplored “cyclopropanated” chemical space highly difficult to reach by current strategies.}, archive = {J_JACS}, author = {Eric Palomo and Anastasiya Krech and Yu Jen Hsueh and Zexian Li and Marcos G. Suero}, doi = {10.1021/jacs.5c02331}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13120--13125}, shortjournal = {J. Am. Chem. Soc.}, title = {Rh-catalyzed enantioselective aryl C–H bond cyclopropylation}, volume = {147}, year = {2025}, }
• (2025). Semiartificial photoelectrochemistry for CO2-mediated enantioselective organic synthesis. JACS, 147(16), 13114--13119. (www)

  @article{ , abstract = {Photoelectrochemical (PEC) cells are under intensive development for the synthesis of solar fuels, but CO 2 reduction typically only results in simple building blocks such as HCOO – . Here, we demonstrate that CO 2 -converting PEC cells can drive integrated enzymatic domino catalysis to produce chiral organic molecules by using CO 2 /HCOO – as a sustainable redox couple. First, we establish a semiartificial electrode consisting of three enzymes co-immobilized on a high surface area electrode based on carbon felt covered by a mesoporous indium tin oxide (ITO) coating. When applying a mild cathodic potential (−0.25 V vs the reversible hydrogen electrode (RHE)), CO 2 is reduced to HCOO – using a W-formate dehydrogenase (FDH NvH ) from Nitratidesulfovibrio vulgaris Hildenborough, which then enables the reduction of NAD + to NADH by an NAD + -cofactor-dependent formate dehydrogenase from Candida boidinii (FDH CB ). Subsequently, an alcohol dehydrogenase (ADH) uses NADH generated from CO 2 /HCOO – cycling to reduce acetophenone to chiral 1-phenylethanol in good enantiomeric excess (93%) and conversion yields (38%). Depending on the specific ADH (ADH S or ADH R ), either ( S )- or ( R )-1-phenylethanol can be synthesized at pH 6 and 20 °C. To illustrate solar energy utilization, we integrate the three nanoconfined enzymes with a PEC platform based on an integrated organic semiconductor photocathode to allow for enantioselective synthesis (at +0.8 V vs RHE) based on a solar fuel device. This proof-of-principle demonstration shows that concepts and devices from artificial photosynthesis can be readily translated to precise and sustainable biocatalysis, including the production of chiral organic molecules using light.}, archive = {J_JACS}, author = {Tessel Bouwens and Samuel J. Cobb and Celine W. S. Yeung and Yongpeng Liu and Guilherme Martins and Inês A. C. Pereira and Erwin Reisner}, doi = {10.1021/jacs.5c02250}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13114--13119}, shortjournal = {J. Am. Chem. Soc.}, title = {Semiartificial photoelectrochemistry for CO2-mediated enantioselective organic synthesis}, volume = {147}, year = {2025}, }
• (2025). Non-canonical type II terpene cyclases deliver rare terpenoid architectures. JACS, 147(16), 13108--13113. (www)

  @article{ , abstract = {Terpene cyclases (TCs) catalyze the generation of complex polycyclic terpenoids through elaborate mechanistic cascades. Very little is known about the unusual type II TCs responsible for generation of a large diverse family of meroterpenoids known as indole diterpenoids (IDTs). The radarins are insecticidal and cytotoxic IDTs that possess an unusual core architecture for which the catalytic machinery is unknown. Here, we interrogate the genome of Aspergillus fresenii to reveal the biosynthetic machinery responsible for delivering the specific radarin scaffold. We demonstrate that a bespoke regioselective IDT epoxidase (RadM) acts at the terminal olefin of precursor 3′-geranylgeranylindole, providing access to this distinct class of IDT architectures. Coexpression of this epoxidase with a noncanonical type II TC RadB led to the biosynthesis of radarin C, in a complex skeletal rearrangement that proceeds via rare alcoholic deprotonation and ketone formation. Our modeling of RadB reveals that catalysis by RadB is enabled by a unique His residue that acts as both the proton donor and acceptor. Intriguingly, coexpression of RadM with an alternative A. fresenii IDT cyclase gene, which does not share this catalytic His, revealed an alternate partial cyclization of 14,15-epoxy-3′-GGI, producing a new decalin IDT. This work solves the final piece of the biosynthetic puzzle to access the full suite of known IDT architectures, informs type II cyclase engineering efforts, and expands the repertoire of impressive chemistry catalyzed by noncanonical TCs.}, archive = {J_JACS}, author = {Rose M. McLellan and Daniel Berry and Rosannah C. Cameron and Emily J. Parker}, doi = {10.1021/jacs.4c18232}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13108--13113}, shortjournal = {J. Am. Chem. Soc.}, title = {Non-canonical type II terpene cyclases deliver rare terpenoid architectures}, volume = {147}, year = {2025}, }
• (2025). Evidence of a three-state mechanism in DNA hairpin folding. JACS, 147(16), 13101--13107. (www)

  @article{ , abstract = {DNA hairpins are a model system for biomolecule folding as well as key structures in biology and nanotechnology. However, limitations in traditional solution-phase spectroscopy shorten the window of observable kinetics and cannot account for static heterogeneity. Here, we show that the application of two-dimensional fluorescence lifetime correlation spectroscopy (2DFLCS) to a solution-phase molecule trapped in an anti-Brownian electrokinetic (ABEL) trap bypasses those limitations, enabling kinetic analysis of the dynamics of single solution-phase molecules on a broad range of time scales down to microseconds. The analysis unambiguously shows that DNA hairpin folding proceeds via a three-state system, where hairpins fold initially on the scale of tens to hundreds of microseconds from a random coil to a partially closed intermediate and then form a stable fully closed state.}, archive = {J_JACS}, author = {Brendan Cullinane and Kunihiko Ishii and Simi Kaur and Tahei Tahara and Randall H. Goldsmith}, doi = {10.1021/jacs.4c17471}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13101--13107}, shortjournal = {J. Am. Chem. Soc.}, title = {Evidence of a three-state mechanism in DNA hairpin folding}, volume = {147}, year = {2025}, }
• (2025). Role of water in green carbon science. JACS, 147(16), 13083--13100. (www)

  @article{ , abstract = {Within the context of green chemistry, the concept of green carbon science emphasizes carbon balance and recycling to address the challenge of achieving carbon neutrality. The fundamental processes in this field are oxidation and reduction, which often involve simple molecules such as CO 2 , CO, CH 4 , CH x , and H 2 O. Water plays a critical role in nearly all oxidation–reduction processes, and thus, it is a central focus of research in green carbon science. Water can act as a direct source of dihydrogen in reduction reactions or participate in oxidation reactions, frequently involving O–O coupling to produce hydrogen peroxide or dioxygen. At the atomic level, this coupling involves the statistically unfavorable proximity of two atoms, requiring optimization through a catalytic process influenced by two types of factors, as described by the authors. Extrinsic factors are related to geometrical and electronic criteria associated with the catalytic metal, involving its d -orbitals (or bands in the case of zerovalent metals and electrodes). Intrinsic factors are related to the coupling of oxygen atoms via their p -orbitals. At the mesoscopic or microscopic scale, the reaction medium typically consists of mixtures of lipophilic and hydrophilic phases with water, which may exist under supercritical conditions or as suspensions of microdroplets. These reactions predominantly occur at phase interfaces. A comprehensive understanding of the phenomena across these scales could facilitate improvements and even lead to the development of novel conversion processes.}, archive = {J_JACS}, author = {Bo Peng and Kun Zhang and Yuhan Sun and Buxing Han and Mingyuan He}, doi = {10.1021/jacs.5c00347}, journal = {Journal of the American Chemical Society}, month = {4}, number = {16}, pages = {13083--13100}, shortjournal = {J. Am. Chem. Soc.}, title = {Role of water in green carbon science}, volume = {147}, year = {2025}, }
• (2025). Retraction of “Metallic conductivity in a two-dimensional cobalt dithiolene Metal–Organic framework”. JACS, 147(15), 13082. (www)

  @article{ , archive = {J_JACS}, author = {Andrew J. Clough and Jonathan M. Skelton and Courtney A. Downes and Ashley A. de la Rosa and Joseph W. Yoo and Aron Walsh and Brent C. Melot and Smaranda C. Marinescu}, doi = {10.1021/jacs.4c13151}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {13082}, shortjournal = {J. Am. Chem. Soc.}, title = {Retraction of “Metallic conductivity in a two-dimensional cobalt dithiolene Metal–Organic framework”}, volume = {147}, year = {2025}, }
• (2025). Expanding the electrochemical stability window: Unraveling the role of solvent polarity and a WiSE-compatible strategy. JACS, 147(15), 13071--13081. (www)

  @article{ , abstract = {Expanding the electrochemical stability window (ESW) of aqueous batteries significantly enhances their safety and energy density, addressing performance limitations and elevating their position in energy storage systems. Over the past decade, water-in-salt electrolyte (WiSE) has led to groundbreaking advancement in this field. However, a pressing question arises: can we further broaden the ESW through novel approaches? This study delves into this question, leveraging atomistic simulation along with ESW estimation and WiSE continuum theory to uncover that interfacial solvent polarity, subtly modulated by adding minor organic solvents, expands the ESW as well as promotes ion intercalation and transport. The strategy of incorporating minor organic solvents is compatible with WiSE, which not only advances our comprehension but also forges new research paths for post-WiSE era aqueous battery innovation. More importantly, our study provides a systematic way for theoretically estimating ESW and analyzing its enhancement mechanism in aqueous batteries.}, archive = {J_JACS}, author = {Guobin Lai and Jinguo Lin and Weixing Mo and Xinzhu Li and Xuting Jin and Mingmao Wu and Feng Liu}, doi = {10.1021/jacs.5c04782}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {13071--13081}, shortjournal = {J. Am. Chem. Soc.}, title = {Expanding the electrochemical stability window: Unraveling the role of solvent polarity and a WiSE-compatible strategy}, volume = {147}, year = {2025}, }
• (2025). Graphene-based glucose sensors with an attomolar limit of detection. JACS, 147(15), 13059--13070. (www)

  @article{ , abstract = {Diabetes mellitus, a prevalent metabolic disorder affecting hundreds of millions of people worldwide, demands continuous glucose monitoring for effective management. Current blood glucose monitoring methods, such as commercial glucometers, are accurate but are often perceived as uncomfortable. Motivated by the need for noninvasive, ultrasensitive alternatives, our study presents electrolyte-gated graphene field-effect transistors functionalized with glucose oxidase. We developed an optimized fabrication process that integrates a 32-transistor matrix within a miniaturized 1000 μm 2 footprint, ensuring high device uniformity while enabling detection in 40 μL analyte volume. A comprehensive suite of techniques─including Raman spectroscopy, X-ray photoelectron spectroscopy, and water contact angle measurements─reveals the stepwise evolution of graphene chemistry and surface properties leading to the controlled immobilization of glucose oxidase. Our findings demonstrate p-type doping and tensile strain in the graphene channel across the nanomolar–millimolar glucose concentration range. The enzyme-catalyzed oxidation of glucose produces hydrogen peroxide in close proximity to the graphene channel, inducing a systematic shift in the Dirac point voltage toward more positive values. Under these conditions, the biosensor achieves an attomolar limit of detection and a sensitivity of 10.6 mV/decade, outperforming previously reported glucose sensors. Selectivity tests against common interferents such as lactate and ascorbic acid, as well as validation in artificial and human tears, demonstrate its robustness for real-world applications. Altogether, these findings position the electrolyte-gated graphene field-effect transistor as a transformative, noninvasive glucose-sensing platform, paving the way for next-generation continuous monitoring devices, including wearable formats for real-time, user-friendly diabetes management.}, archive = {J_JACS}, author = {Vicente Lopes and Tiago Abreu and Mafalda Abrantes and Siva Sankar Nemala and Francesco De Boni and Mirko Prato and Pedro Alpuim and Andrea Capasso}, doi = {10.1021/jacs.5c03552}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {13059--13070}, shortjournal = {J. Am. Chem. Soc.}, title = {Graphene-based glucose sensors with an attomolar limit of detection}, volume = {147}, year = {2025}, }
• (2025). Nanoscale grain boundary-weakened Ce–O covalency and surface confinement intrinsically boosting ceria surface oxygen reactivity. JACS, 147(15), 13050--13058. (www)

  @article{ , abstract = {Promoting the reactivity of surface lattice oxygen atoms of oxide nanomaterials is critical for enhancing their catalytic performances in oxidation, hydrogenation, and electrocatalytic reactions; however, the fundamental electronic mechanisms governing this surface reactivity have long remained insufficiently understood. Here, we reveal the electronic mechanism of how the nanoscale grain boundary (GB) boosts the intrinsic surface reactivity of CeO 2 nanomaterials, in which GBs are introduced by pyrolyzing the precursors of cerium carbonate and formate. The results of X-ray absorption near-edge structures (XANES) at the O K- and Ce L 3 -edges reveal that GBs can reduce the degree of covalency of Ce–O bonds, while H 2 -TPR and Raman spectra show that this decreased orbital overlap can further weaken the confinement strength of surface oxygen atoms by the lattice potential. This electronic effect can fundamentally boost the leaving activity of surface lattice oxygen atoms, which further promotes the formation of oxygen vacancies and the activation of the O 2 molecules to oxidize benzyl alcohol into benzaldehyde with 100% selectivity. This structure–function relationship based on reduction in lattice covalency provides a new electronic perspective to understand how GBs and size reduction enhance nanomaterial surface reactivity.}, archive = {J_JACS}, author = {Weixin Zhao and Wenyu Jia and Jun Zhou and Tianyu Zhai and Yuefeng Wu and Zohaib Rana and Peng Sun and Yimeng Liu and Shuyuan Zhou and Guolei Xiang and Xun Wang}, doi = {10.1021/jacs.5c03536}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {13050--13058}, shortjournal = {J. Am. Chem. Soc.}, title = {Nanoscale grain boundary-weakened Ce–O covalency and surface confinement intrinsically boosting ceria surface oxygen reactivity}, volume = {147}, year = {2025}, }
• (2025). Water-mediated radical kinetic resolution of terminal activated N-carbamate aziridines. JACS, 147(15), 13039--13049. (www)

  @article{ , abstract = {Optically active terminal aziridines are fundamental building blocks for constructing complex nitrogen-containing molecules. Notably, the protecting group on the amino moiety critically governs not only the reactivity and enantioselectivity during aziridine formation but also the efficiency of downstream functionalization. While carbamates are among the most widely employed protecting groups in amine-related synthesis due to their versatility and orthogonality, their enantioselective incorporation into aziridines remains a long-standing challenge. Herein, we present the first radical approach for kinetic resolution of aziridines, enabling efficient access to a broad range of aziridines bearing diverse carbamate protecting groups and substituents. This transformation exploits the dual functionality of a dinuclear titanium radical catalyst, which enables enantiodiscriminative activation of racemic aziridines and coordinative activation of H 2 O as a sustainable hydrogen-atom donor. Mechanistic studies reveal that the optimal distribution of the catalyst between aziridine and H 2 O is crucial for sustaining the cooperative catalytic cycle.}, archive = {J_JACS}, author = {Shuo Yang and Longfei Li and Fangkun Wang and Xuelian Dong and Jie Jiang and Yong-Qiang Zhang}, doi = {10.1021/jacs.5c03408}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {13039--13049}, shortjournal = {J. Am. Chem. Soc.}, title = {Water-mediated radical kinetic resolution of terminal activated N-carbamate aziridines}, volume = {147}, year = {2025}, }
• (2025). Adapting atomic configuration steers dynamic half-occupied state for efficient CO2 electroreduction to CO. JACS, 147(15), 13027--13038. (www)

  @article{ , abstract = {Electronic structures stand at the center to essentially understand the catalytic performance and reaction mechanism of atomically dispersed transition-metal–nitrogen–carbon catalysts (ADTCs). However, under realistic electrocatalytic conditions, the dynamic electronic disturbance at metal centers originating from complicated interactions with microenvironments is commonly neglected, which makes a true structure–property correlation highly ambiguous. Here, we employ operando time-resolved X-ray absorption spectroscopy to delve deeply into dynamic electronic behaviors of a family of transition-metal centers that are observed to adaptively vary in the metal–ligand configuration during the CO 2 electroreduction reaction. We identify dynamic electronic/geometric configuration and d-orbital occupation under working conditions, demonstrating an unprecedentedly precise activity descriptor, i.e., dynamic axial d z 2 electron, for the CO 2 -to-CO conversion. Direct results validate that the half-occupied state suggests the optimum binding behaviors with intermediates, significantly promoting CO production, which has been demonstrated by a significant kinetics enhancement of 1 to 2 orders of magnitude as compared with fully occupied and unoccupied states. This work presents the first empirical demonstration for a real correlation between the dynamic electronic/geometric configuration and catalytic kinetics in ADTCs, paving a new way for modulating catalysts and designing highly efficient reaction pathways.}, archive = {J_JACS}, author = {Jiali Wang and Hui Ying Tan and Chia-Shuo Hsu and You-Chiuan Chu and Ching-Wei Chan and Kuan-Hsu Chen and Xuan-Rou Lin and Yi-Chun Lee and Hsiao-Chien Chen and Hao Ming Chen}, doi = {10.1021/jacs.5c03121}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {13027--13038}, shortjournal = {J. Am. Chem. Soc.}, title = {Adapting atomic configuration steers dynamic half-occupied state for efficient CO2 electroreduction to CO}, volume = {147}, year = {2025}, }
• (2025). Empowering diastereoselective cyclopropanation of unactivated alkenes with sulfur ylides through nucleopalladation. JACS, 147(15), 13017--13026. (www)

  @article{ , abstract = {Regio- and stereoselective cyclopropanation of unactivated alkenes under mild conditions remains a challenging yet fundamental transformation. We present a versatile palladium(II)-catalyzed method for the diastereoselective cyclopropanation of alkenyl amines and alkenyl acids, which leverages the nucleopalladation mechanism and the unique ambiphilic reactivity of sulfur ylides. This Pd(II)/Pd(IV) catalytic protocol selectively delivers anti- cyclopropanes for allylamines with a removable isoquinoline-1-carboxamide auxiliary, while enabling excellent syn -selectivity for alkenyl acid derivatives containing a 2-(aminomethyl)pyridine derivative as a directing group. The protocol is operationally simple and scalable, features a wide substrate generality, and also remains effective in the presence of various medicinally relevant scaffolds. The cyclopropane products were further transformed into 1,2,3-trifunctionalized cyclopropanes and engaged in an aza-Piancatelli reaction, introducing additional molecular complexity. DFT studies were performed to shed light on the reaction mechanism and the origins of the observed stereoselectivity.}, archive = {J_JACS}, author = {Nityananda Ballav and Chandan Kumar Giri and Shib Nath Saha and Manoj V. Mane and Mahiuddin Baidya}, doi = {10.1021/jacs.5c03146}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {13017--13026}, shortjournal = {J. Am. Chem. Soc.}, title = {Empowering diastereoselective cyclopropanation of unactivated alkenes with sulfur ylides through nucleopalladation}, volume = {147}, year = {2025}, }
• (2025). Asymmetric cascade photocycloaddition-acyloin rearrangement enabled by cage-confined visible-light catalysis. JACS, 147(15), 13008--13016. (www)

  @article{ , abstract = {Enzymatic catalysis in biological systems is characterized by the specific pocket confinement imposed by various protein matrixes, enabling the synthesis of a diverse array of functional biomolecules. Development of new catalysts that incorporate multiple catalytic centers within the enzyme-mimic confined spaces presents a meaningful yet challenging project for synthetic chemists. Here, we present our recent achievement in synthesizing a chiral photosensitive metal–organic cage (cPMOC), Δ 4 -/ Λ 4 -MOC-68-Ru 4 , which possesses multiple chiral pockets that can facilitate the visible-light-induced asymmetric cascade intermolecular [2 + 2] cycloaddition/acyloin rearrangement for the first time. The current photochemical transformation affords various bicyclo[3.2.1]octanes with opposite regiospecificity in contrast to well-established thermodynamically favored cascade [3 + 2] cycloaddition transformations with similar reaction counterparts. The distinctive pocket size of cage 2 inhibits the dimerization of α,β-unsaturated ketones and promotes the heterocycloaddition between the ketone and smaller cyclic 1,2-dione, underscoring the critical role of the microenvironmental shape and size for guest binding in determining the confined catalytic reactivity.}, archive = {J_JACS}, author = {Jie Chen and Yu-Lin Lu and Yongxian Huang and Fang Zhang and Haoren Ye and Yin-Hui Huang and Xiao-Dong Zhang and Zhiwei Jiao and Cheng-Yong Su}, doi = {10.1021/jacs.5c03074}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {13008--13016}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric cascade photocycloaddition-acyloin rearrangement enabled by cage-confined visible-light catalysis}, volume = {147}, year = {2025}, }
• (2025). Excess cations alter *CO intermediate configuration and product selectivity of cu in acidic electrochemical CO2 reduction reaction. JACS, 147(15), 12996--13007. (www)

  @article{ , abstract = {Concentrated cations are often employed to promote electrochemical CO 2 reduction reaction (CO 2 RR) selectivity in acidic electrolytes. Here, we investigate the influence of excess cations on the *CO adsorption configuration and the product distribution of the CO 2 RR. Operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) reveals that increasing the Cs + concentration shifts the preference of the *CO intermediate on the Cu surface from the atop (*CO atop ) to the bridge (*CO bridge ) configuration. This transition leads to a sharp decline in C–C coupling and an increase in the hydrogen evolution reaction at high Cs + concentrations (0.7 and 1.0 M) under acidic conditions. Time-resolved SEIRAS scans show that *CO atop is kinetically dominant and the proportion of *CO bridge increases gradually only at high cation concentrations. Density functional theory simulations confirm that Cs + on the Cu surface can interact electrostatically with *CO and stabilize *CO bridge over *CO atop on the Cu surface. The evolution of *CO bridge is also observed on Ag catalysts, indicating that the effect at high concentrations is not limited to Cu. Furthermore, polymeric binders on the Cu surface mitigate these detrimental effects on the CO 2 RR and restore C 2 H 4 production by preventing the cation from altering the *CO adsorption sites on the catalyst surface. This study provides new insights into the effects of cations on catalyst performance, with implications for catalyst design and operation.}, archive = {J_JACS}, author = {Suhwan Yoo and Sejin Park and Jihoon Son and Jiseon Kim and Hyeyoung Shin and Yun Jeong Hwang}, doi = {10.1021/jacs.5c02954}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12996--13007}, shortjournal = {J. Am. Chem. Soc.}, title = {Excess cations alter *CO intermediate configuration and product selectivity of cu in acidic electrochemical CO2 reduction reaction}, volume = {147}, year = {2025}, }
• (2025). Selective aliphatic aldimine formation and stabilization by a hydrophobic capsule in water. JACS, 147(15), 12989--12995. (www)

  @article{ , abstract = {Imines and enamines are useful intermediates in biochemical aldol-type reactions since their acid/base characteristics are accessible near neutrality. However, the generation of aldimines in water is a challenge as the equilibrium favors the components alkyl amines and aldehydes. Here, we report the generation, recognition, and protection of aldimines accomplished by a water-soluble capsule. The capsule provides a well-defined hydrophobic cavity isolating aldimines from the medium by a dry seam of Se–N chalcogen bonds instead of a wet seam of hydrogen bonds in water. A series of diverse aldimines are formed in situ and trapped rapidly (within 45 min at mM concentrations) in D 2 O with more than 90% yields. The encapsulated aldimines are stable for at least one month under ambient conditions. The aliphatic aldimines are selectively formed in the capsule even though they are less stable than aromatic imines in solution. The aldimines can be released from the capsule containers by competitive guests such as adamantane.}, archive = {J_JACS}, author = {Ya Gao and Yujie Zhu and Mingkai Zhao and Julius Rebek, Jr. and Yang Yu}, doi = {10.1021/jacs.5c02779}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12989--12995}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective aliphatic aldimine formation and stabilization by a hydrophobic capsule in water}, volume = {147}, year = {2025}, }
• (2025). Spin filtering with surface-active helicene- and twistacene-based perylene diimides. JACS, 147(15), 12982--12988. (www)

  @article{ , abstract = {Creating new chiral molecular and macromolecular systems that can polarize the spin of electrons has the dual promise of both applications in spintronics and a fundamental understanding of their origins. Here, we put forward two optically active helical ladder dimers from perylene diimide-based twistacenes and helicenes. We detail a scalable method to separate the helices for each of these systems and methods to functionalize them with thiol groups that allow for self-assembled monolayer formation on metal surfaces. We probed these monolayers with conductive atomic force microscopy, revealing that they are highly conductive. If the substrate is magnetized, then the current we measure with conductive atomic force microscopy is controlled by the handedness of the helices used to form the monolayers. Furthermore, helices of the same handedness for either the twistacene or helicene (right-handed helices vs left-handed helices) produce high (or low) currents in devices with the same magnetization. Importantly, we find a correlation between the magnetic field dependence of the conductivity and the helicity of the molecules, suggesting a link between these two properties, independent of the sign of their electronic circular dichroism.}, archive = {J_JACS}, author = {Haoyu Jiang and Daniel Čavlović and Qifeng Jiang and Fay Ng and Si Tong Bao and Evan J. Telford and Michael L. Steigerwald and Xavier Roy and Colin Nuckolls and Jeffrey M. McNeill}, doi = {10.1021/jacs.5c02723}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12982--12988}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin filtering with surface-active helicene- and twistacene-based perylene diimides}, volume = {147}, year = {2025}, }
• (2025). Multifunctional janus nanoparticles capable of anchoring to the cell membrane and serving as “Cellular backpacks” for advanced theranostics. JACS, 147(15), 12973--12981. (www)

  @article{ , abstract = {A cell-based theranostic system can be fabricated by attaching nanomedicines to the surface of carrier cells, but it remains a challenge to achieve the attachment without involving endocytosis. Herein, we address this challenge by developing multifunctional Janus nanoparticles with orthogonal surface properties for the two opposite halves. When incubated with carrier cells, the hydrophobic half made of polystyrene readily inserts into the plasma membrane, whereas the hydrophilic SiO 2 half grafted with poly(ethylene glycol) protrudes away from the cell surface. Additionally, the SiO 2 half can be made with a cavity to hold theranostic agents and thus serves as a “backpack” for the carrier cell. By confining the theranostic agents in the SiO 2 compartment and outside the carrier cell during the delivery process, their adverse impact on the cell is minimized. Upon release in an in vitro spheroid model, the agents quickly eradicate cancer cells. Moreover, the polystyrene half can be loaded with superparamagnetic nanoparticles to enhance magnetic resonance imaging contrast and enable magnetic manipulation, facilitating image-guided and target-directed treatments. By further optimizing the interactions between the multifunctional Janus nanoparticles and carrier cells, this system can be developed into a robust platform for cell-based theranostics.}, archive = {J_JACS}, author = {Min Hao and Yidan Chen and Johannes Leisen and Ted J. Whitworth and Younan Xia}, doi = {10.1021/jacs.5c02587}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12973--12981}, shortjournal = {J. Am. Chem. Soc.}, title = {Multifunctional janus nanoparticles capable of anchoring to the cell membrane and serving as “Cellular backpacks” for advanced theranostics}, volume = {147}, year = {2025}, }
• (2025). Nucleation and growth of monodisperse CdTe and CdTe/ZnSe core/shell nanocrystals: Roles of cationic precursors, ligands, and solvents. JACS, 147(15), 12962--12972. (www)

  @article{ , abstract = {With CdTe nanocrystals as a model system, we discover a new synthetic strategy for control of size and size distribution of colloidal semiconductor nanocrystals in both nucleation and growth stages. Especially in the nucleation stage, an in situ-formed cadmium complex with approximately one alkanoate and one alkylphosphonate ligand enables both high-yield nucleation by reacting the reactive cadmium-carboxylate bond with Te precursors and efficient size control by immediate passivation with the close-proximity alkylphosphonate ligand from the same complex. Conversely, control on size distribution during either homoepitaxial or heteroepitaxial growth requires reactive cadmium (or zinc) alkanoates as the cationic precursors with a minimum concentration of alkylphosphonate ligands in the novel synergistic solvents. This new strategy not only yields monodisperse CdTe and CdTe/ZnSe core/shell nanocrystals with unprecedented optical quality but also provides a much-needed alternative route for synthesizing monodisperse semiconductor nanocrystals, which is commonly hindered by the growth barrier of the dense ligand monolayer.}, archive = {J_JACS}, author = {Shangxin Lin and Chuanzhong Yan and Jie Zhu and Yida Lu and Xiaogang Peng}, doi = {10.1021/jacs.5c02597}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12962--12972}, shortjournal = {J. Am. Chem. Soc.}, title = {Nucleation and growth of monodisperse CdTe and CdTe/ZnSe core/shell nanocrystals: Roles of cationic precursors, ligands, and solvents}, volume = {147}, year = {2025}, }
• (2025). Palladium-catalyzed transfer iodination from aryl iodides to nonactivated C(sp3)–H bonds. JACS, 147(15), 12956--12961. (www)

  @article{ , abstract = {We report a new strategy for the catalytic iodination of nonactivated C( sp 3 )–H bonds. The method merges the concepts of shuttle and light-enabled palladium catalysis to employ aryl iodides as both hydrogen atom transfer reagents and iodine donors. A noncanonical Pd 0 /Pd I catalytic cycle is harnessed to transfer iodine from a C( sp 2 ) to a C( sp 3 )–H bond under mild conditions, which tolerate sensitive functional groups. This mechanism is also applied to implement a C( sp 3 )–H thiolation that exploits reversible steps of the system.}, archive = {J_JACS}, author = {Emilien Le Saux and Bill Morandi}, doi = {10.1021/jacs.5c02553}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12956--12961}, shortjournal = {J. Am. Chem. Soc.}, title = {Palladium-catalyzed transfer iodination from aryl iodides to nonactivated C(sp3)–H bonds}, volume = {147}, year = {2025}, }
• (2025). Charging of single molecules mediated by the quantum phase of molecular orbitals. JACS, 147(15), 12949--12955. (www)

  @article{ , abstract = {Enriching the observable consequences of quantum phases has been a long-standing pursuit for quantum frontiers. Here, we demonstrate that the quantum phases of molecular orbitals can be manifested from the charging process of single NTCDA molecules. The self-assembled monolayer molecules form moiré patterns with the underlying Pb(111) substrate. The moiré pattern modulates the energy alignment between the molecule orbitals and the substrate Fermi level, resulting in three types of molecules. Scanning tunneling microscopy measurements indicate that all types of molecules can be gated by the tip electric field to incur charge state transitions but with different threshold fields. Intriguingly, the charge rings surrounding individual molecules exhibit intensity variations and even reversals with pertinent directional dependence. Such an observation is ascribed to the antisymmetric quantum phase of the charged molecular orbital, resulting in destructive tunneling along its highly symmetric molecular axis. This work opens up a new platform for utilizing the quantum phase of molecular orbitals in the control of charge transport in molecular junctions.}, archive = {J_JACS}, author = {Gang Chen and Rui-Jing Sun and Dao-Bo Wang and Wen-Ao Liao and Wen-Hao Zhang and Chao-Fei Liu and Ying-Shuang Fu}, doi = {10.1021/jacs.5c02539}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12949--12955}, shortjournal = {J. Am. Chem. Soc.}, title = {Charging of single molecules mediated by the quantum phase of molecular orbitals}, volume = {147}, year = {2025}, }
• (2025). Expedient assembly of multiantennary N-glycans from common N-glycan cores with orthogonal protection for the profiling of glycan-binding proteins. JACS, 147(15), 12937--12948. (www)

  @article{ , abstract = {Complex-type N -glycans are structurally diverse molecules, responsible for many biological processes, yet the specific sequences of N -glycans involved in biological recognition remain largely unknown. Despite the recent development of many efficient chemoenzymatic approaches, it is still lacking a general approach to produce structurally diverse complex-type N -glycans. Here, we designed two common precursors equipped with orthogonal protecting groups for antennary differentiation and selective glycan elongation. The N -acetyllactosamine (LacNAc) repeat modules were synthesized separately based on iterative Au(I) promoted glycosylation and programmable one-pot strategy and were incorporated into the N -glycan core structure in a site-specific manner. The final removal of benzyl groups was cleanly achieved using pressurized flow chemistry. A total of 51 N -glycans were assembled and presented as an array to study the binding specificity toward a panel of influenza hemagglutinins and other lectins. The established method allows a rapid and previously infeasible synthesis of asymmetric bi- and triantennary N -glycans, especially with the LacNAc repeats residing at a specific arm, bringing in new opportunities to study carbohydrate–receptor interactions.}, archive = {J_JACS}, author = {Ruofan Li and Pengxi Chen and Yi-Fang Zeng and Tzu-Hao Tseng and Veeranjaneyulu Gannedi and Larissa Krasnova and Chi-Huey Wong}, doi = {10.1021/jacs.5c02356}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12937--12948}, shortjournal = {J. Am. Chem. Soc.}, title = {Expedient assembly of multiantennary N-glycans from common N-glycan cores with orthogonal protection for the profiling of glycan-binding proteins}, volume = {147}, year = {2025}, }
• (2025). Luminescence thermometry via multiparameter sensing in YV1–xPxO4:Eu3+, er3+. JACS, 147(15), 12925--12936. (www)

  @article{ , abstract = {Luminescence thermometry is a remote temperature sensing technique that utilizes temperature-dependent luminescence properties. Lanthanide-doped materials with two thermally coupled emitting levels displaying a variation in luminescence intensity ratio (LIR) with temperature have been successfully explored to design sensitive luminescent thermometers. However, the low absorption strength of lanthanide parity-forbidden 4f n → 4f n transitions reduces the brightness. Also, this Boltzmann-type thermometer is only sensitive within a limited temperature range. To address these issues, we report here YV 1– x P x O 4 :Eu 3+ , Er 3+ as a luminescent thermometer. This material utilizes the sensitized emission of Ln 3+ by strong and broad vanadate charge transfer absorption and has a wide and tunable optimum temperature range by controlling the thermal quenching of Eu 3+ emission through a variation of x . The new temperature probe offers a single material with multiple temperature-dependent luminescence properties, viz. the LIR of 2 H 11/2 / 4 S 3/2 emission of Er 3+ , the LIR of the integrated Er 3+ and Eu 3+ emission intensities, and the Eu 3+ emission lifetime. Both micro- and nanocrystalline temperature probes are reported to achieve relative sensitivities ( S r ) from ∼0.5%/K to over 5%/K in a wide temperature range of 300–873 K. To demonstrate practical applicability, the luminescent thermometer was applied to in situ chip temperature detection revealing temperature accuracies better than 1 K.}, archive = {J_JACS}, author = {Yixuan Ma and Xiaopeng Zhou and Jiapeng Wu and Zhijie Dong and Lizhi Cui and Yuhua Wang and Andries Meijerink}, doi = {10.1021/jacs.5c02306}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12925--12936}, shortjournal = {J. Am. Chem. Soc.}, title = {Luminescence thermometry via multiparameter sensing in YV1–xPxO4:Eu3+, er3+}, volume = {147}, year = {2025}, }
• (2025). Energetics of covalent bonding from wave function tiles. JACS, 147(15), 12917--12924. (www)

  @article{ , abstract = {The mechanism of covalent bonding has been debated for a century, with proponents variously championing kinetic or potential energy as the driver. While detailed calculations have revealed the bonding mechanism for model systems such as H 2 + and H 2 , a consensus on larger systems exhibiting covalent C–C bonds has been elusive. Here, the bond energetics of the model system ethane are inspected by decomposing the 54-dimensional electronic wave function into repeating tiles related by permutation of like spin electrons, using our dynamic Voronoi Metropolis sampling algorithm. Within each tile, electrons are found to correspond to distinct chemical identities. The energies of the electrons are inspected as a function of C–C bond length, and the dominant contributors to the binding energy are found to be the pair of electrons in the C–C bonding region, as expected. A decomposition of the C–C bond energy into kinetic and potential terms shows that the bonding energetics mirror those of H 2 , with an initial dip in kinetic energy upon methyl fragment interaction, followed by an increase in kinetic energy and a decrease in potential energy as the bond is formed. The decrease in potential energy is accompanied by a marked contraction of the C–C bonding electron density. These results show the similarity between the model C–C bond and that of H 2 and that wave function tiles are a convenient method to decompose the contributors to covalent bonding energetics in high dimensionalities, agnostic to the method used to calculate the wave function.}, archive = {J_JACS}, author = {Yu Liu and Terry J. Frankcombe and Timothy W. Schmidt}, doi = {10.1021/jacs.5c02274}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12917--12924}, shortjournal = {J. Am. Chem. Soc.}, title = {Energetics of covalent bonding from wave function tiles}, volume = {147}, year = {2025}, }
• (2025). Phenothiazine sulfoxides as active photocatalysts for the synthesis of γ-lactones. JACS, 147(15), 12908--12916. (www)

  @article{ , abstract = {N -substituted phenothiazines are prominent and highly effective organic photoredox catalysts, particularly known for their strong reducing capabilities. Despite their wide utility, the closely related phenothiazine sulfoxides, which easily form upon oxidation, have been largely overlooked and have not been explored in the context of photocatalysis. Herein, we describe the discovery and application of N -phenylphenothiazine sulfoxide as a photocatalyst for the reductive activation of cyclic malonyl peroxides, giving access to complex γ-lactones starting from simple olefins. Detailed mechanistic studies were carried out to better understand the in situ formation of the active catalyst species from a commercial precursor, as well as the catalyst species interconversion and the photocatalytic mechanism for the formation of γ-lactone products. Specifically, we employed a broad range of mechanistic tools, including time-resolved spectroscopy, spectroelectrochemistry, transient UV–vis absorption spectroscopy, cyclic voltammetry, isotopic labeling, radical trapping experiments, NMR spectroscopy, and density functional theory (DFT) calculations. The synthetic utility of this protocol is demonstrated in a substrate scope study, highlighting the facile access to complex spirocyclic γ-lactones, which are widely recognized for their biological importance.}, archive = {J_JACS}, author = {Niklas Hölter and Nils H. Rendel and Leander Spierling and Adrian Kwiatkowski and Roman Kleinmans and Constantin G. Daniliuc and Oliver S. Wenger and Frank Glorius}, doi = {10.1021/jacs.5c01988}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12908--12916}, shortjournal = {J. Am. Chem. Soc.}, title = {Phenothiazine sulfoxides as active photocatalysts for the synthesis of γ-lactones}, volume = {147}, year = {2025}, }
• (2025). Spontaneous exciton dissociation in sc-doped rutile TiO2 for photocatalytic overall water splitting with an apparent quantum yield of 30%. JACS, 147(15), 12897--12907. (www)

  @article{ , abstract = {Achieving high-efficiency photocatalytic overall water splitting with earth-abundant materials like TiO 2 under ambient conditions is a compelling renewable energy solution. However, this remains challenging due to both the presence of rich deep-level defects and lack of strong driving force in particulate photocatalysts, limiting the separation of photogenerated charges. Here, we developed a scandium (Sc)-doped rutile TiO 2 with fully passivated detrimental Ti 3+ defects and very strong built-in electric field arising from engineered (101)/(110) facet junctions. The Sc 3+ doping enables a much lower exciton binding energy of 8.2 meV (28.6 meV for undoping) than room-temperature thermal fluctuation energy, indicating spontaneous exciton dissociation. These features enable the photogenerated electrons and holes to selectively transfer to the (110) and (101) facets, respectively. The resulting Sc-doped TiO 2 with cocatalyst delivers photocatalytic overall water splitting with an apparent quantum yield of 30.3% at 360 nm and a solar-to-hydrogen conversion efficiency of 0.34%, representing the highest values reported for TiO 2 -based photocatalysts under ambient conditions.}, archive = {J_JACS}, author = {Fei Qin and Yuyang Kang and Xingyuan San and Yun-Long Tang and Jianjun Li and Xin Zhang and Kangyu Zhang and Gang Liu}, doi = {10.1021/jacs.5c01936}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12897--12907}, shortjournal = {J. Am. Chem. Soc.}, title = {Spontaneous exciton dissociation in sc-doped rutile TiO2 for photocatalytic overall water splitting with an apparent quantum yield of 30%}, volume = {147}, year = {2025}, }
• (2025). Conversion of syngas to ethanol over a RhFe alloy catalyst. JACS, 147(15), 12890--12896. (www)

  @article{ , abstract = {The direct conversion of syngas to ethanol is a promising route for the sustainable production of value-added chemicals and fuels. While Fe-promoted Rh-based catalysts have long been studied because of their notable activity and selectivity toward ethanol, the catalyst structure and the nature of Rh–Fe interaction remain poorly understood under reaction conditions, due to the intrinsic complexity of heterogeneous catalysts prepared by conventional approaches. In this work, we construct well-defined RhFe@SiO 2 model catalysts via surface organometallic chemistry, composed of small and narrowly distributed nanoparticles supported on silica. Such a RhFe@SiO 2 catalyst converts syngas into ethanol, reaching an overall ethanol selectivity of 38% among all products at 8.4% CO conversion, while the nonpromoted Rh@SiO 2 catalyst mostly yields methane (selectivity >90%) and no ethanol. Detailed in situ X-ray absorption spectroscopy and diffuse-reflectance infrared Fourier transform spectroscopy studies reveal that the RhFe@SiO 2 catalyst corresponds to an Rh–Fe alloy with ca. 3:1 Rh/Fe ratio alongside residual Fe II single sites. The alloy is stable under working conditions, promoting high activity and ethanol selectivity.}, archive = {J_JACS}, author = {Wei Zhou and Scott R. Docherty and Erwin Lam and Christian Ehinger and Xiaoyu Zhou and Yuhui Hou and Paco Laveille and Christophe Copéret}, doi = {10.1021/jacs.5c01751}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12890--12896}, shortjournal = {J. Am. Chem. Soc.}, title = {Conversion of syngas to ethanol over a RhFe alloy catalyst}, volume = {147}, year = {2025}, }
• (2025). Investigating reactivity and selectivity in a palladium-catalyzed heteroleptic ligand system for electrophilic arene fluorination. JACS, 147(15), 12878--12889. (www)

  @article{ , abstract = {Methods to access fluorinated molecules are of significant interest to the medicinal and agrochemical industries. We report a series of high-valent Pd IV complexes stabilized by two distinct ligand cores, which mediate electrophilic fluorination reactions with excellent yields and good regioselectivity. Using high-throughput experimentation and kinetic analysis, the distinct roles of each ligand were uncovered. Synthetic modulation of the catalyst alongside density functional theory transition state modeling provided evidence into the turnover-limiting step while revealing key insights into the origin of regioselectivity. This workflow presents a general strategy for exploring heteroleptic systems as well as synthetic enhancements to electrophilic fluorination reactions relevant to both industrial and academic settings.}, archive = {J_JACS}, author = {Shubham Deolka and Mohammad H. Samha and Aleria Garcia Roca and Graham C. Haug and James R. Howard and David Dalmau and Jesus Sandres and Serhii Vasylevskyi and Ryan T. VanderLinden and Robert S. Paton and Matthew S. Sigman}, doi = {10.1021/jacs.5c01738}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12878--12889}, shortjournal = {J. Am. Chem. Soc.}, title = {Investigating reactivity and selectivity in a palladium-catalyzed heteroleptic ligand system for electrophilic arene fluorination}, volume = {147}, year = {2025}, }
• (2025). Characterization of the biosynthesis of pimprinine-type indolyloxazoles unravels an unusual d-configurational substrate metabolic streamline. JACS, 147(15), 12866--12877. (www)

  @article{ , abstract = {Pimprinine-type indolyloxazole alkaloids (PIAs), originally discovered in Streptomyces , show a diverse range of important pharmaceutical and agricultural bioactivities, yet their biosynthesis remains unknown. Herein, we report the identification of the biosynthetic enzymes responsible for the formation of the indolyloxazole structure of PIAs from a rhizosphere-derived Streptomyces netropsis NZY3, which involves three key enzymes, PimA (GCN5-related N -acetyltransferase, GNAT), PimB (pyridoxal 5′-phosphate-dependent tryptophan racemase), and PimC (Fe II /α-ketoglutarate-dependent dioxygenase, Fe II /αKGD), notably by an unprecedented d -configurational substrate metabolic streamline. First, PimB acts as a gatekeeper to donate the d -tryptophan precursor for the PIA pathway from the l -tryptophan pool of primary metabolism. Subsequently, a unique d -tryptophan GNAT, PimA, catalyzes the formation of N -acyl d -tryptophan. Finally, another novel N -acyl d -tryptophan-specific Fe II /αKGD, PimC, finishes the formation of an indolyloxazole structure through a proposed radical rearrangement-mediated ring closure mechanism, which is supported by a series of deuterium- and 18 O-labeling experiments in vitro . PimC also catalyzes the formation of the trans -vinyl group containing shunt products 1a to 3a through an oxygen-rebound mechanism followed by dehydration and decarboxylation or a carbocation-involved decarboxylation pathway. Furthermore, comparative genomic mining reveals that PIA biosynthetic gene clusters (PIAs BGCs) are widely distributed in Actinobacteria and Myxobacteria , suggesting the potential for discovering new PIA-producing strains. This work expands our knowledge about the biosynthetic mechanisms of pharmaceutic-valued indolyloxazole alkaloids, laying an important foundation for their future production through synthetic biology and metabolic engineering strategies.}, archive = {J_JACS}, author = {Yuyang Zhang and Yanni Zhao and Ningning Wang and Haoran Wang and Pan Yang and Yi-Jie Zhai and Lukuan Hou and Wenli Li}, doi = {10.1021/jacs.5c01705}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12866--12877}, shortjournal = {J. Am. Chem. Soc.}, title = {Characterization of the biosynthesis of pimprinine-type indolyloxazoles unravels an unusual d-configurational substrate metabolic streamline}, volume = {147}, year = {2025}, }
• (2025). Na[B3IO7(OH)] and Na2[B4IO9](IO3): Explorations of boroiodates with strong second harmonic generation response and large birefringence. JACS, 147(15), 12858--12865. (www)

  @article{ , abstract = {In the exploration of nonlinear optical (NLO) materials, developing new functional groups for high performance is essential. Achieving a balance among band gap, second harmonic generation (SHG), and birefringence within a compound is quite challenging. By directly connecting iodates and borates by B–O–I bridges, two boroiodates with novel [B 3 IO 8 (OH)] 3– and [B 4 IO 11 ] 5– anionic functional groups, namely, Na[B 3 IO 7 (OH)] ( NBIO-I ) and Na 2 [B 4 IO 9 ](IO 3 ) ( NBIO-II ), were successfully synthesized for the first time through the boric acid melting method under different molar ratios of H 3 BO 3 /NaIO 3 . NBIO-I ( Pbca ) features a unique 1D ∞ 1 [B 3 IO 7 (OH)] − chain composed of corner-sharing [B 3 O 6 (OH)] 4– groups with [IO 3 ] − groups hanging on both sides of the chain. In contrast, NBIO-II ( Cc ) displays a novel 2D layer of ∞ 2 [B 4 IO 9 ] − , in which all of the [IO 3 ] − groups are hanging on the same side of the ∞ 2 [B 4 O 7 ] 2– layer formed by corner-sharing [B 3 O 7 ] 5– and [BO 3 ] 3– groups. Remarkably, NBIO-II exhibits a wide band gap (4.3 eV), large birefringence (0.298@546 nm), and strongest SHG response (7.8 × KDP) among borate-iodates reported previously. This work not only discovered NBIO-II as promising NLO crystals but also provided an effective synthetic route for new boroiodates with excellent optical properties.}, archive = {J_JACS}, author = {Ya-Lan Deng and Chun-Li Hu and Xiang Xu and Ming-Zhi Zhang and Jiang-Gao Mao}, doi = {10.1021/jacs.5c01673}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12858--12865}, shortjournal = {J. Am. Chem. Soc.}, title = {Na[B3IO7(OH)] and Na2[B4IO9](IO3): Explorations of boroiodates with strong second harmonic generation response and large birefringence}, volume = {147}, year = {2025}, }
• (2025). Taming inert B–H bond with low energy light: A near-infrared light-induced approach to facile carborane cluster-amino acid coupling. JACS, 147(15), 12845--12857. (www)

  @article{ , abstract = {The selective functionalization of inert B–H bonds in carborane clusters has been a formidable challenge. Recent advances have witnessed such reactions through photoredox methods utilizing ultraviolet or visible light irradiation. However, high-energy light sources often suffer from poor energy efficiency, a limited substrate scope, undesired side reactions, and low scalability. Here, we present the first successful B–H bond functionalization under low-energy near-infrared (NIR) light using a carborane-based electron donor–acceptor complex. Both photophysical investigations and theoretical modeling reveal a facile single-electron transfer from the carborane cage to the electron-deficient photocatalyst, generating a carborane cage radical under NIR light irradiation. The follow-up radical pathway enables the direct coupling of carboranes with amino acids or oligopeptides, yielding a diverse array of carborane-functionalized amino acids or oligopeptides. Beyond expanding the known chemical space of boron cluster derivatives, we further demonstrate that carborane-based amino acids with imaging and targeting capabilities could serve as promising multifunctional boron carriers for boron neutron capture therapy. Thus, the selective B–H bond functionalization of the carboranes via NIR light not only provides a straightforward and practical strategy in boron cluster synthetic chemistry but also lays the foundation for the development of next-generation boron-containing biomolecules and advanced functional materials.}, archive = {J_JACS}, author = {Shengwen Xu and Hongjian Zhang and Jibo Zong and Houji Cao and Deshuang Tu and Chang-sheng Lu and Hong Yan}, doi = {10.1021/jacs.5c01610}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12845--12857}, shortjournal = {J. Am. Chem. Soc.}, title = {Taming inert B–H bond with low energy light: A near-infrared light-induced approach to facile carborane cluster-amino acid coupling}, volume = {147}, year = {2025}, }
• (2025). Resolving complex K–Pt–Sn interactions in PtSn@K-MFI catalysts for alkane dehydrogenation. JACS, 147(15), 12833--12844. (www)

  @article{ , abstract = {K and Sn contents were rationalized during the synthesis of PtSn@K-MFI to maximize metal dispersion and stability along the MFI crystallites. Experimental results and theoretical calculations reveal a stoichiometry of ∼1 K per unit cell of MFI, limiting then the final K incorporation within siliceous MFI crystals at ∼0.7 wt %. Above this stoichiometry, K is not incorporated into the final solids unless significant amounts of Sn are simultaneously present, leading to the formation of tin-silicate precipitates. The optimized PtSn@K-MFI catalysts improve the catalytic performance of well-established references, as PtSn/SiO 2 , for the propane dehydration (PDH) reaction. In particular, low Sn loadings (below 0.5 wt %) result in higher time-on-stream (TOS) deactivation catalytic profiles but excellent regenarability after consecutive PDH reaction, while higher Sn content (close to 1 wt %) minimizes TOS deactivation due to the maximization of Pt–Sn bonds but consecutive regenerations result in significant metal sintering. Increasing Sn contents within MFI crystallites facilitates Pt sintering and, thus, occurring catalyst deactivation upon regeneration cycles. As a result of complex interconnected nucleation/crystallization processes, fine-tuning rationalizations of one-pot synthesis approaches can substantially influence the final atomic and subnanometric metal interactions and, consequently, the catalytic and sintering-resistance properties when exposed to highly demanding industrial conditions.}, archive = {J_JACS}, author = {Adrián Martínez Gómez-Aldaraví and Reisel Millán and Isabel Millet and Aroa Alós and Alejandro Vidal-Moya and Randall J. Meyer and Cristina Martínez and Avelino Corma and Mercedes Boronat and Pedro Serna and Manuel Moliner}, doi = {10.1021/jacs.5c01536}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12833--12844}, shortjournal = {J. Am. Chem. Soc.}, title = {Resolving complex K–Pt–Sn interactions in PtSn@K-MFI catalysts for alkane dehydrogenation}, volume = {147}, year = {2025}, }
• (2025). Engineered artificial nanochannels with cell membrane nanointerface for ultrasensitive detection and discrimination of multiple bacterial infections. JACS, 147(15), 12821--12832. (www)

  @article{ , abstract = {Bacterial infection is a major threat to global public health, which urgently require rapid and reliable analytical techniques for complex biological samples but remains a challenge. Herein, we developed an artificial affinity nanochannel with a cell membrane nanointerface, which enables broad-spectrum capture and specifically discriminates multiple pathogens. The macrophage membrane is pre-engineered with azide groups by a biometabolic process and then modified on a porous anodized aluminum oxide substrate via click reactions, preserving dynamic lateral fluidity and broad-spectrum recognition capacity. The macrophage membrane/anodized aluminum oxide membrane is evaluated with remarkable ion current rectification performance with a distinct current response upon bacterial binding, which realizes ultrasensitive detection of bacteria. Moreover, discrimination of bacterial species is achieved by further introducing specific antibodies. The nanochannel-based biosensor allows accurately capturing and quantifying multiple bacteria over a broad linear range, with a detection limit as low as 2.7 CFU/mL. Finally, this nanoplatform is successfully applied for broad-spectrum capture of bacterial species in several practical application scenarios including water, serum, and blood samples, achieving ultrasensitive detection and identification of bacteria below 10 CFU/mL. Overall, the proposed nanochannel with cell membrane nanointerface shows broad applicability in bacterial analysis, highlighting its potential in diagnosing infectious diseases.}, archive = {J_JACS}, author = {Jin Wang and Chengcheng Zhu and Jing Tan and Jing-Juan Xu and Chen Wang}, doi = {10.1021/jacs.5c01542}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12821--12832}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineered artificial nanochannels with cell membrane nanointerface for ultrasensitive detection and discrimination of multiple bacterial infections}, volume = {147}, year = {2025}, }
• (2025). Activating the gate-opening of a Metal–Organic framework and maximizing its adsorption capacity. JACS, 147(15), 12811--12820. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) are well-known porous materials owing to their useful adsorption properties; however, some MOFs have limited adsorption capabilities, which can significantly undermine their success as porous materials. Therefore, maximizing their porosity is critical for unlocking their full potential and expanding their practical utilization, such as gas storage, separation, and removal. In this study, flexible MOFs with defined defects were synthesized using a ligand-mixing strategy to improve their porosity and maximize their adsorption capacities. Specifically, we employed a combination of two organic linkers, 4,4′-biphenyldicarboxylic acid (H 2 BPDC) and 1,4-benzenedicarboxylic acid (H 2 BDC), in various ratios, to fabricate flexible In-MIL-53D hybrids containing controllable defects within the structure due to the incorporation of the short linker (H 2 BDC) compared to the original linker (H 2 BPDC). These structural defects in the In-MIL-53D hybrids activated their gate-openings and enhanced gas adsorption capacities for N 2 and CO 2 . Moreover, the gate-opened activated hybrids exhibited excellent adsorption capacity for the harmful chemical warfare agent simulant, 2-chloroethyl ethyl sulfide (CEES). However, excessive incorporation of defects disrupted the framework’s integrity, compromising its stability and increasing the risk of collapse. Therefore, achieving an optimal level of defect incorporation is essential to balance structural stability with enhanced functionality. Among the hybrids, the sample with approximately 39% incorporation of the short linker exhibited up to an 11-fold increase in adsorption capacity for CO 2 at 1 P / P 0 . In addition, this hybrid demonstrated up to 5-fold higher CEES adsorption capacity compared to the pristine In-MIL-53D, highlighting its potential for advanced utilization in relevant fields.}, archive = {J_JACS}, author = {Gihyun Lee and Dayeon Choi and Moonhyun Oh}, doi = {10.1021/jacs.5c01399}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12811--12820}, shortjournal = {J. Am. Chem. Soc.}, title = {Activating the gate-opening of a Metal–Organic framework and maximizing its adsorption capacity}, volume = {147}, year = {2025}, }
• (2025). Enantioselective desymmetrization of biaryls via cooperative Photoredox/Brønsted acid catalysis and its application to the total synthesis of ancistrobrevolines. JACS, 147(15), 12800--12810. (www)

  @article{ , abstract = {Photoredox catalysis has emerged as a powerful tool for forming and breaking chemical bonds, further taking hold with its integration with asymmetric catalysis. While the dual-catalytic approach has led to successful examples of the control of stereogenic centers, the control of stereogenic axes has remained underexplored. In this study, an acylimine intermediate was generated through photoredox catalysis, and a symmetric substrate, 2-arylresorcinol, was desymmetrized with the aid of chiral phosphoric acid catalysis. Using this approach, a stereogenic center and stereogenic axis were successfully controlled to provide a natural-product-driven compound. The origins of enantioselectivity and diastereoselectivity were investigated through a density functional theory study of four possible enantiodetermining transition states. Consequently, the first total syntheses of the ring-contracted naphthylisoquinoline alkaloid ancistrobrevolines A and B were accomplished concisely. This approach provides not only a novel methodology and strategy to synthesize naphthylisoquinoline alkaloids but also a direction to advance catalytic research and total synthesis studies.}, archive = {J_JACS}, author = {Junsoo Moon and Eunjoo Shin and Yongseok Kwon}, doi = {10.1021/jacs.5c01480}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12800--12810}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective desymmetrization of biaryls via cooperative Photoredox/Brønsted acid catalysis and its application to the total synthesis of ancistrobrevolines}, volume = {147}, year = {2025}, }
• (2025). Bioinspired nucleic acid-based bandpass filters and their concentration-adaptive functions. JACS, 147(15), 12786--12799. (www)

  @article{ , abstract = {Natural signaling networks can act as bandpass filters to interpret external stimuli within defined concentration ranges for differential cellular activities. Replicating such a bandpass filtering mechanism by synthetic networks poses a significant challenge. Herein, we introduce a modular design of nucleic acid-based multilayer threshold-gated incoherent feedforward networks as multiband bandpass filters to produce mutually exclusive responses within defined input concentration ranges. In these networks, nucleic acids demonstrate triple functionality by acting as threshold-gated entities to discern input concentration levels, serving as network nodes to assemble incoherent feedforward loops for nonlinear signal processing, and functioning as signal transduction units for coupling downstream functional modules. These modular networks enable the fine-tuning of filtering performance in terms of band position, bandwidth, cascades, and responses. A mathematical simulation model allows us to predict the filtering behaviors under various conditions. Also, the networks are integrated with upstream signal conversion modules to process concentration information on molecules beyond nucleic acids, such as adenosine and its derivatives. Furthermore, connections to downstream functional modules allow the system to regulate various processes in a concentration bandpass manner, realizing concentration-adaptive DNAzyme biocatalysis, tristate logic operations, RNA transcription, and DNA condensate formation. These findings underscore the potential of enzyme-free DNA reaction networks in complex signal processing and lay a solid foundation for developing chemical and material systems with highly adaptive and autonomous behaviors.}, archive = {J_JACS}, author = {Si Chen and Weijun Shu and Shan Wang and Liang Yue and Weihong Tan}, doi = {10.1021/jacs.5c01331}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12786--12799}, shortjournal = {J. Am. Chem. Soc.}, title = {Bioinspired nucleic acid-based bandpass filters and their concentration-adaptive functions}, volume = {147}, year = {2025}, }
• (2025). Iso-dibenzo[g,p]chrysene-fused bis-dicarbaporphyrin: Pd coordination-induced global aromaticity and stabilization of double in-plane Pd(IV) cations. JACS, 147(15), 12777--12785. (www)

  @article{ , abstract = {An iso-dibenzo[ g , p ]chrysene (DBC)-fused bis-dicarbaporphyrin ( 4 ) with two adj -CCNN cores was synthesized. This bis-dicarbaporphyrin can be regarded as an isomer of the previously reported DBC-fused bis-dicarbacorrole obtained by tuning the orientation of the DBC bridge. This subtle change has significant impacts on structure and properties. As prepared, 4 has a highly twisted figure-eight conformation, whereas DBC-fused bis-dicarbacorrole adopts roughly a planar conformation with slight distortion. The incorporation of two Pd(II) cations can induce a transformation in the molecular framework, resulting in a curved, arch-shaped π-system. Utilizing crystallographic data, along with the electron density of delocalized bonds (EDDB), electron localization function-π (ELF-π), harmonic oscillator model of aromaticity (HOMA), the anisotropy of the induced current density (ACID), and nucleus-independent chemical shift (NICS) calculations, a 34π-electron global aromatic pathway was elucidated for the bis-Pd(II) complex ( 5 ). The Pd coordination-induced global aromaticity is a distinctive feature that has not been observed in the previously reported bis-Pd complexes of DBC-fused bis-dicarbacorrole. Moreover, the treatment of 5 with CuCl 2 leads to the formation of a rare in-plane bis-Pd(IV) complex 6 with two axial coordinated Cl anions. The bis-Pd(IV) complex retains the global aromatic feature and arch-shaped conformation. To our knowledge, this is the first well-defined in-plane bis-Pd(IV) organometallic complex using a porphyrinoid-type macrocyclic ligand.}, archive = {J_JACS}, author = {Zhaohui Zong and Xiaotong Zhang and Ningchao Liu and Sang Mok Jung and Juwon Oh and Xian-Sheng Ke}, doi = {10.1021/jacs.5c01135}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12777--12785}, shortjournal = {J. Am. Chem. Soc.}, title = {Iso-dibenzo[g,p]chrysene-fused bis-dicarbaporphyrin: Pd coordination-induced global aromaticity and stabilization of double in-plane Pd(IV) cations}, volume = {147}, year = {2025}, }
• (2025). Visualizing the sliding motion of dynamic rotaxanes by surface wrinkles. JACS, 147(15), 12766--12776. (www)

  @article{ , abstract = {Visualizing the sliding dynamics of a topological network can provide critical insight into determining the design and properties of mechanically interlocked materials. Although several auxiliary techniques have been proposed to infer the microscopic motion of rotaxanes, employing intuitive and convenient methods to explore the microscopic dynamics of a mechanically interlocked polymer remains a significant challenge. Herein, this work introduces a mechanically interlocked network (MIN) into the patterned surfaces for visualizing and regulating the sliding process of [2]rotaxane units through the evolution of surface wrinkles. Upon the photodimerization of the anthracene-functionalized polymer chain, the surface wrinkle can be formed after thermal treatment and subsequent cooling to room temperature. Specifically, the cross-linked films exhibit visible changes in wrinkle topography through the disruption of host–guest recognition by alkaline stimuli. Moreover, by leveraging the unique mechanical properties of surface wrinkles, we prolonged and amplified the originally extremely transient and difficult-to-detect sliding motion of rotaxane units in terms of time scale. Through statistical analysis of the changes in wrinkle morphology, we were able to correspondingly deconstruct the three processes of the rotaxane sliding motion: (I) unrestricted rapid sliding following host–guest dissociation; (II) restricted sliding; and (III) termination of sliding. The novel approach we propose opens a new avenue for studying the microscopic molecular motion of mechanically interlocked materials, facilitating the advancement and application of mechanically interlocked structures. In addition to using macroscopic surface patterns to visualize and explore microscopic molecular motion, the motion of microscopic molecules can also be used to regulate macroscopic surface patterns.}, archive = {J_JACS}, author = {Shuzhen Yan and Mengling Yang and Xinlu Deng and Guoquan Liu and Xiaxin Gao and Shuai Chen and Lin Cheng and Tiantian Li and Tianjiao Ma and Mengda Xu and Jin Li and Zhaoming Zhang and Li Yang and Wei Yu and Xuzhou Yan and Xuesong Jiang}, doi = {10.1021/jacs.5c00968}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12766--12776}, shortjournal = {J. Am. Chem. Soc.}, title = {Visualizing the sliding motion of dynamic rotaxanes by surface wrinkles}, volume = {147}, year = {2025}, }
• (2025). Intramolecular histidine cross-links formed via copper-catalyzed oxidation of histatin peptides. JACS, 147(15), 12749--12765. (www)

  @article{ , abstract = {Histidine is a versatile amino acid with metal-binding, nucleophilic, and basic properties that endow many peptides and proteins with biological activity. However, histidine itself is susceptible to oxidative modifications via post-translational modifications, photo-oxidation, and metal-catalyzed oxidation. Despite multiple investigations into these different oxidation systems, the varied attributions and differential outcomes point to significant gaps in our understanding of the coordination requirements, spectral features, and reaction products that accompany the Cu-catalyzed oxidation of histidine-containing peptides. Here, we use model peptides of Histatin-5, a salivary peptide with Cu-potentiated antifungal activity that relies on its histidine residues, to characterize the complex mixture resulting from the reaction with Cu under physiologically relevant reducing and oxidizing conditions. Characterization via LC–MS, MS/MS, UV–vis, and NMR revealed that adjacent histidine residues of the bis -His site are the main target of Cu-catalyzed oxidation, with predominant modifications being 2-oxo-His and His-His cross-links that give rise to distinctive electronic absorption features between 300–400 nm. Doubly- and triply-oxygenated peptides, intramolecular His-His cross-links, and multimers in the case of a shorter model peptide were also observed. The configuration of the bis -His motif may enable Cu reactivity not available in systems where His residues are not adjacent in sequence or space. These results expand the possibilities of oxidative modifications available to other proteins and peptides containing multiple histidines.}, archive = {J_JACS}, author = {Leah J. Bontreger and Annastassia D. Gallo and Jaewon Moon and Peter Silinski and Eric E. Monson and Katherine J. Franz}, doi = {10.1021/jacs.5c01363}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12749--12765}, shortjournal = {J. Am. Chem. Soc.}, title = {Intramolecular histidine cross-links formed via copper-catalyzed oxidation of histatin peptides}, volume = {147}, year = {2025}, }
• (2025). Reflexive chirality transfer (RCT): Asymmetric 1,3-dipolar cycloaddition of α-amino acid schiff base with nonchiral copper catalyst. JACS, 147(15), 12740--12748. (www)

  @article{ , abstract = {Although optically pure α-amino acids are ubiquitous, their chirality is usually lost during the α-C–H deprotonation. Consequently, precious chiral catalysis has been necessary to synthesize optically active α-tetrasubstituted unnatural α-amino acid derivatives, even when starting with optically pure α-amino acids. However, here, we report a catalytic asymmetric 1,3-dipolar cycloaddition that preserves the α-carbon chirality of α-amino acid derivatives. This process directly converts readily available optically active α-amino acid Schiff bases into optically active α-tetrasubstituted pyrrolidine derivatives without external chiral additives, despite the temporary loss of α-carbon chirality through the formation of planar 1,3-dipole intermediates. Mechanistic studies revealed that the α-carbon chirality of the α-amino acid Schiff base is transiently transferred to metal-centered chirality in enolates and subsequently restored as the carbon-centered chirality of the products. This conceptually novel “reflexive chirality transfer (RCT)” strategy offers a simple and cost-effective approach to optically active unnatural α-amino acid derivatives, addressing the current limitations of chiral pool synthesis.}, archive = {J_JACS}, author = {Kazuhiro Morisaki and Yuto Furuki and Rento Kousaka and Serika Nagai and Yoshihiro Oonishi and Yoshihiro Sato}, doi = {10.1021/jacs.5c00965}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12740--12748}, shortjournal = {J. Am. Chem. Soc.}, title = {Reflexive chirality transfer (RCT): Asymmetric 1,3-dipolar cycloaddition of α-amino acid schiff base with nonchiral copper catalyst}, volume = {147}, year = {2025}, }
• (2025). Ultrasmall organic nanocrystal photocatalyst realizing highly efficient symmetry breaking charge separation and transport. JACS, 147(15), 12730--12739. (www)

  @article{ , abstract = {The high exciton binding energy and short exciton diffusion length (typical 5–10 nm) of organic photocatalysts (OPCs) hinder efficient charge separation and subsequent charge transfer, limiting their potential for solar energy conversion. Inspired by the symmetry breaking charge separation (SBCS) in natural photosystem II, we employed a freeze assembly (FA) strategy to assemble symmetric perylene diimide (PDI) dimers into ultrasmall (sub-5 nm) nanocrystals (NCs) with ordered molecular stacking, exhibiting SBCS characteristics. The SBCS NCs ( p -5 nm) showed 12.3-fold enhancement in charge separation efficiency compared to non-SBCS NCs (PDI-5 nm). Furthermore, the charge transfer efficiency in p -5 nm (94.7%) was 1.6 times greater than that of weak SBCS NCs ( m -5 nm, 60.4%). Consequently, we achieved a comparable photocatalytic hydrogen evolution rate (1824 μmol h –1 g –1 ) among the PDI-based photocatalysts in p -5 nm. This study highlights the importance of ultrasmall NCs in fulfilling bioinspired SBCS and the potential of the FA strategy for developing high-performance OPCs.}, archive = {J_JACS}, author = {Junqiang Mao and Qingrui Fan and Zequan Yan and Xiaoran Chen and Shuai Zhao and Youhua Lu and Shasha Li and Wei Jiang and Zihao Xu and Zhaohui Wang and Jianjun Wang}, doi = {10.1021/jacs.5c01205}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12730--12739}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrasmall organic nanocrystal photocatalyst realizing highly efficient symmetry breaking charge separation and transport}, volume = {147}, year = {2025}, }
• (2025). Mechanoluminescence from amorphous organic luminogens. JACS, 147(15), 12722--12729. (www)

  @article{ , abstract = {The ability of mechanoluminescent (ML) materials to convert mechanical energy into visualizable patterns through light emission offers a wide range of applications in advanced stress sensing, human–machine interfaces, biomedical science, etc. However, the development remains in its infancy, and more importantly, the reliance on specific crystalline structures in most existing ML materials limits their processability and practical utility. Here, we introduce a series of purely organic amorphous ML materials incorporating flexible skeletons and twisted donor–acceptor–acceptor’ structures designed to enhance dipole moment and flexibility. These materials exhibit multicolor ML in amorphous states and possess low glass transition temperatures, allowing facile and in situ regeneration and processing. The stress-induced short-range molecular ordering within the amorphous phase generates local piezoelectricity, enabling ML without crystallinity. This approach overcomes the limitations of traditional crystalline ML materials, facilitating the development of flexible ML films and expanding the practical utility of organic ML systems.}, archive = {J_JACS}, author = {Zongliang Xie and Huangjun Deng and Xiangyu Ge and Zhenguo Chi and Bin Liu}, doi = {10.1021/jacs.5c00894}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12722--12729}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanoluminescence from amorphous organic luminogens}, volume = {147}, year = {2025}, }
• (2025). Cooperative heterobimetallic CO2 activation involving a mononuclear Aluminum(II) intermediate. JACS, 147(15), 12715--12721. (www)

  @article{ , abstract = {Molecular chemistry of aluminum most commonly involves Al III ions due to their noble gas electronic configurations. In contrast, the chemistry of Al II ions is underexplored and may contain undiscovered reaction manifolds. Here, we report the CO 2 activation chemistry of a transient Al II intermediate supported by a chelating, dianionic ligand and investigate the electronic structure details and reaction mechanisms required to access this reactivity. We found that a heterobinuclear complex, (NON)Al–FeCp(CO) 2 ( 1 ), undergoes Al–Fe bond homolysis at ambient conditions to reveal the [(NON)Al] • /[CpFe(CO) 2 ] • radical pair in situ . The presence of predominantly Al-centered spin density (i.e., an Al II ion) within this radical pair was established by quantum-chemical calculations and with experiments in which radical scavengers (TEMPO, benzophenone) induce Al–Fe bond homolysis. Exposure of 1 to CO 2 atmosphere resulted in insertion of CO 2 into the Al–Fe bond. This net 2-electron CO 2 reduction process was computationally modeled using density functional theory and direct dynamics simulations, revealing that reduction involves two 1-electron steps and, thus, depends on stabilization of high-energy [CO 2 ] •– by coordination to aluminum. This mechanism for CO 2 activation is unexpected given the canonical predisposition of CO 2 for multielectron reduction processes and demonstrates the possibility of discovering new reaction profiles using earth-abundant elements in unusual oxidation states.}, archive = {J_JACS}, author = {Roushan Prakash Singh and Kevin P. Quirion and Joshua Telser and Daniel H. Ess and Neal P. Mankad}, doi = {10.1021/jacs.5c00944}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12715--12721}, shortjournal = {J. Am. Chem. Soc.}, title = {Cooperative heterobimetallic CO2 activation involving a mononuclear Aluminum(II) intermediate}, volume = {147}, year = {2025}, }
• (2025). Donor–Acceptor-π-Acceptor–Donor-type photosensitive covalent organic framework for effective photocatalytic aerobic oxidation. JACS, 147(15), 12704--12714. (www)

  @article{ , abstract = {Developing effective photocatalysts for the oxidation reaction is of great significance in chemical synthesis but is still challenging. Herein, linking photochromic triphenylamine with pyrene units by the in situ formed robust imidazole moieties, a covalent organic framework (COF), PyNTB-COF , containing a rare donor–acceptor-π-acceptor–donor (D-A-π-A-D) fragment, was successfully synthesized for photocatalytic aerobic oxidation. Structure characterizations confirm its crystalline framework, high porosity, and good stability. Property studies reveal its photoelectric semiconductor feature with high photoresponsive charge separation and migration activity derived from the D-A-π-A-D fragments, proven by the experimental results and theoretical calculations. Photocatalytic experiments not only display its highly effective photoresponsive activity in triggering the generation of ·O 2 – under visible light irradiation but also exhibit its high photocatalytic efficiency in the aerobic oxidations of toluene and the amidation of aldehydes. This work demonstrates that the integration of photochromic units into framework materials to construct π-conjugated D–A moieties could enhance photocatalytic charge separation and migration efficiency, achieving promising photocatalysts for photocatalytic aerobic oxidation.}, archive = {J_JACS}, author = {Tian-Xiang Luan and Ling-Bao Xing and Ning Lu and Xin-Long Li and Shuo Kong and William W. Yu and Pei-Zhou Li and Yanli Zhao}, doi = {10.1021/jacs.5c00750}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12704--12714}, shortjournal = {J. Am. Chem. Soc.}, title = {Donor–Acceptor-π-Acceptor–Donor-type photosensitive covalent organic framework for effective photocatalytic aerobic oxidation}, volume = {147}, year = {2025}, }
• (2025). 84-nuclearity lanthanide-aluminum cyclic clusters: Promising materials for iodine capture and storage. JACS, 147(15), 12696--12703. (www)

  @article{ , abstract = {Developing high-performance adsorbents for iodine uptake and storage has become an urgent priority for safe disposal and long-term storage of nuclear waste. In this work, two cyclic lanthanide-aluminum clusters with the formula [Ln 12 Al 72 (hmp) 60 (C 2 H 5 O 2 ) 6 (μ 2 –OH) 120 (μ 3 –OH) 18 (H 2 O) 30 ]Cl 24 ·(NO 3 ) 24 ·(H 2 O) x (Ln = Tb, x ≈ 80, Tb 12 Al 72 ; Ln = Gd, x ≈ 100, Gd 12 Al 72 ; Hhmp = 2-(hydroxymethyl)pyridine and C 2 H 6 O 2 = ethylene glycol) are reported. Single-crystal analysis reveals that its inner diameter is approximately 1.1 nm, with an outer diameter of 4.1 nm and a thickness of 3.1 nm. The packing of cyclic clusters through intermolecular interactions generates a 3D supramolecular structure with one-dimensional channels. Investigation of the iodine adsorption performance of the cluster indicates an uptake capacity of 3.14 g g –1 for Tb 12 Al 72 and 3.1 g g –1 for Gd 12 Al 72 . The effectiveness of iodine adsorption is largely due to the accessible micropore structure along with the high density of pyridine rings and abundant hydroxyl oxygen atoms. Consistently, DFT calculations indicate that the [Al(μ–OH) n ] clusters and pyridine ring regions synergistically facilitate iodine adsorption, effectively promoting the dissociation of I 2 into I – anions. This unique micropore environment enhances the electrostatic stabilization of polyiodide anions through a strong Coulombic attraction, significantly boosting the capture of iodine.}, archive = {J_JACS}, author = {Man-Ting Chen and Ming-Xuan Zhang and Qiao-Fei Xu and Gui-Lin Zhuang and La-Sheng Long and Lan-Sun Zheng}, doi = {10.1021/jacs.5c00684}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12696--12703}, shortjournal = {J. Am. Chem. Soc.}, title = {84-nuclearity lanthanide-aluminum cyclic clusters: Promising materials for iodine capture and storage}, volume = {147}, year = {2025}, }
• (2025). Molecular anodes for electrocatalytic water oxidation based on self-assembled bilayers driven by electron transfer mediators. JACS, 147(15), 12686--12695. (www)

  @article{ , abstract = {The generation of solar fuels via water splitting with sunlight requires, among others, robust and efficient electrodes for the water oxidation reaction. For this purpose, the combination of powerful molecular catalysts and graphitic materials has been shown to work outstandingly well. However, in oxide-based materials, that are of enormous importance as conductive or semiconductive materials, the molecular catalysts either do not work or are transformed into the corresponding oxides. Here, we use a supramolecular strategy based on self-assembled bilayers where a silanolate with long alkyl chains is bonded to the electrode surface and acts as a platform to supramolecularly interact with multiple long alkyl chains attached to the water oxidation catalyst. In this manner, the catalyst and the electrolyte assembly are isolated from the oxide surface, conferring great stability, but at the same time, they are sufficiently close so that efficient electron transfer can take place from the catalyst to the electrode. Our best hybrid molecular anode works efficiently as a water oxidation catalyst at pH 7 without practically any activity losses, at current densities of 0.40 mA/cm 2 for 15 h, giving more than 33,800 TONs and with a Faradaic efficiency of over 92% while maintaining intact its molecular nature. This work provides a successful proof of concept of the benefit of properly combining molecular catalysts with oxide-based materials to obtain the best of both worlds.}, archive = {J_JACS}, author = {Paula Tris-Marzo and Daniele Veclani and Alessandro Venturini and Marta Martínez-Belmonte and Marcos Gil-Sepulcre and Antoni Llobet}, doi = {10.1021/jacs.5c00489}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12686--12695}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular anodes for electrocatalytic water oxidation based on self-assembled bilayers driven by electron transfer mediators}, volume = {147}, year = {2025}, }
• (2025). Design of vinylboron monomers for the comprehensive structural control of poly(vinyl alcohol)s via stereospecific controlled radical polymerization and subsequent side-chain replacement. JACS, 147(15), 12672--12685. (www)

  @article{ , abstract = {A series of vinylboron monomers was designed, wherein the boron atom is protected by N -alkyl-substituted anthranilamide moieties, in order to prepare poly(vinyl alcohol) (PVA) polymers via stereospecific RAFT polymerization and subsequent oxidation of the pendant boron groups with comprehensive control over primary structural factors, i.e., branching structure, molecular weight, tacticity, and block sequencing with other monomers. In contrast to vinylboron monomers that are protected by nonsubstituted anthranilamide moieties, those protected with N -alkyl-substituted anthranilamide moieties allowed suppressing backbiting reactions during the radical polymerization, thus enabling the generation of linear PVAs. In particular, when relatively bulky substituents such as isobutyl and neopentyl groups were installed on the anthranilamide protecting group, the polymerization proceeded in an isospecific fashion through helical conformation, yielding isotactic PVAs. Stereoblock PVAs and a vinyl alcohol–acrylamide block copolymer were also synthesized via RAFT polymerization, and the thermal properties specific to tacticity, e.g., dual melting behavior affected by the two segments, were observed.}, archive = {J_JACS}, author = {Hiroshi Suzuki and Tsuyoshi Nishikawa and Makoto Ouchi}, doi = {10.1021/jacs.5c00336}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12672--12685}, shortjournal = {J. Am. Chem. Soc.}, title = {Design of vinylboron monomers for the comprehensive structural control of poly(vinyl alcohol)s via stereospecific controlled radical polymerization and subsequent side-chain replacement}, volume = {147}, year = {2025}, }
• (2025). Cross-electrophile coupling of aryl chlorides with alkyl chlorides using rotating magnetic field and metal rods. JACS, 147(15), 12664--12671. (www)

  @article{ , abstract = {The pursuit of sustainable and environmentally benign methods and techniques continues to challenge organic chemists. Herein, we report the development of a novel approach in which electromagnetic induction could participate in the coupling of organic chlorides using a rotating magnetic field and metal rods. In particular, we describe the application of this strategy to the nickel-catalyzed cross-electrophile coupling of aryl chlorides with alkyl chlorides. Using these abundant and commercially available organochlorides, such a system allows reactions to proceed with a broader scope than the current protocols under mild conditions.}, archive = {J_JACS}, author = {Xiaomei Feng and Xiangye Li and Ning Zhang and Lizhi Zhang and Fenggang Sun and Hui Liu and Zengdian Zhao and Xinjin Li}, doi = {10.1021/jacs.5c00381}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12664--12671}, shortjournal = {J. Am. Chem. Soc.}, title = {Cross-electrophile coupling of aryl chlorides with alkyl chlorides using rotating magnetic field and metal rods}, volume = {147}, year = {2025}, }
• (2025). Few-atom copper cluster facilitates H2O2 activation to promote selective oxidation of benzene to phenol. JACS, 147(15), 12652--12663. (www)

  @article{ , abstract = {The catalytic oxidation of benzene faces challenges in achieving high activity and selectivity. While single-atom catalysts present intriguing potential for this transformation, their practical implementation is hindered by intrinsic limitations in the mass-specific activity. In this context, few-atom cluster catalysts have emerged as an alternative, leveraging well-defined metal ensemble effects that enable precisely tailored active sites and enhanced interatomic synergies. Herein, we introduce an atomic cluster supported on a graphitic carbonitride (CN) catalyst (Cu 3 /CN), exhibiting excellent catalytic performance for selective oxidation of benzene to phenol, with superior turnover frequency (TOF) to that of single-atom Cu 1 /CN (719 h –1 vs 280 h –1 ) and suppressing phenol selectivity to that of nanoparticle Cu NP /CN (95.3% vs 77.2%). Multimodal mechanistic investigations unambiguously identify the critical role of the adsorbed O* on the Cu site (Cu═O*) for C–H-oxidation, verified by both in situ spectroscopic monitoring and ex situ surface analysis. Complementary density functional theory calculations validate Cu atomic cluster (Cu 3 ) site features a higher d-band center and larger charge transfer with the H 2 O 2 molecule than that of the isolated Cu 1 site. The sufficient charge transfer stretches the O–O bond in H 2 O 2 to facilitate the formation of the Cu═O* species. Furthermore, the resulting Cu═O* in the Cu 3 site demonstrates a significant hybridization of the O 2p orbitals and Cu 3d orbitals at the Fermi level, which endows it with high activity for benzene activation. The appropriate ensemble effect of the unique Cu 3 architecture is the key to its higher catalytic performances. This work establishes a structure–performance correlation that highlights the critical role of atomic cluster architecture in optimizing catalytic functionality.}, archive = {J_JACS}, author = {Ting Zhang and Haishan Su and Xianwen Zhang and Yang Zhao and Jian Zhou and Lili Zhang and Shengfa Ye and Yuxiao Ding and Xiaoyan Sun}, doi = {10.1021/jacs.5c00340}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12652--12663}, shortjournal = {J. Am. Chem. Soc.}, title = {Few-atom copper cluster facilitates H2O2 activation to promote selective oxidation of benzene to phenol}, volume = {147}, year = {2025}, }
• (2025). Realization of intrinsic colossal magnetoresistance in Pb(Pb1/3Hg2/3)3Mn4O12: An a site-ordered quadruple perovskite oxide. JACS, 147(15), 12644--12651. (www)

  @article{ , abstract = {Colossal magnetoresistance (CMR) effects have been extensively studied in ABO 3 perovskite manganites where the Mn 3+ –O–Mn 4+ double-exchange mechanism plays a pivotal role. However, A-site-ordered AA′ 3 B 4 O 12 -type quadruple perovskite oxides exhibit significantly suppressed double exchange due to their extremely small B–O–B bond angles (≈140°), hindering the realization of intrinsic CMR effects. Here, we report the design and synthesis of a novel quadruple perovskite oxide Pb(Pb 1/3 Hg 2/3 ) 3 Mn 4 O 12 (PPHMO) characterized by an unusually increased Mn–O–Mn bond angle of up to 153°. This compound crystallizes into a cubic Im 3̅ structure with the charge distribution Pb 2+ (Pb 1/3 3.5+ Hg 2/3 2+ ) 3 Mn 4 3.63+ O 12 . A ferromagnetic phase transition is observed at the Curie temperature T C ≈ 120 K, accompanied by an insulator-to-metal transition. Furthermore, applying magnetic fields significantly reduces the resistivity, resulting in intrinsic CMR effects with an absolute MR value of 650% at 8 T, increasing to 2250% at 16 T near T C . The large intrinsic MR is thereby realized unprecedentedly in an A-site-ordered quadruple perovskite oxide. Related origins for the intrinsic CMR effects presented in the current PPHMO are discussed in detail.}, archive = {J_JACS}, author = {Jie Zhang and Xubin Ye and Xiao Wang and Zhao Pan and Maocai Pi and Shuai Tang and Cheng Dong and Chien-Te Chen and Jin-Ming Chen and Chang-Yang Kuo and Zhiwei Hu and Xi Shen and Xiaohui Yu and Yao Shen and Richeng Yu and Youwen Long}, doi = {10.1021/jacs.5c00186}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12644--12651}, shortjournal = {J. Am. Chem. Soc.}, title = {Realization of intrinsic colossal magnetoresistance in Pb(Pb1/3Hg2/3)3Mn4O12: An a site-ordered quadruple perovskite oxide}, volume = {147}, year = {2025}, }
• (2025). Recyclable molecular ferroelectrics to harvest mechanical energy for sustained hydrogen generation. JACS, 147(15), 12635--12643. (www)

  @article{ , abstract = {Production of hydrogen fuel from water and renewable energy offers one of the most promising pathways for carbon neutrality and sustainable development. However, existing hydrogen generation technologies struggle with durability issues, such as poisoning, coking, and fouling, so it is a crucial economic concern to find a long-term hydrogen generation catalyst or approach. Herein, we report a recyclable cyclic supersaturation strategy harnessing molecular ferroelectric (TMFM) 0.26 (TMCM) 0.74 CdCl 3 (MF-1) for hydrogen generation, which enables cycles of recrystallization and dissolution of molecular ferroelectric nanocrystals in supersaturated aqueous solution systems. The molecular ferroelectric nanocrystals generate hydrogen through the piezoelectric effect and dissolve in aqueous solution, enabling complete hydrogen desorption. Additionally, their low acoustic impedance, closely matching that of water, facilitates efficient mechanical energy transmission, thereby enhancing hydrogen generation efficiency. We achieve a robust hydrogen generation rate of record-high 11.56 mmol g –1 h –1 (mechanical-to-hydrogen energy conversion efficiency of 35.6%), with outstanding durability surpassing 1500 h. This work not only provides a new strategy for efficient and sustainable hydrogen generation but also boosts the outlook for the application of water-soluble molecular ferroelectric materials.}, archive = {J_JACS}, author = {Lutao Li and Chen Wang and Chao-Ran Huang and Wei-Qiang Liao and Xiaoli Xu and Lingbo Xiao and Ruonan Wang and Weiyu Cheng and Tiwei He and Shan Cong and Zhenhui Kang and Ren-Gen Xiong and Guifu Zou}, doi = {10.1021/jacs.4c18462}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12635--12643}, shortjournal = {J. Am. Chem. Soc.}, title = {Recyclable molecular ferroelectrics to harvest mechanical energy for sustained hydrogen generation}, volume = {147}, year = {2025}, }
• (2025). Serendipitous discovery of photolytic thiosulfoxide formation: Application for visible-light-inducible manipulation of supersulfide level in biological systems. JACS, 147(15), 12627--12634. (www)

  @article{ , abstract = {Tools to enable spatiotemporally controlled upregulation of supersulfides, which are highly reactive, unstable sulfur species, are needed to study the pathophysiological roles of post-translational protein modification with catenated sulfur atoms. Here, we set out to design N , N -diethylaminocoumarin (DEAC)-based visible-light-responsive N -acetylcysteine persulfide donors ( NAC-SS-DEAC ), and serendipitously found that upon visible light irradiation, they donate a sulfane sulfur (S 0 ) atom to nucleophiles, including thiols and cyanate. Light-assisted tautomerization of the disulfide moiety of NAC-SS-DEAC to transiently afford unstable thiosulfoxide plays a key role in the S 0 donation. We show that this reaction can be utilized to achieve visible-light-inducible manipulation of supersulfide levels in living cells.}, archive = {J_JACS}, author = {Mitsuyasu Kawaguchi and Katsutoshi Yoshino and Tomoaki Ida and Hibiki Moriyama and Naoya Ieda and Yuhei Ohta and Shingo Kasamatsu and Hideshi Ihara and Hidehiko Nakagawa}, doi = {10.1021/jacs.5c00196}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12627--12634}, shortjournal = {J. Am. Chem. Soc.}, title = {Serendipitous discovery of photolytic thiosulfoxide formation: Application for visible-light-inducible manipulation of supersulfide level in biological systems}, volume = {147}, year = {2025}, }
• (2025). Enhanced pyridine-oxazoline ligand-enabled Pd(II)-catalyzed aminoacetoxylation of alkenes for the asymmetric synthesis of biaryl-bridged 7-membered N-heterocycles and atropisomers. JACS, 147(15), 12614--12626. (www)

  @article{ , abstract = {A new class of binaphthyl unit-enhanced pyridine-oxazoline ligands was developed to promote the Pd-catalyzed enantioselective intramolecular 7- exo aminoacetoxylation of unactivated biaryl alkenes. Biaryl-bridged 7-membered N -heterocycles bearing a chiral center were obtained in good yields with excellent enantioselectivities (up to 99:1 er). Computational investigations on a series of biaryl-bridged 7-membered rings provided insights into the rotational barrier of the potentially chiral biaryl unit by the substituent effect including the heteroatom, the protecting group, and the chiral center. The kinetic resolution of racemic axially chiral biaryls via intramolecular enantioselective aminoacetoxylation of alkenes has also been achieved, affording previously inaccessible biaryl-bridged 7-membered N -heterocycles bearing both a chiral center and a chiral axis, as well as axially chiral biaryl amino alcohols.}, archive = {J_JACS}, author = {Beibei Guo and Xiaoyang Yan and Zicong Wang and Chen Shen and Weifu Chen and Shouyi Cen and Qian Peng and Zhipeng Zhang}, doi = {10.1021/jacs.5c00077}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12614--12626}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhanced pyridine-oxazoline ligand-enabled Pd(II)-catalyzed aminoacetoxylation of alkenes for the asymmetric synthesis of biaryl-bridged 7-membered N-heterocycles and atropisomers}, volume = {147}, year = {2025}, }
• (2025). Bioinspired chloride-assisted protein channels: Enhancing proton transport for sustainable energy harvesting from acidic wastewater. JACS, 147(15), 12604--12613. (www)

  @article{ , abstract = {Highly efficient proton transfer in biological processes has driven the pursuit of synthetic analogs; however, replicating high proton permeance in natural systems remains a significant challenge. Herein, inspired by the function of the ClC-ec1 protein, we report the design of Cl – -assisted proton transport channels within a hybrid membrane composed of covalent organic frameworks (COFs) integrated with aramid nanofibers (ANFs). By leveraging buffer layer-mediated interfacial polymerization and the flocculation behavior of ANF in aqueous environments, we establish robust hydrogen-bonding interactions between COFs and ANFs. The hydride material enables Cl – binding, significantly accelerating proton transport in a manner similar to that of the ClC-ec1 protein channel. In the presence of a small concentration of Cl – ions (0.1% of the proton concentration), the proton permeation rate is enhanced approximately by 3 times, reaching 9.8 mol m –2 h –2 . Notably, the membrane facilitates sustainable osmotic power generation from acidic wastewater, delivering an output power density of 434.8 W m –2 . Theoretical calculations revealed that ANF preferentially binds Cl – , promoting proton hopping and lowering the energy barrier for proton transport. This study establishes a new paradigm for bioinspired ion-assisted proton transport, presenting an approach for sustainable energy harvesting from acidic wastewater.}, archive = {J_JACS}, author = {Wenxiu Jiang and Xuan Ding and Zihao Huang and Xiaochen Feng and Meiling Wang and Xinyue Zhang and Shuyu Ying and Huanting Wang and Jun Gao and Ying Zhu and Lei Jiang}, doi = {10.1021/jacs.4c18730}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12604--12613}, shortjournal = {J. Am. Chem. Soc.}, title = {Bioinspired chloride-assisted protein channels: Enhancing proton transport for sustainable energy harvesting from acidic wastewater}, volume = {147}, year = {2025}, }
• (2025). A rationally designed sulfonium lipoglycopeptide with micelles self-assembly to combat multidrug resistance via dual enhanced cell wall-membrane inhibition and T7SS proteins downregulation. JACS, 147(15), 12587--12603. (www)

  @article{ , abstract = {Multidrug-resistant Gram-positive superbugs pose a significant menace to global public health, urgently demanding the advent of novel antibiotics. In this study, three biphenyl sulfonium lipoglycopeptides derived from vancomycin were rationally designed and synthesized to combat such resistance. Among them, the most promising derivative, BD-V-2 , exhibited outstanding in vitro activity against a diverse array of refractory strains. Notably, in two highly challenging lethal sepsis models induced by MRSA and VREm ( vanA ), BD-V-2 achieved complete protection of the infected mice with remarkably low single-dose administrations of merely 7 and 2.5 mg/kg, respectively, vividly demonstrating its potent in vivo efficacy. Furthermore, its in vivo pharmacokinetic profile and toxicity assessment indicated favorable druggability. Interestingly, BD-V-2 was found to impart a novel self-assembly property into micelles. In addition, independent and synergistic mechanisms of action targeting the bacterial membrane, via phosphatidylglycerol (PG) interaction, and cell wall, via two more binding sites on lipid II, respectively, interpeptide bridge and pyrophosphate motif, were elucidated. Astonishingly, BD-V-2 was capable of significantly downregulating the expression of the type VII secretion system proteins, uncovering an unprecedented antivirulence mechanism for glycopeptide antibiotics. Collectively, these findings unraveled the hitherto unknown roles of the sulfonium strategy and established BD-V-2 as a highly prospective candidate for future pharmaceutical development.}, archive = {J_JACS}, author = {Yuanyuan Xie and Xiaowen Wang and Fang Li and Zhifu Chen and Qun Li and Shuhui Liu and Jingwen Zhang and Hui Wang and Zhenyong Wu and Jinyong Zhang and Dongliang Guan}, doi = {10.1021/jacs.4c18630}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12587--12603}, shortjournal = {J. Am. Chem. Soc.}, title = {A rationally designed sulfonium lipoglycopeptide with micelles self-assembly to combat multidrug resistance via dual enhanced cell wall-membrane inhibition and T7SS proteins downregulation}, volume = {147}, year = {2025}, }
• (2025). Trimethylaluminum activates zeolite-confined lanthanum borohydrides to enhance catalytic C–H borylation. JACS, 147(15), 12574--12586. (www)

  @article{ , abstract = {AlMe 3 -treatment of the borylation precatalyst La(BH 4 ) 2 (THF) 2.5 -Ph 3 Si-HY 30 affords La(BH 4 ) 2 (AlMe 3 )-Ph 3 Si-HY 30 , which is the superior lanthanum-based precatalyst for benzene borylation with pinacolborane (HBpin), giving higher turnovers (>285) and improved yields (up to 42%) of phenylpinacolborane (PhBpin). Solid-state NMR spectroscopy, X-ray adsorption spectroscopy, and theoretical studies characterized the precatalytic sites in La(BH 4 ) 2 (AlMe 3 )-Ph 3 Si-HY 30 as κ 2 - O , O -{≡SiO(=Al)≡SiO}La(BH 4 ) 2 (AlMe 3 ), revealing that AlMe 3 had displaced the THF ligands. In contrast to the expected high reactivity of THF-free organolanthanum, the turnover frequency (TOF) for PhBpin formation catalyzed by La(BH 4 ) 2 (AlMe 3 )-Ph 3 Si-HY 30 (2.7 h –1 ) is slightly lower than that of untreated La(BH 4 ) 2 (THF) 2.5 -Ph 3 Si-HY 30 (3.6 h –1 ), implying that AlMe 3 is a stronger inhibitor than THF for lanthanum. On the other hand, AlMe 3 -treatment of inactive La(BH 4 ) 2 (THF) 2.2 -SiO 2 generates an active benzene borylation catalyst. AlMe 3 also desorbs surface–O-B x H y species and quenches residual Brønsted acid sites (BAS) and silanols. Alumination of the BAS inhibits HBpin degradation, while alumination of silanols creates sites for that reaction. The 8-fold inhibition of the BAS-catalyzed HBpin decomposition rate by AlMe 3 treatment gives a kinetic advantage to the lanthanum-catalyzed C–H borylation, leading to increased yields and turnovers. Knowledge of the competing roles of sites in La(BH 4 ) 2 (AlMe 3 )-Ph 3 Si-HY 30 and the catalytic rate law law enables identification of favorable conditions of low [HBpin] to maximize turnovers or PhBpin yield. Sterics affect the selectivity in borylation of substituted arenes and heteroarenes, which can proceed without the precoordination of a donor. These steric effects, as well as the AlMe 3 treatment having an opposite effect on the activity of lanthanum in HY vs SiO 2 , point to confinement-activated sites.}, archive = {J_JACS}, author = {Yuting Li and Takeshi Kobayashi and Debora M. Meira and Lun An and Long Qi and Aaron D. Sadow}, doi = {10.1021/jacs.4c18569}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12574--12586}, shortjournal = {J. Am. Chem. Soc.}, title = {Trimethylaluminum activates zeolite-confined lanthanum borohydrides to enhance catalytic C–H borylation}, volume = {147}, year = {2025}, }
• (2025). Unraveling the roles of amines in atom transfer radical polymerization in the dark. JACS, 147(15), 12562--12573. (www)

  @article{ , abstract = {Multidentate amines have been widely used as ligands (L) for Cu-catalysts in atom transfer radical polymerization (ATRP) and as electron donors in photochemically induced polymerizations. However, mechanistic aspects of the role of amines in ATRP in the dark have remained elusive. Herein, the structure–activity relationship and the related electron transfer reactions with Br–Cu II /L complexes and/or with alkyl bromides (R-Br) were investigated for 25 amines. Amines function as electron donors and reducing agents for Br–Cu II /L complexes via an outer sphere electron transfer (OSET) mechanism, enabling slow but continuous generation of Cu I /L activators and inducing controlled ATRP. However, two amines, diazabicyclo(5.4.0)undec-7-ene (DBU) and 1,1,3,3-tetramethylguanidine (TMG), reduced Br–Cu II /L faster, suggesting an inner sphere electron transfer (ISET) process. ATRP, starting with initial deactivators (Br–Cu II /L) species, proceeded in the dark in the presence of an excess of tertiary amines, such as tris[2-(dimethylamino)ethyl]amine (Me 6 TREN), 1,4-diazabicyclo[2.2.2]octane (DABCO), and TMG at room temperature and afforded polymers with low dispersities ( Đ ≤ 1.15). With copper(II) triflate complex (Cu II /L +2 , – (OTf) 2 ), which has a more positive reduction potential, ATRP proceeded at room temperature with several inexpensive secondary and tertiary amines including triethylamine (TEA) and dimethylethanolamine (DMAE). Interestingly, multidentate amines also served as direct R-Br activators at elevated temperatures (60 °C). In all cases, chains were initiated with R-Br and not by the amine radical cations as byproducts of electron transfer. Amines also enabled ATRP in the presence of residual air in flasks with a large headspace, underpinning them as a robust and accessible reducing agent for practical applications.}, archive = {J_JACS}, author = {Arman Moini Jazani and Gorkem Yilmaz and Mitchell Baumer and Julian Sobieski and Stefan Bernhard and Krzysztof Matyjaszewski}, doi = {10.1021/jacs.4c18496}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12562--12573}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the roles of amines in atom transfer radical polymerization in the dark}, volume = {147}, year = {2025}, }
• (2025). S-block metal-lanthanide bonding: Direct comparison of Mg–Yb and Mg–Ca complexes. JACS, 147(15), 12555--12561. (www)

  @article{ , abstract = {Despite considerable progress in understanding the fundamental aspects of metal–metal bonding, lanthanide-metal bonding is limited to interactions between lanthanide (Ln) metals and electron-rich p - or d -block metals. Exemplified by a Mg–Yb complex, we present synthesis and extensive computational analyses of the first s -block metal-Ln bond. Key to its formation is the unique Mg 0 complex [(BDI*)MgNa] 2 ( 1 ) which can be viewed as a dimer consisting of two magnesyl anions, (BDI*)Mg – , bridged by two Na + cations (BDI* = HC[C( t Bu)N-DIPeP] 2 , DIPeP = 2,6-CHEt 2 -phenyl). Reaction of dimeric 1 with (YbN’’ 2 ) 2 (N’’ = N(SiMe 3 ) 2 ) quantitatively gave the mixed complex [(BDI*)MgNa/YbN’’ 2 ] ( 2 -Yb) in which (BDI*)Mg – anions bridge between Yb 2+ and Na + cations (Mg–Yb: 3.466(1), Mg–Na: 3.415(1) Å). Atoms-In-Molecules shows Mg–Yb and Mg–Na bond paths corresponding to weak electrostatic interactions. Complex 2 -Yb is isostructural to previously reported [(BDI*)MgNa/CaN’’ 2 ] ( 2 -Ca). Weak Mg 0 -M 2+ (M = Ca, Yb) bonding is supported by facile exchange reactions with (SrN’’ 2 ) 2 leading to formation of [(BDI*)MgNa/SrN’’ 2 ] ( 2 -Sr). Energy decomposition analysis (EDA-NOCV) confirmed major electrostatic Mg 0 -M 2+ bonding (63–66%), while orbital interactions are less significant (19–20%). Both, 2 -Ca and 2 -Yb show considerable Mg 0 → M 2+ electron transfer leading to oxidation-state ambiguities (Mg 0 -M +II ↔ Mg +I -M +I ). Effective-Oxidation-State calculations assign the following metal oxidation states, Na +I -Mg 0 -M +II , with a reliability index of 69–72%. Despite structural and electronic similarities, there are differences in reactivities. Complex 2 -Ca reacts only as a 2-electron reducing agent whereas 2 -Yb can deliver up to three electrons. This study includes reactions with N 2 O, TEMPO, and Me 3 PX (X = O, S, Se). While only 2 -Ca could be converted in a complex with incorporated O 2– , complexes with S 2– or Se 2– have been isolated for both.}, archive = {J_JACS}, author = {Sandeep Kumar Thakur and Nil Roig and Johannes Maurer and Jens Langer and Mercedes Alonso and Sjoerd Harder}, doi = {10.1021/jacs.4c17853}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12555--12561}, shortjournal = {J. Am. Chem. Soc.}, title = {S-block metal-lanthanide bonding: Direct comparison of Mg–Yb and Mg–Ca complexes}, volume = {147}, year = {2025}, }
• (2025). Impact of heterocore atoms on CO2 electroreduction in atomically precise silver nanoclusters. JACS, 147(15), 12546--12554. (www)

  @article{ , abstract = {Understanding the effect of internal atoms in metal nanoparticles on heterogeneous catalytic processes is crucial for achieving high activity and selectivity. This requires meticulous synthetic control over the size, composition, and atomic arrangement of nanoparticles. Here, we report the design of ligand-exchange-induced structure transformation and nanomolecule-templated atomic-level galvanic exchange strategies to synthesize PtAg 24 (IPBT) 18 (denoted as PtAg 24 ) and AuAg 24 (IPBT) 18 (denoted as AuAg 24 ) nanoclusters (NCs). Both NCs exhibit identical total metal atom and ligand (IPBT: 2-isopropylbenzenethiolate) counts, as well as atomic-level structure, except for the difference in the core atom (Pt and Au). Using these model NCs, we uncover the impact of heterocore atoms on the electrochemical CO 2 reduction reaction (eCO 2 RR) activity and selectivity. The central Pt atom in PtAg 24 is less favorable for eCO 2 RR activity, with an activity approximately 4 times smaller than that of Au in AuAg 24 . The eCO 2 RR product CO selectivity is <30% for PtAg 24 , while it exceeds 70% for AuAg 24 , revealing the critical role of the central atom in surface catalytic pathways. Furthermore, AuAg 24 exhibits high activity, with a CO partial current density of −202.2 mA cm –2 , and stability over 24 h, retaining 90% CO selectivity in a membrane electrode assembly configuration. Operando spectroscopy and density functional theory calculations suggest the weaker adsorption of *CO intermediates and smaller energy barrier facilitate CO production on AuAg 24 compared to PtAg 24 , providing valuable atomistic insights into the reaction intermediates and mechanism. The findings in this work will inspire the design of more atomically precise model nanocatalysts to explore the role of their remarkable features in the catalytic activity and selectivity for renewable energy conversion and storage.}, archive = {J_JACS}, author = {Seungwoo Yoo and Dayeon Kim and Guocheng Deng and Yuping Chen and Kangjae Lee and Suhwan Yoo and Xiaolin Liu and Qing Tang and Yun Jeong Hwang and Taeghwan Hyeon and Megalamane S. Bootharaju}, doi = {10.1021/jacs.4c17770}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12546--12554}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of heterocore atoms on CO2 electroreduction in atomically precise silver nanoclusters}, volume = {147}, year = {2025}, }
• (2025). A multiagent-driven robotic AI chemist enabling autonomous chemical research on demand. JACS, 147(15), 12534--12545. (www)

  @article{ , abstract = {The successful integration of large language models (LLMs) into laboratory workflows has demonstrated robust capabilities in natural language processing, autonomous task execution, and collaborative problem-solving. This offers an exciting opportunity to realize the dream of autonomous chemical research on demand. Here, we report a robotic AI chemist powered by a hierarchical multiagent system, ChemAgents, based on an on-board Llama-3.1-70B LLM, capable of executing complex, multistep experiments with minimal human intervention. It operates through a Task Manager agent that interacts with human researchers and coordinates four role-specific agents─Literature Reader, Experiment Designer, Computation Performer, and Robot Operator─each leveraging one of four foundational resources: a comprehensive Literature Database, an extensive Protocol Library, a versatile Model Library, and a state-of-the-art Automated Lab. We demonstrate its versatility and efficacy through six experimental tasks of varying complexity, ranging from straightforward synthesis and characterization to more complex exploration and screening of experimental parameters, culminating in the discovery and optimization of functional materials. Additionally, we introduce a seventh task, where ChemAgents is deployed in a new robotic chemistry lab environment to autonomously perform photocatalytic organic reactions, highlighting ChemAgents’s scalability and adaptability. Our multiagent-driven robotic AI chemist showcases the potential of on-demand autonomous chemical research to accelerate discovery and democratize access to advanced experimental capabilities across academic disciplines and industries.}, archive = {J_JACS}, author = {Tao Song and Man Luo and Xiaolong Zhang and Linjiang Chen and Yan Huang and Jiaqi Cao and Qing Zhu and Daobin Liu and Baicheng Zhang and Gang Zou and Guoqing Zhang and Fei Zhang and Weiwei Shang and Yao Fu and Jun Jiang and Yi Luo}, doi = {10.1021/jacs.4c17738}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12534--12545}, shortjournal = {J. Am. Chem. Soc.}, title = {A multiagent-driven robotic AI chemist enabling autonomous chemical research on demand}, volume = {147}, year = {2025}, }
• (2025). Impact of noncompensating ions on the electrochemical performance of n-type polymeric mixed conductors. JACS, 147(15), 12523--12533. (www)

  @article{ , abstract = {Organic mixed ionic-electronic conductors (OMIECs) have emerged as essential materials for applications in bioelectronics, neuromorphics, and energy storage, owing to their ability to transport both ions and electrons. While significant progress has been made in understanding their operation, the role of noncompensating ions in polymer redox processes remains underexplored, particularly in the context of their impact on charge compensation and device performance. In this study, we systematically investigate the influence of noncompensating ions on the performance of n-type OMIECs with and without polar side chains, focusing on their interactions with electrolytes containing anions from the Hofmeister series. Our findings reveal a stark contrast in charging behavior and organic electrochemical transistor (OECT) performance based on side-chain chemistry. Polar oligoether side chains promote interactions with anions, resulting in significant performance variations. We demonstrate the critical role of polymer side-chain interactions with the different anions, where polyatomic anions capable of infiltrating the film degrade device performance, particularly in terms of transconductance and operational stability. In contrast, OMIECs without side chains exhibit performance independent of the noncompensating ion nature. Through electrochemical analysis, spectroscopic techniques, and molecular dynamics simulations, we provide a comprehensive understanding of how ion incorporation and polymer–electrolyte interactions shape device behavior. This study highlights the transformative role of side-chain functionality in tailoring the properties of the OMIEC and offers a design framework for high-performance OECTs, enabling advancements in biosensing, neuromorphic computing, and beyond.}, archive = {J_JACS}, author = {David Ohayon and Amer Hamidi-Sakr and Jokubas Surgailis and Shofarul Wustoni and Busra Dereli and Nimer Wehbe and Stefan Nastase and Xingxing Chen and Iain McCulloch and Luigi Cavallo and Sahika Inal}, doi = {10.1021/jacs.4c17579}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12523--12533}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of noncompensating ions on the electrochemical performance of n-type polymeric mixed conductors}, volume = {147}, year = {2025}, }
• (2025). From structure to function: Designing iridium catalysts with spin-forbidden excitation for low-energy light-driven reactions. JACS, 147(15), 12511--12522. (www)

  @article{ , abstract = {Herein we describe a comprehensive study of ligand effects on optoelectronic properties of a series of Ir(III) catalysts which undergo formally spin-forbidden excitation using low-energy light. We demonstrate that electronic and steric tuning of several variables can be explained by their impact on the HOMO and LUMO energies of the complex. Density functional theory calculations of the catalysts’ adiabatic triplet energies agree with the experimental results to within 0.05 eV on average. As many of these subtle effects are independent of each other, the merger of them in a single complex tends to have an additive effect and we thus succeeded in developing a family of highly oxidizing iridium photocatalysts that operate by spin-forbidden excitation.}, archive = {J_JACS}, author = {Eva Bednářová and Robin Grotjahn and Chenxi Lin and Katherine A. Xie and Yuzuka Karube and Jonathan S. Owen and Candice L. Joe and Brendan C. Lainhart and Trevor C. Sherwood and Tomislav Rovis}, doi = {10.1021/jacs.4c17584}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12511--12522}, shortjournal = {J. Am. Chem. Soc.}, title = {From structure to function: Designing iridium catalysts with spin-forbidden excitation for low-energy light-driven reactions}, volume = {147}, year = {2025}, }
• (2025). Multi-generation recycling of thermosets enabled by fragment reactivation. JACS, 147(15), 12503--12510. (www)

  @article{ , abstract = {Thermosets are used in numerous industrial applications due to their excellent stabilities and mechanical properties; however, their covalently cross-linked structures limit chemical circularity. Cleavable comonomers (CCs) offer a practical strategy to impart new end-of-life opportunities, such as deconstructability or remoldability, to thermosets without altering critical properties, cost, or manufacturing workflows. Nevertheless, CC-enabled recycling of thermosets has so far been limited to one cycle with a 25% recycled content. Here, we introduce a “fragment reactivation” strategy, wherein the oligomeric fragments obtained from CC-enabled thermoset deconstruction are activated with functional groups that improve fragment solubility and reactivity for subsequent rounds of recycling. Using polydicyclopentadiene (pDCPD), an industrial hydrocarbon thermoset material, containing low loadings of a siloxane-based CC, we first demonstrate two rounds of chemical recycling by incorporating 40 wt % norbornene silyl ether-reactivated fragments derived from the prior generation’s deconstruction. Then, we show that the two-step sequence of deconstruction and reactivation can be unified into a single-step process, referred to as “deconstructive reactivation.” Using this approach, we demonstrate three rounds of chemical recycling with 40–45 wt % fragments incorporated per cycle while maintaining key material properties and deconstructability. These three generations of recycling effectively extend the lifespan of deconstructable pDCPD thermosets by ∼2.6 times. Combined with CCs, fragment reactivation presents a promising and potentially generalizable strategy to improve the chemical recycling efficiency of thermosets.}, archive = {J_JACS}, author = {Kwangwook Ko and Edgar B. Mejia and Hayden E. Fowler and Suong T. Nguyen and Yasmeen AlFaraj and Yuyan Wang and Samuel C. Leguizamon and Nancy R. Sottos and Jeremiah A. Johnson}, doi = {10.1021/jacs.4c17395}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12503--12510}, shortjournal = {J. Am. Chem. Soc.}, title = {Multi-generation recycling of thermosets enabled by fragment reactivation}, volume = {147}, year = {2025}, }
• (2025). CO-tolerant pt1-MoOx/Mo2N catalyst for efficient activation of C–H and O–H bonds toward alcohol dehydrogenation. JACS, 147(15), 12491--12502. (www)

  @article{ , abstract = {Excessively strong adsorption of CO onto a Pt-based catalyst results in the poisoning effect during numerous CO-containing catalysis reactions, including the dehydrogenation process of alcohols. Traditional strategies via modifying the electronic state of Pt atoms are beneficial for weakening CO adsorption; however, they are normally detrimental to C–H cracking, thereby degrading catalytic efficiency toward alcohol dehydrogenation reaction. In this work, we present a synergistic function of Pt 1 single atoms and heterostructured MoO x /Mo 2 N for efficiently dehydrogenating alcohols, allowing high CO resistance along with excellent capacity for C–H and O–H activation. This conjunction renders electron transfer via a strong Pt-MoO x /Mo 2 N interaction and thus induces the low 5d occupancy of Pt sites, enabling the facile CO desorption, which thereby boosts the efficiency of entire reaction cycles. Based on in situ structural characterizations and isotopic labeling analysis, we found that the spontaneously formed thin MoO x -O v layer enables the barrierless breakage of O–H bonds even at as low as room temperature, which further energetically facilitates C–H cracking on interfacial Pt 1 sites. Therefore, this strategy can be applied to fabricate CO-tolerant Pt-based catalysts toward numerous CO-containing reactions without compromising reactivity by coupling the advantages of single-atom and defective support materials.}, archive = {J_JACS}, author = {Ming Zhang and Xin-Pu Fu and Shan-Qing Li and Wei-Wei Wang and Ding Ma and Chun-Jiang Jia}, doi = {10.1021/jacs.4c17409}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12491--12502}, shortjournal = {J. Am. Chem. Soc.}, title = {CO-tolerant pt1-MoOx/Mo2N catalyst for efficient activation of C–H and O–H bonds toward alcohol dehydrogenation}, volume = {147}, year = {2025}, }
• (2025). MFM-300 as high-performance sorbents for water-adsorption-driven cooling. JACS, 147(15), 12481--12490. (www)

  @article{ , abstract = {Adsorption-driven heat transfer is potentially a sustainable technology to decarbonize heating and cooling. However, the development of high-performance adsorbent–adsorbate working pairs remains extremely challenging. Here, we report a metal–organic framework/water working pair that can operate at an ultralow driving temperature (62 °C), showing a high coefficient of performance (COP) of 0.8 for cooling. The desirable features of MFM-300(M) (M = Al, Fe, Cr, V) for water adsorption have been elucidated by combined crystallographic and spectroscopic techniques. In situ neutron powder diffraction reveals the structural evolution of the MFM-300-D 2 O system via direct observation of the location of D 2 O at different stages of adsorption. Host–guest binding dynamics have been interrogated by in situ solid-state nuclear magnetic resonance spectroscopy and inelastic neutron scattering combined with modeling. This system promotes the use of renewable low-grade thermal energy rather than electricity to drive cooling.}, archive = {J_JACS}, author = {Xue Han and Yinlin Chen and Jiangnan Li and Wanpeng Lu and Wenyuan Huang and Yuanjun Wang and Guixiang Wang and Ivan da Silva and Yongqiang Cheng and Luke L. Daemen and Pascal Manuel and Anibal J. Ramirez-Cuesta and Daniel Lee and Sihai Yang and Martin Schröder}, doi = {10.1021/jacs.4c16752}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12481--12490}, shortjournal = {J. Am. Chem. Soc.}, title = {MFM-300 as high-performance sorbents for water-adsorption-driven cooling}, volume = {147}, year = {2025}, }
• (2025). In situ neutron reflectometry reveals the interfacial microenvironment driving electrochemical ammonia synthesis. JACS, 147(15), 12469--12480. (www)

  @article{ , abstract = {Electrified interfaces are critical to the performance of energy systems and often demonstrate substantial complexity under operating conditions. A nanoscale understanding of the interfacial microenvironment, i.e., the solid-electrolyte interphase (SEI), in lithium-mediated nitrogen reduction (Li–N 2 R) is key for realizing efficient ammonia (NH 3 ) production. Herein, we used time-resolved neutron reflectometry (NR) to observe SEI formation under Li–N 2 R conditions. We found that the LiBF 4 -based electrolyte provided a substantially more well-defined SEI layer than previous SEI NR interrogations that used LiClO 4 , highlighting the underlying chemistry that dictates electrolyte design and enabling new NR-based studies. Using in situ NR, we found that the LiBF 4 -derived SEI under Li–N 2 R conditions comprises a thick, diffuse outer layer and a thin, compact inner layer at low current cycling (<2 mA/cm 2 ), revealing a structure which ex situ studies have not been able to probe. Increased current cycling and sustained current cycling led to the merging of the layers into a single-layer SEI. We used isotope contrast methods with d 6 -EtOH and d 8 -THF to drive time-resolved tracking of SEI growth at low current cycling, revealing that the proton donor modifies the inner layer, and the solvent modifies the outer layer. Li dendritic growth was observed in the absence of a proton donor. Neutron absorption also indicated the presence of boron in the SEI, underscoring the value of neutron-based interrogation. Our results inform Li-based systems and reaction microenvironments, and these methods can be applied broadly to interfacial energy technologies.}, archive = {J_JACS}, author = {Valerie A. Niemann and Mathieu Doucet and Peter Benedek and Niklas H. Deissler and Jon Bjarke Valbaek Mygind and Sang-Won Lee and Isabela Rios Amador and Wrayzene L. Willoughby and Ib Chorkendorff and Adam C. Nielander and William A. Tarpeh and Thomas F. Jaramillo}, doi = {10.1021/jacs.4c16636}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12469--12480}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ neutron reflectometry reveals the interfacial microenvironment driving electrochemical ammonia synthesis}, volume = {147}, year = {2025}, }
• (2025). Selective electrochemical capture of monovalent cations using crown ether-functionalized COFs. JACS, 147(15), 12460--12468. (www)

  @article{ , abstract = {Electrochemical adsorption offers a promising approach for the separation of monovalent cations, which is an important but challenging subject in separation science. However, progress in this area has been hampered by the lack of suitable materials with effective ion selectivity. In this work, we present the synthesis of covalent organic frameworks (COFs) functionalized with a series of crown ethers (NCx-TAB-COFs, x donate 12, 15, 18, indicating the size of crown ether) for the efficient and highly selective electrochemical capture of monovalent cations. In our design, crown ether moieties act as confinement sites, imparting high selectivity for different monovalent cations depending on the cavity dimensions of the crown ether present. COFs electrodes prepared using the novel crown-COFs exhibit superior performance for the selective sequestration of monovalent (alkali metal) cations. Notably, 18-crown-6 ether-substituted COF (NC18-TAB-COF) shows a remarkable selectivity (14.26) for K + over Na + and a substantial Rb + /Na + selectivity of 22.4. Furthermore, NCx-TAB-COFs maintain their remarkable selectivity and capacity under mixed-cation conditions. Density functional theory calculations and molecular dynamics simulations suggest that the unexpectedly high selectivity for larger cations is likely due to diverse binding modes in conjunction with the porous structure of the COFs. Given their lower dehydration-free energies and smaller hydrodynamic radii, K + , Rb + , and Cs + more readily permeate the confined channels of COFs. In contrast, Na + and Li + , with higher dehydration-free energies and hydrodynamic radii, diffuse into the NCx-TAB-COFs structure at a much slower rate and are bound predominantly to the surfaces of the COFs.}, archive = {J_JACS}, author = {Dong Jiang and Jonathan P. Hill and Joel Henzie and Ho Ngoc Nam and Quan Manh Phung and Liyang Zhu and Jie Wang and Wei Xia and Yingji Zhao and Yunqing Kang and Toru Asahi and Ran Bu and Xingtao Xu and Yusuke Yamauchi}, doi = {10.1021/jacs.4c16346}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12460--12468}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective electrochemical capture of monovalent cations using crown ether-functionalized COFs}, volume = {147}, year = {2025}, }
• (2025). Spaser nanoprobes family for narrow-band multiplexed cell imaging. JACS, 147(15), 12449--12459. (www)

  @article{ , abstract = {Spaser nanoprobes, with their ultranarrow emission line widths and nanoscale sizes, are emerging as leading contenders for the next generation of biological luminescent probes. However, modulating spasing wavelengths across a broad spectral range remains a formidable challenge that constrains their application in multiplexed sensing and imaging. Here, we introduced a novel wavelength-tunable spaser system, successfully creating a nanoprobe family with 9 distinct spasing wavelengths. These nanoprobes exhibit ultranarrow emission line widths of 3–8 nm with a low pump threshold of 0.5 mJ cm –2 . We further investigated the influences of energy matching between the gain medium and the cavity on the emission performance of the spaser nanoprobes and successfully realized narrow-band luminescence in both individual and aggregated spaser particles under commercial confocal instruments. Moreover, we demonstrated the multiplexed imaging capability of 6 distinct spaser nanoprobes in a single HeLa cell within an imaging window of 200 nm, free of spectral crosstalk. Our results address the long-standing issue of wavelength tunability in spaser nanoprobes and also clarify previous disputes on the luminescence origin of single nanoparticles, marking a significant advancement in their application for ultramultiplexed biological imaging and sensing.}, archive = {J_JACS}, author = {Shao-Peng Wang and Pei Song and Hao-Yang Li and Kuan-Yu Ma and Jing-Juan Xu and Hong-Yuan Chen and Bin Kang}, doi = {10.1021/jacs.4c15182}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12449--12459}, shortjournal = {J. Am. Chem. Soc.}, title = {Spaser nanoprobes family for narrow-band multiplexed cell imaging}, volume = {147}, year = {2025}, }
• (2025). Microenvironment tailoring for electrocatalytic CO2 reduction: Effects of interfacial structure on controlling activity and selectivity. JACS, 147(15), 12438--12448. (www)

  @article{ , abstract = {The performance of the electrocatalytic CO 2 reduction reaction (CO 2 RR) is highly dependent on the microenvironment around the cathode. Despite efforts to optimize the microenvironment by modifying nanostructured catalysts or microporous gas diffusion electrodes, their inherent disorder presents a significant challenge to understanding how interfacial structure arrangement within the electrode governs the microenvironment for CO 2 RR. This knowledge gap limits fundamental understanding of CO 2 RR while also hindering efforts to enhance CO 2 RR selectivity and activity. In this work, we investigate this knowledge gap using a tunable system featuring superhydrophobic hierarchical Cu nanowire arrays with microgrooves (NAMs). Adjusting the NAM structure tunes multiple synergistic effects in the microenvironment, which include stabilization of the microwetting state, confinement of CO*, improvement to local CO 2 concentration, and modulation of the local pH. Notably, using mass transport modeling, we quantify the role of the gas–liquid–solid interface in boosting local CO 2 concentrations within several microns of the interface itself. Leveraging these effects, we elucidate how CO* and H* competitively occupy active sites, influencing reaction pathways toward multicarbon products based on tuning the microenvironment. Consequently, we provide new insights into why the optimized configuration significantly increased CO 2 RR activity by 690% (as normalized by electrochemical active surface area), C 2+ product selectivity by 72%, and Faradaic efficiency by 36%, compared to CO 2 RR with hydrophobic Cu foil. Based on these insights, our findings unlock new opportunities to engineer the CO 2 RR microenvironment through the rational organization of hierarchical interface materials in gas diffusion electrodes toward improved CO 2 RR selectivity and activity.}, archive = {J_JACS}, author = {Yaqi Cheng and Qixun Li and Muhammad Iskandar B. Salaman and Chaolong Wei and Qilun Wang and Xuehu Ma and Bin Liu and Andrew Barnabas Wong}, doi = {10.1021/jacs.4c13494}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12438--12448}, shortjournal = {J. Am. Chem. Soc.}, title = {Microenvironment tailoring for electrocatalytic CO2 reduction: Effects of interfacial structure on controlling activity and selectivity}, volume = {147}, year = {2025}, }
• (2025). Molecular compasses for modulating electronic communication in pillar[5]quinone. JACS, 147(15), 12425--12437. (www)

  @article{ , abstract = {Just as a pointer, which moves freely and points to the magnetic North in a compass, affords us with a device for tracking direction on a global scale, a dipole moment in a molecule is capable of aligning itself in a compass-like manner in response to an electric field at the molecular level. Here, we demonstrate that dipole moment pointers, based on amide and ester groups in the dumbbell components of [2]rotaxanes, are susceptible to changes in pole–dipole and dipole–dipole interactions within a redox-active pillar[5]quinone ring component when subjected to redox control. Distinct from free pillar[5]quinone, these molecular compasses exhibit a 1–1–1–1–1 electron-uptake pattern during the first-electron transfers. Density functional theory (DFT) calculations reveal that, upon the reduction of quinoid units in the amide-based molecular compass, the positive end of the dipole moment pointer in the dumbbell component becomes oriented toward the reduced anionic quinone in the ring component, courtesy of hydrogen bonding. The negative end of the dipole moment pointer in the dumbbell component lowers the reduction potentials of the other four quinoid units as a result of electrostatic repulsions, which explain its 1–1–1–1–1 electron-uptake pattern. Our findings highlight how electronic communication between the dipole moment pointers and the quinoid units in the ring component enables the [2]rotaxane to act as a molecular compass, precisely reorienting its dipole moments in response to redox changes.}, archive = {J_JACS}, author = {Tae-woo Kwon and Guangcheng Wu and Sheng-Nan Lei and J. Fraser Stoddart}, doi = {10.1021/jacs.4c12280}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12425--12437}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular compasses for modulating electronic communication in pillar[5]quinone}, volume = {147}, year = {2025}, }
• (2025). Dirhodium complexes heterochiral-at-the-metal centers: An alternative type of paddlewheel catalyst for asymmetric synthesis. JACS, 147(15), 12418--12424. (www)

  @article{ , abstract = {The prototype of an entirely new class of dirhodium paddlewheel complexes is disclosed, which is chiral at both inequivalent metal centers although it carries just three different achiral μ-bridging equatorial ligands. One of them is a carboxamidate, which ensures selective carbene formation at the Rh[O 3 N] face of the catalyst; moreover, the −NH group engages the ester carbonyl of the emerging rhodium carbene intermediate derived from α-stannylated α-diazoacetate in interligand hydrogen bonding, which is critically important for controlling the stereochemical course of the ensuing [2 + 1] cycloaddition. The new heterochiral catalyst furnished stannylated cyclopropane derivatives with excellent diastereo- and enantioselectivity; moreover, a cyclopropane with a quaternary trifluoromethylated stereocenter was obtained with an unprecedented level of asymmetric induction.}, archive = {J_JACS}, author = {Matthias Peeters and Lorenzo Baldinelli and Sofia Lerda and Giovanni Bistoni and Alois Fürstner}, doi = {10.1021/jacs.5c03567}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12418--12424}, shortjournal = {J. Am. Chem. Soc.}, title = {Dirhodium complexes heterochiral-at-the-metal centers: An alternative type of paddlewheel catalyst for asymmetric synthesis}, volume = {147}, year = {2025}, }
• (2025). Chiral lewis acid-catalyzed intramolecular [2 + 2] photocycloaddition: Enantioselective synthesis of azaarene-functionalized azabicyclo[2.1.1]hexanes and bicyclo[1.1.1]pentanes. JACS, 147(15), 12410--12417. (www)

  @article{ , abstract = {We present an asymmetric intramolecular [2 + 2] photocycloaddition reaction enabled by a dual catalyst system involving DPZ as a photosensitizer and chiral Sc(III) complex, leading to azaarene-functionalized 2-azabicyclo[2.2.1]hexanes (aza-BCHs). The approach efficiently preventing racemization during subsequent nitrogen-deletion skeletal editing of aza-BCHs to yield 2-substituted bicyclo[1.1.1]pentanes (BCPs). The method achieves high ee and broad substrate scope, including the successful formation of all-carbon quaternary stereocenters. Furthermore, the successful activation of simple azaarene substrates by chiral Lewis acids in asymmetric photocatalysis highlights a notable contribution to this field.}, archive = {J_JACS}, author = {Dong Tian and Yixing Pan and Xiaowei Zhao and Yanli Yin and Zhiyong Jiang}, doi = {10.1021/jacs.5c03542}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12410--12417}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral lewis acid-catalyzed intramolecular [2 + 2] photocycloaddition: Enantioselective synthesis of azaarene-functionalized azabicyclo[2.1.1]hexanes and bicyclo[1.1.1]pentanes}, volume = {147}, year = {2025}, }
• (2025). Multiscale structural analysis of aggregation-induced emission nanocrystals by combining electron and confocal microscopy. JACS, 147(15), 12405--12409. (www)

  @article{ , abstract = {Aggregation-induced emission (AIE) materials have attracted intense interest due to their remarkable luminescent properties and potential applications in biological and medical fields. A comprehensive structural analysis from atomic-level to micrometer-scale is essential for rationally designing AIE materials and understanding their structure–property relationships. However, this remains a challenge due to the lack of proper methods. Herein, we present a strategy for multiscale structural analysis of AIE materials through a combination of electron and confocal microscopy. One mechanically induced fluorescent AIE material consisting of a chiral Au(I) complex was prepared and studied. The correlation of scanning electron and optical microscope images reveals that the fluorescence is closely related to the anisotropy of nanocrystals with strong signals on fracture {110} facets. Furthermore, instead of growing large single crystals, atomic-level crystal structures of individual nanocrystals were directly resolved using three-dimensional electron diffraction (3D ED), highlighting the changes in molecular arrangement before and after mechanical treatment. The results provide experimental evidence for the previously proposed mechanically induced Restriction of Intramolecular Rotation (RIR) mechanism.}, archive = {J_JACS}, author = {Shitao Wu and Jianyu Zhang and Jing Zhang and Yanhang Ma}, doi = {10.1021/jacs.5c02745}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12405--12409}, shortjournal = {J. Am. Chem. Soc.}, title = {Multiscale structural analysis of aggregation-induced emission nanocrystals by combining electron and confocal microscopy}, volume = {147}, year = {2025}, }
• (2025). Copper-catalyzed enantioselective three-component carboamidation of styrenes with alkanes and amides. JACS, 147(15), 12397--12404. (www)

  @article{ , abstract = {Efficient assembly of valuable chiral molecules from readily available and low-cost chemical feedstocks remains one of the most challenging tasks in synthetic chemistry today. Radical-mediated three-component carboamination of alkenes offers an attractive strategy for addressing this challenge. However, most existing reports focus on racemic examples and are largely limited to activated alkenes, preactivated alkylation reagents, or sufficiently active nucleophiles. Herein, we report a highly enantioselective three-component carboamidation of styrenes with unactivated alkanes and weakly nucleophilic amides. Enantioselective control is achieved by using chiral cationic copper catalysts. This method enables the synthesis of a variety of optically active amides with excellent enantioselectivity. Mechanistic studies reveal that the reaction proceeds via hydrogen atom transfer from the alkane followed by radical addition to the olefin.}, archive = {J_JACS}, author = {Ying-Ying Chen and Ling Dai and Xuan-Ge Zhang and Qi-Lin Zhou}, doi = {10.1021/jacs.5c02348}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12397--12404}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper-catalyzed enantioselective three-component carboamidation of styrenes with alkanes and amides}, volume = {147}, year = {2025}, }
• (2025). Maleimide polyacetylene: A highly conductive n-type polymer. JACS, 147(15), 12392--12396. (www)

  @article{ , abstract = {Despite significant interest in conjugated polymers for a wide range of applications in electronics, n-type materials have lagged in performance relative to their p-type counterparts. Polyacetylene is a promising scaffold for addressing this deficiency, as the most conductive conjugated polymer to date when p-doped. However, it displays orders of magnitude lower conductivity in the n-doped state and is not stable under ambient conditions. The systematic introduction of electron-withdrawing groups to the backbone could solve this issue, but few such examples exist. Herein, we address this gap by introducing maleimide polyacetylene (mPA) as a new n-type conjugated polymer. The alternating vinylene-maleimide sequence introduces strongly electron-withdrawing groups to the polyacetylene core while retaining backbone planarity, conferring both ambient stability (LUMO = −4.35 eV) and good conductivity (σ = 22 S/cm) in the n-doped state. The versatile synthetic approach uses ring opening metathesis polymerization to generate nonconjugated precursor polymers with low dispersity and controlled molecular weight. These are then converted to mPA by an unusual base-mediated oxidation that leverages the acidity of the maleimide α-protons.}, archive = {J_JACS}, author = {Harrison M. Bergman and Timothy M. Swager}, doi = {10.1021/jacs.5c01955}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12392--12396}, shortjournal = {J. Am. Chem. Soc.}, title = {Maleimide polyacetylene: A highly conductive n-type polymer}, volume = {147}, year = {2025}, }
• (2025). Terphenylthiolate-ligated lanthanide terminal methyl complexes form crystallographically characterizable terminal acyls and trimethylcyclopropanetriolates from carbon monoxide. JACS, 147(15), 12386--12391. (www)

  @article{ , abstract = {The sterically bulky terphenylthiolate ligand {S[C 6 H 3 -2,6-(C 6 H 2 -2,4,6- i Pr 3 ) 2 ]} 1– , (SAr i Pr6 ) 1– , has permitted the isolation of the terminal methyl complexes Ln(SAr i Pr6 ) 2 CH 3 , 1-Ln , Ln = La and Nd, from salt metathesis between Ln(SAr i Pr6 ) 2 I and methyllithium. These complexes react with carbon monoxide to afford the first structurally authenticated examples of terminal acyl complexes of the rare-earth elements, Ln(SAr i Pr6 ) 2 (η 2 -OCCH 3 ), 2-Ln . However, in the presence of lithium iodide, the reaction between Ln(SAr i Pr6 ) 2 CH 3 and CO forms the unique trimethylcyclopropanetriolate trianion, [cyclo-(OCCH 3 ) 3 ] 3– , in the complex [Ln(SAr i Pr6 )(μ-I)(μ-OCCH 3 )] 3 , 3-Ln . This CO insertion product arises from the formation of six C–C bonds, demonstrating the power of the (SAr i Pr6 ) 1– ligand to generate new organometallic rare-earth metal reaction chemistry with CO.}, archive = {J_JACS}, author = {Makayla R. Luevano and Cary R. Stennett and Joseph W. Ziller and William J. Evans}, doi = {10.1021/jacs.5c01065}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12386--12391}, shortjournal = {J. Am. Chem. Soc.}, title = {Terphenylthiolate-ligated lanthanide terminal methyl complexes form crystallographically characterizable terminal acyls and trimethylcyclopropanetriolates from carbon monoxide}, volume = {147}, year = {2025}, }
• (2025). Unveiling repulsion in intramolecular H-bonded systems. JACS, 147(15), 12381--12385. (www)

  @article{ , abstract = {Intramolecular H-bonds govern molecular conformation and play critical roles in pharmaceutical design, catalysis, and supramolecular chemistry. Despite this, the experimental influence of ortho -substituents on the energetics of an adjacent H-bond defies classical Hammett analysis. By using synthetic molecular balances, we show that substituents positioned ortho to an OH H-bond donor can compete strongly with H-bonding to an external acceptor. Computational dissection of the experimental trends reveals that this competition is rarely dominated by stabilizing OH···R H-bonds, but rather by the avoidance of repulsive HO···R interactions. We provide a framework for rationalizing the influence of ortho -substituents on molecular conformation and the energetics of intramolecular H-bonds. Our work challenges the intuitive bias of attributing close contacts to attractive interactions and highlights the critical role of repulsion in molecular design.}, archive = {J_JACS}, author = {Ivan V. Smolyar and Scott L. Cockroft}, doi = {10.1021/jacs.5c00385}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12381--12385}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling repulsion in intramolecular H-bonded systems}, volume = {147}, year = {2025}, }
• (2025). Metal-based approaches for the fight against antimicrobial resistance: Mechanisms, opportunities, and challenges. JACS, 147(15), 12361--12380. (www)

  @article{ , abstract = {The rapid emergency and spread of antimicrobial-resistant (AMR) bacteria and the lack of new antibiotics being developed pose serious threats to the global healthcare system. Therefore, the development of more effective therapies to overcome AMR is highly desirable. Metal ions have a long history of serving as antimicrobial agents, and metal-based compounds are now attracting more interest from scientific communities in the fight against AMR owing to their unique mechanism. Moreover, they may also serve as antibiotic adjuvants to enhance the efficacy of clinically used antibiotics. In this perspective, we highlight important showcase studies in the last 10 years on the development of metal-based strategies to overcome the AMR crisis. Specifically, we categorize these metallo-antimicrobials into five classes based on their modes of action (i.e., metallo-enzymes and metal-binding enzyme inhibitors, membrane perturbants, uptake/efflux system inhibitors/regulators, persisters inhibitors, and oxidative stress inducers). The significant advantages of metallo-antimicrobials over traditional antibiotics lie in their multitargeted mechanisms, which render less likelihood to generate resistance. However, we notice that such modes of action of metallo-antimicrobials may also raise concern over their potential side effects owing to the low selectivity toward pathogens and host, which appears to be the biggest obstacle for downstream translational research. We anticipate that combination therapy through repurposing (metallo)drugs with antibiotics and the optimization of their absorption route through formulation to achieve a target-oriented delivery will be a powerful way to combat AMR. Despite significant challenges, metallo-antimicrobials hold great opportunities for the therapeutic intervention of infection by resistant bacteria.}, archive = {J_JACS}, author = {Chenyuan Wang and Xueying Wei and Liang Zhong and Chun-Lung Chan and Hongyan Li and Hongzhe Sun}, doi = {10.1021/jacs.4c16035}, journal = {Journal of the American Chemical Society}, month = {4}, number = {15}, pages = {12361--12380}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal-based approaches for the fight against antimicrobial resistance: Mechanisms, opportunities, and challenges}, volume = {147}, year = {2025}, }
• (2025). Correction to “Discovery of a natural ent-kaurene diterpenoid oridonin as an e3 ligase recruiter for PROTACs”. JACS, 147(14), 12360. (www)

  @article{ , archive = {J_JACS}, author = {Jie Huang and Xuekun Fu and Fang Qiu and Zhijian Liang and Chunhao Cao and Zhuqian Wang and Hongzhen Chen and Siran Yue and Duoli Xie and Yiying Liang and Aiping Lu and Chao Liang}, doi = {10.1021/jacs.5c03656}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12360}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Discovery of a natural ent-kaurene diterpenoid oridonin as an e3 ligase recruiter for PROTACs”}, volume = {147}, year = {2025}, }
• (2025). Chiral all-inorganic perovskite subnanowires. JACS, 147(14), 12347--12359. (www)

  @article{ , abstract = {The phenomenon of chiral symmetry breaking during the crystallization of achiral molecules or ions, which leads to the formation of controllable enantiomerically pure crystals, has garnered significant interest but remains a challenge to fully overcome. This presents a particularly formidable obstacle in the creation of three-dimensional (3D) structured chiral all-inorganic perovskites, further complicated by their achiral crystalline space groups. In this report, we successfully synthesized right- or left-handed (P/M) chiral 3D P/M-CsPbX 3 (X = Cl, Cl–Br, Br, Br–I) perovskite subnanowires (SNWs), in which Pb(II) can be partially substituted by hetero ions, such as Cu(II), Sn(II), and Mn(II). The selective control of the SNW handedness was achieved through the strategic incorporation of trace chiral amine enantiomers. The chiroptical activity arises from the helical structure of the SNWs. The mechanisms underlying the formation of this chiral structure were systematically investigated and interpreted by using a thermodynamic model. We utilized the chiral P/M-CsPbBr 3 SNWs to fabricate circularly polarized light (CPL) photodetectors, which exhibited an impressive photocurrent dissymmetry factor ( g Iph ) of 0.75. In the field of spin light-emitting diodes (spin-LEDs), circularly polarized electroluminescence (CPEL) was accomplished by employing the SNWs as a dual-functional material that provides both chiral-induced spin selectivity (CISS) and CPL emission capabilities.}, archive = {J_JACS}, author = {Gaoyu Chen and Kunhong Zhou and Qingda Liu and Junli Liu and Xiangxing Xu and Wenxiong Shi and Jinzhou Jiang and Xinwen Zhang and Lizhu Dong and Linghai Xie and Xiaoyu Zhang and Niuniu Zhang and Dongdong Xu and Jianchun Bao and Xun Wang}, doi = {10.1021/jacs.5c04134}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12347--12359}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral all-inorganic perovskite subnanowires}, volume = {147}, year = {2025}, }
• (2025). De novo design of proteins for autocatalytic isopeptide bond formation. JACS, 147(14), 12338--12346. (www)

  @article{ , abstract = {Isopeptide bonds (IPBs)─formed between the amine group of a Lys residue and the carboxamide/carboxy group of Asn/Gln or Asp/Glu─play essential roles in many biological processes, ranging from cellular signaling and regulation to blood clotting and bacterial pathogenesis. The formation of IPBs is not a spontaneous process and requires enzymatic machinery that provides a specialized active site environment to enable this challenging catalytic reaction. Here we report the de novo design and characterization of two proteins (dnIPB-1 and dnIPB-2) capable of autocatalytic IPB formation. While these designed proteins preserve the key active-site residues of their structural template (the bacterial pilin protein RrgA), they possess less than 31% sequence identity to RrgA. Extensive structural and Ala-scanning analyses indicate that IPB formation requires a solvent-protected core motif composed of several critical residues, yet there is also a large tolerance to different protein topologies and overall protein sizes in terms of accommodating an IPB-forming motif. Notably, the structural insights gained from the study of dnIPB-1 and dnIPB-2 also guided the redesign of an initially failed construct (dnIPB-3) and enabled it to form an IPB, highlighting the value of de novo design in examining sequence–structure–function relationships not explored in natural evolution. Our study highlights the versatility of IPBs as designable elements which can be used to construct functional proteins or protein-based materials with enhanced chemical, thermal, and mechanical stabilities.}, archive = {J_JACS}, author = {Suppachai Srisantitham and Alyssa L. Walker and Ulrich Markel and F. Akif Tezcan}, doi = {10.1021/jacs.5c03319}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12338--12346}, shortjournal = {J. Am. Chem. Soc.}, title = {De novo design of proteins for autocatalytic isopeptide bond formation}, volume = {147}, year = {2025}, }
• (2025). A fresh twist on the phospha-(Aza)-wittig reaction. JACS, 147(14), 12331--12337. (www)

  @article{ , abstract = {The reactivity of an unsupported phosphinidene oxide, BnArNP═O (Bn = benzyl; Ar = bulky aryl group), as the electrophilic partner in Wittig reactions with ylides is described. Reactions with methylene-triphenylphosphorane (H 2 C═PPh 3 ) and ethylidene-triphenyl-phosphorane (HMeC═PPh 3 ), proceed as expected, giving rise to the phosphaalkene metathesis products and triphenylphosphine oxide. This reaction can be extended to other ylides such as N -(triphenylphosphoranylidene)methanamine (MeN═PPh 3 ), to afford an aminoiminophosphane BnArNP═NMe. In these reactions the phosphinidene oxide plays the role of an electrophile, which would typically be the remit of an organic carbonyl in classical Wittig reactions. Further mechanistic insight into such transformations can be gained by altering the nature of the phosphorus-ylide. Upon reacting BnArNP═O with H 2 C═PMe 3 (which possesses a smaller, more Lewis basic, phosphine) an alternative product is formed. This transformation supports the formation of a betaine intermediate that subsequently undergoes hydrogen-migration to afford an oxidized phosphorus(V) compound related to phosphorus acid.}, archive = {J_JACS}, author = {Chenyang Hu and Maren Pink and Jose M. Goicoechea}, doi = {10.1021/jacs.5c02865}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12331--12337}, shortjournal = {J. Am. Chem. Soc.}, title = {A fresh twist on the phospha-(Aza)-wittig reaction}, volume = {147}, year = {2025}, }
• (2025). Extrinsic and intrinsic factors governing the electrochemical oxidation of propylene in aqueous solutions. JACS, 147(14), 12318--12330. (www)

  @article{ , abstract = {The electrochemical synthesis of commodity chemicals such as epoxides and glycols offers a sustainable alternative to conventional methods that involve hazardous chemicals. Efforts to improve the yield and selectivity of propylene oxidation using Pd-based catalysts have been shown to be highly sensitive to applied potential, pH, and electrochemical cell design. Record efficiencies and yields were obtained by substitution of PdO by 4d or 5d transition metals, including Pt, with thus far little rationale regarding the origin for the improvement. Through electrochemical analysis, scanning transmission electron microscopy, X-ray absorption spectroscopy, and surface-enhanced infrared absorption spectroscopy, we investigated the mechanism of propylene oxidation on Pd-based catalysts. We demonstrate that adsorbates forming on PdO, where Pd adopts a square-planar coordination [PdO 4 ], differ from that forming on the surface of oxidized metallic Pd catalysts with an oxo intermediate mediating propylene oxidation on PdO. We further show that Pt substitution in PdO does not modify this oxo intermediate. Varying pH, we found that the onset for propylene oxidation is pH independent, indicating a potential-determining step where the proton is not involved in and similar reaction pathway in acidic and near-neutral conditions. Finally, our work undoubtedly demonstrates that high Faradaic efficiency toward propylene glycol and propylene oxide formation, such as those previously reported in the literature, can be achieved by means of electrode engineering and mastery of mass transport and local pH. Notably, we achieved ≈100% faradaic efficiency for propylene glycol at 1.7 V vs RHE in acidic media using a Pt-substituted PdO catalyst loaded onto a gas diffusion electrode.}, archive = {J_JACS}, author = {Tae Gyu Yun and Boqiang Chen and Sarah Wells and Younghwan Lim and Jun Seop Kim and Ana Guilherme Buzanich and Martin Radtke and Matthias M. Waegele and Marcel Risch and Alexis Grimaud}, doi = {10.1021/jacs.5c02585}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12318--12330}, shortjournal = {J. Am. Chem. Soc.}, title = {Extrinsic and intrinsic factors governing the electrochemical oxidation of propylene in aqueous solutions}, volume = {147}, year = {2025}, }
• (2025). Photolytic access to oxaspirodecanes and chromenes from vinyldiazo ester cycloaddition with p-quinones: A vinylcarbene is not involved. JACS, 147(14), 12308--12317. (www)

  @article{ , abstract = {Synthetic methods that provide access to skeletally diverse heterocyclic motifs are poised to accelerate drug discovery and streamline the synthesis of advanced intermediates and materials. However, the development of such synthetic methods necessitates leveraging previously unexplored mechanistic pathways. We report herein an efficient blue light-emitting diode light-induced reaction of vinyldiazoacetates and quinones that produces spirocyclic dihydrofurans, featuring the synthetically challenging oxaspiro[4,5]decane core of numerous medicinal agents, agrochemicals, and natural products. In a departure from the well-established photochemical reactivity of diazo compounds, these reactions do not involve vinylcarbene intermediates formed by photolytic dinitrogen extrusion. Instead, they result from photoexcitation of the quinone to its triplet state with subsequent triplet energy transfer to the vinyldiazo ester. The subsequent addition of the vinylogous carbon of the triplet vinyldiazoacetate to the quinone oxygen affords the triplet diradical that collapses to the spirocyclic dihydrofuran upon the loss of dinitrogen. A strain release-driven and Bro̷nsted acid-catalyzed rearrangement of the spirocyclic products unravels the fused bicyclic ring system of equally synthetically and medicinally valuable chromenes, enabling facile skeletal diversification of the important heterocyclic motifs.}, archive = {J_JACS}, author = {Soumen Biswas and Ramon Trevino and Seth O. Fremin and Luis Mario Sanchez-Palestino and Babu Raj Dhungana and Arka Porey and William B. Hughes and Hadi D. Arman and Oleg V. Larionov and Michael P. Doyle}, doi = {10.1021/jacs.5c02500}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12308--12317}, shortjournal = {J. Am. Chem. Soc.}, title = {Photolytic access to oxaspirodecanes and chromenes from vinyldiazo ester cycloaddition with p-quinones: A vinylcarbene is not involved}, volume = {147}, year = {2025}, }
• (2025). Reactivating molecular cobalt catalysts for electrochemical CO2 conversion to methanol. JACS, 147(14), 12298--12307. (www)

  @article{ , abstract = {Molecular catalysts immobilized on a carbon support have demonstrated electrocatalytic CO 2 conversion capabilities distinct from those of metallic surfaces. For instance, cobalt phthalocyanine supported on carbon nanotubes (CoPc/CNT) is capable of selective CO 2 -to-methanol conversion with ∼30% selectivity, which cannot be accomplished by other metal catalysts, such as cobalt, silver, and copper. However, despite its promising methanol selectivity, the CoPc/CNT catalyst exhibits a gradual decrease in the methanol production rate during the electrochemical CO 2 reduction reaction (CO 2 RR). This catalytic instability impedes its practical application, yet little is known about the origin of the activity decay and viable solutions to circumvent it. In this study, we show that the catalytic deactivation is not an irreversible process caused by the chemical degradation of the catalyst and present reactivation strategies to recover the catalytic performance for stable methanol production. We propose that formaldehyde, an intermediate generated during the CO 2 RR, can act as a poisoning species, and its adsorption configuration on the cobalt site can determine the fate of its reaction pathway: carbon-down (*CH 2 O) versus oxygen-down (*OCH 2 ) pathways. In contrast to the carbon-down configuration leading to methanol production, the oxygen-down configuration can inhibit its further reduction, poisoning the cobalt active site and causing the deactivation.}, archive = {J_JACS}, author = {Sunmoon Yu and Hiroki Yamauchi and Davide Menga and Shuo Wang and Antonia Herzog and Hongbin Xu and Daniel J. Zheng and Xiao Wang and Haldrian Iriawan and Botao Huang and Alexander Nitsche and Yang Shao-Horn}, doi = {10.1021/jacs.5c02411}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12298--12307}, shortjournal = {J. Am. Chem. Soc.}, title = {Reactivating molecular cobalt catalysts for electrochemical CO2 conversion to methanol}, volume = {147}, year = {2025}, }
• (2025). Catalytic aldehyde decarbonylase activity by a thiolate-bound iron porphyrin: Observation of a peroxyhemiacetal intermediate during catalysis. JACS, 147(14), 12285--12297. (www)

  @article{ , abstract = {Aldehyde decarbonylation is a key chemical step in nature that is involved in the biosynthesis of hormones and long-chain hydrocarbons where O 2 is the oxidant. A cytochrome P450 enzyme, aromatase, catalyzes this reaction, where a thiolate-bound ferric peroxide is proposed to be the oxidant. Despite several attempts, only substoichiometric yields have been reported by synthetic iron porphyrins in organic solvents using peroxide. Several synthetic nonheme complexes have been reported to catalyze decarbonylation in stoichiometric yields using peroxides as oxidants. Catalytic decarbonylation with molecular O 2 using either heme or nonheme complexes remains elusive. Iron picket-fence porphyrin is attached to thiol-terminated self-assembled monolayers. In situ resonance Raman spectroscopy reveals the accumulation of an Fe(III)-OOH intermediate with Fe–O and O–O vibrations at 579 cm –1 and 798 cm –1 , respectively, during heterogeneous electrocatalytic O 2 reduction in a pH 7 buffer solution. In the presence of different aldehydes in solution, catalytic aldehyde decarbonylase reactivity is observed with TON and TOF of ∼ 83000 and 277 s –1 , respectively, for 2-methyl-2-phenylpropionaldehyde and ∼ 13000 and 45 s –1 , respectively, for undecanal using molecular O 2 in a pH 7 buffer solution. In situ SERRS-RDE in the presence of 2-phenylpropionaldehyde indicates the formation of a peroxyhemiacetal species with Fe–O, O–O, and C–O vibrations at 520 cm –1 , 833 cm –1 , and 1185 cm –1 , respectively, as an intermediate in catalytic aldehyde decarbonylase activity.}, archive = {J_JACS}, author = {Soumya Samanta and Srijan Sengupta and Triparna Roy and Apurba Pal and Abhishek Dey}, doi = {10.1021/jacs.5c01859}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12285--12297}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic aldehyde decarbonylase activity by a thiolate-bound iron porphyrin: Observation of a peroxyhemiacetal intermediate during catalysis}, volume = {147}, year = {2025}, }
• (2025). Ligand-controlled enantioselective copper-catalyzed hydroboration and ring-opening dihydroboration of arylidenecyclobutanes. JACS, 147(14), 12273--12284. (www)

  @article{ , abstract = {Arylidenecyclobutanes are readily accessible and versatile reagents in synthetic chemistry due to the multifaceted reactivity exhibited by their alkene and strained cyclobutane moieties. However, metal-catalyzed enantioselective functionalization of arylidenecyclobutanes, particularly the controllable ring-retaining and ring-opening reactions, is rarely explored. Considering the versatile synthetic utility of enantioenriched organoboronate compounds, herein we report ligand-controlled enantioselective copper-catalyzed ring-retaining hydroboration and ring-opening dihydroboration reactions of arylidenecyclobutanes that afford chiral α -cyclobutyl benzylboronate and 1,5-diboronate compounds with high enantioselectivity when ( S )-DTBM-Segphos and ( S , S )-Ph-BPE are employed, respectively. Mechanistic studies reveal that the ring-opening process of arylidenecyclobutanes via β-C elimination is significantly slower than that of arylidenecyclopropanes in the presence of CuOAc and ( S , S )-Ph-BPE. The synthetic utility of these two enantioselective protocols is further demonstrated through conducting various stereospecific and site-selective transformations of the enantioenriched organoboron products, including concise synthesis of bioactive molecules.}, archive = {J_JACS}, author = {Wenrui Zheng and Yuhan Cao and Boon Beng Tan and Yifan Wang and Shaozhong Ge and Yixin Lu}, doi = {10.1021/jacs.5c01729}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12273--12284}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand-controlled enantioselective copper-catalyzed hydroboration and ring-opening dihydroboration of arylidenecyclobutanes}, volume = {147}, year = {2025}, }
• (2025). Criegee intermediates significantly reduce atmospheric (CF3)2CFCN. JACS, 147(14), 12263--12272. (www)

  @article{ , abstract = {Sulfur hexafluoride (SF 6 ) is widely used for many industrial purposes due to its superior insulating properties; however, it is also a potent greenhouse gas with a high global warming potential (GWP) and an atmospheric lifetime of approximately 3,200 years. Here, we investigate heptafluoroisobutyronitrile ((CF 3 ) 2 CFCN, also called C4-fluoronitrile or C4-FN) to help determine if it is a sustainable alternative to SF 6 . We present experimental measurements and high-level quantum chemical calculations with a new computational strategy to elucidate the reaction kinetics between C4-FN and Criegee intermediates (CIs), specifically CH 2 OO and syn -CH 3 CHOO. By employing a new strategy to obtain CCSDT(Q)/CBS-level accuracy for a larger system than has previously been possible, combined with state-of-the-art kinetics methods, we obtain good agreement between theoretical and experimental rate constants. We find that the reactions between C4-FN and CIs are substantially faster than previously known degradation pathways, particularly the OH radical reaction. This shows the importance of incorporating additional reactive species into atmospheric chemistry models and climate impact assessments, paving the way for more effective climate change mitigation. Including the CI reactions in two possible scenarios gives a predicted atmospheric lifetime of C4-FN of 2–34.5 years, with a significant reduction in its global warming potential. This supports C4-FN’s potential as an environmentally friendly substitute for SF 6 .}, archive = {J_JACS}, author = {Haotian Jiang and Chaolu Xie and Yue Liu and Chunlei Xiao and Weiqing Zhang and Hongwei Li and Bo Long and Wenrui Dong and Donald G. Truhlar and Xueming Yang}, doi = {10.1021/jacs.5c01737}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12263--12272}, shortjournal = {J. Am. Chem. Soc.}, title = {Criegee intermediates significantly reduce atmospheric (CF3)2CFCN}, volume = {147}, year = {2025}, }
• (2025). A systematic approach for incorporating structural flexibility in high-throughput computational screening of Metal–Organic frameworks for xylene separation. JACS, 147(14), 12251--12262. (www)

  @article{ , abstract = {Separation of xylene isomers poses a significant challenge due to their similar physicochemical properties. Currently, zeolites are utilized as adsorbents for this purpose in the chemical industry despite suboptimal separation performance. With tunable pore size and chemical functionality, metal–organic frameworks (MOFs) are promising adsorbents for separation. By virtue of high-throughput computational screening (HTCS), the adsorption performance of a large collection of MOFs can be evaluated in silico by using Monte Carlo (MC) simulations. Unlike prior studies assuming rigid structures of MOFs during screening, we develop a systematic approach for incorporating flexibility in HTCS for xylene separation. First, MOFs are judiciously classified with external flexibility (volume/shape changes) and internal flexibility (intraframework fluctuations), respectively, based on the nature and extent of structural deformation from molecular dynamics (MD) simulations. Afterward, adsorption in MOFs with external flexibility is simulated by hybrid MC/MD method, the flexible snapshot method is used for MOFs with a sort of internal flexibility, and grand-canonical MC (GCMC) method is employed for MOFs with negligible flexibility. Finally, top-performing MOFs are identified for xylene separation. While substantially reducing computational cost, this study also delivers more reliable results compared to the assumption of rigid structures. The HTCS approach is versatile and can be extended beyond MOFs, offering a robust tool for the virtual screening of other soft-porous materials for a wide range of important applications.}, archive = {J_JACS}, author = {Saad Aldin Mohamed and Rui Zheng and Nengxiu Zhu and Dan Zhao and Jianwen Jiang}, doi = {10.1021/jacs.5c01749}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12251--12262}, shortjournal = {J. Am. Chem. Soc.}, title = {A systematic approach for incorporating structural flexibility in high-throughput computational screening of Metal–Organic frameworks for xylene separation}, volume = {147}, year = {2025}, }
• (2025). Dynamic and diverse coacervate architectures by controlled demembranization. JACS, 147(14), 12239--12250. (www)

  @article{ , abstract = {The dynamics of membranes are integral to regulating biological pathways in living systems, particularly in mediating intra- and extracellular communication between membraneless and membranized nano- and microcompartments. Mimicking these dynamics using biomimetic cell structures deepens our understanding of biologically driven processes, including morphological transformations, communication, and molecular sequestration within distinct environments (e.g., (membraneless) organelles, cytoplasm, cells, and the extracellular matrix). In this context, the demembranization of membranized coacervates represents a promising approach to endow them with additional functionalities and dynamic reconfiguration capabilities in response to external or biological stimuli. This versatility broadens their applicability in synthetic biology, systems biology, and biotechnology. Here, we present a strategy for controlled demembranization of membranized coacervate droplets. The membranized coacervates are created by coating membraneless coacervates with terpolymer-based nanoparticles to form a solid-like membrane. The addition of an anionic polysaccharide then triggers the demembranization process arising from electrostatic competition with the membrane components, resulting in polysaccharide-containing demembranized coacervate droplets. This membranization/demembranization process not only allows for the controlled structural reconfiguration of the coacervate entities but also varies their permeability toward (biological) (macro)molecules and nano- and microscale objects. Additionally, integrating an additional polymersome layer in this process facilitates the creation of bilayer and ″Janus-like″ membranized coacervates, advancing the development of coacervate protocells with hierarchical and asymmetric membrane structures. Our work highlights the control over both membranization and demembranization processes of coacervate protocells, establishing a platform for creating advanced protein-containing synthetic protocells with dynamic and diverse (membrane(less)) architectures.}, archive = {J_JACS}, author = {Yang Zhou and Manfred F. Maitz and Kehu Zhang and Brigitte Voit and Dietmar Appelhans}, doi = {10.1021/jacs.5c01526}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12239--12250}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic and diverse coacervate architectures by controlled demembranization}, volume = {147}, year = {2025}, }
• (2025). Subnanometric nickel phosphide heteroclusters with highly active Niδ+–Pδ− pairs for nitrate reduction toward ammonia. JACS, 147(14), 12228--12238. (www)

  @article{ , abstract = {The development of efficient electrocatalysts for the neutral nitrate reduction reaction (NO 3 – RR) toward ammonia (NH 3 ) is essential to address the environmental issues caused by NO 3 – but remains considerably challenging owing to the sluggish reaction kinetics of NO 3 – RR in neutral media. Herein, we report subnanometric heteroclusters with strongly coupled nickel–phosphorus (Ni–P) dual-active sites as electrocatalysts to boost the neutral NO 3 – RR. Experimental and theoretical results reveal that the subnanometric feature of Ni–P heteroclusters promotes the electron transfer from Ni to P, generating Ni δ+ –P δ− active pairs, in which Ni δ+ species are highly active for the NO 3 – RR and P δ− tunes the interfacial water hydrogen bonding network to promote the water dissociation step and accelerate proton transfer during the NO 3 – RR. Consequently, in the neutral NO 3 – RR, Ni–P heteroclusters exhibit a large NH 3 yield rate of 0.61 mmol h –1 cm –2 at −0.8 V versus reversible hydrogen electrode, which is 2.8- and 3.3-fold larger than those on Ni–P nanoparticles and Ni clusters, respectively, and the generated NH 3 exists as NH 4 + in electrolytes. This study offers an efficient approach to boosting electrocatalytic reactions with multiple intermediates by designing subnanometric heteroclusters with strongly coupled active sites.}, archive = {J_JACS}, author = {Qi Hu and Chunyan Shang and Xinbao Chen and Shuai Qi and Qihua Huo and Hengpan Yang and Chuanxin He}, doi = {10.1021/jacs.5c01455}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12228--12238}, shortjournal = {J. Am. Chem. Soc.}, title = {Subnanometric nickel phosphide heteroclusters with highly active Niδ+–Pδ− pairs for nitrate reduction toward ammonia}, volume = {147}, year = {2025}, }
• (2025). Synthesis of electron-deficient BisAzaCoroneneDiimide-conjugated polymers by light-locking dynamic covalent bonds. JACS, 147(14), 12218--12227. (www)

  @article{ , abstract = {We present a novel light-locked dynamic covalent polymerization methodology to synthesize conjugated polymers based on BisAzaCoroneneDiimides (BACDs). This metal-free process converts reversible poly imines into kinetically locked conjugated polymers using visible light, generating minimal side products. By incorporating aldehyde-functionalized comonomers, the approach enables the creation of diverse n-type semiconducting polymers with tunable optical band gaps and low LUMO levels. The polymers exhibit exceptional thermal, electrochemical, and photostability with strong interchain interactions upon electrochemical reduction observed in solution, attributed to the BACD core. Broad absorption from the visible to the near-infrared range underscores their potential in charge and energy transport applications for organic electronics. This scalable, sustainable strategy unlocks access to a versatile class of n-type diimide polymers.}, archive = {J_JACS}, author = {Adèle Gapin and Elarbi Chatir and Olivier Alévêque and Clara Pasgrimaud and Arthur H. G. David and Anaïs De Maria and Mélanie Legros and Laura Le Bras and Eric Levillain and Antoine Goujon}, doi = {10.1021/jacs.5c01351}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12218--12227}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of electron-deficient BisAzaCoroneneDiimide-conjugated polymers by light-locking dynamic covalent bonds}, volume = {147}, year = {2025}, }
• (2025). Reduction by oxidation: Selective hydrodehalogenation of aryl halides by mediated oxalate oxidation. JACS, 147(14), 12206--12217. (www)

  @article{ , abstract = {Electro-organic reduction reactions are canonically carried out at a cathode at which a significant negative potential is applied. Specifically, at carbon electrodes, aryl bromides and chlorides undergo heterogeneous reduction in organic solvents at potentials more negative than −2 V vs E 0′ for the Fc/Fc + couple (Fc = ferrocene). To decrease the overpotential for reduction reactions, homogeneous or heterogeneous electrocatalysis strategies are often employed. Here, we present an electrochemical method to reduce aryl bromides and chlorides that is initiated by an oxidation reaction at very mild potentials (∼0 V vs Fc/Fc + ). Specifically, electrochemical oxidation of an outer-sphere redox mediator, 1,1-dimethylferrocene, in dry N,N -dimethylformamide (DMF) containing oxalate (C 2 O 4 2– ), results in the homogeneous one-electron oxidation of C 2 O 4 2– . The resulting C 2 O 4 •– decomposes in ∼1 μs to release the carbon dioxide radical anion (CO 2 •– ), a potent reductant that is oxidized to CO 2 at –2.68 V vs Fc/Fc + . In this way, an oxidation reaction at low electrode potentials enables homogeneous reduction of aryl bromides and chlorides, which are otherwise directly reduced at very negative potentials. Using this method, selective hydrodehalogenations of electron-deficient aryl bromides and chlorides are carried out at a reticulated vitreous carbon anode with up to quantitative conversion yields. Cyclic voltammetry and finite difference simulations are used to characterize the hydrodehalogenation of 4-bromobenzonitrile via C 2 O 4 2– oxidation. Additionally, we show that the efficiency of hydrodehalogenation is tuned by deliberate additions of water to DMF solutions, leading to a substantial improvement in overall conversion yields without interference from water or proton reduction.}, archive = {J_JACS}, author = {Joshua A. Beeler and Rune P. Walkingshaw and Safiya A.S. Hamud and Henry S. White}, doi = {10.1021/jacs.5c01366}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12206--12217}, shortjournal = {J. Am. Chem. Soc.}, title = {Reduction by oxidation: Selective hydrodehalogenation of aryl halides by mediated oxalate oxidation}, volume = {147}, year = {2025}, }
• (2025). Catalytic enantioselective smiles rearrangement enabled by the directed evolution of p450 radical aryl migratases. JACS, 147(14), 12197--12205. (www)

  @article{ , abstract = {Despite its synthetic potential, catalytic enantioselective Smiles rearrangement has remained elusive. Through the directed evolution of P450 radical aryl migratases (P450 Smiles ’s), we describe the first example of catalytic enantioselective Smiles rearrangement. A range of racemic N -arylsulfonyl-α-chloroamides could be transformed by P450 Smiles in an enantioconvergent manner, affording acyclic amide products possessing an all-carbon quaternary stereocenter with excellent chemo- and enantioselectivity. Both electron-rich and electron-deficient substituents were compatible with the migrating aryl group, demonstrating this P450-catalyzed Smiles rearrangement is insensitive to the electronic properties of the migrating group. Importantly, our evolved P450 variants were capable of overriding the innate cyclization activity of the N -alkyl amidyl radical intermediate, allowing the chemoselective reductive formation of acyclic products. Classical molecular dynamics (MD) simulations revealed this unusual enzyme-controlled chemoselectivity stems from the restricted conformation of the amidyl radical within the enzyme active site, disfavoring the cyclization pathway. This new-to-nature biocatalytic asymmetric Smiles rearrangement showcases the synthetic potential of enzymatic chemo- and enantioselectivity control over highly reactive radical intermediates eluding small-molecule catalysts.}, archive = {J_JACS}, author = {Wenzhen Fu and Katherina Murcek and Jasper Chen and An Liu and Yunlong Zhao and Peng Liu and Yang Yang}, doi = {10.1021/jacs.5c01179}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12197--12205}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic enantioselective smiles rearrangement enabled by the directed evolution of p450 radical aryl migratases}, volume = {147}, year = {2025}, }
• (2025). Controlling reaction pathways of ethylene hydroformylation using isolated bimetallic Rhodium–Cobalt sites. JACS, 147(14), 12185--12196. (www)

  @article{ , abstract = {Designing efficient ligand-free heterogeneous catalysts for ethylene hydroformylation to produce C 3 oxygenates is of importance for both fundamental research and practical applications, but it is often hindered by insufficient catalytic activity and selectivity. This work designs isolated rhodium–cobalt (Rh–Co) sites confined within a ZSM-5 zeolite to enhance ethylene hydroformylation rates and selectivity while maintaining catalyst stability. By adjusting the Co/Al ratio in Co-ZSM-5, different sizes of Co are formed; subsequent Rh introduction produces isolated Rh 1 Co x clusters with different Rh–Co coordination numbers (CNs). In-situ characterizations and density functional theory calculations reveal that a Rh–Co CN of 3, corresponding to an isolated Rh 1 Co 3 site, provides optimal bindings to reaction intermediates and thus achieves the highest hydroformylation rates among supported Rh-based catalysts. This study demonstrates the role of coordination-tuning via a secondary metal in effectively controlling the reaction pathway over single Rh atom catalysts.}, archive = {J_JACS}, author = {Yong Yuan and Tianyou Mou and Sooyeon Hwang and William N. Porter and Ping Liu and Jingguang G. Chen}, doi = {10.1021/jacs.5c01105}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12185--12196}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlling reaction pathways of ethylene hydroformylation using isolated bimetallic Rhodium–Cobalt sites}, volume = {147}, year = {2025}, }
• (2025). Site-specific O-glycosylation in oncofetal fibronectin IIICS domain creates cancer stage-specific biomarkers. JACS, 147(14), 12170--12184. (www)

  @article{ , abstract = {Despite the pathological importance of oncofetal fibronectin isoforms associated with cancer cell progression and metastasis, our understanding of the structural and molecular details that occurred in this abundant and ubiquitous extracellular matrix component remains largely unknown. Here, we communicate that site-specific O -glycosylation in the oncofetal fibronectin creates cancer stage-specific serum biomarkers for hepatocellular carcinoma (HCC) by quantitative MS-based glycoproteomic approach. Selective reaction monitoring (SRM) using a structure-defined synthetic glycopeptide library enabled absolute quantitation of the targeted label-free tryptic fragments bearing cancer-relevant O -glycans derived from the type III homology connective segment (IIICS) domain of the oncofetal fibronectin (onfFN) in the sera of HCC patients and healthy controls. We found site-specific O -glycoform alteration from T/sialyl T antigens to Tn/sialyl Tn antigens at the consecutive threonine residues 2155 Thr-Thr-Ala 2157 within this fragment during cancer progression. Surprisingly, this dynamic glycoform alteration is observed specifically in the patient sera diagnosed newly as stage 2–4 groups not in the normal control and stage 1 patient groups. Our results provide compelling evidence that site-specific glycoform changes observed in the onfFN IIICS domain during the tumor proliferation elaborate new class cancer stage-relevant “dynamic epitopes” as highly potential cancer diagnostic and therapeutic targets.}, archive = {J_JACS}, author = {Nozomi Hirane and Yasuhiro Yokoi and Aiko Kobayashi and Misaki Yamada and Taiki Konno and Hiroyuki Kumeta and Hajime Wakui and Michiru Otaki and Yoshiaki Miura and Tatsuhiko Kakisaka and Toshiya Kamiyama and Akinobu Taketomi and Kazuhiro Nouso and Satoshi Kimura and Shin-Ichiro Nishimura}, doi = {10.1021/jacs.5c00333}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12170--12184}, shortjournal = {J. Am. Chem. Soc.}, title = {Site-specific O-glycosylation in oncofetal fibronectin IIICS domain creates cancer stage-specific biomarkers}, volume = {147}, year = {2025}, }
• (2025). Reorganizing the pt surface water structure for highly efficient alkaline hydrogen oxidation reaction. JACS, 147(14), 12162--12169. (www)

  @article{ , abstract = {The hydrogen oxidation reaction (HOR) in alkaline electrolytes exhibits markedly slower kinetics than that in acidic electrolytes. This poses a critical challenge for alkaline exchange membrane fuel cells (AEMFCs). The slower kinetics in alkaline electrolytes is often attributed to the more sluggish Volmer step (hydrogen desorption). It has been shown that the alkaline HOR activity on the Pt surface can be considerably enhanced by the presence of oxophilic transition metals (TMs) and surface-adsorbed hydroxyl groups on TMs (TM–OH ad ), although the exact role of TM–OH ad remains a topic of active debates. Herein, using single-atom Rh-tailored Pt nanowires as a model system, we demonstrate that hydroxyl groups adsorbed on the Rh sites (Rh–OH ad ) can profoundly reorganize the Pt surface water structure to deliver a record-setting alkaline HOR performance. In situ surface characterizations, together with theoretical studies, reveal that surface Rh–OH ad could promote the oxygen-down water (H 2 O ↓ ) that favors more hydrogen bond with Pt surface adsorbed hydrogen (H 2 O ↓ ···H ad -Pt) than the hydrogen-down water (OH 2↓ ). The H 2 O ↓ further serves as the bridge to facilitate the formation of an energetically favorable six-membered-ring transition structure with neighboring Pt–H ad and Rh–OH ad , thus reducing the Volmer step activation energy and boosting HOR kinetics.}, archive = {J_JACS}, author = {Chengzhang Wan and Zisheng Zhang and Sibo Wang and Qiang Sun and Ershuai Liu and Heting Pu and Ao Zhang and Zhengyue Chen and Aamir Hassan Shah and Xiaoyang Fu and Anastassia N. Alexandrova and Qingying Jia and Yu Huang and Xiangfeng Duan}, doi = {10.1021/jacs.5c00775}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12162--12169}, shortjournal = {J. Am. Chem. Soc.}, title = {Reorganizing the pt surface water structure for highly efficient alkaline hydrogen oxidation reaction}, volume = {147}, year = {2025}, }
• (2025). Enzyme-mimic photoinitiated flow-polymerization with high stereoselectivity under mild conditions. JACS, 147(14), 12150--12161. (www)

  @article{ , abstract = {Enzymatic reactions can achieve efficient flow-polymerization with specificity and high stereoselectivity. However, current enzyme-mimic polymerization systems cannot achieve high stereoregularity in flow reactions under mild conditions. This inefficient chain control may be due to the absence of a specific catalyst structure for the target monomer. This study reports a model of enzyme-mimic catalytic material for the polymerization of a specific monomer. In particular, the specific enzyme-mimic photoinitiated flow-polymerization of benzyl acrylate was realized at 22 °C using zinc porphyrin metal–organic framework (Zn-PMOF) membranes with one-dimensional nanochannels, achieving the efficient synthesis of highly heterotactic polymers. Under visible light irradiation, the zinc porphyrin core on the membrane surface could initiate polymerization, while copper porphyrin MOF with similar structures could not. The specific channel structure of the Zn-PMOF membrane provided space for stereochemical control. Control experiments, density functional theory simulations, and spectroscopic characterizations show that the combination of size effect and channel–monomer interactions realized higher monomer conversion and polymer stereoregularity in the flow reaction. Furthermore, the crystallinity, shear stress, and ionic conductivity of enzyme-mimic polymers were considerably better than those of bulk polymerization products. Thus, this study provides a method for enzyme-mimic polymerization with high stereoselectivity under mild conditions.}, archive = {J_JACS}, author = {Yuhui Zhang and Shuai Pang and Jiangwei Fu and Xiang Li and Yinting MoZeng and Guandi He and Zhenyuan Fang and Wei Li and Daoling Peng and Xiqi Zhang and Lei Jiang}, doi = {10.1021/jacs.5c00736}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12150--12161}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzyme-mimic photoinitiated flow-polymerization with high stereoselectivity under mild conditions}, volume = {147}, year = {2025}, }
• (2025). Redox studies of the scandium metallocene (C5H2tBu3)2ScII lead to a terminal side-on (N═N)2– complex: [(C5H2tBu3)2ScIII(η2-n2)]−. JACS, 147(14), 12138--12149. (www)

  @article{ , abstract = {Cyclic voltammetry measurements on the scandium(II) metallocene, Cp ttt 2 Sc II (Cp ttt = C 5 H 2 t Bu 3 ), reveal a −1.87 V vs Fc + /Fc event assigned to the [Cp ttt 2 Sc] +/0 redox couple and a −3.09 V process assigned to the [Cp ttt 2 Sc] 0/– redox couple, which are consistent with subsequent chemical studies. Chemical oxidation of Cp ttt 2 Sc II with AgBPh 4 gives the scandocenium cation salt [Cp ttt 2 Sc III ][BPh 4 ], 1 . The [Cp ttt 2 Sc III ] + cation does not coordinate the [BPh 4 ] − anion or THF solvent; however, one of the methyl groups of a tert -butyl substituent has a close interaction with the Sc(III) ion. Decomposition occurs in the presence of a [ n Bu 4 N][PF 6 ] supporting electrolyte, and chemical studies indicate that 1 reacts with the [PF 6 ] − anion by fluoride abstraction to form Cp ttt 2 Sc III F and PF 5 . Chemical reduction of 1 to Cp ttt 2 Sc II proceeds with Cp* 2 Sm II and Cp* 2 Co II (Cp* = C 5 Me 5 ), which is consistent with the measured reduction potentials. Cp ttt 2 Sc II was not observed to react with N 2 ; however, the treatment of Cp ttt 2 Sc II with KC 8 and 18-crown-6 (crown) under N 2 forms the (N═N) 2– complex, Cp ttt 2 Sc III (μ-η 2 :η 2 -N 2 )K(crown), 2 . The reaction of Cp ttt 2 Sc II with KC 8 in the presence of 2.2.2-cryptand (crypt) generates [K(crypt)][Cp ttt 2 Sc III (η 2 -N 2 )], 3 , which is the first isolable complex of any metal with a terminal side-on (N═N) 2– ligand. These Ln II A 2 /M/N 2 reactions (M = alkali metal; (A) − = anion) are the Ln(II)/Ln(I) analogs of the previously reported Ln(III)/Ln(II) reactions, Ln III A 3 /M/N 2 , in which reduction of Ln(III) complexes generates Ln(II) reactivity to form (N═N) 2– complexes.}, archive = {J_JACS}, author = {Joshua D. Queen and Ahmadreza Rajabi and Joseph W. Ziller and Filipp Furche and William J. Evans}, doi = {10.1021/jacs.5c00607}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12138--12149}, shortjournal = {J. Am. Chem. Soc.}, title = {Redox studies of the scandium metallocene (C5H2tBu3)2ScII lead to a terminal side-on (N═N)2– complex: [(C5H2tBu3)2ScIII(η2-n2)]−}, volume = {147}, year = {2025}, }
• (2025). Single-crystal X-ray structures of homochiral brønsted acidic covalent organic frameworks. JACS, 147(14), 12127--12137. (www)

  @article{ , abstract = {Determining the crystal structures of covalent organic frameworks (COFs) with atomic precision is pivotal for uncovering their properties and optimizing functionalities. However, the synthesis of high-quality single crystals of COFs suitable for X-ray diffraction analysis, especially chiral COFs (CCOFs), remains a formidable challenge. In this work, we report two three-dimensional (3D) CCOFs synthesized via imine condensation of tetrahedral tetraamine and tetraaldehydes derived from optically active 1,1′-biphenol phosphoryl chloride or thiophosphoryl chloride. Single crystals of varying sizes are obtained through either a low-temperature modulation strategy, yielding large crystals up to 100 μm, or a solvothermal method. The large single crystals are structurally characterized by single-crystal X-ray diffraction, achieving a resolution of 0.90 Å. These two CCOFs are isostructural and each features a 4-fold interpenetrated diamondoid open framework with all phosphoric acid groups periodically aligned within tubular helical channels, displaying enhanced Brønsted acidity compared to non-immobilized acids. The frameworks exhibit permanent porosity, chemical resistance in boiling water, 14 M NaOH, and 0.1 M HCl, and thermal stability up to 400 °C. Notably, these CCOFs serve as efficient and recyclable heterogeneous Brønsted acid catalysts in the asymmetric addition to aromatic aldehydes, enantioselective transfer hydrogenation of ketimines, and three-component direct asymmetric Mannich reactions involving aldimines and cyclic ketones, achieving good to high enantioselectivities (up to 99.5% ee) that surpass those obtained in analogous systems with homogeneous catalysts. This work represents the first successful demonstration of single-crystal structures of homochiral COFs, paving the way for in-depth investigations into structure–property relationships in enantioselective processes and facilitating the design of novel functional chiral organic materials.}, archive = {J_JACS}, author = {Bang Hou and Xing Han and Haomiao Xie and Chen Yuan and Yu Guo and Xinfa Chen and Xianhui Tang and Shengyi Su and Hong Jiang and Zi-Ming Ye and Kent O. Kirlikovali and Yan Liu and Omar K. Farha and Yong Cui}, doi = {10.1021/jacs.5c00458}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12127--12137}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-crystal X-ray structures of homochiral brønsted acidic covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Record-high-molecular-weight polyesters from ring-opening copolymerization of epoxides and cyclic anhydrides catalyzed by hydrogen-bond-functionalized imidazoles. JACS, 147(14), 12115--12126. (www)

  @article{ , abstract = {Polyesters, with potential for degradability and sustainability, are some of the most versatile polymer materials. However, the limitation of molecular weight (MW) presents a barrier to their applications. The synthesis of polyesters with high MW by the ring-opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is promising but rare and challenging. Herein, we report a series of air-stable, hydrogen-bond-functionalized imidazole catalysts for the copolymerization. These catalysts can produce polyesters (4 examples) using cyclohexane oxide (CHO), propylene oxide (PO), phenyl glycidyl ether (PGE), 4-vinyl-1-cyclohexene 1,2-epoxide (VCHO), and phthalic anhydride (PA) with record-high MW: M n = 171.2 kDa for poly(CHO- alt -PA), M n = 518.5 kDa for poly(PO- alt -PA), M n = 100.5 kDa for poly(PGE- alt -PA), and M n = 236.4 kDa for poly(VCHO- alt -PA). Furthermore, it can achieve an unprecedented efficiency of 15.6 kg of polyester/g of catalyst at a molar ratio of catalyst/PA/PO = 1:40000:60000. The record-high MW achieved can be attributed to the unique anionic-cationic coexisting ROCOP mechanism, which can reduce transesterification, chain transfer, and annulation side reactions. All high M n polyesters showed excellent thermal stability, high tensile strength, and a Young’s modulus comparable to some commodity thermoplastics like polystyrene and polylactic acid.}, archive = {J_JACS}, author = {Zhenbiao Xie and Zhenjie Yang and Chenyang Hu and Fu-Quan Bai and Nuonan Li and Zhiwei Wang and Sitian Ku and Xuan Pang and Xuesi Chen and Xianhong Wang}, doi = {10.1021/jacs.5c00426}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12115--12126}, shortjournal = {J. Am. Chem. Soc.}, title = {Record-high-molecular-weight polyesters from ring-opening copolymerization of epoxides and cyclic anhydrides catalyzed by hydrogen-bond-functionalized imidazoles}, volume = {147}, year = {2025}, }
• (2025). Rational design for monodisperse gallium nanoparticles by in situ monitoring with small-angle X-ray scattering. JACS, 147(14), 12105--12114. (www)

  @article{ , abstract = {Colloidal chemistry is a well-known synthetic platform for producing size-uniform nanoparticles. However, the optimization of each material system still relies on a tedious trial-and-error approach in a multiparametric space, commonly referred to as design-of-experiments. This process is particularly laborious for emerging material classes for which only a handful of syntheses have been reported. Alternative approaches for the rational design of colloidal nanoparticles involve studying the reaction with in situ methods, thereby revealing the true underlying rules for the synthesis of monodisperse nanoparticles. Here, we focus on highly promising but little-studied colloidal gallium nanoparticles, using synchrotron-based small-angle X-ray scattering as a highly suitable in situ monitoring technique. We investigate the intertwined effects of process temperature, concentration of reactants, and the sterics of surface ligands during the hot-injection synthesis of gallium colloids. For quantitative comparison, we provide a description of gallium synthesis through the timestamps of partially overlapping reaction, nucleation, and growth stages. Our results reveal the key role of surface ligands in balancing the kinetics of nucleation and growth, as well as in enabling colloidal stability during the synthesis. Furthermore, we demonstrate that the large overlap between the nucleation and growth stages does not preclude the formation of monodisperse gallium nanoparticles. Our in situ experiments suggest several possible strategies for achieving size-uniform colloidal nanoparticles, thus enabling a rational design for the peculiar system of liquid metal nanodroplets and offering insights that can be extended to other monodisperse colloids prepared via hot-injection synthesis.}, archive = {J_JACS}, author = {Florian M. Schenk and Simon Wintersteller and Jasper Clarysse and Hanglin He and Jean-Marc von Mentlen and Nuri Yazdani and Markus Wied and Vanessa Wood and Christian Prehal and Maksym Yarema}, doi = {10.1021/jacs.5c00317}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12105--12114}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design for monodisperse gallium nanoparticles by in situ monitoring with small-angle X-ray scattering}, volume = {147}, year = {2025}, }
• (2025). Motivation on intramolecular through-space charge transfer for the realization of thermally activated delayed fluorescence (TADF)–Thermally stimulated delayed phosphorescence (TSDP) in C^C^N Gold(III) complexes and their applications in organic light-emitting devices. JACS, 147(14), 12092--12104. (www)

  @article{ , abstract = {Thermally activated delayed fluorescence (TADF) and the very recently established thermally stimulated delayed phosphorescence (TSDP) are two promising approaches for enhancing the performance of organic light-emitting devices (OLEDs). Here, we have developed a new class of through-space charge transfer (TSCT) carbazolylgold(III) C^C^N complexes with unique TADF–TSDP properties by introducing a rigid arylamine on the carbazolyl auxiliary ligand. The highly twisted conformation between the C^C^N and carbazolyl ligands induces strong through-bond ligand-to-ligand charge transfer (TB-LLCT) character in their lowest singlet and triplet excited states, with small singlet–triplet energy gaps for efficient TADF. Moreover, the close spatial proximity between the cyclometalating ligand and the lateral arylamine enables appreciable intramolecular through-space electronic coupling that allows the generation of relatively low-lying triplet through-space ligand-to-ligand charge transfer ( 3 TS-LLCT) excited states. The TADF–TSDP properties are verified by temperature-dependent emission, lifetimes, and ultrafast transient absorption studies. Interestingly, through better alignment with extended planarity and the strengthening of the electron-donating ability of the lateral arylamine, the enhanced through-space electronic coupling can effectively perturb the energies of 3 TBCT, 3 TSCT, and intraligand ( 3 IL) excited states and thus manipulates the TSDP efficiency. Orange-emitting vacuum-deposited OLEDs made with these gold(III) complexes demonstrate respectable maximum external quantum efficiencies of >10% and long operational half-lifetimes of up to 65,314 h at a luminance of 100 cd m –2 . This work not only demonstrates the realization of interesting TADF–TSDP and TSCT properties in the gold(III) C^C^N cyclometalated system but also enriches the diversity of molecular design for high-performance TSDP and TSCT emitters.}, archive = {J_JACS}, author = {Panpan Li and Ziyong Chen and Ming-Yi Leung and Shiu-Lun Lai and Shun-Cheung Cheng and Wing-Kei Kwok and Chi-Chiu Ko and Mei-Yee Chan and Vivian Wing-Wah Yam}, doi = {10.1021/jacs.5c00121}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12092--12104}, shortjournal = {J. Am. Chem. Soc.}, title = {Motivation on intramolecular through-space charge transfer for the realization of thermally activated delayed fluorescence (TADF)–Thermally stimulated delayed phosphorescence (TSDP) in C^C^N Gold(III) complexes and their applications in organic light-emitting devices}, volume = {147}, year = {2025}, }
• (2025). Outcompeting thermodynamics: Ion-pairing and coulombic interactions to trigger perfluoroacetate intra-ionic photooxidation for perfluoroalkylation reactions. JACS, 147(14), 12082--12091. (www)

  @article{ , abstract = {Trifluoromethylation is a key transformation in drug and agrochemical synthesis, yet current reagents often suffer from high cost, low atom economy, and low scalability. Trifluoroacetate derivatives represent ideal reagents as they are highly abundant and cheap, but their very positive one electron oxidation potential (∼2.3 V vs NHE) often hampers their widespread use in photoredox catalysis. Indeed, at these potentials, selectively oxidizing trifluoroacetate over reaction solvent or partner substrates becomes challenging. Herein, we present a novel approach that circumvents these limitations through the use of a pentacationic Ir(III) photosensitizer that forms a strong 1:1 ion-pair with trifluoroacetate in acetonitrile ( K eq = 6 × 10 4 M –1 ). This ion-pair formation enables rapid and efficient photooxidation of trifluoroacetate in ∼90 ps without significant solvent or partner substrate oxidation, as indicated by femtosecond and nanosecond UV–visible transient absorption spectroscopy. The CF 3 • radicals so generated are shown to trifluoromethylate a range of partner substrates, including aromatic compounds, heterocycles, natural products and pharmaceutically relevant products, in moderate yields (20–60%). Control experiments reveal that ion-pairing is crucial for the successful generation of CF 3 • as photosensitizers that oxidize trifluoroacetate without forming ion pairs were ineffective for trifluoromethylation. This probably originates from the more thermodynamically accessible substrate oxidation outcompeting diffusional trifluoroacetate oxidation. The reaction was further exemplified to allow functionalization with a variety of perfluoroalkyl groups of different chain lengths. The approach reported herein could also be used for the removal and/or use of perfluoroalkyl substances (PFAS), often called “forever chemicals”, that have recently raised environmental and health concern.}, archive = {J_JACS}, author = {Pengju Li and Céline Bourgois and Felix Glaser and Simon De Kreijger and Alejandro Cadranel and Ludovic Troian-Gautier and Ke Hu}, doi = {10.1021/jacs.5c00129}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12082--12091}, shortjournal = {J. Am. Chem. Soc.}, title = {Outcompeting thermodynamics: Ion-pairing and coulombic interactions to trigger perfluoroacetate intra-ionic photooxidation for perfluoroalkylation reactions}, volume = {147}, year = {2025}, }
• (2025). Exquisite complex reaction cascade in the natural 1,2,4-triazine assembly. JACS, 147(14), 12075--12081. (www)

  @article{ , abstract = {1,2,4-Triazine ring is a scaffold widely found in biologically active compounds, but how nature makes it remains enigmatic. In this study, we unveil the complex enzymatic and nonenzymatic cascade reactions that assemble the 1,2,4-triazine moiety found in the structures of the natural products pseudoiodinine and toxoflavin. Through biochemical studies, isotope labeling, and the application of substrate analogues, we propose a plausible pathway for the 1,2,4-triazine assembly from a common precursor in riboflavin biosynthesis. This process involves four two-electron oxidation steps, C–N bond formation, decarboxylation, and the N–N bond forming step catalyzed by a metal-dependent WD40-repeat (WDR) protein. This study thus not only provides the first biocatalytic route for the 1,2,4-triazine assembly but also identifies a previously unrecognized catalytic role of a large WDR protein family.}, archive = {J_JACS}, author = {Yiyuan Cheng and Haoran Pang and Wenjun Zhang}, doi = {10.1021/jacs.4c18761}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12075--12081}, shortjournal = {J. Am. Chem. Soc.}, title = {Exquisite complex reaction cascade in the natural 1,2,4-triazine assembly}, volume = {147}, year = {2025}, }
• (2025). Inner–Outer sheath synergistic shielding of polysulfides in asymmetric solvent-based electrolytes for stable Sodium–Sulfur batteries. JACS, 147(14), 12061--12074. (www)

  @article{ , abstract = {Room-temperature sodium–sulfur (RT Na–S) batteries are garnering interest owing to their high theoretical energy density and low cost. However, the notorious shuttle behavior of sodium polysulfides (NaPS) and uncontrollable dendrite growth lead to the poor cycle stability of RT Na–S cells. In this work, we report the use of 1,2-dimethoxypropane (DMP) and 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether (TFTFE) as inner solvent and outer diluent, respectively, in a localized high-concentration electrolyte system. Impressively, the asymmetric DMP as the inner solvent, introduced to replace the conventional solvent 1,2-dimethoxyethane (DME), shields NaPS effectively from incorporation into the inner solvation structure due to the extra methyl groups in the molecular structure. Furthermore, the TFTFE diluent, which contains electron-withdrawing perfluoro segments (−CF 3 – and −CF 2 −), exhibits significantly low solvation power. Consequently, the outer sheath TFTFE diluent further minimizes NaPS dissolution, thereby enhancing the cycle stability. This inner–outer sheath synergistic effect leads to the formation of highly effective cathode-electrolyte interphase (CEI) and solid-electrolyte interphase (SEI) layers simultaneously, significantly alleviating the shuttle effect and reducing the side reactions between NaPS and sodium metal. Remarkably, the Na–S cells with the designed electrolyte present long-cycling reversibility with 530 mAh g –1 over 600 cycles at a C/2 rate and a low capacity decay rate of 0.077% per cycle. This study provides a profound understanding of the electrolyte structure involving NaPS and offers a firm basis for the rational design of electrolytes for rechargeable metal–sulfur battery systems.}, archive = {J_JACS}, author = {Weiqi Yao and Min-Hao Pai and Arumugam Manthiram}, doi = {10.1021/jacs.4c18374}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12061--12074}, shortjournal = {J. Am. Chem. Soc.}, title = {Inner–Outer sheath synergistic shielding of polysulfides in asymmetric solvent-based electrolytes for stable Sodium–Sulfur batteries}, volume = {147}, year = {2025}, }
• (2025). Excited-state aromatization drives nonequilibrium planarization dynamics. JACS, 147(14), 12051--12060. (www)

  @article{ , abstract = {Excited-state aromaticity is one of the most widely applied concepts in the field of chemistry, often used as a rational guideline for predicting conformational changes of cyclic π-conjugated systems induced by photoexcitation. Yet, the details of the relationship between the corresponding photoinduced electronic and structural dynamics have remained unclear. In this work, we applied femtosecond transient absorption and time-resolved time-domain Raman spectroscopies to track the nonequilibrium planarization dynamics of a cyclooctatetraene (COT) derivative associated with the excited-state aromaticity. In the femtosecond time-resolved Raman data, the bent-to-planar structural change was clearly captured as a continuous peak shift of the marker band, which was unambiguously identified with 13 C labeling. Our findings show that the planarization occurs after a significant change in the electronic structure, suggesting that the system first becomes aromatic, followed by a conformational change. This work provides a unique framework for understanding the excited-state aromaticity from a dynamical aspect.}, archive = {J_JACS}, author = {Yusuke Yoneda and Tomoaki Konishi and Kensuke Suga and Shohei Saito and Hikaru Kuramochi}, doi = {10.1021/jacs.4c18623}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12051--12060}, shortjournal = {J. Am. Chem. Soc.}, title = {Excited-state aromatization drives nonequilibrium planarization dynamics}, volume = {147}, year = {2025}, }
• (2025). Infrared spectroscopic signatures of the fluorous effect arise from a change of conformational dynamics. JACS, 147(14), 12040--12050. (www)

  @article{ , abstract = {Per- and polyfluoroalkyl substances (PFAS) are synthetic compounds widely employed in society due to their chemical inertness. These substances accumulate in the environment, from where they enter human bodies, leading to harmful effects like cancer. PFAS exhibit omniphobic properties, which often cause them to separate from both aqueous and organic phases, forming a fluorous phase. Yet, the physical nature of this fluorous effect is unknown. Here, we shed light on the fluorous effect by analyzing the infrared absorption spectra of perfluorinated and semifluorinated alkanes in various solvents. We find that specific bands in the C–F stretching vibrational region exhibit selective behaviors in fluorous and nonfluorous environments. In a fluorous environment, these bands undergo significant broadening, and the asymmetric CF 3 stretching bands decrease in intensity. Using static density functional theory calculations and force-field molecular dynamics simulations, we decipher the underlying molecular mechanisms: The decrease in absorption intensities is related to the intermolecular vibrational coupling of the perfluoroalkyl chains, while an acceleration of conformational changes in the carbon backbone of the molecules causes the observed band broadening. Given the high specificity of the reported spectral changes to a fluorous environment, bands in the C–F stretching range can serve as spectroscopic markers for the fluorous phase, facilitating the study of PFAS aggregation. Such knowledge can lead to the rational design of absorber materials for PFAS, which are aimed at mitigating their environmental impact.}, archive = {J_JACS}, author = {R. Cruz and M. R. Becker and J. Kozuch and K. Ataka and R. R. Netz and J. Heberle}, doi = {10.1021/jacs.4c18434}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12040--12050}, shortjournal = {J. Am. Chem. Soc.}, title = {Infrared spectroscopic signatures of the fluorous effect arise from a change of conformational dynamics}, volume = {147}, year = {2025}, }
• (2025). 3-center-3-electron σ-adduct enables silyl radical transfer below the minimum barrier for silyl radical formation. JACS, 147(14), 12024--12039. (www)

  @article{ , abstract = {Transition-metal-catalyzed cleavage of the Si–H bond in silanes to yield silyl radicals requires substantial amounts of energy, which are commonly supplied by photons. For Rh(II) porphyrins, efficient hydrosilylation catalysis becomes accessible only upon site isolation in a metal–organic framework (MOF), and the formation of free silyl radicals likewise requires irradiation. Within the MOF, however, an uncommonly facile direct silyl radical transfer to olefin substrates is also possible, which makes thermal olefin hydrosilylation accessible at room temperature. The ability of MOF-supported Rh(II) metalloradicals to furnish an unprecedented 3-center-3-electron (3c-3e) Rh(II)-silane σ-adduct enables the assembly of a tricomponent transition state that is comprised of Rh(II), silane, and ethylene. The tricomponent transition state bypasses the high-energy silyl radical species and enables silyl radical transfer with an activation free energy ∼15 kcal·mol –1 below the minimum energy barrier for silyl radical formation. We report direct observation of the 3c-3e silane σ-adduct, which is a stable species in the absence of light and olefins. Furthermore, a combination of experiments and quantum chemical calculations shows that direct silyl radical transfer to ethylene is promoted by the temporary oxidation of the transition structure by a proximal Rh(II) center. Thus, the crucial role of the MOF matrix is to fix the inter-Rh separation in our catalyst at a value large enough for 3c-3e silane adduct formation but short enough for facile electron transfer.}, archive = {J_JACS}, author = {Zihang Qiu and Paolo Cleto Bruzzese and Zikuan Wang and Hao Deng and Markus Leutzsch and Christophe Farès and Sonia Chabbra and Frank Neese and Alexander Schnegg and Constanze N. Neumann}, doi = {10.1021/jacs.4c18445}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12024--12039}, shortjournal = {J. Am. Chem. Soc.}, title = {3-center-3-electron σ-adduct enables silyl radical transfer below the minimum barrier for silyl radical formation}, volume = {147}, year = {2025}, }
• (2025). Polarization rearrangement induced high-efficiency piezocatalytic overall pure water splitting in ultrathin (001)-confined PbTiO3. JACS, 147(14), 12012--12023. (www)

  @article{ , abstract = {Facing the emergencies of global warming and energy shortages, nano ferroelectrics, which exhibit superior charge separation capabilities and polarization tunability, are extensively utilized in piezocatalytic H 2 production. However, acquiring polarized structures that behave with robust ferroelectricity and strong piezoelectricity in ultralow dimension nanomaterials for efficient piezocatalysis remains a huge challenge. This research achieved exceptional piezocatalytic overall pure water splitting performance in 3.5 nm-thick (001)-confined PbTiO 3 nanosheets, reaching a H 2 evolution rate of 1068 μmol g –1 h –1 , exceeding those of similar ferroelectric oxides. The highly confined crystallographic polarization orientation in nanosheets induced polarization rearrangement from the c -axis to other nonpolarized crystallographic orientations, as evidenced by piezoelectric force microscopy and phase field simulations, which improve piezoelectricity and boost piezocatalytic behavior significantly. Local structure investigations jointly by neutron pair distribution function, X-ray absorption spectrum, and atomic-scale scanning transmission electron microscopy methods show that the rearranged structure arises from the lattice inhomogeneous tensile strain. TiO 6 octahedrons were distorted, with the Ti atom moving diagonally toward the symmetry center. Such ferroelectric reconstruction of a practical nanopolarized structure with remarkable performance in this work will promote the development of high-performance nano ferroelectrics.}, archive = {J_JACS}, author = {Peixi Zhang and Qiang Li and Ran Su and Haoyu Wang and Xiaoming Shi and Shiqing Deng and Yang Bai and Hua Zeng and Xiaoxia Yu and Zhiguo Li and Han Wu and Fan Xue and Mingxin Lv and Chengyi Yu and Yili Cao and Xin Chen and Jinxia Deng and Jun Miao and Kun Lin and Xianran Xing}, doi = {10.1021/jacs.4c18542}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {12012--12023}, shortjournal = {J. Am. Chem. Soc.}, title = {Polarization rearrangement induced high-efficiency piezocatalytic overall pure water splitting in ultrathin (001)-confined PbTiO3}, volume = {147}, year = {2025}, }
• (2025). Bacillus subtilis utilizes decarboxylated S-adenosylmethionine for the biosynthesis of tandem aminopropylated microcin c, a potent inhibitor of bacterial aspartyl-tRNA synthetase. JACS, 147(14), 11998--12011. (www)

  @article{ , abstract = {The biosynthetic pathways of natural products involve unusual biochemical reactions catalyzed by unique enzymes. Aminopropylation, although apparently simple, is an extremely rare modification outside polyamine biosynthesis. The canonical pathway used in the biosynthesis of peptide-adenylate antibiotic microcin C of E. coli ( Eco -McC) entails alkylation by the S -adenosyl-methionine-derived 3-amino-3-carboxypropyl group of the adenylate moiety and subsequent decarboxylation to yield the bioactive aminopropylated compound. Here, we report the structure and biosynthesis of a new member of the microcin C family of antibiotics, Bsu -McC, produced by Bacillus subtilis MG27, which employs an alternative aminopropylation pathway. Like Eco -McC, Bsu -McC consists of a peptide moiety that facilitates prodrug import into susceptible bacteria and a warhead, a nonhydrolyzable modified isoasparaginyl-adenylate, which, when released into the cytoplasm, binds aspartyl-tRNA synthetase (AspRS) inhibiting translation. In contrast to the Eco -McC, whose warhead carries a single aminopropyl group attached to the phosphate moiety of isoasparaginyl-adenylate, the warhead of Bsu -McC is decorated with a tandem of two aminopropyl groups. Our in silico docking of the Bsu -McC warhead to the AspRS-tRNA complex suggests that two aminopropyl groups form extended interactions with the enzyme and tRNA, stabilizing the enzyme–inhibitor complex. We show that tandem aminopropylation results in a 32-fold increase in the biological activity of peptidyl-adenylate. We also show that B. subtilis adopted an alternative pathway for aminopropylation in which two homologous 3-aminopropyltransferases utilize decarboxylated S-adenosylmethionine as a substrate. Additionally, Bsu -McC biosynthesis alters the social behavior of the B. subtilis producer strain, resulting in a sharp decrease in their ability to form biofilms.}, archive = {J_JACS}, author = {Alexey Kulikovsky and Eldar Yagmurov and Anastasiia Grigoreva and Aleksandr Popov and Konstantin Severinov and Satish K. Nair and Guy Lippens and Marina Serebryakova and Sergei Borukhov and Svetlana Dubiley}, doi = {10.1021/jacs.4c18468}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11998--12011}, shortjournal = {J. Am. Chem. Soc.}, title = {Bacillus subtilis utilizes decarboxylated S-adenosylmethionine for the biosynthesis of tandem aminopropylated microcin c, a potent inhibitor of bacterial aspartyl-tRNA synthetase}, volume = {147}, year = {2025}, }
• (2025). How temperature change affects the lattice parameters, molecular conformation, and reaction cavity in enantiomeric and racemic crystals of thalidomide. JACS, 147(14), 11988--11997. (www)

  @article{ , abstract = {For the single crystals of thalidomide (C 13 H 10 N 2 O 4 , TD) grown by the solvent evaporation method, the temperature dependences of the crystal structures have been investigated over a wide temperature range between 100 and 423.15 K. Comparing the α-form of a racemic TD crystal, which consists of symmetric heterochiral dimers and belongs to P 2 1 / n space group, with the enantiomeric TD crystal, which belongs to P 2 1 and consists of asymmetric (pseudosymmetric) homochiral dimers, there have been clear differences in the temperature-dependent changes of the lattice parameters, the isobaric linear thermal expansion coefficients (along the crystallographic and the principal Cartesian axes), the volumetric expansion coefficients of the unit cell, and the structures of hydrogen-bonded dimer in the crystal such as intra- and intermolecular dihedral angles, cavities (reaction cavities), and the hydrogen-bond length. In the asymmetric homochiral dimers, one monomer with a larger reaction cavity changes its intramolecular dihedral angle with temperature, while the other monomer with a smaller cavity does not. In contrast, in the symmetric heterochiral dimers, two monomers with the same cavity volume similarly change their intramolecular dihedral angles with the temperature. Such differences in the temperature-dependent conformational changes between asymmetric and symmetric dimers cause differences between enantiomeric and racemic crystals.}, archive = {J_JACS}, author = {Ayaka Matsumoto and Kenta Nakagawa and Takuya Nakanishi and Akiko Sekine and Sosuke Kojo and Mizuki Kira and Sota Sato and Norio Shibata and Toru Asahi}, doi = {10.1021/jacs.4c18394}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11988--11997}, shortjournal = {J. Am. Chem. Soc.}, title = {How temperature change affects the lattice parameters, molecular conformation, and reaction cavity in enantiomeric and racemic crystals of thalidomide}, volume = {147}, year = {2025}, }
• (2025). Chemoselective hydrogenation of halonitrobenzenes by platinum nanoparticles with auxiliary Co–N4 single sites in sandwiched catalysts. JACS, 147(14), 11975--11987. (www)

  @article{ , abstract = {The chemoselective hydrogenation of halonitrobenzenes to haloanilines is of great importance but remains challenging to simultaneously achieve high catalytic activity, excellent selectivity, and good reusability, especially for ortho -substituted substrates. This is due to the occurrence of hydrogenolysis of halogen groups, as well as the easy migration and aggregation of active species on the catalyst surface during the hydrogenation of nitro groups. In this study, we integrate Pt nanoparticles (NPs) with auxiliary Co–N 4 single sites from a porphyrinic metal–organic framework [known as PCN-221(Co)] in a sandwiched nanostructure as a catalyst for the chemoselective hydrogenation of ortho -halonitrobenzenes at 80 °C and 1 MPa H 2 in a 50 mL batch microreactor. This sandwiched catalyst achieves 97.3% selectivity for ortho -chloroaniline at nearly complete conversion of ortho -chloronitrobenzene, with an exceptionally high turnover frequency (TOF) of 11,625 h –1 and good reusability over ten cycles, outperforming state-of-the-art heterogeneous supported metal catalysts. Theoretical and experimental investigations reveal that the nitro group in ortho -chloronitrobenzene is preferentially hydrogenated by Pt NPs, while the ortho -chloro group is selectively adsorbed by Co–N 4 single sites in PCN-221(Co), preventing its hydrogenolysis and enhancing selectivity for ortho -chloroaniline. Furthermore, the PCN-221(Co) shell in the sandwiched catalyst plays a key role in enriching ortho -chloronitrobenzene and stabilizing the supported Pt NPs, thus leading to high catalytic activity and good reusability. Additionally, at nearly complete conversion of ortho -fluoronitrobenzene and ortho -bromonitrobenzene, this sandwiched Pt catalyst displays 100% selectivity for ortho -fluoroaniline with a TOF of 8680 h –1 and 99.2% selectivity for ortho -bromoaniline with a TOF of 5859 h –1 , respectively. When meta - and para -halonitrobenzenes are used as substrates, high activity and excellent selectivity for the corresponding haloanilines are also achieved by the sandwiched Pt catalysts.}, archive = {J_JACS}, author = {Tian Lin and Zhouwen Cao and Junqi Pei and Bohua Wang and Hanlin Liu and Bin Tu and Caoyu Yang and Fengbin Zheng and Wenxing Chen and Qiaojun Fang and Wei Liu and Zhiyong Tang and Guodong Li}, doi = {10.1021/jacs.4c18288}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11975--11987}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemoselective hydrogenation of halonitrobenzenes by platinum nanoparticles with auxiliary Co–N4 single sites in sandwiched catalysts}, volume = {147}, year = {2025}, }
• (2025). A lanthanide Nanoparticle–Aggregation-induced emission photosensitizer complex system drives coupled triplet energy transfer for enhanced radio-photodynamic therapy. JACS, 147(14), 11964--11974. (www)

  @article{ , abstract = {Cerenkov light (CL), utilized as an internal excitation source for photodynamic therapy (PDT), addresses the limitations of laser penetration and has substantial potential for seamlessly integrating clinical radiotheranostics with phototheranostics. Nevertheless, the effectiveness of CL-mediated PDT is significantly hindered by challenges, such as the low intensity of CL and inadequate energy transfer between the CL donor and photosensitizers (PSs). In this study, a novel approach is introduced for enhanced radionuclide-activated radio-photodynamic therapy utilizing a hybrid nanoparticle system composed of lanthanide nanoparticles and an aggregation-induced emission photosensitizer (AIE PS), designated LnNP–TQ NPs. This system enables lanthanide nanoparticles to optimize the decay energy of radionuclides, effectively sensitizing the AIE PS through triplet energy transfer (TET)-mediated processes with an efficiency approaching 100%. When activated by the clinical radionuclide 18 F for positron emission tomography imaging, the LnNP–TQ NPs substantially inhibited tumor growth via effective singlet oxygen ( 1 O 2 ) generation. This strategy, which optimally harnesses radionuclide energy and achieves efficient energy transfer, offers a promising pathway for enhancing radiotherapy–phototherapy efficacy in tumor treatment.}, archive = {J_JACS}, author = {Yibo An and Dazhuang Xu and Pan He and Ziying Wang and Yun Li and Jiang Ming and Renyuan Liu and Jingchao Li and Zhixiang Lu and Gang Liu}, doi = {10.1021/jacs.4c18033}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11964--11974}, shortjournal = {J. Am. Chem. Soc.}, title = {A lanthanide Nanoparticle–Aggregation-induced emission photosensitizer complex system drives coupled triplet energy transfer for enhanced radio-photodynamic therapy}, volume = {147}, year = {2025}, }
• (2025). O-cyanobenzaldehydes irreversibly modify both buried and exposed lysine residues in live cells. JACS, 147(14), 11955--11963. (www)

  @article{ , abstract = {Lysine residue represents an attractive site for covalent drug development due to its high abundance (5.6%) and critical functions. However, very few lysines have been characterized to be accessible to covalent ligands and perturb the protein functions, owing to their protonation state and adjacent steric hindrance. Herein, we report a new lysine bioconjugation chemistry, O -cyanobenzaldehyde (CNBA), that enables selective modification of the lysine ε-amine to form iso-indolinones under physiological conditions. Activity-based proteome profiling enabled the mapping of 3451 lysine residues and 85 endogenous kinases in live cells, highlighting its potential for modifying hyper-reactive lysines within the proteome or buried catalytic lysines within the kinome. Further protein crystallography and mass spectrometry confirmed that K271_ABL1 and K162_AURKA are covalently targetable sites in kinases. Leveraging a structure-based drug design, we incorporated CNBA into the core structure of Nutlin-3 to irreversibly inhibit the MDM2-p53 interaction by targeting an exposed lysine K94 on the surface of murine double minute 2. Importantly, we have demonstrated the potential application of CNBA as a lysine-recognized bioconjugation agent for developing new antibody-drug conjugates. The results collectively validate CNBA as a new selective and efficient modifying agent with broad applications for both buried and exposed lysine residues in live cells.}, archive = {J_JACS}, author = {Huan Ling and Lin Li and Liping Duan and Weixue Huang and Jiangnan Zheng and Shijie Zhang and Xinling Li and Xiaorong Qiu and Yang Zhou and Nan Ma and Xiaomei Ren and Jinwei Zhang and Zhen Wang and Yujun Zhao and Ruijun Tian and Zhi-Min Zhang and Ke Ding}, doi = {10.1021/jacs.4c18006}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11955--11963}, shortjournal = {J. Am. Chem. Soc.}, title = {O-cyanobenzaldehydes irreversibly modify both buried and exposed lysine residues in live cells}, volume = {147}, year = {2025}, }
• (2025). Polymorphic ROYalty: The 14th ROY polymorph discovered via high-throughput crystallization. JACS, 147(14), 11949--11954. (www)

  @article{ , abstract = {Polymorphism, when a substance can exist in more than one crystalline form yet return to the same liquid or solution phase, is characterized by differences in packing or molecular conformation. Polymorphs often exhibit differing physical properties, and are therefore particularly important in the development of materials and pharmaceuticals. However, gaining a thorough understanding of the solid-state landscape of a molecule requires exhaustive experimental screening of crystallization conditions, a particular challenge when using classical crystallization methods. We show that high-throughput Encapsulated Nanodroplet Crystallization (ENaCt) can enable the rapid and efficient exploration of the solid-state landscape of highly polymorphic molecules, through an in-depth study of 5-methyl-2-((2-nitrophenyl)amino)thiophene-3-carbonitrile (ROY), the most polymorphic small molecule known. An ENaCt screen encompassing 1536 individual crystallization experiments, spanning 320 unique conditions, resulted in direct access to single crystals, suitable for X-ray diffraction analysis, for all six of the known polymorphs accessible from solution (Y, R, YN, ON, ORP and R18). In addition, two polymorphs (Y04 and Y19) previously accessed only via melt and heteroseeded melt experiments, and a new polymorph of ROY (O22) were obtained. Furthermore, ENaCt screening resulted in the identification of the first ROY solvate (ROY· methyl anthranilate) and the first example of a ROY dimer, formed via in situ oxidation. ENaCt is thus shown to be an impactful tool for the experimental mapping of the solid-state landscape of highly polymorphic molecules and, through the discovery of a new polymorph O22, has ensured that tetradecamorphic ROY retains the record for the most polymorphic small molecule.}, archive = {J_JACS}, author = {Jake Weatherston and Michael R. Probert and Michael J. Hall}, doi = {10.1021/jacs.4c17826}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11949--11954}, shortjournal = {J. Am. Chem. Soc.}, title = {Polymorphic ROYalty: The 14th ROY polymorph discovered via high-throughput crystallization}, volume = {147}, year = {2025}, }
• (2025). Bilayer kagome ferrimagnet exhibiting exceptional spontaneous exchange bias in TbMn6(Ge,Ga)6. JACS, 147(14), 11941--11948. (www)

  @article{ , abstract = {Manipulating interlayer interactions in two-dimensional (2D) materials has led to intriguing behaviors. Borrowing these 2D signatures to bulk materials is likely to unlock exceptional properties. Here, we report an emergent 2D-like bilayer Kagome ferrimagnet through reducing the interbilayer magnetic interaction to nearly zero. This concept is realized within bulk TbMn 6 (Ge,Ga) 6 compounds, characterized by an isolated and pure Mn Kagome lattice, simply by the chemical substitution of Ge with Ga. Specifically, the targeted compound TbMn 6 Ge 5 Ga 1 exhibits a giant spontaneous exchange bias (SEB) of approximately 1.6 T, which is more than twice that observed in known materials. Field-dependent neutron diffraction reveals the robust nature of the compensated ferrimagnetic (FiM), characterized by almost two-thirds of the moments being pinned and irreversible under fields up to 9 T. Through magnetic and structural analysis, alongside theoretical calculations, we demonstrate that the substantial SEB is related to the intense competition between local robust and weak FiM states within the bilayer Kagome configuration, which are stabilized by an incommensurate spin arrangement. The concept of a bilayer Kagome magnet offers new opportunities for discovering attractive properties in 2D-like materials.}, archive = {J_JACS}, author = {Hankun Xu and Wenjie Li and Junjie Chen and Sergii Khmelevskyi and Dmitry Khalyavin and Pascal Manuel and Chuanying Xi and Shogo Kawaguchi and Jing Chen and Wanda Yang and Qinghua Zhang and Yili Cao and Chengyi Yu and Yang Ren and Kun Lin and Xianran Xing}, doi = {10.1021/jacs.4c17505}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11941--11948}, shortjournal = {J. Am. Chem. Soc.}, title = {Bilayer kagome ferrimagnet exhibiting exceptional spontaneous exchange bias in TbMn6(Ge,Ga)6}, volume = {147}, year = {2025}, }
• (2025). Adding a twist to lateral flow immunoassays: A direct replacement of antibodies with helical affibodies, from selection to application. JACS, 147(14), 11925--11940. (www)

  @article{ , abstract = {Immunoreagents, most commonly antibodies, are integral components of lateral flow immunoassays. However, the use of antibodies comes with limitations, particularly relating to their reproducible production, and poor thermal and chemical stability. Here, we employ phage display to develop affibodies, a class of nonimmunoglobulin affinity proteins based on a small three-helix bundle scaffold, against SARS-CoV-2 Spike protein. Subsequently, we demonstrate the utility and viability of affibodies to directly replace antibodies in lateral flow immunoassays. In addition, we highlight several physiochemical advantages of affibodies, including their ability to withstand exposure to high temperature and humidity while maintaining superior performance compared to their antibody counterparts. Furthermore, we investigate the adsorption mechanism of affibodies to the surface of gold nanoparticle probes via a His 6 -tag, introduced to also facilitate recombinant purification. Through molecular dynamics simulations, we elucidate the structural and physical characteristics of affibody dimers which result in high-performing detection probes when immobilized on nanoparticle surfaces. This work demonstrates that affibodies can be used as direct replacements to antibodies in immunoassays and should be further considered as alternatives owing to their improved physiochemical properties and modular design.}, archive = {J_JACS}, author = {Christy J. Sadler and Adam Creamer and Kim Anh Giang and Kevion K. Darmawan and André Shamsabadi and Daniel A. Richards and Johan Nilvebrant and Jonathan P. Wojciechowski and Patrick Charchar and Ross Burdis and Francesca Smith and Irene Yarovsky and Per-Åke Nygren and Molly M. Stevens}, doi = {10.1021/jacs.4c17452}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11925--11940}, shortjournal = {J. Am. Chem. Soc.}, title = {Adding a twist to lateral flow immunoassays: A direct replacement of antibodies with helical affibodies, from selection to application}, volume = {147}, year = {2025}, }
• (2025). Precision self-assembly of 3D DNA crystals using microfluidics. JACS, 147(14), 11915--11924. (www)

  @article{ , abstract = {Controlling the uniformity in size and quantity of macroscopic three-dimensional (3D) DNA crystals is essential for their integration into complex systems and broader applications. However, achieving such control remains a major challenge in DNA nanotechnology. Here, we present a novel strategy for synthesizing monodisperse 3D DNA single crystals using microfluidic double-emulsion droplets as nanoliter-scale microreactors. These uniformly sized droplets can shrink and swell without leaking their inner contents, allowing the concentration of the DNA solution inside to be adjusted. The confined volume ensures that, once a crystal seed forms, it rapidly consumes the available DNA material, preventing the formation of additional crystals within the same droplet. This approach enables precise control over crystal growth, resulting in a yield of one DNA single crystal per droplet, with a success rate of up to 98.6% ± 0.9%. The resulting DNA crystals exhibit controlled sizes, ranging from 19.3 ± 0.9 μm to 56.8 ± 2.6 μm. Moreover, this method can be applied to the controlled growth of various types of DNA crystals. Our study provides a new pathway for DNA crystal self-assembly and microengineering.}, archive = {J_JACS}, author = {Xugen Chen and Pan Fu and Karol Woloszyn and Yuemeng Zhang and Huanhuan Hu and Likai Hou and Xiaoyu Li and Jia Liu and Wenting Jiang and Lebing Wang and Simon Vecchioni and Yoel P. Ohayon and Ruojie Sha and Jianping Zheng and Feng Zhou}, doi = {10.1021/jacs.4c17455}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11915--11924}, shortjournal = {J. Am. Chem. Soc.}, title = {Precision self-assembly of 3D DNA crystals using microfluidics}, volume = {147}, year = {2025}, }
• (2025). Ligand-controlled regioselective dearomative vicinal and conjugate hydroboration of quinolines. JACS, 147(14), 11906--11914. (www)

  @article{ , abstract = {A dearomative strategy to regioselectively modify arenes using a “diene” synthon within aromatic rings provides access to highly functionalized heterocycles from abundant aromatic feedstocks and represents an alternative synthetic approach besides traditional cross-coupling and C–H functionalization methodologies. In this study, we present an efficient method for selectively introducing boron onto quinolines through dearomative hydroboration using easily accessible and stable phosphine-ligated borane complexes. The vicinal 5,6- and conjugate 5,8-hydroborated products could be obtained regioselectively by modifying the phosphine ligand. Drawing inspiration from diverse organoboron transformations, these borane building blocks were diversified by a range of downstream functionalizations, providing modular pathways for the skeletal modifications of quinolines to access a variety of challenging functionalized heterocycles.}, archive = {J_JACS}, author = {Chao Hu and Chen-Yan Cai and Elizabeth S. Barta and Rohan R. Merchant and Bryan S. Matsuura and Si-Jie Chen and Shuming Chen and Tian Qin}, doi = {10.1021/jacs.4c17247}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11906--11914}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand-controlled regioselective dearomative vicinal and conjugate hydroboration of quinolines}, volume = {147}, year = {2025}, }
• (2025). Mechanistic characterization of diterpene synthase pairs for tricyclic diterpenes from cyanobacteria. JACS, 147(14), 11896--11905. (www)

  @article{ , abstract = {In recent years, genome mining in cyanobacteria has revealed abundant gene clusters related to natural product biosynthesis. However, only a few terpene synthases (TSs) have been identified from this bacterial phylum. Pfam profiles, such as PF03936 and PF19086, which are frequently used for TS retrieval, are built from plant, bacterial, and fungal TSs. Herein, we constructed a new hidden Markov model (HMM) specific to bacterial TSs on the basis of 110 bacterial TSs experimentally validated in recent years. Using this model, we identified a pair of diterpene synthases, Cpt11 (class II TS) and Cts11 (class I TS), in the cyanobacterium Scytonema tolypothrichoides . In vitro experiments demonstrated that Cpt11 catalyzes the formation of syn -copalyl diphosphate from geranylgeranyl diphosphate and that Cts11 subsequently converts syn -copalyl diphosphate into a rare 6,6,7-tricyclic diterpene alcohol. Its biosynthesis was established through isotope labeling experiments, which revealed a unique sequence of a 1,6-proton shift and ring expansion to a seven-membered ring. We solved the crystal structure of Cts11 at a resolution of 1.76 Å. Additionally, via site-directed mutagenesis experiments, we identified two amino acid residues whose exchanges affected the formation of the original diterpene alcohol, leading to the formation of two new compounds: a 6,6,7-tricyclic diterpene hydrocarbon and another 6,6,6-tricyclic diterpene alcohol. A BLAST search revealed several sequences that shared over 70% identity with Cts11 from cyanobacteria that could produce diverse diterpenes. This study demonstrates the potential for cyanobacteria to produce unprecedented terpenoids and lays the foundation for studying the physiological activities of terpenoids in cyanobacteria.}, archive = {J_JACS}, author = {Jiayi Yu and Taro Shiraishi and Kizerbo A. Taizoumbe and Yusaku Karasuno and Ayako Yoshida and Makoto Nishiyama and Jeroen S. Dickschat and Tomohisa Kuzuyama}, doi = {10.1021/jacs.4c16710}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11896--11905}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic characterization of diterpene synthase pairs for tricyclic diterpenes from cyanobacteria}, volume = {147}, year = {2025}, }
• (2025). Low-temperature direct arylation polymerization for the sustainable synthesis of a library of low-defect Donor–Acceptor conjugated polymers via Pd/Ag dual-catalysis. JACS, 147(14), 11886--11895. (www)

  @article{ , abstract = {Donor–acceptor alternating conjugated polymers (D–A CPs) are one of the best materials for high-performance organic electronic devices, owing to their low bandgap and high charge carrier mobility. However, most of the D–A CPs are synthesized by less sustainable polymerization methods. To address this issue, direct arylation polymerization (DArP), eliminating the need for transmetalating agents, was developed over the past two decades. Nevertheless, C–H activation during DArP still requires significantly harsh reaction conditions, limiting the precision and applicability of CPs. In this report, we demonstrate a versatile and sustainable Pd/Ag dual-catalytic DArP conducted at low or even room temperatures, thereby yielding low-defect D–A CPs. Initially, electron-deficient acceptor substrates with various electronic properties and p K a underwent successful concerted-metalation-deprotonation (CMD) via Ag catalysis with mild conditions and highly chemoselective Pd-catalyzed C–C coupling. This synergistic dual-catalysis allowed for the library synthesis of D–A and A–A CPs from acceptor C–H monomers and aryl halide monomers at low temperatures (25–70 °C) in sustainable solvents such as p -cymene. Interestingly, the D–A CPs obtained via Pd/Ag DArP displayed higher structural regularity and crystallinity, eventually outperforming those prepared by conventional synthetic methods in device performances of ambipolar organic field-effect transistors (μ e up to 0.80 cm 2 V –1 s –1 ) and complementary metal-oxide semiconductor inverters (gain up to 102).}, archive = {J_JACS}, author = {Hwangseok Kim and Hyeonjin Yoo and Hongsik Kim and Jun-Mo Park and Byoung Hoon Lee and Tae-Lim Choi}, doi = {10.1021/jacs.4c16831}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11886--11895}, shortjournal = {J. Am. Chem. Soc.}, title = {Low-temperature direct arylation polymerization for the sustainable synthesis of a library of low-defect Donor–Acceptor conjugated polymers via Pd/Ag dual-catalysis}, volume = {147}, year = {2025}, }
• (2025). Synthesis and superconductivity of ternary a15-(Lu, Y)4H23 at high pressures. JACS, 147(14), 11879--11885. (www)

  @article{ , abstract = {Ternary hydrides, formed by introducing new elements into binary hydrides, are a crucial pathway for enhancing superconducting transition temperatures ( T c ) or reducing the stable pressures. In this work, we have acquired the ternary hydride formed by Lu and Y atoms, inspired by the low stabilization pressure of the Lu–H system with its fully filled 4 f electrons, as well as the higher T c of the Y–H system. By effectively controlling the high-pressure and high-temperature conditions, we have successfully synthesized Pm -3 n (Lu, Y) 4 H 23 (A15-type). The synthesized Pm -3 n (Lu, Y) 4 H 23 reveals the highest T c of 112 K at 215 GPa, which is the record T c among A15-type superconductors. Compared to the binary Pm -3 n Lu 4 H 23 , the Pm -3 n (Lu, Y) 4 H 23 exhibits a 60% increase in T c and a 61% enhancement in the upper critical field μ 0 H c2 (0). Interestingly, Pm -3 n (Lu, Y) 4 H 23 displays minimal volume expansion and a slight increase in the H–H bond distance relative to Pm -3 n Lu 4 H 23 due to the introduction of Y atoms. Combined theoretical and experimental analyses indicate that the substitution of Lu atoms with Y atoms enhances electron–phonon coupling (EPC) through modified electronic bands and phonon softening caused by the expansion of H–H bonds, collectively driving the significant enhancement of T c in Pm -3 n (Lu, Y) 4 H 23 . Our work demonstrates a crucial strategy for adjusting and enhancing the superconducting performance of hydrides and offers valuable practical experience for developing ternary hydrides.}, archive = {J_JACS}, author = {Kexin Zhang and Jingkun Yu and Yuchen Zhang and Jianning Guo and Yulong Wang and Chuang Jiang and Xiaoli Huang and Tian Cui}, doi = {10.1021/jacs.4c16805}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11879--11885}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis and superconductivity of ternary a15-(Lu, Y)4H23 at high pressures}, volume = {147}, year = {2025}, }
• (2025). Kinetic steering of amyloid formation and polymorphism by canagliflozin, a type-2 diabetes drug. JACS, 147(14), 11859--11878. (www)

  @article{ , abstract = {Amyloid formation is involved in widespread health conditions such as Alzheimer’s disease, Parkinson’s disease, and type-2 diabetes. Amyloid fibrils have a similar cross-β architecture, but fibrils formed by a single protein sequence can have diverse structures, varying with time, self-assembly conditions, and sequence modifications. Fibril structure has been proposed to be diagnostic of disease, but why different structures result under different conditions, especially in vitro, remains elusive. We previously identified a small molecule, YX-I-1, which inhibits in vitro amyloid formation by islet amyloid polypeptide (IAPP), a peptide hormone whose amyloid formation is involved in type-2 diabetes. Here, using YX-I-1 as a lead, we identified regulator-approved drugs with similar structures by chemical similarity analysis and substructure searches and monitored the effect of 24 of these potential ligands on IAPP amyloid assembly in vitro. We show that one such compound, canagliflozin (Invokana), a type-2 diabetes drug already in clinical use, can strongly delay the kinetics of IAPP amyloid formation, an activity independent of its intended mode of action [sodium-glucose linked transporter 2 (SGLT2) inhibitor] that may have important therapeutic implications. Combining analysis of amyloid self-assembly kinetics, biophysical characterization of monomer and fibril binding, and cryo-EM of the assembly products, we show that YX-I-1 and canagliflozin target IAPP early in aggregation, remodeling the energy landscape of primary nucleation and profoundly altering the resulting fibril structures. Early binding events thus imprint long-lasting effects on the amyloid structures that form.}, archive = {J_JACS}, author = {Alexander I. P. Taylor and Yong Xu and Martin Wilkinson and Pijush Chakraborty and Alice Brinkworth and Leon F. Willis and Anastasia Zhuravleva and Neil A. Ranson and Richard Foster and Sheena E. Radford}, doi = {10.1021/jacs.4c16743}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11859--11878}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetic steering of amyloid formation and polymorphism by canagliflozin, a type-2 diabetes drug}, volume = {147}, year = {2025}, }
• (2025). Dissolved oxygen redox as the source of hydrogen peroxide and hydroxyl radical in sonicated emulsive water microdroplets. JACS, 147(14), 11851--11858. (www)

  @article{ , abstract = {Sonicated emulsive water microdroplets (SEWMs) accelerate and enable a variety of catalyst-free chemical transformations. However, significant unanswered questions remain regarding the chemical intermediates they form and their possible redox origin. In this study, we identified dissolved O 2 as the primary originator of reactive oxygen species (ROS) such as OH • and H 2 O 2 . We uncovered the role of dissolved O 2 redox by using a combination of microelectrochemical methods to detect H 2 O 2 , isotopic methods to identify the source of H 2 O 2 , and a combination of electron spin resonance and the DMPO spin trap to detect radicals such as OH • . Notably, we found that H 2 O 2 production is correlated with O 2 content via a reduction pathway enabled by a sufficiently large reducing power that can additionally generate H 2 and even perform Pb electroless deposition on Au and Cu metal substrates. Building on our findings, continuous O 2 bubbling of SEWMs showed accumulation of H 2 O 2 up to ∼88 mM in the aqueous phase within 1 h of sonication, demonstrating the scale-up promise of this method. Distinct to sonochemistry of a single phase, this study advances our understanding of the confluence of redox and chemical reaction mechanisms within SEWMs as a biphasic system. This insight paves the way for improving their reaction kinetics, yield, and selectivity, positioning these attractive redox microreactors as alternatives to traditional electrolyzers.}, archive = {J_JACS}, author = {Abdelilah Asserghine and Aravind Baby and Jeanne N’Diaye and Adolfo I. B. Romo and Supriya Das and Chloe A. Litts and Prashant K. Jain and Joaquín Rodríguez-López}, doi = {10.1021/jacs.4c16759}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11851--11858}, shortjournal = {J. Am. Chem. Soc.}, title = {Dissolved oxygen redox as the source of hydrogen peroxide and hydroxyl radical in sonicated emulsive water microdroplets}, volume = {147}, year = {2025}, }
• (2025). Solvent medium-induced changes to internal pressure in the layered host VOPO4·2H2O and the influence on intercalation reactions. JACS, 147(14), 11841--11850. (www)

  @article{ , abstract = {Layered vanadium phosphate dihydrate, VOPO 4 ·2H 2 O, has been chosen as a host for ferrocene intercalation to explore the influence of solvent-guest and solvent-host interactions on rates and product selection. After eliminating solvents that react directly with the VOPO 4 ·2H 2 O host, ferrocene intercalation was evaluated in a series of seven solvents that do not themselves intercalate or otherwise alter the host structure. The intercalation kinetics are analyzed in acetone, butanone, pentanone, acetonitrile, propionitrile, butyronitrile, and DMF. No intercalation is observed in DMF, but all other solvents yield a mixture of stage 1 and stage 2 ferrocenium intercalation products with reaction rates and product ratios varying across the series of solvents. Using ex situ as well as in situ PXRD methods, faster reactions yield more stage 1 product, while a higher degree of stage 2 product is seen for slower kinetics. The results are interpreted in the context of competition between intercalation rates and the buildup of elastic strain between intercalated domains and unintercalated host. To understand solvent effects, both solvent-guest and solvent-host effects are considered. None of the typically considered solvent-guest effects, such as guest desolvation energy, dielectric constant, and guest oxidation potential, correlate with the observed reaction kinetics. On the other hand, different solvent environments are shown to change the internal pressure, P eff , within the layered hosts, a consequence of changing surface energy and surface tension (stress) in particles with nanometer scale dimensions. The VOPO 4 ·2H 2 O interlayer spacing decreases when particles are suspended in DMF and organonitrile solvents, while the layers separate slightly in acetone, butanone, and pentanone. Using calculated elastic constants, the structural changes correspond to changes in P eff in the range 0.22 GPa > Δ P eff > −0.11 GPa across the series of solvents. A density functional theory analysis of the influence of pressure on ferrocene diffusion adds support for the idea that intercalation kinetics are altered by changing internal pressure. The results show solvent environments can be responsible for altering the effective pressure within intercalation hosts, influencing intercalation rates and product selection, even if the solvents do not react directly with the host solids.}, archive = {J_JACS}, author = {Jiahui Liu and Yuan Liu and Timothy Yoo and Miho Itoi and Honggyu Kim and Simon R. Phillpot and Daniel R. Talham}, doi = {10.1021/jacs.4c16643}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11841--11850}, shortjournal = {J. Am. Chem. Soc.}, title = {Solvent medium-induced changes to internal pressure in the layered host VOPO4·2H2O and the influence on intercalation reactions}, volume = {147}, year = {2025}, }
• (2025). An atomically dispersed mn photocatalyst for vicinal dichlorination of nonactivated alkenes. JACS, 147(14), 11829--11840. (www)

  @article{ , abstract = {A novel Mn-based single-atom photocatalyst is disclosed in this study, designed for the dichlorination of alkenes to achieve vicinal dichlorinated products using N -chlorosuccinimide as a mild chlorinating agent, which have widespread applications as pest controlling agents, polymers, flame retardants, and pharmaceuticals. In developing this innovative catalyst, we achieved the atomic dispersion of Mn on aryl-amino-substituted graphitic carbon nitride ( f- C 3 N 4 ). This marks the first instance of a heterogeneous version, offering an operationally simple, sustainable, and efficient pathway for dichlorination of alkenes, including drugs, bioactive compounds, and natural products. This material was extensively characterized by using techniques such as UV–vis spectroscopy, X-ray absorption near-edge structure (XANES), extended X-ray absorption fine structure (EXAFS), high-resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), magic-angle spinning (MAS), and solid-state nuclear magnetic resonance (ssNMR) spectroscopy to understand it at the atomic level. Furthermore, mechanistic studies based on multiscale molecular modeling, combining classical reactive molecular dynamics (RMD) simulations and quantum chemistry (QC) calculations, illustrated that the controlled formation of Cl radicals from the in situ formed Mn–Cl bond is responsible for the dichlorination reaction of alkenes. In addition, gram-scale and reusability tests were also performed to demonstrate the applicability of this approach on an industrial scale.}, archive = {J_JACS}, author = {Prakash Kumar Sahoo and Rakesh Maiti and Peng Ren and Juan José Delgado Jaén and Xingchao Dai and Giovanni Barcaro and Susanna Monti and Alina Skorynina and Anna Rokicińska and Aleksander Jaworski and Laura Simonelli and Piotr Kuśtrowski and Jabor Rabeah and Shoubhik Das}, doi = {10.1021/jacs.4c16413}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11829--11840}, shortjournal = {J. Am. Chem. Soc.}, title = {An atomically dispersed mn photocatalyst for vicinal dichlorination of nonactivated alkenes}, volume = {147}, year = {2025}, }
• (2025). 3D imaging reveals widespread stacking disorder in single crystal 2D covalent organic frameworks. JACS, 147(14), 11821--11828. (www)

  @article{ , abstract = {Although tailored porosity is a defining feature of layered, two-dimensional (2D) polymers known as 2D covalent organic frameworks (COFs), understanding the interplanar stacking of 2D COFs and their resulting three-dimensional (3D) pore structure remains challenging. Here, we use scanning transmission electron microscopy and ptychography, an emerging 3D angstrom-scale imaging method, to study single-crystalline particles of the imine-linked 2D COF TAPB-DMPDA. Previously assumed to adopt an average-eclipsed structure with only angstrom-level stacking disorder, we find the crystals contain widespread stacking disorder of larger magnitudes, including interplanar shifts up to a half unit cell and nanoscale inhomogeneities in stacking and tilt. 3D visualizations show pore channels are distorted by this stacking disorder. The extensive stacking disorder found in even high-quality 2D COFs has profound implications for envisioned applications and should motivate the development of design strategies to control their 3D structures.}, archive = {J_JACS}, author = {Priti Kharel and Patrick T. Carmichael and Anusree Natraj and Chloe E. Pelkowski and Sang hyun Bae and William R. Dichtel and Pinshane Y. Huang}, doi = {10.1021/jacs.4c16207}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11821--11828}, shortjournal = {J. Am. Chem. Soc.}, title = {3D imaging reveals widespread stacking disorder in single crystal 2D covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Interface preconstruction enables robust passivation of the ah-level aqueous li-ion batteries. JACS, 147(14), 11811--11820. (www)

  @article{ , abstract = {The solid electrolyte interphase (SEI) offers effective passivation on the anode for aqueous lithium-ion batteries (ALIBs). Conventional passivation in ALIBs mainly relies on the LiF-contained SEI originating from anion reduction in the electrolyte. However, such SEI formation is a competitive reaction negatively impacted by the parasitic hydrogen evolution reaction (HER), resulting in high Li + irreversible consumption and imperfect bare flaws. To address this issue, we propose preconstructing an artificial interphase by introducing a multifunctional interface additive CsF to build superior passivation on the anode in ALIBs. CsF first undergoes a displacement reaction with LiTFSI from the fresh electrolyte to form the LiF in situ on the interface of the anode before the cycles, avoiding the extra Li + irreversible consumption. Meanwhile, we uncover that the dissolving Cs + in the electrolyte can destroy the hydrogen bond network of the water to lower water activity on the anode interface and strongly interact with TFSI – to form the cation–anion complex, facilitating the anion proximity to the anode interface. The anion reduction based on the artificial interphase can finally help achieve the robust SEI in ALIBs. Such passivation stabilizes the aqueous electrolyte, significantly suppressing the side reaction of the HER that allows ALIBs to obtain a superior long life above 2000 cycles. The ampere-hour-level (Ah-level) pouch cell achieves an energy density of 57 Wh/kg and 176 Wh/L with high energy efficiency (∼94%).}, archive = {J_JACS}, author = {Anxing Zhou and Jinkai Zhang and Ming Chen and Xinyan Li and Shuwei Li and Jintao Ma and Tianshi Lv and Xiangzhen Zhu and Guang Feng and Liumin Suo}, doi = {10.1021/jacs.4c15852}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11811--11820}, shortjournal = {J. Am. Chem. Soc.}, title = {Interface preconstruction enables robust passivation of the ah-level aqueous li-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Structural context modulates the conformational ensemble of the intrinsically disordered amino terminus of α-synuclein. JACS, 147(14), 11800--11810. (www)

  @article{ , abstract = {Regions of intrinsic disorder play crucial roles in biological systems, yet they often elude characterization by conventional biophysical techniques. To capture conformational distributions across different time scales, we employed a freezing approach coupled with solid-state NMR analysis. Using segmentally isotopically labeled α-synuclein (α-syn), we investigated the conformational ensembles of the six alanines, three glycines, and a single site (L8) in the disordered amino terminus under three distinct conditions: in 8 M urea, as a frozen monomer in buffer, and within the disordered regions flanking the amyloid core. The experimental spectra varied significantly among these conditions and deviated from those of a statistical coil. In 8 M urea, monomeric α-syn exhibited the most restricted conformational sampling, rarely accessing chemical shifts characteristic of α-helices or β-strands. In buffer, monomeric α-syn showed a broader conformational sampling, favoring α-helical conformations and, to a lesser extent, random coil states. Notably, amino acids in the disordered regions flanking the amyloid core demonstrated the most extensive conformational sampling, with broad peaks encompassing the entire range of possible chemical shifts and a marked increase in highly extended β-strand conformations. Collectively, this work demonstrates that intrinsically disordered regions exhibit distinct conformational ensembles, which are influenced not only by the chemical environment but also by the conformations of adjacent protein sequences. The differences in the conformational ensembles of the disordered amino terminus may explain why the monomer and the amyloid form of α-syn interact with different biomolecules inside cells.}, archive = {J_JACS}, author = {Rania Dumarieh and Dominique Lagasca and Sakshi Krishna and Jaka Kragelj and Yiling Xiao and Shoyab Ansari and Kendra K. Frederick}, doi = {10.1021/jacs.4c15653}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11800--11810}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural context modulates the conformational ensemble of the intrinsically disordered amino terminus of α-synuclein}, volume = {147}, year = {2025}, }
• (2025). Plasmonic charge localization and C–H activation at single-atom sites in dilute copper platinum alloys. JACS, 147(14), 11789--11799. (www)

  @article{ , abstract = {The role of energy transfer in plasmonic alloys is critical for advancing photocatalysis to industrially and societally relevant chemical processes. In this study, we synthesized and characterized CuPt dilute alloy catalysts to explore the impact of dopant concentration on energy transfer in plasmon-assisted nonoxidative propane dehydrogenation. By leveraging the localized surface plasmon resonance (LSPR) in copper nanoparticles, we examined how single-atom and ensemble Pt sites influence (photo)catalytic performance. In situ diffuse reflectance infrared Fourier transform spectroscopy, along with kinetic analysis of photocatalytic experiments, provided evidence that Pt single-atom sites enhance nonthermal charge carrier generation and energy transfer processes, accelerating C–H scission, resulting in a significant increase in light-driven reaction rates compared to CuPt alloys with ensemble Pt sites. The photochemical enhancement enabled by dilute plasmonic alloys is proposed to result from transient oxidative potentials (i.e., hot holes) localized on isolated dopant sites. These findings demonstrate the potential of engineering active sites in dilute plasmonic alloys for tailored electronic properties, paving the way for broader applications in plasmonic photocatalysis.}, archive = {J_JACS}, author = {Emma-Rose Newmeyer and Yicheng Wang and Zachary Alexander Long and Jamie D. North and Yixuan Shi and Dayne F. Swearer}, doi = {10.1021/jacs.4c14842}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11789--11799}, shortjournal = {J. Am. Chem. Soc.}, title = {Plasmonic charge localization and C–H activation at single-atom sites in dilute copper platinum alloys}, volume = {147}, year = {2025}, }
• (2025). Nitric oxide inhibition of glycyl radical enzymes and their activases. JACS, 147(14), 11777--11788. (www)

  @article{ , abstract = {Innate immune response cells produce high concentrations of the free radical nitric oxide (NO) in response to pathogen infection. The antimicrobial properties of NO include nonspecific damage to essential biomolecules and specific inactivation of enzymes central to aerobic metabolism. However, the molecular targets of NO in anaerobic metabolism are less understood. Here, we demonstrate that the Escherichia coli glycyl radical enzyme pyruvate formate lyase (PFL), which catalyzes the anaerobic metabolism of pyruvate, is irreversibly inhibited by NO. Using electron paramagnetic resonance and site-directed mutagenesis we show that NO destroys the glycyl radical of PFL. The activation of PFL by its cognate radical S -adenosyl- l -methionine-dependent activating enzyme (PFL-AE) is also inhibited by NO, resulting in the conversion of the essential iron–sulfur cluster to dinitrosyl iron complexes. Whole-cell EPR and metabolic flux analyses of anaerobically growing E. coli show that PFL and PFL-AE are inhibited by physiologically relevant levels of NO in bacterial cell cultures, resulting in diminished growth and a metabolic shift to lactate fermentation. The class III ribonucleotide reductase (RNR) glycyl radical enzyme and its corresponding RNR-AE are also inhibited by NO in a mechanism analogous to those observed in PFL and PFL-AE, which likely contributes to the bacteriostatic effect of NO. Based on the similarities in reactivity of the PFL/RNR and PFL-AE/RNR-AE enzymes with NO, the mechanism of inactivation by NO appears to be general to the respective enzyme classes. The results implicate an immunological role of NO in inhibiting glycyl radical enzyme chemistry in the gut.}, archive = {J_JACS}, author = {Juan Carlos Cáceres and Nathan G. Michellys and Brandon L. Greene}, doi = {10.1021/jacs.4c14786}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11777--11788}, shortjournal = {J. Am. Chem. Soc.}, title = {Nitric oxide inhibition of glycyl radical enzymes and their activases}, volume = {147}, year = {2025}, }
• (2025). Fluorinated ribonucleocarbohydrate nanoparticles allow ultraefficient mRNA delivery and protein expression in tumor-associated myeloid cells. JACS, 147(14), 11766--11776. (www)

  @article{ , abstract = {Ribonucleic acids (RNA) are commonly formulated into lipid nanoparticles (LNP) for in vivo use, but challenges exist with systemic delivery and low in vivo expression efficiency. Inspired by ribonucleoprotein complexes in cells, we created synthetic ribonucleocarbohydrate (RNC) complexes based on cyclodextrin nanoparticles with ferrocenyl fluorocarbons capable of carrying mRNA and additional small-molecule drug payloads, facilitating lysosomal escape and immune stimulation all in the same nanoparticle. We show that this strategy results in highly efficient myeloid cell targeting (dendritic cells and MHC expressing macrophages) and protein expression following systemic administration. The RNC platform should have broad applications in vaccine development, immunosuppression, and immunostimulation for various diseases.}, archive = {J_JACS}, author = {Hyung Shik Kim and Grant Gerald Simpson and Fan Fei and Christopher Garris and Ralph Weissleder}, doi = {10.1021/jacs.4c14474}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11766--11776}, shortjournal = {J. Am. Chem. Soc.}, title = {Fluorinated ribonucleocarbohydrate nanoparticles allow ultraefficient mRNA delivery and protein expression in tumor-associated myeloid cells}, volume = {147}, year = {2025}, }
• (2025). Discovering key activation hotspots in the m2 muscarinic receptor. JACS, 147(14), 11754--11765. (www)

  @article{ , abstract = {The M 2 muscarinic receptor (M 2 R) is a prototypical G protein-coupled receptor (GPCR) that serves as a model system for understanding ligand recognition and GPCR activation. Here, using vibrational spectroscopy, we identify the mechanisms governing M 2 R activation by its native agonist, acetylcholine. Combined with mutagenesis, computational chemistry, and organic synthetic chemistry, our analyses found that the precise distance between acetylcholine and Asn404, one of the amino acids constituting the ligand-binding site, is important for M 2 R activation and that the N404Q mutant undergoes partial active state-like conformational changes. We discovered that a water molecule bridging acetylcholine and Asn404 forms a precise and flexible hydrogen bond network, triggering the outward movement of transmembrane helix 6 in M 2 R. Consistent with this observation, disruptions in this hydrogen bond network via chemical modification at the α- or β-position of acetylcholine failed to activate M 2 R. Collectively, our findings pinpoint Asn404 as a critical residue that both senses acetylcholine binding and induces M 2 R activation.}, archive = {J_JACS}, author = {Yuya Sugiura and Tatsuya Ikuta and Yuji Sumii and Hirokazu Tsujimoto and Kohei Suzuki and Ryoji Suno and Putri Nur Arina Binti Mohd Ariff and So Iwata and Norio Shibata and Asuka Inoue and Takuya Kobayashi and Hideki Kandori and Kota Katayama}, doi = {10.1021/jacs.4c14385}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11754--11765}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovering key activation hotspots in the m2 muscarinic receptor}, volume = {147}, year = {2025}, }
• (2025). Rational design principles for de novo α-helical peptide barrels with dynamic conductive channels. JACS, 147(14), 11741--11753. (www)

  @article{ , abstract = {Despite advances in peptide and protein design, the rational design of membrane-spanning peptides that form conducting channels remains challenging due to our imperfect understanding of the sequence-to-structure relationships that drive membrane insertion, assembly, and conductance. Here, we describe the design and computational and experimental characterization of a series of coiled coil-based peptides that form transmembrane α-helical barrels with conductive channels. Through a combination of rational and computational design, we obtain barrels with 5 to 7 helices, as characterized in detergent micelles. In lipid bilayers, these peptide assemblies exhibit two conductance states with relative populations dependent on the applied potential: (i) low-conductance states that correlate with variations in the designed amino-acid sequences and modeled coiled-coil barrel geometries, indicating stable transmembrane α-helical barrels; and (ii) high-conductance states in which single channels change size in discrete steps. Notably, the high-conductance states are similar for all peptides in contrast to the low-conductance states. This indicates the formation of large, dynamic channels, as observed in natural barrel-stave peptide channels. These findings establish rational routes to design and tune functional membrane-spanning peptide channels with specific conductance and geometry.}, archive = {J_JACS}, author = {Ai Niitsu and Andrew R. Thomson and Alistair J. Scott and Jason T. Sengel and Jaewoon Jung and Kozhinjampara R. Mahendran and Mikiko Sodeoka and Hagan Bayley and Yuji Sugita and Derek N. Woolfson and Mark I. Wallace}, doi = {10.1021/jacs.4c13933}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11741--11753}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design principles for de novo α-helical peptide barrels with dynamic conductive channels}, volume = {147}, year = {2025}, }
• (2025). Encoded display of chemical libraries on nanoparticles as a versatile selection tool to discover protein ligands. JACS, 147(14), 11726--11740. (www)

  @article{ , abstract = {DNA-encoded library (DEL) technology is a powerful tool for discovering potent ligands for biological targets but constrained by limitations, including the insolubility of DNA in organic solvents and its instability under various reaction conditions, which restrict the reactivity scope and structural diversity achievable in library synthesis. Here, we present a new strategy called nanoDEL, where library molecules and DNA tags are displayed on the surface of nanoparticles. Since nanoparticles disperse well in both organic solvents and aqueous solutions, DEL synthesis can be accomplished using well-established organic solvent-based conditions, eliminating the need for aqueous conditions. Moreover, nanoDEL enables air-sensitive reactions that are inaccessible with conventional DEL methods relying on aqueous conditions. Notably, in nanoDEL, multiple copies of a DNA tag are attached to an individual nanoparticle to encode a single compound, significantly enhancing tolerance to DNA-damaging conditions. Even when most DNA tags are damaged, sequence analysis remains feasible via amplification of intact tags. Consequently, nanoDEL facilitates the convenient use of existing organic reactions without the necessity to develop DNA-compatible reactions. The potential of nanoDEL was validated by affinity selection against streptavidin as a model system and successfully applied to the discovery of potent small-molecule inhibitors for a kinase and stapled peptide inhibitors targeting a protein–protein interaction, exhibiting dissociation constants in the nanomolar range. Furthermore, we demonstrated that a large combinatorial library can be efficiently synthesized on nanoparticles using a synthetic scheme including moisture-sensitive reaction steps, which are not feasible with conventional DELs.}, archive = {J_JACS}, author = {Kang Ju Lee and Hee Myeong Wang and Minkyung Kim and Jun Hyung Park and Jungyeon Kim and Seungyoon Jang and Dahye Im and Beomjoon Goh and Min Hyeon Shin and Ji Hoon Shim and Sungjee Kim and Jongcheol Seo and Hyun-Suk Lim}, doi = {10.1021/jacs.4c13487}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11726--11740}, shortjournal = {J. Am. Chem. Soc.}, title = {Encoded display of chemical libraries on nanoparticles as a versatile selection tool to discover protein ligands}, volume = {147}, year = {2025}, }
• (2025). Nature of the reactive biferric peroxy intermediate p′ in the arylamine oxygenases and related binuclear fe enzymes. JACS, 147(14), 11707--11725. (www)

  @article{ , abstract = {Binuclear nonheme iron enzymes activate O 2 to perform a wide range of chemical transformations. The process of O 2 activation typically involves a biferric peroxy-level intermediate P. It has been previously found that this intermediate undergoes further activation, either protonation or rearrangement to form P′ or further oxidation to form high-valent intermediates Q or X. This study defines the structure of the P′ intermediate in the N -oxygenases CmlI (and AurF based on previous data) using nuclear resonance vibrational spectroscopy (NRVS) in conjugation with density functional theory (DFT) calculations. These results, combined with variable temperature variable field (VTVH) magnetic circular dichroism (MCD) spectroscopy on the 1-electron cryoreduced P′, define the structure of the P′ intermediate as a μ-1,2-hydroxoperoxo biferric site with a second hydroxide bridge. Reaction coordinate calculations demonstrate that single electron transfer (SET) is facilitated by protonation of the peroxo, activating its reductive cleavage, and that the additional hydroxide bridge does not impact this reaction. VTVH MCD studies further reveal that the hydroxide bridge is absent in the biferrous site, suggesting that during the O 2 reaction with the biferrous site, a water molecule forms the hydroxide bridge in providing the proton that activates the peroxide in P′ for reactivity.}, archive = {J_JACS}, author = {Lars H. Böttger and Dory E. DeWeese and Shyam R. Iyer and Anna J. Komor and Melanie S. Rogers and Kyle Sutherlin and Ari B. Jacobs and Yoshitaka Yoda and Shinji Kitao and Yasuhiro Kobayashi and Jiyong Zhao and Esen Ercan Alp and Makina Saito and Makoto Seto and Lawrence Que, Jr. and John D. Lipscomb and Edward I. Solomon}, doi = {10.1021/jacs.4c11712}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11707--11725}, shortjournal = {J. Am. Chem. Soc.}, title = {Nature of the reactive biferric peroxy intermediate p′ in the arylamine oxygenases and related binuclear fe enzymes}, volume = {147}, year = {2025}, }
• (2025). Configuration retention in P-trifluoromethyl phosphine enabled Rh(I)-catalyzed decarbonylative coupling of carboxylates and boroxines. JACS, 147(14), 11700--11706. (www)

  @article{ , abstract = {As compared with asymmetric catalysis, the memory of chirality provides another promising strategy to introduce chiral centers in light of numerous chiral starting materials that can be accessed. Decarboxylative coupling has become an important strategy for C–C or C–X bond formation over decades of development for its versatility and the low cost and structural diversity of carboxylic acids. However, the memory of chirality or more general configuration retention in this transformation has seldom been studied. Here, we report a novel π acceptor-type ligand P -trifluoromethyl phosphine enabled Rh(I)-catalyzed decarbonylative coupling of carboxylates and boroxines. The configuration of the α-carbon can be fully retained in this transformation for chiral, cis- , or trans -substrates. Several P -trifluoromethyl phosphine-Rh(I) carbonyl complexes were prepared and their v (CO) values were compared with known complexes, which indicated that the π-accepting property of the ligand is important to the decarbonylative reaction.}, archive = {J_JACS}, author = {Shouzhi Zhang and Bo Li and Suhua Li}, doi = {10.1021/jacs.5c03546}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11700--11706}, shortjournal = {J. Am. Chem. Soc.}, title = {Configuration retention in P-trifluoromethyl phosphine enabled Rh(I)-catalyzed decarbonylative coupling of carboxylates and boroxines}, volume = {147}, year = {2025}, }
• (2025). Defined glycan ligands for detecting rare l-sugar-binding proteins. JACS, 147(14), 11693--11699. (www)

  @article{ , abstract = {Most cells are decorated with distinct sugar sequences that can be recognized by carbohydrate-binding proteins (CBPs), such as antibodies and lectins. While humans utilize ten monosaccharide building blocks, bacteria biosynthesize hundreds of activated sugars to assemble diverse glycans. Monosaccharides absent in mammals are termed “rare” and are enriched in deoxy l -sugars beyond the “common” sugar l -fucose ( l -Fuc) found across species. While immune proteins recognize microbial surfaces, there are limited probes to identify CBPs for the many rare sugars that may mediate these interactions. Here, we devise chemoenzymatic strategies to defined glycoconjugates containing l -Fuc and its structural analog l -colitose ( l -Col), a bacterial dideoxysugar believed to bind immune proteins. We report a concise synthesis of l -Col and semisynthetic routes to several activated l -sugars. Incorporation of these sugars into glycans is evaluated using bacterial and mammalian glycosyltransferases (GTs) annotated to transfer l -Col or l -Fuc, respectively. We find that each GT can transfer both l -sugars, along with the rare hexose l -galactose ( l -Gal), onto various glycan acceptors. Incorporation of these l -sugars into the resulting glycoconjugates is confirmed using known CBPs. Finally, these glycan ligands are employed to detect rare sugar-binding proteins in human serum. Overall, this work reveals similarities between bacterial and mammalian GTs that may be exploited for in vitro glycoconjugate construction to unveil novel mediators of host–pathogen interactions.}, archive = {J_JACS}, author = {Hanee Kim and Tania J. Lupoli}, doi = {10.1021/jacs.5c03251}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11693--11699}, shortjournal = {J. Am. Chem. Soc.}, title = {Defined glycan ligands for detecting rare l-sugar-binding proteins}, volume = {147}, year = {2025}, }
• (2025). Spontaneous generation of an endogenous RORγt agonist. JACS, 147(14), 11688--11692. (www)

  @article{ , abstract = {The transcription factor RORγt regulates the development of Th17 cells and their inflammatory cytokine IL-17─a pathway that can both clear bacterial pathogens and drive autoimmune diseases. An endogenous RORγt agonist with a noncanonical structure, a lysophosphatidylethanolamine (1-18:1-LPE or 1 ), was recently identified, and its identity both increases our understanding of immune regulation and creates options for therapeutic intervention. Compound 1 could be formed directly through enzymatic cleavage of a suitable phosphatidylethanolamine (PE) by a phospholipase A2 (PLA2) or by “triggering” of a suitable plasmalogen with accompanying 1,2-acyl migration from the sn -2 to sn -1 positions of glycerol. This study illustrates the plausibility of a plasmalogen-based pathway through synthesis of the plasmalogen precursor ( 2 ) and triggering the plasmalogen’s electron-rich vinyl ether with small electrophiles characteristic of inflammatory and tumor environments to create 1-18:1-LPE ( 1 ). The plasmalogen-based pathway is consistent with previous studies on the formation of 1 , and it also conforms to Lands rules for acyl chain distribution and provides a mechanism for immune signaling with both spatial and temporal control.}, archive = {J_JACS}, author = {Xiao Corey Ma and Jon Clardy}, doi = {10.1021/jacs.5c02724}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11688--11692}, shortjournal = {J. Am. Chem. Soc.}, title = {Spontaneous generation of an endogenous RORγt agonist}, volume = {147}, year = {2025}, }
• (2025). Degradable alternating copolymers from living radical copolymerization of natural levoglucosenone and dienes. JACS, 147(14), 11682--11687. (www)

  @article{ , abstract = {Here, we present an efficient synthetic route to biobased alternating copolymers via the living radical copolymerization of naturally occurring levoglucosenone (LGO) and dienes. By employing reversible addition–fragmentation chain transfer (RAFT) polymerization, well-defined LGO-derived copolymers were readily synthesized featuring high degrees of alternation, well-controlled molecular weights, and excellent end-group fidelity. Additionally, the alternating copolymers exhibited thermal and mechanical properties comparable to those of the commodity polystyrene. Furthermore, an on-demand metathesis degradation was identified, highlighting their potential as degradable materials.}, archive = {J_JACS}, author = {Lianqian Wu and Hongsik Kim and Tae-Lim Choi}, doi = {10.1021/jacs.5c02397}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11682--11687}, shortjournal = {J. Am. Chem. Soc.}, title = {Degradable alternating copolymers from living radical copolymerization of natural levoglucosenone and dienes}, volume = {147}, year = {2025}, }
• (2025). Enantiospecific synthesis of α-tertiary amines: Ruthenium-catalyzed allylic amination with aqueous ammonia. JACS, 147(14), 11675--11681. (www)

  @article{ , abstract = {Ammonia stands out as the most available, cost-effective, and atom-economical source of nitrogen for organic synthesis. In the laboratory, it is safely and most conveniently handled in aqueous solution. Despite the advantages, the direct application of aqueous ammonia in the field of transition-metal catalysis remains a significant challenge. In this study, we report the first ruthenium-catalyzed allylic substitution using ammonia. The catalytic system, consisting of [Cp*Ru(MeCN) 3 ]PF 6 and a phenoxythiazoline ligand, enables the enantiospecific amination of tertiary allylic carbonates in aqueous media and affords enantioenriched primary amines as single regioisomers in high yields.}, archive = {J_JACS}, author = {Sven M. Papidocha and Henrik R. Wilke and Kacper J. Patej and Mayuko Isomura and Tim J. Stucky and Lukas Rothenbühler and Erick M. Carreira}, doi = {10.1021/jacs.5c01928}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11675--11681}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantiospecific synthesis of α-tertiary amines: Ruthenium-catalyzed allylic amination with aqueous ammonia}, volume = {147}, year = {2025}, }
• (2025). Enantioselective dearomative [2π + 2σ] photocycloaddition of naphthalene derivatives with bicyclo[1.1.0]butanes enabled by Gd(III) catalysis. JACS, 147(14), 11667--11674. (www)

  @article{ , abstract = {The cycloaddition reactions of bicyclo[1.1.0]butanes with alkenes, imines, nitrones, or aziridines have served as an efficient platform to create conformationally restricted saturated bicyclic scaffolds. However, the use of readily available aromatics in such reactions, especially in an asymmetric manner, remains underexplored. Herein, we report a highly regio- and enantioselective dearomative [2π + 2σ] photocycloaddition reaction between naphthalene derivatives and bicyclo[1.1.0]butanes, enabled by Gd(III) catalysis. Bicyclo[1.1.0]butanes and naphthalenes adorned with a diverse array of functional groups are well-tolerated under mild conditions, affording enantioenriched pharmaceutically important bicyclo[2.1.1]hexanes in 30–96% yields with 81–93% ee and 12:1 → >20:1 rr. The synthetic versatility of this reaction is further demonstrated by the facile removal of directing group and derivatizations of the dearomatized product. UV–vis absorption spectroscopy studies suggest the involvement of an excited naphthalene species in the reaction process.}, archive = {J_JACS}, author = {Wen-Jie Shen and Xin-Xuan Zou and Muzi Li and Yuan-Zheng Cheng and Shu-Li You}, doi = {10.1021/jacs.5c01506}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11667--11674}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective dearomative [2π + 2σ] photocycloaddition of naphthalene derivatives with bicyclo[1.1.0]butanes enabled by Gd(III) catalysis}, volume = {147}, year = {2025}, }
• (2025). The role of protons in CO2 reduction on gold under acidic conditions. JACS, 147(14), 11662--11666. (www)

  @article{ , abstract = {Carbonate formation constitutes a major obstacle in the electrochemical CO 2 reduction reaction (CO 2 RR), restricting the industrial implementation of this reaction. Even when adopting mild acidic electrolytes, carbonate formation is still observed. The fundamental reason lies in the inevitable OH – generation when H 2 O is the proton donor, leading to subsequent carbonate formation. Thus, exploring the reaction pathway of the CO 2 RR in the acid, especially if a proton can directly participate in the reaction, is critical. Herein, we employed a rotating ring-disk electrode and surface interrogation scanning electrochemical microscopy to investigate the electrode process of the CO 2 RR in acid. A pH-dependent behavior of CO 2 RR is observed, indicating proton acting as the reactant in the RDS, originating from the early onset of CO 2 adsorption under locally acidic conditions.}, archive = {J_JACS}, author = {Weixing Wu and Ying Wang}, doi = {10.1021/jacs.5c01149}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11662--11666}, shortjournal = {J. Am. Chem. Soc.}, title = {The role of protons in CO2 reduction on gold under acidic conditions}, volume = {147}, year = {2025}, }
• (2025). An amplificative detection approach for autocatalytic sensing of ethylene. JACS, 147(14), 11654--11661. (www)

  @article{ , abstract = {Amplified sensing offers the potential for high sensitivity; however, the vast majority of molecular strategies involve stoichiometric detection and signal transduction, including numerous recent examples of systems inspired by transition-metal-catalyzed reactions. Activation of latent precatalysts by a target analyte represents an attractive strategy for detecting low-concentration species. Analyte amplification represents another attractive approach, akin to PCR-based assays. Here we report an autocatalytic detection system based on the ethylene activation of Ru–I2 olefin metathesis precatalysts. Signal transduction is amplified by both catalytic ring closing metathesis of profluorescent substrates and ethylene propagation to activate additional units of catalyst. High sensitivity is observed as a result of this dual-mode amplified detection of ethylene. Detection of endogenous ethylene from fruit and oxidation-decomposition of polyunsaturated fatty acids via lipid peroxides is demonstrated.}, archive = {J_JACS}, author = {Autumn I. Giger and Jaiden C. Voldrich and Brian W. Michel}, doi = {10.1021/jacs.5c00854}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11654--11661}, shortjournal = {J. Am. Chem. Soc.}, title = {An amplificative detection approach for autocatalytic sensing of ethylene}, volume = {147}, year = {2025}, }
• (2025). Construction of c4-spirocyclic chiral covalent organic frameworks via asymmetric multicomponent povarov reaction for enantioselective sensing. JACS, 147(14), 11647--11653. (www)

  @article{ , abstract = {Although many chiral covalent organic frameworks (CCOFs) have been synthesized, the rapid development of this field has been severely restricted by the limitations of CCOFs synthesis methods and the scarcity of their chiral structural unit types. Herein we report, for the first time, the construction of C4-spirocyclic CCOFs via the asymmetric multicomponent Povarov reaction under ambient conditions. The obtained C4 - spiro -(2 S , 4 R )- TMTT - COF can be as a novel chiral fluorescent sensor to discriminate D/L-PAL enantiomers. This finding will provide a simple and universal method for constructing CCOFs with novel chiral structural groups and might open new insights into the construction of the CCOFs featuring multiple distinct types of carbon chiral centers.}, archive = {J_JACS}, author = {Zhi Chen and Zi-Ran Liu and Jun Zhang and Wen-Ting Yang and Jing-Lan Kan and Jianzhong Fan and Wen-Yan Li and Jian-Cheng Wang and Yu-Bin Dong}, doi = {10.1021/jacs.4c18474}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11647--11653}, shortjournal = {J. Am. Chem. Soc.}, title = {Construction of c4-spirocyclic chiral covalent organic frameworks via asymmetric multicomponent povarov reaction for enantioselective sensing}, volume = {147}, year = {2025}, }
• (2025). Ligand enabled iridium-catalyzed enantioselective hydroalkenylation of α-olefins and styrenes with acrylamides. JACS, 147(14), 11639--11646. (www)

  @article{ , abstract = {A new type of chiral spiro diphosphite ligand has been developed. Using these ligands, iridium-catalyzed highly enantioselective hydroalkenylation of α-olefins and styrenes with acrylamides has been realized. A variety of aliphatic and aromatic alkenes were successfully coupled with acrylamides to produce γ-substituted chiral acrylamides. The reaction exhibits excellent branched selectivity and high enantioselectivity along with broad substrate scope and good functional group tolerance. DFT calculations indicate that the methyl groups in the ligand play a crucial role in controlling both regioselectivity and enantioselectivity of the reaction.}, archive = {J_JACS}, author = {Kai Wang and Kai-Yuan Tian and Xin-Ning Wang and Jing-Hao Chen and Chao Fan and Qi-Lin Zhou}, doi = {10.1021/jacs.4c18412}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11639--11646}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand enabled iridium-catalyzed enantioselective hydroalkenylation of α-olefins and styrenes with acrylamides}, volume = {147}, year = {2025}, }
• (2025). A facile micelle-assisted self-assembly method to covalent organic framework helical nanoarchitectures. JACS, 147(14), 11632--11638. (www)

  @article{ , abstract = {We present a micelle-assisted self-assembly strategy for synthesizing covalent organic framework (COF) helical hollow nanoribbons by using achiral monomers and surfactants. The process involves polymerization of nanowires within rod-like micelle cores, followed by their attachment to form helical nanoribbons and solvothermal crystallization to create hollow COF architectures. This method allows for the controllable synthesis of COF helical nanostructures with tunable pitch and morphology and can be extended to other COF helical architectures by variation of the amine monomer. This strategy provides new insights into designing COF helical nanostructures using achiral building blocks within micellar systems.}, archive = {J_JACS}, author = {Shanshan Li and Ji Han and Ruigang Sun and Bin Zhao and Tianyu Wu and Chengyue Yang and Qi Guo and Yuanbo Sun and Guangrui Chen and Bohan Liu and Haidong Xu and Guiyuan Zhong and Song Lin Zhang and Qianrong Fang and Buyuan Guan}, doi = {10.1021/jacs.4c13237}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11632--11638}, shortjournal = {J. Am. Chem. Soc.}, title = {A facile micelle-assisted self-assembly method to covalent organic framework helical nanoarchitectures}, volume = {147}, year = {2025}, }
• (2025). Titanium phosphinidene and phosphide moieties from oxidative phosphorylation and desilylation. JACS, 147(14), 11625--11631. (www)

  @article{ , abstract = {A unique entry into mononuclear titanium complexes bearing phosphinidene and phosphide ligand moieties is reported. Reaction of [K(crypt)][(PN) 2 TiCl] ( 1 , crypt = 2.2.2-cryptand) with [Na(OCP)] results in [K(crypt)][(PN) 2 Ti(OCP)] ( 2 ) and such species can be oxidized to the derivative [(PN) 2 Ti(OCP)] ( 3 ), both of which do not undergo decarbonylation. However, the reaction of 1 and [NaP(SiMe 3 ) 2 ] leads to an unprecedented Ti III phosphinidene, [K(crypt)][(PN) 2 Ti═PSiMe 3 ] ( 4 ), through an oxidative phosphorylation reaction. To promote the formation of a Ti≡P bond, complex 4 was treated with 0.5 equivalent XeF 2 , resulting in an oxidative desilylation step forming a molecular titanium phosphide complex, [K(crypt)][(PN) 2 Ti≡P] ( 5 ), which showed a characteristic downfield chemical shift at 1449.8 pmm in the 31 P NMR spectrum. Complex 5 can be further functionalized to generate a terminal Ti IV phosphinidene, [(PN) 2 Ti═PSiMe 3 ] ( 6 ), and the latter can be independently accessed through oxidation of 4 . All new complexes were characterized structurally and as appropriate by multinuclear NMR, CW X-band EPR (for Ti III ), and HFEPR (for Ti II ) spectroscopies.}, archive = {J_JACS}, author = {Jacob S. Mohar and Mrinal Bhunia and Alexander L. Laughlin and Andrew Ozarowski and J. Krzystek and Taylor M. Keller and Michael R. Gau and Kyle M. Lancaster and Joshua Telser and Daniel J. Mindiola}, doi = {10.1021/jacs.4c12242}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11625--11631}, shortjournal = {J. Am. Chem. Soc.}, title = {Titanium phosphinidene and phosphide moieties from oxidative phosphorylation and desilylation}, volume = {147}, year = {2025}, }
• (2025). Molecular design principles for photoactive transition metal complexes: A guide for “Photo-motivated” chemists. JACS, 147(14), 11608--11624. (www)

  @article{ , abstract = {Luminescence and photochemistry involve electronically excited states that are inherently unstable and therefore spontaneously decay to electronic ground states, in most cases by nonradiative energy release that generates heat. This energy dissipation can occur on a time scale of 100 fs (∼10 –13 s) and usually needs to be slowed down to at least the nanosecond (∼10 –9 s) time scale for luminescence and intermolecular photochemistry to occur. This is a challenging task with many different factors to consider. An alternative emerging strategy is to target dissociative excited states that lead to metal–ligand bond homolysis on the subnanosecond time scale to access synthetically useful radicals. Based on a thorough review at the most recent advances in the field, this article aims to provide a concise guide to obtaining luminescent and photochemically useful coordination compounds with d-block elements. We hope to encourage “photo-motivated” chemists who have been reluctant to apply their synthetic and other knowledge to photophysics and photochemistry, and we intend to stimulate new approaches to the synthetic control of excited state behavior.}, archive = {J_JACS}, author = {Giacomo Morselli and Christian Reber and Oliver S. Wenger}, doi = {10.1021/jacs.5c02096}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11608--11624}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular design principles for photoactive transition metal complexes: A guide for “Photo-motivated” chemists}, volume = {147}, year = {2025}, }
• (2025). Methanol to olefins (MTO): Understanding and regulating dynamic complex catalysis. JACS, 147(14), 11585--11607. (www)

  @article{ , abstract = {The research and development of methanol conversion into hydrocarbons have spanned more than 40 years. The past four decades have witnessed mutual promotion and successive breakthroughs in both fundamental research and industrial process development of methanol to olefins (MTO), demonstrating that MTO is an extremely dynamic, complex catalytic system. This Perspective summarizes the endeavors and achievements of the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, in the continuous study of reaction mechanisms and process engineering of the dynamic, complex MTO reaction system. It elucidates fundamental chemical issues concerning the essence of the dynamic evolution of the MTO reaction and the cross-talk mechanisms among diffusion, reaction, and catalyst (coke modification), which are crucial for technology development and process optimization. By integrating the chemical principles, the reaction-diffusion model, and coke formation kinetics of MTO, a mechanism- and model-driven modulation of industrial processes has been achieved. The acquisition of a deepening understanding in chemistry and engineering has facilitated the continuous optimization and upgrading of MTO catalysts and processes.}, archive = {J_JACS}, author = {Shanfan Lin and Hua Li and Peng Tian and Yingxu Wei and Mao Ye and Zhongmin Liu}, doi = {10.1021/jacs.4c12145}, journal = {Journal of the American Chemical Society}, month = {4}, number = {14}, pages = {11585--11607}, shortjournal = {J. Am. Chem. Soc.}, title = {Methanol to olefins (MTO): Understanding and regulating dynamic complex catalysis}, volume = {147}, year = {2025}, }
• (2025). Correction to “Unravelling size-dependent upconversion luminescence in ytterbium and erbium codoped NaYF4 nanocrystals”. JACS, 147(13), 11584. (www)

  @article{ , archive = {J_JACS}, author = {Xingxu Liu and Langping Tu and Feng Li and Dingxin Huang and Hans Ågren and Guanying Chen}, doi = {10.1021/jacs.5c03655}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11584}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Unravelling size-dependent upconversion luminescence in ytterbium and erbium codoped NaYF4 nanocrystals”}, volume = {147}, year = {2025}, }
• (2025). Uridine embedded within DNA is repaired by uracil DNA glycosylase via a mechanism distinct from that of ribonuclease h2. JACS, 147(13), 11574--11583. (www)

  @article{ , abstract = {Uridine (rU) and 2′-deoxyuridine (dU) are common DNA lesions. dU is repaired through a base excision repair (BER) pathway initiated by uracil DNA glycosylase (UDG), while rU is typically removed from DNA via ribonucleotide excision repair, mediated by RNase H2. In this study, we report that rU is also repaired through the UDG-mediated BER pathway. We found that UDG catalyzes the removal of uracil from rU embedded in DNA, but exhibits no activity toward rU in RNA. Biochemical and crystallographic analyses revealed that the 2′–OH group of rU is effectively accommodated by UDG and directly participates in catalyzing the hydrolysis of the N -glycosidic bond. The abasic site product generated upon removal of uracil from rU by UDG is further processed by downstream BER enzymes to restore undamaged DNA. Our findings suggest that UDG-initiated BER constitutes a previously unrecognized pathway for the repair of rU-specific ribonucleotides. Additionally, we developed a method for selectively quantifying rU content in DNA. Using this method, we determined that rU repair by UDG is not a major pathway in human cells. This discovery expands our understanding of the diverse biological functions of UDG, and inspires further investigation to determine the role of its rU-removal in cells.}, archive = {J_JACS}, author = {Chaochao Fan and Xuelin Zhan and Fengmin Guo and Qiang Li and Kuan Lu and Xiajing Shan and Yifei Zhou and Mengtian Ren and Marc M. Greenberg and Yijin Liu and Chuanzheng Zhou}, doi = {10.1021/jacs.5c01436}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11574--11583}, shortjournal = {J. Am. Chem. Soc.}, title = {Uridine embedded within DNA is repaired by uracil DNA glycosylase via a mechanism distinct from that of ribonuclease h2}, volume = {147}, year = {2025}, }
• (2025). Synthesis of amorphous graphene and graphene oxide analogues. JACS, 147(13), 11564--11573. (www)

  @article{ , abstract = {Graphene and graphene oxide (GO) are promising two-dimensional nanomaterials. An ultimate goal is to achieve large-scale bottom-up syntheses of perfect graphene and GO. However, controlled syntheses of perfect graphitic structures still remain challenges in chemistry and materials science. Moreover, amorphous types have not received much attention. The present work shows syntheses, structures, and applications of amorphous graphene and GO analogues alternative to the ideal ones. The simultaneous multiple reactions of two conjugated monomers provide amorphous conjugated polymer networks containing low-crystalline graphitic domains and their stacking. The stacked amorphous graphene and GO are exfoliated into thin nanosheets including few-layers and monolayers. Moreover, in situ syntheses of the amorphous GO analogues are applied to obtain a reinforced plastic with high mechanical strength. The present work implies that various functional nanocarbons can be designed and synthesized by tailored combinations of conjugated monomers.}, archive = {J_JACS}, author = {Tomoki Sakuma and Ryoichi Sato and Akihiro Yamaguchi and Hiroaki Imai and Noriyoshi Arai and Yuya Oaki}, doi = {10.1021/jacs.5c00548}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11564--11573}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of amorphous graphene and graphene oxide analogues}, volume = {147}, year = {2025}, }
• (2025). Mechanism of unexpected in-trans post-PKS polyketide reduction in cochliodone biosynthesis. JACS, 147(13), 11555--11563. (www)

  @article{ , abstract = {Cochliodone A, a dimeric azaphilone-type compound, is the major product and one of many natural products produced by Chaetomium globosum , a filamentous fungus. Cochliodone A exerts antimalarial and antimycobacterial activities in addition to being cytotoxic against KB, BC1, and NCI-H187 human cancer cell lines. The potential of cochliodone A and its analogues as effective therapeutics against cancer, tuberculosis, and malaria, together with its complex dimeric chemical structure, are reasons enough for continued investigation. Here, sequence analyses of the open reading frames found in the previously identified cochliodone A biosynthetic gene cluster, together with a series of gene-knockout experiments, heterologous in vivo production of pathway intermediates in Aspergillus nidulans and in vitro assays of key enzymes allowed us to propose a biosynthetic pathway and detailed mechanisms leading to the production of cochliodones. In addition, we identified that the elimination of the dimerizing multicopper oxidase CcdJ from the ccd pathway led to pathway crosstalk between the ccd pathway and an unrelated benzaldehyde-producing biosynthetic pathway formation to generate new secondary metabolites. Most interestingly, however, through the in vitro study, we established that the sequential actions of an acetyltransferase, an acetate lyase, and an enoyl reductase achieve a full reduction of the unsaturated backbone of the polyketide (PKs) product generated by the nonreducing polyketide synthase (PKS) CcdL. This alternative mode of reducing a polyketomethylene chain could be engineered further to develop a facile chemoenzymatic modification of the polyketide backbone saturation level postpolyketide synthesis in trans .}, archive = {J_JACS}, author = {Christopher Sarmales-Murga and Michio Sato and Motoki Kosaka and Fumito Akaoka and Kenji Watanabe}, doi = {10.1021/jacs.5c03717}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11555--11563}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanism of unexpected in-trans post-PKS polyketide reduction in cochliodone biosynthesis}, volume = {147}, year = {2025}, }
• (2025). Nuclear quantum effects accelerate hot carrier relaxation but slow down recombination in metal halide perovskites. JACS, 147(13), 11543--11554. (www)

  @article{ , abstract = {Inorganic semiconductors are composed of heavy elements whose vibrational motions are well described by classical mechanics. Heavy elements, such as Pb and I, support charge carriers in metal halide perovskites. Nevertheless, the soft structure and strong coupling between the organic and inorganic components create conditions in which nuclear quantum effects (NQEs) can play important roles. By combining ab initio, ring-polymer, and nonadiabatic molecular dynamics approaches with time-domain density functional theory, we demonstrate how NQEs influence structural and electronic properties and electron-vibrational dynamics in hybrid organic–inorganic (MAPbI 3 ) and all-inorganic (CsPbI 3 ) perovskites. Quantum zero-point fluctuations enhance structural disorder, reduce the band gap, and accelerate elastic electron-vibrational scattering responsible for coherence loss. NQEs have opposite influences on intraband carrier relaxation and interband recombination. These inelastic scattering events are governed by the product of the overlap-like electron–phonon matrix element and atomic velocity. NQEs reduce the overlap and increases the velocity. The intraband carrier relaxation involves many states. Reduction of overlap between some states is offset by other pathways, while an increased velocity makes intraband relaxation faster. Electron–hole overlap in band-edge states plays a key role in the recombination, and its reduction by NQEs-enhanced disorder makes the recombination slower. This phenomenon is seen with both MAPbI 3 and CsPbI 3 and is much more pronounced when a light organic component is present. This study offers a detailed understanding of the role of NQEs in the carrier relaxation processes of perovskites, offering important theoretical insights into hot carriers and carrier recombination that govern the performance of solar cells and other optoelectronic devices.}, archive = {J_JACS}, author = {Yulong Liu and Shiying Shen and Oleg V. Prezhdo and Run Long and Wei-Hai Fang}, doi = {10.1021/jacs.5c02139}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11543--11554}, shortjournal = {J. Am. Chem. Soc.}, title = {Nuclear quantum effects accelerate hot carrier relaxation but slow down recombination in metal halide perovskites}, volume = {147}, year = {2025}, }
• (2025). Dearomative skeletal editing of benzenoids via diradical. JACS, 147(13), 11533--11542. (www)

  @article{ , abstract = {Dearomative skeletal editing of benzenoids represents a promising yet challenging strategy for the rapid construction of high-value carbon frameworks from readily accessible starting materials. Büchner reaction is a unique type of expansive skeletal editing that transforms benzenoids into functionalized cycloheptatrienes. However, due to challenges in compatibility and selectivity, achieving seamless integration of this reaction with dearomative cycloaddition within a unified system remains undeveloped. Here, we demonstrated an energy-transfer-induced intermolecular dearomative skeletal editing reaction of benzenoids with a range of electronically diverse alkynes. This protocol employed N -acylimines as diradical precursors to efficiently construct various structurally diverse polycyclic frameworks in high chemo-, regio-, and diastereoselectivities that have been previously inaccessible. The challenges related to general reactivity and selectivity issues were circumvented through the smooth merging of photoinduced skeletal editing with dearomative cycloaddition. Experimental and computational studies were performed to support the diradical mechanism and interpret the origins of the observed chemo-, regio-, and diastereoselectivities.}, archive = {J_JACS}, author = {Xiang-Xin Zhang and Shan-Tong Xu and Xue-Ting Li and Ting-Ting Song and Ding-Wei Ji and Qing-An Chen}, doi = {10.1021/jacs.5c01983}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11533--11542}, shortjournal = {J. Am. Chem. Soc.}, title = {Dearomative skeletal editing of benzenoids via diradical}, volume = {147}, year = {2025}, }
• (2025). Heteroepitaxial growth of narrow band gap carbon-rich carbon nitride using in situ polymerization to empower sunlight-driven photoelectrochemical water splitting. JACS, 147(13), 11511--11532. (www)

  @article{ , abstract = {We describe an in situ -polymerized conformal thin layer coating of narrow band gap carbon-rich carbon nitride (NBG-CRCN) on titania nanorod arrays to design a binary semiconductor heterojunction photocatalyst. The in situ polymerization creates a strong interaction between the TiO 2 nanorod substrate and the carbon nitride film, which prevents leaching of CRCN in liquid electrolytes. A unique aspect of our work is developing an easy and inexpensive technique for the heteroepitaxial growth of mechanically and photochemically stable carbon nitride thin films with intimate contact at the CN:TNR heterojunction interface. This method aids in overcoming one of the main problems with carbon nitride (CN), namely, the inability to produce an evenly distributed CN coating on a substrate. The synthesized NBG-CRCN@TNR extends the visible light absorption to 700 nm (E g = 1.7 eV) and red-shifts the photoluminescence (PL) emission peak to 580 nm. The peak shifts and broadening in the Raman spectra of the NBG-CRCN@TNR hybrid compared to those in TNR confirm an unusually strong interaction between TiO 2 and NBG-CRCN. An easy and inexpensive technique to heteroepitaxially grow CRCN (002) on rutile TiO 2 (110) is confirmed by advanced characterization. High-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction (SAED), and grazing-incidence wide-angle X-ray scattering (GIWAXS) suggest the heteroepitaxial growth of (002) CRCN on rutile TiO 2 (110). Under AM1.5G solar illumination, the NBG-CRCN@TNR hybrid shows superior performance in photoelectrochemical water splitting, generating a photocurrent density as high as 4.3 mA cm –2 in 1 M KOH under 0.6 V external bias, rising to 8.4 mA cm –2 in the presence of a hole scavenger (methanol). An impressive hydrogen evolution rate of 26.51 μmol h –1 with 88.12% Faradaic efficiency is recorded. Establishing a high-quality interface between g-C 3 N 4 and titania permits effective charge carrier separation, leading to enhanced photocatalytic activity.}, archive = {J_JACS}, author = {Narendra Chaulagain and Kazi M. Alam and John C. Garcia and Damini Vrushabendrakumar and Julian E. Heger and Guangjiu Pan and Navneet Kumar and Md. Masud Rana and Harshitha Rajashekhar and Riley W. Hooper and Saeid Kamal and Vladimir K. Michaelis and Alkiviathes Meldrum and Peter Müller-Buschbaum and Karthik Shankar}, doi = {10.1021/jacs.5c01824}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11511--11532}, shortjournal = {J. Am. Chem. Soc.}, title = {Heteroepitaxial growth of narrow band gap carbon-rich carbon nitride using in situ polymerization to empower sunlight-driven photoelectrochemical water splitting}, volume = {147}, year = {2025}, }
• (2025). Aqueous-S vs organic-S battery: Volmer-step involved sulfur reaction. JACS, 147(13), 11501--11510. (www)

  @article{ , abstract = {Aqueous-S batteries (ASBs) are emerging as promising energy storage technologies due to their high safety, low cost, and high theoretical energy density. However, the present understanding of sulfur evolution in water relies on experience derived from conventional organic electrolyte-based sulfur batteries (OSBs). The gap between ASB and OSB has impeded progress in advancing the rational design of sulfur catalysts in the aqueous phase. Herein, we reveal the unique interaction between H 2 O and S species, which is fundamentally distinguishable from the organic counterparts. A series of spectroscopy analyses discloses that elemental sulfur is initially reduced to polysulfides (mainly S 4 2– ), which subsequently react with H 2 O to generate HS – , involving both polysulfide conversion and the Volmer step of water dissociation. Combined electrochemical and computational analysis further proposes an aqueous-S catalyst selection metric based on simultaneous polysulfide adsorption and Volmer-step catalysis. As a proof of concept, we have successfully prioritized the Mo 2 C-catalyzed ASBs with a superior rate capability of 1040 mAh g –1 than the Fe 3 C (693 mAh g –1 ) and pure C (510 mAh g –1 ) at a high current density of 5 A g –1 . This work provides insights into the aqueous-S charge storage mechanism and establishes a foundational catalyst research paradigm for advancing the following ASBs.}, archive = {J_JACS}, author = {Tengsheng Zhang and Yilong Zhao and Yutong Feng and Boya Wang and Yanyan Zhang and Xinran Li and Jiawei Liu and Wanhai Zhou and Wei Li and Xin Liu and Dongyuan Zhao and Dongliang Chao}, doi = {10.1021/jacs.5c01727}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11501--11510}, shortjournal = {J. Am. Chem. Soc.}, title = {Aqueous-S vs organic-S battery: Volmer-step involved sulfur reaction}, volume = {147}, year = {2025}, }
• (2025). Molecularly responsive aptamer-functionalized hydrogel for continuous plasmonic biomonitoring. JACS, 147(13), 11485--11500. (www)

  @article{ , abstract = {Continuous in vivo monitoring of small molecule biomarkers requires biosensors with reversibility, sensitivity in physiologically relevant ranges, and biological stability. Leveraging the real-time, label-free detection capability of surface plasmon resonance (SPR) technology, a molecularly responsive hydrogel film is introduced to enhance small molecule sensitivity. This advanced biosensing platform utilizes split-aptamer-cross-linked hydrogels (aptagels) engineered using 8-arm poly(ethylene glycol) macromers, capable of directly and reversibly detecting vancomycin. Investigation through SPR and optical waveguide mode, along with quartz crystal microbalance with dissipation (QCM-D) monitoring, reveals that the reversible formation of analyte-induced ternary molecular complexes leads to aptagel contraction and significant refractive index changes. Optimization of aptamer cross-link distribution and complementarity of split-aptamer pairs maximizes conformational changes of the aptagel, demonstrating a detection limit of 160–250 nM for vancomycin (6–9 fold improvement over monolayer counterpart) with a broad linear sensing range up to 1 mM. The aptagel maintains stability over 24 h in blood serum and 5 weeks in diluted blood plasma (mimicking interstitial fluid). This structurally responsive aptagel platform with superior stability and sensitivity offers promising avenues for continuous in vivo monitoring of small molecules.}, archive = {J_JACS}, author = {Soohyun Park and Alice Gerber and Cátia Santa and Gizem Aktug and Bastian Hengerer and Heather A. Clark and Ulrich Jonas and Jakub Dostalek and Khulan Sergelen}, doi = {10.1021/jacs.5c01718}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11485--11500}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecularly responsive aptamer-functionalized hydrogel for continuous plasmonic biomonitoring}, volume = {147}, year = {2025}, }
• (2025). Reversible optical control of receptor tyrosine kinase activity and ERK dynamics using azobenzene-carrying DNA aptamer agonist. JACS, 147(13), 11477--11484. (www)

  @article{ , abstract = {Receptor tyrosine kinases (RTKs) play a pivotal role in cell signaling through their activation via dimerization. Recent studies have demonstrated the importance of the temporal dynamics of RTK activity and downstream signals, such as ERK, in determining the cell fate. To better understand these dynamics, it is essential to develop methods capable of controlling the RTK activity with high temporal resolution. However, techniques for precisely modulating the activity of endogenous RTKs without requiring genetic modification remain insufficiently established. In this study, we developed a DNA aptamer agonist, Met-azo-aptamer, which enables reversible optical control of the activity of the c-Met receptor, a member of the RTK family. This was achieved by incorporating azobenzene, a photoisomerizable molecule, into a DNA aptamer that binds to c-Met. This design allows light-induced switching between the active and inactive structures of the aptamer. When the aptamer was applied to HeLa cells and exposed to ultraviolet or blue light, phosphorylation signals within the cells were activated in response to the light patterns. Furthermore, by variation of the light patterns, the Met-azo-aptamer successfully controlled the timing, amplitude, and duration of downstream ERK activation. The Met-azo-aptamer developed in this study offers a high-resolution method for investigating the relationship between RTK activation patterns and cell function or fate.}, archive = {J_JACS}, author = {Masahiro Wakano and Masaya Tsunoda and Keiji Murayama and Jumpei Morimoto and Ryosuke Ueki and Saeko Aoyama-Ishiwatari and Yusuke Hirabayashi and Hiroyuki Asanuma and Shinsuke Sando}, doi = {10.1021/jacs.5c01559}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11477--11484}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible optical control of receptor tyrosine kinase activity and ERK dynamics using azobenzene-carrying DNA aptamer agonist}, volume = {147}, year = {2025}, }
• (2025). In situ identification of zinc sites as potential-dependent selectivity switch over dual-atom catalysts for H2O2 electrosynthesis. JACS, 147(13), 11465--11476. (www)

  @article{ , abstract = {Controllably breaking the activity–selectivity trade-offs in the electrocatalytic oxygen reduction reaction to produce H 2 O 2 has long been a challenge in renewable energy technologies. Herein, by assigning the activity and selectivity requirements to two independent single-atom sites, we deliberately engineered a Co–Zn DAC for promising H 2 O 2 electrosynthesis, from which the Co sites provided the activity response for oxygen reduction, and the Zn sites regulated the reaction selectivity toward the 2e – pathway. Through multidimensional in situ characterizations, a potential-dependent switching function of the Zn sites was revealed, which made the increase in H 2 O 2 production at various reaction stages controllable. As a result, efficient H 2 O 2 selectivity switching from 11.1% in the single Co atom catalyst to 94.8% in the Co–Zn DAC was realized, with a prominent turnover frequency of 2.7 s –1 among the reported H 2 O 2 -producing catalysts. Notably, a similar effect was also observed in M–Zn DACs (M = Pt, Ru, or Ni), which demonstrated the universal switcher role of the Zn sites. The real-time catalytic site behavior insights gained through this integrated experimental and theoretical study are envisioned to be valuable not only for the ORR but also for other energy catalysis reactions involving activity–selectivity trade-off issues.}, archive = {J_JACS}, author = {Qizheng An and Xupeng Qin and Xuan Sun and Xu Zhang and Yuhao Zhang and Jianglong Guo and Jingjing Jiang and Jing Zhang and Baojie Li and Yaling Jiang and Hui Zhang and Xin Chen and Yuanli Li and Kun Zheng and Weiren Cheng and Dingsheng Wang and Qinghua Liu}, doi = {10.1021/jacs.5c01449}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11465--11476}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ identification of zinc sites as potential-dependent selectivity switch over dual-atom catalysts for H2O2 electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Dissecting the effects of cage structure in the catalytic activation of imide chlorenium-ion donors. JACS, 147(13), 11456--11464. (www)

  @article{ , abstract = {Imide-based chlorinating reagents are mild and easy to use yet can lack the reactivity of charged chlorenium-ion donors. Here, we present a simple strategy for increasing the reactivity of these neutral chlorinating species by encapsulation inside a cationic coordination cage. Using this approach, we demonstrate that two different-sized Pd 2 L 4 cages can catalyze chlorolactonization and chlorocycloetherification reactions of acid and alcohol functionalized α and β-substituted styrene substrates with either 1,3-dichloro-5,5-dimethylhydantoin (DCDMH) or N -chlorosuccinimide (NCS) as the chlorenium sources. A kinetic study shows that the cages are proficient catalysts with a significant acceleration up to 10 5 . However, an unexpected dichotomy is revealed wherein the smaller cage, which is best preorganized to bind and nominally provide maximum activation of the imide reagent, shows an order of magnitude less acceleration than the larger cage that has apparently mismatched host–guest chemistry. When the scope of reactions is further extended to the chlorination of simple, unfunctionalized α-methylstyrene, the same pattern of cage reactivity is observed, suggesting that differences are not explained by coencapsulation. Computational studies indicate that the trend in reactivity is caused by the transition state being less fixed in the larger cage, allowing it to find optimal binding and thereby generate stronger interactions. This investigation highlights the importance of understanding the underlying mechanisms of cage reactivity to design new noncovalent catalysts for a greater range of transformations.}, archive = {J_JACS}, author = {Hang Zhou and Tomasz K. Piskorz and Keyu Liu and Yining Lu and Fernanda Duarte and Paul J. Lusby}, doi = {10.1021/jacs.5c01249}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11456--11464}, shortjournal = {J. Am. Chem. Soc.}, title = {Dissecting the effects of cage structure in the catalytic activation of imide chlorenium-ion donors}, volume = {147}, year = {2025}, }
• (2025). Acylphosphine route to colloidal InP quantum dots. JACS, 147(13), 11446--11455. (www)

  @article{ , abstract = {InP-based quantum dots (QDs) represent the major commercial success of colloidal semiconductor nanocrystals (NCs). A combination of the robust, mostly covalent, structure and nontoxic nature of the constituent elements makes them a QD material of choice for display and LED technologies. Despite successful commercial realization, InP NCs still lack synthetic versatility and robustness, seen, for instance, as a continued quest to substitute a commonly used pyrophoric and expensive tris(trimethylsilyl)phosphine precursor. Herein, we propose solid-state, nonpyrophoric, and synthetically readily accessible acylphosphines as convenient phosphorus precursors for the synthesis of InP NCs. When combined with suitable anionic nucleophiles, such as arylthiolates, both tris(acyl)phosphines and indium complexes of bis(acyl)phosphines act as efficient sources of the P 3– anion, as corroborated by NMR spectroscopy and powder X-ray diffraction studies. This type of reactivity is utilized in colloidal synthesis of uniform InP QDs with well-defined excitonic features in their optical absorption spectra, spanning 460–600 nm. The conversion kinetics and therefore the final NC size are controlled by the nature of acyl substituents and by the use of either indium or zinc long-chain carboxylates as ligands. The proposed acylpnictide route is anticipated to foster the development of other metal phosphide and metal arsenide NCs.}, archive = {J_JACS}, author = {Andriy Stelmakh and Georgios Marnieros and Erik Schrader and Georgian Nedelcu and Oleh Hordiichuk and Eduard Rusanov and Ihor Cherniukh and Daniel Zindel and Hansjörg Grützmacher and Maksym V. Kovalenko}, doi = {10.1021/jacs.5c01305}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11446--11455}, shortjournal = {J. Am. Chem. Soc.}, title = {Acylphosphine route to colloidal InP quantum dots}, volume = {147}, year = {2025}, }
• (2025). Nonheme manganese-catalyzed oxidative N-dealkylation of tertiary amides: Manganese(IV)-oxo aminopyridine cation radical species and hydride transfer mechanism. JACS, 147(13), 11432--11445. (www)

  @article{ , abstract = {The development of efficient and practical N -dealkylation reactions stands as a longstanding objective in synthetic chemistry. Inspired by the oxidative N -dealkylation reactions mediated by heme and nonheme metalloenzymes, we disclose a biomimetic oxidative N -dealkylation catalysis that utilizes a nonheme manganese complex bearing anthryl-appended aminopyridine ligand and hydrogen peroxide (H 2 O 2 ) as the terminal oxidant. A variety of Weinreb amides and cyclic aliphatic amines are efficiently transformed into valuable methyl hydroxamates and ω-amino acids through oxidative C–N bond cleavage. Mechanistic studies, including density functional theory (DFT) calculations, reveal that a manganese(IV)-oxo aminopyridine cation radical species, which is formed via the bromoacetic acid-assisted heterolytic O–O bond cleavage of a presumed manganese(III)-hydroperoxo aminopyridine species and the subsequent intramolecular electron transfer (ET) from the anthryl group of the aminopyridine ligand to the manganese center, is the active intermediate that initiates the oxidative N -dealkylation reactions; this process is reminiscent to the heterolytic O–O bond cleavage of iron(III)-hydroperoxo porphyrin intermediates (Cpd 0) to form iron(IV)-oxo porphyrin π-cation radicals (Cpd I) that are responsible for diverse selective oxidation reactions. Moreover, it is revealed that the oxidative activation of the C–H bond adjacent to the nitrogen atom proceeds via a hydride transfer (HT) mechanism, which involves a concerted asynchronous proton-coupled electron transfer (PCET), followed by an ET process. Thus, this study reports the first instance of catalytic oxidative N -dealkylation of a variety of tertiary amides, such as Weinreb amides and cyclic aliphatic amines, mediated by a Cpd I-like nonheme manganese(IV)-oxo aminopyridine cation radical species via an initial HT pathway.}, archive = {J_JACS}, author = {Chunxia Wu and Shoujun Wang and Dongru Sun and Jie Chen and Wenhua Ji and Yong Wang and Wonwoo Nam and Bin Wang}, doi = {10.1021/jacs.5c01391}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11432--11445}, shortjournal = {J. Am. Chem. Soc.}, title = {Nonheme manganese-catalyzed oxidative N-dealkylation of tertiary amides: Manganese(IV)-oxo aminopyridine cation radical species and hydride transfer mechanism}, volume = {147}, year = {2025}, }
• (2025). Revision of the formycin a and pyrazofurin biosynthetic pathways reveals specificity for d-glutamic acid and a cryptic N-acylation step during pyrazole core formation. JACS, 147(13), 11425--11431. (www)

  @article{ , abstract = {Formycin A and pyrazofurin are two naturally occurring pyrazole-derived C -nucleosides with antibacterial and antiviral activities. While earlier studies have established the chemistry of C -glycosidic bond formation as well as the subsequent steps in the biosynthesis of formycin A and pyrazofurin, how the pyrazole ring itself is constructed remains elusive. While N–N bond formation in the pyrazole ring was previously reported to involve coupling of N 6 -hydroxylated l -lysine and l -glutamic acid catalyzed by the hydrazine synthetase PyfG, herein PyfG and its homologue ForJ are shown instead to recognize d -glutamate instead of l -glutamate. The hydrazine product of ForJ/PyfG catalysis then releases α-hydrazino d -glutamic acid upon processing by the NAD-dependent oxidoreductase ForL. Furthermore, N -acylation of α-hydrazino d -glutamate with an amino acid catalyzed by the ATP-grasp ligase ForM/PyfJ is indispensable for recognition by the FAD-dependent oxidoreductase ForR/PyfK to perform dehydrogenation of the Cα–N bond and thereby form a hydrazone intermediate. This work not only demonstrates that d -glutamic acid is the correct substrate for hydrazine biosynthesis but also reveals a cryptic N -acylation step in the assembly of the pyrazole core. These results thus provide significant insights into the biosynthesis of pyrazole rings that are rarely seen in natural products.}, archive = {J_JACS}, author = {Ziyang Zheng and Daan Ren and Yeonjin Ko and Hung-wen Liu}, doi = {10.1021/jacs.5c01277}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11425--11431}, shortjournal = {J. Am. Chem. Soc.}, title = {Revision of the formycin a and pyrazofurin biosynthetic pathways reveals specificity for d-glutamic acid and a cryptic N-acylation step during pyrazole core formation}, volume = {147}, year = {2025}, }
• (2025). Enantioselective hydrodifluoroalkylation of alkenes with conformationally tuned peptidyl hydrogen atom transfer catalysts. JACS, 147(13), 11412--11424. (www)

  @article{ , abstract = {We report the enantioselective hydrodifluoroalkylation of alkenes proceeding via an asymmetric hydrogen atom transfer (HAT) event catalyzed by thiol-containing tetrapeptides. Photocatalytic generation of a difluoroacetyl radical followed by carbon–carbon bond formation results in a prochiral carbon-centered radical that engages with the chiral catalyst. A trialkylamine reductant is proposed to turn over the catalyst in this net-reductive transformation. Notably, incorporating an ( S )-β-methyl-substituted cysteine as the N -terminal residue improved selectivity relative to that of the native N -terminal cysteine (Cys) residue, and X-ray crystallographic analysis supports the conformational underpinning of this effect. A range of enantioenriched γ-substituted amides were synthesized in up to a 96:4 enantiomeric ratio, demonstrating the broad functional group tolerance of this method. Models accounting for asymmetric induction are proposed with supporting DFT calculations.}, archive = {J_JACS}, author = {Marcus Vinicius Pinto Pereira Junior and Eric P. Geunes and Huiling Shao and Yiran Zhang and Jinkai Cheng and Samantha V. Magpantay and Brandon Q. Mercado and James M. Mayer and Kendall N. Houk and Robert R. Knowles and Scott J. Miller}, doi = {10.1021/jacs.5c01166}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11412--11424}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective hydrodifluoroalkylation of alkenes with conformationally tuned peptidyl hydrogen atom transfer catalysts}, volume = {147}, year = {2025}, }
• (2025). High-connectivity triazolate-based Metal–Organic framework for water harvesting. JACS, 147(13), 11407--11411. (www)

  @article{ , abstract = {Increasing the connectivity of structural units presents a potentially valuable approach to improve hydrolytic stability in metal–organic frameworks (MOFs). We herein leverage this strategy by synthesizing the first tritopic benzotriazolate MOF, Zn 5 (OAc) 4 (TBTT) 2 (H 3 TBTT = 2,4,6-tris(1 H -benzo[ d ][1,2,3]triazol-5-yl)-1,3,5-triazine), which exhibits open metal sites, high connectivity, high porosity, and significant water uptake capacity. The MOF adopts a previously unknown topology with (3,6,6)-connectivity, which is supported by single-crystal electron diffraction and elemental analysis. The framework undergoes postsynthetic metal and anion exchange with NiCl 2 , which increases the accessible pore volume and the net hydrophilicity of the framework. With this exchange, the apparent BET surface area increases from 1994 to 3034 m 2 /g, and the water uptake step shifts from 56 to 33% relative humidity (RH). The high gravimetric capacity of the Ni-rich MOF, 0.98 g/g, translates to a working capacity of 0.64 g/g during a pressure swing cycle between 20 and 40% RH at 25 °C. Combining this performance with a less than 2% loss in working capacity over 100 cycles, the new material rivals the best MOF water sorbents to date.}, archive = {J_JACS}, author = {Karla Ravin and Patrick Sarver and Bhavish Dinakar and Lukáš Palatinus and Peter Müller and Julius Oppenheim and Mircea Dincă}, doi = {10.1021/jacs.5c01062}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11407--11411}, shortjournal = {J. Am. Chem. Soc.}, title = {High-connectivity triazolate-based Metal–Organic framework for water harvesting}, volume = {147}, year = {2025}, }
• (2025). Microdroplet chemistry with unactivated droplets. JACS, 147(13), 11399--11406. (www)

  @article{ , abstract = {Microdroplet chemistry has attracted much attention owing to its ability to accelerate otherwise slow reactions and to trigger thermodynamically forbidden reactions. The cause of this unique behavior is the intrinsic properties of the droplets, such as the spontaneously generated electric field on the droplet surface. However, some have argued that the droplet generation methods provided energy to the reactions, and the different interfaces that the droplets contact also played important roles; therefore, it is the droplet activation or the environment, not the intrinsic properties, that is responsible for the observed chemistry. In this study, we used adiabatic expansion and dry ice in water to generate homogeneous, contactless, supercooled, and unactivated microdroplets. A large variety of reactions were successfully tested. We opine that it is the intrinsic properties, and not droplet activation, that are responsible for microdroplet chemistry.}, archive = {J_JACS}, author = {Huan Chen and Xiaoxu Li and Bowen Li and Yeye Chen and Haoran Ouyang and Youcun Li and Xinxing Zhang}, doi = {10.1021/jacs.5c01072}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11399--11406}, shortjournal = {J. Am. Chem. Soc.}, title = {Microdroplet chemistry with unactivated droplets}, volume = {147}, year = {2025}, }
• (2025). Hand milling induced phase transition for marcasite-type carbodiimide. JACS, 147(13), 11390--11398. (www)

  @article{ , abstract = {While high-pressure phase transitions have been widely studied in inorganic compounds such as oxides and chalcogenides, relatively little attention has been given to compounds containing molecular anions, such as carbodiimides and cyanamides. This study investigates the phase transition of marcasite-type orthorhombic Ba 0.9 M 0.1 NCN carbodiimides, where a transformation to a CsCl-type tetragonal phase was observed at room temperature under hydrostatic pressure of 0.8 GPa (M = Ca) and 0.3 GPa (M = Sr). This transition, accompanied by an increase in the metal coordination under from 6 to 8, occurs at pressures significantly lower than those required for the high-pressure phase transitions of rock-salt-type metal halides and marcasite-type metal diantimonides. Remarkably, partial phase transitions were also induced by hand milling, a process that applies localized shear forces, distinct from the particle-crushing effects of high-energy ball milling. The transition mechanism, analyzed via variable-cell nudged elastic band (VCNEB) calculations, revealed that while the linear NCN 2– anions remain stable, the shear-sliding of Ba 2+ cations and the rotation of NCN 2– anions are critical to the structural transformation. These findings underscore the potential of hand milling to effectively induce phase transitions in compounds containing linear molecular anions, offering new strategies for predicting and controlling such transitions in similar materials.}, archive = {J_JACS}, author = {Yuzuki Yamamoto and Kazuki Kume and Suzuka Miyazaki and Ayako Shinozaki and Peng Song and Sayed Sahriar Hasan and Kenta Hongo and Ryo Maezono and Hiroki Ubukata and Hiroshi Kageyama and Mikio Higuchi and Yuji Masubuchi}, doi = {10.1021/jacs.5c00962}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11390--11398}, shortjournal = {J. Am. Chem. Soc.}, title = {Hand milling induced phase transition for marcasite-type carbodiimide}, volume = {147}, year = {2025}, }
• (2025). Unraveling the kinetics of hydride formation and decomposition at Pd–Au bimetallic interfaces: A combined spectroscopic and computational study. JACS, 147(13), 11378--11389. (www)

  @article{ , abstract = {Supported Pd–Au bimetallic nanoparticles make up a promising class of catalysts used for hydrogenation and oxidation reactions. Recently, the role of dynamic restructuring of Pd regions at and near the nanoparticle surface in response to modulating gas (H 2 and O 2 ) concentrations was highlighted for controlling the surface Pd oxide stoichiometry. Here, we investigate the mechanism of formation and decomposition of Pd hydride (PdH x ) at and near the bimetallic nanoparticle surfaces, a key species for controlling the activity, selectivity, and stability of Pd catalysts in many hydrogenation reactions. We employ modulation excitation X-ray absorption spectroscopy (ME-XAS) to directly observe the time scale of PdH x formation and decomposition on the surface of Pd–Au nanoparticles. Density functional theory (DFT) calculations provide additional insights into the stability and energetics of PdH x formation under varying H fractions and Pd substructures. Our results reveal a complex interplay between Pd ensemble size, surface structure, and hydrogen environment in determining the kinetics and thermodynamics of PdH x formation. By elucidating the mechanisms underlying surface PdH x formation and decomposition, the rational design of dynamic catalysts with controlled Pd hydride stoichiometries can become possible.}, archive = {J_JACS}, author = {Prahlad K. Routh and Xihan Liu and Evgeniy Redekop and Jin Soo Lim and Sebastian Prodinger and Jessi E. S. van der Hoeven and Joanna Aizenberg and Maarten Nachtegaal and Adam H. Clark and Philippe Sautet and Anatoly I. Frenkel}, doi = {10.1021/jacs.5c00842}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11378--11389}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the kinetics of hydride formation and decomposition at Pd–Au bimetallic interfaces: A combined spectroscopic and computational study}, volume = {147}, year = {2025}, }
• (2025). Photochemical dual radical coupling of carboxylates with Alkenes/Heteroarenes via diradical equivalents. JACS, 147(13), 11368--11377. (www)

  @article{ , abstract = {Carboxylate diradical intermediates, with α-carbon and carboxylic oxygen acting as reactive radical centers, represent a highly attractive and long-sought species in reaction design and synthesis. However, capturing these intermediates for diradical coupling reactions poses a formidable challenge due to their inherent instability and spontaneous decarboxylation. Here, we addressed this challenge by temporarily masking the carboxylate oxygen radical reactivity via a photocleavable dynamic oxygen–iodine bond. This approach effectively prevents unwanted decarboxylation and enables the controlled utilization of the carboxylate oxygen radical in forming new bonds. Carboxylates and alkenes/heteroarenes, among the most readily available raw materials, can now seamlessly couple via radical pathways to form γ-butyrolactones, which are common motifs found in numerous natural products and bioactive molecules. Ionic reaction pathways via traditional intermediates of carboxylates are ruled out based on experimental studies and density functional theory (DFT) calculations. This strategy overcomes the substrate limitations of traditional methods, significantly expanding the range of applicable alkenes/heteroarenes. Our method allows transforming carboxylates and alkenes via new reaction modes to diverse products and offers new insights into developing di- and multiradical equivalents for unprecedented reactions and synthetic designs.}, archive = {J_JACS}, author = {Guanjie Wang and Jingxin Ding and Ji-Chun Wu and Jiamiao Jin and Xinglong Zhang and Shiqing Huang and Shichao Ren and Yonggui Robin Chi}, doi = {10.1021/jacs.5c00835}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11368--11377}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemical dual radical coupling of carboxylates with Alkenes/Heteroarenes via diradical equivalents}, volume = {147}, year = {2025}, }
• (2025). η6-benzene tetra-anion complexes of early and late rare-earth metals. JACS, 147(13), 11359--11367. (www)

  @article{ , abstract = {A novel synthetic route to the triple-decker benzene tetra-anion complexes [(η 5 -C 5 i Pr 5 )M(μ:η 6 :η 6 -C 6 H 6 )M(η 5 -C 5 i Pr 5 )] is reported for a range of early and late rare-earth elements, i.e., M = Y, La, Sm, Gd, and Dy ( 1 M ). The lanthanum complex 1 La is the first benzene tetra-anion complex of the largest rare-earth element. Aromaticity in the 10π-electron benzene ligands is confirmed through crystallographic studies of all compounds and nucleus-independent chemical shift calculations on 1 Y and 1 La . Analysis of the bonding in 1 Y and 1 La using density functional theory revealed strong covalency in the metal-benzene interactions, with very similar contributions from the metal 4d/5d orbitals, respectively, and the benzene π* orbitals. Magnetic susceptibility measurements on 1 Sm , 1 Gd , and 1 Dy are also consistent with the presence of a benzene tetra-anion ligand. The origins of the appreciable exchange coupling constant of J exch = −3.35 cm –1 (−2 J formalism) in 1 Gd are established through a computational study of the interacting magnetic orbitals. The dynamic magnetic properties of 1 Dy are also described. The clear absence of SMM behavior in the dysprosium complex is explained using multireference calculations and an ab initio ligand-field theory description of the 4f orbitals, which clearly show that the benzene tetra-anion ligand provides a dominant equatorial contribution.}, archive = {J_JACS}, author = {Ming Liu and Yan-Cong Chen and Arpan Mondal and Huan Wang and Ming-Liang Tong and Richard A. Layfield and Fu-Sheng Guo}, doi = {10.1021/jacs.5c00707}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11359--11367}, shortjournal = {J. Am. Chem. Soc.}, title = {η6-benzene tetra-anion complexes of early and late rare-earth metals}, volume = {147}, year = {2025}, }
• (2025). Flexible organic crystalline fibers and loops with strong second harmonic generation. JACS, 147(13), 11346--11358. (www)

  @article{ , abstract = {Flexible organic crystals represent a novel class of smart materials that open many opportunities for optical applications. While it has been established that elastic or plastic deformation of slender molecular crystals can be commonly induced by external intervention, crystals that grow in bent or curled shapes naturally are rarely reported. This study introduces an extraordinarily flexible organic crystalline fibrous material, ( Z )-3-(2,3-dichloropyridin-4-yl)-2-(3,5-dimethylphenyl)acrylonitrile (DPA), that crystallizes both as straight and curled crystals. Crystals of DPA are easily obtained from solution either as long fibers or as crystals that are curled to various extent, and sometimes even closed into a loop. The straight crystalline fibers can be bent mechanically by applying force or photochemically by exposure to ultraviolet light. The straight and curled crystals are both polar and capable of highly efficient second harmonic generation (SHG) with respective intensities of 2.03 ± 0.15 and 1.52 ± 0.12 times (equivalent strain ≈ 1%) that of urea. Curling during crystal growth provides direct access to curved SHG-active flexible organic optical waveguiding elements, such as crystalline optical ring resonators, thereby circumventing the necessity for manual crystal bending, which is usually not readily scalable. This work highlights the unconventional properties and capabilities that fibrous molecular crystalline materials bring to the global materials space and their potential applications as shape-conforming, nonlinear organic materials.}, archive = {J_JACS}, author = {Jiawei Lin and Shi Tang and Liang Li and Liwen Fang and Qun Zeng and Guangxu Sun and Songgu Wu and Panče Naumov and Junbo Gong}, doi = {10.1021/jacs.5c00598}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11346--11358}, shortjournal = {J. Am. Chem. Soc.}, title = {Flexible organic crystalline fibers and loops with strong second harmonic generation}, volume = {147}, year = {2025}, }
• (2025). Diversity synthesis using glutarimides as rhodium carbene precursors in enantioselective C–H functionalization and cyclopropanation. JACS, 147(13), 11336--11345. (www)

  @article{ , abstract = {Cereblon E3 ligase modulatory drugs (CELMoDs) can be used to target proteins and mark them for proteasomal degradation by recruiting them to cereblon (CRBN), the substrate receptor of the CRL4 CRBN E3 ubiquitin ligase complex. Modifications to the stereochemistry and regiochemistry of distal functionality on CELMoDs have been shown to have large effects on degradation activity and selectivity; however, methods allowing the rapid and selective introduction of enantioenriched moieties are rare. Herein, we report that classical CRBN-binding glutarimide cores can be successfully derivatized to aryl diazoacetates. These diazo derivatives, when in the presence of a dirhodium catalyst, successfully undergo high-yielding and highly enantioselective C–H functionalization of hydrocarbons and cyclopropanation of styrene. These products can be used to create not only molecular glue degrader-like compounds but also intermediates that can be elaborated into effective bifunctional ligand-directed degraders. Our findings highlight both the effectiveness of dirhodium catalysis in a drug discovery context and a new method for preparing diverse and stereoenriched glutarimide-containing compounds.}, archive = {J_JACS}, author = {William F. Tracy and Jack C. Sharland and Duc Ly and Geraint H. M. Davies and Djamaladdin G. Musaev and Hua Fang and Jesus Moreno and Emily C. Cherney and Huw M. L. Davies}, doi = {10.1021/jacs.5c00568}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11336--11345}, shortjournal = {J. Am. Chem. Soc.}, title = {Diversity synthesis using glutarimides as rhodium carbene precursors in enantioselective C–H functionalization and cyclopropanation}, volume = {147}, year = {2025}, }
• (2025). Imine-based transient supramolecular polymers. JACS, 147(13), 11327--11335. (www)

  @article{ , abstract = {Systems that change properties upon exposure to chemical stimuli offer the interesting prospect of (partially) mimicking the functions of living systems. Over the past decade, numerous supramolecular systems whose chemical composition and properties are regulated by the dissipation of chemical fuels have been reported. These systems are typically based on the transient transformation of a “dormant” species into an active, self-assembling supramolecular monomer. The process is powered by fuel consumption and terminates upon fuel depletion, restoring the initial dormant state. Previously reported out-of-equilibrium supramolecular polymerizations relied on the activation of the dormant species by adding or removing small structural units to enable supramolecular polymerization. Here, we present an approach that combines the reversibility of dynamic covalent chemistry and supramolecular chemistry to trigger transient supramolecular polymerizations by “recycling” the components of a dynamic combinatorial library (DCL). Treatment of an equilibrated DCL of aliphatic imines and aromatic amines with an activated carboxylic acid (ACA) generates a dissipative dynamic combinatorial library of aromatic imines and protonated aliphatic amines. The transient acidic conditions enable the creation of a supramolecular polymer held together by interactions between the protonated aliphatic amines and the crown ether moieties embedded in the scaffold of the aromatic imines. Thus, fuel dissipation reshuffles the chemical connectivity and enables the temporary transformation of a purely covalent (polymeric) system into a supramolecular polymer. We demonstrate the strategy using two different covalent dormant feedstocks consisting of a diimine macrocycle involving a calix[4]arene scaffold and a distribution of imine (cyclo)oligomers derived from an isophthalaldehyde skeleton.}, archive = {J_JACS}, author = {Gabriele Melchiorre and Lucia Visieri and Matteo Valentini and Roberta Cacciapaglia and Alessandro Casnati and Laura Baldini and José Augusto Berrocal and Stefano Di Stefano}, doi = {10.1021/jacs.5c00274}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11327--11335}, shortjournal = {J. Am. Chem. Soc.}, title = {Imine-based transient supramolecular polymers}, volume = {147}, year = {2025}, }
• (2025). Dicationic boron derivatives of schlenk’s and thiele’s hydrocarbon. JACS, 147(13), 11318--11326. (www)

  @article{ , abstract = {In recent years, neutral NHC-stabilized boryl radicals have been investigated as reactive species in various organic transformations. However, cationic boron radicals have been significantly less explored. In addition, boron-centered open-shell species with S > 1/2 have emerged as attractive synthetic targets. In this study, we provide a synthetic route to an NHC-stabilized boryl radical cation as a salt of the weakly coordinating [Al(OR F ) 4 ] − ( R F = C(CF 3 ) 3 ) anion. The synthetic procedure was extended to dicationic diboron derivatives of Schlenk’s and Thiele’s hydrocarbons with meta - and para -phenylene coupling units between the spin centers. While most known isolable boron biradicals have a singlet ground-state with a thermally accessible triplet state, the boron version of Schlenk’s hydrocarbon occupies a ground-state triplet spin-state, as shown by combined electron paramagnetic resonance spectroscopy and density functional theory studies. Furthermore, initial reactivity studies of the dications with elemental sulfur and diphenyldiselenide are presented.}, archive = {J_JACS}, author = {Philipp Dabringhaus and Andrew Molino and Noah D. McMillion and Robert J. Gilliard, Jr}, doi = {10.1021/jacs.5c00236}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11318--11326}, shortjournal = {J. Am. Chem. Soc.}, title = {Dicationic boron derivatives of schlenk’s and thiele’s hydrocarbon}, volume = {147}, year = {2025}, }
• (2025). Late-stage photoredox-catalyzed aryl C–H bond diazomethylation with atomic carbon reagents. JACS, 147(13), 11309--11317. (www)

  @article{ , abstract = {Herein, we present a novel class of diazo compounds as atomic carbon reagents substituted with two orthogonal redox-active leaving groups that were exploited in the late-stage construction of chiral centers with aryl C–H bonds from aromatic feedstocks and drug molecules. Key to the strategy was the use of photoredox catalysis to enable an initial C–H diazomethylation reaction able to generate diazomethyl-substituted redox-active esters. Subsequent construction of chiral centers with readily available starting materials proceeded using a broad range of well-known diazo and redox-active ester functionalizations. Moreover, the applicability of our novel atomic carbon reagent was tested in the automated parallel synthesis of a library of Fenofibrate derivatives.}, archive = {J_JACS}, author = {Alessio Puggioli and Liyin Jiang and Ana G. Herraiz and Leonardo J. Nannini and Karen de la Vega-Hernández and Anxo Rey-Blanco and Alejandro Diéguez-Vázquez and Santiago Cañellas and Marcos G. Suero}, doi = {10.1021/jacs.5c00045}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11309--11317}, shortjournal = {J. Am. Chem. Soc.}, title = {Late-stage photoredox-catalyzed aryl C–H bond diazomethylation with atomic carbon reagents}, volume = {147}, year = {2025}, }
• (2025). Hydroformylation over zeolite catalysts with solvophobic micropores. JACS, 147(13), 11301--11308. (www)

  @article{ , abstract = {Traditional gas–liquid–solid triphase reactions are often limited by gas solubility and diffusion in the liquid phase. We reported that a solvophobic catalyst with gas-filled micropores could enrich enormous amounts of gas molecules to accelerate Rh-catalyzed hydroformylation. This reaction used siliceous MFI zeolite fixed Rh nanoparticles in a mesitylene solvent. Owing to the shape selectivity, zeolite micropores prevent mesitylene from wetting the solid, allowing the rapid transport and efficient enrichment of gaseous reactants. This catalyst catalyzed ethylene hydroformylation with a propanal production rate significantly higher than those of the generally supported catalysts.}, archive = {J_JACS}, author = {Yuexin Wu and Zhiqiang Liu and Hai Wang and Hui Shi and Wentao Yuan and Yong Wang and Yifeng Liu and Yating Lv and Xuedi Qin and Anmin Zheng and Liang Wang and Feng-Shou Xiao}, doi = {10.1021/jacs.4c18771}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11301--11308}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydroformylation over zeolite catalysts with solvophobic micropores}, volume = {147}, year = {2025}, }
• (2025). Dynamics of DNA repair by class-II photolyases via a unified electron-transfer bifurcating mechanism. JACS, 147(13), 11291--11300. (www)

  @article{ , abstract = {The class-II photolyases (PLs) are distantly related to the microbial class-I photolyases with low sequence similarity, yet they maintain a similar structural topology and repair the same UV-induced cyclobutane pyrimidine dimer (CPD). The class-I photolyases have been well characterized through a direct electron-transfer (ET) tunneling mechanism with high repair quantum yield, but such a mechanism seemingly does not apply to all of the members in the diversified photolyase family. Here, using femtosecond spectroscopy, we show our systematic characterization of CPD repair by the class-II photolyases from Methanosarcina mazei and Drosophila melanogaster and reveal their complete photocycles with determination of reaction times of all ten elementary steps, including seven electron-transfer processes. We found that the initial electron injection bifurcates along two parallel routes, direct tunneling and two-step hopping. Unlike the class-I photolyases, the direct tunneling process here is significantly slower, occurring in several nanoseconds. This slow tunneling route leads to shifting of the branching yield toward the intrinsic two-step hopping pathway through the adenine intermediate. Throughout the photolyase family, the enzymes have adopted a unified bifurcating electron-transfer strategy as a universal repair mechanism through evolution.}, archive = {J_JACS}, author = {Xiaodan Cao and Luyao Yan and Chao Yang and Lijuan Wang and Meng Zhang and Dongping Zhong}, doi = {10.1021/jacs.4c18557}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11291--11300}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamics of DNA repair by class-II photolyases via a unified electron-transfer bifurcating mechanism}, volume = {147}, year = {2025}, }
• (2025). Intramolecular singlet fission in individual graphene Nanoribbons─Competition with a charge transfer. JACS, 147(13), 11277--11290. (www)

  @article{ , abstract = {Graphene nanoribbons (NRs) constitute a versatile platform for developing novel materials, where their structure governs their optical, electronic, and magnetic properties while also shaping their excited-state dynamics. Here, we investigate a set of three twisted N-doped molecular NRs of increasing length, obtained by linearly fusing perylene diimide to pyrene and pyrazino- or thiadiazolo-quinoxaline residues. By employing various temperature-dependent time-resolved spectroscopy techniques, we reveal how the flexible twisted NR geometry promotes the formation of a mixed electronic state with varying contributions from locally excited and charge-transfer (CT) states. The fate of this mixed state is highly sensitive to the molecular geometry, length, and solvent polarity. For the shortest NR, intersystem crossing dominates the deactivation pathway, efficiently generating triplets in low-polarity solvents. In contrast, for the extended NRs, intramolecular singlet fission (SF) takes place within a single nanoribbon. This is enabled by enhanced superexchange coupling due to a pronounced push–pull nature and the existence of multiple localized π-electron states caused by heteroatom doping, thereby circumventing the need for dimeric interactions typically associated with conventional SF systems. In higher-polarity environments, evidence of a (diabatic) CT state emerges. These findings underscore the intricate relationship between geometry, energy levels, and excited-state dynamics in twisted N-doped NRs.}, archive = {J_JACS}, author = {Phillip M. Greißel and Giovanni M. Beneventi and René Weiß and Anna-Sophie Wollny and Rajeev K. Dubey and Manuel Melle-Franco and Timothy Clark and Aurelio Mateo-Alonso and Dirk M. Guldi}, doi = {10.1021/jacs.4c18051}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11277--11290}, shortjournal = {J. Am. Chem. Soc.}, title = {Intramolecular singlet fission in individual graphene Nanoribbons─Competition with a charge transfer}, volume = {147}, year = {2025}, }
• (2025). Donor–Acceptor nanohoops: Impact of the ratio and arrangement of the fluorenone and carbazole moieties. JACS, 147(13), 11267--11276. (www)

  @article{ , abstract = {We report herein the synthesis and characterization of four donor–acceptor nanohoops incorporating fluorenone and carbazole as electron-poor and electron-rich units, respectively. The well-known platinum-mediated cyclization reaction here provides, in high yields, a mixture of four nanohoops possessing different and unexpected molecular arrangements. The four nanohoops have been isolated and characterized, and the impact of the number and arrangement of the carbazole and fluorenone moieties has been studied by spectroscopic and electrochemical analyses. Thanks to the intramolecular charge transfer resulting from the interaction between the carbazole and fluorenone units, their fluorescence was significantly red-shifted by 100 nm compared with a cyclic 2,7-tetracarbazole. This work highlights the singularity of the platinum-mediated cyclization reaction to construct donor–acceptor nanohoops with molecular arrangements, which are challenging to reach by other synthetic methods.}, archive = {J_JACS}, author = {Clément Brouillac and Elodie Dureau and Olivier Jeannin and Joëlle Rault-Berthelot and Cyril Poriel and Cassandre Quinton}, doi = {10.1021/jacs.4c18293}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11267--11276}, shortjournal = {J. Am. Chem. Soc.}, title = {Donor–Acceptor nanohoops: Impact of the ratio and arrangement of the fluorenone and carbazole moieties}, volume = {147}, year = {2025}, }
• (2025). Pore space partition enabled by Lithium(I) chelation of a Metal–Organic framework for benchmark C2H2/CO2 separation. JACS, 147(13), 11257--11266. (www)

  @article{ , abstract = {Adsorptive separation of acetylene (C 2 H 2 ) from carbon dioxide (CO 2 ) offers a promising approach to purify C 2 H 2 with low-energy footprints. However, the development of ideal adsorbents with simultaneous high C 2 H 2 adsorption and selectivity remains a great challenge due to their very small molecular sizes and physical properties. Herein, we report a lithium(I)-chelation strategy for pore space partition (PSP) in a microporous MOF (Li + @NOTT-101-(COOH) 2 ) to achieve simultaneous high C 2 H 2 uptake and selectivity. The chelation model of Li + ions within the framework was visually identified by single-crystal X-ray diffraction studies. The immobilized Li + ions were found to have two functions: (1) partitioning large pore cages into smaller ones while maintaining high surface area and (2) providing specific binding sites to selectively take up C 2 H 2 over CO 2 . The resulting Li + @NOTT-101-(COOH) 2 exhibits a rare combination of a simultaneous high C 2 H 2 capture capacity (205 cm 3 g –1 ) and C 2 H 2 /CO 2 selectivity (13) at ambient conditions, far surpassing that of NOTT-101-(COOH) 2 (148 cm 3 g –1 and 3.8, respectively) and most top-tier materials reported. Theoretical calculations and gas-loaded SCXRD studies reveal that the chelated Li + ions combined with the segmented small cages can selectively bind with a large amount of C 2 H 2 through the unique π-complexation, accounting for the improved C 2 H 2 uptake and selectivity. Breakthrough experiments validated its excellent separation capacity for actual C 2 H 2 /CO 2 mixtures, providing one of the highest C 2 H 2 productivities of 118.9 L kg –1 (>99.5% purity) in a single adsorption–desorption cycle.}, archive = {J_JACS}, author = {Yi-Zhan Hao and Kai Shao and Xu Zhang and Yi-Hong Yu and Di Liu and Hui-Min Wen and Yuanjing Cui and Bin Li and Banglin Chen and Guodong Qian}, doi = {10.1021/jacs.4c18209}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11257--11266}, shortjournal = {J. Am. Chem. Soc.}, title = {Pore space partition enabled by Lithium(I) chelation of a Metal–Organic framework for benchmark C2H2/CO2 separation}, volume = {147}, year = {2025}, }
• (2025). Stabilizing the unstable: Enhancing OER durability with 3d-orbital transition metal multielemental alloy nanoparticles by atomically dispersed 4d-orbital pd for a 100-fold extended lifetime. JACS, 147(13), 11250--11256. (www)

  @article{ , abstract = {Earth-abundant 3 d -orbital late transition metals are the most used and highly desired catalysts for the oxygen evolution reaction (OER) but are prone to quick oxidative dissolution, leading to poor durability. We first report that FeCoNiCu multielemental alloy nanoparticles (MEA NPs) can be stabilized with only 0.3 at. % Pd, a 4 d -orbital element. Although pure Pd is known for extremely poor OER activity and durability, Pd-FeCoNiCu sustains 1000 h at 10 mA cm –2 . In an accelerating durability test (ADT) at 100 mA cm –2 , it exhibits a mere 8.9 mV increase over 25 h with a degradation rate of 0.356 mV h –1 , which is 1/350th that of FeCoNiCu (125 mV h –1 ) and among the most stable OER catalysts reported so far. Aberration-corrected HAADF-STEM and X-ray absorption fine structure (XAFS) reveal that atomically dispersed Pd atoms, surrounded by Fe, Co, Ni, and Cu atoms, contributed to a more delocalized electronic structure and stronger bonding via strong d-d/sp hybridization and the vibronic coupling induced by atomic displacement. The altered local density of states (LDOS) of Fe, Co, Ni, and Cu mitigates the oxidation of FeCoNiCu in OER by over 50%, quantified by hard X-ray photoelectron spectroscopy (HAXPES), making the combination of these five dissoluble elements a durable catalyst.}, archive = {J_JACS}, author = {Bing Zhu and Shaoda Huang and Okkyun Seo and Minna Cao and Daiju Matsumura and Huayu Gu and Dongshuang Wu}, doi = {10.1021/jacs.4c18109}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11250--11256}, shortjournal = {J. Am. Chem. Soc.}, title = {Stabilizing the unstable: Enhancing OER durability with 3d-orbital transition metal multielemental alloy nanoparticles by atomically dispersed 4d-orbital pd for a 100-fold extended lifetime}, volume = {147}, year = {2025}, }
• (2025). Restoring the redox and norepinephrine homeostasis in mouse brains promotes an antidepressant response. JACS, 147(13), 11239--11249. (www)

  @article{ , abstract = {Effective diagnosis and treatment of major depressive disorder remains a major challenge because diagnostic criteria overlap with other conditions and 50% of patients are resistant to conventional treatments. Emerging evidence has indicated that oxidative stress and reduced norepinephrine are key pathological features of depression. Herein, we constructed a smart organic small-molecule fluorescence-based therapeutic system (Cou-NE-H 2 O 2 ) for the diagnosis and treatment of depression targeted at restoring redox homeostasis and efficiently upregulating norepinephrine in the brain. Utilizing Cou-NE-H 2 O 2 , we could evaluate the depressive phenotype via the fluorescence monitoring of the redox state in mouse brains. By reducing hydrogen peroxide and continuously increasing norepinephrine, Cou-NE-H 2 O 2 elicited a synergistic antidepressant action. Furthermore, we identified that Cou-NE-H 2 O 2 can promote the expression of genes such as Grin2a, Drd1, and Fxyd2 related to the cyclic adenosine monophosphate signaling pathway, upregulate glutathione and cysteine to alleviate oxidative stress, and boost neuronal activity by enhancing dopaminergic synapses, ultimately achieving an effective antidepressant response. Taken together, this work provides a new strategy for the evaluation of depression and appropriate treatments and identifies the mechanisms underlying antioxidant and norepinephrine disorders in the brain as potential targets for the development of novel diagnostics and treatments for depression.}, archive = {J_JACS}, author = {Qi Ding and Deqiang Li and Xin Zhang and Xue Xue and Ran Zhang and Di Su and Tony D. James and Ping Li and Xin Wang and Bo Tang}, doi = {10.1021/jacs.4c18046}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11239--11249}, shortjournal = {J. Am. Chem. Soc.}, title = {Restoring the redox and norepinephrine homeostasis in mouse brains promotes an antidepressant response}, volume = {147}, year = {2025}, }
• (2025). Conversion of compositionally diverse plastic waste over earth-abundant sulfides. JACS, 147(13), 11227--11238. (www)

  @article{ , abstract = {Chemical deconstruction of polyolefin plastic wastes via hydroconversion is promising for mitigating plastic accumulation in landfills and the environment. However, hydroconversion catalysts cannot handle complex feedstocks containing multiple polymers, additives, and heteroatom impurities. Here, we report a single-step strategy using earth-abundant metal sulfide catalysts to deconstruct these wastes. We show that NiMoS x /HY catalysts deconstruct polyolefin feedstocks, achieving ∼81–94% selectivity to liquid products. Postsynthetic zeolite modification enhances the catalyst’s activity by >2.5 times, achieving over 95% selectivity to liquid fuels with controllable product distribution in the naphtha, jet fuel, and diesel range. The catalyst is resilient to increasingly complex feedstocks, such as additive-containing polymers and mixed plastics composed of polyolefins and heteroatom-containing polymers, including poly(vinyl chloride). We extend the strategy to single-use polyolefin wastes that can generate toxic byproducts, such as HCl and NH 3 , and eliminate their emissions by integrating reaction and sorption in a one-step process.}, archive = {J_JACS}, author = {Esun Selvam and Zoé O. G. Schyns and Jessie A. Sun and Pavel A. Kots and Yeonsu Kwak and LaShanda T. J. Korley and Raul F. Lobo and Dionisios G. Vlachos}, doi = {10.1021/jacs.4c18001}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11227--11238}, shortjournal = {J. Am. Chem. Soc.}, title = {Conversion of compositionally diverse plastic waste over earth-abundant sulfides}, volume = {147}, year = {2025}, }
• (2025). Molybdenum–Iron–Sulfur cluster with a bridging carbide ligand as a partial FeMoco model: CO activation, EPR studies, and bonding insight. JACS, 147(13), 11216--11226. (www)

  @article{ , abstract = {Nitrogenase enzymes catalyze the reduction of N 2 to NH 3 at a complex Fe-M (M = Mo, Fe, or V) cofactor (FeMco), which displays eight metal centers and sulfide and carbide bridges with a MFe 7 S 8 C composition. The role of the unusual μ 6 -carbide ligand and its effects on the metal centers remain unclear. Here, we describe the transfer of a carbide ligand to a MoFe 3 S 3 cluster supported by a bisphenoxide ligand from a previously reported terminal Mo carbide complex to yield a pentametallic cluster of MoS 3 Fe 3 CMo composition, which also displays a bridging CO that resembles the lo-CO form of nitrogenase. This cluster has an S = 1/2 spin state amenable to studies by pulse EPR spectroscopy, revealing a significantly larger carbide 13 C hyperfine interaction ( a iso ( 13 C) = 12.5 MHz) than any observed for various states of FeMoco studied by EPR thus far (| a iso ( 13 C)| = 0.89 to 2.7 MHz). This report provides a strategy for the synthesis of carbide-containing iron–sulfur clusters relevant to nitrogenase cluster modeling, as well as benchmarking information for the metal–carbon interactions by EPR methods.}, archive = {J_JACS}, author = {Linh N. V. Le and Tianyi He and Justin P. Joyce and Paul H. Oyala and Serena DeBeer and Theodor Agapie}, doi = {10.1021/jacs.4c17893}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11216--11226}, shortjournal = {J. Am. Chem. Soc.}, title = {Molybdenum–Iron–Sulfur cluster with a bridging carbide ligand as a partial FeMoco model: CO activation, EPR studies, and bonding insight}, volume = {147}, year = {2025}, }
• (2025). Cathelicidin-BF: A potent antimicrobial peptide leveraging charge and phospholipid recruitment against multidrug-resistant clinical bacterial isolates. JACS, 147(13), 11199--11215. (www)

  @article{ , abstract = {Cathelicidin-BF (CatBF) is a LL-37 homologous antimicrobial peptide (AMP) isolated from Bungarus fasciatus with an exceptional portfolio of antimicrobial, antiviral, antifungal, and anticancer activities. Contrary to many AMPs, it showed a good pharmacological profile with a half-life of at least 1 h in serum and efficacy against bacterial infections in mice. To evaluate its potential against resistant nosocomial infections, we assessed its activity against 81 clinically relevant resistant bacterial isolates. CatBF exhibited minimum inhibitory concentrations (MICs) as low as 0.5 μM against carbapenem-resistant Acinetobacter baumannii , Klebsiella pneumoniae , and Escherichia coli . Its wide-ranging activity, unaffected by resistance mechanisms or Gram phenotype, prompted us to investigate its molecular mode of action. NMR spectroscopy, paramagnetic probes, and molecular dynamics (MD) simulations were employed to define its structure, penetration depth, and orientation in various membrane models, including micelles, bicelles, oriented bilayers, and vesicles. We found that CatBF’s potent activity relies on its strong charge, allowing membrane neutralization at low peptide/lipid ratios and selective recruitment of charged phospholipids. At higher concentrations, a change in peptide orientation reveals membrane invagination and the formation of transient pores possibly leading to bacterial death. Our findings highlight the potential of CatBF as a model for developing resistance-independent agents to combat multidrug-resistant (MDR) bacterial infections.}, archive = {J_JACS}, author = {Evgeniy Salnikov and Morgane Adélaïde and Francisco Ramos-Martín and Ahmad Saad and Jennifer Schauer and Martina Cremanns and Mariam Rima and Christopher Aisenbrey and Saoussen Oueslati and Thierry Naas and Niels Pfennigwerth and Söeren Gatermann and Catherine Sarazin and Burkhard Bechinger and Nicola D’Amelio}, doi = {10.1021/jacs.4c17821}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11199--11215}, shortjournal = {J. Am. Chem. Soc.}, title = {Cathelicidin-BF: A potent antimicrobial peptide leveraging charge and phospholipid recruitment against multidrug-resistant clinical bacterial isolates}, volume = {147}, year = {2025}, }
• (2025). Intercepting a mycobacterial biosynthetic pathway with covalent labeling. JACS, 147(13), 11189--11198. (www)

  @article{ , abstract = {The mycobacterial cell envelope plays both infectious and protective roles. Understanding its structure is crucial for unlocking the molecular basis underlying these functions. Studying glycans, the primary components of the cell envelope, is challenging due to their limited native functional handles for chemoselective modification. New labeling methods exploit biorthogonal chemistry, using small molecule mimics that intercept cellular metabolism or late-stage glycan biosynthesis. However, these strategies can have practical limitations, including probe delivery and effectiveness. An ideal small molecule probe should be easily deployed and exploit the critical enzyme–substrate relationships of natural substrates. To this end, we developed a “probegenic” strategy to label mycobacteria. Our approach eliminates the need for explicit substrate mimicry, as the relevant functionality is revealed by a target enzyme. Specifically, we synthesized an azide-substituted trans- β-lactone probe (AzLac), which adopts a substrate-like structure upon covalent enzyme labeling. This probe is incorporated by mycolyltransferases into a core mycobacterial cell envelope glycan, including in the pathogen Mycobacterium tuberculosis . Unlike other probes of the cell envelope, AzLac facilitates selective covalent labeling of the inner leaflet of the mycomembrane. Using Corynebacterium glutamicum mycolyltransferase deletion strains, we implicated Cmt2 as the primary mycolyltransferase target. We leveraged the ability to modify the cell envelope by demonstrating that AzLac could be used to attach a DNA barcode to mycobacteria, which would help track infection dynamics. Thus, we expect AzLac will be a valuable means of monitoring and tracking the mycobacterial cell envelope. Moreover, we anticipate masking and revealing recognition motifs in probes can be applied to diverse cellular targets.}, archive = {J_JACS}, author = {Theodore C. Warner and Victoria M. Marando and Omar A. Santiago-Reyes and Elizabeth M. Hart and Stephanie R. Smelyansky and Alan W. Carter and Thomas G. Bernhardt and Bryan D. Bryson and Daria E. Kim and Laura L. Kiessling}, doi = {10.1021/jacs.4c17913}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11189--11198}, shortjournal = {J. Am. Chem. Soc.}, title = {Intercepting a mycobacterial biosynthetic pathway with covalent labeling}, volume = {147}, year = {2025}, }
• (2025). Relaxation optimized heteronuclear experiments for extending the size limit of RNA nuclear magnetic resonance. JACS, 147(13), 11179--11188. (www)

  @article{ , abstract = {The application of NMR to large RNAs has been limited by the inability to perform heteronuclear correlation experiments essential for resolving overlapping 1 H NMR signals, determining interproton distance restraints and interhelical orientations for structure calculations, and evaluating conformational dynamics. Approaches exploiting 1 H– 13 C correlations that are routinely applied to proteins and small RNAs of ∼60 nucleotides or fewer are impractical for larger RNAs due to rapid dipolar relaxation of protons by their attached carbons. Here we report a 2 H-enhanced, 1 H– 15 N correlation approach that enables atom-specific NMR characterization of much larger RNAs. Purine H8 transverse relaxation rates are reduced ∼20-fold with ribose perdeuteration, enabling efficient magnetization transfer via two-bond 1 H– 15 N couplings. We focus on H8–N9 correlation spectra which benefit from favorable N9 chemical shift anisotropy. Chemical shift assignment is enabled by retention of protons at the C1′ position, which allow measurement of two-bond H1′–N9 and through-space H1′–H8 correlations with only a minor effect on H8 relaxation. The approach is demonstrated for the 232 nucleotide HIV-1 Rev response element, where chemical shift assignments, 15 N-edited nuclear Overhauser effects, and 1 H– 15 N residual dipolar couplings are readily obtained from sensitive, high-resolution spectra. Heteronuclear correlated NMR methods that have been essential for the study of proteins can now be extended to RNAs of at least 78 kDa.}, archive = {J_JACS}, author = {Aarsh Shah and Heer Patel and Arjun Kanjarpane and Michael F. Summers and Jan Marchant}, doi = {10.1021/jacs.4c17823}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11179--11188}, shortjournal = {J. Am. Chem. Soc.}, title = {Relaxation optimized heteronuclear experiments for extending the size limit of RNA nuclear magnetic resonance}, volume = {147}, year = {2025}, }
• (2025). Th2Mo2Ir2Si4C: An intergrown superconductor by structure design. JACS, 147(13), 11172--11178. (www)

  @article{ , abstract = {Exploration of new superconductors in multicomponent complex systems remains challenging. Among complex superconductors, those containing distinct superconducting layers are quite rare. In this work, based on the block-layer model together with formation energy calculations, we have designed and successfully synthesized a quinary intermetallic compound, Th 2 Mo 2 Ir 2 Si 4 C. The new material crystallizes in an intergrowth structure with an alternate stacking of superconducting ThMo 2 Si 2 C and ThIr 2 Si 2 block layers along the crystallographic c axis. The interblock-layer interaction is dominated by the Si–Ir bonding, which results in a relatively shorter interlayer distance and a stronger coupling between [Mo 2 Si 2 C] and fluorite-type [Si 2 Ir 2 ] layers. Enhanced superconductivity, with a superconducting transition temperature of T c = 3.4 K and a zero-temperature upper critical field of H c2 (0) = 9.5 kOe, is revealed by measurements of electrical resistivity, magnetic susceptibility, and specific heat. The strategy of the block-layer design demonstrated here can be extended to other intergrowth systems with various functional motifs.}, archive = {J_JACS}, author = {Hua-Xun Li and Yi-Qiang Lin and Wu-Zhang Yang and Chang-Chao Liu and Jia-Yi Lu and Jia-Xin Li and Zhi Ren and Cao Wang and Hao Jiang and Yun-Lei Sun and Guang-Han Cao}, doi = {10.1021/jacs.4c17616}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11172--11178}, shortjournal = {J. Am. Chem. Soc.}, title = {Th2Mo2Ir2Si4C: An intergrown superconductor by structure design}, volume = {147}, year = {2025}, }
• (2025). Competition between hydrogen and chalcogen bonding in homodimers of chalcogen hydrides (H2X)2, x = o, s, se, te. JACS, 147(13), 11152--11171. (www)

  @article{ , abstract = {The structural and chemical bonding motifs manifested by the competition between hydrogen and chalcogen bonding in the homodimers of chalcogen hydrides (H 2 X) 2 , where X = O, S, Se, Te have been characterized using high-level electronic structure calculations and analysis of the electron density based on Quasi-atomic orbital (QUAO) and the Symmetry-adapted perturbation theory (SAPT) methods. The QUAO analysis clearly identifies a three-center interaction responsible for either hydrogen or chalcogen bonds: in the former, the σ-bond connecting the donor and hydrogen atom participating in the hydrogen bond interacts with the lone pair on the nucleophile acceptor via the hydrogen atom, while in the latter this same σ-bond interacts with the nucleophile lone pair via the donor chalcogen. The number of minimum energy structures increase dramatically from one for (H 2 O) 2 , three for (H 2 S) 2 , four for (H 2 Se) 2 , and finally six for (H 2 Te) 2 . The emergence of the chalcogen-bonded arrangements appears for (H 2 S) 2 with their subsequent energetic stabilization over the hydrogen-bonded minima manifesting in (H 2 Se) 2 and (H 2 Te) 2 . In particular, one of the (H 2 S) 2 , two of the (H 2 Se) 2 , and three of the (H 2 Te) 2 dimers are chalcogen bonded. Induction plays a small but important role in stabilizing hydrogen over chalcogen-bonded structures, while dispersion is more important for chalcogen bonds.}, archive = {J_JACS}, author = {Maxwell P. Hoffman and Sotiris S. Xantheas}, doi = {10.1021/jacs.4c17428}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11152--11171}, shortjournal = {J. Am. Chem. Soc.}, title = {Competition between hydrogen and chalcogen bonding in homodimers of chalcogen hydrides (H2X)2, x = o, s, se, te}, volume = {147}, year = {2025}, }
• (2025). Electron inversion and tunneling at silicon thermal oxide interfaces for solar-driven molecular catalysis to syngas. JACS, 147(13), 11145--11151. (www)

  @article{ , abstract = {Semiconductor photoelectrodes are regularly coupled to solid-state heterogeneous catalysts to perform solar-driven reduction of CO 2 . Less frequently, molecular catalysts are employed to better control the reactivity toward desired products, yet the development of robust semiconductor/molecule interfaces has proven challenging. Here, we demonstrate that a 2–3 nm thermal oxide layer on Si exhibits stability in aqueous solution, high photovoltage, and a photocurrent density of ∼10 mA/cm 2 for the solar-driven photoelectrochemical reduction of a homogeneous molecular catalyst, producing syngas with an ∼2:1 H 2 to CO ratio. Because of a low defect density, the oxide interface forms an electron inversion layer with metal-like electron density at cathodic potentials. This inversion layer facilitates electron transfer to redox-active molecules via tunneling even if the molecule’s reduction potential is beyond the semiconductor’s conduction band edge. Using an electrolyte solution composed of a homogeneous cobalt bis(terpyridine) catalyst in a water/organic solvent mixture, stable photoelectrochemistry was observed under 1-sun illumination, exhibiting an ∼30% Faradaic efficiency for CO that was similar to a glassy carbon electrode under comparable conditions. The results demonstrate that an ultrathin thermal oxide interface is a robust platform for development of aqueous-stable, molecule-driven photoelectrocatalysis.}, archive = {J_JACS}, author = {Shi He and Samuel R. Bottum and John C. Dickenson and Hannah R. M. Margavio and Niklas D. Keller and Oluwaseun A. Oyetade and Ryan J. Gentile and Taylor S. Teitsworth and Samuel J. Shin and Jillian L. Dempsey and Alexander J. M. Miller and Renato N. Sampaio and Stephen J. Tereniak and Carrie L. Donley and Matthew R. Lockett and Gregory N. Parsons and Gerald J. Meyer and James F. Cahoon}, doi = {10.1021/jacs.4c17251}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11145--11151}, shortjournal = {J. Am. Chem. Soc.}, title = {Electron inversion and tunneling at silicon thermal oxide interfaces for solar-driven molecular catalysis to syngas}, volume = {147}, year = {2025}, }
• (2025). Photoinduced synergism of Ferroptosis/Pyroptosis/Oncosis by an o2-independent photocatalyst for enhanced tumor immunotherapy. JACS, 147(13), 11132--11144. (www)

  @article{ , abstract = {Due to O 2 dependence, hypoxia-induced apoptosis resistance, and immunosuppressive microenvironment, the effect of traditional photodynamic therapy toward hypoxic solid tumors is severely limited. Herein, we report an O 2 -independent photocatalyst (EBSe) for tumor immunotherapy potentiation via synergism of near-infrared (NIR) light-induced ferroptosis/pyroptosis/oncosis. Simple Se and ethyl modifications on methylene blue (MB) endow EBSe with a remarkable phototoxicity enhancement (>2500 folds) and an excellent phototoxicity index (PI > 32,000) to 4T1 cells under hypoxia. EBSe exhibits self-adaptive photodynamic processes that generate enhanced type I/II ROS under normoxia and elevate carbon radical production under hypoxia. Interestingly, EBSe shows much higher cell uptake and undergoes photoinduced lysosomal-to-nucleus translocation, which activates ferroptosis, pyroptosis, and oncosis. The synergism of three nonapoptotic pathways potentiates antitumor immune responses in 4T1 tumor-bearing mice. This work offers a reliable strategy for developing powerful PSs to overcome the apoptosis resistance and immunosuppressive microenvironment of hypoxic tumors.}, archive = {J_JACS}, author = {Shankun Yao and Fengwu Xu and Ying Wang and Jizhen Shang and Shumeng Li and Xinyu Xu and Zhipeng Liu and Weijiang He and Zijian Guo and Yuncong Chen}, doi = {10.1021/jacs.4c17268}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11132--11144}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoinduced synergism of Ferroptosis/Pyroptosis/Oncosis by an o2-independent photocatalyst for enhanced tumor immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Mycobacterium tuberculosis CrgA forms a dimeric structure with its transmembrane domain sandwiched between cytoplasmic and periplasmic β-sheets, enabling multiple interactions with other divisome proteins. JACS, 147(13), 11117--11131. (www)

  @article{ , abstract = {CrgA is a key transmembrane (TM) protein in the cell division process of Mycobacterium tuberculosis ( Mtb ), the pathogen responsible for tuberculosis. While many of the Mtb divisome proteins have been identified, their structures and interactions remain largely unknown. Previous studies of CrgA using oriented-sample solid-state NMR have defined the tilt and rotation of the TM helices, but the cytoplasmic and periplasmic domains and even the oligomeric state were uncharacterized. Here, by combining oriented-sample and magic-angle spinning solid-state NMR spectra, we solved the full-length structure of CrgA. The structure features a dimer with a TM domain sandwiched between a cytoplasmic β-sheet and a periplasmic β-sheet. The β-sheets stabilize dimerization, which in turn increases CrgA’s ability to participate in multiple protein interactions. Within the membrane, CrgA binds FtsQ, CwsA, PbpA, FtsI, and MmPL3 via its TM helices; in the cytoplasm, Lys23 and Lys25 project outward from the β-sheet to interact with acidic residues of FtsQ and FtsZ. The structural determination of CrgA thus provides significant insights into its roles in recruiting other divisome proteins and stabilizing their complexes for Mtb cell wall synthesis and polar growth.}, archive = {J_JACS}, author = {Yiseul Shin and Ramesh Prasad and Nabanita Das and Joshua A. Taylor and Huajun Qin and Wenhao Hu and Yan-Yan Hu and Riqiang Fu and Rongfu Zhang and Huan-Xiang Zhou and Timothy A. Cross}, doi = {10.1021/jacs.4c17168}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11117--11131}, shortjournal = {J. Am. Chem. Soc.}, title = {Mycobacterium tuberculosis CrgA forms a dimeric structure with its transmembrane domain sandwiched between cytoplasmic and periplasmic β-sheets, enabling multiple interactions with other divisome proteins}, volume = {147}, year = {2025}, }
• (2025). Tetrafluororesorcin[4]arene hexameric capsule enables the expansion of the reactivity space in supramolecular catalysis. JACS, 147(13), 11108--11116. (www)

  @article{ , abstract = {This study presents the development and catalytic applications of the tetrafluororesorcin[4]arene hexameric capsule (capsule II) as a novel supramolecular catalyst. It demonstrates unprecedented catalytic activity, enabling the β-selective glycosylation of glycals to 2-deoxy glycosides─a transformation that has not been achieved before in molecular and supramolecular catalysis. Mechanistic investigations, including experimental and computational studies, revealed that the high β-selectivity arises from a proton wire mechanism along the capsule’s surface, coupling glycal protonation with nucleophile deprotonation. Control experiments confirmed the unique reactivity of capsule II compared to its nonfluorinated predecessor, capsule I, showcasing its potential to expand the boundaries of supramolecular catalysis.}, archive = {J_JACS}, author = {Tian-Ren Li and Chintu Das and GiovanniMaria Piccini and Konrad Tiefenbacher}, doi = {10.1021/jacs.4c17029}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11108--11116}, shortjournal = {J. Am. Chem. Soc.}, title = {Tetrafluororesorcin[4]arene hexameric capsule enables the expansion of the reactivity space in supramolecular catalysis}, volume = {147}, year = {2025}, }
• (2025). Organic ionic Host–Guest phosphor with dual-confined nonradiation for constructing ultrahigh-temperature X-ray scintillator. JACS, 147(13), 11098--11107. (www)

  @article{ , abstract = {Scintillators with X-ray-excitable luminescence have attracted great attention in the fields of medical radiography, nondestructive inspection, and high-energy physics. However, thermal quenching significantly reduces radioluminescence efficiency, particularly for those phosphorescent scintillators with promising radiation-induced triplet exciton utilization, ultimately limiting their applications in high-temperature scenarios. Herein, we develop ultrahigh-temperature scintillators based on organic ionic host–guest phosphorescence systems with unprecedented thermal-stable emissions up to 673 K. The guest phosphor features spin-vibronic coupling-assisted intersystem crossing, effectively transforming phosphorescence to thermally activated delayed fluorescence for overcoming thermal inactivation of triplet excitons. Meanwhile, the rigid ionic host and guest with robust electrostatic interactions minimize both the intrinsic and extrinsic nonradiations of excitons, the so-called dual-confined nonradiation. These two mechanisms work synergistically, contributing to the highly efficient triplet exciton-based luminescence with a room-temperature phosphorescence efficiency of 38.7% and ultrahigh-temperature-resistant dual emissions. Such an innovative ionic host–guest scintillator achieves an impressively low X-ray detection limit of 71.5 nGy s –1 and remarkably bright photoluminescence (efficiency of 80.4% at 483 K), enabling ultrahigh-temperature X-ray imaging.}, archive = {J_JACS}, author = {Ying Wang and Jiahong Yu and Zixing Zhou and Weijun Zhao and Yilong Wang and Jiaqiang Zhao and Chenggong Ma and Zhen-Yi Lin and Yongzhen Wu and Xiao Wang and Huili Ma and Wei-Hong Zhu}, doi = {10.1021/jacs.4c16935}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11098--11107}, shortjournal = {J. Am. Chem. Soc.}, title = {Organic ionic Host–Guest phosphor with dual-confined nonradiation for constructing ultrahigh-temperature X-ray scintillator}, volume = {147}, year = {2025}, }
• (2025). Anodized aluminum oxide membrane ionic memristors. JACS, 147(13), 11089--11097. (www)

  @article{ , abstract = {Memory effect in ion transport (IT) at the solid–solution interface is uniquely attractive in that the conductance depends on or “memorizes” the previous states. Hysteretic and rectified transport properties offer exciting potential to developing advanced iontronics and neuromorphic functions, improving the efficiency of energy conversion and electrochemical processes, and overcoming the selectivity-throughput bottleneck in the enrichment of low abundant species for environment- and energy-friendly separations, among others. Herein, memory effects are discovered in the rectified electrokinetic IT through anodized aluminum oxide (AAO) membranes containing densely packed highly ordered nanochannels (10 10 per cm 2 ). Characteristic memristor responses of pinched current–potential loops are resolved in voltammetric experiments and successfully reproduced through finite element simulation. Excitatory and inhibitory conductance states are shown to arise from the enrichment and depletion of mobile charge carriers. Structurewise, the transport symmetry is broken by the barrier oxide layer (BOL) on the one end of the cylindrical nanochannels across the AAO membranes. Charge selectivity is attributed to the gradient(s) of the space charge density across the BOL characterized by depth profiling via X-ray photoelectron spectroscopy analysis. The space charge gradient(s) overcomes the fundamental limitation of widely exploited surface charge effects to enable intense rectification and hysteresis prevailing at very high ionic concentrations up to 1–2 M. A new strategy is developed for controlling the preferential IT direction and selectivity via counterion intercalation and extraction/exchange. Mechanistic understanding is further confirmed through parameter variations such as potential scan rate and ionic strength, which also demonstrates convenient controls of the related functions.}, archive = {J_JACS}, author = {Dipak Baram and Maksim Kvetny and Sarah Ake and Ruoyu Yang and Gangli Wang}, doi = {10.1021/jacs.4c16835}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11089--11097}, shortjournal = {J. Am. Chem. Soc.}, title = {Anodized aluminum oxide membrane ionic memristors}, volume = {147}, year = {2025}, }
• (2025). Photocatalyzed epimerization of quaternary stereocenters. JACS, 147(13), 11080--11088. (www)

  @article{ , abstract = {Quaternary stereocenters play a crucial role in shaping both the molecular topology of small molecules and the outcome of stereoselective transformations. While considerable progress has been achieved in constructing highly substituted carbon centers with varied substitution patterns, the stereoselective synthesis of quaternary carbon centers remains a significant challenge. Here we report a protocol for the precise manipulation of quaternary stereocenters through epimerization. The critical design element of our ketone α-epimerization process was developing a photoactive imine, which circumvents the numerous deleterious pathways of carbonyl photochemistry. Excitation of this imine with visible light in the presence of a photocatalyst enables reversible C–C bond cleavage and reformation to vary the stereochemistry of the quaternary center. This approach allows us to override intrinsic stereochemical outcomes of C–C bond construction, therefore providing novel tactics for retrosynthetic planning. The broad utility of this protocol was demonstrated by the topological alteration of various classes of carbocyclic scaffolds bearing diverse functional groups.}, archive = {J_JACS}, author = {Licheng Wu and Baylee N. McIntyre and Supeng Wu and Ziqi Jiao and Carter B. Fox and Nathan D. Schley and Alexander W. Schuppe}, doi = {10.1021/jacs.4c16769}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11080--11088}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalyzed epimerization of quaternary stereocenters}, volume = {147}, year = {2025}, }
• (2025). Surface-conducting lithium superionic conductors for solid-state batteries. JACS, 147(13), 11072--11079. (www)

  @article{ , abstract = {Bulk Li + -conducting lithium superionic conductors are susceptible to disruption by grain boundaries and interparticle porosity, necessitating high densification and consequently limiting the gravimetric energy density of solid-state batteries. Here, we discovered a new class of surface-conducting lithium superionic conductors achieved through surface chemisorption. After bonding with ligands, surface atoms of inert substrates become binding sites for lithium salt dissociation and hopping sites for fast surface Li + diffusion, transforming inert materials into surface-conducting Li + conductors. Using two-dimensional TiO 2 nanosheets as a proof of concept, we show that ethylene glycolate-chemisorbed TiO 2 significantly enhances lithium salt dissociation and promotes fast Li + hopping between surface oxygen atoms, achieving a high surface ion mobility of 3.61 × 10 –7 cm 2 ·V –1 ·s –1 ─an improvement of 600% over the bulk Li + mobility of Li 7 La 3 Zr 2 O 12 solid oxide electrolytes. Benefiting from surface Li + conduction, an ultralight oxide aerogel solid-state electrolyte was developed with an unprecedented low density of 0.29 g·cm –3 , which is only 25% of that of liquid electrolytes and 5.7% of garnet-type solid electrolytes. A LiFePO 4 -based solid-state battery utilizing this new electrolyte exhibits a significantly high energy density of ∼295 Wh·kg –1 , achieving 160% of that of a Li 7 La 3 Zr 2 O 12 -based solid-state battery even with the same electrolyte thickness. Furthermore, this guideline for designing surface-conducting superionic conductors is generalizable and can be extended to diverse cations and substrates, promising lightweight, highly conductive solid-state electrolytes with broad implications beyond solid-state batteries.}, archive = {J_JACS}, author = {Bing Ai and Wenru Zhao and Malin Li and Wei Zhang and Donghai Mei and Jihong Yu}, doi = {10.1021/jacs.4c16447}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11072--11079}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface-conducting lithium superionic conductors for solid-state batteries}, volume = {147}, year = {2025}, }
• (2025). Molecular engineering of emissive molecular qubits based on spin-correlated radical pairs. JACS, 147(13), 11062--11071. (www)

  @article{ , abstract = {Spin chemistry of photogenerated spin-correlated radical pairs (SCRPs) offers a practical approach to control chemical reactions and molecular emissions by using weak magnetic fields. This capability to harness magnetic field effects (MFEs) paves the way for developing SCRPs-based molecular qubits. Here, we introduce a new series of donor–chiral bridge–acceptor (D−χ–A) molecules that demonstrate significant MFEs on fluorescence intensity and lifetime in solution at room temperature─critical for quantum sensing. By precisely tuning the donor site through torsional locking, distance extension, and planarization, we achieved remarkable control over key quantum properties, including field-response range and line width. In the most responsive systems, emission lifetimes increased by over 200%, and the total emission intensity was modulated by up to 30%. This level of tunability shows the power of synthetic spin chemistry. The rational design principle of optically addressable SCRP-based molecular systems, presented in this work, represents a major leap toward functional synthetic molecular qubits, advancing the field of molecular quantum technologies.}, archive = {J_JACS}, author = {Neo Lin and Miu Tsuji and Isabella Bruzzese and Angela Chen and Michael Vrionides and Noen Jian and Farhan Kittur and Thomas P. Fay and Tomoyasu Mani}, doi = {10.1021/jacs.4c16164}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11062--11071}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular engineering of emissive molecular qubits based on spin-correlated radical pairs}, volume = {147}, year = {2025}, }
• (2025). Synergistic π-tunnel clamps in β-sheets for long-range dry-state conduction: Toward neural restoration. JACS, 147(13), 11049--11061. (www)

  @article{ , abstract = {The ordered arrangement of π–π networks within nanostructures is advantageous for the construction of artificial electronic transport (ETp) systems. Building such structures with biocompatible peptides offers a potential for prescribed structural addressability and enhanced ETp capability with implications for targeted neural tissue engineering. However, creating ordered π–π tunnels in peptide nanostructures composed entirely of natural amino acids presents challenges resulting from the flexible side chains and the free movement of aromatic residues, causing unpredictable orientation. In this study, a novel peptide nanostructure was constructed through rational design and high-throughput screening leveraging hierarchical β-sheets to achieve molecular programmability. Precise regulation of key residues at the aromatic–hydrophilic junctions within the peptide chain facilitated the transition from single interaction forces (hydrophobic or hydrogen bonding) to synergistic forces, enabling the formation of supramolecular clamps during the lateral stacking of β-sheets. The clamps compel the torsion-angle alternation between aromatic residues and the β-plane, increasing the stacking order of aromatic rings and reducing the π–π distance in the optimized RT peptide system. The RT system promotes the formation of an orderly delocalized electron tunnel, achieving dry-state molecular conductivity composed entirely of natural amino acids. Besides ETp, the RT system also provides neural-targeting capability, flexibility, and mechanical strength, allowing it to support axon elongation and neural restoration, serving as an advanced neuro-electronic interface.}, archive = {J_JACS}, author = {Yao Yu and Limin Zhang and Bo Wang and Jinge Zhao and Kai Han and Ying Qi and Jiaqing Li and Xin Wang and Beilei Sun and Jian Zhang and Jingtian Cao and Bokai Ma and Xubiao Peng and Jie Cao and Yubin Ke and Weizhi Wang}, doi = {10.1021/jacs.4c16008}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11049--11061}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic π-tunnel clamps in β-sheets for long-range dry-state conduction: Toward neural restoration}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of enlicitide decanoate. JACS, 147(13), 11036--11048. (www)

  @article{ , abstract = {We report the total synthesis of enlicitide decanoate, an orally bioavailable inhibitor of proprotein convertase subtilisin/kexin type 9 that is being developed for the treatment of atherosclerotic cardiovascular disease. It is a highly complex macrocyclic peptide with a significant number of nonpeptide structural elements that presents a daunting synthetic chemistry challenge. We describe the development of a convergent, efficient, and robust manufacturing process that enables the large-scale production of enlicitide.}, archive = {J_JACS}, author = {Hongming Li and David A. Thaisrivongs and Gao Shang and Yonggang Chen and Qinghao Chen and Lushi Tan and Kai-Jiong Xiao and Reed T. Larson and Jeffrey T. Kuethe and Joshua Lee and Nicholas R. Deprez and Andrew F. Nolting and Marc Poirier and Paul G. Bulger and Erik L. Regalado and Mirlinda Biba and Fuh-Rong Tsay and Jimmy DaSilva and Chris K. Prier and Christopher A. Strulson and Kerstin Zawatzky and Zhu Liu and Justin A. Newman and Kathleen Sokolowsky and Weijuan Tang and Kari Hullen and Nimisha Thakur and Cody Welch and Smit Patel and Yu He and Jing Xu and Narayan Variankaval and Artis Klapars and Jongrock Kong and Richard Desmond and Richard Varsolona and Peter E. Maligres and Carlos A. Pons Siepermann and Lee Robison and Tiffany Piou and Clara Hartmanshenn and Anagha Chandra and Anisha Patel and Marc R. Becker and Guiquan Liu and Jianjun Duan and Baoqiang Wan and Chengqian Xiao and Yongpeng Yuan and Xiaohui Cao and Lu Chen and Ruxia Yi and Zheng Wu and Minyi Feng and Donghong Li and Zhiyan Song and Yawei Dong and Julin Sun and Biao Li and Guangxin Shao and Louis-Charles Campeau and Jingjun Yin}, doi = {10.1021/jacs.4c15966}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11036--11048}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of enlicitide decanoate}, volume = {147}, year = {2025}, }
• (2025). Hydrogen-vacancy-induced stable superconducting niobium hydride at high pressure. JACS, 147(13), 11028--11035. (www)

  @article{ , abstract = {In recent years, the discovery of unconventional polyhydrides under high pressure, including notable instances like CaH 6 , YH 9 , and LaH 10 , with superconducting critical temperature ( T c ) above 200 K, has ignited considerable interest in the quest for high-temperature superconductivity in hydrogen-based materials. Recent studies have suggested the highly probable existence of hydrogen vacancies in these high- T c superconducting hydrides, although there is no conclusive evidence. In this study, taking niobium (Nb) hydride as a model, we showcase the observation of nonstoichiometric face-centered cubic ( fcc ) NbH 4-δ (δ∼0.23–0.51) at pressures ranging from 113 to 175 GPa, employing in situ high-pressure X-ray diffraction experiments in conjunction with first-principles calculations. Remarkably, our further analyses indicate that the hydrogen vacancies, along with the resulting configurational entropy, play crucial roles in stabilizing this nonstoichiometric fcc NbH 4-δ . Electrical transport measurements confirmed the superconductivity, as evidenced by zero resistance as well as suppression of T c with applying magnetic fields, with a T c reaching up to 34 K. Our current results not only confirm the presence of hydrogen vacancies in high- T c hydrides, but also provide key insights into the understanding of hydrogen-vacancy-induced stability for nonstoichiometric hydrides under high pressure.}, archive = {J_JACS}, author = {Chuanheng Ma and Yuan Ma and Hui Wang and Hongbo Wang and Mi Zhou and Guangtao Liu and Hanyu Liu and Yanming Ma}, doi = {10.1021/jacs.4c15868}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11028--11035}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen-vacancy-induced stable superconducting niobium hydride at high pressure}, volume = {147}, year = {2025}, }
• (2025). Ti-catalyzed 1,2-diamination of alkynes using 1,1-disubstituted hydrazines. JACS, 147(13), 11019--11027. (www)

  @article{ , abstract = {Ti-catalyzed alkyne diamination and alkyne hydrohydrazination proceed through a common N -aminoazatitanacyclobutene intermediate. These reactions have historically existed as processes catalyzed by distinct molecular Ti compounds, with several reports for hydrohydrazination and only a single example for diamination. Here, we demonstrate that a diamidoamine Ti catalyst, (NNN)Ti(═NN R 2 ) ( 1, (NNN)H 2 = N -methyl- N ’, N ″-bis(trimethylsilyl)diethylenetriamine; R = alkyl, aryl), is capable of catalyzing both diamination and hydrohydrazination, where the selectivity is dictated by simple changes to the reaction conditions. This approach capitalizes on the fact that there are entropic differences at the selectivity branch point between diamination (unimolecular) and hydrohydrazination (bimolecular). This discovery leads to an expanded substrate scope for alkyne diamination and provides an understanding of how structure–activity relationships can impact the relative rates (selectivity) of diamination and hydrohydrazination. These structure–activity relationships, anchored on 15 N NMR descriptors, were then used to design a novel, highly active, and selective diamination catalyst, (NNN SiMe2Ph )Ti(═NN R 2 ) ( 1f ), which contains bulkier flanking amide ligands. More broadly, these results suggest that this strategy may be applied more generally to Ti hydrohydrazination catalysts to uncover new catalysts capable of alkyne diamination with 1,1-disubstituted hydrazines.}, archive = {J_JACS}, author = {Partha Sarathi Karmakar and Yuya Kakiuchi and Jaekwan Kim and Michael R. Harris and Daniel N. Huh and Alexander G. Sell and Christophe Copéret and Ian A. Tonks}, doi = {10.1021/jacs.4c15765}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11019--11027}, shortjournal = {J. Am. Chem. Soc.}, title = {Ti-catalyzed 1,2-diamination of alkynes using 1,1-disubstituted hydrazines}, volume = {147}, year = {2025}, }
• (2025). Catalytic enantioselective nucleophilic desymmetrization at Phosphorus(V): A three-phase strategy for modular preparation of phosphoramidates. JACS, 147(13), 11010--11018. (www)

  @article{ , abstract = {Chiral phosphoramidates characterized by at least a P–N bond without a P–C bond demonstrate a significant applicative value within nucleoside phosphoramidate prodrugs. Despite the availability of methodologies for the selective construction of diverse chiral organophosphorus entities, achieving P-stereocenters solely substituted by heteroatoms often relies on diastereomeric synthesis. Here, we present a catalytic enantioselective desymmetrization strategy using an electrophilic phosphorus reagent with three leaving groups as a substrate, enabling a three-phase nucleophilic attack with various alcohols and amines. By generating a broad range of possible substituent combinations around phosphorus atoms, this synthetic strategy may expedite the synthesis and screening of biologically active phosphoramidates.}, archive = {J_JACS}, author = {Xiao-kang Nie and Shi-qi Zhang and Xu-yang Wang and Wan-ting Yang and Xia Zhang and Shang-jing Chen and Xin Cui and Zhuo Tang and Guang-xun Li}, doi = {10.1021/jacs.4c15587}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {11010--11018}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic enantioselective nucleophilic desymmetrization at Phosphorus(V): A three-phase strategy for modular preparation of phosphoramidates}, volume = {147}, year = {2025}, }
• (2025). Enantioselective Alkyl–Acyl radical cross-coupling enabled by metallaphotoredox catalysis. JACS, 147(13), 10999--11009. (www)

  @article{ , abstract = {Radical–radical cross-coupling (RCC) offers a promising approach for carbon–carbon bond formation in organic synthesis, particularly for creating complex, three-dimensional molecules. However, achieving both cross- and enantioselectivity in RCC reactions has remained a significant challenge. Here, we report a novel metallaphotoredox platform that enables highly enantioselective decarboxylative coupling of carboxylic acid derivatives with aldehydes. Our strategy leverages independent control over radical generation and subsequent enantioselective bond formation through fine-tuning of a common photocatalyst and a simple chiral bis(oxazoline) nickel catalyst. This redox-neutral protocol requires no exogenous oxidants or reductants and demonstrates broad substrate scope and functional group compatibility in the synthesis of enantioenriched α-aryl and α-amino ketones. The α-amino ketone products can be readily transformed into valuable β-amino alcohols, streamlining access to these important motifs. Furthermore, we showcase the potential of this approach for more challenging enantioselective C(sp 3 )–C(sp 3 ) alkyl–alkyl RCC reactions. This unified platform for enantioselective alkyl–acyl radical cross-coupling represents a significant advance in asymmetric catalysis and underscores the potential for metallaphotoredox catalysis to exploit new mechanisms to solve long-standing synthetic problems.}, archive = {J_JACS}, author = {Tao Li and Zhen Xu and Yongliang Huang and Weisai Zu and Haohua Huo}, doi = {10.1021/jacs.4c15275}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10999--11009}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective Alkyl–Acyl radical cross-coupling enabled by metallaphotoredox catalysis}, volume = {147}, year = {2025}, }
• (2025). Heavy atom-induced Spin–Orbit coupling to quench singlet oxygen in a Li–O2 battery. JACS, 147(13), 10992--10998. (www)

  @article{ , abstract = {Li–O 2 batteries have aroused considerable interest due to high theoretical energy density; however, the singlet oxygen ( 1 O 2 ) generated in both discharge and charge processes induces severe parasitic reactions and leads to their low round-trip efficiency and poor rechargeability. Herein, a universal heavy atom-induced quenching mechanism is proposed to suppress 1 O 2 and related side reactions. Br in tris(4-bromophenyl)amine (TBPA) induces strong heavy atom-induced spin–orbit coupling (SOC), enhancing the interaction between the spin angular momentum and the orbital angular momentum of the electron. It enables TBPA to capture electrophilic 1 O 2 to form a singlet complex and then effectively drives the spin-forbidden spin-flip process to form a triplet complex. This accelerates the conversion of 1 O 2 to ground-state 3 O 2 through a heavy atom-induced intersystem crossing mechanism, and it efficiently eliminates its attack on organic solvents and carbon cathodes. These endow the Li–O 2 battery with reduced overvoltages and prolonged lifespan for over 350 cycles when coupled with a RuO 2 catalyst. This work highlights the heavy atom-induced SOC to quench 1 O 2 in oxygen evolution reaction-related devices.}, archive = {J_JACS}, author = {Zhuoliang Jiang and Bo Wen and Yaohui Huang and Yuzhe Wang and Hengyi Fang and Fujun Li}, doi = {10.1021/jacs.4c15230}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10992--10998}, shortjournal = {J. Am. Chem. Soc.}, title = {Heavy atom-induced Spin–Orbit coupling to quench singlet oxygen in a Li–O2 battery}, volume = {147}, year = {2025}, }
• (2025). Assigning surface hole polaron configurations of titanium oxide materials to excited-state optical absorptions. JACS, 147(13), 10981--10991. (www)

  @article{ , abstract = {For water splitting, a comprehensive understanding of the underlying reaction intermediates and pathways is crucial for optimizing catalyst design. Among the most well-known active photoanodes for the oxygen evolution half-reaction are TiO 2 -based materials. A hole polaron, which consists of a metal-oxide distortion around trapped holes, has been suggested as a local reactive oxygen configuration. While first-principles calculations identify new electronic states in the middle of the band gap and the influence of trapped hole dynamics on transport, an assignment of hole polaron configurations to a measured spectrum has been challenging due to broad optical transitions in the visible regime. Here, we compare the excited-state absorption (ESA) for two titanium oxide materials with a similar electronic structure but differing crystal structure. The ESA maximum for ultrafast time scales (<1 ps) is isolated by a principal component analysis and shifts from 3.1 eV in rutile TiO 2 (100) to 2.2 eV in perovskite SrTiO 3 . Density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations predict the energies of the midgap states for stable hole polarons and their corresponding spectra. The shift in the ESA is rationalized by the transition optical dipole originating from both edge and deeper states in the valence band being bright for certain configurations of hole polarons in rutile TiO 2 (100) (terminal O •– ) versus STO (lateral Ti 2 O •– ). The spectral assignment of a shifting ESA between two titanium oxide materials informs the assignment of hole polaron configurations for oxygen evolution catalysis and, more generally, photodriven processes.}, archive = {J_JACS}, author = {Cassius Boyd and Shay McBride and Michael Paolino and Moritz Lang and Geoffroy Hautier and Tanja Cuk}, doi = {10.1021/jacs.4c15043}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10981--10991}, shortjournal = {J. Am. Chem. Soc.}, title = {Assigning surface hole polaron configurations of titanium oxide materials to excited-state optical absorptions}, volume = {147}, year = {2025}, }
• (2025). Electrochemical control of heterolytic and homolytic hydrogenation pathways at a palladium surface. JACS, 147(13), 10974--10980. (www)

  @article{ , abstract = {Here, we use a palladium membrane reactor to investigate hydrogen transfer pathways at the palladium surface. The palladium membrane reactor uses electrochemistry to facilitate the controlled adsorption of hydrogen, sourced from water, into one face of the palladium membrane. This hydrogen permeates through palladium and reacts with unsaturated species in the opposing chamber. The amount of hydrogen loaded into the palladium can be controlled electrochemically to form a well-defined and static PdH x ratio for studying chemical hydrogenation. These static PdH x ratios are otherwise difficult to achieve. We show a preference for homolytic hydrogen transfer pathways at lower current densities and heterolytic hydrogen transfer pathways at higher current densities. We also show reaction conditions that favor hydrogen reacting as either a hydrogen radical (H • ), a proton (H + ), or a hydride (H – ).}, archive = {J_JACS}, author = {Mia D. Stankovic and Bowen Ge and Jessica F. Sperryn and Curtis P. Berlinguette}, doi = {10.1021/jacs.4c14671}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10974--10980}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical control of heterolytic and homolytic hydrogenation pathways at a palladium surface}, volume = {147}, year = {2025}, }
• (2025). Fano resonance in CO2 reduction catalyst functionalized quantum dots. JACS, 147(13), 10966--10973. (www)

  @article{ , abstract = {Molecular catalyst functionalized semiconductor quantum dots (QDs) are a promising modular platform for developing novel hybrid photocatalysts. The interaction between adsorbed catalyst vibrations and the QD electron intraband absorption can influence the photophysical properties of both the QD and the catalysts and potentially their photocatalysis. In CdSe QDs functionalized by the CO 2 reduction catalyst, Re(CO) 3 (4,4’-bipyridine-COOH)Cl, we observe that the transient Fano resonance signal resulting from coupling of the catalyst CO stretching mode and the QD conduction band electron mid-IR intraband absorption appears on an ultrafast time scale and decays with the electron population, irrespective of the occurrence of photoreduced catalysts. The Fano asymmetry factor increases with an increase in the adsorbed catalyst number and a decrease in QD sizes. The latter can be attributed to an enhanced charge transfer interaction between the more strongly quantum-confined QD conduction band and catalyst LUMO levels. These results provide a more in-depth understanding of interactions in excited QD-catalyst hybrid photocatalysts.}, archive = {J_JACS}, author = {Sara T. Gebre and Luis Martinez-Gomez and Christopher R. Miller and Clifford P. Kubiak and Raphael F. Ribeiro and Tianquan Lian}, doi = {10.1021/jacs.4c14499}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10966--10973}, shortjournal = {J. Am. Chem. Soc.}, title = {Fano resonance in CO2 reduction catalyst functionalized quantum dots}, volume = {147}, year = {2025}, }
• (2025). Elucidating the proton source for CO2 electro-reduction on cu(100) using many-body perturbation theory. JACS, 147(13), 10954--10965. (www)

  @article{ , abstract = {The protonation of CO is recognized as the rate-determining step in the generation of C1 products during the electrochemical CO 2 reduction reaction (CO 2 RR) on Cu surfaces. However, the detailed mechanism and the precise proton source remain elusive. While density functional theory (DFT) calculations at the GGA level have been widely used, they struggle to accurately describe adsorbate-metal interactions and surface stability. Here, we employed the Random Phase Approximation (RPA), a method based on many-body perturbation theory, to overcome these limitations. We coupled the RPA framework with the linearized Poisson–Boltzmann equation to model solvation effects and a surface charging method to account for the influence of the electrochemical potential. Our study reveals that in neutral or alkaline electrolytes, adsorbed surface water acts as the proton source for *CO reduction to *COH over a broad potential range via the Grotthuss mechanism. At highly negative potentials, solvent water becomes the primary proton donor, with multiple competing mechanisms observed. In contrast, DFT-GGA functionals significantly underestimate the reaction barriers for *COH formation and consistently predict solvent water as the proton source across all potentials of interest. Additionally, RPA offers distinct insights into H 2 O adsorption and highlights the significant range of reducing potentials within which surface *OH can exist, which is crucial for accurate CO 2 RR modeling. These insights illustrate a pronounced divergence between RPA and DFT-GGA results. Our findings offer a fresh perspective on proton transfer in CO 2 RR and establish a framework for future theoretical studies on electrochemical processes.}, archive = {J_JACS}, author = {Dongfang Cheng and Ziyang Wei and Philippe Sautet}, doi = {10.1021/jacs.4c14108}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10954--10965}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating the proton source for CO2 electro-reduction on cu(100) using many-body perturbation theory}, volume = {147}, year = {2025}, }
• (2025). In situ detection of the molecule-crowded aqueous Electrode–Electrolyte interface. JACS, 147(13), 10943--10953. (www)

  @article{ , abstract = {Electrode–electrolyte interface plays a crucial role in determining the stability and behavior of electrochemical electrodes. Although X-ray photoelectron spectroscopy has been established as a powerful analytical technique for interface chemistry, the necessity for ultrahigh vacuum remains a significant obstacle to directly detecting dynamic interfacial evolution, particularly in aqueous environments. Here, we employ tender-energy ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to bridge the gap between ultrahigh vacuum and near-atmospheric pressure, enabling an in-depth investigation of the molecule-crowded aqueous interface evolution in a Zn metal anode. The results demonstrate that the persistent presence of additive molecules effectively inhibits direct contact between reactive Zn and H 2 O, while also facilitating uniform Zn deposition. In situ optical microscopy observations and synchrotron radiation X-ray diffraction further verified the uniform and dense Zn deposition, attributed to lateral growth induced by the (002) crystal facet evolution. As proof of its effectiveness, batteries incorporating the Zn//Zn, Zn//Cu, and full cell with the additive demonstrate significantly improved stability and reversibility. This finding opens up new avenues for exploration of interfacial chemistry at the molecule level, offering insights into the design of highly stable metal anodes of aqueous ion batteries for practical applications.}, archive = {J_JACS}, author = {Shiqiang Wei and Hongwei Shou and Zheng-Hang Qi and Shuangming Chen and Yong Han and Shucheng Shi and Yixiu Wang and Pengjun Zhang and Jialin Shi and Zijun Zhang and Yuyang Cao and Changda Wang and Jiewu Cui and Xiaojun Wu and Zhi Liu and Li Song}, doi = {10.1021/jacs.4c14053}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10943--10953}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ detection of the molecule-crowded aqueous Electrode–Electrolyte interface}, volume = {147}, year = {2025}, }
• (2025). Quantum spin wave excited from a Cr–Dy single-molecule magnet. JACS, 147(13), 10935--10942. (www)

  @article{ , abstract = {The efficient excitation and controlled propagation of nanoscale spin waves remain significant challenges, as their intrinsic dispersion relations are primarily determined by magnetic dipole and exchange interactions. Here we report the first observed coexistence of quantum spin wave excitation and single-molecule magnet behavior in a mixed chromium(III) and dysprosium(III) complex, namely Dy 4 Cr 2 ( μ 3 -F) 2 (mdea) 3 (piv) 10 , which shows a large ferrimagnetic ground moment with a restricted quantum tunneling gap (<3.8 × 10 –7 cm –1 ) up to nine levels, leading to an axial anisotropic energy barrier of 12 cm –1 and opened hysteresis loop at 0.4 K. More importantly, quantized spin wave excitations ranging from 108 to 352 GHz have been observed by using inelastic neutron scattering spectroscopy, and the data can be well explained by the L & E -band theory with Δ /2 = 2.08 cm –1 and ε ( q ) = 2.5 cm –1 , providing unambiguous evidence for nanoscale spin waves.}, archive = {J_JACS}, author = {Bo-Kai Ling and Ming Chang and Yuan-Qi Zhai and Jiewei Deng and Maiko Kofu and Hanjie Guo and Jinkui Zhao and Zhendong Fu and Yan-Zhen Zheng}, doi = {10.1021/jacs.4c13628}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10935--10942}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantum spin wave excited from a Cr–Dy single-molecule magnet}, volume = {147}, year = {2025}, }
• (2025). Prolonged trapping of adeno-associated virus capsids reveals that genome packaging affects single-ion mass spectrometry measurements. JACS, 147(13), 10925--10934. (www)

  @article{ , abstract = {Recombinant adeno-associated viruses (rAAVs) play an important role in gene therapy, yet the optimal preparation of these biotherapeutics remains challenging, with often incomplete incorporation of genome cargo, negatively affecting therapeutic use. Genome packaging has traditionally been difficult to investigate. Charge detection mass spectrometry (CDMS) has gained prominence, as it provides the ability to mass analyze and resolve empty and filled rAAVs, enabling the quantitative determination of empty-to-filled rAAV ratios. Such measurements require a high mass resolving power and depend on the unbiased detectability of the distinct rAAV particles. The mass resolving power in the Orbitrap mass analyzers scales with transient recording times. Therefore, we extended the capability of recording ions from 1 or 2 to 24 s. When we record these 24 s transients to analyze rAAVs, we not only observe a substantial improvement in accuracy and mass resolution but also find that this can lead to erroneous artifacts in the empty-to-filled ratios. Artifacts originate from the distinct behavior between orbiting ions from either empty or filled particles, mainly due to differences in desolvation and charge losses. Ions from empty rAAVs appear much more susceptible to charge losses, which negatively affect their tracing, artificially decreasing the empty-to-filled ratios. Further elucidating the causes of this undesirable ion behavior, we provide the means to minimize charge losses, thus regaining accurate AAV quantification at an increased charge precision and mass-resolving power. As the Orbitrap-based CDMS has become a method of choice to determine this important quality control attribute, our findings are important to avoid reporting incorrect empty-to-filled ratios.}, archive = {J_JACS}, author = {Eduard H. T. M. Ebberink and Victor C. Yin and Evolène Deslignière and Arjan Barendregt and Tobias P. Wörner and Kyle L. Fort and Alexander A. Makarov and Albert J. R. Heck}, doi = {10.1021/jacs.4c13393}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10925--10934}, shortjournal = {J. Am. Chem. Soc.}, title = {Prolonged trapping of adeno-associated virus capsids reveals that genome packaging affects single-ion mass spectrometry measurements}, volume = {147}, year = {2025}, }
• (2025). Charged water microdroplets enable dissociation of surrounding dioxygen. JACS, 147(13), 10916--10924. (www)

  @article{ , abstract = {The cleavage of dioxygen (O 2 ) into its atomic constituents typically requires harsh conditions and metal catalysts. We present a remarkable discovery demonstrating that dioxygen can be activated, dissociated, and subsequently transformed into the ozone anion (O 3 – ) without any catalyst at the air–water interface in charged microdroplet sprays. Using online mass spectrometry, we directly detected the dioxygen splitting products O 3 – and H 2 O·O 3 – in microdroplets. The high electric field at the air–water interface, along with microlightning between oppositely charged water microdroplets, induces an electrical discharge responsible for the O–O bond cleavage, leading to the formation of reactive oxygen species (ROS). Isotope labeling experiments further reveal that various ROS, i.e., ·OH, CO 3 – , and HCO 4 – , can be generated through the reaction of dioxygen splitting products with water or CO 2 . This study introduces a sustainable pathway for molecular oxygen utilization and offers new insights into ROS generation in microdroplets.}, archive = {J_JACS}, author = {Jian Zhou and Qing Wang and Gongkui Cheng and Wei Shen and Richard N. Zare and Xiaoyan Sun}, doi = {10.1021/jacs.4c12740}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10916--10924}, shortjournal = {J. Am. Chem. Soc.}, title = {Charged water microdroplets enable dissociation of surrounding dioxygen}, volume = {147}, year = {2025}, }
• (2025). Fluorogenic, subsingle-turnover monitoring of enzymatic reactions involving NAD(P)H provides a generalized platform for directed ultrahigh-throughput evolution of biocatalysts in microdroplets. JACS, 147(13), 10903--10915. (www)

  @article{ , abstract = {Enzyme engineering and discovery are crucial for a sustainable future bioeconomy. Harvesting new biocatalysts from large libraries through directed evolution or functional metagenomics requires accessible, rapid assays. Ultrahigh-throughput screening formats often require optical readouts, leading to the use of model substrates that may misreport target activity and necessitate bespoke synthesis. This is a particular challenge when screening glycosyl hydrolases, which leverage molecular recognition beyond the target glycosidic bond, so that complex chemical synthesis would have to be deployed to build a fluoro- or chromogenic substrate. In contrast, coupled assays represent a modular “plug-and-play” system: any enzyme–substrate pairing can be investigated, provided the reaction can produce a common intermediate which links the catalytic reaction to a detection cascade readout. Here, we establish a detection cascade producing a fluorescent readout in response to NAD(P)H via glutathione reductase and a subsequent thiol-mediated uncaging reaction, with a low nanomolar detection limit in plates. Further scaling down to microfluidic droplet screening is possible: the fluorophore is leakage-free and we report 3 orders of magnitude-improved sensitivity compared to absorbance-based systems, with a resolution of 361,000 product molecules per droplet. Our approach enables the use of nonfluorogenic substrates in droplet-based enrichments, with applicability in screening for glycosyl hydrolases and imine reductases (IREDs). To demonstrate the assay’s readiness for combinatorial experiments, one round of directed evolution was performed to select a glycosidase processing a natural substrate, beechwood xylan, with improved kinetic parameters from a pool of >10 6 mutagenized sequences.}, archive = {J_JACS}, author = {Matthew Penner and Oskar James Klein and Maximilian Gantz and Friederike E. H. Nintzel and Anne-Cathrin Prowald and Sally Boss and Paul Barker and Paul Dupree and Florian Hollfelder}, doi = {10.1021/jacs.4c11804}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10903--10915}, shortjournal = {J. Am. Chem. Soc.}, title = {Fluorogenic, subsingle-turnover monitoring of enzymatic reactions involving NAD(P)H provides a generalized platform for directed ultrahigh-throughput evolution of biocatalysts in microdroplets}, volume = {147}, year = {2025}, }
• (2025). Holdup multiplex assay for high-throughput measurement of Protein–Ligand affinity constants using a mass spectrometry readout. JACS, 147(13), 10886--10902. (www)

  @article{ , abstract = {The accurate description and subsequent modeling of protein interactomes require quantification of their affinities at the proteome-wide scale. Here we develop and validate the Holdup Multiplex, a versatile assay with a mass spectrometry (MS) readout for profiling the affinities of a protein for large pools of peptides. The method can precisely quantify, in one single run, thousands of affinity constants over several orders of magnitude. The throughput, dynamic range, and sensitivity can be pushed to the performance limit of the MS readout. We applied the Holdup Multiplex to quantify in a few sample runs the affinities of the 14–3–3s, phosphoreader proteins highly abundant in humans, for 1000 different phosphopeptides. The seven human 14–3–3 isoforms were found to display similar specificities but staggered affinities, with 14–3–3γ being always the best binder and 14–3–3ε and σ being the weakest. Hundreds of new 14–3–3 binding sites were identified. We also identified dozens of 14–3–3 binding sites, some intervening in key signaling pathways, that were either stabilized or destabilized by the phytotoxin Fusicoccin-A. The results were corroborated by X-ray crystallography. Finally, we demonstrated the transferability of the Holdup Multiplex by quantifying the interactions of a PDZ domain for 5400 PBM peptides at once. The approach is applicable to any category of protein-binding ligands that can be quantifiable by mass spectrometry.}, archive = {J_JACS}, author = {François Delalande and So̷ren Østergaard and Gergo Gogl and Alexandra Cousido-Siah and Alastair G. McEwen and Yushi Men and Farida Salimova and Aurélien Rohrbacher and Camille Kostmann and Yves Nominé and Renaud Vincentelli and Pascal Eberling and Christine Carapito and Gilles Travé and Elodie Monsellier}, doi = {10.1021/jacs.4c11102}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10886--10902}, shortjournal = {J. Am. Chem. Soc.}, title = {Holdup multiplex assay for high-throughput measurement of Protein–Ligand affinity constants using a mass spectrometry readout}, volume = {147}, year = {2025}, }
• (2025). Structure-based mechanism and specificity of human galactosyltransferase β3GalT5. JACS, 147(13), 10875--10885. (www)

  @article{ , abstract = {Human β1,3-galactosyltransferase 5 (β3GalT5) is a key enzyme involved in the synthesis of glycans on glycoproteins and glycolipids that are associated with various important biological functions, especially tumor malignancy and cancer progression, and has been considered as a promising target for development of anticancer agents. In this study, we determined the X-ray structures of β3GalT5 in complex with the stable donor analogue UDP-2-fluorogalactose or the native donor substrate UDP-galactose (UDP-Gal) and several glycan acceptors at different reaction steps. Based on the structures obtained from our experiments, β3GalT5 catalyzes the transfer of galactose from UDP-Gal to a broad spectrum of glycan acceptors with an S N 2-like mechanism; however, in the absence of a glycan acceptor, UDP-Gal is slowly converted to UDP and two other products, one is galactose through an S N 2-like mechanism with water as an acceptor and the other is an oxocarbenium-like product, presumably through an S N 1-like mechanisms. The structure, mechanism, and specificity of β3GalT5 presented in this study advance our understanding of enzymatic glycosylation and provide valuable insights for application to glycan synthesis and drug design targeting β3GalT5-associated cancer.}, archive = {J_JACS}, author = {Jennifer M. Lo and Chih-Chuan Kung and Ting-Jen Rachel Cheng and Chi-Huey Wong and Che Ma}, doi = {10.1021/jacs.4c11724}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10875--10885}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure-based mechanism and specificity of human galactosyltransferase β3GalT5}, volume = {147}, year = {2025}, }
• (2025). Expression of human β3GalT5–1 in insect cells as active glycoforms for the efficient synthesis of cancer-associated globo-series glycans. JACS, 147(13), 10864--10874. (www)

  @article{ , abstract = {The globo-series glycosphingolipids (GSLs) are unique glycolipids exclusively expressed on the cell surface of various types of cancer and have been used as targets for the development of cancer vaccines and therapeutics. A practical enzymatic method has been developed for the synthesis of globo-series glycans, where the conversion of Gb4 to Gb5 (SSEA-3) glycan based on the microbial galactosyltransferase LgtD is relatively inefficient compared to other steps. To improve the efficiency, we explored the two human galactosyltransferase (β3GalT5) isozymes in cancer cells for this reaction and found that isozyme 1 (β3GalT5–1) is more active than isozyme 2 (β3GalT5–2). We then identified a common soluble domain of the two β3GalT5 isozymes as a candidate and evaluated the activity and substrate specificity of the glycosylated and nonglycosylated glycoforms. The glycoforms expressed in Sf9 cells were selected, and a site-specific alanine scan was performed to identify S66A β3GalT5 variant with 10-fold more efficiency than LgtD for the synthesis of globo-series glycans. The X-ray structure of β3GalT5–1 was determined for molecular modeling, and the result together with kinetic data were used to rationalize the improvement in catalysis.}, archive = {J_JACS}, author = {Chih-Chuan Kung and Jennifer M. Lo and Kuo-Shiang Liao and Chung-Yi Wu and Li-Chun Cheng and Cinya Chung and Tsui-Ling Hsu and Che Ma and Chi-Huey Wong}, doi = {10.1021/jacs.4c11723}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10864--10874}, shortjournal = {J. Am. Chem. Soc.}, title = {Expression of human β3GalT5–1 in insect cells as active glycoforms for the efficient synthesis of cancer-associated globo-series glycans}, volume = {147}, year = {2025}, }
• (2025). Photoinduced, copper-catalyzed enantioconvergent synthesis of β-aminoalcohol derivatives. JACS, 147(13), 10859--10863. (www)

  @article{ , abstract = {In view of the frequent occurrence of carbon–nitrogen bonds in organic compounds, the development of powerful new methods for the construction of such bonds is expected to greatly impact many of the fields that utilize organic molecules. While the substitution of an alkyl electrophile by a nitrogen nucleophile is a seemingly straightforward approach to generating a carbon–nitrogen bond, in practice classical substitution pathways have very substantial limitations in the case of unactivated secondary and tertiary alkyl electrophiles. Recent reports that transition metals can catalyze certain substitution reactions of such electrophiles are therefore of considerable significance; however, virtually no methods have been developed wherein absolute stereochemistry is controlled together with carbon–nitrogen bond formation. Herein, we address this dual challenge of reactivity and enantioselectivity, describing a photoinduced, copper-catalyzed enantioconvergent synthesis of β-aminoalcohol derivatives via the coupling of anilines with racemic, unactivated β-haloethers. We apply this method to a catalytic asymmetric synthesis of metolachlor, and we report an array of mechanistic studies that are consistent with the reaction pathway that we propose.}, archive = {J_JACS}, author = {Arup Mondal and Gregory C. Fu}, doi = {10.1021/jacs.5c02417}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10859--10863}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoinduced, copper-catalyzed enantioconvergent synthesis of β-aminoalcohol derivatives}, volume = {147}, year = {2025}, }
• (2025). Pyrroline ring assembly via N-prenylation and oxidative carbocyclization during biosynthesis of aeruginosin derivatives. JACS, 147(13), 10853--10858. (www)

  @article{ , abstract = {Aeruginosins are linear peptide natural products isolated from cyanobacteria and contain various arginine derivatives at their termini. 1-Amino-2-( N -amidino-3-Δ3-pyrrolinyl)ethane (Aeap) is a structurally unique arginine derivative, as it has an unusual pyrroline ring with two additional carbon atoms of unknown biosynthetic origin. Here, we demonstrate that Aer3, a member of a newly identified subfamily of prenyltransferases, catalyzes selective isopentenylation of the internal N atom of agmatine. Rieske oxygenase AerC then catalyzes both carbocyclization and C–C bond cleavage to construct the pyrroline ring in Aeap. This pyrroline ring formation in Aeap biosynthesis, involving two novel enzymes, represents a unique route for heterocycle formation in nature.}, archive = {J_JACS}, author = {Wenhe Zhang and Richiro Ushimaru and Masahiro Kanaida and Ikuro Abe}, doi = {10.1021/jacs.5c01994}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10853--10858}, shortjournal = {J. Am. Chem. Soc.}, title = {Pyrroline ring assembly via N-prenylation and oxidative carbocyclization during biosynthesis of aeruginosin derivatives}, volume = {147}, year = {2025}, }
• (2025). Viologen covalent organic framework mediates near-infrared light-induced electron transfer for catalytic oxidative coupling reactions. JACS, 147(13), 10846--10852. (www)

  @article{ , abstract = {Near-infrared (NIR) light-driven photoreactions are advantageous over visible light-driven ones because NIR photons have lower energy and fewer side reactions, deeper penetration in reaction media, and high abundance in the solar spectrum. However, currently available covalent organic frameworks (COFs) absorb in the UV–vis region and catalyze photoreactions under blue or white light irradiation. Herein, we report a linker-to-linker charge transfer process in a viologen-linked porphyrin COF (Vio-COF), leading to a novel type of hyperporphyrin effect and extending the absorption into the NIR region with an absorption edge at 998 nm. Under NIR irradiation, photoinduced charge separation in Vio-COF generates a viologen radical that efficiently reduces oxygen to form superoxide radicals for catalytic oxidative coupling reactions. The proximity of porphyrin and viologen units within the framework significantly enhances the catalytic performance of Vio-COF, outperforming its homogeneous counterparts in aerobic oxidative amidation and amine coupling reactions. Vio-COF was readily recycled and used in six oxidative coupling reactions.}, archive = {J_JACS}, author = {Zhibei Zhou and Zitong Wang and Abigail L Blenko and Jinhong Li and Wenbin Lin}, doi = {10.1021/jacs.5c00686}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10846--10852}, shortjournal = {J. Am. Chem. Soc.}, title = {Viologen covalent organic framework mediates near-infrared light-induced electron transfer for catalytic oxidative coupling reactions}, volume = {147}, year = {2025}, }
• (2025). Reticular design and synthesis of covalent organic frameworks with irregular hexagonal tiling. JACS, 147(13), 10840--10845. (www)

  @article{ , abstract = {Reticular chemistry has greatly stimulated the development of framework materials, yet covalent organic frameworks (COFs) featuring irregular tiling are rare, because of the strict constraints on irregular tile lengths and angles. Guided by reticular chemistry, we deconstructed type III irregular hexagonal tiling into a combination of D 2 h + D 2 h monomers and achieved the first successful synthesis of 2D COFs featuring such tiling with hit topology. By tuning the crystal growth conditions, we obtained a set of reticular isomers, COF-hit and COF-bex, with distinct reticular structures. Powder X-ray diffraction and high-resolution transmission electron microscopy were employed to precisely characterize their topology structures. COF-hit demonstrates outstanding water absorption capabilities under high humidity conditions. This rational design of COFs using irregular tiling opens a new avenue to diversify the structural types and topological varieties of COFs and promote the development of reticular chemistry.}, archive = {J_JACS}, author = {Hong Li and Xiao-Rui Ren and Yan Wang and Daliang Zhang and Zitao Wang and Lan-Ting Wei and Xin-Lan Wang and Dong Wang}, doi = {10.1021/jacs.5c00494}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10840--10845}, shortjournal = {J. Am. Chem. Soc.}, title = {Reticular design and synthesis of covalent organic frameworks with irregular hexagonal tiling}, volume = {147}, year = {2025}, }
• (2025). Reactive ZIF-L crystal surface for organophosphorous degradation and acetylcholinesterase reactivation. JACS, 147(13), 10834--10839. (www)

  @article{ , abstract = {The importance of crystal surface reactivity of reticular materials is exemplified by exfoliation of nonporous layered zeolitic imidazolate framework Zn(mIm) 2 ·0.5mImH (ZIF-L, mImH = 2-methylimidazole). Sonication of ZIF-L ethanolic suspensions leads to exfoliation of microcrystals along the 2 0 0 planes, giving rise to 1.5 μm wide × 25 nm thick flakes, which we term ZIF-L_exf. ZIF-L_exf exhibits a high reactivity toward hydrolytic degradation of extremely toxic G-type nerve agents, Soman (GD), and simulant diisopropylfluorophosphate (DIFP). The reactivity of the crystal surface of ZIF-L_exf toward P–F bond breakdown gives rise to framework structural degradation, releasing nucleophilic mImH molecules that reactivate organophosphate-inhibited acetylcholinesterase within 10 min. This detoxification process can be taken as a proof of concept for reversing organophosphorous poisoning. More generally, this approach underscores the importance of the crystal surface nature and composition to control the reactivity of reticular materials.}, archive = {J_JACS}, author = {Emilio Borrego-Marin and Pablo Garrido-Barros and Gregory W. Peterson and Rebecca Vismara and Francisco J. Carmona and Elisa Barea and Jorge A. R. Navarro}, doi = {10.1021/jacs.5c00382}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10834--10839}, shortjournal = {J. Am. Chem. Soc.}, title = {Reactive ZIF-L crystal surface for organophosphorous degradation and acetylcholinesterase reactivation}, volume = {147}, year = {2025}, }
• (2025). Bismuth vanadate capable of driving one-step-excitation photocatalytic overall water splitting. JACS, 147(13), 10829--10833. (www)

  @article{ , abstract = {Solar-driven one-step-excitation overall water splitting is one of the most straightforward ways of achieving scalable solar hydrogen production. Despite its advantage in visible-light response and stability, the pristine bismuth vanadate (BiVO 4 ) alone is not capable of achieving overall water splitting due to its conduction band energy level being insufficient for the proton reduction reaction, further limited by the severe charge recombination. Here, we demonstrate the three-dimensionally ordered macroporous BiVO 4 with a carefully enlarged bandgap of 2.58 eV and a conduction band energy of −0.49 eV versus normal hydrogen electrode at pH 7.0. On loading Rh/Cr 2 O 3 as a hydrogen evolution cocatalyst, the stochiometric evolution of hydrogen and oxygen in a recyclable manner is accomplished under visible light with an apparent quantum yield of 0.47% at 400 nm. Further study by Kelvin probe force microscopy reveals an intensified internal electric field with a downward band bending from the interconnection part to the internal wall of the periodic porous structure upon loading the cocatalysts. Our findings transform BiVO 4 from a typical water oxidation photocatalyst into a new paradigm for single-component photocatalysts for overall water splitting.}, archive = {J_JACS}, author = {Hao Wu and Songying Qu and Yun Hau Ng}, doi = {10.1021/jacs.4c18733}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10829--10833}, shortjournal = {J. Am. Chem. Soc.}, title = {Bismuth vanadate capable of driving one-step-excitation photocatalytic overall water splitting}, volume = {147}, year = {2025}, }
• (2025). Pushing limits of ultra-wideline solid-state NMR spectroscopy: NMR signatures of 209Bi and 127I in Metal–Organic frameworks at ultra-high magnetic fields. JACS, 147(13), 10823--10828. (www)

  @article{ , abstract = {Bismuth- and iodine-containing metal–organic frameworks (MOFs) are crucial in catalysis, gas adsorption, and luminescence, with local environments of Bi and I ions shaping their performance. Using 209 Bi and 127 I solid-state NMR (SSNMR) for characterization is extremely challenging due to the exceedingly large quadrupolar interactions in MOFs. Here, we present ultra-wideline (UW) SSNMR spectra of eight MOFs acquired at ultra-high magnetic fields up to 36 T, with breadths of 8–50 MHz, revealing very large quadrupolar couplings. These spectra uncover key structural details, including dehydration, guest adsorption, phase transitions, and disorder. This study establishes 209 Bi and 127 I UW SSNMR as powerful tools for probing Bi and I ions in weight-dilute systems, offering broad applications in catalysis, solar cells, biochemistry, and beyond.}, archive = {J_JACS}, author = {Wanli Zhang and Yijue Xu and Amrit Venkatesh and Ivan Hung and Shuting Li and Zhehong Gan and Yining Huang}, doi = {10.1021/jacs.4c17499}, journal = {Journal of the American Chemical Society}, month = {4}, number = {13}, pages = {10823--10828}, shortjournal = {J. Am. Chem. Soc.}, title = {Pushing limits of ultra-wideline solid-state NMR spectroscopy: NMR signatures of 209Bi and 127I in Metal–Organic frameworks at ultra-high magnetic fields}, volume = {147}, year = {2025}, }
• (2025). Mechanistic insights into regioselectivity and its evolution in on-surface polymerization. JACS, 147(12), 10815--10822. (www)

  @article{ , abstract = {Surface-catalyzed polymerization is crucial in both chemical science and industrial manufacturing, yet achieving regioselective radical polymerization on the surface remains challenging. Here, we demonstrate the regioselective Ullmann polymerization of nonsymmetrical 2,8-dibromoquinoline (DBQ) on an Au(111) surface. By combining scanning tunneling microscopy, density functional theory calculations, and kinetic modeling, we reveal the regioselectivity and its evolution with surface temperature at the molecular level. At 348–368 K, DBQ monomers primarily form covalent dimers through energetically favored head-to-head (HtH) coupling. As the temperature increases to 390–473 K, oligomers and long polymer chains are formed, with less favored head-to-tail (HtT) linkages emerging and eventually dominating over HtH linkages. Such regioselectivity evolution from HtH to HtT is suggested to be related to a sequential monomer addition mode and a shift in the distribution of reactive sites at the end and tail of the polymer chains during polymerization. This result provides molecular-level mechanistic insights into the regiochemistry of surface-catalyzed polymerization.}, archive = {J_JACS}, author = {Longzhu Zhang and Zi-Cong Wang and Ruoning Li and Jichen Dong and Zhi-Hao Li and An-Jing Zhao and Guan Luo and Ting Chen and Dong Wang and Li-Jun Wan}, doi = {10.1021/jacs.5c03595}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10815--10822}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic insights into regioselectivity and its evolution in on-surface polymerization}, volume = {147}, year = {2025}, }
• (2025). Lone pairs-mediated multiple through-space interactions for efficient room-temperature phosphorescence. JACS, 147(12), 10803--10814. (www)

  @article{ , abstract = {The simultaneous generation and stabilization of triplet excitons are the key to realizing efficient organic room temperature phosphorescence (RTP), which is challenging owing to the obscure mechanism and structure–property relationships. Herein, a strategy of lone-pair-mediated multiple through-space interactions (TSIs) is proposed to availably induce RTP. By incorporating heteroatoms to facilitate through-space n–n and n−π interactions, the lone pairs are delocalized throughout the structure, resulting in the dense splitting of the excited-state energy levels. Thus, more matched energy levels with a small energy gap between singlet and triplet states (Δ E ST ) emerge, resulting in multiple intersystem crossing (ISC) transition channels that assist triplet excitons generation. The strong TSIs also effectively rigidify the molecular structures and thus stabilize triplet excitons for radiation. Furthermore, the manipulation of TSI intensity allows efficiency enhancement, persistent time prolongation, and tolerance to high temperatures of RTP. This work not only explores the fundamental principle of the RTP mechanism from a new view but also provides a universal strategy for ISC promotion and triple excitons stabilization.}, archive = {J_JACS}, author = {Fulong Ma and Bo Wu and Siwei Zhang and Jinhui Jiang and Jinghong Shi and Zeyang Ding and Yue Zhang and Haozhe Tan and Parvej Alam and Jacky W. Y. Lam and Yu Xiong and Zhen Li and Ben Zhong Tang and Zheng Zhao}, doi = {10.1021/jacs.5c02567}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10803--10814}, shortjournal = {J. Am. Chem. Soc.}, title = {Lone pairs-mediated multiple through-space interactions for efficient room-temperature phosphorescence}, volume = {147}, year = {2025}, }
• (2025). Atroposelective synthesis of pyridoindolones bearing two remote distinct C–N axes through cobalt-catalyzed enantioselective C–H activation. JACS, 147(12), 10791--10802. (www)

  @article{ , abstract = {C–N axially chiral compounds represent an important class of atropisomers that are prevalent in bioactive and material molecules. Despite recent advances in synthetic methodologies, the asymmetric construction of atropisomers featuring multiple C–N axes has been rarely explored, significantly limiting their further applications. Herein, we report a novel atroposelective synthesis of diaxially chiral pyridoindolones featuring both six–five and six–six C–N axes through cobalt-catalyzed asymmetric C–H annulation. This approach demonstrates exceptional efficiency, yielding a diverse array of chiral pyridoindolones with excellent yields and atroposelectivities (60 examples, up to >99% yield, >99% ee, and >20:1 dr). Mechanistic studies revealed that the stereochemistry of both C–N axes were generated and fixed simultaneously during the C–H cyclometalation step, along with an unexpected asymmetric amplification effect. The practicality of this protocol is further underscored by successful gram-scale syntheses and various transformations, including the formation of a chiral phosphine ligand. Notably, exceptional photoluminescence quantum yields ( Φ F up to 0.99) and positive solvatochromism were observed, coupled with significant chiroptical properties, underscoring the potential applications of these compounds in organic fluorescent materials.}, archive = {J_JACS}, author = {Pu-Fan Qian and Yan-Xuan Wu and Jia-Heng Hu and Jia-Hao Chen and Tao Zhou and Qi-Jun Yao and Zi-Hang Zhang and Bing-Jie Wang and Bing-Feng Shi}, doi = {10.1021/jacs.5c02428}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10791--10802}, shortjournal = {J. Am. Chem. Soc.}, title = {Atroposelective synthesis of pyridoindolones bearing two remote distinct C–N axes through cobalt-catalyzed enantioselective C–H activation}, volume = {147}, year = {2025}, }
• (2025). Iridium nanocrystals enriched with defects and atomic steps to enhance oxygen evolution reaction performance. JACS, 147(12), 10784--10790. (www)

  @article{ , abstract = {The presence of defects can significantly improve catalytic activity and stability, as they influence the binding of the reactants, intermediates, and products to the catalyst. Controlling defects in the structures of nanocrystal catalysts is synthetically challenging. In this study, we demonstrate the ability to control the growth of Ir nanocrystals, enabling the tuning of both structural and surface defects. The Ir nanocrystals have unique structures that range from single crystals of a few nanometers to twinned nanoparticles and multiply twinned crystallites with a high density of atomic steps. This approach of defect engineering enables us to understand their roles in enhancing the performance of the OER and producing an Ir catalyst with both high activity and stability. Our results show the importance of the concept of using synthetic control of structural and surface defects in metal nanoparticles as a strategy to improve catalytic performance.}, archive = {J_JACS}, author = {Farhat Ikram and Soshan Cheong and Ingemar Persson and Zeno R. Ramadhan and Agus R. Poerwoprajitno and J. Justin Gooding and Richard D. Tilley}, doi = {10.1021/jacs.5c02151}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10784--10790}, shortjournal = {J. Am. Chem. Soc.}, title = {Iridium nanocrystals enriched with defects and atomic steps to enhance oxygen evolution reaction performance}, volume = {147}, year = {2025}, }
• (2025). Fully methylated siloxane-based electrolyte for practical lithium metal batteries. JACS, 147(12), 10772--10783. (www)

  @article{ , abstract = {Developing solvents with balanced physicochemical properties for high-voltage cathodes and lithium metal anodes is crucial for a sustainable and intelligent future. Herein, we report fully methylated tetramethyl-1,3-dimethoxydisiloxane (TMMS) as a single solvent for lithium metal batteries. We demonstrate that the fully methylated structure and Si–O bonds within TMMS can effectively elevate the dehydrogenation energy barrier, migrating the oxidation decomposition of the electrolyte. Additionally, the weak solvating power of TMMS favors the formation of an anion-rich solvation structure that induces the generation of an inorganic-rich electrode/electrolyte interphase layer at both the cathode and anode. Accordingly, the formulated electrolyte exhibits remarkable stability against high-voltage cathodes and lithium metal anodes. Notably, LiNi 0.8 Co 0.1 Mn 0.1 O 2 ||Li (NCM811||Li) full cells with TMMS-based electrolytes realize a significant improvement in capacity retention compared with a dimethoxyethane-based electrolyte at both room temperature and 50 °C. This work provides insight into full methylation and the Si–O bond strategy and paves the way for the development of high-voltage lithium metal batteries.}, archive = {J_JACS}, author = {Yuankun Wang and Youxuan Ni and Shuo Xu and Yong Lu and Long Shang and Zhuo Yang and Kai Zhang and Zhenhua Yan and Weiwei Xie and Jun Chen}, doi = {10.1021/jacs.5c02140}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10772--10783}, shortjournal = {J. Am. Chem. Soc.}, title = {Fully methylated siloxane-based electrolyte for practical lithium metal batteries}, volume = {147}, year = {2025}, }
• (2025). Electrocatalytic oxidation of ammonia to nitrate occurs on NiOOH with OH/O vacancies. JACS, 147(12), 10758--10771. (www)

  @article{ , abstract = {The ammonia electrooxidation reaction (AOR) has attracted significant attention for both wastewater treatment and energy storage applications. However, AOR pathways generating oxygenated products such as nitrite or nitrate remain unresolved. Attenuated total reflection–surface-enhanced infrared absorption spectroscopy (ATR–SEIRAS) and density functional theory (DFT) have been combined to determine the potential-dependent intermediates, active catalytic sites, and AOR pathways on Ni electrodes under alkaline conditions. The OH/O vacancy sites on NiOOH, revealed by XPS, are found by DFT calculations to be the active sites for the AOR, catalyzing the complete (eight-electron) oxidation of ammonia into nitrate. The formation of isolated OH/O vacancies on NiOOH is thermodynamically more favorable than that of paired vacancies in the potential range conducive to NiOOH formation and the AOR, with an increasing formation barrier at higher potentials. This synergistic ATR–SEIRAS and DFT study reveals that the selectivity of nitrite and nitrate production is potential-dependent, with nitrite and hydrazine formation initiated at moderate anodic potentials, whereas larger potentials promote conversion of nitrite into nitrate species. The release of adsorbed nitrite and nitrate, which is crucial for liberating catalytic sites for the continuous AOR, is spectroscopically and computationally shown to be facilitated at relatively low potentials. Comprehending AOR mechanisms on Ni-based catalysts as achieved in this study can pave the way for future research on catalyst design and optimization of AOR performance.}, archive = {J_JACS}, author = {Vi Thuy Thi Phan and Quy P. Nguyen and Bin Wang and Ian J. Burgess}, doi = {10.1021/jacs.5c02130}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10758--10771}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrocatalytic oxidation of ammonia to nitrate occurs on NiOOH with OH/O vacancies}, volume = {147}, year = {2025}, }
• (2025). Machine learning potential for copper hydride clusters: A neutron diffraction-independent approach for locating hydrogen positions. JACS, 147(12), 10750--10757. (www)

  @article{ , abstract = {Determining hydrogen positions in metal hydride clusters remains a formidable challenge, which relies heavily on unaffordable neutron diffraction. While machine learning has shown promise, only one deep learning-based method has been proposed so far, which relies heavily on neutron diffraction data for training, limiting its general applicability. In this work, we present an innovative strategy─SSW-NN (stochastic surface walking with neural network)─a robust, non-neutron diffraction-dependent technique that accurately predicts hydrogen positions. Validated against neutron diffraction data for copper hydride clusters, SSW-NN proved effective for clusters where only X-ray diffraction data or DFT predictions are available. It offers superior accuracy, efficiency, and versatility across different metal hydrides, including silver and alloy hydride systems, currently without any neutron diffraction references. This approach not only establishes a new research paradigm for metal hydride clusters but also provides a universal solution for hydrogen localization in other research fields constrained by neutron sources.}, archive = {J_JACS}, author = {Cong Fang and Zhuang Wang and Ruixian Guo and Yuxiao Ding and Sicong Ma and Xiaoyan Sun}, doi = {10.1021/jacs.5c02046}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10750--10757}, shortjournal = {J. Am. Chem. Soc.}, title = {Machine learning potential for copper hydride clusters: A neutron diffraction-independent approach for locating hydrogen positions}, volume = {147}, year = {2025}, }
• (2025). Profiling nascent tumor extracellular vesicles via metabolic timestamping and aptamer-driven specific click chemistry. JACS, 147(12), 10737--10749. (www)

  @article{ , abstract = {Tumor-derived extracellular vesicles (tEVs) are essential mediators of tumor progression and therapeutic resistance, yet their secretion dynamics and cargo composition in response to therapies remain poorly understood. Here, we present STAMP, s pecific click- t agging driven by a ptamer for tEV labeled with a m etabolic timestam p , which exploits the unique kinetics and thermodynamics of aptamer to significantly enhance the local concentration of clickable probes on tEVs for their covalent attachment to the timestamp, resulting in the selective microfluidic isolation of nascent tEVs following stimulation. In a PD-L1 antibody-treated model, we demonstrated the feasibility of STAMP and revealed a robust positive correlation between the nascent EpCAM + EV levels and tumor volume. Proteome profiling of isolated nascent tEVs identified previously unknown upregulated vesicle proteins following immunotherapy, including key regulators of immune activation and suppression, suggesting that tumors orchestrate an intricate dual adaptive response through tEV secretion modulation to simultaneously elicit therapeutic sensitivity and resistance. Notably, among the upregulated proteins, we identified HSP70, whose enhanced presentation on tEVs promotes antitumor immunity and inhibits tumor growth. Thus, STAMP provides an effective gateway for studying EV dynamics with cell-origin accuracy and for identifying potential therapeutic targets based on EV transitions.}, archive = {J_JACS}, author = {Qiuyue Wu and Yinyan Zeng and Wencheng Wang and Sinong Liu and Yihao Huang and Yuqian Zhang and Ximing Chen and Zhenlong You and Chi Zhang and Tonghao Wang and Chaoyong Yang and Yanling Song}, doi = {10.1021/jacs.5c01973}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10737--10749}, shortjournal = {J. Am. Chem. Soc.}, title = {Profiling nascent tumor extracellular vesicles via metabolic timestamping and aptamer-driven specific click chemistry}, volume = {147}, year = {2025}, }
• (2025). Chemical probe-enabled lipid droplet proteomics. JACS, 147(12), 10724--10736. (www)

  @article{ , abstract = {Emerging evidence indicates that lipid droplets (LDs) play important roles in lipid metabolism, energy homeostasis, and cell stress management. Notably, dysregulation of LDs is tightly linked to numerous diseases, including lipodystrophies, cancer, obesity, atherosclerosis, and others. The pivotal physiological roles of LDs have led to an exploration of research in recent years. The functions of LDs are inherently connected to the composition of their proteome. Current methods for profiling LD proteins mostly utilize LD fractionation, including those based on proximity-based labeling techniques. Global profiling of the LD proteome in live cells without the isolation of LDs is still challenging. Herein, we disclose two small-molecule chemical probes, termed LDF and LDPL . Both LDF / LDPL are small in size and could freely and specifically migrate within the lipid context of LDs. Consequently, they were successfully used for live-cell fluorescence imaging of LDs and from animal tissues. We further showed that LDPL was capable of large-scale profiling of the LD proteome without the need of LD isolation. By using LDPL , 1584 high-confidence proteins, most of which could be annotated to prominent LD functions, were next identified. Importantly, further validation studies by using representative “hit” proteins revealed that CHMP6 and PRDX4 could act as the lipophagy receptor and lipolysis suppressor, respectively. Our results thus confirmed for the first time that LDPL is a powerful chemical tool for in situ profiling of LD proteomes. With the ability to provide a deeper understanding of LD proteomics from the native cellular environments, our newly developed strategy may be used in future to decipher the dynamics and molecular mechanism of LDs in various diseases.}, archive = {J_JACS}, author = {Jing Xiang and Tao Li and Junzhe Zhang and Wenxian Wu and Guangyu Xu and Jiaqian Yan and Hao Wang and Suyuan Chen and Shao Q. Yao and Miaomiao Wang and Fan Yi and Jigang Wang and Yusheng Xie}, doi = {10.1021/jacs.5c01710}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10724--10736}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemical probe-enabled lipid droplet proteomics}, volume = {147}, year = {2025}, }
• (2025). Spatial symmetry operation breaking sulfur-chiral photoswitchable ferroelectrics. JACS, 147(12), 10715--10723. (www)

  @article{ , abstract = {Ferroelectrics with switchable spontaneous polarization have gained enormous attention for a century. However, the structural phase transitions of conventional ferroelectrics have been mainly limited to the ones with crystallographic point group changes accompanied by the breaking of spatial symmetry elements. Moreover, although chiral and photoswitchable ferroelectrics have both been of great interest in recent years, heteroatomic chiral photoswitchable ferroelectrics have never been reported. Herein, for the first time, we designed a pair of sulfur-chiral photoswitchable ferroelectrics ( R s and S s ) -N -(3-bromo-5-chloro-2-hydroxybenzylidene)-2-methylpropane-2-sulfinamide (1- R s and 1- S s ). Notably, they undergo a structural phase transition from the chiral polar C 2 to P 2 1 space group of point group 2 at around 142 K, accompanied by the symmetry operation breaking from 2-fold rotation and screw rotation in C 2 to only 2-fold screw rotation in P 2 1 . Such a structural phase transition with the same point group, while different space groups with the breaking of symmetry operations, is significantly distinct from the structural phase transition with different point groups and space groups in conventional ferroelectrics. Furthermore,1- R s exhibits the highest piezoelectric d 33 value of 10 pC/N among organic photoswitchable ferroelectrics and shows optical control of ferroelectric polarization. To our knowledge, this is the first report of sulfur-chiral photoswitchable ferroelectrics showing phase transitions with only the space group change. This work enriches the family of chiral ferroelectrics and provides great inspiration for the exploitation of heteroatomic chiral photoswitchable ferroelectrics.}, archive = {J_JACS}, author = {Huan-Huan Chen and Hang Peng and Zhe-Kun Xu and Xian-Jiang Song and Xiao-Gang Chen and Ren-Gen Xiong and Wei-Qiang Liao}, doi = {10.1021/jacs.5c01725}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10715--10723}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatial symmetry operation breaking sulfur-chiral photoswitchable ferroelectrics}, volume = {147}, year = {2025}, }
• (2025). Pressure-driven circularly polarized luminescence enhancement and chirality amplification. JACS, 147(12), 10706--10714. (www)

  @article{ , abstract = {Achieving ultrahigh-color-purity circularly polarized luminescence (CPL) in low-dimensional chiral perovskites is challenging due to strong electron–phonon coupling caused by lead halide octahedral distortion. Herein, the circularly polarized piezoluminescence behaviors of six novel chiral perovskites, ( S / R -3-XPEA) 2 PbBr 4 (PEA = phenethylamine; X = F, Cl, Br), were systematically investigated. Upon compression, ( S / R -3-ClPEA) 2 PbBr 4 exhibits significant piezofluorochromic behaviors, transforming from yellow CPL to ultrahigh-color-purity deep-blue CPL. At 2.5 GPa, the deep-blue CPL intensity increases by an order of magnitude and its luminescence asymmetry factors ( g lum ) are amplified from the initial ±0.03 to ±0.1. ( S / R -3-BrPEA) 2 PbBr 4 presents a similar piezochromic response, realizing deep-blue CPL at 1.7 GPa, while ( S / R -3-FPEA) 2 PbBr 4 retains a yellow CPL under high pressure. High-pressure structural characterization and theoretical calculations confirm that pressure-enhanced halogen bonds reduce the penetration depth of S / R -3-BrPEA + and S / R -3-ClPEA + into the [PbBr 6 ] 4– frameworks, significantly suppressing electron–phonon coupling and increasing magnetic transition dipole moment in ( S / R -3-BrPEA) 2 PbBr 4 and ( S / R -3-ClPEA) 2 PbBr 4 , which are responsible for the ultrahigh-purity deep-blue CPL and chirality amplification, respectively.}, archive = {J_JACS}, author = {Meng-En Sun and Fei Wang and Manman He and Ya-Ni Yang and Ji-Kun Yang and Meng-Jie Zhu and Qiu-Yang Wan and Gaosong Chen and Yonggang Wang and Yongping Fu and Qi Li and Zhenling Wang and Lei Jiang and Yuchen Wu and Shuang-Quan Zang}, doi = {10.1021/jacs.5c01503}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10706--10714}, shortjournal = {J. Am. Chem. Soc.}, title = {Pressure-driven circularly polarized luminescence enhancement and chirality amplification}, volume = {147}, year = {2025}, }
• (2025). Intermolecular 1,2,4-thiadiazole synthesis enabled by enzymatic halide recycling with vanadium-dependent haloperoxidases. JACS, 147(12), 10698--10705. (www)

  @article{ , abstract = {The enzymatic synthesis of heterocycles is an emerging biotechnology for the sustainable construction of societally important molecules. Herein, we describe an enzyme-mediated strategy for the oxidative dimerization of thioamides enabled by enzymatic halide recycling by vanadium-dependent haloperoxidase enzymes. This approach allows for intermolecular biocatalytic bond formation using a catalytic quantity of halide salt and hydrogen peroxide as the terminal oxidant. The established method is applied to a diverse range of thioamides to generate the corresponding 1,2,4-thiadiazoles in moderate to high yields with excellent chemoselectivity. Mechanistic experiments suggest that the reaction proceeds through two distinct enzyme-mediated sulfur halogenation events that are critical for heterocycle formation. Molecular docking experiments provide insight into reactivity differences between biocatalysts used in this study. Finally, the developed biocatalytic oxidative dimerization is applied to a preparative scale chemoenzymatic synthesis of the anticancer agent penicilliumthiamine B. These studies demonstrate that enzymatic halide recycling is a promising platform for intermolecular bond formation.}, archive = {J_JACS}, author = {Manik Sharma and Cameron A. Pascoe and Stacey K. Jones and Sophia G. Barthel and Katherine M. Davis and Kyle F. Biegasiewicz}, doi = {10.1021/jacs.5c01175}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10698--10705}, shortjournal = {J. Am. Chem. Soc.}, title = {Intermolecular 1,2,4-thiadiazole synthesis enabled by enzymatic halide recycling with vanadium-dependent haloperoxidases}, volume = {147}, year = {2025}, }
• (2025). A catalysis-driven dual molecular motor. JACS, 147(12), 10690--10697. (www)

  @article{ , abstract = {We report on a head-to-tail dual molecular motor consisting of two (identical) motor units whose pyrrole-2-carboxylic rings are turned in contra-rotary (i.e., disrotatory) fashion about a common phenyl-2,5-dicarboxylic acid stator. The motors directionally rotate via information ratchet mechanisms, in which the hydration of a carbodiimide (fuel) to form urea (waste) is catalyzed through the chemomechanical cycle of a motor unit, resulting in directional rotation about a biaryl C–N bond. The head-to-tail arrangement of the motor units produces coaxial contra-rotation of the end groups while the central phenyl ring of the axis remains dynamically unbiased. The electron-rich nature of the phenyl stator contributes to rotary catalysis by the dual-motor (and therefore motor rotation itself) being ∼7× faster than the parent 1-phenylpyrrole-2,2-dicarboxylic acid single-motor when operated under identical conditions, and 90× faster than the single-motor operated using the originally reported reaction conditions. Under batch-fueled operation (i.e., all of the fuel present at the start of motor operation), the dual-motor rotates at an initial rate of 0.43 rotations per minute (rpm). Chemostating the fuel concentration by syringe pump addition produced sustained repetitive contra-rotation at a rate of 0.24 rpm for a period of 100 min. The demonstration of chemically fueled continuous contra-rotation on a time scale of 2–4 min per rotation significantly advances the chemistry and mechanics of artificial catalysis-driven molecular machinery.}, archive = {J_JACS}, author = {Peng-Lai Wang and Enzo Olivieri and Stefan Borsley and George F. S. Whitehead and Avantika Hasija and David A. Leigh}, doi = {10.1021/jacs.5c01275}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10690--10697}, shortjournal = {J. Am. Chem. Soc.}, title = {A catalysis-driven dual molecular motor}, volume = {147}, year = {2025}, }
• (2025). Tailoring octahedron-tetrahedron synergism in spinel catalysts for acidic water electrolysis. JACS, 147(12), 10678--10689. (www)

  @article{ , abstract = {The instability issues of oxide-based electrocatalysts during the oxygen evolution reaction (OER) under acidic conditions, caused by the oxidation and dissolution of the catalysts along with the current-capacitance effect, constrain their application in proton exchange membrane water electrolysis (PEMWE). To address these challenges, we tailored the spinel structure of Co 3 O 4 and exploited the synergism between the tetrahedron and octahedron sites by partially substituting Co with Ni and Ru (denoted as NiRuCoO x ), respectively. Such a catalyst design creates a Ru–O–Ni electronic coupling effect, facilitating a direct dioxygen radical-coupled OER pathway. Density-functional theory (DFT) calculations and in situ Raman spectroscopy results confirm that Ru is the active site in the diatomic oxygen mechanism while Ni stabilizes lattice oxygen and the Ru–O bonding. The designed NiRuCoO x catalyst exhibits an exceptionally low overpotential of 166 mV to achieve a current density of 10 mA cm –2 . Moreover, when serving as the anode in PEMWE, the NiRuCoO x requires 1.72 V to reach a current density of 3A cm –2 , meeting the 2026 target set by the U.S. Department of Energy (DOE: 1.8 V@3A cm –2 ). The PEMWE device can operate stably for more than 1500 h with a significantly reduced performance decay rate of 0.025 mV h –1 compared to commercial RuO 2 (2.13 mV h –1 ). This work provides an efficient method for tailoring the octahedron-tetrahedron sites of spinel Co 3 O 4 , which significantly improves the activity and stability of PEMWE.}, archive = {J_JACS}, author = {Mengtian Huo and Hao Sun and Zhao Jin and Wei Liu and Yu Liang and Jingyao Liu and Changpeng Liu and Zihao Xing and Yang Yang and Jinfa Chang}, doi = {10.1021/jacs.5c00665}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10678--10689}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailoring octahedron-tetrahedron synergism in spinel catalysts for acidic water electrolysis}, volume = {147}, year = {2025}, }
• (2025). Selective asymmetric hydrogenation of waste polyethylene terephthalate via controlled sorption through precisely tuned moderate acid sites. JACS, 147(12), 10662--10677. (www)

  @article{ , abstract = {The partial hydrogenation of waste polyethylene terephthalate (PET) offers a great opportunity to produce valuable chemicals, yet achieving precise catalytic control remains challenging. Herein, for the first time, we realized one-pot selective hydrogenation of waste PET to p -toluic acid ( p -TA) with a record-high yield of 53.4%, alongside a 36.4% yield of p -xylene (PX), using a specially designed PtW/MCM-48 catalyst. Mechanistic investigations revealed that the exceptional catalytic performance arises from synergistic interaction between Pt nanoparticles and WO x species. Low-valent WO x enhances Pt dispersion, while Pt stabilizes WO x as low-polymerized polytungstates. The moderate acidity of PtW 1.5 /MCM-48 ensures controlled desorption of p -TA, preventing overhydrogenation to PX. The catalyst demonstrated robust performance with real-world PET waste. Life cycle assessment and technical and economic evaluation further highlight its practical feasibility. This study establishes a sustainable pathway for PET chemical upcycling and provides a framework for designing advanced catalysts for selective hydrogenation reactions, addressing critical challenges in circular chemistry and plastic waste management.}, archive = {J_JACS}, author = {Yue Zhu and Zhouying Mao and Weixiang Wu and Buxing Han and Qingqing Mei}, doi = {10.1021/jacs.5c01209}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10662--10677}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective asymmetric hydrogenation of waste polyethylene terephthalate via controlled sorption through precisely tuned moderate acid sites}, volume = {147}, year = {2025}, }
• (2025). Identification of a selective anticancer agent from a collection of complex-and-diverse compounds synthesized from stevioside. JACS, 147(12), 10647--10661. (www)

  @article{ , abstract = {Compounds constructed by distorting the ring systems of natural products serve as a ready source of complex and diverse molecules, useful for a variety of applications. Herein is presented the use of the diterpenoids steviol and isosteviol as starting points for the construction of >50 new compounds through this complexity-to-diversity approach, featuring novel ring system distortions and a noteworthy thallium(III) nitrate (TTN)-mediated ring fusion. Evaluation of this collection identified SteviX4 as a potent and selective anticancer compound, inducing cell death at low nanomolar concentrations against some cancer cell lines in culture, compared to micromolar activity against others. SteviX4 induces ferroptotic cell death in susceptible cell lines, and target identification experiments reveal SteviX4 acts as an inhibitor of glutathione peroxidase 4 (GPX4), a critical protein that protects cancer cells against ferroptosis. In its induction of cell death, SteviX4 displays enhanced cell line selectivity relative to most known GPX4 inhibitors. SteviX4 was used to reveal dependency on GPX4 as a vulnerability of certain cancer cell lines, not tied to any one type of cancer, suggesting GPX4 inhibition as a cancer type-agnostic anticancer strategy. With its high fraction of sp 3 -hybridized carbons and considerable cell line selectivity and potency, SteviX4 is unique among GPX4 inhibitors, serving as an outstanding probe compound and basis for further translational development.}, archive = {J_JACS}, author = {Rachel E. Schaaf and Jonathan C. K. Quirke and Maryam Ghavami and Emily J. Tonogai and Hyang Yeon Lee and Samantha L. Barlock and Thomas R. Trzupek and Kyle R. Abo and Matthew G. Rees and Melissa M. Ronan and Jennifer A. Roth and Paul J. Hergenrother}, doi = {10.1021/jacs.5c00919}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10647--10661}, shortjournal = {J. Am. Chem. Soc.}, title = {Identification of a selective anticancer agent from a collection of complex-and-diverse compounds synthesized from stevioside}, volume = {147}, year = {2025}, }
• (2025). Discrimination of perfluorinated Arenes/Alkanes by modulable polyaromatic capsules. JACS, 147(12), 10640--10646. (www)

  @article{ , abstract = {Efficient and selective binding of perfluorocarbons (PFCs), comprising only fluorine and carbon atoms, unlike hydrocarbons, remains quite difficult owing to the repulsive nature of fluorine. Here we describe that a cavity modulation strategy enables metal-linked polyaromatic capsules to quantitatively bind PFCs with excellent selectivity. From a mixture of perfluoroarene and the corresponding perfluoroalkane (i.e., perfluoronaphthalene and perfluorodecalin), a Pt(II)-linked capsule exclusively binds the arenes in water at room temperature, via effective D-A-A-D π-stacking interactions. The size-selective binding toward perfluoroarenes (i.e., perfluoronaphthalene and perfluorobenzene) is improved by using the analogous N-doped capsule from 85% to quantitative selectivity. Furthermore, unlike the Pt(II)-capsule, an isostructural Pd(II)-linked capsule displays the unusual length/shape-selective binding of linear/cyclic perfluoroalkanes (i.e., perfluoroheptane and perfluorodecalin) under similar conditions. Recognition of substituted hydrogen atoms on perfluorobiphenyl can also be accomplished using the Pt(II)-capsule. Various PFCs are thus clearly distinguished for the first time by the modulable polyaromatic capsules under ambient aqueous conditions.}, archive = {J_JACS}, author = {Urara Kai and Ryuki Sumida and Yuya Tanaka and Michito Yoshizawa}, doi = {10.1021/jacs.5c00904}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10640--10646}, shortjournal = {J. Am. Chem. Soc.}, title = {Discrimination of perfluorinated Arenes/Alkanes by modulable polyaromatic capsules}, volume = {147}, year = {2025}, }
• (2025). Boraporphyrins: Unlocking global aromaticity in organoboron macrocycles. JACS, 147(12), 10629--10639. (www)

  @article{ , abstract = {We report the synthesis of 5-bora-21,22-dioxaporphyrin 5 and its main-group and d-block metal complexes 6 and 7 , respectively. These macrocyclic boranes constitute the first examples of neutral porphyrins with boron in a meso -position that exhibit global aromaticity. This is evidenced by spectroscopic and structural features as well as calculated nucleus independent chemical shifts (NICS) and anisotropic induced current densities (ACID). The boraporphyrins absorb light strongly in the red spectral region (Q bands) and show enhanced fluorescence with higher quantum yields ( 5 : 29%) compared to conventional porphyrins. DFT calculations reveal that the incorporation of the borane moiety has a distinct impact on the frontier orbital energies, thus leading to altered electrochemical and optical properties.}, archive = {J_JACS}, author = {Lukas Swoboda and Jonas Klopf and Manuel Buckel and Bernd Engels and Holger Helten}, doi = {10.1021/jacs.5c00849}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10629--10639}, shortjournal = {J. Am. Chem. Soc.}, title = {Boraporphyrins: Unlocking global aromaticity in organoboron macrocycles}, volume = {147}, year = {2025}, }
• (2025). The ulcerative colitis-associated gene NXPE1 catalyzes glycan modifications on colonic mucin. JACS, 147(12), 10618--10628. (www)

  @article{ , abstract = {Colonic mucus forms a first line of defense against bacterial invasion while providing nutrition to support coinhabiting microbes in the gut. Mucus is composed of polymeric networks of mucin proteins, which are heavily modified post-translationally. The full compendium of enzymes responsible for these modifications and their roles in health and disease remain incompletely understood. Herein, we determine the biochemical function of NXPE1 , a gene implicated in ulcerative colitis (UC), and demonstrate that it encodes an acetyltransferase that modifies mucin glycans. Specifically, NXPE1 utilizes acetyl-CoA to regioselectively modify the mucus sialic acid, 5- N -acetylneuraminic acid (Neu5Ac), at the 9-OH group to generate 9- O -acetylated Neu5Ac (Neu5,9Ac 2 ). We further demonstrate that colonic organoids derived from donors harboring the missense variant NXPE1 G353R, which is protective against UC, exhibit severely impaired acetylation of Neu5Ac on mucins. Together, our findings support a model in which NXPE1 masks the alcohols of mucus sialoglycans via acetylation, which is important for modulating mucus barrier properties that limit interactions with commensal microbes.}, archive = {J_JACS}, author = {Ranad Humeidi and Noriko Oshiro-Rapley and Xiebin Gu and Joon Soo An and Ashwin N. Ananthakrishnan and Elizabeth A. Creasey and Mark J. Daly and Stuart L. Schreiber and Daniel B. Graham and Mohammad R. Seyedsayamdost and Ramnik J. Xavier}, doi = {10.1021/jacs.5c00769}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10618--10628}, shortjournal = {J. Am. Chem. Soc.}, title = {The ulcerative colitis-associated gene NXPE1 catalyzes glycan modifications on colonic mucin}, volume = {147}, year = {2025}, }
• (2025). Enantioselective biosynthesis of (+)- and (−)-auranthines. JACS, 147(12), 10612--10617. (www)

  @article{ , abstract = {In nature, organisms produce various bioactive natural products (NPs). Most NPs target naturally occurring macromolecules, such as proteins and nucleotides. Thus, NPs are produced in a stereocontrolled manner except for the cases where nonenzymatic reactions are involved in the biosynthesis. This is why stereoisomers, especially enantiomers, are rarely found among metabolites from natural sources. During the biosynthetic study of auranthine, a fungal NP containing a nitrile group, we discovered that the (−)-isomer of auranthine ( 1 ) is produced by Aspergillus lentulus strains isolated in Japan, while a previously unreported (+)-enantiomer 2 is produced by those isolated elsewhere. The biosynthetic genes for both isomers were determined by transcriptomic, gene deletion, and heterologous expression experiments, revealing that two different nonribosomal peptide synthetases (NRPSs) NitA and NitC were involved in the biosynthesis of 1 and 2 , respectively. Both NitA and NitC are bimodular NRPSs, as is the case for the asperlicin-synthesizing enzyme AspA. All incorporate two molecules of anthranilic acid and one molecule of amino acid to form the peptide core. However, only NitC contains an epimerization domain, suggesting that is how the enantiomeric pair is biosynthesized by NitA and NitC. Furthermore, biosynthesis of the nitrile-bearing l -γ-cyanohomoalanine that is incorporated into 1 and 2 was found to be catalyzed by an argininosuccinate synthetase-like NitB using l -glutamine as a substrate. This study reports not only the unique mechanism of nitrile-containing amino acid biosynthesis but also the intriguing production of an enantiomeric pair of secondary metabolites by different strains of the same fungal species (250/250).}, archive = {J_JACS}, author = {Shinji Kishimoto and Tsubasa Tamura and Takumi Okamoto and Kenji Watanabe}, doi = {10.1021/jacs.5c00470}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10612--10617}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective biosynthesis of (+)- and (−)-auranthines}, volume = {147}, year = {2025}, }
• (2025). Stabilization of the Ferryl═Oxoheme form of staphylococcus aureus IsdG by electron transfer from a second-sphere tryptophan. JACS, 147(12), 10598--10611. (www)

  @article{ , abstract = {The ferryl heme forms of Staphylococcus aureus IsdG and IsdI have novel UV/vis absorption spectra that are distinct from those of the three forms of ferryl heme typically found in biological systems: compound I, compound II, and compound ES. In this work, the ferryl heme form of IsdG was characterized because it is an analogue for the immediate product of enzyme-catalyzed heme hydroxylation. The ferryl heme form of IsdG generated following the addition of meta-chloroperoxybenzoic acid to the ferric heme form of IsdG has a half-life of 4.0 ± 0.2 min, which is more than 100 times longer than the half-life for the ferryl heme form of human heme oxygenase (hHO). Magnetic circular dichroism characterization of the IsdG species yielded spectral data and zero-field splitting parameters consistent with either a compound II- or compound ES-like ferryl heme. Further characterization of isotopically enriched samples with electron paramagnetic resonance spectroscopy revealed the presence of a protein-based organic radical, as would be expected for compound ES. Finally, multiscale quantum mechanics/molecular mechanics and time-dependent density functional theory strongly suggest that the ferryl heme form of IsdG has a ruffled porphyrin ligand and an oxo ligand. Thus, the ferryl heme form of IsdG is assigned to a compound ES-like species with a Trp67-based radical. Electron transfer from Trp67 to porphyrin will stabilize the immediate product of heme hydroxylation and provide a thermodynamic driving force for the reaction. Furthermore, the ability to transfer an electron between Trp67 and the substrate may explain the differential reactivity of meso-hydroxyheme in IsdG and hHO.}, archive = {J_JACS}, author = {Aarzoo Grover and Matthew A. Conger and Matthew D. Liptak}, doi = {10.1021/jacs.5c00453}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10598--10611}, shortjournal = {J. Am. Chem. Soc.}, title = {Stabilization of the Ferryl═Oxoheme form of staphylococcus aureus IsdG by electron transfer from a second-sphere tryptophan}, volume = {147}, year = {2025}, }
• (2025). Synergistic bifunctional covalent organic framework for efficient photocatalytic CO2 reduction and water oxidation. JACS, 147(12), 10587--10597. (www)

  @article{ , abstract = {The scientific community has been actively researching artificial photosynthesis to promote ecologically sustainable living and address environmental issues. However, designing photocatalysts with active sites that are effective for both CO 2 reduction and water oxidation remains a significant challenge. Thus, we present the development of a donor–acceptor covalent organic framework (D–A COF), that integrates two distinct metal coordination environments through structure–activity relationships. Either cobalt or nickel ion is anchored on the D–A COF backbone to create N-metal–nitrogen and N-metal–sulfur coordination configurations, serving as bifunctional reduction and oxidation active sites, respectively. Remarkably, the as-synthesized Co-Btt-Bpy COF generated CO at a rate of 9,800 μmol g –1 h –1 and O 2 at 242 μmol g –1 h –1 under visible light irradiation. The CO generation rate was 127 times higher than that of pristine D–A COF. More importantly, Co-Btt-Bpy COF facilitates artificial photosynthesis with a CO release rate of 7.4 μmol g –1 h –1 . The outstanding photocatalytic performance can be attributed to the synergistic interaction between the dispersed single-atom sites and Btt-Bpy COF, as well as the rapid migration of photogenerated electrons. In situ attenuated total reflection Fourier transform infrared (ATR FT-IR) spectra and theoretical calculations indicated that introducing Co sites effectively lowered the reaction energy barriers for the crucial intermediates *COOH and *OH. This work provides state-of-the-art designs of photocatalysts at the molecular level and in-depth insights for efficient artificial photosynthesis.}, archive = {J_JACS}, author = {Qiang Xu and Jingwei Han and Fengkun Tian and Xue Zhao and Jiaxin Rong and Jing Zhang and Ping She and Jun-Sheng Qin and Heng Rao}, doi = {10.1021/jacs.5c00432}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10587--10597}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic bifunctional covalent organic framework for efficient photocatalytic CO2 reduction and water oxidation}, volume = {147}, year = {2025}, }
• (2025). Compression of molybdenum blue polyoxometalate cluster rings. JACS, 147(12), 10579--10586. (www)

  @article{ , abstract = {The self-assembly of polyoxometalate (POM) clusters remains challenging because they heavily depend on highly sensitive synthetic conditions that produce a vast library of potential building blocks and subunits such that explicit control is hard. This work reports new strategies to construct compressed molybdenum blue (MB) type cluster rings with a new range of giant MB POM clusters {Mo 54 }, {Mo 58 }, {Mo 85 }, and {Mo 108 }. These MB clusters prove the limits of the ring structure archetype, showing that it is possible to compress the ring by 100 metal atoms from 154 to 54 yet keep the electronic structure and ring shape. These structures comprise distorted pentagonal building blocks. The compression of the ring is achieved by using a {Mo 3 S} unit and {Mo 5 } bridging units. The {Mo 85 } and {Mo 108 } clusters exhibit a unique closed architecture, and redox studies demonstrate the reduced nature of these clusters.}, archive = {J_JACS}, author = {Vishal Lakhanpal and Melanie Guillén-Soler and Laia Vilà-Nadal and De-Liang Long and Leroy Cronin}, doi = {10.1021/jacs.5c00187}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10579--10586}, shortjournal = {J. Am. Chem. Soc.}, title = {Compression of molybdenum blue polyoxometalate cluster rings}, volume = {147}, year = {2025}, }
• (2025). A signal-harmonizing hybrid neural pathway enabled by bipolar-chemo-synapse spiking interneuron. JACS, 147(12), 10570--10578. (www)

  @article{ , abstract = {To realize human-machine fusion, a hybrid neural pathway operating in the same modality with biological systems becomes imperative, which requires an interneuron unit to encode information in biorecognizable spike sequences and tune the frequency upon excitatory and inhibitory neurotransmitters. Existing artificial interneurons cannot encode information upon different neurotransmitters, and the activation threshold and frequency responsivity do not align with those of biological counterparts, leading to limited success in constructing a signal-harmonizing hybrid neural pathway for neuroprosthetics, neurorehabilitation, and other neuroelectronic applications. Herein, we develop a bipolar-chemosynapse interneuron to encode the spike frequency in a highly bionic paradigm. Bipolar synapses dynamically respond to excitatory and inhibitory neurotransmitters and translate time-series chemical signals into the spike sequence, achieving the lowest activation threshold (6.25 μM) and the highest frequency responsivity (0.55 Hz μM –1 ) to date, close to the biological counterpart. A signal-harmonizing hybrid sensorimotor pathway mediated by excitatory and inhibitory neurotransmitters is constructed for the first time, which encodes upstream mechanical stimuli, modulates the downstream leg swing frequency of a mouse, and balances neural activity accordingly.}, archive = {J_JACS}, author = {Shi Luo and Shen Zhang and Daizong Ji and Shuai Jiang and Xuejun Wang and Bo Chen and Yiheng Chen and Xinjie Pei and Changhao Dai and Dingding Jiang and Wentao Liu and Yuetong Yang and Enming Song and Dapeng Wei and Derong Kong and Yunqi Liu and Dacheng Wei}, doi = {10.1021/jacs.5c00198}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10570--10578}, shortjournal = {J. Am. Chem. Soc.}, title = {A signal-harmonizing hybrid neural pathway enabled by bipolar-chemo-synapse spiking interneuron}, volume = {147}, year = {2025}, }
• (2025). Enantioselective synthesis of 1-dihydrobenzazepines through Rh2(II)-catalyzed cycloisomerization of 1,6-enyne. JACS, 147(12), 10560--10569. (www)

  @article{ , abstract = {The 1-dihydrobenzazepine skeleton has emerged as a privileged structural motif in bioactive molecules. However, due to a lack of asymmetric methodology, access to chiral 1-dihydrobenzazepines has remained limited. Herein, we report the first intermolecular asymmetric cycloisomerization of benzo-fused enynes for the synthesis of chiral 1-dihydrobenzazepines via dirhodium catalysis. This methodology features high efficiency (up to 98% yield), high enantioselectivity (up to 99% ee), and broad scope of nucleophiles, including oxygen nucleophiles (alcohols, phenols, and carboxylic acids) and carbon nucleophiles (silyl enol ethers). Theoretical and experimental mechanistic studies reveal that the reaction pathway encompasses an asymmetric cycloisomerization, which gives rise to a dirhodium carbene containing a donor–acceptor (D-A) cyclopropane moiety, followed by a ring-opening process and stereoselective nucleophilic attack by external nucleophiles on the cyclopropyl ring. Control experiments demonstrate the pivotal role of the terminal group capped on the alkynyl group of substrates in achieving good efficiency.}, archive = {J_JACS}, author = {Chuntao Wang and Zi-Hao Liao and Rui Wu and Kai Chen and Shifa Zhu}, doi = {10.1021/jacs.5c00053}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10560--10569}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective synthesis of 1-dihydrobenzazepines through Rh2(II)-catalyzed cycloisomerization of 1,6-enyne}, volume = {147}, year = {2025}, }
• (2025). Concept of future glycoprotein drugs: Synthesis of a thioglycosidically linked α-N-acetylgalactosamine-carrying cyclic peptide as a model of miniature macrophage activating factor. JACS, 147(12), 10549--10559. (www)

  @article{ , abstract = {Glycoproteins are often considered as drug candidates. However, the regulation of post-translational glycan attachment remains an issue. We hypothesized that replacing the oxygen atom in the glycosidic linkage with sulfur atoms would stabilize the labile linkage against glycosidases, resulting in improved pharmacokinetics. In this study, we focused on the macrophage-activating factor (MAF) carrying O -linked N -acetylgalactosamine (GalNAc) and creating a miniature glycopeptide associated with MAF. A partial structure of MAF with a chemical mutation at three amino acid residues was designed in which threonine was replaced with cysteine (Cys), leading to a thioglycosidically linked GalNAc and a conformationally stable cyclic peptide due to the disulfide bond. GalNAc-Cys was used in solid-phase peptide synthesis, and the desired cyclic glycopeptide was synthesized. In the synthesis of GalNAc-Cys, glycosylation reactions were carried out based on the hard and soft acids and bases concept, where glycosyl trichloroacetimidate and fluoride were successfully used to couple with the thiol group in Cys. GalNAc-Cys was also evaluated as a substrate of α-GalNAc-ase and was shown to resist hydrolysis, supporting our concept. The synthesized cyclic miniature MAF induced LPS-assisted IL-12 production and resisted against α-GalNAc-ase.}, archive = {J_JACS}, author = {Kotaro Kanzaki and Yuma Nakagomi and Yuri Asami and Haruki Honma and Yoshitaka Yokoyama and Honoka Seki and Tomoka Imamine and Miho Nanaumi and Toshiki Izawa and Sayako Misawa and Michio Iwaoka and Naoya Kojima and Hidekazu Katayama and Yoshimi Kanie and Osamu Kanie}, doi = {10.1021/jacs.4c18712}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10549--10559}, shortjournal = {J. Am. Chem. Soc.}, title = {Concept of future glycoprotein drugs: Synthesis of a thioglycosidically linked α-N-acetylgalactosamine-carrying cyclic peptide as a model of miniature macrophage activating factor}, volume = {147}, year = {2025}, }
• (2025). Mobility control of mechanical bonds to modulate energy dissipation in mechanically interlocked networks. JACS, 147(12), 10540--10548. (www)

  @article{ , abstract = {Mechanically interlocked networks (MINs) with dense mechanical bonds can amplify the dynamic behaviors of the mechanical bonds to exhibit decent mechanical properties. Energy dissipation resulting from mechanical bond motion is essential for improving toughness, yet effective strategies to optimize this process remain underexplored. Here, by designing mechanical bond models with controllable mobility, we establish a fortification strategy for the two key factors governing energy dissipation, host–guest recognition and sliding friction, thereby enabling mechanical property enhancement of mechanically interlocked materials. Specifically, the [2]rotaxanes in MIN- 1 and MIN- 2 exhibit identical axle structures, with MIN- 1 incorporating a small benzo-21-crown-7 ring and MIN- 2 incorporating a large benzo-24-crown-8 ring. Strain rate-dependent cyclic tensile tests reveal that the energy required to drive mechanical bond motion in MIN- 1 and MIN- 2 is 510 and 260 kJ/m 3 , respectively, indicating that the small wheel size enhances host–guest recognition. Furthermore, the apparent activation energy for the sliding motion of the mechanical bonds in MIN- 1 (11.0 kJ/mol) is higher than that in MIN- 2 (6.70 kJ/mol), suggesting increased sliding friction in MIN- 1 . Due to these two aspects, MIN- 1 exhibits superior energy dissipation performance (damping capacity = 92%) compared to MIN- 2 (78%), translating to a higher toughness (7.50 vs 5.70 MJ/m 3 ).}, archive = {J_JACS}, author = {Xue Yang and Wenbin Wang and Ruixue Bai and Zhewen Guo and Lin Cheng and Zhaoming Zhang and Wei Yu and Xuzhou Yan}, doi = {10.1021/jacs.5c00108}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10540--10548}, shortjournal = {J. Am. Chem. Soc.}, title = {Mobility control of mechanical bonds to modulate energy dissipation in mechanically interlocked networks}, volume = {147}, year = {2025}, }
• (2025). Ligand-to-ligand charge transfer induced red-shifted room temperature phosphorescence in Metal–Organic frameworks. JACS, 147(12), 10530--10539. (www)

  @article{ , abstract = {Research on room temperature phosphorescence (RTP) of metal–organic frameworks (MOFs) has been rapidly developed in recent years. However, it is still challenging to realize long-wavelength RTP (>580 nm). In this article, a new strategy is proposed to achieve the red-shifted RTP through constructing dual-ligand MOFs. Different from the single-ligand MOF, which lacks intermolecular interaction, the dual-ligand MOF can build up a stable donor–acceptor (D-A) relationship between two suitable simple ligands. Therefore, the induced charge transfer (CT) process from the donor units to the acceptor units in the framework can decrease the energy gap between the frontier orbitals, reducing the excited state energy levels. Moreover, by modulating the electron density and conjugation of the acceptor ligand, the energy of the triplet states of MOFs can be further reduced. As a result, the RTP centered at 588 nm is successfully achieved in a dual-ligand MOF. Also, we clearly describe the electron transporting path among the ground, 1 CT, and 3 CT states, revealing the emitting mechanism of the long-wavelength RTP. This work not only extends the D–A structure from the molecular level to the periodic structure of MOFs but also solves the problem of achieving long-wavelength RTP in MOFs from a new perspective.}, archive = {J_JACS}, author = {Qicheng Yu and Zihao Deng and Rundao Chen and Jianyu Zhang and Ryan T. K. Kwok and Jacky W. Y. Lam and Jianwei Sun and Ben Zhong Tang}, doi = {10.1021/jacs.4c18686}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10530--10539}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand-to-ligand charge transfer induced red-shifted room temperature phosphorescence in Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Phase change-mediated capture of carbon dioxide from air with a molecular triamine network solid. JACS, 147(12), 10519--10529. (www)

  @article{ , abstract = {The efficient removal of CO 2 from exhaust streams and even directly from air is necessary to forestall climate change, lending urgency to the search for new materials that can rapidly capture CO 2 at high capacity. The recent discovery that diamine-appended metal–organic frameworks can exhibit cooperative CO 2 uptake via the formation of ammonium carbamate chains begs the question of whether simple organic polyamine molecules could be designed to achieve a similar switch-like behavior with even higher separation capacities. Here, we present a solid molecular triamine, 1,3,5-tris(aminomethyl)benzene (TriH), that rapidly captures large quantities of CO 2 upon exposure to humid air to form the porous, crystalline, ammonium carbamate network solid TriH(CO 2 ) 1.5 · x H 2 O (TriHCO 2 ). The phase transition behavior of TriH converting to TriHCO 2 was studied through powder and single-crystal X-ray diffraction analysis, and additional spectroscopic techniques further verified the formation of ammonium carbamate species upon exposing TriH to humid air. Detailed breakthrough analyses conducted under varying temperatures, relative humidities, and flow rates reveal record CO 2 absorption capacities as high as 8.9 mmol/g. Computational analyses reveal an activation barrier associated with TriH absorbing CO 2 under dry conditions that is lowered under humid conditions through hydrogen bonding with a water molecule in the transition state associated with N–C bond formation. These results highlight the prospect of tunable molecular polyamines as a new class of candidate absorbents for high-capacity CO 2 capture.}, archive = {J_JACS}, author = {Adrian J. Huang and Ankur K. Gupta and Henry Z. H. Jiang and Hao Zhuang and Malia B. Wenny and Ryan A. Klein and Hyunchul Kwon and Katie R. Meihaus and Hiroyasu Furukawa and Craig M. Brown and Jeffrey A. Reimer and Wibe A. de Jong and Jeffrey R. Long}, doi = {10.1021/jacs.4c18643}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10519--10529}, shortjournal = {J. Am. Chem. Soc.}, title = {Phase change-mediated capture of carbon dioxide from air with a molecular triamine network solid}, volume = {147}, year = {2025}, }
• (2025). Manganese-driven plasmid nanofibers formed in situ for cancer gene delivery and metalloimmunotherapy. JACS, 147(12), 10504--10518. (www)

  @article{ , abstract = {While nucleic-acid-based cancer vaccines hold therapeutic potential, their limited immunogenicity remains a challenge due in part to the low efficiency of cytoplasmic delivery caused by lysosomal entrapment. In this work, we found that plasmids encoding both an antigen and a STING agonist protein adjuvant can self-assemble into coordination nanofibers, triggered by manganese ions. We developed a strategy to construct a DNA vaccine, termed MnO 2 -OVA-CDA-mem, formed by the coencapsulation of manganese dioxide (MnO 2 ), an antigen-expressing plasmid (encoding ovalbumin, OVA), and an adjuvant enzyme-expressing plasmid (encoding STING agonist, CDA) within dendritic cell (DC) membranes. Upon uptake into acidic lysosomes, Mn 2+ released from MnO 2 triggered the nucleic acids to undergo a morphological change from nanospheres (∼180 nm diameter) to nanofibers (∼1 μm length), resulting in an increase in mechanical strength by about 9-fold and consequently lysosomal membrane disruption. The antigen OVA and adjuvants Mn 2+ and CDA in the cytoplasm triggered strong DC activation and antigen-specific CD8 + T cell metalloimmune responses, significantly inhibiting the growth of B16-OVA tumors and inducing long-term immune memory. Altogether, MnO 2 -OVA-CDA-mem holds potential as a platform for nucleic acid antigen and adjuvant delivery using an in situ self-assembly strategy in a metal-driven, stimulus-responsive, and programmable manner for cancer metalloimmunotherapy.}, archive = {J_JACS}, author = {Jiexin Li and Ruiqi Yang and Chen Zhang and Jonathan F Lovell and Yumiao Zhang}, doi = {10.1021/jacs.4c18511}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10504--10518}, shortjournal = {J. Am. Chem. Soc.}, title = {Manganese-driven plasmid nanofibers formed in situ for cancer gene delivery and metalloimmunotherapy}, volume = {147}, year = {2025}, }
• (2025). Direct electrooxidation of ethylene to ethylene glycol over 90% faradaic efficiency enabled by cl– modification of the pd surface. JACS, 147(12), 10493--10503. (www)

  @article{ , abstract = {Direct electrochemical ethylene-to-ethylene glycol (C 2 H 4 -to-EG) conversion can potentially reduce the consumption of fossil fuels and the emission of carbon dioxide (CO 2 ) compared with the traditional thermo-catalytic approach. Palladium (Pd) prepared by electrodeposition is represented as a promising electrocatalyst; however, it exhibits low Ethylene glycol (EG) current density (<4 mA cm –2 ), Faradaic efficiency (<60%), and productivity (<10 μmol h –1 ), hindering practical applications. Herein, we report a nanodendrite palladium catalyst supported on a large-area gas diffusion electrode. This catalyst gives high EG current density (12 mA cm –2 ) and productivity (227 μmol h –1 ) but low Faradaic efficiency (65%). With further Cl – ions modification, Faradaic efficiency increased to a record-high value of 92%, and EG current density (18 mA cm –2 ) and productivity (∼340 μmol h –1 ) were also promoted. Experimental data suggest that the strong electron-withdrawing feature of Cl – reduces the oxidation ability of in situ generated Pd–OH species, inhibiting EG overoxidation to glycol aldehyde. Meanwhile, Cl – alters EG adsorption configuration─from parallel and dual-site coordination to vertical and single-site coordination─over the Pd surface, thus preventing C–C bond cleavage of EG to CO 2 . In addition, Cl – adsorption facilitates the generation of Pd–OH active species to improve catalytic activity. This work demonstrates the great potential of surface ion modification for improving activity and selectivity in direct electrochemical C 2 H 4 -to-EG conversion, which may have implications for diverse value-added chemicals electrosynthesis.}, archive = {J_JACS}, author = {An-Zhen Li and Xiongbo Wang and Shuwei Li and Bo-Jun Yuan and Xi Wang and Ruo-Pu Li and Liang Zhang and Bi-Jie Li and Haohong Duan}, doi = {10.1021/jacs.4c18345}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10493--10503}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct electrooxidation of ethylene to ethylene glycol over 90% faradaic efficiency enabled by cl– modification of the pd surface}, volume = {147}, year = {2025}, }
• (2025). Dynamics of globular proteins when interacting with zwitterionic silica nanoparticles by nuclear magnetic resonance spin relaxation. JACS, 147(12), 10485--10492. (www)

  @article{ , abstract = {The many emerging applications of nanoparticles in diverse fields in chemistry and biology require the characterization of interactions between nanoparticles and surrounding biomolecules such as proteins. Nuclear magnetic resonance spin relaxation of proteins, which is highly sensitive to interactions with nanoparticles, contains rich information about protein mobility and binding kinetics. The interactions of globular proteins with silica nanoparticles differ markedly from those with liposome nanoparticles, although both are driven by electrostatic forces. For unmodified silica nanoparticles, their interactions with an internally rigid protein like ubiquitin uniformly increase the backbone amide 15 N transverse R 2 relaxation for most residues. In contrast, for ubiquitin-POPG liposome interactions, their characteristic transverse R 2 profiles indicate that ubiquitin undergoes diffusive rotational motions on the liposome surface. Here, we show that coating silica nanoparticles with sulfobetaine siloxane zwitterionic molecules profoundly alters their interactions with proteins in a manner that closely resembles the mode of interaction observed with liposomes. 15 N- R 2 relaxation reveals that ubiquitin and the Ras-binding domain of B-Raf both exhibit axial reorientational motions about an axis perpendicular to the nanoparticle surface in the bound state, where the interactions involve predominantly positively charged surface regions. These findings point toward a global dynamics mechanism of proteins when interacting with organic or inorganic nanoparticles with densely charged soft surfaces. This information may help tailor the coatings of nanoparticles to adopt specific modes of interaction with proteins that can be used to control their function in vivo and in vitro.}, archive = {J_JACS}, author = {Xinyao Xiang and Lei Bruschweiler-Li and Joseph B. Schlenoff and Rafael Brüschweiler}, doi = {10.1021/jacs.4c18380}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10485--10492}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamics of globular proteins when interacting with zwitterionic silica nanoparticles by nuclear magnetic resonance spin relaxation}, volume = {147}, year = {2025}, }
• (2025). Asymmetric synthesis of strained multichiral spirocyclobutanes through cage-confined cross [2 + 2] photocycloaddition. JACS, 147(12), 10475--10484. (www)

  @article{ , abstract = {Chiral spirocycles possess the ability to undergo diverse modifications in three-dimensional space, offering advantages in terms of physicochemical property and structural variability over conventional organic scaffolds and holding promising potential for the design of biologically active molecules and drugs. Among them, highly strained spirocyclobutanes with multiple chiral center-containing four-membered rings have attracted significant attention, but their viable and efficient synthesis poses a great challenge. By virtue of cage-confined asymmetric photocatalysis, we successfully construct spirocycle and bispirocycle compounds containing multiple quaternary and tertiary chiral carbon centers in cyclobutane rings through cross [2 + 2] photocycloaddition with visible-light-induced and mild reactions. The mechanistic studies unveil that the chiral open pockets of a cage photoreactor facilitate dynamic bimolecular recognition to render preferential heteromolecular cross-cycloaddition with enhanced reactivity, unconventional enantioselectivity, and good substrate tolerance, providing a promising direction for enzyme-mimetic catalyst design for challenging asymmetric photochemical transformations.}, archive = {J_JACS}, author = {Jia Ruan and Yu-Lin Lu and Peng Hu and Cheng-Yong Su}, doi = {10.1021/jacs.4c18358}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10475--10484}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric synthesis of strained multichiral spirocyclobutanes through cage-confined cross [2 + 2] photocycloaddition}, volume = {147}, year = {2025}, }
• (2025). Exploring the structural origins of optically efficient one-dimensional lead halide perovskite nanostructures. JACS, 147(12), 10466--10474. (www)

  @article{ , abstract = {Metal halide perovskites have excellent optoelectronic properties. This study aims to determine how the optoelectronic properties of a model perovskite, cesium lead bromide (CsPbBr 3 ), change with length and thickness in one dimension (1D). By examining the photophysics of CsPbBr 3 quantum dots (QDs), nanowires (NWs), and nanorods (NRs), we observe the influence of confinement, exciton diffusion, and trapping on their optical properties. Our findings reveal that exciton diffusion to trap states limits the photoluminescence quantum yield (PLQY) of 1D CsPbBr 3 in the weakly confined regime (8–14 nm) and explains their long-lived exciton dynamics, while enhanced radiative rates contribute to achieving near-unity PLQY in the strongly confined regime (<7 nm). Consequently, blue-emitting, 2.4 nm-thick CsPbBr 3 NRs were 3.6X more emissive than the conventional CsPbBr 3 QDs. This study underscores how structural optimization can improve the optoelectronic performance of CsPbBr 3 and provides insight into the complex interplay of radiative and nonradiative processes in 1D ionic semiconductors.}, archive = {J_JACS}, author = {Alexander M. Oddo and Daniel Chabeda and Jaydeep Basu and Marcel Arnold and Chengyu Song and Eran Rabani and Peidong Yang}, doi = {10.1021/jacs.4c18320}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10466--10474}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploring the structural origins of optically efficient one-dimensional lead halide perovskite nanostructures}, volume = {147}, year = {2025}, }
• (2025). Polymer binder blends stabilize alkaline hydrogen evolution by heterogenized molecular phen-based cobalt electrocatalysts through coordination and environmental control. JACS, 147(12), 10459--10465. (www)

  @article{ , abstract = {With the increase in greenhouse gas emissions and their detrimental effect on the environment, there is a push to develop a renewable way to produce H 2 , a fuel source that has nonharmful byproducts, unlike traditional methods of energy production. Alkaline water electrolysis has seen increasing focus as a viable way to produce H 2 , but efficient and stable electrocatalysts are required to facilitate this process. Here, a heterogenized Co(II) phenanthroline-based complex for the production of H 2 from alkaline water is disclosed. Activity was improved by considering the role of axial Co ligation and the reaction environment created by the polymer binder in the catalyst inks by using variable ratios of Nafion and poly-4-vinylpyridine (P4VP). A ratio of 1:1 Nafion:P4VP was found to have the highest stability, and Co nanoparticle formation was not observed when P4VP was included as part of the binder mixture. The activity and stability enhancement could not be replicated by the addition of molecular pyridine or the use of poly-2-vinylpyridine, which is sterically prevented from coordinating to Co. The increased electrochemical performance caused by the inclusion of Nafion as part of the polymer binder is attributed to a role in mass transfer to and from the Co active site during catalysis, complementing the stabilizing effect of P4VP on the molecular active site.}, archive = {J_JACS}, author = {Elizabeth K. Johnson and Daniel P. Musikanth and Christopher K. Webber and T. Brent Gunnoe and Sen Zhang and Charles W. Machan}, doi = {10.1021/jacs.4c18295}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10459--10465}, shortjournal = {J. Am. Chem. Soc.}, title = {Polymer binder blends stabilize alkaline hydrogen evolution by heterogenized molecular phen-based cobalt electrocatalysts through coordination and environmental control}, volume = {147}, year = {2025}, }
• (2025). Inhibiting overoxidation of dynamically evolved RuO2 to achieve a Win–Win in Activity–Stability for acidic water electrolysis. JACS, 147(12), 10446--10458. (www)

  @article{ , abstract = {Proton exchange membrane (PEM) water electrolysis offers an efficient route to large-scale green hydrogen production, in which the RuO 2 catalyst exhibits superior activity but limited stability. Unveiling the atomic-scale structural evolution during operando reaction conditions is critical but remains a grand challenge for enhancing the durability of the RuO 2 catalyst in the acidic oxygen evolution reaction (a-OER). This study proposes an adaptive machine learning workflow to elucidate the potential-dependent state-to-state global evolution of the RuO 2 (110) surface within a complex composition and configuration space, revealing the correlation between structural patterns and stability. We identify the active state with distorted RuO 5 units that self-evolve at low potential, which exhibits minor Ru dissolution and an activity self-promotion phenomenon. However, this state exhibits a low potential resistance capacity (PRC) and evolves into inert RuO 4 units at elevated potential. To enhance PRC and mitigate the overevolution of the active state, we explore the metal doping engineering and uncover an inverse volcano-type doping rule: the doped metal–oxygen bond strength should significantly differ from the Ru–O bond. This rule provides a theoretical framework for designing stable RuO 2 -based catalysts and clarifies current discrepancies regarding the roles of different metals in stabilizing RuO 2 . Applying this rule, we predict and confirm experimentally that Na can effectively stabilize RuO 2 in its active state. The synthesized Na–RuO 2 operates in a-OER for over 1800 h without any degradation and enables long-term durability in PEM electrolysis. This work enhances our understanding of the operando structural evolution of RuO 2 and aids in designing durable catalysts for a-OER.}, archive = {J_JACS}, author = {Wenjing Li and Dingming Chen and Zhenxin Lou and Haiyang Yuan and Xiaopeng Fu and Hao Yang Lin and Miaoyu Lin and Yu Hou and Haifeng Qi and Peng Fei Liu and Hua Gui Yang and Haifeng Wang}, doi = {10.1021/jacs.4c18300}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10446--10458}, shortjournal = {J. Am. Chem. Soc.}, title = {Inhibiting overoxidation of dynamically evolved RuO2 to achieve a Win–Win in Activity–Stability for acidic water electrolysis}, volume = {147}, year = {2025}, }
• (2025). Lipid-siRNA organization modulates the intracellular dynamics of lipid nanoparticles. JACS, 147(12), 10430--10445. (www)

  @article{ , abstract = {Lipid nanoparticles (LNPs) are widely used for delivering therapeutic nucleic acids, yet the relationship between their internal structure and intracellular behavior, particularly before RNA release, remains unclear. Here, we elucidate how lipid-siRNA organization within LNPs can modulate their intracellular delivery dynamics. We use cryo-electron microscopy and photochemical assays to reveal that increased siRNA loading can reduce helper lipids’ distribution to the LNP surface, while siRNA consistently localizes near the surface. These alterations in lipid-siRNA organization affect LNP membrane fluidity, enhancing LNP fusion with cellular membranes and promoting cytosolic siRNA delivery, primarily via macropinocytosis. Using photosensitive lipids and live cell imaging, we demonstrate that lipid-siRNA organization regulates LNP responsiveness to external stimuli, significantly affecting siRNA endosomal escape efficiency upon light activation. We further confirm this observation using convex lens-induced confinement microscopy and single-particle imaging. Overall, our findings provide critical insights into how lipid-siRNA organization shapes LNP intracellular dynamics, offering rational design principles for optimizing LNP-based RNA therapeutics.}, archive = {J_JACS}, author = {Yulin Mo and Alexander F. A. Keszei and Shagun Kothari and Heyi Liu and Anni Pan and Paige Kim and Jiachuan Bu and Albert Kamanzi and David L. Dai and Mohammad T. Mazhab-Jafari and Juan Chen and Sabrina Leslie and Gang Zheng}, doi = {10.1021/jacs.4c18308}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10430--10445}, shortjournal = {J. Am. Chem. Soc.}, title = {Lipid-siRNA organization modulates the intracellular dynamics of lipid nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Ferroelectricity and strong Spin–Orbit coupling to enhance molecular spin-electric coupling. JACS, 147(12), 10423--10429. (www)

  @article{ , abstract = {The electric control of magnetism has been considered to be promising for molecular spintronics and quantum information. However, the spin-electric coupling strength appears to be insufficient for application in most cases. Two major factors capable of amplifying the relative effect are spin–orbit coupling and ferroelectricity. Herein, we chose four compounds as examples to study the contribution of spin–orbit coupling and ferroelectricity to spin-electric coupling. The relative orientation-dependent Hamiltonian terms were determined via electric-field modulated continuous-wave electron paramagnetic resonance. The origins of the spin-electric coupling effect in the four compounds are discussed and determined according to the characteristics of the experimental spectra. Meanwhile, the results demonstrated that strong spin–orbit coupling is crucial for producing significant spin-electric coupling and that the effect can be amplified by about 2 orders of magnitude by ferroelectricity. This work can guide the rational screen and design of materials with applicable spin-electric coupling strength, which may provoke techniques including low-power spintronics and precise manipulation of the quantum behavior of spins.}, archive = {J_JACS}, author = {You-Chao Liu and Jia-Xin Chen and Jun-Fei Bu and Peng-Xiang Fu and Ye-Xin Wang and Zheng Liu and Song Gao and Shang-Da Jiang}, doi = {10.1021/jacs.4c17949}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10423--10429}, shortjournal = {J. Am. Chem. Soc.}, title = {Ferroelectricity and strong Spin–Orbit coupling to enhance molecular spin-electric coupling}, volume = {147}, year = {2025}, }
• (2025). Characterization and engineering of a bisabolene synthase reveal an unusual hydride shift and key residues critical for mono-, bi-, and tricyclic sesquiterpenes formation. JACS, 147(12), 10413--10422. (www)

  @article{ , abstract = {Sesquiterpene synthases (STSs) catalyze carbocation cascade reactions with various hydrogen shifts and cyclization patterns that generate structurally diverse sesquiterpene skeletons. However, the molecular basis for hydrogen shifts and cyclizations, which determine STS product distributions, remains enigmatic. In this study, an elusive STS SydA was identified in the biosynthesis of sydonol, which synthesized a new bisabolene-type sesquiterpene 6 with a unique saturated terminal pendant isopentane. Extensive evidence from isotope labeling experiments, crystal structures of SydA and its variant, quantum chemical calculations, and mutagenesis experiments reveal a plausible mechanism for the formation of 6 involving an unusual 1,7-hydride shift, which may be a key branchpoint for monocyclic, bicyclic, and tricyclic products. Structure-based engineering resulted in SydA variants that promote different reaction pathways, leading to the production of bicyclic α-cuprenene and (+)-β-chamigrene and tricyclic 7- epi -β-cedrene and β-microbiotene. These findings not only reveal a new bisabolene and its biosynthesis but also provide insights into the molecular basis of the hydride shifts and cyclizations, which pave the way for engineering STSs to produce complex terpenoid products.}, archive = {J_JACS}, author = {Mengyue Wu and Ian Torrence and Yuanning Liu and Jingshuai Wu and Rui Ge and Ke Ma and Dong Liu and Jinwei Ren and Shilong Fan and Ming Ma and Justin B. Siegel and Dean J. Tantillo and Wenhan Lin and Aili Fan}, doi = {10.1021/jacs.4c17818}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10413--10422}, shortjournal = {J. Am. Chem. Soc.}, title = {Characterization and engineering of a bisabolene synthase reveal an unusual hydride shift and key residues critical for mono-, bi-, and tricyclic sesquiterpenes formation}, volume = {147}, year = {2025}, }
• (2025). Uniform single-domain liquid crystalline hexagonal rods by synchronized polymerization and self-assembly using disc-shaped monomers. JACS, 147(12), 10401--10412. (www)

  @article{ , abstract = {The fabrication of nanostructures from polycyclic aromatic hydrocarbons (PAHs) is highly attractive owing to their unique optical, electrical, and magnetic properties. However, the creation of uniform and well-defined PAH nanostructures by self-assembly still remains a significant challenge. Herein, we report that highly uniform hexagonal rods can be obtained from triphenylene (TP)-derived monomers by synchronized polymerization and self-assembly (SPSA). These rods have a single-domain columnar liquid crystalline structure in which columns formed from stacked TPs are along the long axis of the rods. The length/diameter ratios of the rods can be tuned over a wide range. Key factors to achieve SPSA of PAHs were analyzed, and the formation mechanism was clarified. In particular, it is observed that successful SPSA occurs below an upper critical temperature, which could be attributed to insufficient microphase separation between the side chains and the main chains and should be a general principle for SPSA. Furthermore, we demonstrate that the columnar stacking of TP units significantly promotes the intersystem crossing of the singlet excited state to the triplet excited state, resulting in simultaneous fluorescence and phosphorescence emission at room temperature. This work may be extended to a wide range of PAHs to regulate their self-assembly and light emission properties.}, archive = {J_JACS}, author = {Minchao Li and Yuanxin Ma and Jing Li and Xiaoli Zhang and Zihao Xu and An-Chang Shi and Bing Liu}, doi = {10.1021/jacs.4c17729}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10401--10412}, shortjournal = {J. Am. Chem. Soc.}, title = {Uniform single-domain liquid crystalline hexagonal rods by synchronized polymerization and self-assembly using disc-shaped monomers}, volume = {147}, year = {2025}, }
• (2025). Tunable Hydro/Dicarboxylation of ethylene with CO2 via a barrierless radiolytic free-radicals pathway. JACS, 147(12), 10391--10400. (www)

  @article{ , abstract = {The hydro/dicarboxylation of ethylene (C 2 H 4 ) feedstock with CO 2 to produce high-value carboxylic acids is an industrially relevant yet challenging reaction due to their extremely low reactivities. Herein, we present an effective strategy to synthesize propionic acid and succinic acid from a mixture of CO 2 and C 2 H 4 catalyzed by high-energy water radiolysis. The process involves the generation of CO 2 radical anions via the barrierless attachment of hydrated electrons to CO 2 , facilitating an ambient, continuous carboxylation of C 2 H 4 with an efficiency of 81.4%. Utilizing easily available electron beam irradiation, we achieved a combined production rate of 0.34 mmol L –1 min –1 for carboxylic acids, which is unattainable by the existing methods. Notably, product selectivity between hydro- and dicarboxylation was dose-rate/beam intensity-dependent: high-dose-rate irradiation favored succinic acid formation with a proportional yield of up to 65.4%, while milder conditions resulted in an 85.1% yield of propionic acid. We suggested that the simplicity and efficiency of the present carboxylation approach promote circular carbon in the sustainable chemical industry.}, archive = {J_JACS}, author = {Hang Zhang and Zhiwen Jiang and Changjiang Hu and Pengfei Zheng and Jun Ma}, doi = {10.1021/jacs.4c17761}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10391--10400}, shortjournal = {J. Am. Chem. Soc.}, title = {Tunable Hydro/Dicarboxylation of ethylene with CO2 via a barrierless radiolytic free-radicals pathway}, volume = {147}, year = {2025}, }
• (2025). Photoredox/Pyridine N-oxide catalyzed carbohydroxylation and aminohydroxylation of α-olefins. JACS, 147(12), 10382--10390. (www)

  @article{ , abstract = {Regioselective carbohydroxylation and aminohydroxylation of α-olefins were developed by a photoredox catalyst and pyridine N -oxide. This approach offers the catalytic and direct conversion of unactivated alkenes to a series of primary alcohols, including those bearing β-quaternary carbon centers and β-amino alcohols. The regioselective difunctionalization is enabled by the radical addition of α-olefin from the pyridine N -oxy radical, which is generated from readily available pyridine N -oxide via photoredox catalyzed single-electron oxidation. A combination of experimental and computational mechanistic studies was employed to lend support for the proposed reaction mechanism that proceeds via interwoven radical steps and polar substitution. The implications of this method for regioselective difunctionalization of α-olefins were further demonstrated by the examples of carboetherification, carboesterification, and lactone formation.}, archive = {J_JACS}, author = {Cristina Ascenzi Pettenuzzo and Deepak Ranjan Pradhan and Jujhar Singh and Lichuan Liu and Gabe Cuffel and Mathew J. Vetticatt and Yongming Deng}, doi = {10.1021/jacs.4c17657}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10382--10390}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoredox/Pyridine N-oxide catalyzed carbohydroxylation and aminohydroxylation of α-olefins}, volume = {147}, year = {2025}, }
• (2025). Superfast and wafer-scale superlattice film engineering enabled by an ultralow-interfacial-energy microenvironment. JACS, 147(12), 10369--10381. (www)

  @article{ , abstract = {The assembly of molecules or nanoparticles (NPs) into superlattice metamaterials endows them with remarkable optical, electrical, and magnetic properties, enabling applications in sensing, catalysis, and optical displays. However, traditional methods face challenges, such as complex procedures, long processing times, limited assembly areas, and poor reproducibility. The root cause of these challenges lies mainly in the complex and difficult-to-control interactions between assembly units such as ligands and NPs. In this study, a novel ultralow-interfacial-energy microenvironment between the water and oil phase is proposed for a rapid and large-scale superlattice assembly of NPs. The formation of the independently formed interfacial “third-phase” microenvironment hinges on two crucial factors. First, there is high immiscibility between densely packed perfluorodecanethiol ligands and a biphasic solvent system. Second, the coalescence events are accelerated at elevated temperatures. This microenvironment plays a dual role. Thermodynamically, it mitigates interparticle sintering and promotes the rapid establishment of supersaturation conditions that are conducive to the homogeneous nucleation of superlattices. Kinetically, it accelerates the coalescence process of “superlattice domains” through van der Waals interactions between neighboring NPs. This strategy reduces assembly time to under 80 min for forming superlattice monolayer films over areas up to 11 cm 2 . Furthermore, the method is versatile, applicable to mono- and double-layer superlattices with subnanometer- to micrometer-scale materials. This work represents a breakthrough in traditional superlattice construction concepts. It offers new perspectives for ultrafast and large-scale superlattice assembly and broadens the application prospects of superlattice films of NPs in burgeoning fields such as biosensing and flexible displays.}, archive = {J_JACS}, author = {Liping Song and Xinyi Zhu and Junsheng Yang and Xujing Li and Yilin Yu and Yi Liu and Licheng Huang and Shiqi Jiang and Youju Huang}, doi = {10.1021/jacs.4c17238}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10369--10381}, shortjournal = {J. Am. Chem. Soc.}, title = {Superfast and wafer-scale superlattice film engineering enabled by an ultralow-interfacial-energy microenvironment}, volume = {147}, year = {2025}, }
• (2025). Light-induced conformational heterogeneity induces positive photoswitching in photoconvertible fluorescent proteins of the EosFP family. JACS, 147(12), 10357--10368. (www)

  @article{ , abstract = {Green-to-red photoconvertible fluorescent proteins (PCFPs) of the EosFP family are commonly used in ensemble pulse-chase and single-molecule localization or tracking approaches. However, these fluorescent proteins exhibit highly complex photophysical behaviors. In the green-form, recent NMR experiments revealed that mEos4b and other PCFP variants exist in two different conformational states at thermal equilibrium, which limits their effective photoconversion efficiency. Here, we investigate the conformational heterogeneity of mEos4b in the photoconverted red-form, employing a combination of solution NMR, UV–vis spectroscopy and fluorescence imaging. Only a single red population of mEos4b is observed at thermal equilibrium. However, a second population emerges under illumination with 405 or 488 nm light, which slowly decays in the dark or can be swiftly reverted under 561 nm light. This second population manifests itself through a pH-dependent positive photoswitching mechanism that adds to the already characterized negative photoswitching assigned to cis – trans isomerization of the chromophore. Our data indicate that positive photoswitching, instead, results from the light-induced formation of a second fluorescent state with a cis configuration of the chromophore that exhibits a substantially increased p K a . Such a mechanism, suggested to result from rewiring of the H-bonding network around the first amino acid of the chromophore, adds to the panoply of switching scenarios observed in fluorescent proteins. It bears consequences for the spectroscopic characterization of PCFPs, reduces their apparent brightness and generates short-lived off-times perturbing single-molecule localization microscopy applications.}, archive = {J_JACS}, author = {Jip Wulffelé and Arijit Maity and Isabel Ayala and Serge Gambarelli and Bernhard Brutscher and Dominique Bourgeois}, doi = {10.1021/jacs.4c17311}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10357--10368}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-induced conformational heterogeneity induces positive photoswitching in photoconvertible fluorescent proteins of the EosFP family}, volume = {147}, year = {2025}, }
• (2025). Visible-light-driven methanol-to-ethanol conversion via carbene pathway by frustrated lewis pairs. JACS, 147(12), 10349--10356. (www)

  @article{ , abstract = {Carbenes are critical intermediates in organic chemistry, recognized for their exceptional reactivity and versatility. However, conventional methods for carbene generation are often associated with safety risks and hazardous procedures. This study presents a Ga-ZnO 1– x nanosheets photocatalyst with a (100) preferred orientation, featuring abundant refined frustrated Lewis pair (FLP) sites, excellent light absorption, and efficient charge transport properties. Under visible light irradiation, this catalyst activates methanol to generate a methyl carbene (methylene) intermediate, which subsequently reacts with another methanol molecule to produce ethanol. In situ experiments and theoretical calculations reveal that FLP sites, composed of oxygen vacancies and Ga, respectively activate C–H and C–O bonds while efficiently capturing photogenerated electrons and holes, making the most significant contribution to the formation of carbene intermediates. This research not only offers an eco-friendly route for methanol-to-ethanol conversion but also establishes a safer and more efficient method for methyl carbene production under mild conditions.}, archive = {J_JACS}, author = {Yumeng Qian and Qingyun Zhan and Zhenlu Li and Ruike Tan and Xiaowei Mu and Lu Li and Chao-Jun Li}, doi = {10.1021/jacs.4c17227}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10349--10356}, shortjournal = {J. Am. Chem. Soc.}, title = {Visible-light-driven methanol-to-ethanol conversion via carbene pathway by frustrated lewis pairs}, volume = {147}, year = {2025}, }
• (2025). Low-voltage electrooxidation of benzyl alcohol to benzoic acid enhanced by PtZn-ZnOx interface. JACS, 147(12), 10339--10348. (www)

  @article{ , abstract = {The electrocatalytic oxidation of benzyl alcohol to benzoic acid is a process that often requires high voltage, leading to increased energy consumption, side reactions (oxygen evolution reaction (OER)), and catalyst degradation. Herein, our study introduces a novel approach. We demonstrate that a PtZn-ZnO x catalyst featuring a PtZn intermetallic structure with abundant PtZn-ZnO x interfaces on the surface allows for the electrocatalytic oxidation of benzyl alcohol to benzoic acid with an impressive selectivity of 99.5% at a low potential of 0.725 V (vs a reversible hydrogen electrode, RHE), which is 0.6 V lower than most reported studies. This high selectivity is a testament to the efficiency of our catalyst, as it significantly reduces the occurrence of side reactions, leading to a more efficient and sustainable process. The experimental and density functional theory calculations demonstrated that the adsorption of Ph–CH 2 OH and Ph–CHO and the generation of electrophilic OH* were promoted due to the unsaturated coordination of the Zn atom in the PtZn-ZnO x interfaces. Furthermore, the potential-determining step of coupling OH* with Ph–CHO was promoted due to the low energy barrier at the PtZn-ZnO x interface, leading to improved catalytic activity and selectivity. This study outlines a novel approach to designing highly efficient electrocatalysts for high-efficiency alcohol valorization at low voltages.}, archive = {J_JACS}, author = {Renfeng Liu and Wenjing Tu and An Pei and Wei-Hsiang Huang and Yanyan Jia and Peng Wang and Daoru Liu and Qiqi Wu and Qizhen Qin and WeiWei Zhou and Linan Zhou and Keyou Yan and Yun Zhao and Guangxu Chen}, doi = {10.1021/jacs.4c17193}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10339--10348}, shortjournal = {J. Am. Chem. Soc.}, title = {Low-voltage electrooxidation of benzyl alcohol to benzoic acid enhanced by PtZn-ZnOx interface}, volume = {147}, year = {2025}, }
• (2025). Biosynthesis of the central tricyclic skeleton of trichothecene mycotoxins. JACS, 147(12), 10331--10338. (www)

  @article{ , abstract = {Trichothecenes are a widespread family of sesquiterpenoid toxins that can pose significant risks to food and feed safety as well as environmental health. A defining feature of all trichothecenes is their central tricyclic 12,13-epoxytrichothec-9-ene (EPT) motif. Although the formation of the EPT central skeleton has long been presumed to be a spontaneous process, the nonenzymatic cyclization reaction forming the tetrahydropyran ring in EPT requires acid catalysis; otherwise, it occurs too slowly to sustain efficient trichothecene biosynthesis under physiological conditions. Here, we resolved this decades-old problem by identifying the missing enzymes for EPT biosynthesis. We demonstrate that the C11 hydroxyl group of universal trichothecene precursors, isotrichodiol and isotrichotriol, must be acetylated by a strictly conserved O -acetyltransferase Tri3 to furnish a better leaving group. These acetylated intermediates preferentially undergo spontaneous allylic rearrangement with water to give shunt products, trichodiol and trichotriol. Therefore, a novel cyclase, Tri14, which was previously annotated as a hypothetical protein, is required to overcome the kinetically unfavored oxide bridge closure and meanwhile suppress the spontaneous formation of any shunt products.}, archive = {J_JACS}, author = {Jinmin Gao and Dong Liu and Carolyn Nguyen and Susan P. McCormick and Robert H. Proctor and Shenggan Luo and Yike Zou and Yang Hai}, doi = {10.1021/jacs.4c16973}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10331--10338}, shortjournal = {J. Am. Chem. Soc.}, title = {Biosynthesis of the central tricyclic skeleton of trichothecene mycotoxins}, volume = {147}, year = {2025}, }
• (2025). Expansion of the stereochemical space of triterpenes by mining noncanonical oxidosqualene cyclases across the diversity of green plants. JACS, 147(12), 10320--10330. (www)

  @article{ , abstract = {Triterpenoids and steroids are structurally complex polycyclic natural products with potent biological functions, for example, as hormones. In all eukaryotes, the carbon skeletons of these compounds are generated by oxidosqualene cyclases, which carry out a polycyclization cascade to generate four or five rings with up to nine stereogenic centers in a targeted manner. The tight stereochemical control of this cascade reaction severely limits the stereochemical space accessible by known oxidosqualene cyclases. Considering that naturally occurring hormone stereoisomers have markedly different biological activities, finding ways to produce stereoisomers of triterpenes would be highly desirable to open new avenues for developing triterpenoid and steroid drugs. Here, we present a plant kingdom-wide sequence mining approach based on sequence similarity networks to search for noncanonical oxidosqualene cyclases that might produce triterpene stereoisomers. From 1,891 oxidosqualene cyclase sequences representing the diversity of green plants, six candidates were selected for functional evaluation by heterologous production in Nicotiana benthamiana . Of these six candidates, three produced rare or previously inaccessible triterpene stereoisomers, namely, (3 S ,13 S )-malabarica-17,21-diene-3β,14-diol, 19- epi -lupeol, and a previously unknown hopanoid stereoisomer that we call protostahopenol. Site-directed mutagenesis revealed key residues important for catalytic activity. The sequence similarity network mining strategy employed here will facilitate the targeted discovery of enzymes with unusual activity in higher organisms, which are not amenable to common genome mining approaches. More importantly, our work expands the accessible stereochemical space of triterpenes and represents the first step to the development of new triterpenoid-derived drugs.}, archive = {J_JACS}, author = {Samuel Edward Hakim and Shenyu Liu and Ronja Herzog and Ahmed Arafa and Jan de Vries and Gerald Dräger and Jakob Franke}, doi = {10.1021/jacs.4c16956}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10320--10330}, shortjournal = {J. Am. Chem. Soc.}, title = {Expansion of the stereochemical space of triterpenes by mining noncanonical oxidosqualene cyclases across the diversity of green plants}, volume = {147}, year = {2025}, }
• (2025). Multimodal in situ characterization uncovers unexpected stability of a cobalt electrocatalyst for acidic sustainable energy technologies. JACS, 147(12), 10309--10319. (www)

  @article{ , abstract = {An accelerated development of durable and affordable sustainable energy technologies is often hindered by a limited understanding of how nonprecious materials within these systems degrade. In acidic proton exchange membrane fuel cells and water electrolyzers, metallic cobalt (Co) is considered an unstable component that is often combined with precious metals or other stabilizers. To understand the mechanisms behind Co instability, we employ an experimental platform that quantifies dissolution with on-line inductively coupled plasma mass spectrometry and product formation with electrochemical mass spectrometry during electrochemical testing, along with ex situ characterization. Under varied conditions (electrocatalysis, time, gas-type saturation, and ion concentration), windows of Co stability are observed that are different than predicted with classical chemical thermodynamics, suggesting new stabilization and degradation mechanisms than previously understood. Notably, Co is active for the hydrogen evolution reaction (HER), with prolonged stability that is ∼300 mV greater than thermodynamically projected. Additionally, in an oxygenated environment, Co concurrently performs the HER and the oxygen reduction reaction (ORR) yet undergoes different morphology changes and dissolution mechanisms. Interestingly, at open-circuit voltage, there is a 22× decrease in dissolution in an oxygen-free environment, proposing a route to decrease Co losses during device shutdown protocols. Lastly, under more extreme operating conditions, Co becomes stable after a substantial amount of dissolution, suggesting that high concentrations of Co 2+ ions in the microenvironment induce the formation of a stable CoHO 2 surface. Altogether, these results can be leveraged to improve the design and development of more robust and cost-effective sustainable energy technologies, as well as promote strategic strategies for prolonged material utilization.}, archive = {J_JACS}, author = {Ashton M. Aleman and Colin F. Crago and Gaurav A. Kamat and Aniket S. Mule and Jaime E. Avilés Acosta and Jesse E. Matthews and Nathaniel Keyes and Ryan T. Hannagan and Adam C. Nielander and Michaela Burke Stevens and Thomas F. Jaramillo}, doi = {10.1021/jacs.4c16707}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10309--10319}, shortjournal = {J. Am. Chem. Soc.}, title = {Multimodal in situ characterization uncovers unexpected stability of a cobalt electrocatalyst for acidic sustainable energy technologies}, volume = {147}, year = {2025}, }
• (2025). Electrochemical N-formylation of amines: Mechanistic insights and sustainable synthesis of formamides via a methylisocyanide intermediate. JACS, 147(12), 10298--10308. (www)

  @article{ , abstract = {Electrochemical methodologies offer a transformative approach to sustainable chemical synthesis by enabling precise, energy-efficient transformations. Here, we report the selective electrochemical N-formylation of methylamine using methanol as both reagent and solvent, facilitated by a simple glassy carbon electrode. Under optimized conditions, we achieve a faradaic efficiency (FE) of 34% for methylformamide synthesis in a neutral NaClO 4 electrolyte. Mechanistic insights from in situ Fourier-transform infrared spectroscopy (FTIR) and complementary synthetic experiments reveal two distinct reaction pathways: the direct oxidation of a hemiaminal intermediate and a novel route involving the formation of methylisocyanide, which subsequently hydrates to yield methylformamide. The presence of methylisocyanide was confirmed through mass spectrometry analysis following a successful Ugi multicomponent reaction, demonstrating the ability to safely utilize reactive intermediates within an electrochemical framework. This work underscores the potential of electrosynthesis to unlock metal-free, sustainable pathways to produce value-added nitrogen-containing compounds, paving the way for greener approaches in chemical manufacturing and catalysis.}, archive = {J_JACS}, author = {Pim J. L. Broersen and Lars Wielhouwer and Gadi Rothenberg and Amanda C. Garcia}, doi = {10.1021/jacs.4c16725}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10298--10308}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical N-formylation of amines: Mechanistic insights and sustainable synthesis of formamides via a methylisocyanide intermediate}, volume = {147}, year = {2025}, }
• (2025). Alkane dehydrogenation and H/D exchange by a cationic pincer-Ir(III) hydride: Cooperative C–H addition and β-H elimination modes induce anomalous selectivity. JACS, 147(12), 10279--10297. (www)

  @article{ , abstract = {We report that the cationic iridium complex ( iPr PCP)IrH + catalyzes the transfer-dehydrogenation of alkanes to give alkenes and hydrogen isotope exchange (HIE) of alkanes and arenes. Contrary to established selectivity trends found for C–H activation by transition metal complexes, strained cycloalkanes, including cyclopentane, cycloheptane, and cyclooctane, undergo C–H addition much more readily than n -alkanes, which in turn are much more reactive than cyclohexane. Aromatic C–H bonds also undergo H/D exchange much less rapidly than those of the strained cycloalkanes, but much more favorably than cyclohexane. The order of reactivity toward dehydrogenation correlates qualitatively with the reaction thermodynamics, but the magnitude is much greater than can be explained by thermodynamics. Accordingly, the cycloalkenes corresponding to the strained cycloalkanes undergo hydrogenation much more readily than cyclohexene, despite the less favorable thermodynamics of such hydrogenations. Computational (DFT) studies allow rationalization of the origin of reactivity and the unusual selectivity. Specifically, the initial C–H addition is strongly assisted by β-agostic interactions, which are particularly favorable for the strained cycloalkanes. Subsequent to α-C–H addition, the H atom of the β-agostic C–H bond is transferred directly to the hydride ligand of ( iPr PCP)IrH + to give a dihydrogen ligand. The overall processes, C–H addition and β-H-transfer to hydride, are calculated to generally have minima on the IRC surface although not necessarily on the enthalpy or free energy surfaces; these minima are extremely shallow such that the 1,2-dehydrogenations are effectively concerted although asynchronous.}, archive = {J_JACS}, author = {Ashish Parihar and Thomas J. Emge and Faraj Hasanayn and Alan S. Goldman}, doi = {10.1021/jacs.4c16699}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10279--10297}, shortjournal = {J. Am. Chem. Soc.}, title = {Alkane dehydrogenation and H/D exchange by a cationic pincer-Ir(III) hydride: Cooperative C–H addition and β-H elimination modes induce anomalous selectivity}, volume = {147}, year = {2025}, }
• (2025). Stabilizing ru in multicomponent alloy as acidic oxygen evolution catalysts with machine learning-enabled structural insights and screening. JACS, 147(12), 10268--10278. (www)

  @article{ , abstract = {Developing active, stable, and cost-effective acidic oxygen evolution reaction (OER) catalyst is a critical challenge in realizing large-scale hydrogen (H 2 ) production via electrochemical water splitting. Utilizing highly active and relatively inexpensive Ru is generally challenged by its long-term durability issue. Here, we explore the potential of stabilizing active Ru sites in Ru x (Ir,Fe,Co,Ni) 1– x multicomponent alloy by investigating its phase formation behavior, OER performance, and OER-induced surface reconstruction. The alloy exhibited a multiphase structure composed of major face-centered cubic (fcc) and minor hexagonal close-packed (hcp) phases at near equimolar concentration. Machine-learned interatomic potential (MLIP) coupled with replica-exchange molecular dynamics was utilized to describe the atomic scale mixing behavior of the Ru x (Ir,Fe,Co,Ni) 1– x catalysts and other RuIr-based alloys. The model supports our experimental findings of the well-mixed bulk fcc phase and provides an indication of the minor hcp phase formation. The optimized Ru 0.20 (Ir,Fe,Co,Ni) 0.80 catalyst exhibited improved OER activity with an average overpotential of ∼237 mV measured at 10 mA cm –2 and enhanced stability with a low activity degradation rate of ∼1.1 mV h –1 in 24 h of operation. The acidic OER conditions induced the formation of a thin RuIr-rich oxide shell layer with a trace amount of 3d metals, where Ru was found to be relatively stabilized near the surface of the evolved nanoparticles. The machine learning-accelerated high throughput simulation protocol was further employed to screen other potential RuIr-containing quinary alloys based on expected phase stability. This work highlights the opportunity of stabilizing Ru in a multicomponent alloy matrix with improved activity and stability.}, archive = {J_JACS}, author = {Arifin Luthfi Maulana and Shuang Han and Yu Shan and Peng-Cheng Chen and Carlos Lizandara-Pueyo and Sandip De and Kerstin Schierle-Arndt and Peidong Yang}, doi = {10.1021/jacs.4c16638}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10268--10278}, shortjournal = {J. Am. Chem. Soc.}, title = {Stabilizing ru in multicomponent alloy as acidic oxygen evolution catalysts with machine learning-enabled structural insights and screening}, volume = {147}, year = {2025}, }
• (2025). Plasmonic-promoted formation of surface adsorbed stochastic CO during electrochemical CO2 and CO reduction on cu at extreme low overpotentials. JACS, 147(12), 10260--10267. (www)

  @article{ , abstract = {Reducing the formation overpotential of key reaction intermediates represents a major challenge in developing broad electrocatalytic reactions. Recent vibrational spectroscopic studies of electrochemical CO 2 or CO reduction reaction (CO (2) RR) characterized an interesting formation of stochastic CO (CO stochastic ) intermediate with negligible energy losses under certain circumstances. Yet, the precise formation conditions and mechanisms remain unclear, hindering the correct understanding of related spectroscopic results and utilization of these effects to develop the CO (2) RR and other electrocatalytic reactions. Herein, we combine in situ attenuated total reflection infrared absorption (ATR-IR) and Raman spectroscopies to systematically study the origins and generation mechanisms of these CO stochastic . We reveal for the first time that the CO stochastic originates from plasmonic excitation of Cu by laser excitation and exists only in in situ Raman but not in ATR-IR measurements utilizing the exact same catalysts and electrochemical cell. Both the illumination wavelength and the fluence are important for the formation of CO stochastic . Furthermore, the surface speciation of the catalyst, i.e., the copresence of mixed metallic Cu 0 and Cu + states, is discovered to be crucial for the formation of CO stochastic . These results demonstrate that mechanistic studies of the CO (2) RR and other electrocatalytic reactions utilizing in situ Raman spectroscopy must carefully control the excitation fluence to avoid signals due to plasmonic excitations of the catalysts other than the electrochemical processes. Meanwhile, plasmon-enhanced electrochemistry, although still impractical for promoting CO 2 RR under ordinary illumination, may inspire new strategies for designing light-driven electrochemical reactions at extremely low overpotentials.}, archive = {J_JACS}, author = {Jianyang Zang and Wentao Ye and Qiliang Liu and Jinhui Meng and Wenxing Yang}, doi = {10.1021/jacs.4c16579}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10260--10267}, shortjournal = {J. Am. Chem. Soc.}, title = {Plasmonic-promoted formation of surface adsorbed stochastic CO during electrochemical CO2 and CO reduction on cu at extreme low overpotentials}, volume = {147}, year = {2025}, }
• (2025). Molecular engineering of a SICTERS small molecule with superior in vivo raman imaging and photothermal performance. JACS, 147(12), 10247--10259. (www)

  @article{ , abstract = {Raman-based theranostics has demonstrated great potential for sensitive real-time imaging and treatment. However, these advanced materials, primarily depending on the SERS technique, encounter clinical concerns regarding substrate biosafety. Herein, we molecularly engineered a de novo substrate-free SICTERS small molecule, namely BTT–TPA (bis-thienyl-substituted benzotriazole selenadiazole derivative structures), possessing both ultrasensitive Raman signals and excellent photothermal effects based on self-stacking. The mechanistic studies confirm that BTT maintains the planar structure with polycyclic distorted vibrations required for SICTERS. TPA enhances the donor–acceptor interaction, yielding a Raman sensitivity of BTT higher than previously reported SICTERS molecules; it also acts as a molecular rotor, increasing the photothermal conversion efficiency to 67.44%, which is superior to most of the existing SERS-based photothermal materials. In the tumor model of mouse orthotopic colon cancer, BTT–TPA NPs demonstrate a great Raman imaging-guided photothermal therapy effect in eliminating primary and metastatic tumors, remarkably decreasing the recurrence rate. This work puts forward substrate-free SICTERS small molecules toward Raman-based theranostic applications in vivo .}, archive = {J_JACS}, author = {Yongming Zhang and Wenxian Zhang and Yuanyuan Qiu and Kai Cui and Xinyi Li and Wei Hao and Aoxiang Luo and Zeyu Xiao}, doi = {10.1021/jacs.4c16411}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10247--10259}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular engineering of a SICTERS small molecule with superior in vivo raman imaging and photothermal performance}, volume = {147}, year = {2025}, }
• (2025). Designing polymers with molecular weight distribution-based machine learning. JACS, 147(12), 10238--10246. (www)

  @article{ , abstract = {Commodity plastics such as high density polyethylene (HDPE) have become integral to society. However, the potentially long-lasting ecological impacts of these plastics have spurred researchers to search for more sustainable solutions. One such solution is to develop a method for designing plastics with tunable and improved properties, thus decreasing the amount of material needed for various applications. In this work, we report a machine learning approach that maps the relationship between polymer molecular weight distributions (MWDs) and the physical properties (tensile and rheological) of HDPE. Using this approach, we design and generate HDPE materials with user-specified properties and valorize degraded postconsumer polyethylene waste. Implementation and development of this approach will facilitate the design of next-generation commodity materials and enable more efficient polymer recycling, thereby lowering the overall impact of HDPE on the environment.}, archive = {J_JACS}, author = {Jenny Hu and Zachary M. Sparrow and Brian G. Ernst and Spencer M. Mattes and Geoffrey W. Coates and Robert A. DiStasio, Jr. and Brett P. Fors}, doi = {10.1021/jacs.4c16325}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10238--10246}, shortjournal = {J. Am. Chem. Soc.}, title = {Designing polymers with molecular weight distribution-based machine learning}, volume = {147}, year = {2025}, }
• (2025). Strain-induced photochemical opening of ferrocene[6]cycloparaphenylene: Uncaging of fe2+ with green light. JACS, 147(12), 10231--10237. (www)

  @article{ , abstract = {We present the synthesis, structural analysis, and remarkable reactivity of the first carbon nanohoop that fully incorporates ferrocene in the macrocyclic backbone. The high strain imposed on the ferrocene by the curved nanohoop structure enables unprecedented photochemical reactivity of this otherwise photochemically inert metallocene complex. Visible light activation triggers a ring-opening of the nanohoop structure, fully dissociating the Fe–cyclopentadienyl bonds in the presence of 1,10-phenanthroline. This process uncages Fe 2+ ions captured in the form of [Fe(phen) 3 ] 2+ complex in high chemical yield and can operate efficiently in a water-rich solvent with green light excitation. The measured quantum yields of [Fe(phen) 3 ] 2+ formation show that embedding ferrocene into a strained nanohoop boosts its photoreactivity by 3 orders of magnitude compared to an unstrained ferrocene macrocycle or ferrocene itself. Our data suggest that the dissociation occurs by intercepting the photoexcited triplet state of the nanohoop by a nucleophilic solvent or external ligand. The strategy portrayed in this work proposes that new, tunable reactivity of analogous metallamacrocycles can be achieved with spatial and temporal control, which will aid and abet the development of responsive materials for metal ion delivery and supramolecular, organometallic, or polymer chemistry.}, archive = {J_JACS}, author = {Remigiusz B. Kręcijasz and Juraj Malinčík and Simon Mathew and Peter Štacko and Tomáš Šolomek}, doi = {10.1021/jacs.4c15818}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10231--10237}, shortjournal = {J. Am. Chem. Soc.}, title = {Strain-induced photochemical opening of ferrocene[6]cycloparaphenylene: Uncaging of fe2+ with green light}, volume = {147}, year = {2025}, }
• (2025). Transforming 2D imine into 3D thiazole covalent organic frameworks by conjugated connectors: Fully conjugated photocatalysts. JACS, 147(12), 10219--10230. (www)

  @article{ , abstract = {We developed a robust three-dimensional (3D) covalent organic framework (COF), fully conjugated in both the planar ( x , y ) and interlayer ( z ) directions, using a one-pot sulfurization process. We converted the two-dimensional (2D) imine-linked COF (Py-BDA-COF) to the 3D thiazole-linked COF (3D-Py-BDA-S-COF). In the interlayer direction ( z -axis), the alternating covalently bound acetylene and ethylene arrangements serve as conjugated connectors (“pillars”) and create a fully conjugated and very robust COF in all three dimensions. On top of this, the presence of the sulfur lone pair electrons in the thiazole rings considerably enhances the electron delocalization degree of the frameworks. The 3D-Py-BDA-S-COF is successfully evaluated in the photocatalytic reduction of nitrobenzene.}, archive = {J_JACS}, author = {Maojun Deng and Jeet Chakraborty and Guizhen Wang and Kuber Singh Rawat and Laurens Bourda and Jiamin Sun and Ipsita Nath and Yanwei Ji and Pieter Geiregat and Veronique Van Speybroeck and Xiao Feng and Pascal Van Der Voort}, doi = {10.1021/jacs.4c15825}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10219--10230}, shortjournal = {J. Am. Chem. Soc.}, title = {Transforming 2D imine into 3D thiazole covalent organic frameworks by conjugated connectors: Fully conjugated photocatalysts}, volume = {147}, year = {2025}, }
• (2025). Metal organic chemical vapor deposition of hybrid perovskites. JACS, 147(12), 10212--10218. (www)

  @article{ , abstract = {Semiconductor devices often rely on high-purity materials and interfaces achieved through vapor- and vacuum-based fabrication methods, which can enable precise compositional control down to single atomic layers. Compared to groups IV and III–V semiconductors, hybrid perovskites (HPs) are an emergent class of semiconductor materials with remarkable solution processability and compositional variability that have facilitated rapid experimentation to achieve new properties and progress toward efficient devices, particularly for solar cells. Surprisingly, vapor deposition techniques for HPs are substantially less developed, despite the complementary benefits that have secured vapor methods as workhorse tools for semiconductor fabrication. For instance, metal organic chemical vapor deposition (MOCVD) emerged in the late 1960s as a vital tool to enable production of compound semiconductor and heterojunction devices, giving rise to tremendously important technologies such as solid-state lighting and diode lasers, yet there is no analogous MOCVD process for HPs. Here, using a custom-built two-zone reactor, we report the first MOCVD process for the direct vapor deposition of thick and continuous films of methylammonium lead halide (MAPbX 3 ; X = Br, I) from distinct organolead, halide, and amine vapor sources. Mechanistic investigation via kinetic studies and density functional theory (DFT) calculations suggest a multistep reaction mechanism that should be generalizable to a broad set of HP materials. We anticipate that the continued development of generic HP MOCVD processes will unlock compositional, crystallographic, and morphological control complementary to solution methods, enabling the rational design of material properties and pursuit of new applications.}, archive = {J_JACS}, author = {Alicia C. Bryan and Jonathan K. Meyers and Lorenzo Y. Serafin and Zachary A. Krajnak and Ryan J. Gentile and James F. Cahoon}, doi = {10.1021/jacs.4c15822}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10212--10218}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal organic chemical vapor deposition of hybrid perovskites}, volume = {147}, year = {2025}, }
• (2025). Discovery of perovskite cosolvency and undoped FAPbI3 single-crystal solar cells fabricated in ambient air. JACS, 147(12), 10203--10211. (www)

  @article{ , abstract = {We report the cosolvency effect of formamidinium lead triiodide (FAPbI 3 ) in a mixture of γ-butyrolactone (GBL) and 2-methoxyethanol (2ME), a phenomenon where FAPbI 3 shows higher solubility in the solvent blend than in either alone. We found that FAPbI 3 exhibits 10× higher solubility in 30% 2ME in GBL than in 2ME alone and 40% higher solubility than in GBL alone at 90 °C. This enhanced solubility is attributed to the disruption of the hydrogen bonding network within 2ME, allowing its hydroxyl and ether groups to interact more freely with the solute. Leveraging this phenomenon, we grew phase-stable α-FAPbI 3 thin single crystals under ambient air conditions with no doping. Compared to conventional cesium-doped FAPbI 3 , the undoped FAPbI 3 single-crystal films exhibited lower defect densities and enhanced charge retention and transfer while also avoiding phase segregation linked to cesium incorporation. Solar cells fabricated with these ambient-air-grown single-crystal films achieved an efficiency of 21.56% (17.72% for cesium-doped FAPbI 3 ), retaining 90% of performance after six months of storage. These findings advance our understanding of perovskite solubility in solvent blends and offer an efficient pathway for producing stable, high-efficiency FAPbI 3 single-crystal solar cells through ambient air fabrication, overcoming the limitations of doping.}, archive = {J_JACS}, author = {Parinaz Moazzezi and Vishal Yeddu and I Teng Cheong and Mohammad Reza Kokaba and Sergey Dayneko and Yameen Ahmed and Makhsud I. Saidaminov}, doi = {10.1021/jacs.4c15716}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10203--10211}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of perovskite cosolvency and undoped FAPbI3 single-crystal solar cells fabricated in ambient air}, volume = {147}, year = {2025}, }
• (2025). Highly specific miniaturized fluorescent monoacylglycerol lipase probes enable translational research. JACS, 147(12), 10188--10202. (www)

  @article{ , abstract = {Monoacylglycerol lipase (MAGL) is the pivotal catabolic enzyme responsible for signal termination in the endocannabinoid system. Inhibition of MAGL offers unique advantages over the direct activation of cannabinoid receptors in treating cancer, metabolic disorders, and inflammatory diseases. Although specific fluorescent molecular imaging probes are commonly used for the real-time analysis of the localization and distribution of drug targets in cells, they are almost invariably composed of a linker connecting the pharmacophore with a large fluorophore. In this study, we have developed miniaturized fluorescent probes targeting MAGL by incorporating a highly fluorescent boron-dipyrromethene (BODIPY) moiety into the inhibitor structure that interacts with the MAGL active site. These miniaturized fluorescent probes exhibit favorable drug-like properties such as high solubility and permeability, picomolar potency for MAGL across various species, and high cell selectivity and specificity. A range of translational investigations were conducted, including cell-free fluorescence polarization assays, fluorescence-activated cell sorting analysis, and confocal fluorescence microscopy of live cancer cells, live primary neurons, and human-induced pluripotent stem cell-derived brain organoids. Furthermore, the application of red-shifted analogs or 18 F positron emission labeling illustrated the significant versatility and adaptability of the fluorescent ligands in various experimental contexts.}, archive = {J_JACS}, author = {Axel Hentsch and Mónica Guberman and Silke Radetzki and Sofia Kaushik and Mirjam Huizenga and Yingfang He and Jörg Contzen and Bernd Kuhn and Jörg Benz and Maria Schippers and Jerome Paul and Lea Leibrock and Ludovic Collin and Matthias Wittwer and Andreas Topp and Fionn O’Hara and Dominik Heer and Remo Hochstrasser and Julie Blaising and Jens P. von Kries and Linjing Mu and Mario van der Stelt and Philipp Mergenthaler and Noa Lipstein and Uwe Grether and Marc Nazaré}, doi = {10.1021/jacs.4c15223}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10188--10202}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly specific miniaturized fluorescent monoacylglycerol lipase probes enable translational research}, volume = {147}, year = {2025}, }
• (2025). Phosphorylation-induced self-coacervation versus RNA-assisted complex coacervation of tau proteins. JACS, 147(12), 10172--10187. (www)

  @article{ , abstract = {In this study, the role of phosphorylation in the liquid–liquid phase separation (LLPS) of tau, the underlying driving forces, and the potential implications of this separation on protein conformation and subsequent protein aggregation were investigated. We compared in vivo-produced phosphorylated tau (p-tau) and nonphosphorylated tau under different coacervation conditions without adding crowding agents. Our findings revealed that spontaneous phase separation occurs exclusively in p-tau, triggered by a temperature shift from 4 °C to room temperature, and is driven by electrostatic and hydrophobic interactions. The p-tau self-acervation is reversible with temperature changes. Native mass spectrometry detects only two to nine phosphate groups per p-tau molecule, highlighting the impact of phosphorylation on tau’s structural flexibility. Cross-linking mass spectrometry showed fewer long-range contacts in p-tau, suggesting a looser conformation induced by phosphorylation. Phosphorylation-induced LLPS and RNA-induced LLPS occurred at different timeframes. However, neither tau nor p-tau formed fibrils without the addition of dextran sulfate or RNA as inducers. Using human kidney epithelial cells expressing the tau R domain fused with fluorescent proteins as reporter cells, we observed aggregates in the nuclear envelope (NE) only in the cells treated with LLPS-state p-tau, which correlates with NE occurrences reported in Alzheimer’s disease brain sections. These findings provide deeper insights into the impact of phosphorylation on tau aggregation through an intermediate condensation phase, offering novel perspectives on neurodegenerative disease mechanisms.}, archive = {J_JACS}, author = {Mohammadreza Allahyartorkaman and Ting-Hsuan Chan and Eric H.-L. Chen and See-Ting Ng and Yi-An Chen and Jung-Kun Wen and Meng-Ru Ho and Hsin-Yung Yen and Yung-Shu Kuan and Min-Hao Kuo and Rita P.-Y. Chen}, doi = {10.1021/jacs.4c14728}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10172--10187}, shortjournal = {J. Am. Chem. Soc.}, title = {Phosphorylation-induced self-coacervation versus RNA-assisted complex coacervation of tau proteins}, volume = {147}, year = {2025}, }
• (2025). Identification and quantification of al pairs and their impact on dealumination in zeolites. JACS, 147(12), 10160--10171. (www)

  @article{ , abstract = {Understanding the precise quantity and spatial distribution of paired aluminum (Al) sites in zeolite catalysts is crucial, as they significantly impact the catalytic performance via synergistic effects and long-term stability. In this study, a novel strategy by employing divalent cation titration with varying cation sizes, in combination with advanced quantitative 1 H NMR and 1 H– 1 H homonuclear correlation techniques, has been developed to accurately identify and classify three distinct types of Al pairs. These include two types of Al pairs aligned along six-membered rings (6-MRs) and 10-membered rings (10-MRs), the latter of which are essentially composed of Al atoms located in different 6-MR or 5-MR. The third type comprises two Al atoms located in different channels. The second and third types had been challenging to probe in the past, yet they may be critical for catalysis, particularly the second type demonstrating proximity close enough to accommodate Ba 2+ (with a radius of 1.49 Å). Our strategy for quantifying each type of Al pair marks a significant advancement in the understanding of the zeolite framework. Furthermore, controlled hydrothermal treatments using stepwise steaming reveal that a higher concentration of Al pairs accelerates dealumination, primarily for dynamic reasons of water molecules but not intrinsic structural instability induced by Al pairs. To address this, we propose a “bi-Al” vs “mono-Al” hydrolysis model, offering fresh insights into the pivotal role of Al pairs on zeolite stability. This work opens new avenues for optimizing zeolite-based catalysts for enhanced performance and longevity.}, archive = {J_JACS}, author = {Yuting Sun and Lixin Liang and Min Yang and Yi Ji and Guangjin Hou and Kuizhi Chen}, doi = {10.1021/jacs.4c14741}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10160--10171}, shortjournal = {J. Am. Chem. Soc.}, title = {Identification and quantification of al pairs and their impact on dealumination in zeolites}, volume = {147}, year = {2025}, }
• (2025). Exploring the anion site disorder kinetics in lithium argyrodites. JACS, 147(12), 10151--10159. (www)

  @article{ , abstract = {Lithium argyrodites Li 6 PS 5 X ( X = Cl, Br, I) are a promising class of solid-state electrolytes with the potential to achieve high conductivities (>10 mS·cm –1 ) necessary for use in solid-state batteries. Previous research has shown that structural factors, in particular, site disorder between the sulfide and halide anions, can impact the ionic conductivity of lithium argyrodites. One current hypothesis for this correlation between anion site disorder and ionic transport is a connection to the lithium-ion substructure. However, as there is limited research surrounding the anion disordering process itself, this relationship has yet to be fully understood. This research explores the impact of the composition and synthesis on the anion disordering process through the Li 6+ x P 1– x Si x S 5 Br ( x = 0 to 0.4 in 0.1 steps) series of substitutions quenched from different annealing temperatures. Ex situ and in situ diffraction studies show that the anion site disorder within the compounds increases upon Si introduction only for samples quenched from higher annealing temperatures but remains relatively constant at lower annealing temperatures. Based on in situ diffraction measurements, we further monitor the effects of anion mobility at elevated temperatures allowing inference of slower anion disordering kinetics with changing compositional content. We complement the experimental work using nudged-elastic band calculations showing the overall preference of anions for their specific sites and the possibility of anion mobility. This work provides insight into the argyrodites and shows that the anion disordering can be monitored and that the composition has strong influences on the disordering process.}, archive = {J_JACS}, author = {M. Jewels Fallon and Vasiliki Faka and Martin A. Lange and Marvin A. Kraft and Emmanuelle Suard and Eamonn T. Connolly and Brian E. Francisco and Alexander G. Squires and Wolfgang G. Zeier}, doi = {10.1021/jacs.4c14466}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10151--10159}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploring the anion site disorder kinetics in lithium argyrodites}, volume = {147}, year = {2025}, }
• (2025). Chemical carbonylation of arginine in peptides and proteins. JACS, 147(12), 10139--10150. (www)

  @article{ , abstract = {The chemoselective incorporation of arginine carbonylation post-translational modification (PTM) within proteins represents an underexplored frontier. This is largely due to the poor nucleophilicity and resistance to chemical oxidation of arginine. Drawing inspiration from the metal catalyzed oxidation (MCO) processes of arginine, we introduce a chemical methodology aimed at generating glutamate-5-semialdehyde from arginine residues within peptides and proteins. This innovative chemical approach capitalizes on the inherent weak nucleophilicity and oxidative properties of arginine. We also demonstrate the application of this strategy to selectively introduce both natural and unnatural post-translational modifications (PTMs) in a targeted manner. Our chemical approach offers a rapid, robust, and highly selective technique, facilitating chemoproteomic profiling of arginine sites prone to forming glutamate-5-semialdehyde PTM within the human proteome. Additionally, this methodology serves as a versatile platform for uncovering microenvironments that are susceptible to undergoing arginine carbonylation PTM, enabling the understanding of the effect of oxidative stress on arginine in proteins and the impact of these PTMs on cellular processes.}, archive = {J_JACS}, author = {Lyndsey Prosser and Benjamin Emenike and Pinki Sihag and Rajendra Shirke and Monika Raj}, doi = {10.1021/jacs.4c14476}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10139--10150}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemical carbonylation of arginine in peptides and proteins}, volume = {147}, year = {2025}, }
• (2025). CXC chemokine ligand 12 facilitates gi protein binding to CXC chemokine receptor 4 by stabilizing packing of the Proline–Isoleucine–Phenylalanine motif: Insights from automated path searching. JACS, 147(12), 10129--10138. (www)

  @article{ , abstract = {The activation of G protein-coupled receptors (GPCRs) is a complex multibody multievent process involving agonist binding, receptor activation, G protein coupling, and subsequent G protein activation. The order and energetics of these events, though crucial for the rational design of selective GPCR drugs, are challenging to characterize and remain largely underexplored. Here, we employed molecular dynamics simulations and our recently developed traveling salesman-based automated path searching (TAPS) algorithm to efficiently locate the minimum free-energy paths for the coupling events of the CXC chemokine receptor 4 (CXCR4) with its endogenous ligand CXC chemokine ligand 12 (CXCL12) and Gi protein. We show that, after overcoming three low energy barriers (3.24–6.89 kcal/mol), Gi alone can precouple with CXCR4 even without CXCL12, consistent with previous reports on the existence of the apo CXCR4-Gi complex and our NanoBiT experiments. The highest barrier of 6.89 kcal/mol in this process corresponds to the packing of the proline–isoleucine–phenylalanine (PIF) motif of CXCR4. Interestingly, without Gi, CXCL12 alone cannot activate CXCR4 (high barrier of 18.89 kcal/mol). Instead, it can enhance Gi coupling by circumventing the energy barrier of PIF packing. Shedding new light on the activation mechanism of CXCR4, these results present TAPS as a promising tool for uncovering complete activation pathways of GPCRs and the corresponding agonist design.}, archive = {J_JACS}, author = {Xinyu Li and Yezhou Liu and Jinchu Liu and Wenzhuo Ma and Rujuan Ti and Arieh Warshel and Richard D. Ye and Lizhe Zhu}, doi = {10.1021/jacs.4c14293}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10129--10138}, shortjournal = {J. Am. Chem. Soc.}, title = {CXC chemokine ligand 12 facilitates gi protein binding to CXC chemokine receptor 4 by stabilizing packing of the Proline–Isoleucine–Phenylalanine motif: Insights from automated path searching}, volume = {147}, year = {2025}, }
• (2025). In situ li+ intercalation into nanosized chevrel phase Mo6S8 toward efficient electrochemical nitroarene reduction. JACS, 147(12), 10118--10128. (www)

  @article{ , abstract = {Electrochemical nitroarene reduction enables the green production of anilines at ambient conditions thanks to the manipulated transfer of multiple electrons and protons via controlling potentials and currents, but challenges remain in pH-neutral electrolysis using nonprecious catalysts. Here, Chevrel phase Mo 6 S 8 with high conductivity and insertable frameworks is proposed for the first time as a cost-efficient candidate with prominent performance and, more importantly, as a new platform to unravel cation effects on nitroarene electroreduction. Nanosized Mo 6 S 8 derived from polymer-confined sulfidation affords a high yield (∼95%) and Faradaic efficiency (∼99%) for reducing 4-nitrostyrene to 4-aminostyrene at −0.45 V (vs RHE) in 0.1 M LiClO 4 , outperforming a series of counterparts of metal sulfides and even noble metals. The combination of experimental and theoretical analyses identifies an intercalation-correlated cation effect, expanding the current knowledge limited to the outer Helmholtz plane of electrodes. In situ Li + intercalation into Mo 6 S 8 cavities during electrolysis ameliorates the electronic configurations and thereby promotes the adsorption of the nitro group on low-coordinated Mo sites for hydrogenation via a proton-coupled electron transfer mechanism. Furthermore, the efficient electrosynthesis of aniline derivatives with conserved reducing groups from a wide range of substrates highlights the promise of Mo 6 S 8 for electrochemical refinery.}, archive = {J_JACS}, author = {Jingwen Tan and Lei Feng and Junjie Shao and Wenbiao Zhang and Haoran Qin and Hongxi Liu and Yijin Shu and Lichun Yang and Yuying Meng and Yi Tang and Qingsheng Gao}, doi = {10.1021/jacs.4c14111}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10118--10128}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ li+ intercalation into nanosized chevrel phase Mo6S8 toward efficient electrochemical nitroarene reduction}, volume = {147}, year = {2025}, }
• (2025). Vibrational property tuning of MXenes revealed by sublattice n reactivity in polar and nonpolar solvents. JACS, 147(12), 10104--10117. (www)

  @article{ , abstract = {MXenes, a family of two-dimensional (2D) materials based on transition metal carbides and nitrides, have desirable properties, such as high conductivity, high surface area, and tunable surface groups, for electrocatalysis. Nitride MXenes, in particular, have shown excellent electrocatalytic performance for the nitrogen and oxygen reduction reactions, but a fundamental understanding of how their structures evolve during electrocatalysis remains unknown. Equally important and yet unknown is the effect of the reactivity of the lattice nitrogen on the vibrational behavior of nitride MXenes and the resulting implications in electrocatalysis. Here, we investigate the reactivity of lattice nitrogen and the vibrational properties of titanium nitride MXenes in relevant electrocatalytic solvents using confocal Raman spectroscopy. We found that the vibrational modes of titanium nitride MXenes are attenuated in polar solvents, which is revealed through the alteration of the Raman scattering in solvents. Contrary to polar solvents, the vibrational modes remain unchanged in nonpolar solvents like hydrocarbons due to the inactivity of the lattice nitrogen. We found that this behavior is unique to nitrides because the Raman characteristics of carbides and sulfides are unaffected by the solvent types. However, the inclusion of nitrogen into the carbide structure does exhibit Raman-solvent behavior similar to that of nitrides, suggesting that replacing carbon with nitrogen affects MXene–light interactions. We demonstrated a proof-of-concept utilizing lattice nitrogen reactivity to enhance the electrocatalytic nitrogen reduction reaction for ammonia production. In summary, we elucidate the vibrational properties of nitride MXenes in solvents and demonstrate the tunability of MXene vibrational properties via lattice atom substitution, which in turn can be exploited to advance the applications of MXenes in electrocatalysis.}, archive = {J_JACS}, author = {Ray M. S. Yoo and Bright Ngozichukwu and David Kumar Yesudoss and Hao-En Lai and Kailash Arole and Micah J. Green and Perla B. Balbuena and Abdoulaye Djire}, doi = {10.1021/jacs.4c13878}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10104--10117}, shortjournal = {J. Am. Chem. Soc.}, title = {Vibrational property tuning of MXenes revealed by sublattice n reactivity in polar and nonpolar solvents}, volume = {147}, year = {2025}, }
• (2025). Recombinase-controlled multiphase condensates accelerate nucleic acid amplification and CRISPR-based diagnostics. JACS, 147(12), 10088--10103. (www)

  @article{ , abstract = {Isothermal techniques for amplifying nucleic acids have found extensive applications in genotyping and diagnostic tests. These methods can be integrated with sequence-specific detection strategies, such as CRISPR-based detection, for optimal diagnostic accuracy. In particular, recombinase-based amplification uses proteins from the Escherichia virus T4 recombination system and operates effectively at moderate temperatures in field and point-of-care settings. Here, we discover that recombinase polymerase amplification (RPA) is controlled by liquid–liquid phase separation, where the condensate formation enhances the nucleic acid amplification process. While two protein components of RPA could act as scaffold proteins for condensate formation, we identify T4 UvsX recombinase as the key regulator orchestrating distinct core–shell arrangements of proteins within multiphase condensates, with the intrinsically disordered C-terminus of UvsX being crucial for phase separation. We develop volumetric imaging assays to visualize RPA condensates and the reaction progression in whole volumes, and begin to dissect how macroscopic properties such as size distribution and droplet count could contribute to the overall reaction efficiency. Spatial organization of proteins in condensates may create optimal conditions for amplification, and disruption of such structures may diminish the amplification efficiency, as we demonstrate for the case of reverse transcription-RPA. The insight that RPA functions as a multiphase condensate leads us to identify the UvsX D274A mutant, which has a distinct phase-separation propensity compared to the wild-type enzyme and can enhance RNA detection via RPA-coupled CRISPR-based diagnostics.}, archive = {J_JACS}, author = {Aimorn Homchan and Maturada Patchsung and Pheerawat Chantanakool and Thanakrit Wongsatit and Warunya Onchan and Duangkamon Muengsaen and Thana Thaweeskulchai and Martin Tandean and Theeradon Sakpetch and Surased Suraritdechachai and Kanokpol Aphicho and Chuthamat Panchai and Siraphob Taiwan and Navin Horthongkham and Taweesak Sudyoadsuk and Aleks Reinhardt and Chayasith Uttamapinant}, doi = {10.1021/jacs.4c11893}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10088--10103}, shortjournal = {J. Am. Chem. Soc.}, title = {Recombinase-controlled multiphase condensates accelerate nucleic acid amplification and CRISPR-based diagnostics}, volume = {147}, year = {2025}, }
• (2025). Computational identification of potential organocatalysts (CIPOC) reveals a 2-aminoDMAP/Urea catalyst superior to its thiourea analogue. JACS, 147(12), 10078--10087. (www)

  @article{ , abstract = {Asymmetric organocatalysis by bifunctional acid- and base-type small organic molecules has emerged as a promising way to enhance stereoselective organic transformations since the beginning of this millennium. Takemoto’s tert -amine/thiourea catalyst, an archetype in these endeavors, has encouraged many to design new multifunctional alternatives. However, the discovery of efficient catalysts in a library of thousands of candidates containing the desired functionalities in their structures remains a great challenge both synthetically and computationally. We, toward these ends, developed a computational protocol (CIPOC─Computational Identification of POtential (Organo)Catalysts), which discovered a chiral 2-aminoDMAP/urea catalyst among 1600 multifunctional catalyst candidates enabling conjugate addition of malonates to trans -β-nitroalkenes rapidly (in a few hours) with exquisite selectivities and yields, producing superior results than that of Takemoto’s. The unique activity of this chiral 2-aminoDMAP/urea is attributed to the dual function of the 2-aminoDMAP unit (double H-bonding and π-stacking interactions) in addition to the exceptional performance of the urea unit compared to thiourea, as a result of a lower energetic penalty required to distort the catalyst to its active conformation to provide optimal catalytic interactions.}, archive = {J_JACS}, author = {Sezen Alsancak-Koca and Yeşim Çamlısoy and İrem Bakırcı and Murat Işık and Nihan Çelebi-Ölçüm and Cihangir Tanyeli}, doi = {10.1021/jacs.4c10634}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10078--10087}, shortjournal = {J. Am. Chem. Soc.}, title = {Computational identification of potential organocatalysts (CIPOC) reveals a 2-aminoDMAP/Urea catalyst superior to its thiourea analogue}, volume = {147}, year = {2025}, }
• (2025). Methane beryllation catalyzed by a base metal complex. JACS, 147(12), 10073--10077. (www)

  @article{ , abstract = {The homogeneous catalytic functionalization of methane is extremely challenging due to the relative nonpolarity and high C–H bond strength of this hydrocarbon. Here, using catalytic quantities (10 mol %) of CpMn(CO) 3 or Cp*Re(CO) 3 , the conversion of methane and benzene C–H bonds to C–Be and H–Be bonds by CpBeBeCp has been achieved under photochemical conditions. Possible intermediates in the beryllation reactions─ trans -bis(beryllyl)-manganese and -rhenium complexes─were also isolated. Quantum chemical calculations indicate that the inherent properties of the beryllyl ligands─which are powerfully σ-donating and feature highly Lewis acidic beryllium centers─are decisive in enabling methane functionalization by these systems.}, archive = {J_JACS}, author = {Josef T. Boronski and Agamemnon E. Crumpton and Job J. C. Struijs and Simon Aldridge}, doi = {10.1021/jacs.5c02179}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10073--10077}, shortjournal = {J. Am. Chem. Soc.}, title = {Methane beryllation catalyzed by a base metal complex}, volume = {147}, year = {2025}, }
• (2025). The outstanding ambiphilicity of trialkylstibines among trialkylpnictines: Power for stepwise deoxygenation and N–N coupling of nitroarenes. JACS, 147(12), 10066--10072. (www)

  @article{ , abstract = {The ongoing discovery of highly reactive ambiphilic main-group species has significantly advanced the development of main-group chemistry, particularly in the realms of small molecule activation and catalysis. Theoretically, compounds featuring smaller HOMO–LUMO gaps gain stronger ambiphilicity and higher reactivity. In this work, we fundamentally demonstrate that Me 3 Sb holds the smallest HOMO–LUMO gap among trimethylpnictines, indicating its outstanding ambiphilicity. Correspondingly, the superior reactivity of Me 3 Sb toward deoxygenation of electron-deficient nitroarenes has been unambiguously revealed through control experiments. Furthermore, unprecedented Sb III /Sb V O cycling between trialkylstibines and their oxides has been established for the catalytic transformation of nitroarenes into azoxyarenes/azoarenes. This study opens a new chapter for organoantimony derivatives in the fields of ambiphilic reactivity and redox catalysis.}, archive = {J_JACS}, author = {Zichen Zhang and Kunlong Li and Minghao Huang and Ting Chen and Jiliang Zhou}, doi = {10.1021/jacs.5c01964}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10066--10072}, shortjournal = {J. Am. Chem. Soc.}, title = {The outstanding ambiphilicity of trialkylstibines among trialkylpnictines: Power for stepwise deoxygenation and N–N coupling of nitroarenes}, volume = {147}, year = {2025}, }
• (2025). Catalytic enantioselective α-fluorination of ketones with CsF. JACS, 147(12), 10059--10065. (www)

  @article{ , abstract = {Disclosed here is a catalytic enantioselective nucleophilic α-fluorination of simple ketones. A new hydrogen bonding donor catalyst was designed to not only overcome the competing catalyst deactivation but also enable efficient enantiocontrol in C–F bond formation between racemic α-keto sulfoniums and CsF. Careful condition optimization resulted in a general and mild protocol applicable for the configurational flexible acyclic α-fluoro ketones bearing a tertiary stereogenic center, thus complementary to the previous electrophilic fluorination methods that were only effective to cyclic ketones and/or tetrasubstituted stereogenic centers. Preliminary mechanistic studies support a phase transfer and dynamic kinetic resolution pathway operated by HBD-enabled anion-binding.}, archive = {J_JACS}, author = {Baocheng Wang and Shuaixin Fan and Chaoshen Zhang and Jianwei Sun}, doi = {10.1021/jacs.4c18752}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10059--10065}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic enantioselective α-fluorination of ketones with CsF}, volume = {147}, year = {2025}, }
• (2025). Enantioselective reduction of 1-naphthamides by electrochemical reduction and catalytic asymmetric hydrogenation in tandem. JACS, 147(12), 10052--10058. (www)

  @article{ , abstract = {Chiral 1-tetrahydronaphthamides are the core structures of many bioactive molecules, yet their efficient asymmetric synthesis from a simple feedstock remains a challenge. Herein, we present a one-pot synthesis strategy that combines electrochemical reduction and ruthenium-catalyzed asymmetric hydrogenation to achieve the enantioselective reduction of 1-naphthalenamides to chiral 1-tetrahydronaphthamides. The protocol provides a practical platform for selectively constructing high-value chiral tetrahydronaphthenes from readily available naphthalene feedstock, thereby expanding the scope of asymmetric hydrogenation. The synthetic utility of this protocol is further demonstrated through the synthesis of bioactive molecules.}, archive = {J_JACS}, author = {Xin-Yi Yang and Xuan-Ge Zhang and Qi-Lin Zhou}, doi = {10.1021/jacs.4c18009}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10052--10058}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective reduction of 1-naphthamides by electrochemical reduction and catalytic asymmetric hydrogenation in tandem}, volume = {147}, year = {2025}, }
• (2025). Collective magnetism of spin coronoid via on-surface synthesis. JACS, 147(12), 10045--10051. (www)

  @article{ , abstract = {Polyradicals obtained from open-shell coronoids hold promise for applications in spintronics and quantum technologies due to the strong interactions between spins in fully fused cyclic systems. Coronoid synthesis has long been considered difficult due to the cyclization of nanographene. It becomes an immense challenge to synthesize open-shell coronoids since radicals appear only when the macrocycle size exceeds a critical value. Here we present an open-shell coronoid with six radicals achieved through an on-surface synthesis. This spin coronoid displays a collective spin state arising from both the nearest-neighbor exchange interaction and the next-nearest-neighbor exchange interaction of six unpaired π electrons along the conjugation pathways. The characterization of the spin excitation from the ground state to the excited state was carried out by using inelastic electron tunneling spectroscopy. Additionally, we show that the spin coronoid can be utilized as a nanoscale platform to achieve short antiferromagnetic spin-1/2 Heisenberg chains through tip manipulation. Our findings present a design strategy for creating coronoids with polyradicals, which could provide inspiration for fabrication of open-shell coronoid or cyclic spintronic systems.}, archive = {J_JACS}, author = {Xujie Zhu and Yashi Jiang and Zhou Wang and Yicheng Huang and Zhengqiang Luo and KaKing Yan and Shiyong Wang and Ping Yu}, doi = {10.1021/jacs.4c13998}, journal = {Journal of the American Chemical Society}, month = {3}, number = {12}, pages = {10045--10051}, shortjournal = {J. Am. Chem. Soc.}, title = {Collective magnetism of spin coronoid via on-surface synthesis}, volume = {147}, year = {2025}, }
• (2025). Correction to “Revolutionizing CO2 electrolysis: Fluent gas transportation within hydrophobic porous Cu2O”. JACS, 147(11), 10044. (www)

  @article{ , archive = {J_JACS}, author = {Qinghong Geng and Longlong Fan and Huige Chen and Chunhui Zhang and Zhe Xu and Ye Tian and Cunming Yu and Lei Kang and Yusuke Yamauchi and Cuiling Li and Lei Jiang}, doi = {10.1021/jacs.5c02472}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {10044}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Revolutionizing CO2 electrolysis: Fluent gas transportation within hydrophobic porous Cu2O”}, volume = {147}, year = {2025}, }
• (2025). Photochemical pathways and light-enhanced radical scavenging activity of 1,8-dihydroxynaphthalene allomelanin. JACS, 147(11), 10031--10043. (www)

  @article{ , abstract = {Melanins play important roles in nature, particularly in coloration and photoprotection, where interaction with light is essential. Biomimetic melanins represent an advantageous alternative to natural melanin for technological applications, sharing the same unique biocompatibility, as well as optoelectronic properties. Allomelanin, derived from 1,8-dihydroxynaphthalene, has been reported to exhibit even better photoprotective and antioxidant properties than the most studied example of biomimetic melanin, polydopamine. However, the interaction of allomelanin with light remains largely unexplored. Here we report the excited state dynamics of allomelanin in a wide range of time windows from femtoseconds to microseconds to minutes, using different experimental techniques, i.e., ultrafast transient absorption, nanosecond transient absorption, X-band electron paramagnetic resonance and radical quenching assays. We find that the photophysics of allomelanin starkly differs from that of the widely studied polydopamine, with broadband excitonically coupled states funneling the absorbed energy to a lower energy species in less than 1 ps. Independent of the excitation wavelength, a long-lived (>450 μs) photoproduct is populated in ≈24 ps. Quantum chemistry calculations suggest that the photoproduct primarily exhibits the character of localized 1,8-naphthoquinone radical anions. This light-driven increase in the anionic semiquinone-like radical concentration enhances the antioxidant activity of allomelanin. These results suggest that the two mechanisms considered at the basis of photoprotection, light-extinction and antioxidant action, are indeed synergistic in allomelanin and not independent, paving the way for new applications of allomelanin in nanomedicine, photocatalysis, energy conversion and environmental remediation.}, archive = {J_JACS}, author = {Vasilis Petropoulos and Dario Mordini and Francesco Montorsi and Mert Akturk and Arianna Menichetti and Andrea Olivati and Annamaria Petrozza and Vittorio Morandi and Margherita Maiuri and Nathan C. Gianneschi and Marco Garavelli and Luca Valgimigli and Giulio Cerullo and Marco Montalti}, doi = {10.1021/jacs.5c01855}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {10031--10043}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemical pathways and light-enhanced radical scavenging activity of 1,8-dihydroxynaphthalene allomelanin}, volume = {147}, year = {2025}, }
• (2025). Deconjugative photoisomerization of cyclic enones. JACS, 147(11), 10023--10030. (www)

  @article{ , abstract = {The deconjugative isomerization of α,β-unsaturated carbonyl compounds enables regioisomeric products to be forged with simultaneous Umpolung of alkene reactivity. Although highly enabling, the endergonic nature of the net process coupled with governing regioselectivity outcomes, renders it challenging. Innovations in the positional isomerization of linear species, often by light-triggered activation, have re-energized this area. However, the deconjugative isomerization of cyclic enones is underdeveloped and often associated with impractical reaction conditions, limited substrate scopes, and a lack of mechanistic clarity. Herein, we report an operationally simple photochemical isomerization of cyclic enones using near-UV (372 nm) irradiation with catalytic amounts of Brønsted acid (HCl). This platform enables exocyclic deconjugative isomerization of a diverse array of enones including α-isophorone (a key intermediate in a variety of industrial processes), terpenoids and steroids. Mechanistic studies reveal the pivotal role of the solvent as a key mediator in the isomerization, where sequential hydrogen atom transfer (HAT) and reverse-HAT (RHAT) are proposed to be operational.}, archive = {J_JACS}, author = {Lukas Blank and Jungwon Kim and Constantin G. Daniliuc and Alissa Goetzinger and Marc-André Müller and Jan Schütz and Bettina Wuestenberg and Ryan Gilmour}, doi = {10.1021/jacs.5c01814}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {10023--10030}, shortjournal = {J. Am. Chem. Soc.}, title = {Deconjugative photoisomerization of cyclic enones}, volume = {147}, year = {2025}, }
• (2025). Interface-tailored secondary excitation and ultrafast Charge/Energy transfer in Ti3C2Tx-MoS2 heterostructure films. JACS, 147(11), 10012--10022. (www)

  @article{ , abstract = {Charge/energy separation across interfaces of plasmonic materials is vital for minimizing plasmonic losses and enhancing their performance in photochemical and optoelectronic applications. While heterostructures combining plasmonic two-dimensional transition metal carbides/nitrides (MXenes) and semiconducting transition metal dichalcogenides (TMDs) hold significant potential, the mechanisms governing plasmon-induced carrier dynamics at these interfaces remain elusive. Here, we uncover a distinctive secondary excitation phenomenon and an ultrafast charge/energy transfer process in heterostructure films composed of macro-scale Ti 3 C 2 T x and MoS 2 films. Using Rayleigh–Bénard convection and Marangoni effect-induced self-assembly, we fabricate large-scale (square centimeters) Ti 3 C 2 T x and MoS 2 films composed of edge-connected monolayer nanoflakes. These films are flexibly stacked in a controlled sequence to form macroscopic heterostructures, enabling the investigation and manipulation of excited-state dynamics using transient absorption and optical pump-terahertz probe spectroscopy. In the Ti 3 C 2 T x -MoS 2 heterostructure, we observe a secondary excitation in MoS 2 driven by the surface plasmon resonance of Ti 3 C 2 T x . This phenomenon, with a characteristic rise time constant of ∼70 ps, is likely facilitated by acoustic phonon recycling across the interface. Further interfacial thermal transport engineering─achieved by tailoring the sequence and combination of interfaces in trilayer heterostructures─allows extending the characteristic time to ∼175 ps. Furthermore, we identify a sub-150 fs ultrafast charge/energy transfer process from Ti 3 C 2 T x to MoS 2 . The transfer efficiency is strongly dependent on the excitation photon energy, resulting in amplified photoconductivity in MoS 2 by up to ∼180% under 3.10 eV excitation. These insights are crucial for developing plasmonic MXene-based heterostructures, paving the way for advancements in photochemical and optoelectronic applications.}, archive = {J_JACS}, author = {Jiaxu Zhang and Rafael Muñoz-Mármol and Shuai Fu and Xiaodong Li and Wenhao Zheng and Andrea Villa and Giuseppe M. Paternò and Darius Pohl and Alexander Tahn and Mike Hambsch and Stefan C. B. Mannsfeld and Dongqi Li and Hao Xu and Quanquan Guo and Hai I. Wang and Francesco Scotognella and Minghao Yu and Xinliang Feng}, doi = {10.1021/jacs.5c01826}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {10012--10022}, shortjournal = {J. Am. Chem. Soc.}, title = {Interface-tailored secondary excitation and ultrafast Charge/Energy transfer in Ti3C2Tx-MoS2 heterostructure films}, volume = {147}, year = {2025}, }
• (2025). Kinetic resolution of racemic radicals in asymmetric photoredox minisci reactions with azaarenes for precise construction of two non-adjacent stereocenters. JACS, 147(11), 10002--10011. (www)

  @article{ , abstract = {Despite the significant potential of photocatalysis as a robust synthetic tool, the high reactivity of radicals often presents challenges in achieving optimal chemoselectivity. In this study, we demonstrate that this inherent limitation can be strategically harnessed for asymmetric photoredox catalysis. By utilizing a chiral catalyst to facilitate kinetic resolution between the two enantiomers of racemic radical intermediates, one enantiomer selectively undergoes the desired transformation, while noncatalytic side reactions deplete the other enantiomer. Consequently, an attractive asymmetric photoredox three-component Minisci-type reaction involving bromides, racemic homoallylic tertiary alcohols or amines, and azaarenes has been developed. This approach enables efficient assembly of tertiary alcohols and amines onto the nonadjacent β-position of an azaarene-functionalized tertiary carbon stereogenic center with high levels of enantio- and diastereoselectivity. Therefore, this method not only allows for direct utilization of readily available racemic feedstocks that are challenging to convert into prochiral radicals via redox processes but also provides an efficient strategy for synthesizing complex molecules with multiple stereocenters.}, archive = {J_JACS}, author = {Tianju Shao and Feiyun Nie and Shanshan Cao and Qiang Li and Xiaowei Zhao and Yanli Yin and Zhiyong Jiang}, doi = {10.1021/jacs.5c01623}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {10002--10011}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetic resolution of racemic radicals in asymmetric photoredox minisci reactions with azaarenes for precise construction of two non-adjacent stereocenters}, volume = {147}, year = {2025}, }
• (2025). Mass transport-dependent C–C bond formation for CO electroreduction with alkali cations. JACS, 147(11), 9990--10001. (www)

  @article{ , abstract = {Electrolyte cation identity has been reported to influence the multicarbon (C 2+ ) selectivity in CO 2 /CO electroreduction. However, most of the previous work for cation size effect is based on H-cell configurations, which may inadvertently distort the underlying mechanism of cation effect due to mass transport limitations, particularly for CO reduction. Here, using GDE-type flow electrolyzers, we report that the selectivity of total C 2+ products on Cu is independent of alkali cation identity (Li + , Na + , K + , and Cs + ) in the absence of the CO transport limitation. Notably, a high concentration of strongly hydrated cation (such as Li + ) inhibits the total C 2+ formation in CO reduction, whereas total C 2+ selectivity is retained upon increasing concentrations of weakly hydrated cation (such as K + ). Further investigations reveal that the CO coverage at a low cation concentration is almost independent of the cation identity, but the CO coverage at highly concentrated cations strongly relies on the alkali cation identity.}, archive = {J_JACS}, author = {Wen Yan and Tiantian Wu and Jia Liu and Zhe Zheng and Ming Ma}, doi = {10.1021/jacs.5c01464}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9990--10001}, shortjournal = {J. Am. Chem. Soc.}, title = {Mass transport-dependent C–C bond formation for CO electroreduction with alkali cations}, volume = {147}, year = {2025}, }
• (2025). Regulating Cell–Material interfacial interactions through selective cellular resistance. JACS, 147(11), 9981--9989. (www)

  @article{ , abstract = {Regulating the behavior of different types of cells at the material–tissue interface is pivotal for inducing tissue regeneration. Traditional methods enhance target cell activity using specific ligands such as peptides and antibodies, which have stability issues within biological environments. Herein, we show that selective cell resistance can be realized by fine-tuning the material surface chemistry, achieving strong cell selectivity superior to that of extracellular matrix peptides. A certain degree of adsorption resistance differentially affects the adhesion of various types of cells on material surfaces. Taking this principle into account, a polyethylene glycol (PEG) grafted surface was meticulously fine-tuned to selectively support endothelial cells (ECs) while resisting smooth muscle cell attachment. Mechanistic studies identified that the difference in myosin II expression is crucial for cell selectivity. An EC-selective polymer coating for cardiovascular devices was fabricated to promote rapid surface endothelialization and prevent neointimal hyperplasia in vivo.}, archive = {J_JACS}, author = {Hongye Hao and Yifeng Chen and Weijiang Yu and Xingwang Wang and Cong Wang and Peng Zhang and Jian Ji}, doi = {10.1021/jacs.5c01433}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9981--9989}, shortjournal = {J. Am. Chem. Soc.}, title = {Regulating Cell–Material interfacial interactions through selective cellular resistance}, volume = {147}, year = {2025}, }
• (2025). Photoconductivity switching in semiconducting two-dimensional crystals via molecular tetris. JACS, 147(11), 9972--9980. (www)

  @article{ , abstract = {Two-dimensional organic materials are mainly constructed by using orthogonal anisotropic connectivity of covalent bonding and π–π stacking. The noncovalent connectivity between building blocks is presumed to be too delicate to stabilize the two-dimensional (2D) layers. Contrary to this assumption, we constructed graphite-like 2D layered material by utilizing pure noncovalent connectivity, i.e., weak intermolecular and π–π interaction via a molecular Tetris strategy. We produce X-ray mountable single crystals comprising polycyclic aromatic heterocycles by employing a single-crystal-to-dissolution-to-single-crystal transformation methodology. The macromechanical analysis of this layered crystal shows shearing behavior, which is quantified using nanoindentation experiments. The 2D lattice’s layer space allows reversible intercalation–deintercalation of iodine, which enhances the photoconductivity by 17 folds. Combined efforts of X-ray diffraction, solid-state spectroscopy, and electrochemical studies established the mechanism of intercalation and resulting photoconductivity enhancement.}, archive = {J_JACS}, author = {Kalipada Koner and Kaustav Das and Rajendra Prasad Paitandi and Rohan Mahapatra and Abhradeep Sarkar and Adhra Sury and Yun Hee Koo and Yingying Zhang and Thomas Heine and Agnieszka Kuc and Pramod P. Pillai and Shu Seki and C. Malla Reddy and Rahul Banerjee}, doi = {10.1021/jacs.5c01223}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9972--9980}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoconductivity switching in semiconducting two-dimensional crystals via molecular tetris}, volume = {147}, year = {2025}, }
• (2025). Ultra-specific G-Quadruplex–Colistin interaction for efficient transcriptome-wide g4 mapping. JACS, 147(11), 9962--9971. (www)

  @article{ , abstract = {G-quadruplexes (G4s) are challenging targets for chemical biology interventions, notably because of their dynamic topological polymorphism. We found that the antibiotic small- molecule colistin (COL) interacts specifically with a single subtype of G4 structures, the so-called parallel G4s. This interaction triggers the aggregation of the G4/COL complexes in a structure-specific manner, which can thus be separated from the bulk solution by centrifugation. This unprecedented mode of affinity-precipitation was exploited here to design the COL-induced RNA G4 precipitation and sequencing (CoRP-seq) protocol, which allows for the assessment of the prevalence of RNA G4s in the transcriptome of human cells in a straightforward manner. CoRP-seq shines by its ultraspecificity, simplicity, and practical convenience, which thus advances G4 mapping further and addresses unmet needs in the field of G4omics.}, archive = {J_JACS}, author = {Shijiong Wei and Xiaobo Zhang and Yilong Feng and Shentong Tao and Dehui Qiu and Xinrong Yan and Guangming Li and Lionel Guittat and Wenli Zhang and David Monchaud and Jean-Louis Mergny and Huangxian Ju and Jun Zhou}, doi = {10.1021/jacs.5c01172}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9962--9971}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultra-specific G-Quadruplex–Colistin interaction for efficient transcriptome-wide g4 mapping}, volume = {147}, year = {2025}, }
• (2025). D−π–A fluorophores with strong solvatochromism for single-molecule ratiometric thermometers. JACS, 147(11), 9953--9961. (www)

  @article{ , abstract = {Fluorescence thermometry has emerged as a significant area of research in the field of remote temperature sensing with high accuracy. However, the development of noninvasive and reliable small organic fluorescence thermometers (FTs) remains challenging. In this study, we developed a high-sensitivity, high-resolution small organic ratiometric FT with a solvatochromic dye and analyzed its temperature response mechanism. π-Extended fluorene-based D−π–A-type small solvatochromic dyes ( FπAc , FπF , and FπVC ) were synthesized and characterized. A significant solvatochromic shift of >200 nm was observed between n -hexane and tetrahydrofuran (THF) for both FπF and FπVC , with emission in THF reaching the red region (701 nm, 828 nm). This substantial solvatochromic shift was accompanied by a concurrent decrease in the fluorescence quantum yield and is attributable to accelerated internal conversion. The fluorescence spectra of FπF in THF and FπVC in diethyl ether exhibited blue shifts and increased fluorescence intensities with a decrease in polarity at increased temperatures. Our observations revealed an absolute sensitivity of 21%/°C and a relative sensitivity of 3.0%/°C at the maximum. These results represent the highest sensitivity and resolution reported for single fluorophore small organic ratiometric FTs dispersed in solution. The positive temperature coefficient of the fluorescence intensity was attributed to control of the nonradiative decay pathway by solvatochromism. The temperature responsiveness of FπF could be detected in living HeLa cells by ratiometric confocal microscopy. Using the proposed strategy to develop FTs, we plan to build a library of FTs that will cover various environments of interest in both simple and complex systems.}, archive = {J_JACS}, author = {Alto Hori and Atsushi Matsumoto and Junichi Ikenouchi and Gen-ichi Konishi}, doi = {10.1021/jacs.5c01173}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9953--9961}, shortjournal = {J. Am. Chem. Soc.}, title = {D−π–A fluorophores with strong solvatochromism for single-molecule ratiometric thermometers}, volume = {147}, year = {2025}, }
• (2025). Rational design of lanthanide-binding tags to optimize magnetic anisotropy in paramagnetic protein NMR. JACS, 147(11), 9939--9952. (www)

  @article{ , abstract = {Due to their exceptional anisotropic magnetic properties, lanthanide ion (Ln 3+ ) complexes are of great utility in many fields of chemistry, including magnetic materials, biomedical imaging, and nuclear magnetic resonance (NMR) spectroscopy. How to achieve large magnetic anisotropies in the Ln 3+ complexes coordinated with open-chain ligands is still a challenge. In this study, we started from the open-chain 4PS-PyMTA ligand and assessed the magnetic anisotropy using installed Ln 3+ coordinating pendants by increasing size and rigidity. This approach yielded Ln 3+ complexes with increasing magnetic anisotropies. The magnetic anisotropy and conformational dynamics of these open-chain 4PS-PyMTA-based Ln 3+ complexes were evaluated by NMR spectroscopy. The impact of the coordination arms on the magnetic anisotropy was further characterized by the ligand field parameters derived from europium luminescence spectra. These data show that the design strategy yielded an efficient way to enhance the conformational rigidity of the Ln 3+ chelating moiety and the ligand field strength, which underpins magnetic anisotropy. The magnitudes of pseudocontact shifts and residual dipolar couplings obtained with these 4PS-PyMTA-derived tags installed on a protein rival those obtained previously with synthetically less accessible cyclen-based Ln 3+ tags. Our work provides a practical strategy to open-chain Ln 3+ complexes with large magnetic anisotropies and straightforward synthetic protocols.}, archive = {J_JACS}, author = {Jia-Liang Chen and Shen-Na Chen and Hong-Kai Liu and Bin-Bin Pan and Yu Zhao and Xiang Fu and Gottfried Otting and Xun-Cheng Su}, doi = {10.1021/jacs.5c01192}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9939--9952}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design of lanthanide-binding tags to optimize magnetic anisotropy in paramagnetic protein NMR}, volume = {147}, year = {2025}, }
• (2025). Photoredox-catalyzed nucleophilic aromatic substitution of halophenols with azoles via oligomeric phenylene oxide radicals. JACS, 147(11), 9931--9938. (www)

  @article{ , abstract = {Nucleophilic aromatic substitution (S N Ar) reactions are widely employed in organic synthesis yet typically require the use of electron-deficient arenes for efficient reactivity. Herein, we report a photocatalytic protocol for formal S N Ar of electron-rich 4-halophenols with azole nucleophiles under mild, redox-neutral conditions. The transformation proceeds via a two-stage mechanism consisting of initial halophenol oligomerization to produce a key oligo(phenylene oxide) intermediate and its subsequent breakdown through S N Ar with the azole enabled by photoredox-catalyzed arene umpolung. Reaction monitoring, stoichiometric control experiments, and luminescence quenching data implicate phenoxyl radicals and Brønsted acid-activated oligo(phenylene oxide) radicals as the reactive species in the oligomerization and the S N Ar stages, respectively. The synthetic utility of this method is demonstrated across 17 (pseudo)halophenols bearing a variety of leaving groups (F, Cl, Br, OMs, and OTs) and 22 azole examples.}, archive = {J_JACS}, author = {Jan Seliger and Lydia R. Fries and Jonathan M. Meinhardt and Robert R. Knowles}, doi = {10.1021/jacs.5c01012}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9931--9938}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoredox-catalyzed nucleophilic aromatic substitution of halophenols with azoles via oligomeric phenylene oxide radicals}, volume = {147}, year = {2025}, }
• (2025). Focal point association of core-crystalline micelles with an amphiphilic corona block. JACS, 147(11), 9919--9930. (www)

  @article{ , abstract = {We report the preparation of star-like supermicelles by the secondary association of triblock comicelles or scarf-like micelles driven by a change in solvency. These building blocks were synthesized by seeded growth in which crystallites of a triblock terpolymer, either PFS 27 - b -PTDMA 81 - b -POEGMA 45 (to form triblock comicelles) or PFS 66 - b -PTDMA 81 - b -POEGMA 45 (to form scarf-like micelles), served as seeds for crystallization-driven self-assembly (CDSA). PFS- b -PTDMA unimers were added in the seeded growth step. The corona-forming block PTDMA–POEGMA is amphiphilic and sensitive to polarity changes of the solvents. We sought solvents in which the upper critical solution temperature (UCST, T UCST ) of POEGMA was slightly above room temperature (RT). Examples included 1-decanol and 1-decanol/decane mixtures. Seeded growth proceeded normally in solvents above the UCST of POEGMA. When the solution temperature was lowered below T UCST , or when the triblock comicelles or scarf-like micelles were transferred to a solvent (e.g., 1-decanol) below its T UCST , the center blocks associated to form star-like supermicelles. The addition of small amounts of THF to the medium to increase the solvency for POEGMA led to dissociation of the supermicelles. Transfer of the triblock comicelles to 1-pentanol at RT, below the UCST of PTDMA, also led to controlled secondary association to form supermicelles with a different morphology. Seeded growth with PFS 25 - b -PDMAEMA 184 unimers led to supermicelles in which the poly(dimethylaminoethyl methacrylate) corona chains could serve as carriers for gold nanoparticles (AuNPs). These AuNP@supermicelle complexes could serve as recoverable catalysts, for example to catalyze the condensation polymerization of bis(dimethylsilyl)benzene and pentanediol. They were highly active catalysts and showed excellent mechanical robustness for recovery and reuse.}, archive = {J_JACS}, author = {Shaofei Song and Jun-Ting Xu and Hang Zhou and Ian Manners and Mitchell A. Winnik}, doi = {10.1021/jacs.5c00926}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9919--9930}, shortjournal = {J. Am. Chem. Soc.}, title = {Focal point association of core-crystalline micelles with an amphiphilic corona block}, volume = {147}, year = {2025}, }
• (2025). Palladium-catalyzed site-selective regiodivergent carbocyclization of di- and trienallenes: A switch between substituted cyclohexene and cyclobutene. JACS, 147(11), 9909--9918. (www)

  @article{ , abstract = {Nature efficiently produces a myriad of structurally diverse carbon ring frameworks from common linear precursors via cyclization reactions at specific olefinic sites in dienes or polyenes. In contrast, achieving the site-selective functionalization of diene or polyene substrates remains a formidable challenge in chemical synthesis. Herein, we report a pair of highly site-selective, regiodivergent carbocyclization reactions of dienallenes and trienallenes, enabling the efficient synthesis of cis -1,4-disubstituted cyclohexenes and trans -1,2-disubstituted cyclobutenes from a common precursor with high diastereoselectivity. Remarkably, simple achiral organophosphoric acids and amines are identified as powerful ligands for controlling these palladium-catalyzed regiodivergent carbocyclizations. This approach represents the first example of site-selective regiodivergent carbocyclization, providing a practical method for the stereospecific synthesis of thermodynamically disfavored cis -1,4-disubstituted cyclohexenes and fully substituted trans -1,2-cyclobutenes. Additionally, the methodology developed offers general insights into the development of metal-catalyzed site-selective, regiodivergent carbocyclizations of diene and polyene precursors, mimicking natural carbocyclization processes.}, archive = {J_JACS}, author = {Wei-Jun Kong and Haibo Wu and Jia-Yi Chen and Rong-Zhen Liao and Yaoyao Liu and Zhipu Luo and Ivo Pires Vilela and Pan Fang and Fahmi Himo and Jan-E. Bäckvall}, doi = {10.1021/jacs.5c00739}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9909--9918}, shortjournal = {J. Am. Chem. Soc.}, title = {Palladium-catalyzed site-selective regiodivergent carbocyclization of di- and trienallenes: A switch between substituted cyclohexene and cyclobutene}, volume = {147}, year = {2025}, }
• (2025). C–C Cleavage/Cross-coupling approach for the modular synthesis of medium-to-large sized rings: Total synthesis of resorcylic acid lactone natural products. JACS, 147(11), 9900--9908. (www)

  @article{ , abstract = {The chemical synthesis of medium (8–11 membered) and large sized (≥12 membered) cyclic systems is often challenging. The introduction of transannular strain and loss of degrees of freedom in forming macrocycles often result in poor reaction kinetics and thermodynamics (i.e., thermodynamically disfavored at equilibrium). To address these challenges, we herein report a strategy for the synthesis of medium-to-large sized rings, which leverages strain-release and metal templating through a palladium-mediated C–C cleavage/cross-coupling. By means of DOSY NMR techniques, we identified an undesired competing β-hydrogen elimination pathway, which was substrate dependent. Using a streamlined synthesis of the requisite precursors, our method enables the rapid generation of complex medium-to-large sized rings in a modular fashion through a C(sp 2 )–C(sp 3 ) macrocyclization. The transformation enabled the short total synthesis of various resorcylic acid lactone (RAL) natural products and unnatural analogues of late-stage intermediates. A mechanistic proposal for the macrocyclization is supported by computational studies of the reaction using density functional theory.}, archive = {J_JACS}, author = {Lucas T. Göttemann and Charis Amber and Khalid Mahmood and Philipp Mader and Ismail Kokculer and Théo Andris and Blane P. Zavesky and Richmond Sarpong}, doi = {10.1021/jacs.5c00801}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9900--9908}, shortjournal = {J. Am. Chem. Soc.}, title = {C–C Cleavage/Cross-coupling approach for the modular synthesis of medium-to-large sized rings: Total synthesis of resorcylic acid lactone natural products}, volume = {147}, year = {2025}, }
• (2025). Real-time observation of ultrafast concerted dynamics between energy and chirality transfer by femtosecond time-resolved circular polarization luminescence spectroscopy. JACS, 147(11), 9891--9899. (www)

  @article{ , abstract = {Elucidating the underlying mechanism of effective chirality and energy transfer processes observed in biological assemblies has cross-disciplinary significance, and it is of special interest in the fields of chemistry and biology due to the pivotal role of chirality in life. Challenges in the field include how to achieve real-time monitoring of the chirality and energy transfer dynamics simultaneously, as well as how to distinguish whether these processes take place in the ground or excited state. Herein, we achieve the first attempt at real-time observation of the concerted ultrafast dynamics between the Förster resonance energy transfer (FRET) and the generation of circularly polarized luminescence (CPL) in the excited state in near-infrared CPL supramolecular nanofibers (SNFs) by using femtosecond time-resolved circularly polarized luminescence (fs-TRCPL) spectroscopy. Our findings reveal a cooperative interplay between FRET and CPL emission, unfolding over time scales from several to hundreds of picoseconds. Notably, we identify that the pivotal mechanism leading to a 0.045 g lum value in SNFs is the difference in the FRET rates between left- and right-handed circularly polarized emission channels, which is a reason beyond the well-known relationship of the electronic and magnetic dipoles. Our results not only shed light on the understanding of the chirality transfer mechanism in the excited states but also pave the road for the development of novel CPL materials in the future.}, archive = {J_JACS}, author = {Yunxia Han and Xuefeng Yang and Xueli Wang and Haolai Mao and Kang Huang and Haifeng Pan and Minghua Liu and Pengfei Duan and Jinquan Chen}, doi = {10.1021/jacs.5c00695}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9891--9899}, shortjournal = {J. Am. Chem. Soc.}, title = {Real-time observation of ultrafast concerted dynamics between energy and chirality transfer by femtosecond time-resolved circular polarization luminescence spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Photothermocatalytic wet reforming of waste plastics to syngas. JACS, 147(11), 9879--9890. (www)

  @article{ , abstract = {The increasing accumulation of plastic waste in the environment poses a serious threat to the ecosystem and health sector, urging us to develop sustainable strategies to tackle this issue. Converting plastic waste into platform chemicals using sustainable energy and primary resources can mitigate environmental pollution and reduce CO 2 emissions. In this study, polyolefins were transformed into syngas through a wet reforming process over a nickel-supported oxygen vacancy-rich titanium dioxide (Ni/TiO 2- x ) catalyst with water as the reactant under light irradiation. The focused light irradiation can readily increase the temperature in the reactor for the dehydrogenation and degradation of polyethylene (PE) to occur, followed by the wet reforming of PE-derived compounds and gaseous hydrocarbons to syngas. Additionally, the transfer of electrons from TiO 2- x to the nickel components under light irradiation facilitates the aforementioned reactions. The current work presents a sustainable strategy for valorization of plastic waste to syngas, serving as a platform feedstock for the subsequent production of various chemicals.}, archive = {J_JACS}, author = {Yaxin Zhang and Bo Sun and Chengcheng Cai and Tianfu Wang and Yongjun Gao and Ding Ma}, doi = {10.1021/jacs.5c00620}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9879--9890}, shortjournal = {J. Am. Chem. Soc.}, title = {Photothermocatalytic wet reforming of waste plastics to syngas}, volume = {147}, year = {2025}, }
• (2025). A library of polymetallic alloy nanotubes: From binary to septenary. JACS, 147(11), 9865--9878. (www)

  @article{ , abstract = {The polymetallic alloy nanostructure has received widespread attention in electrocatalytic reactions due to the variability in composition and excellent performance. However, the controllable synthesis of one-dimensional (1D) polymetallic alloy nanomaterials remains a significant challenge. Herein, we propose a new and general low-temperature method to prepare a library of binary to septenary polymetallic alloy nanotubes, and this method can be used to synthesize 18 kinds of polymetallic alloy nanotube (NT), including eight kinds of high-entropy alloy (HEA) NT. A representative Cu 30 Ni 26 Co 19 Ru 14 Ir 11 HEA NT demonstrates efficient and stable catalytic performance for both oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The Cu 30 Ni 26 Co 19 Ru 14 Ir 11 HEA NT exhibits an overpotential of only 121 mV for the HER and 272 mV for the OER, respectively, when measured at a current density of 100 mA cm –2 . In addition, the two-electrode system comprising the Cu 30 Ni 26 Co 19 Ru 14 Ir 11 HEA NT exhibits an impressive efficiency of 100 mA cm –2 during overall water splitting, requiring only a potential of 1.67 V. The high catalytic activity of the Cu 30 Ni 26 Co 19 Ru 14 Ir 11 HEA NT is attributed to the downward shift of the d -band center. In the HER, the downward shift of the d -band center can reduce the binding energy with *H, which is beneficial for the desorption process of hydrogen. In the OER, the downward shift can also reduce the reaction energy barrier associated with the rate-determining step from *O to *OOH. This work seeks to offer a new and general method for synthesizing polymetallic alloy nanotubes with controllable structures and compositions under mild conditions.}, archive = {J_JACS}, author = {Cheng Yang and Jiasai Yao and Senyao Meng and Ping Wang and Miao He and Pangen Li and Peng Xiao and Jianyang Xiao and Yunpeng Liu and Zhenxing Li}, doi = {10.1021/jacs.5c00597}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9865--9878}, shortjournal = {J. Am. Chem. Soc.}, title = {A library of polymetallic alloy nanotubes: From binary to septenary}, volume = {147}, year = {2025}, }
• (2025). Crystalline arylstibinidene chalcogenides: Heavier congeners of aromatic nitroso compounds. JACS, 147(11), 9858--9864. (www)

  @article{ , abstract = {Nitroso compounds, R-N═O, containing N═O double bonds are ubiquitous and widely utilized in organic synthesis. In contrast, heavier congeners of nitroso compounds, namely pnictinidene chalcogenides R-Pn = E (Pn = P, As, Sb, Bi; E = O, S, Se, Te), are highly reactive and scarce. They have been stabilized in the coordination sphere of Lewis acid/base or by pronounced contribution from resonance structures, whereas free species with unperturbed pnictogen-chalcogen double bonds remains elusive. In this work, we report the isolation and characterization of arylstibinidene chalcogenides, which are the first heavier congeners of aromatic nitroso compounds. They are facilely synthesized through the salt metathesis reactions of aryldichlorostibane and dilithium chalcogenides. They bear unperturbed Sb═E (E = S, Se and Te) double bonds due to poor orbital overlap between the C 2p orbitals of the phenyl ring of the substituent and the Sb 5p orbitals. Moreover, they show versatile reactivity, including acting as chalcogen atom transfer reagents and reacting with small molecules via (cyclo)addition.}, archive = {J_JACS}, author = {Xinyi Li and Yizhen Chen and Shicheng Dong and Dongmin Wang and Lei Xu and Jun Zhu and Gengwen Tan}, doi = {10.1021/jacs.5c00328}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9858--9864}, shortjournal = {J. Am. Chem. Soc.}, title = {Crystalline arylstibinidene chalcogenides: Heavier congeners of aromatic nitroso compounds}, volume = {147}, year = {2025}, }
• (2025). Giant enhancement of optical nonlinearity by manipulating guest molecular stacking modes in Metal–Organic frameworks. JACS, 147(11), 9844--9857. (www)

  @article{ , abstract = {The influence of guest stacking interactions in host–guest (H–G) MOF composites on third-order nonlinear optical (NLO) performance remains largely unknown. Herein, we propose for the first time a noncovalent aggregate confinement strategy for synthesizing H–G MOF composites with different guest stacking modes. And [perylene 2 ] n (α-Pe) and [perylene] n (β-Pe) were selected as guests and confined into a novel Ca-based MOF {[Ca(TBAPy)(DMA) 2 ]·3DMA·[N(CH 3 ) 2 ]·H 2 O} n (Ca-MOF-pts). The NLO results showed that compared to β-Pe@Ca-MOF-pts, the saturable absorption (SA) and self-defocusing properties of α-Pe@Ca-MOF-pts were increased by 2.71-fold and 3.82-fold, respectively. Interestingly, α/β-Pe@Ca-MOF-pts can be transformed into α/β-Pe@Ca-MOF-flu (Ca-MOF-flu = {[Ca 1.5 (TBAPy)(H 2 O) 2 ]·DMA·[N(CH 3 ) 2 ]·2H 2 O} n ) through self-adaptive topological evolution, and the corresponding NLO absorption signal change from SA to reverse saturable absorption (RSA). As expected, compared to β-Pe@Ca-MOF-flu, the RSA and self-defocusing properties of α-Pe@Ca-MOF-flu are improved by 2.94-fold and 4.07-fold, respectively, demonstrating the importance of guest stacking modes. Theoretical calculation and transient absorption spectra indicated the enhancement of NLO performance was attributed to the large π–π overlap of α-Pe, which promoted the electron delocalization/transfer and optimized the cross-sectional of the ground state and excited state. This study provides a new strategy for developing H–G MOF composites with excellent NLO properties.}, archive = {J_JACS}, author = {Kangshuai Geng and Yupei Sun and Yujie Zhao and Zhichao Shao and Yi Wei and Jing Huang and Yang Cui and Xiaoyan Xu and Hongwei Hou}, doi = {10.1021/jacs.5c00081}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9844--9857}, shortjournal = {J. Am. Chem. Soc.}, title = {Giant enhancement of optical nonlinearity by manipulating guest molecular stacking modes in Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Modular access from acrylate to a sustainable polyester platform with large-span tunability and chemical circularity under mild conditions. JACS, 147(11), 9836--9843. (www)

  @article{ , abstract = {Making polyesters with conventional vinyl monomers is one of the most economical ways to develop sustainable polymeric materials. For polar vinyls, while their transformation into lactones has been studied extensively, there exists no further access to synthesizing polyesters, presumably due to the nonstrained and nonpolymerizable nature of the obtained lactones. Herein, we report the first facile synthesis of polyesters that originated from one of the most critical classes of polar vinyls-acrylates. Specifically, a series of modular six-membered lactones were rationally designed and synthesized from methyl acrylate together with malonic esters containing diverse functional groups and formaldehyde. The monomers underwent ring-opening polymerization (ROP) to yield the first acrylate-derived polyesters, which further constitute a unique polymer platform with a large scope of potential functionalities and performances as well as easy chemical circularity under mild conditions. Notably, the obtained polyesters are a rare example featuring tunable functionalities on the side ester groups whose impact on certain material properties (e.g., glass transition temperature) is similar to that of polyacrylates, implying potential replacement between polyesters and polyacrylates. In addition, by presenting the special geminal disubstitutions originally from the monomers’ γ-position for the first time, polyesters also exhibited unprecedentedly enhanced thermal and recycling properties: Variation of the geminal disubstitutions offers a unique access to large-span modulation from completely amorphous to high-level crystalline materials, and the melting temperature of the polymer with high crystallinity was drastically increased by 84 °C compared with the reported monosubstituted counterpart. At the same time, compared with polyesters synthesized from other six-membered lactones whose chemical recycling required harsh conditions (>150 °C and high vacuum), the gem-disubstituted polyesters in this work can undergo complete chemical recycling to monomers under much milder conditions (80 °C and ambient pressure). This study informs the design of future high-performance polyesters derived from polar vinyls.}, archive = {J_JACS}, author = {Haoyu Fan and Chenyang Hu and Mingxin Niu and Qi Zhang and Bokun Li and Xuan Pang and Xuesi Chen}, doi = {10.1021/jacs.5c00044}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9836--9843}, shortjournal = {J. Am. Chem. Soc.}, title = {Modular access from acrylate to a sustainable polyester platform with large-span tunability and chemical circularity under mild conditions}, volume = {147}, year = {2025}, }
• (2025). Atomically dispersed catalytic platinum anti-substitutions in molybdenum ditelluride. JACS, 147(11), 9825--9835. (www)

  @article{ , abstract = {Atomic defects, e.g., vacancies, substitutions, and dopants, play crucial roles in determining the functionalities of two-dimensional (2D) materials, including spin glass, single-photon emitters, and energy storage and conversion, due to the introduction of abnormal charge states and noncentrosymmetric distortion. In particular, anti-substitutions are regarded as promising topological defect types, in which substitution occurs at opposite charge sites, fundamentally modifying the atomic and electronic structures of pristine lattices. However, the fabrication of large-scale anti-substitutions remains challenging due to high formation energies and complex reaction paths. Here, we propose an approach for synthesizing atomically dispersed Pt anti-substitutions in defective 1T′-MoTe 2 using the electrochemical exfoliation-assisted leaching–redeposition (EELR) method. Atomic-resolution scanning transmission electron microscopy (STEM) imaging reveals that Pt atoms substitute Te sites, forming unconventional Mo–Pt bonds. A rich variety of Pt anti-substitution configurations and Pt anti-substitutions coupling with Te vacancies have been fabricated by controlled electrochemical conditions. Density functional theory (DFT) calculations suggest that Pt atoms preferentially occupy the Te vacancy sites coupled with neighboring Te vacancies, stabilizing the anti-substitution configurations. The coupled Pt–Te defect complexes exhibit excellent hydrogen evolution reaction, with an overpotential of only 12.9 mV because the paired defect complexes cause charge redistribution and regulate the d-band center of the active sites as suggested by DFT. These findings introduce an effective approach for engineering atomically dispersed anti-substitutions in 2D materials, presenting new opportunities for the precise design of atomic features with targeted functionalities in catalytic and other advanced applications.}, archive = {J_JACS}, author = {Jun Zhao and Xiaocang Han and Junxian Li and Ziyi Han and Xiaoxu Zhao}, doi = {10.1021/jacs.5c00033}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9825--9835}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomically dispersed catalytic platinum anti-substitutions in molybdenum ditelluride}, volume = {147}, year = {2025}, }
• (2025). Real-time tracking of photoinduced Metal–Metal bond formation in a d8d8 di-iridium complex by vibrational coherence and femtosecond stimulated raman spectroscopy. JACS, 147(11), 9810--9824. (www)

  @article{ , abstract = {We report real-time dynamics of photoinduced metal–metal bond formation acquired from ultrafast time-resolved stimulated emission and femtosecond stimulated Raman spectra (FSRS) of [Ir 2 (2,5-dimethyl-2,5-diisocyanohexane) 4 ] 2+ (Ir(TMB)) in the region of low-frequency vibrations. Interpretation was supported by impulsive stimulated Raman experiments and time-dependent density-functional theory (TDDFT) calculations. The Ir–Ir stretching frequency doubled on going from ground to the lowest singlet excited state 1 dσ*pσ, from 53 to 126 cm –1 , demonstrating Ir–Ir bond formation. Spectral evolution during the first 4 ps after excitation showed extremely large-amplitude coherent oscillations of stimulated emission as well as FSRS signal intensities, which occurred with the excited-state Ir–Ir stretching frequency combined with frequencies of several deformation vibrations and the first Ir–Ir overtone. Corresponding vibrations were observed in FSRS directly but most of them vanished in the first 3 ps, indicating that they belonged to transiently populated hot vibrational states. Fourier transforms of intensity oscillations plotted against FSRS frequencies produced two-dimensional (2D-FSRS) maps with diagonal and off-diagonal features due to Franck–Condon-excited and anharmonically coupled vibrations, some of which acquired Raman intensity through coupling with the Ir–Ir stretch. We concluded that optical excitation impulsively shortens the Ir–Ir distance and increases its stretching force constant, assisted by a simultaneously excited network of coupled deformation modes. The electronically/vibrationally excited system then relaxes through periodic strengthening and weakening of the Ir–Ir interaction and changing conformations of the TMB ligand framework, forming a metal–metal bonded 1 dσ*pσ state after 4–5 ps.}, archive = {J_JACS}, author = {Miroslav Kloz and Jakub Dostál and Atripan Mukherjee and Martin Pižl and Filip Šebesta and Michael G. Hill and Harry B. Gray and Stanislav Záliš and Antonín Vlček}, doi = {10.1021/jacs.4c18527}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9810--9824}, shortjournal = {J. Am. Chem. Soc.}, title = {Real-time tracking of photoinduced Metal–Metal bond formation in a d8d8 di-iridium complex by vibrational coherence and femtosecond stimulated raman spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Enhancing T-cell infiltration and immunity in solid tumors via DNA nanolinker-mediated monocyte hitchhiking. JACS, 147(11), 9800--9809. (www)

  @article{ , abstract = {Cytotoxic CD8 + T cells are one of the most powerful effectors in the antitumor immune response. However, their insufficient tumor infiltration severely limits the clinical success of immunotherapy in solid tumors. In this work, by using amphiphilic aptamer-incorporated DNA tetrahedra (aptTDN) as the intercellular nanolinker, we developed a monocyte-hitchhiked T-cell delivery strategy to actively promote the intratumoral infiltration of effector CD8 + T cells. Our results demonstrated that membrane-anchoring of aptTDN enabled the specific and stable ligation of T cells with Ly6c + monocytes, without compromising the migratory behavior of monocytes and the antitumor activity of T cells. By leveraging the intrinsic tumor-homing capability of monocytes, the ligated T cells efficiently accumulated within tumor-associated vasculature and then deeply infiltrated the tumor bed. Additionally, the enhanced intratumoral presence of adoptively transferred effector CD8 + T cells facilitated the establishment of an immunosupportive microenvironment, that further recruited endogenous T cells and ultimately bolstered antitumor immunity. Moreover, our monocyte-hitchhiked T-cell tumor infiltration system could significantly improve the efficacy of immune checkpoint blockade therapy. Collectively, by utilizing chemically synthetic nanolinkers to modulate cellular interactions and develop a delivery system of therapeutic cells, our work presents a new paradigm for the advancement of immunotherapy against solid tumors.}, archive = {J_JACS}, author = {Nachuan Wen and Yao Lu and Yuting Zhuo and Bo Fu and Haiyuan Wang and Yao He and Hui Wu and Zhimin Wang and Weihong Tan and Liping Qiu}, doi = {10.1021/jacs.4c18455}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9800--9809}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing T-cell infiltration and immunity in solid tumors via DNA nanolinker-mediated monocyte hitchhiking}, volume = {147}, year = {2025}, }
• (2025). High-energy density li-ion battery cathode using only industrial elements. JACS, 147(11), 9786--9799. (www)

  @article{ , abstract = {Li-ion batteries are crucial for the global energy transition to renewables; however, their scalability is limited by the supply of key elements used in commercial cathodes (e.g., Ni, Mn, Co, P). Therefore, there is an urgent need for next-generation cathodes composed of widely available and industrially scalable elements. Here, we introduce a Li-rich cathode based on the known material Li 2 FeS 2 , composed of low-cost elements (Al, Fe, S) that are globally mined and refined at an industrial scale. The substitution of redox-inactive Al 3+ for Fe 2+ achieves remarkably high degrees of anion redox, which, in turn, yields high gravimetric capacity (≈450 mAh·g –1 ) and energy density (≳1000 Wh·kg –1 ). We show that Al 3+ enables high degrees of delithiation by stabilizing the delithiated state, suppressing phase transformations that would otherwise prevent deep delithiation and extensive anion redox. This mechanistic insight offers new possibilities for developing scalable, next-generation Li-ion battery cathodes to meet pressing societal needs.}, archive = {J_JACS}, author = {Eshaan S. Patheria and Pedro Guzman and Leah S. Soldner and Michelle D. Qian and Colin T. Morrell and Seong Shik Kim and Kyle Hunady and Elena R. Priesen Reis and Nicholas V. Dulock and James R. Neilson and Johanna Nelson Weker and Brent Fultz and Kimberly A. See}, doi = {10.1021/jacs.4c18440}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9786--9799}, shortjournal = {J. Am. Chem. Soc.}, title = {High-energy density li-ion battery cathode using only industrial elements}, volume = {147}, year = {2025}, }
• (2025). Exploiting photohalide generation in shape and multichromatic color patterning of Polymer–Perovskite nanocomposites. JACS, 147(11), 9774--9785. (www)

  @article{ , abstract = {The ability to arrange brightly fluorescent nanoscale materials into well-defined patterns is critically important in advanced optoelectronic structures. Traditional methods for doing so generally involve depositing different color quantum dot “inks,” irradiating reactive (e.g., cross-linkable) ligands at their surface, and then lifting off the unexposed sections in a developer solvent. Here, we outline a fundamentally different approach for directly patterning the emission color of nanocomposite thin films utilizing mask-based lithographic techniques and laser scanning methods. In this system, a polymer film containing cesium lead halide nanocrystals (NCs) is embedded with an organohalide─termed a “photohalide generator”─which undergoes a light-triggered, perovskite-catalyzed reduction and release of halide anion for uptake by the NC lattice, markedly shifting its band gap. In this manner, a blue emitting (CsPbBr 1.5 Cl 1.5 ) film becomes green and/or red in the exposed areas of a photomask, replicating the mask features as a multichromatic array (e.g., green, red, etc. colors against a blue background). The resolution limits of this materials system were probed using laser scanning tools capable of writing intricate patterns with feature sizes approaching a single micron─more than an order of magnitude smaller than the most comparable methods based on inkjet printing. Lastly, these methods are extended to a combined shape and color patterning process for making free-standing filamentous structures with striped and alternating fluorescence emission along their length.}, archive = {J_JACS}, author = {Christopher Cueto and Dhimitraq Nikolla and Alexander Ribbe and James Chambers and Todd Emrick}, doi = {10.1021/jacs.4c18454}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9774--9785}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploiting photohalide generation in shape and multichromatic color patterning of Polymer–Perovskite nanocomposites}, volume = {147}, year = {2025}, }
• (2025). A [FeFe] Hydrogenase–Rubrerythrin chimeric enzyme functions to couple h2 oxidation to reduction of H2O2 in the foodborne pathogen clostridium perfringens. JACS, 147(11), 9764--9773. (www)

  @article{ , abstract = {[FeFe] hydrogenases are a diverse class of H 2 -activating enzymes with a wide range of utilities in nature. As H 2 is a promising renewable energy carrier, exploration of the increasingly realized functional diversity of [FeFe] hydrogenases is instrumental for understanding how these remarkable enzymes can benefit society and inspire new technologies. In this work, we uncover the properties of a highly unusual natural chimera composed of a [FeFe] hydrogenase and rubrerythrin as a single polypeptide. The unique combination of [FeFe] hydrogenase with rubrerythrin, an enzyme that functions in H 2 O 2 detoxification, raises the question of whether catalytic reactions, such as H 2 oxidation and H 2 O 2 reduction, are functionally linked. Herein, we express and purify a representative chimera from Clostridium perfringens (termed Cper HydR) and apply various electrochemical and spectroscopic approaches to determine its activity and confirm the presence of each of the proposed metallocofactors. The cumulative data demonstrate that the enzyme contains a surprising array of metallocofactors: the catalytic site of [FeFe] hydrogenase termed the H-cluster, two [4Fe-4S] clusters, two rubredoxin Fe(Cys) 4 centers, and a hemerythrin-like diiron site. The absence of an H 2 -evolution current in protein film voltammetry highlights an exceptional bias of this enzyme toward H 2 oxidation to the greatest extent that has been observed for a [FeFe] hydrogenase. Here, we demonstrate that Cper HydR uses H 2 , catalytically split by the hydrogenase domain, to reduce H 2 O 2 by the diiron site. Structural modeling suggests a homodimeric nature of the protein. Overall, this study demonstrates that Cper HydR is an H 2 -dependent H 2 O 2 reductase. Equipped with this information, we discuss the possible role of this enzyme as a part of the oxygen-stress response system, proposing that Cper HydR constitutes a new pathway for H 2 O 2 mitigation.}, archive = {J_JACS}, author = {Jesse Taylor and David W. Mulder and Patrick S. Corrigan and Michael W. Ratzloff and Natalia Irizarry Gonzalez and Carolyn E. Lubner and Paul W. King and Alexey Silakov}, doi = {10.1021/jacs.4c18425}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9764--9773}, shortjournal = {J. Am. Chem. Soc.}, title = {A [FeFe] Hydrogenase–Rubrerythrin chimeric enzyme functions to couple h2 oxidation to reduction of H2O2 in the foodborne pathogen clostridium perfringens}, volume = {147}, year = {2025}, }
• (2025). Room-temperature h2 splitting and n2-hydrogenation induced by a neutral LuII complex. JACS, 147(11), 9752--9763. (www)

  @article{ , abstract = {The direct splitting of H 2 and N 2 molecules is a challenging reaction that is closely related to the Haber–Bosch ammonia synthesis process. Until now, such reactivity has never been observed in the case of molecular lanthanide species. Here, we show that careful selection of the ligand scaffold allows the isolation and characterization of a kinetically stable but highly reactive Lu II complex. This divalent lanthanide species enables direct H 2 splitting at room temperature, an unknown reactivity in lanthanide chemistry, which has been fully corroborated by DFT calculations. In addition, the Lu II complex readily binds N 2 , leading to an end-on coordinated diazenido (N 2 ) 2– lanthanide complex. The latter can be hydrogenated under very smooth conditions (ca. 1.2 bar H 2 , ambient temperature) to form a unique Lu III –NH 2 complex. Direct N 2 hydrogenation and cleavage are thus accessible using low-valent molecular rare-earth metal complexes.}, archive = {J_JACS}, author = {Evangelos Papangelis and Luca Demonti and Iker del Rosal and Angus Shephard and Laurent Maron and Grégory Nocton and Thomas Simler}, doi = {10.1021/jacs.4c18416}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9752--9763}, shortjournal = {J. Am. Chem. Soc.}, title = {Room-temperature h2 splitting and n2-hydrogenation induced by a neutral LuII complex}, volume = {147}, year = {2025}, }
• (2025). Unveiling the fluorination pathway of Ruddlesden–Popper oxyfluorides: A comprehensive in situ X-ray and neutron diffraction study. JACS, 147(11), 9739--9751. (www)

  @article{ , abstract = {Ruddlesden–Popper oxyfluorides exhibit unique properties, but their synthesis is often hindered by low thermodynamic stability. To overcome this challenge, understanding the formation mechanism of these materials is crucial for optimizing the reaction conditions and accessing new products. This study presents an in-depth investigation of the fluorination reaction of La 2 NiO 4 with poly(vinylidene fluoride) (PVDF), targeting the oxyfluorides La 2 NiO 3 F 2 and La 2 NiO 2.5 F 3 , which exhibit distinct structural distortions. In situ X-ray diffraction experiments, performed on a laboratory diffractometer, revealed the presence of four distinct reaction intermediates. The crystal structures of these intermediates were further elucidated through X-ray and neutron powder diffraction experiments, complemented by in situ neutron powder diffraction data obtained using a setup featuring a low-background cell made from single-crystalline sapphire. 19 F MAS NMR spectroscopy was employed to localize the fluoride ions and to track the consumption of PVDF. By systematically optimizing reaction conditions, we successfully obtained both oxyfluorides and quantified the phase evolution of all intermediates through extensive Rietveld refinements, yielding the following reaction steps: La 2 NiO 4 ( I 4/ mmm ) → Inter#1 ( Fmmm ) → Inter#2 ( Fmmm , with increased orthorhombic distortion) → Inter#3 ( C 2/ c ) → La 2 NiO 3 F 2 ( Cccm ). In the presence of 50% excess PVDF, La 2 NiO 3 F 2 is not obtained from Inter#3 and the reaction instead progresses via Inter#4 ( P 4 2 / nnm ) to La 2 NiO 2.5 F 3 ( P 4 2 / nnm , with a larger unit cell). This study demonstrates the power of laboratory in situ XRD experiments in elucidating complex fluorination reaction mechanisms, enabling the synthesis of new oxyfluorides with interesting physical properties. The in situ approach represents a significant advancement over traditional trial-and-error methods, which are still prevalent in solid-state synthesis.}, archive = {J_JACS}, author = {Jonas Jacobs and Andy Bivour and Vadim Sikolenko and Holger Kohlmann and Thomas C. Hansen and James R. Hester and Ke Xu and Jörn Schmedt auf der Günne and Stefan G. Ebbinghaus}, doi = {10.1021/jacs.4c18187}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9739--9751}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling the fluorination pathway of Ruddlesden–Popper oxyfluorides: A comprehensive in situ X-ray and neutron diffraction study}, volume = {147}, year = {2025}, }
• (2025). Janus polymeric giant vesicles on demand: A predictive phase separation approach for efficient formation. JACS, 147(11), 9727--9738. (www)

  @article{ , abstract = {Janus particles, with their intrinsic asymmetry, are attracting major interest in various applications, including emulsion stabilization, micro/nanomotors, imaging, and drug delivery. In this context, Janus polymersomes are particularly attractive for synthetic cell development and drug delivery systems. While they can be achieved by inducing a phase separation within their membrane, their fabrication method remains largely empirical. Here, we propose a rational approach, using Flory–Huggins theory, to predict the self-assembly of amphiphilic block copolymers into asymmetric Janus polymersomes. Our predictions are experimentally validated by forming highly stable Janus giant unilamellar vesicles (JGUVs) with a remarkable yield exceeding 90% obtained from electroformation of various biocompatible block copolymers. We also present a general phase diagram correlating mixing energy with polymersome morphology, offering a valuable tool for JGUV design. These polymersomes can be extruded to achieve quasi-monodisperse vesicles while maintaining their Janus-like morphology, paving the way for their asymmetric functionalization and use as active carriers.}, archive = {J_JACS}, author = {Eloise Equy and Emmanuel Ibarboure and Eric Grelet and Sébastien Lecommandoux}, doi = {10.1021/jacs.4c18003}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9727--9738}, shortjournal = {J. Am. Chem. Soc.}, title = {Janus polymeric giant vesicles on demand: A predictive phase separation approach for efficient formation}, volume = {147}, year = {2025}, }
• (2025). Deep-red and ultrafast photocatalytic proximity labeling empowered in situ dissection of tumor-immune interactions in primary tissues. JACS, 147(11), 9716--9726. (www)

  @article{ , abstract = {Immunotherapy efficacy in solid tumors varies greatly, influenced by the tumor microenvironment (TME) and the dynamic tumor-immune interactions within it. Decoding these interactions in situ with minimal interference with native tissue architecture and delicate immune responses is critical for understanding tumor progression and optimizing therapeutic strategies. Here, we introduce CAT-Tissue, a novel deep-red photocatalytic proximity labeling method that enables ultrafast, high-resolution profiling of tumor-immune interactions in primary tissues. By leveraging nanobody-Chlorin e6 as the photocatalyst and biotin-aniline as the probe, CAT-Tissue enabled the rapid and comprehensive detection of various tumor-immune interactions in both coculture systems and primary tumor sections. Coupled with bulk RNA-sequencing, CAT-Tissue revealed distinct gene expression patterns between tumor-neighboring and tumor-distal lymphocytes, highlighting the recognition and immune responses of tumor-neighboring CD8 + T cells, which exhibited activated, effector, and exhausted phenotypes. By leveraging a deep-red photocatalytic proximity cell labeling strategy with excellent tissue penetration and biocompatibility, CAT-Tissue offers a nongenetically encoded platform with high sensitivity and spatiotemporal controllability for rapid profiling tumor-immune interactions within complex tissue environments in situ , which may advance our understanding of tumor immunology and guide the development of more effective immunotherapies.}, archive = {J_JACS}, author = {Zhizheng Lou and Yan Zhang and Xuan Liang and Mengrui Cao and Yicong Ma and Peng R. Chen and Xinyuan Fan}, doi = {10.1021/jacs.4c17879}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9716--9726}, shortjournal = {J. Am. Chem. Soc.}, title = {Deep-red and ultrafast photocatalytic proximity labeling empowered in situ dissection of tumor-immune interactions in primary tissues}, volume = {147}, year = {2025}, }
• (2025). Extreme pH tolerance in peptide coacervates mediated by multivalent hydrogen bonds for enzyme-triggered oral drug delivery. JACS, 147(11), 9704--9715. (www)

  @article{ , abstract = {Biopolymer-based complex coacervates hold promising prospects in the field of biomedicine. However, their low stability in environments with extreme pH and high salt concentrations, largely due to weakly charged biomacromolecules and insufficient understanding of their assembly processes, has hindered their practical applications in oral drug delivery. Here, we have developed Dopa-containing peptide-based complex coacervates that are stable across a wide range of pH (1–11) and salt concentrations. Large-scale all-atom molecular dynamics simulations reveal that multivalent hydrogen bonds control the assembly pathway of the coacervates and boost their stability. Systematic point mutations reveal that various multivalent molecular interactions can synergistically tune the properties of complex coacervates. Such peptide coacervates show high drug encapsulation efficacy and trypsin-triggered release, presenting great potential for oral drug delivery applications. Our multivalent hydrogen bond-mediated peptide coacervates provide new design principles of engineering functional coacervates for diverse applications.}, archive = {J_JACS}, author = {Shujun Chen and Guijin Zou and Qi Guo and Xuliang Qian and Haopeng Li and Huajian Gao and Jing Yu}, doi = {10.1021/jacs.4c17880}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9704--9715}, shortjournal = {J. Am. Chem. Soc.}, title = {Extreme pH tolerance in peptide coacervates mediated by multivalent hydrogen bonds for enzyme-triggered oral drug delivery}, volume = {147}, year = {2025}, }
• (2025). Unlocking the potential of palmierite oxides: High oxide ion conductivity via induced interstitial defects. JACS, 147(11), 9694--9703. (www)

  @article{ , abstract = {Hexagonal perovskite derivatives such as Ba 7 Nb 4 MoO 20 and Ba 3 NbMoO 8.5 have recently been reported to exhibit high oxide ion conductivity and have potential applications in next-generation solid oxide fuel cells. In contrast, Ba 3 V 2 O 8 and Sr 3 V 2 O 8 that crystallize with the structurally related palmierite structure show oxide ion conductivities orders of magnitude lower. Here we use design principles to enhance the oxide ion conductivity in palmierites. By replacing V 5+ with two cations that are known to display flexible coordination (Mo 6+ and Ti 4+ ) and manipulating the ratio of Mo 6+ :Ti 4+ to insert interstitial oxygen, a high oxide ion conductivity of 3.96 × 10 –3 S cm –1 at 600 °C is observed in Ba 3 Ti 0.9 Mo 1.1 O 8.1 , two orders of magnitude higher than previously reported in palmierites. The oxide ion conductivity of Ba 3 Ti 0.9 Mo 1.1 O 8.1 is also higher than that previously reported for both Ba 7 Nb 4 MoO 20 and Ba 3 NbMoO 8.5 at 600 °C. Introducing interstitial oxygen into the [BaO 2+ x ] layer results in a change in the oxide ion transport from a cog-wheel type motion to an interstitialcy mechanism, demonstrating that palmierites are flexible to doping strategies via the introduction of either vacancies or oxide ion interstitials.}, archive = {J_JACS}, author = {Dylan N. Tawse and Sacha Fop and John W. Still and Oscar J. B. Ballantyne and Clemens Ritter and Ying Zhou and James A. Dawson and Abbie C. Mclaughlin}, doi = {10.1021/jacs.4c17849}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9694--9703}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking the potential of palmierite oxides: High oxide ion conductivity via induced interstitial defects}, volume = {147}, year = {2025}, }
• (2025). Chiral-polar photovoltage-driven efficient self-powered circularly polarized light detection in three-dimensional hybrid perovskites. JACS, 147(11), 9686--9693. (www)

  @article{ , abstract = {The chiral-polar photovoltaic effect (CPPE), widely present in chiral hybrid perovskites, has brought an unprecedented opportunity for self-powered circularly polarized light (CPL) detection. However, on account of spatial limitations of the crystal structure, currently reported CPPE primarily focuses on low-dimensional hybrid perovskites, which have a low CPL photoresponse restricted by lower carrier transport efficiency compared to three-dimensional perovskites. For the first time, we reported chiral-polar photovoltage-driven efficient self-powered CPL detection in three-dimensional chiral-polar perovskites, MHyPbBr 3 (MHy = Methylhydrazinium). Coupled with significant spontaneous polarization (17.1 μC cm –2 ) and superior semiconductor properties, MHyPbBr 3 exhibits a large mobility-lifetime product (1.9 × 10 –2 cm 2 V –1 ) and stable bulk photovoltage (3.9 V). Furthermore, the devices indicate significant chiral-polar photovoltage for self-powered CPL detection with a robust angle anisotropy factor of 0.39. More importantly, benefiting from excellent carrier transport performance, high responsivity and detectivity values of up to 39.2 mA W –1 and 5.8 × 10 12 Jones, respectively, are presented at zero bias, which fall around the highest values of hybrid perovskites. This work will contribute to the research of novel chiral-polar three-dimensional hybrid perovskite semiconductors and promote their application in efficient self-powered CPL detection.}, archive = {J_JACS}, author = {Chengshu Zhang and Zhenyue Wu and Wanning Zhang and Qianwen Guan and Huang Ye and Ruiqing Li and Hang Li and Zeng-Kui Zhu and Peng Wang and Yifei Wang and Yuxi Fang and Junhua Luo}, doi = {10.1021/jacs.4c17796}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9686--9693}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral-polar photovoltage-driven efficient self-powered circularly polarized light detection in three-dimensional hybrid perovskites}, volume = {147}, year = {2025}, }
• (2025). Photochemistry of receptor-bound flavin resolved in living human cells by infrared spectroscopy. JACS, 147(11), 9676--9685. (www)

  @article{ , abstract = {In-cell experiments on proteins have revealed that the cellular environment can exert a considerable influence on protein mechanism and structure. Here, we introduce in-cell infrared difference spectroscopy (ICIRD) as a method to study soluble receptors in living human embryonic kidney cells by applying the attenuated total reflection approach. We demonstrate on the sensory domains of plant cryptochrome and aureochrome1a, a light, oxygen, or voltage (LOV) protein, that experiments can be performed using stable and transient transfection. Cells were cultivated and transfected on an internal reflection element directly inside the spectrometer, while their viability and growth were monitored in situ by infrared spectroscopy. Using ICIRD, we then resolved the photoreactions of oxidized flavin to the flavin neutral radical in cryptochrome and to the flavin–cysteine adduct in LOV inside eukaryotic cells, to our knowledge for the first time, and thus confirmed their photochemical mechanisms in living human cells. However, we observed for LOV a significant upshift in signals of the carbonyl stretching modes of oxidized flavin and cysteine adduct compared to in vitro measurements, which could not be rationalized by effects of molecular crowding, dehydration, or temperature. Accordingly, we identified a strong impact of the eukaryotic cellular environment on the hydrogen bonding network and structure of flavin in LOV, which needs to be considered in physiology and optogenetic applications. In conclusion, we introduce ICIRD as a noninvasive, label-free approach to study soluble photoactivatable receptors in mammalian cells and provide insight into the in-cell mechanisms of two photoreceptors.}, archive = {J_JACS}, author = {Lukas Goett-Zink and Lennard Karsten and Charlotte Mann and Hendrik Horstmeier and Jonas Spang and Kristian M. Müller and Tilman Kottke}, doi = {10.1021/jacs.4c17815}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9676--9685}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemistry of receptor-bound flavin resolved in living human cells by infrared spectroscopy}, volume = {147}, year = {2025}, }
• (2025). A phototautomeric 3D covalent organic framework for ratiometric fluorescence humidity sensing. JACS, 147(11), 9665--9675. (www)

  @article{ , abstract = {Photoinduced proton transfer is an essential photochemical process for designing photocatalysts, white light emitters, bioimaging, and fluorescence sensing materials. However, deliberate control of the excited/ground states and meticulous manipulation of the excited state intramolecular proton transfer (ESIPT) pathway constitute a significant challenge in liquids and dense solids. Here, we present the integration of a hydronaphthoquinone fluorophore into a crystalline, porous, phototautomeric dynamic 3D covalent organic framework (COF) to show guest-induced fluorescence turn-on, emission redshift enhancement, and shortened lifetimes for ratiometric fluorescence humidity sensing. Theoretical and spectroscopic studies provide mechanistic insights into the conformational dynamics, charge transfer coupled with local excitation, and ground-state uphill regulation for the multiple tautomers. We illustrate the sensitive, rapid, steady, and self-calibrated ratiometric fluorescence sensing for a wide range of humidity benefiting from the architectural and chemical robustness and crystallinity of such a phototautomeric 3D COF. These findings provide molecular insights into the design of functional porous materials that integrate host–guest mutual recognition and photoelectronic response for multiplex molecular sensing for environmental monitoring and biomedical diagnostics applications.}, archive = {J_JACS}, author = {Xuan Yao and Youchang Zhang and Yu Qiu and Wentao Jiang and Hao Chen and Tengwu Zeng and Lei Wei and Shan Jiang and Yingbo Zhao and Yanhang Ma and Yue-Biao Zhang}, doi = {10.1021/jacs.4c17776}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9665--9675}, shortjournal = {J. Am. Chem. Soc.}, title = {A phototautomeric 3D covalent organic framework for ratiometric fluorescence humidity sensing}, volume = {147}, year = {2025}, }
• (2025). NIR-responsive double closed-ring isomer of a diarylethene fused dimer synthesized by stepwise photochemical and oxidative cyclization reaction. JACS, 147(11), 9653--9664. (www)

  @article{ , abstract = {The double closed-ring isomer of a diarylethene fused dimer was synthesized by a combination of photochemical and oxidative cyclization reaction. The double closed-ring isomer of a diarylethene fused dimer has fixed π-conjugation in a rigid planar framework so that this compound has been long-desired. However, with respect to the photocyclization of a diarylethene dimer with strong electronic interaction, the second-step cyclization is known to be suppressed due to fast energy transfer into the closed-ring isomer generated in the first-step photocyclization. In this work, instead of photoisomerization, oxidative isomerization was applied for the second-step cyclization, where the oxidized state spontaneously underwent thermal cyclization by radical coupling at room temperature. The resulting double closed-ring isomer showed NIR absorption, owing to a widely extended π-conjugation throughout the entire molecule. The double closed-ring isomer underwent a ring-opening reaction forming the closed-open-ring isomer when exposed to NIR light despite having a very low quantum yield of approximately 10 –8 . As a result, the fused dimer exhibits reversible stepwise switching induced by photo- and redox stimuli in the UV–vis–NIR region.}, archive = {J_JACS}, author = {Kurumi Satake and Naoto Ootsuki and Kenji Higashiguchi and Kenji Matsuda}, doi = {10.1021/jacs.4c17757}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9653--9664}, shortjournal = {J. Am. Chem. Soc.}, title = {NIR-responsive double closed-ring isomer of a diarylethene fused dimer synthesized by stepwise photochemical and oxidative cyclization reaction}, volume = {147}, year = {2025}, }
• (2025). Off-equilibrium hydrothermal synthesis of high-entropy alloy nanoparticles. JACS, 147(11), 9640--9652. (www)

  @article{ , abstract = {High-entropy alloy (HEA) nanoparticles offer unique catalytic properties due to their complex surface coordination and widely tunable electronic structures. Conventional synthesis methods typically involve extreme thermal shock (∼1700 °C) to achieve metal coreduction and mixing. While wet-chemical approaches hold potential for controlling nanoparticle properties, they are hindered by disparities in metal reduction kinetics and a diminished influence of configurational entropy on metal mixing at low temperatures, leading to phase segregation and limited compositional tunability. In this work, we introduce a novel wet-chemical hydrothermal method that enables the synthesis of HEA nanoparticles with enhanced compositional homogeneity and precise property control at low temperatures (∼170 °C). This method utilizes in situ generation of active hydrogen (H • ) via organic dehydrogenation on nuclei/seed surfaces, creating localized off-equilibrium environments within the near-equilibrium wet-chemical system. These conditions mitigate the thermodynamic and kinetic limitations, enabling synchronized metal reduction, precise compositional tunability over a broad range, and improved alloy uniformity. As a proof of concept, we demonstrate the enhanced electrocatalytic methanol oxidation performance of PtCuNiCoFe HEA nanoparticles through surface composition design. This approach offers a robust platform for synthesizing HEA nanoparticles with tailored properties, expanding their catalytic applications.}, archive = {J_JACS}, author = {Zhixue Zhang and Peiping Yu and Zhaojun Liu and Kai Liu and Zerui Mu and Zhibin Wen and Junlin She and Yuke Bai and Qing Zhang and Tao Cheng and Chuanbo Gao}, doi = {10.1021/jacs.4c17756}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9640--9652}, shortjournal = {J. Am. Chem. Soc.}, title = {Off-equilibrium hydrothermal synthesis of high-entropy alloy nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Electron transfer energetics in photoelectrochemical CO2 reduction at viologen redox polymer-modified p-si electrodes. JACS, 147(11), 9629--9639. (www)

  @article{ , abstract = {While redox polymer-mediated catalysis at silicon photoelectrodes has been studied since the 1980s, there have been few detailed studies of these materials in photoelectrochemical CO 2 reduction. Here, we develop silicon photoelectrodes functionalized with a viologen-based polymer that mediates the formation of catalytic gold nanoparticles. The presence of gold was confirmed by X-ray photoelectron spectroscopy (XPS), and the nanoparticles were imaged with high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM). We probed the CO 2 reduction process during bulk photoelectrolysis to find modest, yet consistent CO faradaic efficiencies across a range of applied potentials. Operando surface-enhanced Raman spectroscopy (SERS) was used to measure the Fermi levels of both the viologen polymer and the Au catalyst sites. The operando measurement of the Fermi levels of all three components of the photocathode provides a unified picture of the electron transfer process in the semiconductor-redox polymer–catalyst system. The redox polymer serves as the electron transfer mediator between the Si substrate and Au sites. In addition, the Au Fermi level equilibrates with the Fermi level of the viologen polymer, which in turn fixes the quasi-Fermi level of Au catalysts at the p-Si/redox polymer interface. This suggests a potential future direction of using redox polymers with tunable potentials to modulate the potential of metal cocatalysts and thus control the reaction selectivity.}, archive = {J_JACS}, author = {Colton J. Sheehan and Sa Suo and Sungho Jeon and Yunchangxiang Zheng and Jinhui Meng and Fengyi Zhao and Zhicheng Yang and Langqiu Xiao and Srikar Venkatesan and Amy S. Metlay and Carrie L. Donley and Eric A. Stach and Tianquan Lian and Thomas E. Mallouk}, doi = {10.1021/jacs.4c17762}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9629--9639}, shortjournal = {J. Am. Chem. Soc.}, title = {Electron transfer energetics in photoelectrochemical CO2 reduction at viologen redox polymer-modified p-si electrodes}, volume = {147}, year = {2025}, }
• (2025). Deciphering the competitive charge storage chemistry of metal cations and protons in aqueous MnO2-based supercapacitors. JACS, 147(11), 9620--9628. (www)

  @article{ , abstract = {The complex charge storage mechanisms in aqueous MnO 2 -based supercapacitors have posed significant challenges to a comprehensive understanding of their chemical behavior. In this study, we employed Au-core@MnO 2 -shell nanoparticle-enhanced Raman spectroscopy, alongside electrochemical analysis and X-ray absorption, to systematically investigate the competitive charge storage chemistry of protons and cations within the inner and outer layers of δ-MnO 2 under alkaline conditions. Our findings reveal that δ-MnO 2 operates through a dual mechanism: the intercalation and deintercalation of metal cations dominate charge storage in the inner layer, while surface chemisorption of protons governs the outer layer. Notably, cation insertion induces an irreversible phase transition from MnO 2 to Mn 2 O 3 , whereas the surface redox process involves a reversible transformation among MnO 2 , MnOOH, and Mn(OH) 2 . Additionally, spectral evidence, supported by ab initio molecular dynamics simulations, elucidates the structural changes of interfacial water associated with proton-mediated charge storage in the outer layer. Electrochemical analysis further demonstrates that surface charge storage, primarily mediated by a proton-coupled electron transfer mechanism, is the dominant contributor to the overall capacitance. This work not only advances the molecular-level understanding of electrochemical processes in MnO 2 -based supercapacitors but also highlights the potential for optimizing surface proton-coupled electron transfer mechanisms to enhance capacitive performance.}, archive = {J_JACS}, author = {Huajie Ze and Xue-Ting Fan and Zhi-Lan Yang and Xingyu Ding and Yao-Lin A and Xiaojian Wen and Yi Zhang and Freddy E. Oropeza and Kelvin H. L. Zhang and Yu Gu and Yue-Jiao Zhang and Jun Cheng and Jian-Feng Li}, doi = {10.1021/jacs.4c17458}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9620--9628}, shortjournal = {J. Am. Chem. Soc.}, title = {Deciphering the competitive charge storage chemistry of metal cations and protons in aqueous MnO2-based supercapacitors}, volume = {147}, year = {2025}, }
• (2025). Spatial profiling of multiple enzymatic activities at single tissue sections via fenton-promoted electrochemiluminescence. JACS, 147(11), 9610--9619. (www)

  @article{ , abstract = {Profiling multiple enzymatic activities in tissue is crucial for understanding complex metabolic and signaling networks, yet remains a challenge with existing optical microscopies. Here, we developed a Fenton-promoted luminol electrochemiluminescence (ECL) imaging method to achieve the spatial mapping of multiple enzymatic activities within a single tissue section. This method quantitatively visualizes individual enzymatic activity by combining the enzymatic conversion of substrates with the chemical confinement of the locally produced hydrogen peroxide. To achieve high-resolution spatial imaging by limiting the diffusion (∼500 μm) of hydrogen peroxide, iron oxide nanoparticles were coated on the tissue surface to initiate the Fenton process, locally converting hydrogen peroxide into short-lived hydroxyl radicals with a nanometer-scale diffusion range. The Fenton-promoted ECL emission is confined at the enzymatic conversion sites, offering unprecedented spatial visualization of four tumor-associated oxidases within a single tissue section. Colocalization revealed a synergistic effect between lysyl oxidase and quiescin sulfhydryl oxidase on post-translational modifications of tumor extracellular matrix proteins, along with a previously undiscovered interaction with amiloride-sensitive amine oxidase, which could not be distinguished based on expressions or single enzymatic activity alone. This approach offers a novel activity-based protein profiling tool at the tissue level, providing new data for future enzynomic research and multimodal imaging.}, archive = {J_JACS}, author = {Dongni Han and Neso Sojic and Dechen Jiang}, doi = {10.1021/jacs.4c17749}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9610--9619}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatial profiling of multiple enzymatic activities at single tissue sections via fenton-promoted electrochemiluminescence}, volume = {147}, year = {2025}, }
• (2025). Unraveling dynamic structural evolution of single atom catalyst via in situ surface-enhanced infrared absorption spectroscopy. JACS, 147(11), 9601--9609. (www)

  @article{ , abstract = {Metal–nitrogen-carbon (M–N-C) single-atom catalysts (SACs) have been widely applied in catalyzing electrochemical redox reactions. However, their long-term catalytic stabilities greatly limit their practical applications. This work investigates the dynamic evolution of two model Cu–N–C SACs with different Cu–N coordinations, namely the Cu 1 /N pyri -C and Cu 1 /N pyrr -C, in electrochemical CO reduction reaction (CORR), based on a collection of in situ characterizations including in situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy, in situ X-ray absorption spectroscopy, quasi-in situ electron paramagnetic resonance spectroscopy and in situ ultraviolet–visible spectroscopy, complemented by theoretical calculations. Our findings reveal that the Cu nanoparticle formation rate over Cu 1 /N pyrr -C is more than 6 times higher than that over Cu 1 /N pyri -C during the electrochemical CORR. Quasi-in situ electron paramagnetic resonance and in situ UV–vis spectroscopy measurements demonstrate that hydrogen radicals can be in situ produced during electrochemical CORR, which will attack the Cu–N bonds in the Cu–N–C SACs, causing leaching of Cu 2+ followed by subsequent reduction to form Cu nanoparticles. Kinetic calculations show that Cu 1 /N pyri -C displays a better catalytic stability than Cu 1 /N pyrr -C resulting from the stronger Cu–N pyri bonds. This study deepens the understanding of the deactivation mechanism of SACs in electrochemical reactions and provides guidance for the design of next-generation SACs with enhanced durability.}, archive = {J_JACS}, author = {Jie Ding and Lingyue Liu and Jian Zhang and Yuhang Liu and Hao Xu and Zheng Shen and Hong Bin Yang and Xinliang Feng and Yanqiang Huang and Bin Liu}, doi = {10.1021/jacs.4c17565}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9601--9609}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling dynamic structural evolution of single atom catalyst via in situ surface-enhanced infrared absorption spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Nanocluster-induced liquid-like precursor formation and crystallization: In situ visualization and 3D reconstruction. JACS, 147(11), 9590--9600. (www)

  @article{ , abstract = {Revealing the crystallization mechanism of inorganic materials modulated by organic molecules has broad implications in biomineralization, crystallography, and materials science. However, directly visualizing the participation of organic molecules in the inorganic materials’ crystallization process remains a significant challenge. Here, we introduce carboxyl-functionalized gold nanoclusters (Au NCs) as an alternative to polymers for investigating CaCO 3 crystallization via the transient “Au NCs-induced liquid precursor” phase, similar to “polymer-induced liquid precursor”. Exploiting the ultrasmall size, high density, and stable spontaneous fluorescence properties of Au NCs, this approach enables direct in situ observation of liquid precursor formation and dynamic association/dissociation using light microscopy. Results show that Au NCs are incorporated into the liquid precursor and the quantity of liquid precursor exhibits a nearly linear increase over time until the depletion of free Ca 2+ ions in solution due to crystallization of calcite. Subsequently, the dissolution of the liquid precursor provides ions for further crystal growth. The occlusion and 3D spatial distribution of Au NCs within CaCO 3 throughout the crystallization process can also be visualized using confocal fluorescence microscopy, demonstrating preferential adsorption on specific lattice planes of CaCO 3 . This study substantially enhances our comprehension of the differential growth rates of various crystallographic faces and the spatial distribution of Au NCs within the crystals.}, archive = {J_JACS}, author = {Jin Chen and Guanbin Gao and Zijun Zhang and Taolei Sun and Zhengyi Fu and Zhaoyong Zou}, doi = {10.1021/jacs.4c17643}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9590--9600}, shortjournal = {J. Am. Chem. Soc.}, title = {Nanocluster-induced liquid-like precursor formation and crystallization: In situ visualization and 3D reconstruction}, volume = {147}, year = {2025}, }
• (2025). Triazination/IEDDA cascade modular strategy installing Pyridines/Pyrimidines onto tyrosine enables peptide screening and optimization. JACS, 147(11), 9576--9589. (www)

  @article{ , abstract = {Modular chemical postmodification of peptides is a promising strategy that supports the optimization and innovation of hit peptide therapeutics by enabling rapid derivatization. However, current methods are primarily limited to traditional bio-orthogonal strategies and chemical ligation techniques, which require the preintroduction of non-natural amino acids and impose fixed methods that limit peptide diversity. Here, we developed the Tyrosine-1,2,3-Triazine Ligation (YTL) strategy, which constructs novel linkages (pyridine and pyrimidine) through a “one-pot, two-step” process combining S N Ar and IEDDA reactions, promoting modular post modification of Tyr-containing peptides. After optimizing the YTL strategy and establishing standard procedures, we successfully applied it to the solid-phase postmodification of various biorelated peptides, such as the synthesis of dual-mode imaging probes and long-acting GLP-1 analogs. As a proof of concept, a library of 384 amphipathic peptides was constructed using YTL based on 96-well microfiltration plates. Modular modifications were then performed on the screened template tripeptide RYR, leading to the generation of 20 derivatives. The antibacterial activity of these derivatives was systematically characterized, identifying Z8 as a potential antibacterial candidate.}, archive = {J_JACS}, author = {Quan Zuo and Xinyi Song and Jie Yan and Guangjun Bao and Yiping Li and Jieting Shen and Zeyuan He and Kuan Hu and Wangsheng Sun and Rui Wang}, doi = {10.1021/jacs.4c17615}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9576--9589}, shortjournal = {J. Am. Chem. Soc.}, title = {Triazination/IEDDA cascade modular strategy installing Pyridines/Pyrimidines onto tyrosine enables peptide screening and optimization}, volume = {147}, year = {2025}, }
• (2025). Kinetics of concurrent seed growth and cation exchange in transforming cu2-xS nanocrystals to CuGaS2 nanorods. JACS, 147(11), 9566--9575. (www)

  @article{ , abstract = {Cation exchange can convert nanocrystals that have already been achieved with a well-controlled size, size distribution, and shape to a broad range of compositions. However, cation exchange can often be accompanied by changes in the nanocrystal morphology/shape as exemplified by the synthesis of I–III–VI 2 nanocrystals. We examine the temperature-dependent kinetics of concurrently occurring seed epitaxial growth and cation exchange that convert nearly spherical Cu 2– x S seeds into CuGaS 2 nanorods with varying lengths and degrees of tapering. A simple model is developed to quantify and explain experimentally observed reaction kinetics. Direct epitaxial growth of Cu 2– x S seeds occurs with an activation energy of 96 kJ/mol, while cation exchange to convert the growing seed to CuGaS 2 requires overcoming a 202 kJ/mol energy barrier. Understanding how each reaction rate evolves over time provides insights into the tapering mechanism and a means of predicting when the onset of tapering occurs. The predicted onset is then exploited to synthesize nanorods with a minimized tapering. Our findings provide the basis for developing precise control over the composition and morphology of nanocrystals synthesized through a combination of cation exchange and solution epitaxy.}, archive = {J_JACS}, author = {Yunpei Duan and Moonsub Shim}, doi = {10.1021/jacs.4c17582}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9566--9575}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetics of concurrent seed growth and cation exchange in transforming cu2-xS nanocrystals to CuGaS2 nanorods}, volume = {147}, year = {2025}, }
• (2025). Coherent vibrational dynamics in an isolated peptide captured with two-dimensional infrared spectroscopy. JACS, 147(11), 9556--9565. (www)

  @article{ , abstract = {Quantum mechanical vibrational coherence transfer processes play important roles in energy relaxation, charge transfer, and reaction dynamics in chemical and biological systems but are difficult to directly measure using traditional condensed-phase nonlinear spectroscopies. Recently, we developed a new experimental capability to obtain two-dimensional infrared (2D IR) spectra of molecular systems in the gas phase that enables the direct measurement of coherence pathways. Herein, we report ultrafast 2D IR spectroscopy of the peptide glutathione (GSH) isolated and cryogenically cooled in the gas phase. Six vibrational modes were simultaneously excited within the amide I and II region. The spectral dynamics of both diagonal and off-diagonal cross peak features exhibit long-lived oscillatory behavior consistent with the presence of coherent vibrational dynamics. The oscillatory signatures deviate significantly from the expected quantum beating pathways predicted from standard nonlinear response theories. These deviations indicate the presence of additional nonlinear pathways, including coherence transfer processes. Quantum chemistry calculations indicate large anharmonic couplings between the excited vibrational modes in GSH and, critically, strong coupling between the excited modes and numerous low-frequency modes that act as a bath to mediate coherence transfer. The data provide important new benchmarks for modeling coherence transfer dynamics and system–bath interactions in open quantum systems free from solvent effects.}, archive = {J_JACS}, author = {Zifan Ma and Laura M. McCaslin and Joseph A. Fournier}, doi = {10.1021/jacs.4c17464}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9556--9565}, shortjournal = {J. Am. Chem. Soc.}, title = {Coherent vibrational dynamics in an isolated peptide captured with two-dimensional infrared spectroscopy}, volume = {147}, year = {2025}, }
• (2025). LoreX: A low-energy region explorer boosts efficient crystal structure prediction. JACS, 147(11), 9544--9555. (www)

  @article{ , abstract = {Machine learning has boosted the remarkable development of crystal structure prediction (CSP), greatly accelerating modern materials design. However, slow location of the low-energy regions on the potential energy surface (PES) is still a key bottleneck for the overall search efficiency. Here, we develop a low-energy region explorer (LoreX) to rapidly locate low-energy regions on the PES. This achievement stems from graph-deep-learning-based PES slicing, which classifies structures into different prototypes to divide and conquer the PES. The accuracy and efficiency of LoreX are validated on 27 typical compounds, showing that it correctly locates low-energy regions with only 100 selected samples. The powerful capability of LoreX is demonstrated in solving two challenging problems: discovering new boron allotropes and identifying the puzzling crystal structures of the ordered vacancy compound CuIn 5 Se 8 . This study establishes a new method for rapid PES exploration and offers a highly efficient and generally applicable approach to accelerating CSP.}, archive = {J_JACS}, author = {Chuan-Nan Li and Han-Pu Liang and Siyuan Xu and Haochen Wang and Bai-Qing Zhao and Jingxiu Yang and Xie Zhang and Zijing Lin and Su-Huai Wei}, doi = {10.1021/jacs.4c17343}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9544--9555}, shortjournal = {J. Am. Chem. Soc.}, title = {LoreX: A low-energy region explorer boosts efficient crystal structure prediction}, volume = {147}, year = {2025}, }
• (2025). Halogen bond strength in solids quantified via zeeman-perturbed nuclear quadrupole resonance spectroscopy. JACS, 147(11), 9528--9543. (www)

  @article{ , abstract = {Proton NMR is a ubiquitous and valuable probe of hydrogen bonds. Conversely, 127 I NMR of strong halogen bond (XB) donors is hopeless due to quadrupolar coupling constants ( C Q ) on the order of GHz. We report here an innovative implementation of Zeeman-perturbed nuclear quadrupole resonance (Zp-NQR) spectroscopy, employing adjustable magnetic fields on the order of mT, which renders possible the acquisition and analysis of spectra of 127 I and 79 Br nuclei subject to quadrupolar couplings of up to 2.3 GHz in solid powders. This approach is demonstrated on three series of halogen-bonded cocrystals based on so-called “iconic” strong XB donors p -diiodotetrafluorobenzene, sym -trifluorotriiodobenzene, and p -dibromotetrafluorobenzene (27 compounds). Analysis of the spectra using a diagonalization of the Zeeman-quadrupolar Hamiltonian provides C Q values and quadrupolar asymmetry parameters, thereby overcoming various limitations encountered in pure NMR and pure NQR. Inspection of the data reveals strong correlations with geometrical and structural features of the halogen bond, including its length. Dispersion-corrected zeroth-order regular approximation relativistic DFT computations of the interaction energies of the XB donor are strongly correlated with experimental and computed values of C Q ( 127 I) and C Q ( 79 Br). It is concluded that the electric field gradient at the XB donor site is a useful metric for quantifying XB strength in solids. The XB interaction energies range from ∼5 to 10 kcal mol –1 for the systems studied herein. The Zp-NQR approach is amenable to widespread application to diverse problems in the chemical and materials sciences related to energy materials, crystal engineering, and many systems comprising strongly quadrupolar isotopes.}, archive = {J_JACS}, author = {Alireza Nari and Mubassira Rahman and Patrick M. J. Szell and Volodymyr Semeniuchenko and David L. Bryce}, doi = {10.1021/jacs.4c17321}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9528--9543}, shortjournal = {J. Am. Chem. Soc.}, title = {Halogen bond strength in solids quantified via zeeman-perturbed nuclear quadrupole resonance spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Fabrication of functional 3D nanoarchitectures via atomic layer deposition on DNA origami crystals. JACS, 147(11), 9519--9527. (www)

  @article{ , abstract = {While DNA origami is a powerful bottom-up fabrication technique, the physical and chemical stability of DNA nanostructures is generally limited to aqueous buffer conditions. Wet chemical silicification can stabilize these structures but does not add further functionality. Here, we demonstrate a versatile three-dimensional (3D) nanofabrication technique to conformally coat micrometer-sized DNA origami crystals with functional metal oxides via atomic layer deposition (ALD). In addition to depositing homogeneous and conformal nanometer-thin ZnO, TiO 2 , and IrO 2 (multi)layers inside SiO 2 -stabilized crystals, we establish a method to directly coat bare DNA crystals with ALD layers while maintaining the crystal integrity, enabled by critical point drying and low ALD process temperatures. As a proof-of-concept application, we demonstrate electrocatalytic water oxidation using ALD IrO 2 -coated DNA origami crystals, resulting in improved performance relative to that of planar films. Overall, our coating strategy establishes a tool set for designing custom-made 3D nanomaterials with precisely defined topologies and material compositions, combining the unique advantages of DNA origami and atomically controlled deposition of functional inorganic materials.}, archive = {J_JACS}, author = {Arthur Ermatov and Melisande Kost and Xin Yin and Paul Butler and Mihir Dass and Ian D. Sharp and Tim Liedl and Thomas Bein and Gregor Posnjak}, doi = {10.1021/jacs.4c17232}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9519--9527}, shortjournal = {J. Am. Chem. Soc.}, title = {Fabrication of functional 3D nanoarchitectures via atomic layer deposition on DNA origami crystals}, volume = {147}, year = {2025}, }
• (2025). Electrochemical N–N oxidatively coupled dehydrogenation of 3,5-diamino-1H-1,2,4-triazole for value-added chemicals and bipolar hydrogen production. JACS, 147(11), 9505--9518. (www)

  @article{ , abstract = {Electrochemical H 2 production from water favors low-voltage molecular oxidation to replace the oxygen evolution reaction as an energy-saving and value-added approach. However, there exists a mismatch between the high demand for H 2 and slow anodic reactions, restricting practical applications of such hybrid systems. Here, we propose a bipolar H 2 production approach, with anodic H 2 generation from the N–N oxidatively coupled dehydrogenation (OCD) of 3,5-diamino-1 H -1,2,4-triazole (DAT), in addition to the cathodic H 2 generation. The system requires relatively low oxidation potentials of 0.872 and 1.108 V vs RHE to reach 10 and 500 mA cm –2 , respectively. The bipolar H 2 production in an H-type electrolyzer requires only 0.946 and 1.129 V to deliver 10 and 100 mA cm –2 , respectively, with the electricity consumption (1.3 kWh per m 3 H 2 ) reduced by 68%, compared with conventional water splitting. Moreover, the process is highly appealing due to the absence of traditional hazardous synthetic conditions of azo compounds at the anode and crossover/mixing of H 2 /O 2 in the electrolyzer. A flow-type electrolyzer operates stably at 500 mA cm –2 for 300 h. Mechanistic studies reveal that the Pt single atom and nanoparticle (Pt 1,n ) optimize the adsorption of the S active sites for H 2 production over the Pt 1,n @VS 2 cathodic catalysts. At the anode, the stepwise dehydrogenation of −NH 2 in DAT and then oxidative coupling of −N–N– predominantly form azo compounds while generating H 2 . The present report paves a new way for atom-economical bipolar H 2 production from N–N oxidative coupling of aminotriazole and green electrosynthesis of value-added azo chemicals.}, archive = {J_JACS}, author = {Jiachen Li and Yang Li and Yuqiang Ma and Zihang Zhao and Huarong Peng and Tao Zhou and Ming Xu and Daidi Fan and Haixia Ma and Jieshan Qiu and Zhengxiao Guo}, doi = {10.1021/jacs.4c17225}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9505--9518}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical N–N oxidatively coupled dehydrogenation of 3,5-diamino-1H-1,2,4-triazole for value-added chemicals and bipolar hydrogen production}, volume = {147}, year = {2025}, }
• (2025). Bacteria-mediated intracellular radical polymerizations. JACS, 147(11), 9496--9504. (www)

  @article{ , abstract = {Intracellular radical polymerizations allow for the direct bioorthogonal synthesis of various synthetic polymers within living cells, thereby providing a pathway to polymer-modified cells or the fermentative production of polymers. Here, we show that Escherichia coli cells can initiate the polymerization of various acrylamide, acrylic, and methacrylic monomers through an atom transfer radical reaction triggered by the activity of naturally occurring biomolecules within the bacterial cells. Intracellular radical polymerizations were confirmed by nuclear magnetic resonance spectroscopy, gel permeation chromatography of polymers extracted from the cells, and fluorescence labeling of the polymer directly inside the cells. The effect of polymerization on cell behavior and the response of the cells to polymerization was investigated through fluorescence microscopy and flow cytometry techniques, as well as metabolic and membrane integrity assays. The polymer synthesis and resulting products are cell-compatible, as indicated by the high viability of the polymerized cells. In cellulo synthesis of synthetic polymers containing fluorescent dyes was also achieved. These results not only enhance our understanding of the untapped potential of bacterial cells as living catalysts for polymer production but also reveal intracellular polymerization based on atom transfer radical polymerization initiators as a bioorthogonal tool for cell engineering and synthetic biology.}, archive = {J_JACS}, author = {Eleonora Ornati and Jules Perrard and Tobias A. Hoffmann and Raissa Bonon and Nico Bruns}, doi = {10.1021/jacs.4c17257}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9496--9504}, shortjournal = {J. Am. Chem. Soc.}, title = {Bacteria-mediated intracellular radical polymerizations}, volume = {147}, year = {2025}, }
• (2025). Kinetically trapped nanocrystals with symmetry-preserving shapes. JACS, 147(11), 9487--9495. (www)

  @article{ , abstract = {The shape of nanocrystals is crucial in determining their surface area, reactivity, optical properties, and self-assembly behavior. Traditionally, shape control has been achieved through empirical methods, highlighting the need for a more refined theoretical framework. A comprehensive model should account for the kinetic factors at distinct stages of the shape formation process to identify the key determinants of nanocrystal morphology. By modulating kinetics at terraces, ledges, and kinks, we reveal that the primary factors are the adatom nucleation energies and the geometry of growth islands. Transient sites dominate the growth process, leading to kinetically trapped, metastable shapes. We illustrate these concepts with face-centered cubic nanocrystals, demonstrating diverse shape evolutions, including surface roughening and the preservation of crystal symmetry in cubes, octahedra, rhombic dodecahedra, and their truncated variants. This study reveals the mechanisms driving the formation of cubic nanocrystal shapes and offers guidance for their precise synthesis.}, archive = {J_JACS}, author = {Carlos L. Bassani and Michael Engel}, doi = {10.1021/jacs.4c17157}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9487--9495}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetically trapped nanocrystals with symmetry-preserving shapes}, volume = {147}, year = {2025}, }
• (2025). Improving aptamer affinity and determining Sequence–Activity relationships via motif-SELEX. JACS, 147(11), 9472--9486. (www)

  @article{ , abstract = {The affinity of nucleic acid aptamers isolated in vitro via Systematic Evolution of Ligands by Exponential Enrichment (SELEX) is often limited because the entire potential sequence space cannot be screened. In this study, we introduce Motif-SELEX, a novel method that enables the optimization of existing underperforming aptamers by generating libraries that broadly represent both the sequence and length variations of the parent sequence. This approach enables the isolation of sequences with improved affinity without the biases and limitations of traditional mutagenesis methods like doped SELEX and error-prone PCR. As a demonstration, we applied Motif-SELEX to a DNA-based morphine aptamer and a 2′ fluoro- and methoxy-RNA-based apixaban aptamer, discovering new, better-performing sequences with differing random domain lengths from their parents and up to 10-fold improvements in affinity. These new sequences would be inaccessible to traditional post-SELEX methods. Critically, our analysis of Motif-SELEX pools also enabled us to identify sequence and structural elements crucial for target binding and to predict secondary and tertiary structures for a given aptamer family─even when those structures involve noncanonical nucleotide interactions. We believe that Motif-SELEX offers an effective and generalizable solution for optimizing the structure and binding properties of functional nucleic acid molecules for diverse applications.}, archive = {J_JACS}, author = {Haixiang Yu and Juan Canoura and Caleb Byrd and Obtin Alkhamis and Adara Bacon and Amy Yan and Bruce A Sullenger and Yi Xiao}, doi = {10.1021/jacs.4c17041}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9472--9486}, shortjournal = {J. Am. Chem. Soc.}, title = {Improving aptamer affinity and determining Sequence–Activity relationships via motif-SELEX}, volume = {147}, year = {2025}, }
• (2025). Convection-enhanced delivery of auristatin-conjugated layer-by-layer nanoparticles for glioblastoma treatment. JACS, 147(11), 9457--9471. (www)

  @article{ , abstract = {Glioblastoma (GBM) has limited treatment options, as the restrictive blood–brain barrier (BBB) prevents most therapeutics from accumulating at sufficient levels in the brain. Convection-enhanced delivery (CED) offers a method for administering therapeutics directly into brain tumor tissue, but free drugs can be cleared rapidly and may be toxic to off-target cells. Drug-loaded nanoparticles (NPs) are a promising platform to prolong the residence time and improve cellular targeting of therapeutics. We designed drug-conjugated NPs comprising a liposomal core modified with a layer-by-layer (LbL) polymer coating to promote tumor penetration, retention, and tumor-selective cellular association. Covalent conjugation of the potent microtubule inhibitor monomethyl auristatin-F (MMAF) to lipid headgroups resulted in striking potency against a range of patient-derived GBM cell lines compared to free MMAF and outperformed an EGFR-targeted antibody–drug conjugate of MMAF under clinical investigation. In vivo , a single CED infusion of LbL-functionalized MMAF NPs in orthotopic GBM-bearing mice displayed improved distribution and retention of both the NPs and the MMAF payload within the tumor. The LbL coating promotes selective uptake by GBM cells and prolongs drug retention, overcoming limitations of rapid clearance associated with traditional CED approaches. This treatment inhibited tumor progression and significantly extended survival compared to free MMAF, MMAF-conjugated liposomes, and an EGFR-MMAF antibody–drug conjugate. This NP platform offers a promising strategy for enhancing local GBM therapy by improving drug exposure within tumors while minimizing systemic toxicity.}, archive = {J_JACS}, author = {Andrew J. Pickering and Nicholas G. Lamson and Michael H. Marand and Joelle P. Straehla and Paula T. Hammond}, doi = {10.1021/jacs.4c16898}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9457--9471}, shortjournal = {J. Am. Chem. Soc.}, title = {Convection-enhanced delivery of auristatin-conjugated layer-by-layer nanoparticles for glioblastoma treatment}, volume = {147}, year = {2025}, }
• (2025). Cross-electrophile coupling to form sterically hindered C(sp2)–C(sp3) bonds: Ni and co afford complementary reactivity. JACS, 147(11), 9449--9456. (www)

  @article{ , abstract = {The formation of sterically hindered C(sp 2 )–C(sp 3 ) bonds could be a useful synthetic tool but has been understudied in cross-electrophile coupling. Here, we report two methods that couple secondary alkyl bromides with aryl halides that contain sterically hindered C–X bonds: 1) ortho -substituted aryl bromides with nickel catalysts and 2) di- ortho -substituted aryl iodides with cobalt catalysts. Stoichiometric experiments and deuterium labeling studies show that 1) [Co] is better than [Ni] for oxidative addition of di- ortho -substituted Ar–I and 2) [Co] is better than [Ni] for radical capture/reductive elimination steps with di- ortho -substituted arenes. For both metals, Ar–H side products observed in reactions with low-yielding di- ortho -substituted aryl iodides appear to arise from Ar• formation and hydrogen-atom transfer from the solvent. While the origins of the differences in scope are not yet understood, these studies demonstrate a previously unknown complementarity between nickel and cobalt in cross-electrophile coupling.}, archive = {J_JACS}, author = {Tianrui Wu and Anthony J. Castro and Kasturi Ganguli and Madeline E. Rotella and Ning Ye and Fabrice Gallou and Bin Wu and Daniel J. Weix}, doi = {10.1021/jacs.4c16912}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9449--9456}, shortjournal = {J. Am. Chem. Soc.}, title = {Cross-electrophile coupling to form sterically hindered C(sp2)–C(sp3) bonds: Ni and co afford complementary reactivity}, volume = {147}, year = {2025}, }
• (2025). Olefin metathesis in water: Speciation of a leading water-soluble catalyst pinpoints challenges and opportunities for chemical biology. JACS, 147(11), 9441--9448. (www)

  @article{ , abstract = {The metathetical modification of biomolecules in aqueous environments holds great promise for advances at the interface of chemistry, biology, and medicine. However, rapid degradation of the metathesis catalysts necessitates their use in large stoichiometric excess, resulting in undesired side-reactions promoted by the ruthenium products. Although water is now known to play a central role in catalyst decomposition, the elusive nature of the intermediates has hampered insight into the pathways involved. We describe the detailed speciation in water of AquaMet ( AM ), the dominant ruthenium catalyst used for aqueous metathesis, and implications for catalysis. Potentiometric and spectroscopic speciation studies reveal that only trace AM is present under the pH-neutral, salt-free conditions routinely employed in synthetic applications of aqueous metathesis. Instead, metathesis-inactive hydroxide species dominate. Even at pH 3, Ru–H 2 O complexes dominate in 0.01 M NaCl (aq) , and the water ligands are readily deprotonated as the pH is increased. Raising NaCl (aq) concentrations to 1 M suppresses deprotonation events below pH 8, stabilizing AM as the dominant solution species at neutral pH, and significantly expanding the metathesis-compatible regime. Hitherto unrecognized catalyst solubility issues are also revealed, pointing toward avenues for advance. More broadly, the capacity to directly link catalyst environment to structure and performance opens new opportunities for olefin metathesis in complex, water-rich settings.}, archive = {J_JACS}, author = {Christian O. Blanco and Samantha K. Cormier and Angus J. Koller and Eszter Boros and Deryn E. Fogg}, doi = {10.1021/jacs.4c16700}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9441--9448}, shortjournal = {J. Am. Chem. Soc.}, title = {Olefin metathesis in water: Speciation of a leading water-soluble catalyst pinpoints challenges and opportunities for chemical biology}, volume = {147}, year = {2025}, }
• (2025). Pistol ribozyme-driven catalytic spherical nucleic acid integrates gene and chemotherapy for enhanced cancer therapy. JACS, 147(11), 9424--9440. (www)

  @article{ , abstract = {Gene-targeted therapies are revolutionizing cancer treatment due to their high specificity and low toxicity. Among these, ribozymes hold promise as independent gene therapy agents capable of directly cleaving target mRNAs. The pistol ribozyme, discovered in 2015, stands out for its compact structure and robust cleavage activity, making it a promising candidate for RNA silencing under physiological conditions. However, its clinical application is limited by nuclease susceptibility and biological barrier penetration. To overcome these obstacles, this study presents an innovative gene-regulation strategy incorporating engineered pistol ribozymes into a spherical nucleic acid (SNA) nanocarrier. This catalytic SNA nanocarrier, built on a DNA core–shell framework, combines the ribozyme with doxorubicin (Dox) to form the ApRz-CS/Dox nanoplatform. The design of ApRz-CS/Dox features a homopolymerized DNA core and a reticular DNA shell, enhancing stability. Tumor-targeting aptamers are arranged on its surface, directing it specifically to cancer cells. Within the target cells, the ribozyme is released in response to overexpressed miR-21, facilitating the cleavage of polo-like kinase 1 mRNA. This integrated approach effectively combines gene therapy with the chemotherapeutic effects of Dox, addressing the challenges associated with the delivery of newly developed nucleic acid drugs and offering a promising strategy for enhanced cancer treatment.}, archive = {J_JACS}, author = {Jingjing Zhang and Ming Zhao and Zhiqin Xi and Xiaoqian Liu and Linyi Feng and Jie Bai and Xuelin Zhan and Chunqiu Zhang and Adam C. Midgley and Yijin Liu}, doi = {10.1021/jacs.4c16613}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9424--9440}, shortjournal = {J. Am. Chem. Soc.}, title = {Pistol ribozyme-driven catalytic spherical nucleic acid integrates gene and chemotherapy for enhanced cancer therapy}, volume = {147}, year = {2025}, }
• (2025). Aggregation-free, highly soluble CN-terminated dicyclopentadiene-fused rylenes. JACS, 147(11), 9415--9423. (www)

  @article{ , abstract = {Rylenes, known for their excellent photochemical properties, hold great promise in OLEDs, solar cells, and bioimaging applications. However, the solution-phase synthesis of long rylene molecules is often hindered by poor solubility and low stability. In this work, we present an efficient synthetic strategy for a series of CN-terminated rylenes via base-mediated intramolecular Michael addition and oxidative cyclodehydrogenation (Scholl reaction). The synthesized rylenes feature a cyclopentadiene ring at both bay positions of each perylene subunit and electron-deficient CN groups at the peri-termini. These structural modifications render the rylenes stable, aggregation-free, and highly soluble. Bulky aryl groups attached to the cyclopentadiene rings not only improve solubility but also block intermolecular π-aggregation, as revealed by XRD analysis. Additionally, the electron-withdrawing CN groups stabilize the π-conjugated system. The extended π-conjugation reduces the HOMO–LUMO gap, enhancing absorption and inducing a significant bathochromic shift into the NIR I and II regions.}, archive = {J_JACS}, author = {Liuying Jiao and Ya Zou and Wei Fan and Yi Han and Qifeng Zhou and Jiawei Shao and Jishan Wu}, doi = {10.1021/jacs.4c16524}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9415--9423}, shortjournal = {J. Am. Chem. Soc.}, title = {Aggregation-free, highly soluble CN-terminated dicyclopentadiene-fused rylenes}, volume = {147}, year = {2025}, }
• (2025). [Co3@Ge6Sn18]5–: A giant σ-aromatic cluster analogous to h3+ and li3+. JACS, 147(11), 9407--9414. (www)

  @article{ , abstract = {Aromaticity is one of the most important concepts in chemistry and has been successfully extended to all-metal clusters. However, the study of all-metallic aromatic clusters remains in its early stages, with σ-aromatic clusters mostly limited to small sizes (≤12) that often require external stabilization. In this work, we report the first Ge/Sn-based trimer, [Co 3 @Ge 6 Sn 18 ] 5– , which can be rationalized as the fusion of three [Co – @Ge 3 Sn 6 4– ] units via a Ge 3 face. Theoretical studies have revealed that two σ-electrons are delocalized across the entire trimer, with the spherical aromaticity of each [Co@Ge 3 Sn 6 ] unit and the global σ-aromaticity of [Co 3 @Ge 6 Sn 18 ] 5– further supported by its electron delocalization and magnetic behavior. As a result, this trimer can be viewed as a giant σ-aromatic counterpart to triatomic H 3 + and Li 3 + . Our findings suggest the potential for synthesizing cluster-of-cluster analogs of discrete all-metallic aromatic species, such as Al 4 2– , and further enhance our understanding of chemical bonding.}, archive = {J_JACS}, author = {Ya-Shan Huang and Hong-Lei Xu and Wen-Juan Tian and Zi-Sheng Li and Sílvia Escayola and Miquel Solà and Alvaro Muñoz-Castro and Zhong-Ming Sun}, doi = {10.1021/jacs.4c16401}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9407--9414}, shortjournal = {J. Am. Chem. Soc.}, title = {[Co3@Ge6Sn18]5–: A giant σ-aromatic cluster analogous to h3+ and li3+}, volume = {147}, year = {2025}, }
• (2025). Surface chemical coordination stabilizes ni-rich cathodes for high-energy li-metal batteries. JACS, 147(11), 9396--9406. (www)

  @article{ , abstract = {The stability of the electrode–electrolyte interface is a critical factor influencing the electrochemical performance of Li-metal batteries. However, on the delithiated Ni-rich cathode surface, the strong catalytic effects of transition metals with coordination deficiency significantly aggravate the parasitic reactions with Li-metal-compatible ether-based electrolytes, thereby reducing the cycling stability of high-voltage Ni-rich batteries. Here, we propose an sp 2 -induction mechanism to address coordination deficiency through the coupling of interfacial orbitals between molecules and the cathode surface. Sp 2 -hybrid high-fluorinated olefins, characterized by unsaturated bonds, exhibit highly delocalized electronic properties (electron delocalization index >0.95 au) and elevated anodic stability (ionization potential >10 eV). These characters ensure robust and stable interactions with the Ni-rich cathode, facilitating the formation of induced orbitals. These low-energy orbitals accommodate Ni 3 d electrons, effectively mitigating the interfacial coordination deficiency and inhibiting surface side reactions. Among the sp 2 -hybrid high-fluorinated olefins, (perfluorobutyl)ethylene (PFBE) is identified as an optimal inducing molecule due to its strongest interaction and excellent coordination complementarity on the cathode surface. The PFBE-based electrolyte significantly alleviates the degradation of cathode surface structure and demonstrates remarkable cyclic stability, achieving 80% capacity retention over 320 cycles for a 4.4 V Li||LiNi 0.8 Mn 0.1 Co 0.1 O 2 (30 μm Li, high load 3.7 mAh cm –2 NMC811) full cell, compared to 175 cycles with a PFBE-absent electrolyte. This work elucidates the sp 2 -induction mechanism for passivating the high-catalytic cathode interface, paving the way for durable, high-energy aggressive Li-metal batteries.}, archive = {J_JACS}, author = {Jinze Wang and Shuoqing Zhang and Ruhong Li and Long Chen and Haikuo Zhang and Baochen Ma and Sen Jiang and Tao Zhou and Jiajie Huang and Haotian Zhu and Long Li and Lixin Chen and Tao Deng and Xiulin Fan}, doi = {10.1021/jacs.4c16406}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9396--9406}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface chemical coordination stabilizes ni-rich cathodes for high-energy li-metal batteries}, volume = {147}, year = {2025}, }
• (2025). Observation of dynamic aggregation behavior in thermoresponsive micro- and nanoparticles via diffusion-ordered NMR spectroscopy. JACS, 147(11), 9386--9395. (www)

  @article{ , abstract = {Stimuli-responsive drug delivery systems have expanded the diversity of potential cargos by protecting payloads, extending circulation, and controlling payload release. However, quantitative characterization methods that accurately describe these complex systems are needed to accelerate their translation to the clinic. To this extent, degradable, thermoresponsive polyesters were developed through the ring-opening copolymerization of maleic anhydride and an oligo(ethylene glycol)-functionalized epoxide. The resulting polymers possess a lower critical solution temperature such that they are soluble in aqueous solutions at low temperatures (4–7 °C) but assemble into particles above room temperature (25 °C). The particle size and morphology were tunable through the selection of polymer initiator, forming nanoparticle (ca. 162 nm) and microparticle (ca. 1.85 μm) assemblies using macromolecular polyethylene glycol and small molecule propargyl alcohol initiators, respectively. Diffusion-ordered NMR spectroscopy (DOSY) was used over a range of temperatures to develop molecular weight calibrations using certified poly(ethylene glycol) standards. DOSY was able to monitor the dynamic self-assembly behavior of the thermoresponsive polymers in aqueous solutions, and through distinct diffusion constant shifts, quantify the aggregation number of particle intermediates within the nano- and microparticles.}, archive = {J_JACS}, author = {Anshu Agarwal and Benjamin G. Bobay and Matthew L. Becker}, doi = {10.1021/jacs.4c16415}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9386--9395}, shortjournal = {J. Am. Chem. Soc.}, title = {Observation of dynamic aggregation behavior in thermoresponsive micro- and nanoparticles via diffusion-ordered NMR spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Electrocatalytic reductive amination of aldehydes and ketones with aqueous nitrite. JACS, 147(11), 9378--9385. (www)

  @article{ , abstract = {The electrocatalytic utilization of oxidized nitrogen waste for C–N coupling chemistry is an exciting research area with great potential to be adopted as a sustainable method for generation of organonitrogen molecules. The most widely used C–N coupling reaction is reductive amination. In this work, we develop an alternative electrochemical reductive amination reaction that can proceed in neutral aqueous electrolyte with nitrite as the nitrogenous reactant and via an oxime intermediate. We develop a selection criterion for nitrite reduction electrocatalysts suited for oxime electrosynthesis and, in doing so, find Pd to be a highly efficient catalyst for this reaction, reaching an oxime Faradaic efficiency of 82% at −0.21 V vs the reversible hydrogen electrode. The aliphatic or aromatic structure of the carbonyl reactant impacts the efficacy of the catalyst, with aromatic substrates leading to suppressed oxime formation and detrimental reduction of the carbonyl to the alcohol. We developed a Pb/PbO electrocatalyst that selectively performs oxime reduction in the neutral aqueous electrolyte. With acetone as a model substrate, we demonstrate an efficient one-pot, two-step electrochemical reaction for the conversion of acetone to isopropyl amine with 85% yield and 50% global Faradaic efficiency.}, archive = {J_JACS}, author = {Conor L. Rooney and Qi Sun and Bo Shang and Hailiang Wang}, doi = {10.1021/jacs.4c16344}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9378--9385}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrocatalytic reductive amination of aldehydes and ketones with aqueous nitrite}, volume = {147}, year = {2025}, }
• (2025). Interphase design for lithium-metal anodes. JACS, 147(11), 9365--9377. (www)

  @article{ , abstract = {Electrode–electrolyte interphases are critical determinants of the reversibility and longevity of lithium (Li)-metal batteries (LMBs). However, upon cycling, the inherently delicate interphases, formed from electrolyte decomposition, become vulnerable to chemomechanical degradation and corrosion, resulting in rapid capacity loss and thus short battery life. Here, we present a comprehensive analysis of the complex interplay between the thermodynamic and kinetic properties of interphases on Li-metal anodes, providing insights into interphase design to address these challenges. Direct measurements of ion-transport kinetics across various electrolyte chemistries reveal that interphases with high Li-ion mobility are essential for achieving dense Li deposits. Conversely, sluggish ion transport generates high-surface-area Li deposits that induce Li random stripping and the accumulation of isolated Li deposits. Surprisingly, interphases that support long cycle life do not necessarily require the formation of dense Li deposits but must avoid possible electrochemical/chemical reactions between the Li-metal deposits and electrolytes’ components. By that, in some specific electrolyte systems, isolated Li deposits can recover and electrically rejoin the active Li anodes’ mass. These findings challenge conventional understanding and establish new principles for designing durable LMBs, demonstrating that even with commercial carbonate-based electrolytes, LiNi 0.8 Co 0.1 Mn 0.1 O 2 ||Cu cells can achieve high reversibility.}, archive = {J_JACS}, author = {Qidi Wang and Chenglong Zhao and Shuwei Wang and Jianlin Wang and Fangting Wu and Pierfrancesco Ombrini and Swapna Ganapathy and Stephen Eustace and Xuedong Bai and Baohua Li and Michel Armand and Doron Aurbach and Marnix Wagemaker}, doi = {10.1021/jacs.4c15759}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9365--9377}, shortjournal = {J. Am. Chem. Soc.}, title = {Interphase design for lithium-metal anodes}, volume = {147}, year = {2025}, }
• (2025). Coupled differential electrochemical mass spectrometry and surface-enhanced infrared absorption spectroscopic studies unravel the mechanism of nitric oxide electroreduction on platinum. JACS, 147(11), 9352--9364. (www)

  @article{ , abstract = {The nitric oxide electroreduction reaction (NORR) has received considerable attention due to its importance in electrochemical denitrification of nitrogen oxides in groundwater and industrial waste gases and electrochemical ammonia synthesis. However, the detailed mechanism and the factors that affect product selectivity are far less understood. Employing coupled differential electrochemical mass spectrometry (DEMS) and attenuated total reflection–surface-enhanced infrared absorption (ATR–SEIRA) spectroscopy, adsorbed species and volatile solution products, during the adsorption of NO and NORR on Pt in both alkaline and acidic media, have been simultaneously studied, enabling us to correlate the potential-dependent product selectivity with the surface ad-species. NO ad,M , NO ad,B , NO ad,L , and NO 2,ad were identified using SEIRA spectroscopy as surface ad-species, with their potential-dependent intensities having a strong correlation with the product selectivity. N 2 O is the only reduction product at potentials beyond the hydrogen region and is attributed to the reduction of weakly adsorbed NO. In contrast, the formation of NH 3 and NH 2 OH occurs only in the hydrogen region and is ascribed to the reaction between strongly adsorbed NO and adsorbed H. N 2 is a minor product, and is formed through further reduction of N 2 O by adsorbed H. The formation of N 2 is significantly suppressed in acidic media due to the fast kinetics of NO reduction to NH 3 /NH 2 OH, and thus lowering of NO coverage in the hydrogen region. To achieve the selective reduction of NO to NH 3 /NH 2 OH, the potential should remain at 0.1–0.2 V (vs RHE) in both acidic and alkaline media while a slow NO supply, and acidic media are preferred over alkaline media due to the faster kinetics. These new spectroscopic results and insights about the NORR could advance the design of more effective NORR catalysts and help develop optimal conditions for selective ammonia synthesis.}, archive = {J_JACS}, author = {Hongsen Wang and Héctor D. Abruña}, doi = {10.1021/jacs.4c16057}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9352--9364}, shortjournal = {J. Am. Chem. Soc.}, title = {Coupled differential electrochemical mass spectrometry and surface-enhanced infrared absorption spectroscopic studies unravel the mechanism of nitric oxide electroreduction on platinum}, volume = {147}, year = {2025}, }
• (2025). Direct imaging of chirality transfer induced by glycosidic bond stereochemistry in carbohydrate self-assemblies. JACS, 147(11), 9341--9351. (www)

  @article{ , abstract = {Carbohydrates, essential biological building blocks, exhibit functional mechanisms tied to their intricate stereochemistry. Subtle stereochemical differences, such as those between the anomers maltose and cellobiose, lead to distinct properties due to their differing glycosidic bonds; the former is digestible by humans, while the latter is not. This underscores the importance of precise structural determination of individual carbohydrate molecules for deeper functional insights. However, their structural complexity and conformational flexibility, combined with the high spatial resolution needed, have hindered direct imaging of carbohydrate stereochemistry. Here, we employ noncontact atomic force microscopy integrated with a data-efficient, multifidelity structure search approach accelerated by machine learning integration to determine the precise 3D atomic coordinates of two carbohydrate anomers on Au(111). We observe that the stereochemistry of the glycosidic bond regulates on-surface chiral selection in carbohydrate self-assemblies. The reconstructed models, validated against experimental data, provide reliable atomic-scale structural evidence, uncovering the origin of the on-surface chirality from carbohydrate anomerism. Our study confirms that nc-AFM is a reliable technique for real-space discrimination of carbohydrate stereochemistry at the single-molecule level, providing a pathway for bottom-up investigations into the structure–property relationships of carbohydrates in biological research and materials science.}, archive = {J_JACS}, author = {Shuning Cai and Joakim S. Jestilä and Peter Liljeroth and Adam S. Foster}, doi = {10.1021/jacs.4c16088}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9341--9351}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct imaging of chirality transfer induced by glycosidic bond stereochemistry in carbohydrate self-assemblies}, volume = {147}, year = {2025}, }
• (2025). Aptamer-guided, hydrolysis-resistant deoxyoxanosine enables epitope- and moiety-selective conjugation to nonengineered proteins even in complex environments. JACS, 147(11), 9328--9340. (www)

  @article{ , abstract = {In protein engineering, researchers have extensively explored the incorporation of nonprotein entities into proteins to extend their functionalities to various applications; however, achieving precise modifications of proteins is still challenging. This study demonstrates epitope- and moiety-selective conjugation of nonengineered proteins by integrating “slow-reactive and hydrolysis-resistant” deoxyoxanosine (dOxa) into a “target- and epitope-selective” aptamer. The amine-reactive dOxa-containing aptamers are dominantly single-lysine-selective at recognition sites, achieving significantly high conjugation yields with remarkably low off-target reactions in complex environments under near-physiological conditions through a catalyst-free, one-pot reaction. When stoichiometrically controlled protein–DNA conjugates are efficiently produced for various proteins, high conjugation selectivity enables semipermanent regulation of enzymatic functions, targeted labeling in a protein mixture, and even heterofunctionalization of a single protein. As our dOxa-containing aptamers selectively react with the recognition sites of target proteins among nontargets, we demonstrate bioorthogonal labeling of live-cell surface nucleolin and PTK7 in amine-rich cell media, displaying their distinct distributions. Aptamer-guided dOxa positioning offers a promising strategy for site-specific modification of native proteins in complex environments, opening new avenues for the synergistic collaboration between nucleic acids and proteins.}, archive = {J_JACS}, author = {Hyesung Jo and Seonmin Ju and Minhye Kim and Jiyun Beon and Se-Young Jang and Seung Pil Pack and Chang Yun Son and Jong-Seo Kim and Seung Soo Oh}, doi = {10.1021/jacs.4c15674}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9328--9340}, shortjournal = {J. Am. Chem. Soc.}, title = {Aptamer-guided, hydrolysis-resistant deoxyoxanosine enables epitope- and moiety-selective conjugation to nonengineered proteins even in complex environments}, volume = {147}, year = {2025}, }
• (2025). Multiprobe photoproximity labeling of the EGFR interactome in glioblastoma using red-light. JACS, 147(11), 9316--9327. (www)

  @article{ , abstract = {Photocatalytic proximity labeling has emerged as a valuable technique for studying interactions between biomolecules in a cellular context, providing precise spatiotemporal control over protein labeling. One significant advantage of these methods is their modularity, allowing the use of a single photocatalyst with different reactive probes to expand interactome coverage and capture diverse protein interactions. Despite these advances, fewer methods have been developed using red-light excitation, limiting the use of photoproximity labeling in more complex media such as tissues and animal models. Herein, we develop a platform for proximity labeling under red-light excitation, utilizing a single catalyst and two distinct probe types. We first design a carbene based labeling system that utilizes sulfonium diazo probes. This system is successfully applied on A549 cells to capture the interactome of epidermal growth factor receptor (EGFR) using a Cetuximab-Chlorin e6 conjugate. Benchmarking against established techniques indicates that this approach performs comparably to leading carbene-based proximity labeling methods. Next, we leverage the strong singlet oxygen generation (SOG) ability of Chlorin e6 to establish an alternative labeling system using aniline and hydrazide probes. EGFR directed chemoproteomics experiments reveal significant overlap with the carbene system, with the carbene approach capturing a subset of interactions identified by the SOG system. Finally, we deploy our approach for the characterization of EGFR in resected human glioblastoma (GBM) tissue samples removed from distinct locations in the same tumor, representing the tumor’s infiltrating edge and its viable center, identifying several GBM specific interacting proteins that may serve as a launch point for future therapeutic campaigns.}, archive = {J_JACS}, author = {Feifei Tong and Wuyue Zhou and Michalina Janiszewska and Ciaran P. Seath}, doi = {10.1021/jacs.4c15537}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9316--9327}, shortjournal = {J. Am. Chem. Soc.}, title = {Multiprobe photoproximity labeling of the EGFR interactome in glioblastoma using red-light}, volume = {147}, year = {2025}, }
• (2025). Obtaining narrow distributions of single-molecule peptide signals enables sensitive peptide discrimination with α-hemolysin nanopores. JACS, 147(11), 9304--9315. (www)

  @article{ , abstract = {Biological nanopore technology has emerged as a promising tool for analyzing peptides and post-translational modifications at the single-molecule level. However, a broader application is currently limited by the partial separation of peptides and low-throughput, mainly due to the nonuniform peptide signals detected by nanopores. Narrowing the peptide signal distribution is crucial for improving the nanopore’s sensing ability but remains a bottleneck. Here, we demonstrate that capturing peptides with electrophoretic force against electroosmotic flow can provoke more uniform blockades in α-hemolysin nanopores. By using buffers with 2 M KCl at pH 3.8, we obtain the most uniform peptide signals, which may be correlated to the shape, linearization, and actual dwelling position of peptides. Five peptides with acetylation and phosphorylation, including isomeric peptides, can be readily separated from each other. The citrullination replacement of arginine and the β-hydroxybutyrylation modification in another peptide sequence are also discriminated in a mixture. A series of peptides with different compositions induced uniform peptide blockades when they were analyzed with our method. Our work presents an efficient approach to optimize nanopore signals for peptide analysis using α-hemolysin nanopores.}, archive = {J_JACS}, author = {Xing Wei and Jiaqi Wen and Hao Wu and Zhibei Qu and Gang Huang}, doi = {10.1021/jacs.4c15469}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9304--9315}, shortjournal = {J. Am. Chem. Soc.}, title = {Obtaining narrow distributions of single-molecule peptide signals enables sensitive peptide discrimination with α-hemolysin nanopores}, volume = {147}, year = {2025}, }
• (2025). Intrinsic ion concentration difference induced antipolyelectrolyte effect for promoting stability of zn anodes. JACS, 147(11), 9294--9303. (www)

  @article{ , abstract = {Aqueous zinc-ion batteries have gained significant attention due to their high safety and low cost. However, the cation concentration gradient at the anode/electrolyte interface often causes serious Zn dendrites and side reactions. Herein, cross-linked ion channels were constructed on the anode surface by the antipolyelectrolyte effect of zwitterionic polymer carboxymethyl chitosan (CMCHS) molecules, which is induced by the transient ion concentration difference at the initial Zn 2+ deposition process. The CMCHS channels endow the anode surface with homogeneous ions and electron distributions. Simultaneously, CMCHS molecules enter into Zn 2+ solvation structures and H 2 O molecules are removed, limiting the activity of solvated H 2 O molecules. Therefore, the dendrite growth and water activity are significantly suppressed, resulting in the excellent electrochemical performance of Zn anodes. An average Coulombic efficiency of 99.58% is achieved, which is much superior to the case in the conventional ZnSO 4 electrolyte. To illustrate the feasibility of the CMCHS-contained electrolyte, Zn||V 2 O 5 full batteries were assembled and exhibited enhanced electrochemical performance.}, archive = {J_JACS}, author = {Min Yang and Songshan Bi and Xiao Wang and Yifei Zhang and Yang Hu and Jinlei Tian and LiLi Liu and Zhiqiang Niu}, doi = {10.1021/jacs.4c15126}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9294--9303}, shortjournal = {J. Am. Chem. Soc.}, title = {Intrinsic ion concentration difference induced antipolyelectrolyte effect for promoting stability of zn anodes}, volume = {147}, year = {2025}, }
• (2025). Less-dominant resonance configuration of propargyl radical leads to a growth mechanism for polycyclic aromatic hydrocarbons that preserves the cyclopenta ring. JACS, 147(11), 9283--9293. (www)

  @article{ , abstract = {Understanding the growth of polycyclic aromatic hydrocarbons (PAHs) is essential for combustion, astrochemistry, and carbon-based nanomaterial synthesis. This study presents theory-guided experiments on radical–radical combination reactions of propargyl ( • C 3 H 3 ). The addition of • C 3 H 3 to three cyclopenta-fused PAH radicals─1-indenyl ( • 1-C 9 H 7 ), acenaphthenyl ( • C 12 H 9 ), and 4 H -cyclopenta[ def ]phenanthrenyl ( • C 15 H 9 )─revealed that the reaction between the dominant propyne-3-yl resonance configuration of • C 3 H 3 and the three radicals consistently produces PAHs with all hexagonal rings, while the reaction between the less dominant allene-1-yl resonance configuration of • C 3 H 3 and the three radicals selectively preserves the cyclopenta ring and forms a new hexagonal ring. Elusive intermediates and isomeric products were observed and identified by combining molecular beam-sampling synchrotron photoionization mass spectrometry with gas chromatography–mass spectrometry. The complementary results suggest a high selectivity of the allene-1-yl addition pathway, which is thermodynamically controlled. The findings presented here are based on a combination of experimental capabilities, and they provide new mechanisms and insights into the selective formation of bowl-shaped PAHs, serving as templates for fullerene and nanotube structures. The high selectivity of the allene-1-yl pathway provides a rational synthetic strategy for cyclopenta-fused PAHs, bearing barrierless and facile radical–radical reaction pathways in various environments, including high-temperature combustion, circumstellar envelopes, and cold molecular clouds.}, archive = {J_JACS}, author = {Jinyang Zhang and Jiao Gao and Hong Wang and Jiwen Guan and Guangxian Xu and Lili Xing and Donald G. Truhlar and Zhandong Wang}, doi = {10.1021/jacs.4c15155}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9283--9293}, shortjournal = {J. Am. Chem. Soc.}, title = {Less-dominant resonance configuration of propargyl radical leads to a growth mechanism for polycyclic aromatic hydrocarbons that preserves the cyclopenta ring}, volume = {147}, year = {2025}, }
• (2025). Mobile constituent-boosted dynamic separation of C2H2/C2H4/CO2 ternary mixtures in Metal–Organic frameworks. JACS, 147(11), 9273--9282. (www)

  @article{ , abstract = {The separation of acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), and carbon dioxide (CO 2 ) is critical in the chemical industry, driven by the increasing demand for high-purity C 2 H 2 and C 2 H 4 . While metal–organic frameworks (MOFs) offer an energy-efficient approach for adsorptive gas separation, achieving sub-angstrom precision in pore size adjustment remains challenging. In this work, we leverage two synergistic mechanisms in a double-interpenetrated framework: (1) global structural flexibility, arising from dynamic displacement of subnetworks to tailor pore dimensions, and (2) local flexibility, enabled by counterion and ligand rotation, to modulate the aperture binding affinity for precise molecular discrimination. A series of isostructural MOFs, NUS-33-CF 3 SO 3 and NUS-34-BF 4 , were designed to enable one-step purification of C 2 H 4 and concurrent recovery of C 2 H 2 from ternary gas mixtures. Within pores of optimal dimensions, the synergistic interplay between counterion-mediated host–guest interactions and local framework adaptability enables precise and simultaneous regulation of static and kinetic gas adsorption properties. Notably, NUS-34-BF 4 achieves a dynamic C 2 H 4 productivity of 2.62 mmol/g and a C 2 H 2 uptake of 1.26 mmol/g. This study highlights the pivotal yet underexplored role of counterions as dynamic gatekeepers, offering a tunable strategy to engineer pore environments in flexible MOFs for advanced gas separations.}, archive = {J_JACS}, author = {Qixing Liu and Junyu Ren and Zhaoqiang Zhang and He Li and Nengxiu Zhu and Dan Zhao}, doi = {10.1021/jacs.4c15141}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9273--9282}, shortjournal = {J. Am. Chem. Soc.}, title = {Mobile constituent-boosted dynamic separation of C2H2/C2H4/CO2 ternary mixtures in Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Amide-based cathode interfacial layer with dual-modification mechanisms enables stable organic solar cells with high efficiency achieving 20%. JACS, 147(11), 9261--9272. (www)

  @article{ , abstract = {The cathode interfacial layers (CILs) play a critical role in the performance and long-term stability of the organic solar cells (OSCs). While amine-based CILs have been successful in reducing the work function of metal electrodes, they can also promote the decomposition of acceptor materials, compromising the stability of OSCs. To address this challenge and further improve device performance, we have innovatively designed and synthesized amide-functionalized perylene diimide (PDI)-Leu-am as a dopant-free CIL molecule. Notably, PDI-Leu-am effectively mitigates acceptor decomposition, significantly improving the photostability and thermal stability of OSCs. Moreover, it demonstrates dual-modification capabilities at the active layer/cathode interface, facilitating electron extraction from the active layer while lowering the electrode’s work function. Encouragingly, this dual modification mechanism effectively refined the Ohmic contact, leading to a remarkable power conversion efficiency (PCE) up to 20%. This breakthrough opens up promising avenues for the practical deployment of OSCs and lays a robust foundation for the development of high-performance, enduring, and cost-efficient interface materials.}, archive = {J_JACS}, author = {Xuewen Wang and Qi Liang and Andong Zhang and Nan Wei and Huanxiang Jiang and Yetai Cheng and Haisheng Fang and Suying Li and Hao Lu and Weiwei Li and Zhishan Bo}, doi = {10.1021/jacs.4c15071}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9261--9272}, shortjournal = {J. Am. Chem. Soc.}, title = {Amide-based cathode interfacial layer with dual-modification mechanisms enables stable organic solar cells with high efficiency achieving 20%}, volume = {147}, year = {2025}, }
• (2025). An alloy engineering strategy toward helical microstructures of achiral π-conjugated molecules for circularly polarized luminescence. JACS, 147(11), 9250--9260. (www)

  @article{ , abstract = {Helical assembly has been demonstrated to efficiently facilitate the circularly polarized luminescence (CPL) performances, but the synthesis of micro- and nanohelices from rigid achiral π-conjugated compounds remains challenging due to the absence of bilayer structures or complementary hydrogen-bonding interactions. Here, we develop an alloying strategy for the realization of helical microstructures from achiral anthracene/anthracene derivatives with x -/ x -axis modification or anthracene/tetracene derivatives with x -/ y -axis modification via solution coassembly. Interestingly, two anthracene derivatives bearing asymmetric phenyl/phenylethynyl groups and symmetric phenylethynyl groups can assemble into spiral microribbons with a fractal branching pattern. Using such an alloying strategy, color-tailorable ternary spiral microtubules/microribbons referring to high-efficiency energy transfer processes are achievable. Molecular dynamics simulations reveal that the Von Mises stress produced by symmetry differences of two components induces symmetry breaking of alloy structures associated with twisting. Additionally, the contents of the guest and H 2 O also play a vital role in the formation of intricate helical microstructures. Single binary and ternary spiral microribbons present considerable CPL properties with a dissymmetric factor (′ g lum ′) of more than 0.01. The present work provides new insights into the formation of helical microcrystals with complex topologies and new optoelectronic functions.}, archive = {J_JACS}, author = {Haina Feng and Xiaohui Lan and Zuofang Feng and Sibing Chen and Lulu Zhang and Huixing Gao and Chaoyi Han and Xing Chen and Quanbin Jiang and Zhengong Meng and Yilong Lei}, doi = {10.1021/jacs.4c14988}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9250--9260}, shortjournal = {J. Am. Chem. Soc.}, title = {An alloy engineering strategy toward helical microstructures of achiral π-conjugated molecules for circularly polarized luminescence}, volume = {147}, year = {2025}, }
• (2025). Cu intercalation-stabilized 1T′ MoS2 with electrical insulating behavior. JACS, 147(11), 9242--9249. (www)

  @article{ , abstract = {The intercalated two-dimensional (2D) transition metal dichalcogenides (TMDCs) have attracted much attention for their designable structures and novel properties. Among this family, host materials with low symmetry such as 1T′ phase TMDCs are particularly interesting because of their potentials in inducing unconventional phenomena. However, such systems typically have low quality and poor stability, hindering further study of the structure–property relationship and applications. In this work, we intercalated Cu into 1T′ MoS 2 with high crystallinity and high thermal stability up to ∼300 °C. We identified the distribution and arrangement of Cu intercalators for the first time, and the results show that Cu intercalators occupy partially the tetrahedral interstices aligned with Mo sites. The obtained Cu-1T′ MoS 2 exhibits an insulating hopping transport behavior with a large temperature coefficient of resistance reaching −4∼−2%·K –1 . This work broadens the artificial intercalated structure library and promotes the structure design and property modulation of layered materials.}, archive = {J_JACS}, author = {Huiyu Nong and Junyang Tan and Yujie Sun and Rongjie Zhang and Yue Gu and Qiang Wei and Jingwei Wang and Yunhao Zhang and Qinke Wu and Xiaolong Zou and Bilu Liu}, doi = {10.1021/jacs.4c14945}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9242--9249}, shortjournal = {J. Am. Chem. Soc.}, title = {Cu intercalation-stabilized 1T′ MoS2 with electrical insulating behavior}, volume = {147}, year = {2025}, }
• (2025). Poly(hydrazinophosphine diazide)s (PHPDs): Hybrid Organic–Inorganic polymers via polycondensation between PN cages and organic diazides. JACS, 147(11), 9229--9241. (www)

  @article{ , abstract = {Organic polymers generally feature 1-dimensional chains or 2-dimensional rings in their backbones since synthetic challenges limit the availability of 3-dimensional monomers. Inorganic cages are less strained and more accessible, offering an alternative route to explore this parameter space. However, only two families─carboranes and polyhedral oligomeric silsesquioxanes (POSS)─have been well-studied, revealing materials with valuable mechanical and thermal properties. Further exploration of this frontier requires the development of new inorganic cages that are accessible, stable, and polymerizable. Here we report that an easily assembled, bench-stable PN cage, P(NMeNMe) 3 P, undergoes Staudinger polycondensation with organic diazides to yield robust, solution-processable, and film-forming linear poly(trihydrazino-diphosphine diazide)s─PHPDs─as a new family of hybrid organic–inorganic polymers. Their solubility can be controlled by diazide choice and backbone architecture, which we rationally modify to access alternating or multiblock copolymers. We also show how a tetraphosphorus cage, P 4 (NMe) 6 , can be used to cross-link PHPDs. The T g values for PHPDs are comparable to those of rigid π-conjugated polymers (>150 °C), and, despite a high nitrogen content (up to 32%) and three N–N σ-bonds per repeat unit, they show decomposition temperatures >200 °C with char yields up to 60%. These data support hypotheses of high stability arising from the presence of 3-dimensional backbone units. We further show that PHPDs may be leveraged for halogen-free flame retardancy. Collectively, the results debut new low-carbon polymers with an unusual backbone topology, reveal the design rules for controlling their microstructures and properties, and lay the foundation for future applied studies.}, archive = {J_JACS}, author = {Maryam F. Abdollahi and Erin N. Welsh and Mohsen Shayan and Anthony Olivier and Noémie Wilson-Faubert and Ulrike Werner-Zwanziger and Ali Nazemi and Audrey Laventure and Saurabh S. Chitnis}, doi = {10.1021/jacs.4c14881}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9229--9241}, shortjournal = {J. Am. Chem. Soc.}, title = {Poly(hydrazinophosphine diazide)s (PHPDs): Hybrid Organic–Inorganic polymers via polycondensation between PN cages and organic diazides}, volume = {147}, year = {2025}, }
• (2025). Solid-state NMR spectroscopy investigation of structural changes of mechanically strained mouse tail tendons. JACS, 147(11), 9220--9228. (www)

  @article{ , abstract = {Structural tissues like tendon are subjected to repeated tensile strains in vivo and excessive strains cause irreversible changes to the tissue. Large strains affect the molecular structure and organization of the extracellular matrix, and these are the parameters that drive cell behavior, including tissue repair. Here we describe a method to perform solid-state NMR spectroscopy on in situ strained tissue samples under magic-angle spinning to achieve high-resolution NMR spectra while maintaining the tissue’s native hydration state. The changes observed in the NMR spectra are interpreted using quantum mechanics molecular mechanics (QM/MM) chemical shift calculations on strained collagen triple-helix structures and consideration of changes in the distribution of molecular orientations between strained and relaxed mechanical states. We demonstrate that our tissue strain method in combination with spectral simulations can detect changes in collagen organization between tendons loaded to plastic deformation and subsequent structural relaxation in the unloaded state.}, archive = {J_JACS}, author = {Thomas Kress and Melinda J. Duer}, doi = {10.1021/jacs.4c13930}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9220--9228}, shortjournal = {J. Am. Chem. Soc.}, title = {Solid-state NMR spectroscopy investigation of structural changes of mechanically strained mouse tail tendons}, volume = {147}, year = {2025}, }
• (2025). On-demand catalytic platform for glycerol upgrade and utilization. JACS, 147(11), 9210--9219. (www)

  @article{ , abstract = {Surplus byproducts generated during biomass exploitation, such as glycerol from biodiesel manufacturing, seriously undermine the credibility of renewable energy policies. Here, we establish an on-demand catalytic platform for the upgrade and utilization of glycerol via photoelectro-bioelectro-heterogeneous coupling catalysis. Combining theoretical descriptors, specifically the highest occupied molecular orbital energy levels and dual local softness values, along with systematic experimental validation, we demonstrated the reaction activity of glycerol and its upgraded products on BiVO 4 photoelectrodes. Glyceric acid was identified as the optimal biofuel candidate through monohydroxyl oxidation of glycerol. Coupling the preferential upgrading of glycerol to glyceric acid by night and its reuse as biofuel by day, a hybrid biophotoelectrochemical system delivered an open-circuit voltage of 0.89 ± 0.02 V and a maximum power density of 0.41 ± 0.03 mW cm –2 with stable diurnal operation for over 10 days. This successful model construction provides valuable insights into the strategic integration of multiple energy sources and the exploration of coupling-catalytic platforms, charting new territory for the next-generation sustainable energy systems.}, archive = {J_JACS}, author = {Jianguo Zhao and Shuai Hao and Panpan Zhao and Jiao Ding and Rui Li and He Zhang and Shaojun Dong}, doi = {10.1021/jacs.4c13603}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9210--9219}, shortjournal = {J. Am. Chem. Soc.}, title = {On-demand catalytic platform for glycerol upgrade and utilization}, volume = {147}, year = {2025}, }
• (2025). Colloidal chemistry in molten inorganic salts: Direct synthesis of III–V quantum dots via dehalosilylation of (Me3Si)3Pn (Pn = p, as) with group III halides. JACS, 147(11), 9198--9209. (www)

  @article{ , abstract = {Gallium pnictides, such as GaAs and GaP, are among the most widely used semiconductors for electronic, optoelectronic, and photonic applications. However, solution syntheses of gallium pnictide nanomaterials are less developed than those of many other colloidal semiconductors, including indium pnictides, II–VI and IV–VI compounds, and lead halide perovskites. In this work, we demonstrate that the Wells dehalosilylation reaction can be carried out in molten inorganic salt solvents to synthesize colloidal GaAs, GaP, and GaP 1– x As x nanocrystals. We demonstrate that discrete colloidal nanocrystals can be nucleated and grown in a molten salt with control over their size and composition. Additionally, we found that reaction temperatures above 400 °C are crucial for annealing structural defects in GaAs nanocrystals. We also highlight the utility of the as-synthesized GaP nanocrystals by showing that GaP can be solution-processed into high-refractive-index coatings and patterned by direct optical lithography with micron resolution. Finally, we demonstrate that dehalosilylation reactions in molten salts can be generalized to synthesize indium pnictide (Pn = As, P) and ternary (In 1– x Ga x As and In 1– x Ga x P) quantum dots.}, archive = {J_JACS}, author = {Zirui Zhou and Justin C. Ondry and Yi-Chun Liu and Haoqi Wu and Ahhyun Jeong and Aritrajit Gupta and Yi-Chen Chen and Jun Hyuk Chang and Richard D. Schaller and Dmitri V. Talapin}, doi = {10.1021/jacs.4c13568}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9198--9209}, shortjournal = {J. Am. Chem. Soc.}, title = {Colloidal chemistry in molten inorganic salts: Direct synthesis of III–V quantum dots via dehalosilylation of (Me3Si)3Pn (Pn = p, as) with group III halides}, volume = {147}, year = {2025}, }
• (2025). Observation of an associative state in aqueous hydroxide. JACS, 147(11), 9190--9197. (www)

  @article{ , abstract = {The dynamics of chemical reactions in solution are of paramount importance in fields ranging from biology to materials science. Because the hydrogen-bond network and proton dynamics govern the behavior of aqueous solutions, they have been the subject of numerous studies over the years. Here, we report the observation of a previously unknown associative state in the hydroxide ion that forms when a proton from a neighboring water molecule approaches the hydroxide ion, utilizing resonant inelastic soft X-ray scattering (RIXS) and quantum dynamical simulations. State-of-the-art theoretical analysis reveals state mixing in the electronically excited states between aqueous hydroxide ions and the solvent. Our results give new insights into chemical bonding and excited-state dynamics in the aqueous environment. This investigation of associative states opens up new pathways for spectroscopic studies of chemical reaction dynamics and lays the foundation for directly accessing dynamic proton exchange in solution.}, archive = {J_JACS}, author = {Zhong Yin and Pavel Krasnov and Stephan Thürmer and Evanthia Chatzigeorgiou and Yitao Cui and Kosuke Yamazoe and Jun Miyawaki and Takashi Tokushima and Conny Såthe and Johan Gråsjö and Yoshihisa Harada and Sergey P. Polyutov and Hans Jakob Wörner and Michael Odelius and Faris Gelmukhanov and Jan-Erik Rubensson and Victor Kimberg}, doi = {10.1021/jacs.4c13453}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9190--9197}, shortjournal = {J. Am. Chem. Soc.}, title = {Observation of an associative state in aqueous hydroxide}, volume = {147}, year = {2025}, }
• (2025). Structure and pH dependence of membranolytic mechanisms by truncated oxidized phospholipids. JACS, 147(11), 9175--9189. (www)

  @article{ , abstract = {Membrane lipid oxidation is a universal process that occurs in situations of oxidative stress and is encountered in numerous physiological and pathological situations. Oxidized truncated phospholipids make up a large part of the oxidation products and alter the membrane properties in a way that can lead to cell death. However, the underlying mechanisms are not well understood nor is it clear whether environmental factors, such as pH, can modulate these effects. Using model membranes, we investigate how individual lipid aldehydes and carboxylic acids with truncated acyl chains alter the membrane structure. Our data shows that lipid aldehydes and carboxylic acids have different permeabilization efficiencies towards molecules of varying charge and size and that ΔC9 truncated lipids are usually more efficient in permeabilizing membranes than ΔC5. In terms of physical mechanisms, the ΔC9 truncated lipid carboxylic acid induces permeabilization and membrane curvature in a pH-dependent fashion. This is explained by ionization-dependent exposure of the carboxyl group to the water–bilayer interface, which increases the intrinsic molecular curvature of the oxidized lipid. Conversely, ΔC9 truncated lipid aldehydes and nonionized carboxyls do not induce curved structures but are more efficient in increasing permeability toward larger molecules. We further show that truncated lipids can escape the bilayer and accumulate at interfaces, implying that they might act on neighboring cells. This study indicates that oxidized phospholipids with truncated acyl chains disrupt membrane structure, depending on their specific molecular structure and the pH of the environment, opening a possible route for the design of lipid nanoparticles with pH-dependent drug release.}, archive = {J_JACS}, author = {Min Xie and Maik G. N. Derks and Eveline H. W. Koch and C. Bjorn van Boven and Minchakarn Janlad and Behnaz Bagheri and Zexi Xu and Daria Kovryzhenko and Cornelis A. van Walree and Ana Sobota and Markus Weingarth and Jirasak Wong-ekkabut and Mikko Karttunen and Eefjan Breukink and J. Antoinette Killian and Andreas F. P. Sonnen and Joseph H. Lorent}, doi = {10.1021/jacs.4c12543}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9175--9189}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure and pH dependence of membranolytic mechanisms by truncated oxidized phospholipids}, volume = {147}, year = {2025}, }
• (2025). Counterion lewis acidity determines the rate of hexafluorophosphate hydrolysis in nonaqueous battery electrolytes. JACS, 147(11), 9159--9174. (www)

  @article{ , abstract = {The decomposition of LiPF 6 in nonaqueous battery electrolytes is a well-studied, deleterious process that leads to hydrofluoric acid (HF) driven transition metal dissolution at the positive electrode and gas production (H 2 ) at the anode, often attributed to the inherent moisture sensitivity of the hexafluorophosphate anion. In this work, we use in situ nuclear magnetic resonance (NMR) spectroscopy to demonstrate that the rate of PF 6 – hydrolysis significantly decreases in Na and K systems, where the Lewis acidity of the cation dictates the rate of decomposition according to Li + > Na + > K + . Despite the remarkable stability of Na and K electrolytes, we show that they are still susceptible to hydrolysis in the presence of protons, which can catalyze the breakdown of PF 6 – , indicating that these chemistries are not immune from decomposition when paired with solvent/cathode combinations that generate H + at high voltage. Quantitative in situ multinuclear and multidimensional NMR of decomposed electrolytes shows that after long-term degradation, these systems contain HF, HPO 2 F 2 , and H 2 PO 3 F as well as a variety of defluorinated byproducts, such as organophosphates and phosphonates, that are structurally similar to herbicides/insecticides and may pose health and environmental risks. Taken together, these results have important implications for Na- and K-ion batteries where hazardous and harmful byproducts like HF, soluble transition metals, organophosphates, and phosphonates can be greatly reduced through cell design. Our results also suggest that next-generation chemistries present a pathway to safer batteries that contain lower quantities of flammable gases, like H 2 , if properly engineered.}, archive = {J_JACS}, author = {Pablo J. Buitrago Botero and Andrew W. Ells and Asya Svirinovsky-Arbeli and Mikkel Juelsholt and Lauren E. Marbella}, doi = {10.1021/jacs.4c12469}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9159--9174}, shortjournal = {J. Am. Chem. Soc.}, title = {Counterion lewis acidity determines the rate of hexafluorophosphate hydrolysis in nonaqueous battery electrolytes}, volume = {147}, year = {2025}, }
• (2025). Importance of the ferryl quintet state in determining the electronic properties of p450 compound i. JACS, 147(11), 9147--9158. (www)

  @article{ , abstract = {We previously reported a selenolate-ligated P450 compound I intermediate (SeP450-I) to be more reactive toward C–H bonds than its thiolate-ligated counterpart. To gain insight into how the selenolate axial ligand influences the reactivity of compound I, we have investigated the electronic structure of the SeP450-I intermediate using variable temperature Mössbauer (VTM) spectroscopy. The VTM data indicate that electronic spin relaxation rates are significantly slower in SeP450-I than in P450-I. Analyses of these data provide Δ, the energy spacing between the two lowest electronic energy levels in compound I. This spacing is typically determined by the zero-field splitting of the ferryl moiety, D , and the exchange coupling, J , between the iron(IV)oxo unit and the ligand-based radical. However, the systems examined are antiferromagnetically coupled with | J / D | > 1. As a result, Δ ∼ (3/2) J , and measurements of Δ provide J (to within ∼5%). These measurements reveal that the sign and magnitude of J track with the reactivity of compound I toward C–H bonds. Efforts to analyze these and other data highlight the inadequacy of the standard ligand field model that is often used to explain the electronic properties of compound I. Additional analyses combining our data with state energies from a previous theoretical investigation support predictions of a low-lying quintet state within the iron(IV)oxo unit. We discuss these findings in light of computational studies that suggest that access to excited states, particularly those of a high-spin nature, can promote metal-oxo mediated C–H bond cleavage.}, archive = {J_JACS}, author = {Elizabeth L. Onderko and Mackenzie J. Field and Alexey Silakov and Timothy H. Yosca and Michael T. Green}, doi = {10.1021/jacs.4c11688}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9147--9158}, shortjournal = {J. Am. Chem. Soc.}, title = {Importance of the ferryl quintet state in determining the electronic properties of p450 compound i}, volume = {147}, year = {2025}, }
• (2025). Selective photocatalytic aerobic oxidation of methane to methyl hydroperoxide by ZnO-loaded single-atomic ruthenium oxide catalyst. JACS, 147(11), 9134--9146. (www)

  @article{ , abstract = {Photooxidation of CH 4 to value-added chemicals with high selectivity offers a promising pathway to drive the rational utilization of natural gas resources with renewable energy under mild conditions. However, owing to the poor chemoselectivity of reactive oxygen radical formation and consecutive side reactions of primary products, the synthesis of peroxide directly from CH 4 oxidation remains challenging. Here, we report single-atom ruthenium oxide-doped ZnO as a highly selective photocatalyst for the aerobic oxidation of CH 4 to CH 3 OOH. Under optimal conditions, the CH 3 OOH formation rate over Ru 1 O x /ZnO reaches 321 μmol g cat –1 h –1 with a high selectivity of 90.9% under simulated solar irradiation. Mechanistic studies reveal that the selective generation of •OOH radicals via oxygen reduction and the ability to prevent secondary side reactions of CH 3 OOH are the main advantages of Ru 1 O x /ZnO, accounting for the remarkable selectivity of CH 3 OOH from CH 4 . The single-atom Ru oxide/ZnO catalyst also exhibits remarkable chemoselectivity to alkyl hydroperoxide in the photocatalytic oxidation of low paraffins, which provides a solution to prepare value-added peroxide from a single-step oxidation of hydrocarbon substrates.}, archive = {J_JACS}, author = {Hantao Gong and Li Zhang and Caihao Deng and Mingjie Liu and Xiaolong Liu and Yongkang Huang and Kai Zhou and Peipei He and Jing Li and Yiwen Yang and Liang Wang and Qiwei Yang and Zongbi Bao and Qilong Ren and Ting Tan and Siyu Yao and Zhiguo Zhang}, doi = {10.1021/jacs.4c11685}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9134--9146}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective photocatalytic aerobic oxidation of methane to methyl hydroperoxide by ZnO-loaded single-atomic ruthenium oxide catalyst}, volume = {147}, year = {2025}, }
• (2025). Low-temperature growth of centimeter-sized 2D PdSe2 by self-limiting liquid-phase edge epitaxy. JACS, 147(11), 9122--9133. (www)

  @article{ , abstract = {Two-dimensional (2D) PdSe 2 atomic crystals hold great potential for optoelectronic applications due to their bipolar electrical characteristics, tunable bandgap, high electron mobility, and exceptional air stability. Nevertheless, the scalable synthesis of large-area, high-quality 2D PdSe 2 crystals using chemical vapor deposition (CVD) remains a significant challenge. Here, we present a self-limiting liquid-phase edge-epitaxy (SLE) low-temperature growth method to achieve high-quality, centimeter-sized PdSe 2 films with single-crystal domain areas exceeding 30 μm. The SLE growth mechanism, clarified by theoretical calculations and time-of-flight secondary ion mass spectrometry (ToF-SIMS), reveals that hydrogen ions on the precursor surface inhibit vertical growth while promoting lateral growth. The as-grown PdSe 2 few-layer exhibits a surface roughness of 1.20 nm and an average conductivity of 1.67 × 10 –6 S/m, demonstrating their smoothness and uniformity. Temperature-dependent electrical measurements and transfer characteristic curves confirm the orthorhombic PdSe 2 ’s bipolar semiconductor behavior. The photodetector based on few-layer PdSe 2 films exhibit excellent optoelectronic performance in the 405–1650 nm wavelength range, achieving a responsivity of 6262.37 A W –1 , a detectivity of ∼10 12 Jones under 1064 nm illumination, and a fast response time of 37.1 μs, making them highly suitable for broadband photodetection applications. This work provides valuable insights into the scalable synthesis of PdSe 2 few-layers and establishes a foundation for the development of PdSe 2 -based integrated functional devices.}, archive = {J_JACS}, author = {Mingqiang Liu and Tianhao Cui and Junwei Feng and Yao Wu and Jinshun Bi and Abuduwayiti Aierken and Xuefei Liu and Gui-Gen Wang and Zheng Liu}, doi = {10.1021/jacs.4c11531}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9122--9133}, shortjournal = {J. Am. Chem. Soc.}, title = {Low-temperature growth of centimeter-sized 2D PdSe2 by self-limiting liquid-phase edge epitaxy}, volume = {147}, year = {2025}, }
• (2025). In situ recovery of serotonin synthesis by a tryptophan hydroxylase-like nanozyme for the treatment of depression. JACS, 147(11), 9111--9121. (www)

  @article{ , abstract = {Depression is one of the most common mental disorders. The inactivation of tryptophan hydroxylase and the resulting serotonin decrease are the key factors in depression pathology. Herein, we report for the first time that Fe 3 O 4 nanoparticles exhibit tryptophan hydroxylase-like activity and successfully verify their ability to restore serotonin synthesis in the brain for the treatment of depression. To achieve better biocompatibility and brain delivery, the Fe 3 O 4 nanoparticles were functionalized with chitosan (CS) (Fe 3 O 4 @CS), enabling their delivery from the nose to the brain. Fe 3 O 4 @CS catalyzes the transformation of tryptophan into 5-hydroxytryptophan with the participation of high levels of endogenous ascorbic acid and hydrogen peroxide in stressed neurons, thus compensating for the deactivated tryptophan hydroxylase in the brain. In vivo Fe 3 O 4 @CS treatment results in the recovery of 5-hydroxytryptophan and serotonin levels and improvement of neuronal signal transduction ability in a depression mouse model, thus ameliorating depressive-like behaviors. The presented strategy of restoring serotonin synthesis in situ based on a tryptophan hydroxylase-like nanozyme provides a more accurate and efficient approach for the treatment of depression.}, archive = {J_JACS}, author = {Xiao Fang and Yue Wu and Yaling Dai and Han Xiao and Shiqing Li and Xiaoning Chen and Meng Yuan and Yanbei Guo and Liying Ma and Dingyue Lin and Weilin Liu and Chunhua Lu and Huanghao Yang}, doi = {10.1021/jacs.4c10733}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9111--9121}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ recovery of serotonin synthesis by a tryptophan hydroxylase-like nanozyme for the treatment of depression}, volume = {147}, year = {2025}, }
• (2025). Impact of reaction environment on photogenerated charge transfer demonstrated by sequential imaging. JACS, 147(11), 9103--9110. (www)

  @article{ , abstract = {Most photocatalysis research focuses on understanding the photogenerated charge transfer processes within the solid catalysts themselves. However, these studies often overlook the impact of the reaction environment on photogenerated charge separation and reactions. To address this gap, our study employed a sequential imaging methodology that integrates surface photovoltage microscopy (SPVM), in situ atomic force microscopy (AFM), and scanning electrochemical microscopy (SECM) to track the transfer of photogenerated charges from the space charge region to the reactants at the nanoscale on individual BiVO 4 particles. It identifies the key role that surface charges at the photocatalyst–electrolyte interface play in photogenerated charge transfer. Specifically, we demonstrated that the surface charge generates an additional driving force, which adjusts the interface electric field and reverses the photovoltage of {010} facet from 90 to −25 mV in a neutral electrolyte. This competitive or even larger driving force compels the photogenerated electrons, which are confined within the bulk, to migrate to the surface, ultimately leading to the redistribution of photogenerated charges. Furthermore, our findings uncovered that the difference between the solution pH and the isoelectric point of the facet serves as the origin of the interfacial electric field. Overall, our sequential imaging research fills an important gap in understanding the driving and influencing factors of charge transfer across the solid–liquid interface for photocatalytic reactions in solution. It provides significant insights into clarifying the bottleneck issue of charge separation in photocatalytic reactions.}, archive = {J_JACS}, author = {Qian Li and Chenwei Ni and Junhao Cui and Can Li and Fengtao Fan}, doi = {10.1021/jacs.4c10300}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9103--9110}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of reaction environment on photogenerated charge transfer demonstrated by sequential imaging}, volume = {147}, year = {2025}, }
• (2025). Helical sense control of Metal–Peptide torus frameworks leading to the folding and assembly of a Ag21L14 braided peptide nanotube. JACS, 147(11), 9098--9102. (www)

  @article{ , abstract = {The chirality of helical polypeptides is correlated to that of their constituent amino acid residues. For polypeptides with non-natural backbones, however, such correlations are less clear. Here, circular double helices with torus knot/link topologies were assembled from non-natural metal–peptide chains composed of Ag(I) ions and ditopic tripeptides with Gly-Gly-Ala and Gly-Ala-Gly sequences. We found that the chirality of the assembled helical structures is determined by the l -Ala’s dihedral angles. A tubular dimeric structure with an M 21 L 14 composition was further achieved via additional metal cross-linking, showing rational design potential for artificial peptide helices.}, archive = {J_JACS}, author = {Sota Oguma and Yuuki Inomata and Akihiro Hayakawa and Takahiro Nakama and Makoto Fujita and Tomohisa Sawada}, doi = {10.1021/jacs.5c01458}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9098--9102}, shortjournal = {J. Am. Chem. Soc.}, title = {Helical sense control of Metal–Peptide torus frameworks leading to the folding and assembly of a Ag21L14 braided peptide nanotube}, volume = {147}, year = {2025}, }
• (2025). Synthesis of (+)-saxitoxin facilitated by a chiral auxiliary for photocycloadditions involving alkenylboronate esters. JACS, 147(11), 9091--9097. (www)

  @article{ , abstract = {(+)-Saxitoxin, a potent neurotoxin and Na V blocker, poses significant synthetic challenges due to its compact tricyclic framework and guanidinium moieties. We report a concise and asymmetric total synthesis featuring an intramolecular [2 + 2] photocycloaddition of an alkenylboronate ester equipped with a new chiral auxiliary. This auxiliary, compatible with UV light and easily exchangeable on B(pin) derivatives, enabled high stereocontrol through hydrogen-bond-mediated transition-state stabilization. Our approach not only introduces an innovative surrogate for intramolecular Michael addition, particularly addressing transformations with contra-thermodynamic barriers, but also highlights the potential of boron-enabled photochemistry for synthesizing complex molecules.}, archive = {J_JACS}, author = {Yang Jiao and Jiaqi Liu and Weijie Mao and Runting Fang and Tianrun Xia and Qiaorui Lang and Tuoping Luo}, doi = {10.1021/jacs.5c00666}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9091--9097}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of (+)-saxitoxin facilitated by a chiral auxiliary for photocycloadditions involving alkenylboronate esters}, volume = {147}, year = {2025}, }
• (2025). Fontimonas thermophila alkane monooxygenase (FtAlkB) is an alkyl fluoride dehalogenase. JACS, 147(11), 9085--9090. (www)

  @article{ , abstract = {Purified alkane monooxygenase (AlkB) from Fontimonas thermophila (FtAlkB) catalyzes the defluorination of 1-fluorooctane, producing octanal, which is partially reduced under the reaction conditions to generate 1-octanol. This reaction occurs preferentially at the monofluorinated methyl group, with only a minor amount of oxidation at the nonfluorinated end of the molecule. The dehalogenation chemistry is specific to 1-fluorooctane, as neither 1-chlorooctane or 1-bromooctane are dehalogenated to an appreciable extent. Furthermore, P. putida cells containing the structurally related AlkB (PpAlkB) along with the full set of genes required for alkane metabolism, utilize 1-fluorooctane as their sole source of carbon with growth rates comparable to those for cells grown with octane.}, archive = {J_JACS}, author = {Lauren Hendricks and Clorice R. Reinhardt and Tierani Green and Lily Kunczynski and August Jaunzarins Roberts and Naomi Miller and Noga Rafalin and Heather J. Kulik and John T. Groves and Rachel N. Austin}, doi = {10.1021/jacs.5c00386}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9085--9090}, shortjournal = {J. Am. Chem. Soc.}, title = {Fontimonas thermophila alkane monooxygenase (FtAlkB) is an alkyl fluoride dehalogenase}, volume = {147}, year = {2025}, }
• (2025). Enantioselective total synthesis of fortalpinoid q via a TEMPO+BF4–-mediated dehydrative nazarov cyclization. JACS, 147(11), 9079--9084. (www)

  @article{ , abstract = {The family of Cephalotaxus diterpenoids represents a captivating class of natural products that are of significant interest from both structural and biological perspectives within our community. Here we wish to report a 15-step, enantioselective total synthesis of the Cephalotaxus diterpenoid fortalpinoid Q. Our approach highlights (1) a Jacobsen’s catalytic enantioselective Claisen rearrangement that enabled the single-step formation of two vicinal stereogenic centers, including an all-carbon quaternary center; (2) a mild, oxoammonium salt (TEMPO + BF 4 – )-promoted dehydrative Nazarov cyclization that swiftly forged the crucial cyclopentadiene moiety via an unfunctionalized tertiary divinyl carbinol (TDC) substrate; and (3) a facile aldol-lactonization cascade that ultimately resolved the last obstacle in the synthesis.}, archive = {J_JACS}, author = {Hai-Kang Mao and Qian Wang and Jing Xu}, doi = {10.1021/jacs.5c00319}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9079--9084}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective total synthesis of fortalpinoid q via a TEMPO+BF4–-mediated dehydrative nazarov cyclization}, volume = {147}, year = {2025}, }
• (2025). Dual-action-only PROTACs. JACS, 147(11), 9074--9078. (www)

  @article{ , abstract = {Proteolysis targeting chimera (PROTAC)-based degraders are highly potent pseudocatalytic drugs, but on-target off-site homing could yield undesirable consequences. We report here a generalizable AND-logic gated PROTAC, where the concurrent presence of two different disease-relevant endogenous stimuli liberates an active protein degrader. We design Dual-Action-Only PROTAC (DAO-PROTAC) molecules that are dormant and can only be activated in the presence of both hypoxia and cathepsin-L to degrade the protein of interest (POI). We also show that the dormancy of DAO-PROTACs translates to considerable mitigation of cytotoxicity, demonstrating the potential advantages over the corresponding free PROTAC and single-stimulus triggerable pro-PROTACs.}, archive = {J_JACS}, author = {Ranit Dutta and Anirudh Devarajan and Amelia Talluri and Ritam Das and S. Thayumanavan}, doi = {10.1021/jacs.5c00131}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9074--9078}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual-action-only PROTACs}, volume = {147}, year = {2025}, }
• (2025). Rigidity reinforcement of 3D covalent organic frameworks by controlling interpenetration. JACS, 147(11), 9067--9073. (www)

  @article{ , abstract = {Here, we report the synthesis of a 3D covalent organic framework (COF), COF-308, with unique [4 + 2] interpenetration. Rather than inducing unwanted structure dynamics and a drastic drop in surface area, this interpenetration mode enhanced the structural rigidity and achieved a desirable surface area. Such an interpenetration was unveiled by single crystal X-ray diffraction (SCXRD) analysis with a resolution of 0.95 Å. A “face-to-face” packing of tetrahedral shaped building blocks in adjacent frames was observed, locking the slide and twisting the molecular motion. The structure rigidity and permanent porosity were further assessed by in situ small-angle X-ray scattering measured along gas adsorption and desorption processes. The distribution of gases was studied across the entire isotherm, outlining the anisotropy of the pores within COF-308. Such anisotropy, ideally suited for gas storage and separation, was endowed by this new interpenetration mode, where the “face-to-face” packing of building blocks was found to be the critical control.}, archive = {J_JACS}, author = {Huan Wang and Lezhi Yi and Gaoli Hu and Xue Zhou and Hexiang Deng}, doi = {10.1021/jacs.4c18749}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9067--9073}, shortjournal = {J. Am. Chem. Soc.}, title = {Rigidity reinforcement of 3D covalent organic frameworks by controlling interpenetration}, volume = {147}, year = {2025}, }
• (2025). Solution synthesis of single crystalline zinc nanowires. JACS, 147(11), 9062--9066. (www)

  @article{ , abstract = {Nanowires of relatively stable metals, including Au, Ag, Cu, Pt, and Pd have garnered much attention for their highly anisotropic shapes, unique properties, and demonstrated potential applications. However, nanowires of more reactive metals, such as Zn, are much less explored. Here, we report a solution-phase synthesis that generates single crystalline Zn nanowires in high yield that remain air stable for months due to a native oxide layer protecting the metal surface. The diameter of the nanowires is around 50–90 nm and the length extends well over 20 μm along ⟨0001⟩ and ⟨1 2 10⟩ directions. These high aspect ratio nanowires readily form percolated network when blended in resins, which could bring new opportunities for Zn-based anticorrosion coatings. In a proof-of-concept, by replacing Zn microparticles with nanowires, comparable anticorrosion performance can be achieved while reducing Zn loading by 75 wt % and overall coating weight by 60%. This discovery provides a material foundation to explore the synthesis and properties of relatively reactive metal nanostructures.}, archive = {J_JACS}, author = {Dasai Ban and Mingtao Chen and Fan Guo and Shengnan Xu and Jiaxing Huang}, doi = {10.1021/jacs.4c18640}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9062--9066}, shortjournal = {J. Am. Chem. Soc.}, title = {Solution synthesis of single crystalline zinc nanowires}, volume = {147}, year = {2025}, }
• (2025). Cobalt-embedded Metal–Covalent organic frameworks for CO2 photoreduction. JACS, 147(11), 9056--9061. (www)

  @article{ , abstract = {With the pressing urgency to reduce carbon footprint, photocatalytic carbon dioxide reduction has attracted growing attention as a sustainable mitigating option. Considering the important role of catalytic active sites (CASs) in the catalytic processes, control and design of the density and environment of CASs could enhance the catalyst performance. Herein, we report a novel metal–covalent organic framework (MCOF), MCOF-Co-315, featuring earth-abundant Co cocatalysts and conjugation through a covalently bonded backbone. MCOF-Co-315 showed a CO production rate of 1616 μmol g –1 h –1 utilizing Ru(bpy) 3 Cl 2 as photosensitizer and triethanolamine (TEOA) as sacrificial electron donor with a 1.5 AM filter, vis mirror module (390–740 nm), and irradiation intensity adjusted to 1 sun and an especially outstanding apparent quantum yield (AQY) of 9.13% at 450 nm. The photocatalytic reaction was studied with electron paramagnetic resonance (EPR) spectroscopy, X-ray absorption near-edge structure (XANES), and in situ synchrotron Fourier Transform Infrared (FT-IR) spectroscopy, and an underlying mechanism is proposed.}, archive = {J_JACS}, author = {Wanpeng Lu and Claudia E. Tait and Gokay Avci and Xian’e Li and Agamemnon E. Crumpton and Paul Shao and Catherine M. Aitchison and Fabien Ceugniet and Yuyun Yao and Mark D. Frogley and Donato Decarolis and Nan Yao and Kim E. Jelfs and Iain McCulloch}, doi = {10.1021/jacs.4c18450}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9056--9061}, shortjournal = {J. Am. Chem. Soc.}, title = {Cobalt-embedded Metal–Covalent organic frameworks for CO2 photoreduction}, volume = {147}, year = {2025}, }
• (2025). Ultrathin ti-deficient TiO2 nanosheets with pt single atoms enable efficient photocatalytic nitrate reduction to ammonia. JACS, 147(11), 9049--9055. (www)

  @article{ , abstract = {Ti-deficient TiO 2 nanosheets derived from lepidocrocite-type titanate delamination show a p-type conductivity with a band gap widened by the quantum confinement effect to 3.7 eV. This shift in the extended band positions─and thus in the electron transfer level─allows a direct photocatalytic nitrate reduction to ammonia without the use of any hole scavengers; this in contrast to classic TiO 2 . The deposition of Pt single atoms as cocatalysts onto the nanosheets significantly enhances the activity and selectivity toward ammonia, which outperforms classic Pt nanoparticles used as cocatalyst. The present study therefore reports not only on the unique photocatalytic properties of these Ti-deficient TiO 2 nanosheets but also on the beneficial use of the modified electronic properties that enable entirely novel applications, such as the technologically highly important reduction of nitrate to ammonia.}, archive = {J_JACS}, author = {Hayoon Jung and Gihoon Cha and Hyesung Kim and Johannes Will and Xin Zhou and Erdmann Spiecker and Josef Breu and Patrik Schmuki}, doi = {10.1021/jacs.4c18200}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9049--9055}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultrathin ti-deficient TiO2 nanosheets with pt single atoms enable efficient photocatalytic nitrate reduction to ammonia}, volume = {147}, year = {2025}, }
• (2025). Stabilization of sb4 tetrahedra in paramagnetic transition metal carbonyl complexes. JACS, 147(11), 9043--9048. (www)

  @article{ , abstract = {We present a straightforward synthetic route to the novel chromium carbonyl-stabilized paramagnetic Sb 4 -based cluster [Et 4 N] 4 [Sb 4 Cr 6 (CO) 28 ] ([Et 4 N] 4 [ 1 ]), which represented a rare example of the intact Sb 4 tetrahedron structurally characterized in the solid state. Complex 1 exhibited versatile reactivities toward groups 7–9 metal carbonyls, dioxygen, or [Cu(MeCN) 4 ][BF 4 ] to form selective orbital-controlled Sb 4 -based products, including transmetalated paramagnetic complexes [Et 4 N] 4 [Sb 4 Cr 5 Mn(CO) 28 ]Br ([Et 4 N] 4 [ 1-Mn ]Br), [Et 4 N] 4 [Sb 4 Cr 2 Fe 6 (CO) 30 ] ([Et 4 N] 4 [ 1-Fe ]), and [Et 4 N] 2 [Sb 4 Cr 4 Co 4 (CO) 31 ] ([Et 4 N] 2 [ 1-Co ]), the dioxygen-activated paramagnetic cluster [Et 4 N] 4 [O 2 Sb 4 Cr 6 (CO) 28 ] ([Et 4 N] 4 [ 1-O 2 ]), or the spin-quenched complex [Et 4 N] 2 [Sb 4 Cr 6 (CO) 28 ] ([Et 4 N] 2 [ 2 ]), respectively. The structural nature, bonding properties, paramagnetism, and semiconductivity of these unprecedented transition metal carbonyl-protected Sb 4 -based clusters were further realized with DFT calculations.}, archive = {J_JACS}, author = {Yu-Huei Li and Chia-Hsien Lin and Hui-Lung Chen and En-Che Yang and Minghuey Shieh}, doi = {10.1021/jacs.4c13882}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9043--9048}, shortjournal = {J. Am. Chem. Soc.}, title = {Stabilization of sb4 tetrahedra in paramagnetic transition metal carbonyl complexes}, volume = {147}, year = {2025}, }
• (2025). Concise biosynthesis of antifungal papulacandins. JACS, 147(11), 9037--9042. (www)

  @article{ , abstract = {We report the complete biosynthesis of antifungal papulacandins through heterologous expression and enzymatic assays. The papulacandin biosynthesis follows a convergent five-component strategy, involving a linear polyketide chain that is synthesized and installed to the aryl-glucoside by a polyketide synthase fused with a C-terminal acyltransferase domain. The formation of the challenging tricyclic benzannulated spiroketal core is initiated by the C -glycosylation of 5-(hydroxymethyl)resorcinol, followed by spirocyclization catalyzed by a Fe(II)/α-ketoglutarate-dependent oxygenase PpcE.}, archive = {J_JACS}, author = {Chao Yu and Niandi Zhang and Jinmei Li and Mingxin Zheng and Meihui Zhao and Ling-Yan Wang and Zhiqiang An and Gerald F. Bills and Zhuan Zhang}, doi = {10.1021/jacs.4c13101}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9037--9042}, shortjournal = {J. Am. Chem. Soc.}, title = {Concise biosynthesis of antifungal papulacandins}, volume = {147}, year = {2025}, }
• (2025). Electrochemical CO2 reduction in acidic media: A perspective. JACS, 147(11), 9019--9036. (www)

  @article{ , abstract = {The electrochemical CO 2 reduction reaction (eCO 2 RR) is a promising approach for converting CO 2 to useful chemicals and, hence, achieving carbon neutrality. Though high selectivity and activity of products have been achieved recently, all are reported in neutral or alkaline electrolytes. Although these electrolyte media give high selectivity and activity, they face the major challenge of low CO 2 utilization because of carbonate formation, which lowers the overall efficiency of the process. Conducting the eCO 2 RR in acidic media can help overcome the issue of carbonate formation and hence can increase the CO 2 utilization efficiency. However, there are many challenges associated with acidic eCO 2 RR. Two major concerns are the highly competitive hydrogen evolution reaction in acidic media and salt precipitation issues. This Perspective focuses on the fundamentals of acidic eCO 2 RR, recent catalyst development strategies, and relevant problems that need to be addressed in the future. In the end, we provide a future outlook that will give an idea about the problems to focus on in the future in the field of acidic eCO 2 RR.}, archive = {J_JACS}, author = {Nilutpal Dutta and Sebastian C. Peter}, doi = {10.1021/jacs.5c00164}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9019--9036}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical CO2 reduction in acidic media: A perspective}, volume = {147}, year = {2025}, }
• (2025). Advances in organic small molecule-based fluorescent probes for precision detection of liver diseases: A perspective on emerging trends and challenges. JACS, 147(11), 9001--9018. (www)

  @article{ , abstract = {Liver disease poses a significant challenge to global health, and its early diagnosis is crucial for improving treatment outcomes and patient prognosis. Since fluctuation of key biomarkers during the onset and progression of liver diseases can directly reflect liver health and normal/abnormal function, biomarker-based assays are vital tools for the early detection of liver disease. In this context, small molecule fluorescent probes have undeniably emerged as indispensable tools for diagnosis and analysis, with an ever-growing number of small molecule-based fluorescent probes being developed over recent years, with the sole aim of monitoring relevant biomarkers of liver disease. This perspective will focus on the development and application of probes developed primarily over the last 10 years for diagnosing a range liver disease-related processes. It will outline the foundational design strategies for developing promising probes, their optical response to key biomarkers, and how they have been demonstrated in proof-of-concept imaging applications. Current challenges and new developments in the field will be discussed, with the aim of providing insights and highlighting opportunities in the field.}, archive = {J_JACS}, author = {Luling Wu and Zilu Li and Kun Wang and Robin R. Groleau and Xiaodi Rong and Xueting Liu and Caiyun Liu and Simon E. Lewis and Baocun Zhu and Tony D. James}, doi = {10.1021/jacs.4c17092}, journal = {Journal of the American Chemical Society}, month = {3}, number = {11}, pages = {9001--9018}, shortjournal = {J. Am. Chem. Soc.}, title = {Advances in organic small molecule-based fluorescent probes for precision detection of liver diseases: A perspective on emerging trends and challenges}, volume = {147}, year = {2025}, }
• (2025). Correction to “Stacking faults assist lithium-ion conduction in a halide-based superionic conductor”. JACS, 147(10), 9000. (www)

  @article{ , archive = {J_JACS}, author = {Elias Sebti and Hayden A. Evans and Hengning Chen and Peter M. Richardson and Kelly M. White and Raynald Giovine and Krishna Prasad Koirala and Yaobin Xu and Eliovardo Gonzalez-Correa and Chongmin Wang and Craig M. Brown and Anthony K. Cheetham and Pieremanuele Canepa and Raphaële J. Clément}, doi = {10.1021/jacs.5c02447}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {9000}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Stacking faults assist lithium-ion conduction in a halide-based superionic conductor”}, volume = {147}, year = {2025}, }
• (2025). Synthesis and structure of uranium disilyl-substituted alkylidene complexes. JACS, 147(10), 8991--8999. (www)

  @article{ , abstract = {Understanding the participation of f-orbitals of actinide elements in covalent bond formations is less explored, compared to the well-studied d-orbitals of transition metals, leading to the significant interest in actinide–carbon multiple bonds. Uranium alkylidene complex, containing an alkylidene linkage of the form U═CR 2 (R = H, alkyl, silyl), represents a key milestone in actinide-ligand multiple bonding, but their isolation and characterization have remained elusive. Herein, we present the synthesis of an unprecedented uranium disilyl-substituted alkylidene complex, achieved through sequential dehydrogenation reactions of a methyl group under mild conditions. Single-crystal X-ray diffraction reveals the U═C double bond length of 2.332(4) Å. Quantum chemical calculations suggest that both 5f and 6d orbitals of uranium play a key role in the U═C double bond formation.}, archive = {J_JACS}, author = {Yafei Li and Chengxiang Ding and Qianyi Zhao and Shuao Wang and Jin Xie and Sudip Pan and Congqing Zhu}, doi = {10.1021/jacs.5c01486}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8991--8999}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis and structure of uranium disilyl-substituted alkylidene complexes}, volume = {147}, year = {2025}, }
• (2025). N2O activation and NO adsorption control the simultaneous conversion of N2O and NO using NH3 over fe-ZSM-5. JACS, 147(10), 8978--8990. (www)

  @article{ , abstract = {Fe-exchanged zeolites are heterogeneous catalysts that can potentially ensure simultaneous conversion of nitrous oxide (N 2 O) and nitric oxide (NO) using ammonia (NH 3 ) as a selective reducing agent through their selective catalytic reduction reaction (N 2 O-NO-SCR). In this study, we rationalize the origin of the beneficial effect of N 2 O on the NO conversion by combining catalytic experiments with ex situ characterization and in situ/operando X-ray absorption spectroscopy (XAS) and infrared spectroscopy in diffuse reflectance mode (DRIFTS) on a series of Fe-ZSM-5 catalysts where we attempted to control Fe speciation at constant Fe content. The catalytic activity data revealed that N 2 O can promote NO conversion at different temperatures and to different extents. This behavior was found to be related to the activity of the catalysts in the NO-mediated N 2 O decomposition reaction, which ensures the oxidative transformation of NO and thus sustains the N 2 O-NO-SCR chemistry. The oxidation activity is in turn determined by processes of N 2 O activation and NO adsorption, which are a function of the Fe speciation and are likely catalyzed by a minority of isolated Fe 2+ sites coordinated in different cationic environments. In agreement, the concentrations of the Fe species able to activate N 2 O ( C α ) and of the Fe species able to coordinate NO ( C Fe-NO ) decrease with an increasing degree of Fe agglomeration and govern especially the promotion of the NO conversion induced by N 2 O in this dual-site mechanism. Maximization of the concentration of both species is therefore essential to design Fe-exchanged zeolites with the highest activity toward the N 2 O-NO-SCR reaction.}, archive = {J_JACS}, author = {Filippo Buttignol and Alberto Garbujo and Pierdomenico Biasi and Oliver Kröcher and Davide Ferri}, doi = {10.1021/jacs.5c01100}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8978--8990}, shortjournal = {J. Am. Chem. Soc.}, title = {N2O activation and NO adsorption control the simultaneous conversion of N2O and NO using NH3 over fe-ZSM-5}, volume = {147}, year = {2025}, }
• (2025). Pd-catalyzed strain-releasing dyotropic rearrangement: Ring-expanding amidofluorination of methylenecyclobutanes. JACS, 147(10), 8969--8977. (www)

  @article{ , abstract = {Under the Pd(II)/Pd(IV) catalytic cycle, the cyclization of pent-4-en-1-amine derivatives typically yields either pyrrolidines or piperidines depending on the N-protecting group. We report herein an unprecedented Pd(II)-catalyzed oxidative domino process that converts readily accessible N-protected 2-(2-amidoethyl)-1-methylenecyclobutane derivatives to 1-fluoro-2-azabicyclo[3.2.1]octanes. This transformation constructs three chemical bonds under mild conditions [Pd(hfacac) 2 (5.0 mol %), Selectfluor (2.0 equiv), MeCN, 60 °C, 10 min] through a domino sequence involving 5- exo -trig amidopalladation/Pd(II)–oxidation/chemoselective dyotropic rearrangement/C–F bond-forming reductive elimination. Notably, the cyclization mode remains independent of the N-protecting group under these conditions. Furthermore, diverse functional groups can be introduced at the bridgehead position of a bicyclic compound via an apparent anti -Bredt bridgehead iminium intermediate.}, archive = {J_JACS}, author = {Baochao Yang and Guoqiang Yang and Qian Wang and Jieping Zhu}, doi = {10.1021/jacs.5c01108}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8969--8977}, shortjournal = {J. Am. Chem. Soc.}, title = {Pd-catalyzed strain-releasing dyotropic rearrangement: Ring-expanding amidofluorination of methylenecyclobutanes}, volume = {147}, year = {2025}, }
• (2025). Revealing the relationship between publication bias and chemical reactivity with contrastive learning. JACS, 147(10), 8959--8968. (www)

  @article{ , abstract = {A synthetic method’s substrate tolerance and generality are often showcased in a “substrate scope” table. However, substrate selection exhibits a frequently discussed publication bias: unsuccessful experiments or low-yielding results are rarely reported. In this work, we explore more deeply the relationship between such a publication bias and chemical reactivity beyond the simple analysis of yield distributions using a novel neural network training strategy, substrate scope contrastive learning . By treating reported substrates as positive samples and nonreported substrates as negative samples, our contrastive learning strategy teaches a model to group molecules within a numerical embedding space, based on historical trends in published substrate scope tables. Training on 20,798 aryl halides in the CAS Content Collection TM , spanning thousands of publications from 2010 to 2015, we demonstrate that the learned embeddings exhibit a correlation with physical organic reactivity descriptors through both intuitive visualizations and quantitative regression analyses. Additionally, these embeddings are applicable to various reaction modeling tasks like yield prediction and regioselectivity prediction, underscoring the potential to use historical reaction data as a pretraining task. This work not only presents a chemistry-specific machine learning training strategy to learn from literature data in a new way but also represents a unique approach to uncover trends in chemical reactivity reflected by trends in substrate selection in publications.}, archive = {J_JACS}, author = {Wenhao Gao and Priyanka Raghavan and Ron Shprints and Connor W. Coley}, doi = {10.1021/jacs.5c01120}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8959--8968}, shortjournal = {J. Am. Chem. Soc.}, title = {Revealing the relationship between publication bias and chemical reactivity with contrastive learning}, volume = {147}, year = {2025}, }
• (2025). Chiral cross-linked covalent organic framework films for highly sensitive circularly polarized luminescence probing. JACS, 147(10), 8948--8958. (www)

  @article{ , abstract = {The development of covalent organic framework (COF) films featuring circular polarization luminescence (CPL) probing remains a formidable challenge. Herein, we developed a chiral cross-linked COF film to obtain uniform and dense chiral COF films (chirCOFilm) possessing highly sensitive CPL probing for enantiomers. The axial chiral cross-linkers ( R -/ S -BBNA) are initially introduced into the channels of a COF film (COFilm/ R -BBNA or COFilm/ S -BBNA) by the vapor-assisted epitaxial method. Then, olefin groups in R -/ S -BBNA and COF layers undergo a chiral cross-linking reaction under UV irradiation, forming a chirCOFilm. The obtained chirCOFilms have strong chirality with mirror images, fluorescence discoloration, and intense CPL properties. A multitude of rich chiral photopatterns and chirCOFilm/PDMS flexible films are prepared taking advantage of the photochromic properties of the chirCOFilms during UV illumination, showing the potential application of advanced anticounterfeiting. More importantly, the chirCOFilms realize highly sensitive CPL probing of phenethylamine enantiomers at 5% concentration, which can hardly be achieved from their corresponding fluorescence probing. This study not only provides a new strategy for preparing chiral COF films using chiral cross-linking reaction but also opens a new avenue for achieving highly sensitive probing of enantiomers though CPL.}, archive = {J_JACS}, author = {Shui-Ming Jing and Zhi-Gang Gu and Jian Zhang}, doi = {10.1021/jacs.5c00947}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8948--8958}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral cross-linked covalent organic framework films for highly sensitive circularly polarized luminescence probing}, volume = {147}, year = {2025}, }
• (2025). Diatomic C2/NC ligand induced conformation variation of trimetallic clusters within a carbon cage. JACS, 147(10), 8939--8947. (www)

  @article{ , abstract = {Understanding the interplay between conformation and electronic properties of metal complexes at the atomic level is the key for rational design of new functional molecules. Trimetallic clusterfullerenes (TMCFs) encapsulating quinary M 3 C 2 carbide or M 3 NC carbonitride clusters offer an ideal model system for elucidating conformation-electronic property correlation due to its unusual conformational versatility. Herein, we synthesize and isolate two novel lanthanide-transition metal heteronuclear TMCFs, namely, CeTi 2 C 2 @ I h (7)-C 80 and CeTi 2 NC@ I h (7)-C 80 . Crystallographic studies reveal singly bonded C 2 /NC ligands coordinating vertically to the CeTi 2 trimetallic plane within the cluster, drastically different from the bat-ray conformations reported for all homonuclear TMCFs. Such bonding characters give rise to variable electronic structures of [Ce 4+ (Ti 2 ) 8+ (C 2 ) 6– ] 6+ @C 80 6– and [Ce 3+ (Ti 2 ) 8+ (NC) 5– ] 6+ @C 80 6– , featuring a fixed tetravalent oxidation state of Ti and tunable oxidation states of Ce (Ce 4+ /Ce 3+ ), as confirmed by X-ray absorption spectroscopy and magnetic measurements in combination with theoretical studies. Furthermore, scrutinizing all reported TMCFs bearing M 3 C 2 /M 3 NC clusters, we find that the conformations of trimetallic carbide/carbonitride clusters are precisely dictated by the bonding nature of the diatomic C 2 /NC ligand so as to suffice strong coordination interactions with the encapsulated metals. Following such a general rule governing conformational variation, a very strong ligand field is achieved on Ce 3+ in the presence of a singly bonded NC ligand in CeTi 2 NC@C 80 , giving rise to the first Ce-based single-molecule magnet that shows an open magnetic hysteresis at 2 K.}, archive = {J_JACS}, author = {Zhanxin Jiang and Ziqi Hu and Yang-Rong Yao and Xinyi Han and Jinpeng Xin and Shangfeng Yang}, doi = {10.1021/jacs.5c00850}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8939--8947}, shortjournal = {J. Am. Chem. Soc.}, title = {Diatomic C2/NC ligand induced conformation variation of trimetallic clusters within a carbon cage}, volume = {147}, year = {2025}, }
• (2025). Nickel-catalyzed asymmetric homobenzylic hydroamidation of aryl alkenes to access chiral β-arylamides. JACS, 147(10), 8928--8938. (www)

  @article{ , abstract = {Herein, we introduce a Ni-catalyzed asymmetric homobenzylic hydroamidation reaction that efficiently addresses the dual challenges of achieving regio- and enantioselectivity in the synthesis of β-(hetero)arylethylamides. By employing a transposed NiH catalysis approach, this method facilitates the formation of key chiral nickel-amido intermediates, enabling asymmetric insertion into alkenes to produce the desired β-arylamide products with excellent enantioselectivity. The reaction exhibits a high functional group tolerance and utilizes readily available starting materials of vinylarenes to react with dioxazolone as a robust amidating source. Notably, this approach was successfully applied to the synthesis of pharmaceutical compounds and natural products, such as Clobenzorex, Direx, Selegiline, Sacubitril, and Cipargamin.}, archive = {J_JACS}, author = {Xiang Lyu and Eojin Jeon and Changhyeon Seo and Dongwook Kim and Sukbok Chang}, doi = {10.1021/jacs.5c00867}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8928--8938}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-catalyzed asymmetric homobenzylic hydroamidation of aryl alkenes to access chiral β-arylamides}, volume = {147}, year = {2025}, }
• (2025). Enantioselective multicomponent electrochemical difunctionalization of terminal alkynes. JACS, 147(10), 8917--8927. (www)

  @article{ , abstract = {The direct functionalization of alkyne triple bonds using a radical strategy provides an efficient platform for creating a wide range of substituted alkenes. However, developing a multicomponent enantioselective radical reaction using feedstock alkynes to forge all-carbon quaternary stereocenters─while addressing challenges related to compatibility, selectivity, and efficiency─remains relatively rare. Here we report an enantioselective electrochemical nickel-catalyzed three-component cross-coupling of readily available terminal alkynes, diverse racemic alkyl radical precursors, and group transfer reagents (such as (TMS) 3 Si-H, RSe-SeR, RTe-TeR, and CHI 3 ), achieving excellent regio-, stereo-, and enantioselectivities (more than 70 examples, up to 95% ee). Electricity-mediated difunctionalizations significantly expand the scope of both aliphatic and aromatic alkynes, demonstrating excellent functional group compatibility. The key to success lies in the rational design of anodically generated nickel-bound tertiary radical intermediates, which stereoselectively capture alkynes to form vinyl radicals and participate in subsequently diverse group transfer processes to enable the intermolecular and anti -stereoselective difunctionalization of alkynes. This approach allows the transformation of terminal alkynes into diverse structural entities with α-quaternary stereogenic centers.}, archive = {J_JACS}, author = {Qiannan Wang and Xinyu Wang and Yong Liu and Jiayin Zhang and Jin Song and Chang Guo}, doi = {10.1021/jacs.5c00830}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8917--8927}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective multicomponent electrochemical difunctionalization of terminal alkynes}, volume = {147}, year = {2025}, }
• (2025). Photothermal cavitation-driven micromotor to penetrate cell membrane. JACS, 147(10), 8906--8916. (www)

  @article{ , abstract = {Photothermally driven micro/nanomotors efficiently convert light into mechanical motion, making them highly attractive for biomedical applications due to their exceptional biocompatibility and safety. However, one mystery of the photothermally driven micro/nanomotor is the wide range of reported light intensities applied, ranging from 1 W cm –2 to over 10 5 W cm –2 . To address this mystery, we systematically investigated the propulsion of a carbon microbottle-based micromotor under three illumination conditions: continuous laser, pulsed laser, and scanning laser, where a new cavitation-driven mechanism is identified. Using a high-speed camera, we find that the instantaneous deposition of laser energy on the micromotors can lead to transient and localized evaporation of the solvent, creating cavitation bubbles to drive micromotors with ultrafast speed, where instantaneous velocity over 1 m s –1 is observed. Through precise modulation of the scanning orientation and intensity of the laser, directional propulsion and targeted explosions of the microbottles are achieved, where the instant force is strong enough to penetrate live cell membranes. Finally, the cavitation-driven micromotors are exploited as gene transfection tools, where targeted cytoplasmic transfection is demonstrated.}, archive = {J_JACS}, author = {Binglin Zeng and Jialin Lai and Jingyuan Chen and Yaxin Huang and Qingxin Guo and Chao Huang and Xiaofeng Li and Changjin Wu and Shuai Li and Jinyao Tang}, doi = {10.1021/jacs.5c00482}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8906--8916}, shortjournal = {J. Am. Chem. Soc.}, title = {Photothermal cavitation-driven micromotor to penetrate cell membrane}, volume = {147}, year = {2025}, }
• (2025). Self-triggering a locally alkaline microenvironment of Co4Fe6 for highly efficient neutral ammonia electrosynthesis. JACS, 147(10), 8893--8905. (www)

  @article{ , abstract = {Electrochemical nitrate reduction reaction (eNO 3 – RR) to ammonia (NH 3 ) holds great promise for the green treatment of NO 3 – and ambient NH 3 synthesis. Although Fe-based electrocatalysts have emerged as promising alternatives, their excellent eNO 3 – RR-to-NH 3 activity is usually limited to harsh alkaline electrolytes or alloying noble metals with Fe in sustainable neutral electrolytes. Herein, we demonstrate an unusual self-triggering localized alkalinity of the Co 4 Fe 6 electrocatalyst for efficient eNO 3 – RR-to-NH 3 activity in neutral media, which breaks down the conventional pH-dependent kinetics restrictions and shows a 98.6% NH 3 Faradaic efficiency (FE) and 99.9% NH 3 selectivity at −0.69 V vs RHE. The synergetic Co–Fe dual sites were demonstrated to enable the optimal free energies of eNO 3 – RR-to-NH 3 species and balance water dissociation and protonation of adsorbed NO 2 – . Notably, the Co 4 Fe 6 electrocatalysts can attain a high current density of 100 mA cm –2 with a high NH 3 FE surpassing 96% and long-term stability for over 500 h eNO 3 – RR-to-NH 3 in a membrane electrode assembly (MEA) electrolyzer. This work provides insight into tailoring the self-reinforced local-alkalinity on the Fe-based alloy electrocatalysts for eNO 3 – RR-to-NH 3 and thus avoids alkaline electrolytes and noble metals for practical sustainable nitrate upcycling technology.}, archive = {J_JACS}, author = {Yang Yang and Yuting Sun and Yuning Wang and Xiaoxue Zhang and Wenyu Zhang and Zhen-Feng Huang and Lichang Yin and Ali Han and Gang Liu}, doi = {10.1021/jacs.5c00688}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8893--8905}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-triggering a locally alkaline microenvironment of Co4Fe6 for highly efficient neutral ammonia electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Activated corrosion and recovery in lead mixed-halide perovskites revealed by dynamic near-ambient pressure X-ray photoelectron spectroscopy. JACS, 147(10), 8881--8892. (www)

  @article{ , abstract = {Herein, we quantify rates of O 2 -photoactivated corrosion and recovery processes within triple cation CsFAMAPb(IBr) 3 perovskite active layers using dynamic near-ambient pressure X-ray photoemission spectroscopy (NAP-XPS). Activated corrosion is described as iodide oxidation and lead reduction, which occurs only in the presence of both O 2 and light through photoinduced electron transfer. We observe electron density reorganization from the Pb–I bonds consistent with ligand exchange, evident from the nonstoichiometric redox change (i.e., <1 e – ). Approximately half of the Pb centers are reduced to weakly coordinated Pb–higher oxidation number than metallic Pb–with a rate coefficient of ∼3 (±0.3) × 10 –4 atomic percent/s. Hole capture by I – yields I 3 – and is accompanied by increased concentrations of near-surface bromides, hypothesized to be due to anion vacancies and/or oxidation of mobile iodide resulting from ion demixing. Activated corrosion is found to be quasi-reversible; initial perovskite stoichiometry slowly recovers when the O 2 /light catalyst is removed, postulated to be due to mobile halide species present within the film below XPS sampling depth. Small deviations in near-surface composition (<2%) of the perovskite are used to connect reaction rates to quantified, near-band edge donor and acceptor defect concentrations, demonstrating two energetically distinct sites are responsible for the redox process. Collectively, environmental flux and rate quantification are deemed critical for the future elucidation of chemical degradation processes in perovskites, where rate-dependent reaction pathways are expected to be very system dependent (environment and material).}, archive = {J_JACS}, author = {Michel De Keersmaecker and Paul Dietrich and Mounib Bahri and Nigel D. Browning and Neal R. Armstrong and Erin L. Ratcliff}, doi = {10.1021/jacs.5c00668}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8881--8892}, shortjournal = {J. Am. Chem. Soc.}, title = {Activated corrosion and recovery in lead mixed-halide perovskites revealed by dynamic near-ambient pressure X-ray photoelectron spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Tailoring activation intermediates of CO2 initiates C–N coupling for highly selective urea electrosynthesis. JACS, 147(10), 8871--8880. (www)

  @article{ , abstract = {Electrocatalyzed reduction of CO 2 and NO 3 – to synthesize urea is a highly desirable, but challenging reaction. The bottleneck of this reaction is the C–N coupling of CO 2 and NO 3 – reduction intermediates. In particular, the uncertainty of CO 2 multielectron reduction intermediates severely affects the selectivity and activity of C–N coupling processes involving multiple electron and proton transfers. Here, we present a novel tandem catalyst with two compatible single-atom active sites of Au and Cu on red phosphorus (RP-AuCu) that efficiently converts CO 2 and NO 3 – to urea. Experimental and theoretical prediction results confirmed that the active center of Au on red phosphorus promotes electron transfer between CO 2 molecules and red phosphorus, thereby regulating CO 2 activation intermediates to produce electrophilic *COOH. In addition, the active center of Cu on red phosphorus can enhance the electrophilic attack of *COOH species on *NH 2 , thus promoting the selective formation of C–N bonds. Consequently, RP-AuCu exhibited a urea yield of 22.9 mmol g cat. –1 h –1 and a Faraday efficiency of 88.5% (−0.6 V RHE ), representing one of the highest levels of electrocatalytic urea synthesis. This work deepens the understanding of the C–N coupling mechanism and provides an interesting catalyst design approach for the efficient and sustainable production of C–N compounds.}, archive = {J_JACS}, author = {Chao Zhao and Yu Jin and Jingkang Yuan and Qilin Hou and He Li and Xiaoqing Yan and Honghui Ou and Guidong Yang}, doi = {10.1021/jacs.5c00583}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8871--8880}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailoring activation intermediates of CO2 initiates C–N coupling for highly selective urea electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Enantiopurity by directed evolution of crystal stabilities and nonequilibrium crystallization. JACS, 147(10), 8864--8870. (www)

  @article{ , abstract = {Crystallization is a powerful method to isolate enantiopure molecules from racemates if enantiomers self-sort into separate enantiopure crystals. Unfortunately, this behavior is unpredictable and rare (5–10%), as both enantiomers predominantly crystallize together to form racemic crystals, hindering any such chiral sorting. These unfavorable statistics might be overcome using nonequilibrium conditions. Therefore, we systematically characterize energy differences (Δ G Φ ) between racemic and enantiopure crystal phases for libraries of target molecules (phenylglycine, praziquantel) with different chemical modifications. Surprisingly, these libraries reveal wide but similar continuous distributions of Δ G Φ , wherein similar chemical modifications group together. This grouping allows a directed evolution strategy to discover racemic crystals with low Δ G Φ for isolating desired enantiomers by crystallization under nonequilibrium conditions. Comparison with over a hundred previously reported compounds suggests that as many as half of all chiral molecules may kinetically form enantiopure crystals (∼50%). These insights open new previously unconsidered possibilities for isolating enantiopure molecules.}, archive = {J_JACS}, author = {Clément Pinetre and Sjoerd W. van Dongen and Clément Brandel and Anne-Sophie Léonard and Maxime D. Charpentier and Valérie Dupray and Kasper Oosterling and Bernard Kaptein and Michel Leeman and Richard M. Kellogg and Joop H. ter Horst and Willem L. Noorduin}, doi = {10.1021/jacs.5c00569}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8864--8870}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantiopurity by directed evolution of crystal stabilities and nonequilibrium crystallization}, volume = {147}, year = {2025}, }
• (2025). Transition state analysis of SAMHD1 from primary 18O, 33P, and solvent kinetic isotope effects. JACS, 147(10), 8852--8863. (www)

  @article{ , abstract = {Human sterile alpha motif and HD-domain-containing protein 1 (SAMHD1) is an allosterically regulated dNTP triphosphohydrolase (dNTP + H 2 O → dNuc + PPPi) involved in deoxynucleotide regulation and DNA repair. We characterized the chemical features of the SAMHD1 transition state for 2′-deoxyadenosine 5′-triphosphate (dATP) hydrolysis by analysis of 18 O and 33 P primary kinetic isotope effects (KIEs) at the α-phosphoryl of the leaving triphosphate group. The intrinsic KIE values for [5′- 18 O]dATP of 1.028 ± 0.003 and for [α- 33 P]dATP of 1.015 ± 0.004 provide insights into the mechanistic details of the SAMHD1 transition state. Solvent 2 H 2 O isotope effects for the hydrolysis of dATP indicate that a single proton is being transferred at the transition state to give a solvent KIE of 3.2 ± 0.1. Quantum chemical matching of the isotope effects supports a concerted, loose, highly asymmetric D N A N transition state with a Pauling bond order of 0.17 to the attacking hydroxide oxygen nucleophile and 0.53 to the departing deoxyadenosine. The reaction coordinate distance is 4.7 Å from attacking the hydroxyl oxygen to departing 5′-deoxyadenosine oxygen. The solvent KIE is consistent with a near-midpoint proton transfer from the His215 catalytic site proton donor to the deoxyadenosine 5′-oxygen in the transition state. This is the first triphosphohydrolase transition state to be characterized and the first use of a 33 P primary isotope effect to characterize a phosphotransferase transition state.}, archive = {J_JACS}, author = {Ananda K. Ghosh and Daniel P. Groom and Vern L. Schramm}, doi = {10.1021/jacs.5c00521}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8852--8863}, shortjournal = {J. Am. Chem. Soc.}, title = {Transition state analysis of SAMHD1 from primary 18O, 33P, and solvent kinetic isotope effects}, volume = {147}, year = {2025}, }
• (2025). Elucidating gas reduction effects of organosilicon additives in lithium-ion batteries. JACS, 147(10), 8841--8851. (www)

  @article{ , abstract = {Lithium-ion batteries (LIBs) with nonaqueous liquid electrolytes are prone to gas generation at elevated voltages and temperatures, degrading battery performance and posing serious safety risks. Organosilicon (OS) additives are an emerging candidate solution for gassing problems in LIBs, but a detailed understanding of their functional mechanisms remains elusive. In this work, we present a combined computational and experimental study to elucidate the gas-reducing effects of OS additives. Cell volume measurements and gas chromatography–mass spectrometry reveal that OS additives can substantially reduce gas evolution in LIBs, particularly CO 2 regardless of source. Through density functional theory calculations, we identify multiple plausible pathways for CO 2 evolution, including (1) nucleophile-induced ring-opening of ethylene carbonate (EC) and the subsequent electro-oxidation and (2) direct electro-oxidation of lithium carbonate (Li 2 CO 3 ). Correspondingly, we find that OS additives function via two primary mechanisms: (1) scavenging of nucleophiles such as superoxide (O 2 •– ), peroxide (O 2 2– ), and carbonate ion (CO 3 2– ); (2) oligomerization with ethylene carbonate oxide ion and ethylene dicarbonate ion. Moreover, we discover that OS additives possess strong lithium coordination affinity, which helps further reduce the nucleophilic reaction energies and hence increases their nucleophile-scavenging efficiency. Finally, we provide a mechanistic interpretation for the enhanced gas-reduction effects observed with fluorinated OS compounds, corroborated by surface analysis results from X-ray photoelectron spectroscopy. Our study offers the first molecular-level insights into how OS additives contribute to reduced gas formation in LIBs, paving the way for improved safety and performance of LIBs.}, archive = {J_JACS}, author = {Jingyang Wang and Sarah L. Guillot and Monica L. Usrey and Tingzheng Hou and Kristin A. Persson}, doi = {10.1021/jacs.5c00402}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8841--8851}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating gas reduction effects of organosilicon additives in lithium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Rational design of a quasi-Metal–Organic framework by ligand engineering for efficient biomass upgrading. JACS, 147(10), 8832--8840. (www)

  @article{ , abstract = {The electrooxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a monomer for degradable bioplastic, is a promising strategy for biomass upgrade and yet requires well-designed catalysts with high efficiency and selectivity. Taking advantage of the open metal sites of metal–organic frameworks (MOFs), quasi-MOFs represent viable catalysts, but the poor designability and unpredictable structures hinder their development. In this work, a Ni-based quasi-MOF was rationally designed and synthesized by controlled ligand engineering. Compared to the fully occupied metal clusters in the pristine MOFs, the accessible Ni sites in quasi-MOFs can efficiently convert HMF to FDCA with remarkable Faradaic efficiency (99.2%) and FDCA selectivity (98.3%). In situ characterizations and mechanistic analysis revealed that the open Ni sites created by partial ligand disconnection in quasi-MOFs are critical to the formation of high-valent active species and HMF oxidation. Moreover, serving as the anode in an integrated electrolysis system, such a quasi-MOF can not only reduce the cell voltage for hydrogen generation but also produce high-purity FDCA with good yield, offering a new opportunity for the simultaneous production of high value-added chemicals and sustainable hydrogen.}, archive = {J_JACS}, author = {Ning-Yu Huang and Bingxian Chu and Di Chen and Bing Shao and Yu-Tao Zheng and Lei Li and Xin Xiao and Qiang Xu}, doi = {10.1021/jacs.5c00294}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8832--8840}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design of a quasi-Metal–Organic framework by ligand engineering for efficient biomass upgrading}, volume = {147}, year = {2025}, }
• (2025). Mixed 1D/0D structures of chiral hybrid lead halides with an l-nicotinium spacer exhibit broadband photoluminescence and polarized emission. JACS, 147(10), 8820--8831. (www)

  @article{ , abstract = {Hybrid lead halide materials have been highly studied for optoelectronics, but their use with chiral organics in chiro-optoelectronics remains limited. Understanding the ability to impart chirality into bulk materials by incorporating a chiral precursor is of great interest due to unique optical properties directly arising from chirality such as circular dichroism, optical rotatory dispersion, and circularly polarized luminescence. Herein, we used protonated l -nicotine (L-n) (nicotinium cations) as a spacer and templated a variety of structures including a series of (L-n) 3 M 4 X 14 (M = Sn, Pb; X = Cl, Br, I) that take space group P 6 3 in which the lead halide regions template two distinct moieties, both a 1D chain motif and a 0D cluster motif. Hydrogen bonding of the L-n and lone pair expression of the metal play a significant role in structural templating. The materials exhibit large band gaps of 2.70, 3.41, and 3.71 eV for X = I, Br, and Cl, respectively. They also exhibit broadband emission with a large Stokes shift, where the emission can come from both the cluster and chain depending on the composition and excitation. Single crystals exhibit linearly polarized light emission with iodide composition, giving a high degree of polarization of 0.61, among the highest reported for 1D hybrid lead halide materials at room temperature. Solution-processed thin films show strong CD responses corresponding to the choice of organic cation, indicating potential for device investigations.}, archive = {J_JACS}, author = {Jared D. Fletcher and Jadupati Nag and Ramin Yazdaanpanah and Saugata Sarker and Sachin Kulkarni and Isaiah W. Gilley and Koray Aydin and Venkatraman Gopalan and Mercouri G. Kanatzidis}, doi = {10.1021/jacs.5c00234}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8820--8831}, shortjournal = {J. Am. Chem. Soc.}, title = {Mixed 1D/0D structures of chiral hybrid lead halides with an l-nicotinium spacer exhibit broadband photoluminescence and polarized emission}, volume = {147}, year = {2025}, }
• (2025). Electric field-driven long-range order and enhanced polarization switching in high-dipole ionic liquids. JACS, 147(10), 8809--8819. (www)

  @article{ , abstract = {Ionic liquids (ILs) with significant dipole moments exhibit massive electric polarization ( P ) under an applied AC electric field ( E ) at room temperature. Among the various investigated ILs, the p -toluene sulfonate of 1-ethyl-3-methylimidazolium, [C 2 mim][Tos], which has a large dipole moment in the tosylate anion (∼10.99 D), shows large hysteresis in P – E curves with a high saturation polarization ( P s ∼ 92 μC cm –2 ) and a remanent polarization ( P r ∼ 68 μC cm –2 ) at a relatively low electric field E (1.75 kV cm –1 ). The mechanism of polarization and its switching in ILs are corroborated by the switching current peaks observed in current density ( j ) versus E ( j–E ) profiles and the change in fluorescence intensity of a cyanine dye doped in ILs. The reversible cyanine fluorescence intensity changes in response to the applied AC electric field reflect the dynamic orientational changes of the IL, synchronized with the polarization reversal. The dependence of P s and P r values on applied AC electric fields ( E ) is fitted by two straight lines with different slopes, below and above a threshold electric field E th (∼1.25 kV cm –1 ). Long-range order is not obtained below the threshold potential of E th . Under AC electric fields above E th , more significant polarization and cyanine fluorescence responses to the electric field are observed. The present study indicates the presence of long-range ordering of molecular dipole moments over a distance of more than 1 μm from the interfacial adsorption layers through the transition zone to the bulk zone.}, archive = {J_JACS}, author = {Tejwant S. Kang and Masa-aki Morikawa and Manpreet Singh and Nobuo Kimizuka}, doi = {10.1021/jacs.5c00098}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8809--8819}, shortjournal = {J. Am. Chem. Soc.}, title = {Electric field-driven long-range order and enhanced polarization switching in high-dipole ionic liquids}, volume = {147}, year = {2025}, }
• (2025). Preparation of dual-asymmetric acceptors via selenium substitution combined with terminal group optimization strategy for high efficiency organic solar cells. JACS, 147(10), 8796--8808. (www)

  @article{ , abstract = {Improving both the open-circuit voltage ( V OC ) and short-circuit current density ( J SC ) through the development of photovoltaic materials to achieve high power conversion efficiency (PCE) is critical and a significant challenge for organic solar cells (OSCs). Here, we designed novel dual-asymmetric acceptors A-SSe-TCF and A-SSe-LSF by simultaneously asymmetrically regulating the backbone and terminal groups and investigated their synergistic effects on photovoltaic performance in comparison with the monoasymmetric acceptor A-SSe-4F. The dual-asymmetric acceptors exhibit broader spectral absorption and larger half-molecule dipole moment differences, which favored the enhancement of J SC and the reduction of energy loss ( E loss ). Among the binary blends, PM6:A-SSe-TCF exhibits superior phase separation, vertical phase distribution morphology, and more ordered π–π stacking compared to PM6:A-SSe-LSF and PM6:A-SSe-4F. As a result, OSCs based on PM6:A-SSe-TCF achieved a higher PCE of 18.53% with both higher V OC and J SC due to the suppressed nonradiative recombination and enhanced charge extraction capabilities. Furthermore, by incorporating A-SSe-TCF as the third component, the PM6:L8-BO:A-SSe-TCF-based device achieves a champion PCE of 19.73% without V OC loss on account of the decrement of E loss . The novel dual-asymmetric strategy provides new insights into the molecular design and the improvement of PCE for OSCs.}, archive = {J_JACS}, author = {Haoran Yin and Yongjie Cui and Dong Chen and Siqi Liu and Tuhong Wu and Mengqi Yu and Long Ye and Aihui Liang and Yiwang Chen}, doi = {10.1021/jacs.5c00004}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8796--8808}, shortjournal = {J. Am. Chem. Soc.}, title = {Preparation of dual-asymmetric acceptors via selenium substitution combined with terminal group optimization strategy for high efficiency organic solar cells}, volume = {147}, year = {2025}, }
• (2025). Structural influence of the chemical fueling system on a catalysis-driven rotary molecular motor. JACS, 147(10), 8785--8795. (www)

  @article{ , abstract = {Continuous directionally biased 360° rotation about a covalent single bond was recently realized in the form of a chemically fueled 1-phenylpyrrole 2,2′-dicarboxylic acid rotary molecular motor. However, the original fueling system and reaction conditions resulted in a motor directionality of only ∼3:1 (i.e., on average a backward rotation for every three forward rotations), along with a catalytic efficiency for the motor operation of 97% and a fuel efficiency of 14%. Here, we report on the efficacy of a series of chiral carbodiimide fuels and chiral hydrolysis promoters (pyridine and pyridine N -oxide derivatives) in driving improved directional rotation of this motor-molecule. We outline the complete reaction network for motor operation, composed of directional, futile, and slip cycles. Using derivatives of the motor where the final conformational step in the 360° rotation is either very slow or completely blocked, the phenylpyrrole diacid becomes enantiomerically enriched, allowing the kinetic gating of the individual steps in the catalytic cycle to be measured. The chiral carbodiimide fuel that produces the highest directionality gives 13% enantiomeric excess ( e.e. ) for the anhydride-forming kinetically gated step, while the most effective chiral hydrolysis promoter generates 90% e.e . for the kinetically gated hydrolysis step. Combining the best-performing fuel and hydrolysis promoter into a single fueling system results in a 92% e.e. . Under a dilute chemostated fueling regime (to avoid N -acyl urea formation at high carbodiimide concentrations with pyridine N -oxide hydrolysis promoters), the motor continuously rotates with a directionality of ∼24:1 (i.e., a backward rotation for every 24 forward rotations) with a catalytic efficiency of >99% and a fuel efficiency of 51%.}, archive = {J_JACS}, author = {Hua-Kui Liu and Toufic W. Mrad and Axel Troncossi and Stefan Borsley and Benjamin M. W. Roberts and Alexander Betts and David A. Leigh}, doi = {10.1021/jacs.5c00028}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8785--8795}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural influence of the chemical fueling system on a catalysis-driven rotary molecular motor}, volume = {147}, year = {2025}, }
• (2025). Rational construction of layered two-dimensional conjugated Metal–Organic frameworks with room-temperature quantum coherence. JACS, 147(10), 8778--8784. (www)

  @article{ , abstract = {Two-dimensional conjugated metal–organic frameworks (2D c-MOFs) have emerged as an intriguing class of quantum materials due to their high crystallinity, persistent spin centers, and tunable structures and topologies. However, it remains unclear how to achieve long spin relaxation time at room temperature in 2D c-MOFs via a bottom-up design strategy. Herein, we design a hexahydroxytrithiatruxene ligand (HHTH) to minimize the influence of nuclear spin on electron spin relaxation while weakening d –π conjugation to construct a “spin docking” for preserving spin centers, which enables the resulting 2D c-MOFs, Ni 3 HHTH 2 , to exhibit quantum coherence and Rabi oscillations at room temperature. Spin dynamics studies not only reveal an unusual temperature-dependent Rabi frequency in Ni 3 HHTH 2 but also indicate that the coordination mode determines the spin–lattice relaxation behavior via spin–phonon coupling. These investigations provide a general guideline for the development of high-performance quantum qubits based on 2D spin arrays.}, archive = {J_JACS}, author = {Yang Lu and Yubin Fu and Ziqi Hu and Shiyi Feng and Morteza Torabi and Lei Gao and Shuai Fu and Zhiyong Wang and Chuanhui Huang and Xing Huang and Mingchao Wang and Noel Israel and Evgenia Dmitrieva and Hai I. Wang and Mischa Bonn and Paolo Samorì and Renhao Dong and Eugenio Coronado and Xinliang Feng}, doi = {10.1021/jacs.4c18681}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8778--8784}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational construction of layered two-dimensional conjugated Metal–Organic frameworks with room-temperature quantum coherence}, volume = {147}, year = {2025}, }
• (2025). Theory-guided design of N-confused porphyrinic covalent organic frameworks for oxygen reduction reaction. JACS, 147(10), 8769--8777. (www)

  @article{ , abstract = {Covalent organic frameworks (COFs) enable the precise and controlled synthesis of single-atom catalysts with uniformly distributed active metal centers, offering opportunities to elucidate the impact of subtle coordination environment changes on the catalytic performance. Inspired by N-confused porphyrins, we designed 20 metalloporphyrin-based COFs with either M–N 3 C 1 or M–N 4 centers, where M refers to 3 d transition metals from Sc to Zn, for the electrocatalysis of oxygen reduction reaction (ORR). Density functional theory calculations predicted Co-based COFs to be the best ORR catalysts among the screened catalysts. Hence, Co–N 3 C 1 –COF and Co–N 4 –COF with a high crystallinity were synthesized. The Co–N 3 C 1 –COF exhibited improved ORR performance over the parent Co–N 4 –COF, as it had a reduced overpotential and increased four-electron selectivity, corroborating theoretical predictions. The enhanced performance was ascribed to the increase in electron density on Co as the coordination environment transits from Co–N 4 to Co–N 3 C 1 . This not only facilitated the adsorption of O 2 and critical intermediates but also changed the potential-determining step, which in turn made the ORR free energy profile of Co–N 3 C 1 –COF approach equilibrium for all elementary steps, thus leading to a reduced overpotential. This combined theoretical and experimental work exemplified carbon coordination in porphyrin-based COFs as an effective strategy to facilitate the catalytic capability for ORR. A descriptor was also provided to guide the design of coordination-varied Por-COFs catalysts.}, archive = {J_JACS}, author = {Pengpeng Shao and Zhixin Ren and Bo Zhao and Xiao Wang and Jie Li and Jing Xie and Bo Wang and Xiao Feng}, doi = {10.1021/jacs.4c18645}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8769--8777}, shortjournal = {J. Am. Chem. Soc.}, title = {Theory-guided design of N-confused porphyrinic covalent organic frameworks for oxygen reduction reaction}, volume = {147}, year = {2025}, }
• (2025). Iron(III) complexes with luminescence lifetimes of up to 100 ns to enhance upconversion and photocatalysis. JACS, 147(10), 8760--8768. (www)

  @article{ , abstract = {Iron is the most abundant transition metal element and would be the ideal replacement for noble metals in many applications that rely on luminescent and long-lived electronically excited states. We show that efficient reversible energy transfer between doublet excited states of iron complexes and triplet excited states on organic ligands improves energy storage by up to 350-fold. As a result, luminescence lifetimes of up to 100 ns are achieved, the upconversion from red to blue light becomes 68 times more efficient and the yield of benchmark photoredox reactions is significantly improved. These advances make iron coordination compounds more promising candidates for applications in lighting, solar energy conversion and photocatalysis.}, archive = {J_JACS}, author = {Joël Wellauer and Björn Pfund and Isabelle Becker and Franc Meyer and Alessandro Prescimone and Oliver S. Wenger}, doi = {10.1021/jacs.4c18603}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8760--8768}, shortjournal = {J. Am. Chem. Soc.}, title = {Iron(III) complexes with luminescence lifetimes of up to 100 ns to enhance upconversion and photocatalysis}, volume = {147}, year = {2025}, }
• (2025). Highly conductive chiral organic cages and their helical assemblies enable efficient spin filtering. JACS, 147(10), 8751--8759. (www)

  @article{ , abstract = {Chiral molecular cages are demonstrated to have unique applications in enantioselective chemistry owing to their 3D cage-like geometry and intrinsic cavity. Yet, the role of the chirality of molecular cages in their physical properties of condensed materials, for example, the manipulation of electronic spin behaviors, remains elusive. Here, we report that chiral organic molecular cages can become an appealing chiral system to realize highly efficient spin filtering through the chirality-induced spin selectivity (CISS) effect. A pair of triphenylphosphine-containing organic cages (Pcages) with opposite handedness can manifest a very high spin polarization of nearly 90% and a high conductivity that exceeds those of other chiral molecules and structures by 2 orders of magnitude. By fabricating such molecular cages into thin-film spin filter devices, they have outstanding magnetoresistance ratios up to 12% among most of the devices based on the CISS effect. More interestingly, the Pcages can self-assemble with triphenylborane molecules through B–P frustrated Lewis acid–base complexation to form homochiral helical supramolecular nanofibrils. The spin-selective transport capacity and magnetic resistance obtained unexpected enhancement within these cage-based assemblies. This study demonstrates the potential of organic cages as a new chiral platform for controlling spin selectivity and will inspire the creation of new spintronic devices using chiral organic cage materials.}, archive = {J_JACS}, author = {Yixin Wang and Yulian Zhang and Yang-Yang Wang and Qiang Yan}, doi = {10.1021/jacs.4c18520}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8751--8759}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly conductive chiral organic cages and their helical assemblies enable efficient spin filtering}, volume = {147}, year = {2025}, }
• (2025). Ring-expansion metathesis polymerization under confinement. JACS, 147(10), 8741--8750. (www)

  @article{ , abstract = {The cationic molybdenum alkylidyne N -heterocyclic carbene (NHC) complex [Mo(C- p -OMeC 6 H 4 )(OCMe(CF 3 ) 2 ) 2 (IMes)][B(Ar F 4 ] (IMes = 1,3-dimesitylimidazol-2-ylidene) was selectively immobilized inside the pores of ordered mesoporous silica (OMS) with pore diameters of 66, 56, and 28 Å and used in the ring-expansion metathesis polymerization (REMP) of cyclic olefins to yield cyclic polymers. A strong confinement effect was observed for cis -cyclooctene ( c COE), 1,5-cyclooctadiene (COD), (+)-2,3- endo,exo -dicarbomethoxynorborn-5-ene ((+)-DCMNBE), and 2-methyl-2-phenylcycloprop-1-ene (MPCP), allowing for the synthesis of low-molecular-weight cyclic polymers even at a high monomer concentration. The exclusive formation of cyclic polymers was demonstrated by matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry. Confinement also influences stereoselectivity, resulting in a pronounced increase in Z-selectivity and in an increased cis -syndiospecificity.}, archive = {J_JACS}, author = {Patrick Probst and Moritz Lindemann and Johanna R. Bruckner and Boshra Atwi and Dongren Wang and Felix R. Fischer and Marc Högler and Matthias Bauer and Niels Hansen and Michael Dyballa and Michael R. Buchmeiser}, doi = {10.1021/jacs.4c18171}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8741--8750}, shortjournal = {J. Am. Chem. Soc.}, title = {Ring-expansion metathesis polymerization under confinement}, volume = {147}, year = {2025}, }
• (2025). Circular workflow for thermosets: Activatable repeat unit design for regenerative frontal polymerization. JACS, 147(10), 8732--8740. (www)

  @article{ , abstract = {Thermoset materials are indispensable in high-performance applications due to their exceptional mechanical properties, chemical resistance, and thermal stability. However, their cross-linked structure poses significant challenges for sustainable manufacturing and end-of-life reprocessing. Herein, we present a novel approach to regenerate high-performance polydicyclopentadiene (p DCPD ) thermoset materials through a one-pot deconstruction-reactivation strategy enabled by an “activatable repeat unit”, norbornene-furan ( NBF ). The pendant furyl ring of NBF remains intact during the initial curing reaction via frontal ring-opening metathesis polymerization (FROMP) and retains its reactivity for subsequent Diels–Alder cycloaddition with the in situ generated benzyne. Deconstruction-reactivation proceeds in one pot to effectively recover the activated oligomers for further FROMP curing, thereby completing the circular workflow. The regenerated materials demonstrate retention of key properties, including glass transition temperature ( T g ), stiffness, and yield strength, while maintaining their deconstruction capability. This strategy provides a sustainable framework for thermoset material design and regeneration, addressing critical challenges in material circularity and environmental impact.}, archive = {J_JACS}, author = {Zhenchuang Xu and Kecheng Wang and Benjamin A. Suslick and Jeffrey S. Moore}, doi = {10.1021/jacs.4c18018}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8732--8740}, shortjournal = {J. Am. Chem. Soc.}, title = {Circular workflow for thermosets: Activatable repeat unit design for regenerative frontal polymerization}, volume = {147}, year = {2025}, }
• (2025). Cobalt-doped Ru@RuO2 Core–Shell heterostructure for efficient acidic water oxidation in low-ru-loading proton exchange membrane water electrolyzers. JACS, 147(10), 8720--8731. (www)

  @article{ , abstract = {Proton exchange membrane water electrolysis (PEMWE) is a highly promising hydrogen production technology for enabling a sustainable energy supply. Herein, we synthesize a single-atom Co-doped core–shell heterostructured Ru@RuO 2 (Co-Ru@RuO 2 ) catalyst via a combination of ultrafast pulse-heating and calcination methods as an iridium (Ir)-free and durable oxygen evolution reaction (OER) catalyst in acidic conditions. Co-Ru@RuO 2 exhibits a low overpotential of 203 mV and excellent stability over a 400 h durability test at 10 mA cm –2 . When implemented in industrial PEMWE devices, a current density of 1 A cm –2 is achieved with only 1.58 V under an extremely low catalyst loading of 0.34 mg Ru cm –2 , which is decreased by 4 to 6 times as compared to other reported Ru-based catalysts. Even at 500 mA cm –2 , the PEMWE device could work stably for more than 200 h. Structural characterizations and density functional theory (DFT) calculations reveal that the single-atom Co doping and the core–shell heterostructure of Ru@RuO 2 modulate the electronic structure of pristine RuO 2 , which reduce the energy barriers of OER and improve the stability of surface Ru. This work provides a unique avenue to guide future developments on low-cost PEMWE devices for hydrogen production.}, archive = {J_JACS}, author = {Jinghao Chen and Yirui Ma and Chen Cheng and Tao Huang and Ruihao Luo and Jingwen Xu and Xiaoyang Wang and Taoli Jiang and Hongxu Liu and Shuang Liu and Ting Huang and Liang Zhang and Wei Chen}, doi = {10.1021/jacs.4c18238}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8720--8731}, shortjournal = {J. Am. Chem. Soc.}, title = {Cobalt-doped Ru@RuO2 Core–Shell heterostructure for efficient acidic water oxidation in low-ru-loading proton exchange membrane water electrolyzers}, volume = {147}, year = {2025}, }
• (2025). An operationally unsaturated iridium-pincer complex that C–H activates methane and ethane in the crystalline solid-state. JACS, 147(10), 8706--8719. (www)

  @article{ , abstract = {The known complex [Ir( t Bu-PONOP)MeH][BAr F 4 ], 1[BAr F 4 ] [ t Bu-PONOP = κ 3 -2,6-( t Bu 2 PO) 2 C 5 H 3 N); Ar F = 3,5-(CF 3 ) 2 (C 6 H 3 ); J. Am. Chem. Soc. 2009, 131, 8603], is a robust precursor for in crystallo single-crystal to single-crystal (SC-SC) C–H activation of methane and ethane at 80 °C. This contrasts with the reported solution (CD 2 Cl 2 ) behavior, where 1[BAr F 4 ] decomposes by methane loss. Crystalline 1[BAr F 4 ] is accessed as a single polymorph on a gram scale. A single-crystal neutron diffraction study locates the hydride. 13 C{ 1 H} SSNMR experiments on 1[BAr F 4 ] , and its isotopologue [Ir( t Bu-PONOP)(CD 3 )D][BAr F 4 ], d 4 -1[BAr F 4 ] , suggest a rapid and reversible endergonic reductive bond formation is occurring in crystallo to access an Ir(I) σ-methane complex. Heating 1[BAr F 4 ] to 80 °C under high vacuum results in loss of methane and intramolecular C–H activation to form cyclometalated [Ir(cyclo- t Bu-PONOP′)H][BAr F 4 ], 2[BAr F 4 ] , in a SC-SC reaction. This is reversible, and the addition of CH 4 or CD 4 to 2[BAr F 4 ] at 80 °C results in an equilibrium with 1[BAr F 4 ] or d 4 -1[BAr F 4 ] , respectively. Complex 2[BAr F 4 ] is thus an operationally unsaturated source of 14-electron [Ir( t Bu-PONOP)][BAr F 4 ], III , that undergoes C–H activation with methane. Periodic DFT studies, alongside isotope labeling experiments, link 1[BAr F 4 ] and 2[BAr F 4 ] /CH 4 via a reductive elimination/oxidative addition pathway. Heating 2[BAr F 4 ] to 80 °C under N 2 forms [Ir( t Bu-PONOP)(κ 1 -N 2 )][BAr F 4 ], in a SC-SC transformation. Reaction with CO forms [Ir( t Bu-PONOP)(CO)][BAr F 4 ] at room temperature. Calculations suggest reaction with N 2 occurs via an associative process or competitively through III , while with CO only an associative process operates. Heating 2[BAr F 4 ] to 80 °C under an ethane atmosphere results in alkane dehydrogenation, via a SC–SC reaction, forming a ∼1:1 mixture of [Ir( t Bu-PONOP)(η 2 -H 2 C═CH 2 )][BAr F 4 ], and [Ir( t Bu-PONOP)H 2 ][BAr F 4 ].}, archive = {J_JACS}, author = {Matthew R. Gyton and M. Arif Sajjad and Daniel J. Storm and Kristof M. Altus and Joe C. Goodall and Chloe L. Johnson and Samuel J. Page and Alison J. Edwards and Ross O. Piltz and Simon B. Duckett and Stuart A. Macgregor and Andrew S. Weller}, doi = {10.1021/jacs.4c18122}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8706--8719}, shortjournal = {J. Am. Chem. Soc.}, title = {An operationally unsaturated iridium-pincer complex that C–H activates methane and ethane in the crystalline solid-state}, volume = {147}, year = {2025}, }
• (2025). Molecularly woven polymer aerogels. JACS, 147(10), 8695--8705. (www)

  @article{ , abstract = {Aerogels with abundant nanopores and large specific surface areas have extensive potential in various applications but are constrained by fragility and difficulty in degradation. Currently, the exploration of adaptive and reprocessing aerogels has become increasingly urgent, as the demand for intelligent and sustainable materials intensifies. Here, we present a molecular weaving strategy to construct molecularly woven polymer aerogels (WPAs) via catalyst-free aldimine condensation between prewoven aldehyde-functionalized Cu(I) bisphenanthroline (Cu(PBD) 2 ) and flexible 4,4′-diaminodibenzyl (DB). The key feature of this system consists entirely of dense woven nodes that can be readily activated by external stimuli, where Cu(I) ions can also be reversibly removed as needed, while preserving porous structures. Consequently, we achieve adjustable mechanical properties of WPAs, with a 10-fold enhancement in elasticity after removing Cu(I) ions. Moreover, the destroyed WPAs demonstrate a straightforward reprocessing capacity rather than tedious monomer recovery due to the dissociation of Cu(I)-coordination bonds, the activation of sequential polymer thread motions, and the accelerated imine bond exchange enabled by adjacent Cu(I) ions. This work offers a new perspective on designing customizable and sustainable aerogels and verifies the feasibility of the emergent molecularly woven technique in a more complex functional material system.}, archive = {J_JACS}, author = {Xinhai Zhang and Xinwei Chen and Ruixue Bai and Liang Wu and Wenbin Wang and Zhen Luo and Yanhua Cheng and Meifang Zhu and Xuzhou Yan}, doi = {10.1021/jacs.4c18138}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8695--8705}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecularly woven polymer aerogels}, volume = {147}, year = {2025}, }
• (2025). Can the hock process be used to produce phenol from polystyrene?. JACS, 147(10), 8687--8694. (www)

  @article{ , abstract = {Polystyrene (PS) is a widely used thermoplastic polymer, but its very low recycling rate has motivated consideration of chemical conversion strategies to convert waste PS into value-added products. Oxidation methods have been widely studied, but they typically generate benzoic acid, a product with a relatively low market demand. Phenol is a higher volume chemical that would be an appealing target, but no methods currently exist for the conversion of PS into phenol. The repeat unit in PS closely resembles cumene, the primary feedstock used to produce phenol through the Hock process. Here, we investigate prospects for adapting the Hock process to PS, generating hydroperoxides through the autoxidation of benzylic C–H bonds followed by the acid-promoted rearrangement of the hydroperoxides to afford phenol and a partially oxygenated polymer. Experimental and computational studies of dimeric and trimeric PS model compounds show that neighboring phenyl rings impose conformational constraints that raise the barrier to hydrogen-atom transfer from the tertiary benzylic C–H bond. These effects are also evident with PS and contribute to lower yields of phenol when PS is subjected to Hock process conditions. These results provide valuable insights that have important implications for other efforts that seek to adapt small-molecule reactivity to polymeric feedstocks.}, archive = {J_JACS}, author = {Doohyun Baek and Abdullah J. Al Abdulghani and Dylan J. Walsh and Dillon T. Hofsommer and James B. Gerken and Changxia Shi and Eugene Y.-X. Chen and Ive Hermans and Shannon S. Stahl}, doi = {10.1021/jacs.4c18143}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8687--8694}, shortjournal = {J. Am. Chem. Soc.}, title = {Can the hock process be used to produce phenol from polystyrene?}, volume = {147}, year = {2025}, }
• (2025). Efficient metabolomics profiling from plasma extracellular vesicles enables accurate diagnosis of early gastric cancer. JACS, 147(10), 8672--8686. (www)

  @article{ , abstract = {Accurate diagnosis of early gastric cancer is valuable for asymptomatic populations, while current endoscopic examination combined with pathological tissue biopsy often encounters bottlenecks for early-stage cancer and causes pain to patients. Liquid biopsy shows promise for noninvasive diagnosis of early gastric cancer; however, it remains a challenge to achieve accurate diagnosis due to the lack of highly sensitive and specific biomarkers. Herein, we propose a protocol combining metabolomics profiling from plasma extracellular vesicles (EVs) and machine learning to identify the metabolomics discrepancies of early gastric cancer individuals from other populations. Efficient metabolomics profiling is achieved by efficient, high-purity, and damage-free plasma EVs separation using elaborately designed nanotrap-structured microparticles (NanoFisher) by taking advantage of stereoscopic interaction and affinity interaction. Significant metabolomics discrepancies are obtained from 150 early gastric cancer (50), benign gastric disease (50), and non-disease control (50) plasma samples. Machine learning enables ideal distinction between early gastric cancer and non-disease control samples with an area under the curve (AUC) of 1.000, achieves an AUC of 0.875–0.975 for differentiating early gastric cancer from benign gastric diseases, and demonstrates an overall accuracy of 92% in directly classifying these three categories. The plasma EV metabolomics profiling enabled by NanoFisher materials, integrated with machine learning, holds considerable promise for broad clinical acceptance, enhancing gastric cancer screening outcomes.}, archive = {J_JACS}, author = {Fanqin Bu and Xinyi Shen and Haosu Zhan and Duanda Wang and Li Min and Yongyang Song and Shutao Wang}, doi = {10.1021/jacs.4c18110}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8672--8686}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient metabolomics profiling from plasma extracellular vesicles enables accurate diagnosis of early gastric cancer}, volume = {147}, year = {2025}, }
• (2025). Dipolar carbazole ammonium for broadened electric field distribution in high-performance perovskite solar cells. JACS, 147(10), 8663--8671. (www)

  @article{ , abstract = {Perovskite solar cells (PSCs) with ammonium passivation exhibit superior device performance and stability. Beyond typical chemical passivation, ammonium salts control the electronic structure of perovskite surfaces, yet the molecular structure–property relationship requires further understanding, especially the dipole effect. Here, we employed carbazole and its halogenated counterpart as the functional group of ammonium salts. 2-Chloro-carbazol-9-ethylammonium iodide (CzCl-EAI) with a rigid, conjugated molecular structure further provides chemical passivation and enhances the ambient stability of perovskites. In addition, we found that halogenation enhances the intramolecular charge transfer for a larger molecular dipole moment, leading to the depletion region of perovskite films threefold wider than that of the PDAI 2 condition. The power conversion efficiency (PCE) of inverted PSCs based on mixed passivation reached 25.16% and certified 24.35% under the quasi-steady-state (QSS) measurement. Unencapsulated devices retained over 91% of initial PCE under ISOS-D-2 conditions over 1100 h and maintained 80% of their initial performance after 500 h of continuous light illumination in ambient air with a 50–60% relative humidity (RH).}, archive = {J_JACS}, author = {Jialin Wang and Likai Zheng and Hak-Beom Kim and Han He and Sanlong Wang and Felix T. Eickemeyer and Yimhyun Jo and Ying Zhao and Mingyang Wei and Jaeki Jeong and Michael Grätzel and Xiaodan Zhang}, doi = {10.1021/jacs.4c18074}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8663--8671}, shortjournal = {J. Am. Chem. Soc.}, title = {Dipolar carbazole ammonium for broadened electric field distribution in high-performance perovskite solar cells}, volume = {147}, year = {2025}, }
• (2025). Energy threshold of nonlinear sulfur solubility for Li–S batteries. JACS, 147(10), 8652--8662. (www)

  @article{ , abstract = {Unclear regulation mechanisms of solid solubility make it difficult to accurately control its concentration, posing challenges for accelerating chemical reactions. Herein, we use a model system to determine the effects of solvent type and ratio, concentration, and type of lithium salt on sulfur solubility. Our findings reveal a nonlinear relationship between sulfur solubility and both lithium salt concentration and the ratio of different solvents in composite solutions. Importantly, significant differences in sulfur solubility are discovered with changes in the solvation structure regulated by the type of salt anion. Quantitative evaluation of nonlinear sulfur solubility is illustrated to be breaking the threshold value of the interaction energy between the solute and solvent molecules. Based on these findings, simultaneous regulation of sulfur and lithium polysulfide concentrations in ether electrolytes can be achieved by controlling the concentration and type of salts. As a result, a liquid–liquid–solid reaction pathway is supported for lithium–sulfur batteries with a finite amount of electrolyte in the coin cell, and the pouch cell shows an energy density of 554 Wh kg –1 , ranking at the top level of the reported system.}, archive = {J_JACS}, author = {Keying Guo and Xiaosheng Song and Zhengyuan Shen and Xuebing Zhu and Jun Wei and Qing Han and Xueping Qian and Zhaoqing Jin and Jianhao Lu and Weikun Wang and Yong Zhao}, doi = {10.1021/jacs.4c17438}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8652--8662}, shortjournal = {J. Am. Chem. Soc.}, title = {Energy threshold of nonlinear sulfur solubility for Li–S batteries}, volume = {147}, year = {2025}, }
• (2025). Sequential charge transfer and magnetic ordering in quasi-one-dimensional antiferromagnet CrSbS3. JACS, 147(10), 8642--8651. (www)

  @article{ , abstract = {Charge transfer and magnetic ordering are two profound condensed matter phenomena that impart distinct structures and properties to materials. However, such two effects rarely occur successively within a single material. Here, we present a unique case of temperature-induced sequential charge transfer and magnetic ordering in antiferromagnetic CrSbS 3 with quasi-one-dimensional structure. Intriguingly, the contrasting effects of charge transfer between Cr and [Sb 2 S 6 ] units and antiferromagnetic transition on lattice expansion result in diverse thermal expansion behaviors of lattice parameters, which ultimately leads to an anti-Invar effect on the lattice volume. Neutron powder diffraction further unravels a C-type antiferromagnetic order. Moreover, pressure regulation can also induce similar volume collapse, implying potential valence and spin-state transitions. The multiple electronic transitions observed in CrSbS 3 offer a valuable platform for deciphering the interweaving among charge, spin, and lattice degrees of freedom, and shed a new light for exploring novel quantum phenomena in more low-dimensional van der Waals materials.}, archive = {J_JACS}, author = {Chen Li and Ke Liu and Yiming Wang and Chenjie Lou and Nana Li and Jiajia Feng and Haoming Cheng and Qi Feng and Dequan Jiang and Jiazheng Hao and Xiaoli Ma and Ting Wen and Lunhua He and Xiaohui Yu and Binbin Yue and Yonggang Wang}, doi = {10.1021/jacs.4c17892}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8642--8651}, shortjournal = {J. Am. Chem. Soc.}, title = {Sequential charge transfer and magnetic ordering in quasi-one-dimensional antiferromagnet CrSbS3}, volume = {147}, year = {2025}, }
• (2025). Functional design of peptide materials based on supramolecular cohesion. JACS, 147(10), 8629--8641. (www)

  @article{ , abstract = {Peptide materials offer a broad platform to design biomimetic soft matter, and filamentous networks that emulate those in extracellular matrices and the cytoskeleton are among the important targets. Given the vast sequence space, a combination of computational approaches and readily accessible experimental techniques is required to design peptide materials efficiently. We report here on a strategy that utilizes this combination to predict supramolecular cohesion within filaments of peptide amphiphiles, a property recently linked to supramolecular dynamics and consequently bioactivity. Using established coarse-grained simulations on 10,000 randomly generated peptide sequences, we identified 3500 likely to self-assemble in water into nanoscale filaments. Atomistic simulations of small clusters were used to further analyze this subset of sequences and identify mathematical descriptors that are predictive of intermolecular cohesion, which was the main purpose of this work. We arbitrarily selected a small cohort of these sequences for chemical synthesis and verified their fiber morphology. With further characterization, we were able to link the latent heat associated with fiber to micelle transitions, an indicator of cohesion and potential supramolecular dynamicity within the filaments, to calculated hydrogen bond densities in the simulation clusters. Based on validation from in situ synchrotron X-ray scattering and differential scanning calorimetry, we conclude that the phase transitions can be easily observed by very simple polarized light microscopy experiments. We are encouraged by the methodology explored here as a relatively low-cost and fast way to design potential functions of peptide materials.}, archive = {J_JACS}, author = {Simon A. Egner and Mayank Agrawal and Hiroaki Sai and Michael D. Dore and Liam C. Palmer and Samuel I. Stupp}, doi = {10.1021/jacs.4c17867}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8629--8641}, shortjournal = {J. Am. Chem. Soc.}, title = {Functional design of peptide materials based on supramolecular cohesion}, volume = {147}, year = {2025}, }
• (2025). Probing the dynamics of yersinia adhesin a (YadA) in outer membranes hints at requirements for β-barrel membrane insertion. JACS, 147(10), 8618--8628. (www)

  @article{ , abstract = {The vast majority of cells are protected and functionalized by a dense surface layer of glycans, proteoglycans, and glycolipids. This surface represents an underexplored space in structural biology that is exceedingly challenging to recreate in vitro. Here, we investigate β-barrel protein dynamics within an asymmetric outer membrane environment, with the trimeric autotransporter Yersinia adhesin A (YadA) as an example. Magic-angle spinning NMR relaxation data and a model-free approach reveal increased mobility in the second half of strand β2 after the conserved G72, which is responsible for membrane insertion and autotransport, and in the subsequent loop toward β3. In contrast, the protomer–protomer interaction sites (β1 i –β4 i –1 ) are rigid. Intriguingly, the mobility in the β-strand section following G72 is substantially elevated in the outer membrane and less so in the detergent environment of microcrystals. A possible source is revealed by molecular dynamics simulations that show the formation of a salt bridge involving E79 and R76 in competition with a dynamic interplay of calcium binding by E79 and the phosphate groups of the lipids. An estimation of overall barrel motion in the outer membrane and detergent-containing crystals yields values of around 41 ns for both. The global motion of YadA in the outer membrane has a stronger rotational component orthogonal to the symmetry axis of the trimeric porin than in the detergent-containing crystal. In summary, our investigation shows that the mobility in the second half of β2 and the loop to β3 required for membrane insertion and autotransport is maintained in the final folded form of YadA.}, archive = {J_JACS}, author = {Jayasubba Reddy Yarava and Marcella Orwick-Rydmark and David Ryoo and Albert Hofstetter and James C. Gumbart and Michael Habeck and Barth-Jan van Rossum and Dirk Linke and Hartmut Oschkinat}, doi = {10.1021/jacs.4c17726}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8618--8628}, shortjournal = {J. Am. Chem. Soc.}, title = {Probing the dynamics of yersinia adhesin a (YadA) in outer membranes hints at requirements for β-barrel membrane insertion}, volume = {147}, year = {2025}, }
• (2025). Kinetics compensation mechanism in cosolvent electrolyte strategy for aqueous zinc batteries. JACS, 147(10), 8607--8617. (www)

  @article{ , abstract = {Aqueous zinc batteries are the ideal choices to realize intrinsically safe energy storage, but parasitic side reactions make it difficult to achieve in practice. Although the cosolvent electrolyte effectively inhibits zinc dendrites and mitigates unexpected side reactions, it brings inevitable kinetics losses. Here, we systematically investigate and compare the interactions between Zn 2+ and various oxygen-coordinated cosolvents under pure aqueous environments and the interactions between Zn 2+ and OTf – under mixed solvent environments containing different oxygen-coordinated cosolvents. And the differences in the effect of different oxygen-coordinated cosolvents on the solvation structure of Zn 2+ and the kinetics of ion migration are quantitatively analyzed and summarized. On this basis, we propose a new kinetics compensation mechanism in cosolvent electrolyte strategy that can compensate the kinetics losses due to the introduction of cosolvents by weakening the anion–cation pair interaction and increasing the Zn 2+ transfer number. Theory and experiments both demonstrate that this strategy can achieve kinetics compensation of aqueous zinc batteries while improving the electrochemical performance. This work provides a comprehensive and deep understanding of designing cosolvent electrolytes with superior electrochemical performance. More importantly, the proposed strategy can be applied to other cosolvents with similar properties and other aqueous battery systems.}, archive = {J_JACS}, author = {Jianlong Cong and Yueda Wang and Xing Lin and Zhimei Huang and Hua Wang and Jianbo Li and Le Hu and Haiming Hua and Jianxing Huang and Yu-Chang Lin and Henghui Xu and Zhen Li and Yunhui Huang}, doi = {10.1021/jacs.4c16880}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8607--8617}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetics compensation mechanism in cosolvent electrolyte strategy for aqueous zinc batteries}, volume = {147}, year = {2025}, }
• (2025). Regiodivergent alkylation of pyridines: Alkyllithium clusters direct chemical reactivity. JACS, 147(10), 8597--8606. (www)

  @article{ , abstract = {Regiodivergent C–C bond-forming reactions are a powerful tool for constructing diverse molecular architectures from common precursors. While transition metal catalysis has dominated regioselective transformations, achieving similar precision with transition-metal-free methods remains an unmet challenge, particularly when using identical starting materials. In this work, we report a transition-metal-free, regiodivergent direct alkylation of electronically unbiased pyridines using 1,1-diborylalkanes as the sole alkylating agent. The key to controlling regioselectivity lies in the choice of alkyllithium activator of 1,1-diborylalkanes: methyllithium directs alkylation predominantly to the C4 position, while sec -butyllithium promotes C2-alkylation. Mechanistic studies reveal that the structural dynamics of alkyllithium clusters dictate the regioselectivity, with tetrameric clusters favoring C4-alkylation and dimeric clusters preferring C2-alkylation. This method demonstrates broad substrate scope, enables late-stage functionalization of complex molecules, and allows for the sequential installation of two distinct alkyl groups onto a pyridine scaffold. Our approach provides a versatile tool for site-selective pyridine functionalization, offering new possibilities for synthesizing diverse alkylated pyridines in pharmaceutical and materials research.}, archive = {J_JACS}, author = {Woohyun Jo and Chattawat Thangsrikeattigun and Changsu Ryu and Seungcheol Han and Changjin Oh and Mu-Hyun Baik and Seung Hwan Cho}, doi = {10.1021/jacs.4c17198}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8597--8606}, shortjournal = {J. Am. Chem. Soc.}, title = {Regiodivergent alkylation of pyridines: Alkyllithium clusters direct chemical reactivity}, volume = {147}, year = {2025}, }
• (2025). Favoring the originally unfavored oxygen for enhancing nitrogen-to-nitrate electroconversion. JACS, 147(10), 8587--8596. (www)

  @article{ , abstract = {Current nitrate production involves a two-step thermochemical process that is energy-intensive and generates substantial CO 2 emissions. Sustainable NO 3 – production via the nitrogen electrooxidation reaction powered by renewable electricity is highly desirable, but the Faradaic efficiency (FE) at high production rates is unsatisfactory due to competition from the oxygen evolution reaction (OER). In this study, we propose reengineering the catalyst’s microstructure-to-macroenvironment interface by particularly utilizing the previously considered unfavored oxygen from the OER. We demonstrate that the re-engineered interface facilitates a record-breaking FE of 35.52% under 8 atm air, with an impressive increase in FE (41.56%) observed during a continuous electrochemical process lasting for 60 h due to the in situ formation of the O 2 -rich macro-interface environment. The revelation is anticipated to furnish groundbreaking perspectives for the reaction systems design in electrochemical nitrate production and other electrocatalytic fields.}, archive = {J_JACS}, author = {Xin Li and Guangtong Hai and Daniel H. C. Wan and Yiwen Liao and Zhangyi Yao and Fenglin Zhao and Lingzhi Huang and Jinsong Zhou and Gang Li and Gao-Feng Chen and Feng Ryan Wang and Michael K. H. Leung and Haihui Wang}, doi = {10.1021/jacs.4c17380}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8587--8596}, shortjournal = {J. Am. Chem. Soc.}, title = {Favoring the originally unfavored oxygen for enhancing nitrogen-to-nitrate electroconversion}, volume = {147}, year = {2025}, }
• (2025). Bespoke activity-based probes reveal that the pseudomonas aeruginosa endoglycosidase, PslG, is an endo-β-glucanase. JACS, 147(10), 8578--8586. (www)

  @article{ , abstract = {During infection, the human opportunistic pathogen Pseudomonas aeruginosa forms protective biofilms, whose matrix consists of proteins, nucleic acids, and polysaccharides such as alginate, Psl, and Pel. Psl, a polymeric pentasaccharide composed of mannose, rhamnose, and glucose, is produced during the early stages of biofilm formation, serving as a protective barrier against antibiotics and the immune system. The Psl biosynthesis gene cluster, besides encoding various glycosyltransferases, also includes an endoglycosidase, PslG. Here, we show, by activity-based protein profiling, structural studies on enzyme–inhibitor complexes, and defined substrate processing, that PslG is not, as previously suggested, an endo-β-mannosidase but instead a retaining endo-β-glucosidase. This insight allows the design of both competitive and covalent PslG inhibitors, as we show for repeating pentasaccharide mimetics featuring either a reducing end deoxynojirimycin or cyclophellitol moiety. This work provides valuable tools to deepen the understanding of Psl biosynthesis, its function in biofilm formation, and its contribution to antibiotic resistance. We demonstrate the enzyme’s actual endo−β–glucosidase activity, a means to monitor PslG activity in P. aeruginosa biofilms, and a blueprint for inhibitor design.}, archive = {J_JACS}, author = {Gijs Ruijgrok and Wendy A. Offen and Isabelle B. Pickles and Deepa Raju and Thanasis Patsos and Casper de Boer and Tim Ofman and Joep Rompa and Daan van Oord and Eleanor J. Dodson and Alexander Beekers and Thijs Voskuilen and Michela Ferrari and Liang Wu and Antonius P. A. Janssen and Jeroen D. C. Codée and P. Lynne Howell and Gideon J. Davies and Herman S. Overkleeft}, doi = {10.1021/jacs.4c16806}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8578--8586}, shortjournal = {J. Am. Chem. Soc.}, title = {Bespoke activity-based probes reveal that the pseudomonas aeruginosa endoglycosidase, PslG, is an endo-β-glucanase}, volume = {147}, year = {2025}, }
• (2025). Engineering photoswitching dynamics in 3D photochromic Metal–Organic frameworks through a Metal–Organic polyhedron design. JACS, 147(10), 8568--8577. (www)

  @article{ , abstract = {Metal–organic polyhedra (MOPs) are versatile supramolecular building blocks for the design of highly porous frameworks by reticular assembly because of their diverse geometries, multiple degrees of freedom regarding functionalization, and accessible metal sites. Lipophilic functionalization is demonstrated to enable the rational assembly and crystallization with photoactive N-donor ligands in an aliphatic solvent to achieve multiaxially aligned photoresponsive diarylethene (DTE) moieties in 3D frameworks (DUT-210(M), M = Cu and Rh) featuring cooperative switchability. Combined experimental and theoretical investigations based on in situ PXRD, UV–vis spectroscopy, and density functional theory calculations demonstrate deliberate kinetic engineering of photoswitchability based on variations in metal–ligand bond strengths. The novel porous frameworks are an important step toward the knowledge-based development of photon-driven motors, actuators, and release systems.}, archive = {J_JACS}, author = {Eunji Jin and Volodymyr Bon and Shubhajit Das and A. D. Dinga Wonanke and Martin Etter and Martin A. Karlsen and Ankita De and Nadine Bönisch and Thomas Heine and Stefan Kaskel}, doi = {10.1021/jacs.4c17203}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8568--8577}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering photoswitching dynamics in 3D photochromic Metal–Organic frameworks through a Metal–Organic polyhedron design}, volume = {147}, year = {2025}, }
• (2025). Two birds, one stone: Microsecond dark excited-state lifetime and large cage escape yield afforded by an Iron–Anthracene molecular dyad. JACS, 147(10), 8559--8567. (www)

  @article{ , abstract = {Iron photosensitizers represent a holy grail in photochemistry, but their widespread implementation is limited by their short excited-state lifetimes and poor cage escape yields. Here, the introduction of an anthracene moiety appended to an iron(III) complex allowed to solve both limitations and generate a novel dyad exhibiting an extraordinary excited-state lifetime of 11.5 μs. The key to achieving this remarkably long lifetime is the depopulation of the short-lived iron-centered emissive excited state to populate a dark triplet state located on the anthracene-like moiety with a spin-forbidden deactivation. Population of the triplet anthracene only occurs with ∼10% efficiency in acetonitrile but still allows expansion of the scope of reactivity accessible with iron-based photosensitizers, which now encompasses energy transfer to 3 O 2 . In addition, in a proof-of-principle investigation with methyl viologen as electron acceptor, the population of a triplet excited state allows a drastic ten-fold increase of the cage escape yield from 4.5% for the unsubstituted complex to 42% for the molecular dyad. Hence, this new iron-based dyad provides a complementary approach for complexes based on first-row transition metals as alternatives to well-established analogues based on precious metals. We believe that further spectroscopic investigations and synthetic modifications of the energy acceptor and linkage to the photosensitizer will be key to use these innovative dyads for applications in the near future.}, archive = {J_JACS}, author = {Felix Glaser and Simon De Kreijger and Ludovic Troian-Gautier}, doi = {10.1021/jacs.4c17167}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8559--8567}, shortjournal = {J. Am. Chem. Soc.}, title = {Two birds, one stone: Microsecond dark excited-state lifetime and large cage escape yield afforded by an Iron–Anthracene molecular dyad}, volume = {147}, year = {2025}, }
• (2025). Ligand influence on the performance of cesium lead bromide perovskite quantum dots in photocatalytic C(sp3)–H bromination reactions. JACS, 147(10), 8548--8558. (www)

  @article{ , abstract = {Lead halide perovskite quantum dots (LHP QDs) CsPbX 3 generate immense interest as narrow-band emitters for displays, lasers, and quantum light sources. All QD applications rely on suited engineering of surface capping ligands. The first generation of LHP QDs employed oleic acid/oleyl amine capping and have found only a limited use in photoredox catalysis. These catalysts have been reported to be unstable and decompose over the course of the reaction, thus reducing turnover numbers (TONs) and limiting their synthetic ability. Herein, the impact of eight distinct surface ligands on monodisperse CsPbBr 3 QDs is reported, affording a thorough comprehension of their performance in photocatalytic C–H brominations. These efforts yielded QDs operating at extremely low catalyst loadings (<100 ppb) with TONs over 9,000,000 per LHP QD. We emphasize that the optimal catalytic performance requires increased QD surface accessibility without compromising the QD structural and colloidal integrity. Control experiments indicated that well-known photoredox catalysts such as Ir(ppy) 3 , Ru(bpy) 3 Cl 2 , or 4CzlPN are ineffective in the same reaction. Mechanistic studies reveal that the C–Br bond reduction in CH 2 Br 2 is the rate-limiting step and is likely facilitated through interaction with the CsPbBr 3 QD surface. This work outlines a holistic approach toward the design of practically useful photocatalysts out of QDs comprising structurally soft QD cores and dynamically bound capping ligands.}, archive = {J_JACS}, author = {Willi M. Amberg and Henry Lindner and Yesim Sahin and Erich Staudinger and Viktoriia Morad and Sebastian Sabisch and Leon G. Feld and Yuxuan Li and Dmitry N. Dirin and Maksym V. Kovalenko and Erick M. Carreira}, doi = {10.1021/jacs.4c17013}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8548--8558}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand influence on the performance of cesium lead bromide perovskite quantum dots in photocatalytic C(sp3)–H bromination reactions}, volume = {147}, year = {2025}, }
• (2025). Single-handed helical polymer-based polycarboxylate with achiral triarylphosphine pendants as chiral catalysts for asymmetric cross-coupling reactions in pure water. JACS, 147(10), 8534--8547. (www)

  @article{ , abstract = {Helical poly(quinoxaline-2,3-diyl)s (PQX) containing chiral carboxylic acid side chains derived from natural l -lactic acid were synthesized. The newly synthesized helical polycarboxylated polymer was soluble in basic pure water by forming polycarboxylate and adopted the P -helical conformation (right-handed), whereas the M -helical conformation is predominant under weakly acidic aqueous conditions. The water-soluble PQX containing additional monomer units bearing a 2-(diarylphosphino)phenyl group was employed in the asymmetric Suzuki–Miyaura coupling reaction in pure water in the absence of organic cosolvents. Remarkable enantioselectivities up to 99% ee, which were found to be higher than the same coupling reaction in organic solvent using the corresponding lipophilic PQX, were obtained for the couplings of 2-substituted 1-halonaphthalenes. It is presumed that the hydrophobic reaction environment is provided by the hydrophobic main chain of PQX according to the Nile Red-based hydrophobicity test. Recovery of the crude product without using any trace of organic solvent has been demonstrated by the switch of solubility of PQX depending on pH.}, archive = {J_JACS}, author = {Naoaki Kamiya and Takuma Kuroda and Yuuya Nagata and Takeshi Yamamoto and Michinori Suginome}, doi = {10.1021/jacs.4c16952}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8534--8547}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-handed helical polymer-based polycarboxylate with achiral triarylphosphine pendants as chiral catalysts for asymmetric cross-coupling reactions in pure water}, volume = {147}, year = {2025}, }
• (2025). Synergistic Anion–Cation chemistry enables highly stable zn metal anodes. JACS, 147(10), 8523--8533. (www)

  @article{ , abstract = {Engineering aqueous electrolytes with an ionic liquid (IL) for the zinc (Zn) metal anode has been reported to enhance the electrochemical performances of the Zn metal batteries (ZMBs). Despite these advancements, the effects of IL and the mechanisms involving their anions and cations have been scarcely investigated. Here, we introduce a novel electrolyte design strategy that synergizes anion–cation chemistry using a halogen-based IL and elucidates the underlying mechanism. The strongly and preferentially adsorbed halogen anions guide the formation of a water-poor electrical double layer (EDL) by imidazole-based cations, resulting in the formation of a halide-rich inorganic interphase. This synergistic interaction significantly mitigates Zn anode corrosion at the anode–electrolyte interface, while the halide-rich interphase promotes dense Zn deposition. Consequently, the battery exhibits superior performance, including high reversibility (99.74%) and an ultralong cycle life (20,000 cycles). This synergistic anion–cation chemistry strategy combines the traditional single solid electrolyte interphase and the classic EDL mechanism, substantially enhancing the electrochemical performance of ZMBs.}, archive = {J_JACS}, author = {Yanqun Lv and Chenyue Huang and Ming Zhao and Mingzhe Fang and Qianwen Dong and Wanqi Tang and Jingting Yang and Xinxin Zhu and Xianji Qiao and Hongfei Zheng and Chuang Sun and Lijun Zheng and Mengting Zheng and Yunkai Xu and Jun Lu}, doi = {10.1021/jacs.4c16932}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8523--8533}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic Anion–Cation chemistry enables highly stable zn metal anodes}, volume = {147}, year = {2025}, }
• (2025). Extreme defect tolerance for electrochemical intercalation in Wadsley–Roth structures demonstrated by metastable NaNb7O18. JACS, 147(10), 8513--8522. (www)

  @article{ , abstract = {Careful control over the defect chemistry of crystalline compounds is typically critical to transport phenomena (ion, electron, phonon). In one-dimensional (1D) ion conductors, even small concentrations of defects in the diffusion pathway can be pernicious. Wadsley–Roth block phases are 1D ion conductors with high redox capacity and among the highest diffusivity of any battery electrode materials. The origin of their high-rate transport has been attributed to parallel tunnels that could impart defect tolerance, but direct evidence is limited. Herein, a new lithium-ion battery negative electrode material, NaNb 7 O 18 , is described that exhibits extreme defect tolerance. Multimodal characterization combining neutron diffraction, 23 Na solid-state NMR spectroscopy, and DFT calculations reveals that more than half of the Na + in NaNb 7 O 18 is in diffusion tunnel-blocking cuboctahedral environments (similar to the perovskite A-site). Despite the high point-defect concentration, NaNb 7 O 18 can reversibly lithiate to Li 7 NaNb 7 O 18 and cycle 200 mAh·g –1 in 10 h and 100 mAh·g –1 in 3 min in large 4–23 μm (D 10 –D 90 ) particles. Operando synchrotron diffraction shows an anisotropic and asymmetric lithiation/delithiation process with two first-order phase transitions including one with nearly zero volume change. Li x NaNb 7 O 18 also exhibits evidence for reversible Nb–Nb bond formation. From the same operando diffraction measurements, Nb–Nb distances between edge-sharing octahedra at the block peripheries vary from ca . 3.4 to 2.8 and back to 3.4 Å over one lithium insertion/extraction cycle, in quantitative agreement with the Nb–Nb bond formation charge storage mechanism recently proposed from the computational lithiation of several different Wadsley–Roth compounds.}, archive = {J_JACS}, author = {Sarah L. Ko and Jordan A. Dorrell and Ethan D. Alter and Anthony C. Ta and Andrew J. Morris and Kent J. Griffith}, doi = {10.1021/jacs.4c16977}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8513--8522}, shortjournal = {J. Am. Chem. Soc.}, title = {Extreme defect tolerance for electrochemical intercalation in Wadsley–Roth structures demonstrated by metastable NaNb7O18}, volume = {147}, year = {2025}, }
• (2025). Phenol[4]arenes: Excellent macrocyclic precursors for constructing chiral porous organic cages. JACS, 147(10), 8500--8512. (www)

  @article{ , abstract = {The development of new chiral building blocks for constructing complex chiral architectures, such as macrocycles and cages, is both crucial and challenging. Although concave-shaped calixarenes have been established as versatile building blocks for the synthesis of cage compounds, there are no reports on cages constructed from chiral calix[4]arene derivatives. Herein, we present a straightforward and effective method for gram-scale synthesis of a new member of chiral calix[4]arene macrocycle enantiomers, namely, phenol[4]arene (PC[4]A). As a proof of concept, we functionalized these enantiomers into tetraformylphenol[4]arene (PC[4]ACHO) derivatives via the Duff reaction to construct chiral porous organic cages (CPOCs) using polyamine synthons. Specifically, we employ two fluorescent amine synthons, bis(4-aminophenyl)phenylamine and tris(4-aminophenyl)amine, to assemble with PC[4]ACHO enantiomers, resulting in [2 + 4] lantern-shaped and [6 + 8] truncated octahedral CPOCs, respectively. These structures have been unambiguously characterized by single-crystal X-ray diffraction and circular dichroism (CD) spectroscopy. Notably, the [6 + 8] truncated CPOCs exhibit internal diameters of approximately 3.1 nm, a cavity volume of around 5300 Å 3 , and high specific surface areas of up to 1300 m 2 g –1 after desolvation, making them among the largest CPOCs reported. Additionally, investigations into their chiral sensing performance demonstrate that these PC[4]A-based CPOCs enable the enantioselective recognition of amino acids and their derivatives. This work strongly suggests that PC[4]A can serve as an excellent building block for the rational design of chiral materials with practical applications.}, archive = {J_JACS}, author = {Fenglei Qiu and Xinting Zhang and Wenjing Wang and Kongzhao Su and Daqiang Yuan}, doi = {10.1021/jacs.4c16508}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8500--8512}, shortjournal = {J. Am. Chem. Soc.}, title = {Phenol[4]arenes: Excellent macrocyclic precursors for constructing chiral porous organic cages}, volume = {147}, year = {2025}, }
• (2025). Enhancing robustness and charge transfer kinetics of sodium-ion batteries through introduction of anionic anchoring separators. JACS, 147(10), 8488--8499. (www)

  @article{ , abstract = {Ionic transport critically dictates the performance of the batteries. Here, we proposed an anion anchoring strategy for enhancing Na + transport kinetics that was based on introducing a separator with a positive surface potential. Besides, we developed a nuclear magnetic resonance-assisted Hittorf approach to address the limitation of the traditional Bruce–Vincent approach itself in order to accurately quantify the migration dynamics of anions on the time scale. Results indicate that this strategy effectively anchors free anions and increases the proportion of solvent-separated ion pairs in the bulk, reduces the cation transfer energy barrier at the anode, and mitigates parasitic reactions at the cathode. The symmetric Na||Na cells efficiently operate over 1600 h, and the Na||Na 3 V 2 (PO 4 ) 3 cells show stable cycling performance under limited Na excess and lean electrolyte conditions. The assembled HC||Na 3 V 2 (PO 4 ) 3 pouch cells achieve an energy density of up to 225.7 W h kg –1 . Our strategy offers a new option for high-energy and long-cycle sodium-ion batteries.}, archive = {J_JACS}, author = {Xiao Li and Tao Zhang and Yilin Zhao and Xiaoqing Zhu and Aimin Ge and Keith C. Gordon and Fei Wang and Guiyin Xu and Meifang Zhu}, doi = {10.1021/jacs.4c16227}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8488--8499}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing robustness and charge transfer kinetics of sodium-ion batteries through introduction of anionic anchoring separators}, volume = {147}, year = {2025}, }
• (2025). Heterogeneous catalysis expands the toolbox for chemoselective peptide derivatization and labeling. JACS, 147(10), 8478--8487. (www)

  @article{ , abstract = {The ability to chemoselectively modify either the peptide backbone or specific side chains is critical to advance the fields of bioconjugation and peptide pharmaceuticals. Transition-metal catalysis has been widely used in peptide and protein derivatization but mostly under homogeneous conditions. Herein, we present a first-in-class heterogeneous catalytic approach for the site-selective functionalization of histidine-containing peptides with aryl and alkenyl moieties bearing fluorescent and affinity tags, lipids, and conjugation handles. This heterogeneous derivatization strategy employs a copper(II) hexacyanometallate to catalyze the Chan–Lam reaction with boronic acids at either the backbone or the histidine imidazole, thus providing novel results that differ from those previously reported for the homogeneous Cu(OAc) 2 -mediated coupling procedure. A correlation was established between the structural and electronic properties of the copper(II) hexacyanometalate with its ability to catalyze this oxidative cross-coupling. This report expands the toolbox for late-stage peptide derivatization and labeling by unlocking the reactivity of the histidine side chain rather than merely acting as a directing group, thus boosting applications of heterogeneous catalysis in drug discovery and development.}, archive = {J_JACS}, author = {Leslie Reguera and Aldrin V. Vasco and Javiel F. Marrero and Manuel G. Ricardo and Ludger A. Wessjohann and Daniel G. Rivera}, doi = {10.1021/jacs.4c16754}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8478--8487}, shortjournal = {J. Am. Chem. Soc.}, title = {Heterogeneous catalysis expands the toolbox for chemoselective peptide derivatization and labeling}, volume = {147}, year = {2025}, }
• (2025). Unraveling the structure and properties of high-concentration aqueous iron oxide nanocolloids free of steric stabilizers. JACS, 147(10), 8467--8477. (www)

  @article{ , abstract = {Aqueous colloids with a high concentration of nanoparticles and free of steric stabilizers are prospective soft materials, the engineering of which is still challenging. Herein, we prepared superparamagnetic colloids with very large, up to 1350 g/L concentration of 11 nm nanoparticles via Fe 2+ and Fe 3+ coprecipitation, water washing, purification using cation-exchange resin, and stabilization with a monolayer of citrate anions (ζ potential of diluted dispersions about −35 mV). XRD, XPS, Mössbauer, and FTIR spectra elucidated the defective reverse spinel structure of magnetite/maghemite (Fe 3 O 4 /γ-Fe 2 O 3 ) with a reduced content of Fe 2+ cations. The viscosity increases with nanoparticle concentration and depends also on the nature of citrate salt, being one order of magnitude lower for lithium than sodium and potassium as counter-cation. SAXS/USAXS curves show power-law behavior in the scattering vector range between 0.1 and 0.002 nm –1 , suggesting that particles interact forming fractal clusters, which are looser for Na + - and denser for Li + -citrate stabilizers (fractal dimensions of 1.9 and 2.4, respectively). In parallel, ATR-FTIR found increasing proportions of symmetric O–H stretching vibrations of ice-like interfacial water in the concentrated colloids. We hypothesize that the clusters arise due to the attraction of like-charge particles possibly involving the water shells and hydration of counter-cations; overlapping the clusters and transition to continuous non-Newtonian phases is seen at viscosity vs concentration plots at 700–900 g/L. The results shed new light on the structure of very concentrated nanocolloids and pave the way for their manufacturing and tailoring.}, archive = {J_JACS}, author = {Denis V. Karpov and Sergey A. Vorobyev and Oleg A. Bayukov and Yuriy V. Knyazev and Dmitriy A. Velikanov and Sergey M. Zharkov and Yurii V. Larichev and Svetlana V. Saikova and David Zitoun and Yuri Mikhlin}, doi = {10.1021/jacs.4c16602}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8467--8477}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the structure and properties of high-concentration aqueous iron oxide nanocolloids free of steric stabilizers}, volume = {147}, year = {2025}, }
• (2025). Amorphous-to-crystalline transformation: How cluster aggregation drives the multistep nucleation of ZIF-8. JACS, 147(10), 8455--8466. (www)

  @article{ , abstract = {Nucleation, the pivotal first step of crystallization, governs the essential characteristics of crystallization products, including size distribution, morphology, and polymorphism. While understanding this process is paramount to the design of chemical, pharmaceutical, and industrial production processes, major knowledge gaps remain, especially with respect to the crystallization of porous solids. Also for nanocrystalline ZIF-8, one of the most widely studied metal–organic frameworks, questions regarding the species involved in the nucleation pathway and their structural and chemical transformations remain unanswered. By combining harmonic light scattering, inherently sensitive to structural changes, with NMR spectroscopy, which reveals molecular exchanges between particles and solution, we were able to capture the crystallization mechanism of ZIF-8 in unprecedented detail. This dual approach provides concurrent structural and chemical insights, revealing key processes not previously observed in ZIF crystallization. Upon mixing, small charged prenucleation clusters (PNCs) are formed, exhibiting an excess of ligands and net positive charge. We show that nucleation is initiated by aggregation of PNCs, through the release of ligands and associated protons to the liquid. This leads to the formation of charge neutral amorphous precursor particles (APPs), which incorporate neutral monomers from the solution and crystallized ZIF-8. Our work highlights chemical dynamics as a vital, yet often overlooked, dimension in the multistage structural evolution of MOFs. By establishing the critical role of PNCs in the nucleation of ZIF-8, new pathways open up for controlling crystallization of metal–organic frameworks through targeted chemical interactions with these species.}, archive = {J_JACS}, author = {Ahmet Rafet Dok and Sambhu Radhakrishnan and Flip de Jong and Estelle Becquevort and Olivier Deschaume and C. Vinod Chandran and Yovan de Coene and Carmen Bartic and Mark Van der Auweraer and Wim Thielemans and Christine Kirschhock and Monique A. van der Veen and Thierry Verbiest and Eric Breynaert and Stijn Van Cleuvenbergen}, doi = {10.1021/jacs.4c16615}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8455--8466}, shortjournal = {J. Am. Chem. Soc.}, title = {Amorphous-to-crystalline transformation: How cluster aggregation drives the multistep nucleation of ZIF-8}, volume = {147}, year = {2025}, }
• (2025). Selective stepwise reduction of nitrate and nitrite to dinitrogen or ammonia. JACS, 147(10), 8444--8454. (www)

  @article{ , abstract = {This study reports a method for the selective reduction of NO 3 – and NO 2 – to N 2 or NH 3 , extending prior work in our lab where NO 3 – was reduced to NO by [N(afa Cy ) 3 Fe]OTf 2 (N(afa Cy ) 3 = tris(5-cyclohexyl-amineazafulvene-2-methyl)amine, OTf = triflate). The first pathway involves the reduction of NO 2 – to N 2 , where the NO generated in the initial step is transformed to N 2 O by PPh 3 and further reduced to N 2 by the [N(afa Cy ) 3 Fe]OTf 2 complex. An alternative pathway showcases the reduction of the bound NO complex, [N(afa Cy ) 3 Fe(NO)] 2+ , to NH 3 using chemical reductants, albeit with a modest yield of 29%. Confirmation of the nitrogen source as NO is established through 15 N labeling studies. Hydroxylamine (NH 2 OH) is proposed as a plausible intermediate in the reduction of bound NO, supported by independent NH 2 OH reduction experiments and computational studies. Nature employs a well-orchestrated, stepwise process involving several enzymes to reduce N-containing oxyanions, and this approach provides valuable insights into the stepwise reduction mechanisms of nitrate and nitrite, yielding NH 3 or N 2 as the product.}, archive = {J_JACS}, author = {Jewelianna M. Moore and Tabitha J. Miller and Manting Mu and Marconi N. Peñas-Defrutos and Kelly L. Gullett and Lindsey S. Elford and Sebastian Quintero and Max García-Melchor and Alison R. Fout}, doi = {10.1021/jacs.4c16585}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8444--8454}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective stepwise reduction of nitrate and nitrite to dinitrogen or ammonia}, volume = {147}, year = {2025}, }
• (2025). Internal and external pockets in pillar[n]arene sheets and their Host–Guest binding beyond cavity volume limitations. JACS, 147(10), 8433--8443. (www)

  @article{ , abstract = {Constructing binding pockets by hierarchically assembling tailored building blocks and understanding structure–property relationships are challenging goals. Herein, amphiphilic pillar[5]arene and pillar[6]arene were prepared and used to construct 2D sheets, which consisted of well-defined hydrophobic and hydrophilic interlayers. In the hydrophobic interlayers, internal hydrophobic pockets were created by packing pairs of pillar[ n ]arenes, and external hydrophobic pockets were simultaneously generated from gaps between pillar[ n ]arenes due to electrostatic attractions. Aromatic hydrocarbons were accommodated in these hydrophobic pockets by ball milling. Due to the external pockets, bulky guests larger than the pillar[ n ]arene cavity sizes were also captured in the sheets.}, archive = {J_JACS}, author = {Tan-Hao Shi and De-Hui Tuo and Shogo Azuma and Shun Tokuda and Minamo Masaki and Kazuma Yasuhara and Hitoshi Asakawa and Shuhei Furukawa and Shigehisa Akine and Shunsuke Ohtani and Kenichi Kato and Tomoki Ogoshi}, doi = {10.1021/jacs.4c16440}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8433--8443}, shortjournal = {J. Am. Chem. Soc.}, title = {Internal and external pockets in pillar[n]arene sheets and their Host–Guest binding beyond cavity volume limitations}, volume = {147}, year = {2025}, }
• (2025). Precision synthesis and antiliver fibrosis activity of a highly branched acidic 63-mer pectin polysaccharide. JACS, 147(10), 8422--8432. (www)

  @article{ , abstract = {Natural polysaccharides possess various biological functions and have become increasingly important as drug candidates for biomedical development. However, the accessibility to multiple-branched and large-sized acidic polysaccharides with well-defined structures and the identification of related active glycan domains remain challenging. Here, we report the precision synthesis of a highly branched acidic pectin polysaccharide up to a 63-mer containing 10 different glycosidic linkages from Lycium barbarum . The synthetic strategy relies on highly stereoselective modular assembly of an orthogonally protected decasaccharide backbone, efficient synthesis of three side chain glycans by the integration of stereocontrolled one-pot chemoselective glycosylations and a hydrogen-bond-mediated aglycone delivery approach, and convergent assembly of the target polysaccharide in a branched site-specific glycosylation manner via flexible orthogonal protecting group manipulations. Structure–activity relationship studies of synthetic polysaccharide 63-mer and its short fragments (9-mer, 10-mer, 11-mer, and 33-mer) suggest that the decasaccharide as an active glycan domain exhibits better antiliver fibrosis activity.}, archive = {J_JACS}, author = {Chaoyu Hu and Fei He and Ruixue Wu and Wanqi Zhou and Wenjing Ma and Tianhui Hao and Pengjun Cai and Farong Ye and Zhuojia Xu and Hu Zhou and Ping Wang and Kan Ding and Tiehai Li}, doi = {10.1021/jacs.4c16491}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8422--8432}, shortjournal = {J. Am. Chem. Soc.}, title = {Precision synthesis and antiliver fibrosis activity of a highly branched acidic 63-mer pectin polysaccharide}, volume = {147}, year = {2025}, }
• (2025). Noninvasive vagus nerve electrical stimulation for immune modulation in sepsis therapy. JACS, 147(10), 8406--8421. (www)

  @article{ , abstract = {Sepsis presents a significant medical challenge due to its intense inflammatory response to infection, often resulting in high mortality rates. A promising therapeutic strategy targets the cholinergic anti-inflammatory pathway (CAIP), which regulates immune responses. This study investigates the ingestion of piezoelectric particles that adhere to the stomach lining, specifically targeting TRPV1 receptors. In a mouse model of sepsis, these particles, when activated by low-intensity pulsed ultrasound, generate mild electrical pulses. These pulses stimulate vagal afferent fibers, transmitting signals to the brain and modulating the neural-immune network via the CAIP. Consequently, this leads to a reduction in systemic inflammation, mitigating weight loss, alleviating multiple tissue injuries, and preventing death by modulating immune cells in the spleen. This approach addresses the critical need for noninvasive sepsis therapies, potentially improving patient outcomes. Utilizing portable ultrasound equipment with minimal thermal effects, this technique offers a safe and convenient treatment option, even for home use.}, archive = {J_JACS}, author = {Cam-Hoa Mac and Giang Le Thi Nguyen and Dien Thi My Nguyen and Sheng-Min Huang and Hsu-Hsia Peng and Yen Chang and Shih-Kai Lo and Hui-Hua Kenny Chiang and Yuan-Zhen Yang and Hsiang-Lin Song and Wei-Tso Chia and Yu-Jung Lin and Hsing-Wen Sung}, doi = {10.1021/jacs.4c16367}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8406--8421}, shortjournal = {J. Am. Chem. Soc.}, title = {Noninvasive vagus nerve electrical stimulation for immune modulation in sepsis therapy}, volume = {147}, year = {2025}, }
• (2025). Redox-selective macromolecular electrolysis for sequential functionalization and deconstruction. JACS, 147(10), 8398--8405. (www)

  @article{ , abstract = {This study demonstrates that selective macromolecular electrolysis can be achieved on copolymers containing redox-orthogonal targets by controlling the externally applied voltage. We designed macromolecules containing phthalimide ( E 1/2 = −1.8 V vs Ag/AgNO 3 ) and tetrachlorophthalimide ( E 1/2 = −1.3 V vs Ag/AgNO 3 ) (meth)acrylates that have significantly different reduction potentials such that they are separately redox-addressable. The polymer-centered radicals generated by decarboxylation can either undergo (1) hydrogen atom transfer to form olefinic repeat units or (2) β-scission to deconstruct the polymer backbone. Our results reveal selective electrochemical control over postpolymerization modifications, which enables sequential transformations that tune the glass transition temperature of electrochemically generated copolymers over a range of −54 to 125 °C. This method was also shown to maintain its selectivity in a polymer blend and provided access to copolymers (poly(styrene- co -propylene- co -ethylene)) that would be challenging to prepare in other ways. These results demonstrate the potential of macromolecular electrolysis for selective material functionalization and degradation. This approach expands the toolbox for postpolymerization modification and targeted polymer degradation with applications in macromolecular information processing, spatiotemporal patterning, and producing materials with complex architectures that are driven by external stimuli.}, archive = {J_JACS}, author = {Graham C. Gilchrist and Rhys W. Hughes and Sean R. Gitter and Joshua D. Marquez and Brent S. Sumerlin and Austin M. Evans}, doi = {10.1021/jacs.4c16333}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8398--8405}, shortjournal = {J. Am. Chem. Soc.}, title = {Redox-selective macromolecular electrolysis for sequential functionalization and deconstruction}, volume = {147}, year = {2025}, }
• (2025). The binding of cu2+ to lipid membranes is not substantially influenced by electrostatic screening. JACS, 147(10), 8386--8397. (www)

  @article{ , abstract = {Gouy–Chapman theory predicts that salt screening and modulating the interfacial charge density should strongly influence the apparent dissociation constant, K d,app , between Cu 2+ and negatively charged phosphatidylserine (PS) lipids in supported lipid bilayers (SLBs). Specifically, K d,app would be expected to increase (weaken binding) by a factor of 40 when 100 mM NaCl is introduced into the solution because of electrostatic screening between the membrane and Cu 2+ cations. Surprisingly, however, fluorescence quenching measurements demonstrate that K d,app increases by less than a factor of 2 when increasing the salt concentration in the presence of standard buffers, such as tris(hydroxymethyl)aminomethane (Tris). Moreover, increasing the negative surface charge density by a factor of 4 would be predicted to decrease (strengthen binding) K d,app by 3 orders of magnitude. Instead, K d,app increases slightly when 15 mol % phosphatidylglycerol (PG), a negatively charged lipid, is introduced into SLBs already containing 5 mol % PS. Such findings indicate that electrostatic double layer theory is not a useful approach for predicting the binding behavior of transition metal cations to negatively charged interfaces. The problem lies with the fact that standard buffers, such as Tris, form a wide variety of coordination complexes in bulk solution with transition metal cations like Cu 2+ . Typically, dozens of complexes are present simultaneously at any given pH value and the net charge on them ranges from positive to neutral to negative. Such variations in charge on the complexes result in electrostatic screening and interfacial potential effects that are substantially diminished or nonexistent. These results should generally apply to the binding behavior of first row transition metal ions, when the cations predominantly reside in complexes rather than as free ions. This includes in vivo conditions, where the concentration of free transition metal ions is often very low.}, archive = {J_JACS}, author = {Christopher M. Reynolds and Olivia C. Fiebig and Alexa Marroquin and Andrew J. Glaid and Kushaal Chokhany and Ryan G. Zdenek and Maria Laura da Cruz Garcia and Paul S. Cremer}, doi = {10.1021/jacs.4c16066}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8386--8397}, shortjournal = {J. Am. Chem. Soc.}, title = {The binding of cu2+ to lipid membranes is not substantially influenced by electrostatic screening}, volume = {147}, year = {2025}, }
• (2025). Hydrophobic Metal–Formate composites for efficient CO2 capture. JACS, 147(10), 8377--8385. (www)

  @article{ , abstract = {Carbon capture, utilization, and sequestration (CCUS) have emerged as pivotal mitigation strategies in addressing climate change induced by greenhouse gas emissions. In this pursuit, our objective is to enhance the efficacy of adsorptive CO 2 capture by harnessing state-of-the-art framework sorbents engineered for exceptional CO 2 selectivity, high intrinsic stability in the presence of moisture, and facile regeneration. To this end, a series of ultramicroporous mixed aluminum and iron formate framework materials, Fe-ALFs, were synthesized. Furthermore, their moisture stability has been significantly enhanced by passivation with polyvinylidene fluoride (Fe-ALF-PVDF). Gas sorption and breakthrough measurements demonstrate that Fe-ALF-PVDF exhibits outstanding CO 2 adsorption capacities (4.6 mmol/g at 298 K) and remarkable CO 2 /N 2 selectivity (387). In addition, it can be economically produced from readily available chemicals and is easy to regenerate. Fe-ALF-PVDF presents an innovative adsorbent material for efficiently capturing CO 2 from humid postcombustion flue gases and other moisture-rich gas streams.}, archive = {J_JACS}, author = {Rajesh Das and He Li and Hayden A. Evans and Zeyu Deng and Dan Zhao and Anthony K. Cheetham}, doi = {10.1021/jacs.4c16131}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8377--8385}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrophobic Metal–Formate composites for efficient CO2 capture}, volume = {147}, year = {2025}, }
• (2025). High entropy oxide-polyoxometalate sub-1 nm hetero-nanowires as cathode catalysts in Li–O2 batteries. JACS, 147(10), 8367--8376. (www)

  @article{ , abstract = {It is desirable for lithium–oxygen batteries (LOBs) to fabricate the cathode catalysts with high catalytic activity and stability. High entropy oxide (HEO) sub-1 nm nanowires (SNWs) with the nearly 100% active site exposure and intrinsic stability are doubtless one of the best candidates. Herein, under a mild solvothermal condition, by incorporating phosphomolybdic acid (PMA) into multimetal oxide reaction system, a series of HEO-PMA SNWs are successfully prepared, where the variety of metal oxides is adjustable from mono component to six components. When these SNWs as the cathode catalysts are applied to LOBs, the capacity and cycling stability of the LOBs are steadily improved with the metal oxide species increasing stepwise, indicating that the entropy modulation effect plays an important role in enhancing battery performance. Additionally, considering the difference in the intrinsic catalytic activity of various metal oxides, the battery performance is further optimized by keeping the number of elements constant in HEO-PMA SNWs and just adjusting one kind of metal oxide. Particularly, BiCuFeCeWPtO x -PMA SNWs based battery delivers a high capacity (11206 mA h g –1 ) and excellent stability for 213 cycles, making it a promising electrocatalyst candidate for LOBs.}, archive = {J_JACS}, author = {Huaiyun Ge and Wenxiong Shi and Junli Liu and Yu Zhang and Xun Wang}, doi = {10.1021/jacs.4c15979}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8367--8376}, shortjournal = {J. Am. Chem. Soc.}, title = {High entropy oxide-polyoxometalate sub-1 nm hetero-nanowires as cathode catalysts in Li–O2 batteries}, volume = {147}, year = {2025}, }
• (2025). Efficient synthesis and crystal structure of the HCO+ cation. JACS, 147(10), 8361--8366. (www)

  @article{ , abstract = {In this work, we present an efficient way to synthesize the elusive formylium ion, HCO + . Its high reactivity toward even weak nucleophiles necessitates the use of an unconventional solvent like the refrigerant 1,1,1,2-tetrafluoroethane. The stabilization and isolation of the smallest possible acyl cation at low temperatures allowed us to thoroughly investigate its [Sb 2 F 11 ] − salt via vibrational spectroscopy and single-crystal X-ray diffraction. The experimental data, together with quantum chemical calculations at the M06-2X/aug-cc-pVTZ-level of theory, help us to understand the stabilization of the elusive cation in the solid state.}, archive = {J_JACS}, author = {Sebastian Steiner and Tobias Kuhn and Christoph Jessen and Valentin Bockmair and Alan Virmani and Andreas J. Kornath}, doi = {10.1021/jacs.4c15975}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8361--8366}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient synthesis and crystal structure of the HCO+ cation}, volume = {147}, year = {2025}, }
• (2025). Enhancing electron Donor–Acceptor complex photoactivation with a stable perylene diimide Metal–Organic framework. JACS, 147(10), 8350--8360. (www)

  @article{ , abstract = {Electron donor–acceptor complexes are commonly employed to facilitate photoinduced radical-mediated organic reactions. However, achieving these photochemical processes with catalytic amounts of donors or acceptors can be challenging, especially when aiming to reduce catalyst loadings. Herein, we have unveiled a framework-based heterogenization approach that significantly enhances the photoredox activity of perylene diimide species in radical addition reactions with alkyl silicates by promoting faster and more efficient electron donor–acceptor complex formation. Besides offering broad substrate scope in alkene hydroalkylation, the newly developed heterogeneous photocatalysis substantially improves the catalyst turnover numbers in comparison to previous homogeneous photocatalytic systems and demonstrates outstanding catalyst recyclability. These research findings pave the way for the advancement of various efficient and practical organic transformations using framework-supported organocatalysts.}, archive = {J_JACS}, author = {Xia Wu and Ming Cui and Kun Wu and Jun Guo and Tianyu Liu and Dongyi Liu and Zekun Li and Puxin Weng and Ri-Qin Xia and Xiao Xiong and Yong-Liang Huang and Dan Li and Jian He}, doi = {10.1021/jacs.4c16021}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8350--8360}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing electron Donor–Acceptor complex photoactivation with a stable perylene diimide Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Optical waveguiding charge-transfer cocrystals: Examining the impact of molecular rotations on their photoluminescence. JACS, 147(10), 8343--8349. (www)

  @article{ , abstract = {Here, we present the first example of a binary optical waveguiding (OWG) cocrystal with large anisotropy featuring a fluorinated acceptor molecule (CPP-TFPN, 1 ) with on-plane rotational dynamics, confirmed by solid-state NMR ( 19 F T 1 ) and theoretical calculations. Spatially resolved microphotoluminescence and variable-temperature photoluminescence experiments allowed us to examine the OWG performance and photophysical properties of both single crystals and bulk microcrystalline samples. A comparison with an analogous cocrystal containing a regioisomeric acceptor (CPP-TFTN, 2 ) revealed that the photoluminescence characteristics of 1 are associated with the rotational motions of the acceptor, offering insights into how the molecular motion changes this property.}, archive = {J_JACS}, author = {Armando Navarro-Huerta and Takumi Matsuo and Alexander S. Mikherdov and Jan Blahut and Erika Bartůňková and Pingyu Jiang and Martin Dračínský and Simon Teat and Mingoo Jin and Shotaro Hayashi and Braulio Rodríguez-Molina}, doi = {10.1021/jacs.4c15957}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8343--8349}, shortjournal = {J. Am. Chem. Soc.}, title = {Optical waveguiding charge-transfer cocrystals: Examining the impact of molecular rotations on their photoluminescence}, volume = {147}, year = {2025}, }
• (2025). Optical spin hall effect pattern switching in polariton condensates in organic single-crystal microbelts. JACS, 147(10), 8336--8342. (www)

  @article{ , abstract = {Topological polaritons, combining the robustness of the topologically protected edge states against defects and disorder with the strong nonlinear properties of polariton bosons, represent an excellent platform to investigate novel photonic topological phases. We demonstrate the optical spin Hall effect (OSHE) and its symmetry switching in the exciton–polariton regime of pure DPAVBi crystals. Benefiting from the photonic Rashba–Dresselhaus spin–orbit coupling, we observe the separation of left- and right-circularly polarized emission in momentum space and real space, a signature of the OSHE. Above the lasing threshold, the OSHE pattern changes due to transverse quantization in the microbelt. This simple device has great potential applications in topological polaritons, such as information transmission, photonic integrated chips, and quantum information.}, archive = {J_JACS}, author = {Jiahuan Ren and Teng Long and Chunling Gu and Hongbing Fu and Dmitry Solnyshkov and Guillaume Malpuech and Qing Liao}, doi = {10.1021/jacs.4c15894}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8336--8342}, shortjournal = {J. Am. Chem. Soc.}, title = {Optical spin hall effect pattern switching in polariton condensates in organic single-crystal microbelts}, volume = {147}, year = {2025}, }
• (2025). Monodentate σ-accepting boron-based ligands bearing square-planar ni(0) centers. JACS, 147(10), 8326--8335. (www)

  @article{ , abstract = {Transition metals are known to work as electron donors toward electron-accepting heavier-group-13 elements (Al, Ga, and In), called Z-type ligands. However, complexes with boron-based Z-type ligands are stable only in the presence of additional coordination units (the so-called “supported-ligand” strategy). Here, we report the synthesis and characterization of square-planar Ni(0) complexes that bear tris(perfluoroaryl)boranes as monodentate Z-type ligands, even though such coordination geometry has been traditionally associated with Ni(II) species based on the well-established ligand-field theory. A combined theoretical and experimental approach revealed a mixed covalent/dative character for the Ni–B bonds. This strategy uses frustrated L/Z-ligand pairs that combine sterically encumbered electron-donating (L-type) and electron-accepting ligands to form noncovalent interactions over L–M–Z units to achieve unprecedented low-valent transition metal species with monodentate Z-type ligands.}, archive = {J_JACS}, author = {Yutaka Mondori and Yasuhiro Yamauchi and Takahiro Kawakita and Sensuke Ogoshi and Yuta Uetake and Yasuo Takeichi and Hidehiro Sakurai and Yoichi Hoshimoto}, doi = {10.1021/jacs.4c15892}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8326--8335}, shortjournal = {J. Am. Chem. Soc.}, title = {Monodentate σ-accepting boron-based ligands bearing square-planar ni(0) centers}, volume = {147}, year = {2025}, }
• (2025). An mRNA display approach for covalent targeting of a staphylococcus aureus virulence factor. JACS, 147(10), 8312--8325. (www)

  @article{ , abstract = {Staphylococcus aureus ( S. aureus ) is an opportunistic human pathogen that causes over one million deaths around the world each year. We recently identified a family of serine hydrolases termed fluorophosphonate binding hydrolases (Fphs) that play important roles in lipid metabolism and colonization of a host. Because many of these enzymes are only expressed in Staphylococcus bacteria, they are valuable targets for diagnostics and therapeutics. Here, we developed and screened highly diverse cyclic peptide libraries using mRNA display with a genetically encoded oxadiazolone (Ox) electrophile that was previously shown to potently and covalently inhibit multiple Fph enzymes. By performing multiple rounds of counter selections with WT and catalytic dead FphB, we were able to tune the selectivity of the resulting selected cyclic peptides containing the Ox residue toward the active site serine. From our mRNA display hits, we developed potent and selective fluorescent probes that label the active site of FphB at single digit nanomolar concentrations in live S. aureus bacteria. Taken together, this work demonstrates the potential of using direct genetically encoded electrophiles for mRNA display of covalent binding ligands and identifies potent new probes for FphB that have the potential to be used for diagnostic and therapeutic applications.}, archive = {J_JACS}, author = {Sijie Wang and Emily C. Woods and Jeyun Jo and Jiyun Zhu and Althea Hansel-Harris and Matthew Holcomb and Manuel Llanos and Nichole J. Pedowitz and Tulsi Upadhyay and John Bennett and Matthias Fellner and Ki Wan Park and Anna Zhang and Tulio A. Valdez and Stefano Forli and Alix I Chan and Christian N. Cunningham and Matthew Bogyo}, doi = {10.1021/jacs.4c15713}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8312--8325}, shortjournal = {J. Am. Chem. Soc.}, title = {An mRNA display approach for covalent targeting of a staphylococcus aureus virulence factor}, volume = {147}, year = {2025}, }
• (2025). Interfacing flexible design and social self-sorting enables comprehensive control over photophysical and self-assembly properties of supramolecular polymers. JACS, 147(10), 8300--8311. (www)

  @article{ , abstract = {Supramolecular self-assembly offers an intriguing approach to construct microarchitectures, which combine properties of their molecular constituents with dynamic supramolecular features. Control over intermolecular interactions and their resulting properties can sometimes be achieved by targeted design. However, it is often unfeasible to transfer the insights gained from a specific supramolecular synthon to another chromophore without tedious synthetic work guided by trial and error. Herein we demonstrate how a flexible molecular design approach enables access to a diverse library of photophysical properties, which can be further diversified by social self-sorting strategies using a second supramolecular building block as a modulator. By intercalation into the supramolecular polymer the modulator can disrupt interchromophore interactions and modulate the ensembles emissive properties across the visible color space by simply adjusting the ratio between the two building blocks. Furthermore, by combining a chromophore appended synthon with a different morphology than the modulator the mesoscopic size distribution of the coassemblies can be modified to resemble either of its constituents. Crucially, this moldability is not only achievable for systems under thermodynamic control, but can be also employed to tune photophysical properties and thermal stability profiles of kinetically controlled states. Finally, the thermodynamic stability of the modulated polymers can be adjusted by varying the amount of solubilizing alkyl chains in the ensemble. This peripheral stabilization approach does not affect the engineered photophysical or supramolecular properties. Our results demonstrate how flexible molecular design enriched by a supramolecular modulator can offer access to a wide variety of photophysical properties and enable unique fine-tuning of various supramolecular properties.}, archive = {J_JACS}, author = {Nils Bäumer and Saeko Yamada and Soichiro Ogi and Shigehiro Yamaguchi}, doi = {10.1021/jacs.4c15766}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8300--8311}, shortjournal = {J. Am. Chem. Soc.}, title = {Interfacing flexible design and social self-sorting enables comprehensive control over photophysical and self-assembly properties of supramolecular polymers}, volume = {147}, year = {2025}, }
• (2025). Piezoelectrostatic catalysis of the Azide–Alkyne huisgen cycloaddition. JACS, 147(10), 8289--8299. (www)

  @article{ , abstract = {Electric fields are increasingly recognized for their role as ‘smart reagents’ that can trigger or accelerate chemical reactions. Expanding upon this concept, our research introduces an innovative method that exploits electric fields induced by ultrasound on piezoelectric nanoparticles to facilitate the azide–alkyne Huisgen cycloaddition in nonaqueous environments. The intense electric field generated around the BaTiO 3 nanoparticles, as supported by density functional theory calculations, provides the suitable conditions necessary to trigger the cycloaddition of the alkyne-functionalized nanoparticles and the azide present in the solution. To quantitatively assess the occurrence of the click cycloaddition reaction at the nanoparticle surface interface, we tacked the azide with either an electroactive ferrocene moiety or with gold nanoparticles, which act as surface Raman enhancers. These experiments not only provide experimental validation of our approach, but also highlights the potential of piezoelectrostatic catalysts in enhancing the scalability of electrostatic catalysis.}, archive = {J_JACS}, author = {Qiao Tang and Roger Sanchis-Gual and Ni Qin and Hao Ye and Semih Sevim and Andrea Veciana and Carlos Corral-Casas and Kishan Thodkar and Jiang Wu and Bradley J. Nelson and Ismael Díez-Pérez and Xiang-Zhong Chen and Chiara Gattinoni and Josep Puigmartí-Luis and Salvador Pané and Carlos Franco}, doi = {10.1021/jacs.4c15681}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8289--8299}, shortjournal = {J. Am. Chem. Soc.}, title = {Piezoelectrostatic catalysis of the Azide–Alkyne huisgen cycloaddition}, volume = {147}, year = {2025}, }
• (2025). Tracking the fate of therapeutic proteins using ratiometric imaging of responsive shortwave infrared probes. JACS, 147(10), 8280--8288. (www)

  @article{ , abstract = {Monoclonal antibodies (mAbs) are essential agents for cancer treatment and diagnosis. Advanced optical imaging strategies have the potential to address specific questions regarding their complex in vivo life cycle. This study presents responsive shortwave infrared (SWIR) probes and an associated imaging scheme to assess mAb biodistribution, cellular uptake, and proteolysis. Specifically, we identify a Pegylated benzo-fused norcyanine derivative (Benz-NorCy7) that is activated in acidic environments and can be appended to mAbs without significant changes in optical properties. As a mAb conjugate, this agent shows high tumor specificity in a longitudinal imaging study in a murine model. To enable independent tracking of mAb uptake and lysosomal uptake and retention, a two-color ratiometric imaging strategy was employed using an “always-ON” heptamethine cyanine dye (λ ex = 785 nm) and the pH-responsive Benz-NorCy7 (λ ex = 890 nm). To assess proteolytic catabolism, we append a cleavable carbamate to Benz-NorCy7 to create turn-ON probes. These agents facilitate the comparison of two common peptide linkers and provide insights into their in vivo properties. Overall, these studies provide a strategy to assess the fate of protein-based therapeutics using optical imaging.}, archive = {J_JACS}, author = {Pradeep Shrestha and Nimit L. Patel and Joseph D. Kalen and Syed Muhammad Usama and Martin J. Schnermann}, doi = {10.1021/jacs.4c15614}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8280--8288}, shortjournal = {J. Am. Chem. Soc.}, title = {Tracking the fate of therapeutic proteins using ratiometric imaging of responsive shortwave infrared probes}, volume = {147}, year = {2025}, }
• (2025). Transition-state-dependent spontaneous generation of reactive oxygen species by aβ assemblies encodes a self-regulated positive feedback loop for aggregate formation. JACS, 147(10), 8267--8279. (www)

  @article{ , abstract = {Amyloid-β (Aβ) peptides exhibit distinct biological activities across multiple physical length scales, including monomers, oligomers, and fibrils. The transition from Aβ monomers to pathological aggregates correlates with the emergence of chemical toxicity, which plays a critical role in the progression of neurodegenerative disorders. However, the relationship between the physical state of Aβ assemblies and their chemical toxicity remains poorly understood. Here, we show that Aβ assemblies can spontaneously generate reactive oxygen species (ROS) through transition-state-specific inherent nonenzymatic redox activity. During the transition from initial monomers to intermediate oligomers or condensates to final fibrils, interfacial electrochemical environments emerge and vary at the liquid–liquid and liquid–solid interfaces. Determined by the vibrational Stark effect using electronic pre-resonance stimulated Raman scattering microscopy, the interfacial field of such assemblies is on the order of 10 MV/cm. Interfacial activity, which depends on the Aβ transition state, can modulate the spontaneous oxidation of hydroxide anions, which leads to the formation of hydroxyl radicals. Interestingly, this redox activity modifies the chemical composition of Aβ and establishes a self-regulated positive feedback loop that accelerates aggregation and promotes fibril formation, which represents a new functioning mechanism of Aβ aggregation beyond physical cross-linking. Leveraging this mechanistic insight, we identified small molecules capable of disrupting the feedback loop by scavenging hydroxyl radicals or perturbing the interface, thereby inhibiting fibril formation. Our findings provide a nonenzymatic model of neurotoxicity and reveal the critical role of physical interfaces in modulating the chemical dynamics of biomolecular assemblies. These results offer a novel framework for therapeutic intervention in Alzheimer’s disease and related neurodegenerative disorders.}, archive = {J_JACS}, author = {Michael W. Chen and Xiaokang Ren and Xiaowei Song and Naixin Qian and Yuefeng Ma and Wen Yu and Leshan Yang and Wei Min and Richard N. Zare and Yifan Dai}, doi = {10.1021/jacs.4c15532}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8267--8279}, shortjournal = {J. Am. Chem. Soc.}, title = {Transition-state-dependent spontaneous generation of reactive oxygen species by aβ assemblies encodes a self-regulated positive feedback loop for aggregate formation}, volume = {147}, year = {2025}, }
• (2025). Exploration of metastable A-site-ordered perovskites (Ca,Ba)FeO3−δ by computationally guided multistep synthesis. JACS, 147(10), 8260--8266. (www)

  @article{ , abstract = {Perovskite-type iron oxides with Fe 4+ ions have attracted a great deal of attention for their versatile helimagnetic phases. While the introduction of a layered A-site ordered structure to AFeO 3 with Fe 4+ ions potentially leads to novel helimagnetic phases, the synthetic pathway spanning a high-pressure range is apparently difficult to elucidate. Here, we explored new A-site ordered perovskite-type iron oxides (Ca,Ba)FeO 3−δ with Fe 4+ ions with the support of first-principles calculations evaluating thermodynamic stability at selected pressures and chemical compositions. Among the six types of putative A-site ordered perovskites with and without oxygen vacancy, only two types of oxygen-deficient perovskites CaBaFe 2 O 6−δ and Ca(Ba 0.9 Ca 0.1 ) 2 Fe 3 O 9−δ (δ ∼ 1) were successfully obtained by high-pressure synthesis, consistent with the DFT-based convex-hull calculations. Considering the evaluated stability of the putative perovskites at selected pressures, we adopted low-temperature topotactic oxidation using ozone at ambient pressure and obtained the oxidized perovskites CaBaFe 2 O 6−δ (δ ∼ 0.4) and Ca(Ba 0.9 Ca 0.1 ) 2 Fe 3 O 9−δ (δ ∼ 0.6), potentially showing novel helimagnetic phases. This study demonstrates that computational visualization of multistep synthetic pathways involving high pressure can accelerate the search for new metastable perovskites with rich magnetic phases.}, archive = {J_JACS}, author = {Masaho Onose and Hidefumi Takahashi and Hajime Sagayama and Yuichi Yamasaki and Shintaro Ishiwata}, doi = {10.1021/jacs.4c15392}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8260--8266}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploration of metastable A-site-ordered perovskites (Ca,Ba)FeO3−δ by computationally guided multistep synthesis}, volume = {147}, year = {2025}, }
• (2025). Balancing electronic spin state via atomically-dispersed heteronuclear Fe–Co pairs for high-performance Sodium–Sulfur batteries. JACS, 147(10), 8250--8259. (www)

  @article{ , abstract = {Room-temperature sodium–sulfur (Na–S) batteries are emerging as a promising next-generation energy storage technology, offering high energy densities at low cost and utilizing abundant elements. However, their practical application is hindered by the shuttle effect of sodium-polysulfides and the sluggish kinetics of sulfur redox reactions. In this study, we demonstrate a heteronuclear diatomic catalyst featuring Fe and Co bimetallic sites embedded in nitrogen-doped hollow carbon nanospheres (Fe–Co/NC) as an effective sulfur host at the cathode of Na–S batteries. Aberration-corrected high-angle annular dark field scanning transmission electron microscopy demonstrates the presence of isolated Fe–Co atomic pairs, while synchrotron radiation X-ray absorption fine structure analysis confirms the (Fe–Co–N 6 ) coordination structure. Density functional theory calculations show that the introduction of Fe atoms induces electron delocalization in Co(II), shifting the electronic configuration from a low-spin to a higher-spin state. This shift enhances the hybridization of the Co dz 2 orbitals with the antibonding π orbitals of sulfur atoms within the sodium sulfide species that accelerates their catalytic conversion. As a result, Fe–Co/NC-based cathodes exhibit excellent cycling stability (378 mAh g –1 after 2000 cycles) and impressive rate performance (341.1 mAh g –1 under 5 A g –1 ).}, archive = {J_JACS}, author = {Canhuang Li and Jing Yu and Dawei Yang and Hao Li and Yapeng Cheng and Yuchuan Ren and Xiaoyu Bi and Jiachen Ma and Ruirui Zhao and Yingtang Zhou and Jian Wang and Chen Huang and Junshan Li and Ivan Pinto-Huguet and Jordi Arbiol and Haining Zhang and Sen Xin and Andreu Cabot}, doi = {10.1021/jacs.4c15408}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8250--8259}, shortjournal = {J. Am. Chem. Soc.}, title = {Balancing electronic spin state via atomically-dispersed heteronuclear Fe–Co pairs for high-performance Sodium–Sulfur batteries}, volume = {147}, year = {2025}, }
• (2025). Tuning the Structure–Property relationships of metallophthalocyanine-based two-dimensional conductive Metal–Organic frameworks with different metal linkages. JACS, 147(10), 8240--8249. (www)

  @article{ , abstract = {Metallophthalocyanine (MPc)-linked conductive two-dimensional (2D) metal–organic frameworks (MOFs) hold tremendous promise as modular 2D materials in sensing, catalysis, and energy-related applications due to their combinatory bimetallic system from the MPc core and bridging metal nodes, endowing them with high electrical conductivity and multifunctionality. Despite significant advances, there is a gap in fundamental understanding regarding the periodic effects of metal nodes on the structural properties of MPc-linked 2D MOFs. Herein, we report a series of highly crystalline MOFs wherein copper phthalocyanine (CuPc) is linked with Ni, Cu, and Zn nodes (CuPc-O-M, M: Ni, Cu, Zn). The prepared CuPc-O-M MOFs exhibit p -type semiconducting properties with an exceptionally high range of electrical conductivity. Notably, the differences in the 3 d orbital configurations of the Ni, Cu, and Zn nodes in CuPc-O-M MOFs lead to perturbations of the interlayer stacking patterns of the 2D framework materials, which ultimately affect material properties, such as semiconducting band gaps and charge transport within the framework. The Cu 2+ (3 d 9 ) metal node within the eclipsed interlayer stacking of CuPc-O-Cu MOF demonstrates excellent charge transport, which results in the smallest band gap of 1.14 eV and the highest electrical conductivity of 9.3 S m –1 , while the Zn 2+ (3 d 10 ) metal node within CuPc-O-Zn results in a slightly inclined interlayer stacking, leading to the largest band gap of 1.27 eV and the lowest electrical conductivity of 2.9 S m –1 . These findings form an important foundation in the strategic molecular design of this class of materials for multifaceted functionality that builds upon the electronic properties of these materials.}, archive = {J_JACS}, author = {Hyuk-Jun Noh and Evan Cline and Doran L. Pennington and Hao-Yu Greg Lin and Christopher H. Hendon and Katherine A. Mirica}, doi = {10.1021/jacs.4c15272}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8240--8249}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the Structure–Property relationships of metallophthalocyanine-based two-dimensional conductive Metal–Organic frameworks with different metal linkages}, volume = {147}, year = {2025}, }
• (2025). Single-molecule-sensitive three-dimensional atomic heterostructures with extreme light-matter coupling. JACS, 147(10), 8227--8239. (www)

  @article{ , abstract = {Three-dimensional heterostructures (3DHS) with controlled compositions and tuned properties are highly desired for fundamental studies and applications in optoelectronics, nanocatalysis, clean energy, and biomedicine. However, conventional nanostructure engineering is hindered by challenges such as poor structural control, time- and energy-intensive processes, the use of hazardous and expensive chemicals, and harsh conditions. Here, we report plasma-assisted epitaxy (PAE) engineering of a metal–organic 3DHS with extreme light-matter interaction for rapid single-molecule-level sensing. Plasmonic-active 3DHS composed of structure-tuned gold–silver core–shell nanoparticles (AuAgCSNPs) was precisely engineered using stable and scalable microplasma-enabled nanofabrication under ambient conditions. The engineered AuAgCSNP-based 3DHS possessed exceptional Raman enhancement under suitable laser excitation, leading to single-molecule detection of SARS-CoV-2 spike proteins in simulated human saliva via surface-enhanced Raman scattering (SERS). The developed plasma fabrication method allows the production of centimeter-scale SERS-active metal–organic 3DHS on disposable, flexible, lightweight, and cost-effective substrates, thereby opening a new avenue for next-generation biosensing, nanoelectronics, nanocatalysis, and biomedical applications.}, archive = {J_JACS}, author = {Yi-Jui Yeh and Shao-Yu Chen and Wesley Wei-Wen Hsiao and Yoshifumi Oshima and Mari Takahashi and Shinya Maenosono and Kuo-Lun Tung and Wei-Hung Chiang}, doi = {10.1021/jacs.4c15029}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8227--8239}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-molecule-sensitive three-dimensional atomic heterostructures with extreme light-matter coupling}, volume = {147}, year = {2025}, }
• (2025). Photodriven ammonia synthesis from n2 and h2: Recycling of a molecular molybdenum nitride. JACS, 147(10), 8215--8226. (www)

  @article{ , abstract = {The synthesis of ammonia from its elements, N 2 and H 2 , is the most atom-economical and thermodynamically preferred route but presents a high kinetic barrier and thus is rare using molecular compounds. Irradiation of a molecular molybdenum nitride prepared from N 2 cleavage with visible light in the presence of an iridium photocatalyst and 1–4 atm of H 2 produced high yields of ammonia along with the formation of a cationic, formally molybdenum(VI) pentahydride as the major molybdenum-containing product. Continued irradiation of the molybdenum hydride under an N 2 atmosphere resulted in regeneration of the molybdenum nitride that was recycled and used for additional hydrogenation to generate more ammonia, demonstrating superstoichiometric batch ammonia synthesis using only N 2 and H 2 with molecular compounds under ambient conditions.}, archive = {J_JACS}, author = {Junho Kim and Grace B. Panetti and Nidhi Kaul and Sangmin Kim and Paul J. Chirik}, doi = {10.1021/jacs.4c14966}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8215--8226}, shortjournal = {J. Am. Chem. Soc.}, title = {Photodriven ammonia synthesis from n2 and h2: Recycling of a molecular molybdenum nitride}, volume = {147}, year = {2025}, }
• (2025). Photo- and electrocatalytic dual-layer cathode facilitating zn peroxide chemistry in near-neutral Zn–Air batteries. JACS, 147(10), 8205--8214. (www)

  @article{ , abstract = {Rechargeable zinc-air batteries (ZABs) using near-neutral aqueous electrolytes are gaining significant attention due to their high energy density, low cost, high safety, and the excellent reversibility of the zinc (Zn) anode in mild electrolytes. However, the sluggish O 2 /ZnO 2 conversion in the carbon-based cathodes of these batteries leads to a large voltage hysteresis (>600 mV) between charge and discharge. Metal- or metal oxide-based electrocatalysts are rarely used to reduce the overpotentials of this conversion because their presence may trigger undesirable H 2 O-participated oxygen reduction/evolution reactions, disrupting the pH balance of the electrolyte. Here, we propose a dual-layer catalytic cathode comprising an outer photocatalyst layer (exposed to air) of gold (Au) nanoparticles (NPs) decorated tungsten oxide (Au@WO 3 ) loaded on carbon paper, and an inner electrocatalyst layer (exposed to the electrolyte) based on carbon nanotube (CNT). The hydrophobic inner CNT layer not only provides numerous active sites and ample accommodation for O 2 /ZnO 2 conversion but also prevents the electrolyte from contacting the outer photocatalyst layer. Under light, the outer photocatalyst layer effectively separates photogenerated electron–hole pairs, which are then transferred to the inner CNT layer, reducing the overpotential of the O 2 /ZnO 2 electrochemical conversion. As a result, the near-neutral ZAB demonstrates high stability at 0.1 mA cm –2 ; with a very small voltage hysteresis (<150 mV), significantly improving energy efficiency.}, archive = {J_JACS}, author = {Ruiya Wang and Mingze Gao and Guochao Zhao and Jiecheng Chen and Ziyang Guo and Yonggang Wang}, doi = {10.1021/jacs.4c14009}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8205--8214}, shortjournal = {J. Am. Chem. Soc.}, title = {Photo- and electrocatalytic dual-layer cathode facilitating zn peroxide chemistry in near-neutral Zn–Air batteries}, volume = {147}, year = {2025}, }
• (2025). Freezing-activated covalent organic frameworks for precise fluorescence cryo-imaging of cancer tissue. JACS, 147(10), 8188--8204. (www)

  @article{ , abstract = {Cryosurgery represents a transformative approach in the treatment of resistant tumors, utilizing extreme cold to selectively ablate malignant tissue. However, the clinical success of this technique is constrained by the limited ability of current imaging techniques to differentiate effectively between cancerous and healthy tissues with high spatial resolution. To overcome this challenge, we present a nanoscale Covalent Organic Framework, nTG-DFP-COF, specifically designed to enhance fluorescence-guided cryo-imaging. This framework exhibits a unique temperature-dependent luminescence, that results in enhanced fluorescence emission under cryogenic conditions, enabling precise tissue differentiation during surgical procedures. Engineered for biocompatibility and water dispersibility, nTG-DFP-COF demonstrates minimal cytotoxicity and exceptional specificity toward cancer cells. Comprehensive in vitro, in vivo, and ex vivo evaluations confirm its structural stability and functional efficacy under cryogenic conditions. This innovation not only enhances the precision and safety of cryosurgical procedures but also advances the integration of diagnostic and therapeutic functionalities into a unified platform. By substantially improving tumor targeting accuracy, the use of nTG-DFP-COF will reduce the need for repeat surgeries, facilitate faster recovery, and minimize healthcare costs, thus setting a new standard in oncologic imaging and intervention.}, archive = {J_JACS}, author = {Farah Benyettou and Gobinda Das and Maylis Boitet and Sabu Varghese and Mostafa Khair and Akshaya Kumar Das and Zineb Matouk and Thirumurugan Prakasam and Philippe Bazin and Sudhir Kumar Sharma and Sneha Thomas and Yao He and Rainer Straubinger and Bikash Garai and Ramesh Jagannathan and Felipe Gándara and Mohamad El-Roz and Ali Trabolsi}, doi = {10.1021/jacs.4c13848}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8188--8204}, shortjournal = {J. Am. Chem. Soc.}, title = {Freezing-activated covalent organic frameworks for precise fluorescence cryo-imaging of cancer tissue}, volume = {147}, year = {2025}, }
• (2025). 1,4-azaborine participation enables inaccessible cycloarene with unique photophysical properties. JACS, 147(10), 8178--8187. (www)

  @article{ , abstract = {Cycloarenes and heterocycloarenes, characterized by fused macrocyclic π-conjugated structures, hold significant promise in synthetic chemistry and materials science. However, their further development remains constrained by formidable synthetic challenges, particularly for those with contracted cavities. Inspired by advances in the synthesis of organoboron-based multiresonance thermally activated delayed fluorescence (TADF) emitters, we herein report the convenient access and detailed characterization of a 1,4-azaborine-embedded cycloarene that features the smallest cavity among known (hetero)cycloarenes. The contracted cavity induces a bowl-shaped molecular geometry, as confirmed by crystallographic analysis, while also triggering through-space conjugation with delocalized π-electrons at the cavity site. Comparative studies between this compound and its helical analogue reveal a substantial topological impact on photophysical properties, including a bathochromic-shifted and broadened emission band, prolonged radiative decay process, and more efficient triplet-to-singlet spin-flip. Capitalizing on its efficient TADF with a remarkably high quantum yield, we successfully fabricated the first (hetero)cycloarene-based organic light-emitting diodes, achieving over 30% external quantum efficiency and minimal efficiency roll-off. These findings offer new insights into the design of topologically distinct organic compounds with unique properties.}, archive = {J_JACS}, author = {Wentao Xie and Xiaosong Cao and Manli Huang and Ke Xu and Chenghao Gui and Zhanxiang Chen and Xiu-Fang Song and Yaxiong Wei and He Liu and Tao Hua and Ming Yang and Xiaojun Yin and Jingsheng Miao and Chuluo Yang}, doi = {10.1021/jacs.4c13264}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8178--8187}, shortjournal = {J. Am. Chem. Soc.}, title = {1,4-azaborine participation enables inaccessible cycloarene with unique photophysical properties}, volume = {147}, year = {2025}, }
• (2025). Solar-driven paired CO2 Reduction–Alcohol oxidation using semiartificial suspension, photocatalyst sheet, and photoelectrochemical devices. JACS, 147(10), 8168--8177. (www)

  @article{ , abstract = {Fuel-forming enzymes can display excellent performance, achieving high rates of catalysis with unity selectivity at minimal overpotentials, but they are generally considered to be fragile and difficult to handle in combination with synthetic semiconductors in light-driven chemical synthesis. Here, we demonstrate a biohybrid platform that is assembled from cyanamide-functionalized carbon nitride (CN X ) as a scalable and inexpensive photosensitizer that selectively photo-oxidizes 4-methyl benzyl alcohol (MBA) to its aldehyde (MBAld), indium tin oxide (ITO) nanoparticles as electron conduit and biocatalyst support material, and the enzyme formate dehydrogenase (FDH) for selective CO 2 -to-formate reduction. This integrated semiartificial multicomponent system can be assembled and used in several configurations to drive bias-free operation, including (i) a photocatalytic suspension, (ii) a photocatalyst sheet, and (iii) a photoelectrochemical cell. The unprecedented adaptability and robustness of the assembled biohybrid systems motivated us to select the best performing and scalable system in practical solar chemical production by deploying a 50 cm 2 CN X –ITO|FDH photosheet device for 3 days under natural sunlight to produce 41 (mmol formate) m –2 and 35 (mmol aldehyde) m –2 . We have therefore demonstrated that CN X –ITO|FDH provides a robust and versatile platform that enables solar chemical synthesis for several days in outdoor operation using natural sunlight.}, archive = {J_JACS}, author = {Motiar Rahaman and Carolina Pulignani and Melanie Miller and Subhajit Bhattacharjee and Ariffin Bin Mohamad Annuar and Rita R. Manuel and Inês A. C. Pereira and Erwin Reisner}, doi = {10.1021/jacs.4c10519}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8168--8177}, shortjournal = {J. Am. Chem. Soc.}, title = {Solar-driven paired CO2 Reduction–Alcohol oxidation using semiartificial suspension, photocatalyst sheet, and photoelectrochemical devices}, volume = {147}, year = {2025}, }
• (2025). Magnetic hysteresis in a dysprosium bis(amide) complex. JACS, 147(10), 8156--8167. (www)

  @article{ , abstract = {Here, we present the synthesis and characterization of two mononuclear dysprosium molecules. The first complex is neutral and contains two triarylamide ligands coordinating to a Dy III ion that is additionally ligated to a chloride anion, in the form of (NHAr*) 2 DyCl ( 1 ). Treatment of 1 with Tl[BArF 24 ] prompted the removal of the chloride as TlCl from the first coordination sphere to afford the mononuclear Dy III complex, [(NHAr*) 2 Dy][BArF 24 ] ( 2 ), with a cationic [(NHAr*) 2 Dy] + core. 1 and 2 were investigated through single-crystal X-ray diffraction analysis, UV–vis spectroscopy, and SQUID magnetometry. Both compounds are single-molecule magnets with magnetic hysteresis. The determined effective spin-reversal barriers and preattempt times for 1 and 2 are U eff = 601(2) cm –1 and 598(2) cm –1 , and τ 0 = 4.2(1) × 10 –10 s and 3.1(2) × 10 –10 s, respectively. Ab initio calculations were conducted on both molecules which uncovered the energy of the crystal field states of Dy III and affirmed the effective energy barrier height. Notably, the extrusion of the halide ion has huge ramifications on the magnetic relaxation: While 1 features butterfly hysteresis loops up to 8 K that are closed at zero field at all temperatures probed, 2 exhibits a much higher magnetic blocking temperature of T B = 19.0 K and substantial coercivity of H C = 1.03 T. Remarkably, both the T B and H C observed for 2 constitute a record for mononuclear single-molecule magnets where the metal is either sandwiched by two arene ligands or stabilized by amide functionalities, respectively.}, archive = {J_JACS}, author = {Florian Benner and Rashmi Jena and Aaron L. Odom and Selvan Demir}, doi = {10.1021/jacs.4c08137}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8156--8167}, shortjournal = {J. Am. Chem. Soc.}, title = {Magnetic hysteresis in a dysprosium bis(amide) complex}, volume = {147}, year = {2025}, }
• (2025). Quantum dynamics of charge carriers in fullerenes encapsulated by covalent organic polyhedra: Choice of fullerene matters. JACS, 147(10), 8145--8155. (www)

  @article{ , abstract = {Charge separation is at the heart of solar energy applications, and efficient materials require fast photoinduced electron transfer (ET) and slow charge recombination (CR). Using time-dependent self-consistent charge density functional tight-binding theory combined with nonadiabatic (NA) molecular dynamics, we report a detailed analysis of ET and CR in hybrids composed of photoactive covalent organic polyhedra (COP) and encapsulated fullerenes. The ET occurs on a subpicosecond time scale and accelerates with increasing fullerene diameter, C 60 to C 70 to C 84 . As the fullerene size increases, the π-electron system available for interaction with the COP grows, the fullerene-COP separation decreases, and the number of fullerene states available to accept the photoexcited electron increases, accelerating the ET. In comparison, the CR occurs on a nanosecond time scale and correlates with the length of the fullerene shortest axis because the relevant fullerene state is polarized in that direction. The largest and least symmetrical C 84 exhibits the fastest ET and the slowest CR, making COP@C 84 the most promising hybrid. Both high-frequency bond stretching and bending vibrations and low-frequency breathing modes are involved in the ET and CR processes, with more modes present in the C 84 system due its lower symmetry. The 10–20 fs vibrationally induced coherence loss in the electronic subsystem contributes to long lifetimes of the charge-separated states. The comprehensive investigation of the structure–property relationship of the charge carrier dynamics in the COP@fullerene hybrids provides a detailed atomistic understanding of interfacial ET processes and generates guidelines for rational design of high-performance materials for solar energy and related applications.}, archive = {J_JACS}, author = {Shrabanti Mondal and Uttam Chowdhury and Md Habib and Shriya Gumber and Ranjan Das and Thomas Frauenheim and Ritabrata Sarkar and Oleg V. Prezhdo and Sougata Pal}, doi = {10.1021/jacs.4c05856}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8145--8155}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantum dynamics of charge carriers in fullerenes encapsulated by covalent organic polyhedra: Choice of fullerene matters}, volume = {147}, year = {2025}, }
• (2025). Generation of stereocenters via single-carbon-atom doping using N-isocyanides. JACS, 147(10), 8138--8144. (www)

  @article{ , abstract = {Atomic carbon remains a challenging species for organic synthesis despite its potential to form four covalent bonds in a single step. Single-carbon-atom doping (SCAD) offers a powerful approach to enhancing molecular complexity in one process without atom loss. However, synthetically viable SCAD reactions capable of generating stereocenters have not been realized. Here, we report an SCAD reaction that creates stereocenters by unlocking the reactivity of ( N -isocyanoimino)phosphorane as an atomic carbon equivalent. This reagent facilitates the single-step conversion of various acyl chlorides into homologated α-chloro cyclic ketones, proceeding via the formation of four different bonds: one C–Cl, one C–H, and two C–C bonds at the incorporated carbon atom.}, archive = {J_JACS}, author = {Hayato Fujimoto and Teruki Nishioka and Kazuya Imachi and Satoshi Ogawa and Rio Nishimura and Mamoru Tobisu}, doi = {10.1021/jacs.5c00882}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8138--8144}, shortjournal = {J. Am. Chem. Soc.}, title = {Generation of stereocenters via single-carbon-atom doping using N-isocyanides}, volume = {147}, year = {2025}, }
• (2025). Enantioselective total syntheses of (+)-kobusine, (+)-spirasine IX and the purported structure of (+)-orgetine: Strategic use of C–H bonds. JACS, 147(10), 8132--8137. (www)

  @article{ , abstract = {Enantioselective total syntheses of (+)-kobusine, (+)-spirasine IX and the proposed structure of (+)-orgetine were achieved. A unique approach was developed to construct a cage-like hexacyclic ring system that underwent an HAT-initiated radical rearrangement to forge the hetisine-type scaffold. Subsequent late-stage redox manipulations, including an intramolecular hydride shift, were deployed to provide different C20-diterpenoid alkaloids.}, archive = {J_JACS}, author = {Mengping Deng and Fanrui Wu and Tianran Liu and Zhe Jiang and Tuoping Luo}, doi = {10.1021/jacs.5c00650}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8132--8137}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective total syntheses of (+)-kobusine, (+)-spirasine IX and the purported structure of (+)-orgetine: Strategic use of C–H bonds}, volume = {147}, year = {2025}, }
• (2025). Dopant-assisted crystallization enables germanium quantum dots with enhanced product yields and optoelectronic properties. JACS, 147(10), 8125--8131. (www)

  @article{ , abstract = {Colloidal germanium quantum dots (GeQDs) show great potential for optoelectronics, but traditional synthesis methods face challenges such as low yield and uneven particle sizes due to Ge sublimation and domain overgrowth at high temperatures. This study introduces a dopant-assisted synthesis method that enhances the crystallization process of GeQDs. By incorporating cobalt dopants into sol–gel precursors, we have effectively reduced the GeQD formation temperature to 350 °C. This approach boosts product yield over 60%, a 3.6-fold increase over conventional methods. The resulting GeQDs exhibit uniform particle sizes, enhanced solution processability, and improved charge carrier mobilities. We further constructed the GeQD-based solar cells that demonstrate an AM1.5 solar power conversion efficiency of 3.5 × 10 –5 % with a 0.83 V open-circuit voltage.}, archive = {J_JACS}, author = {Ming Lai and Linfeng Wei and Meiqi Lin and Haoyuan Zhang and Yuduo Zhou and Da Wang and Lei Shi and Zhenyu Yang}, doi = {10.1021/jacs.5c00423}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8125--8131}, shortjournal = {J. Am. Chem. Soc.}, title = {Dopant-assisted crystallization enables germanium quantum dots with enhanced product yields and optoelectronic properties}, volume = {147}, year = {2025}, }
• (2025). Catalyst-controlled regiodivergent oxidation of unsymmetrical diols. JACS, 147(10), 8118--8124. (www)

  @article{ , abstract = {In this work we use aminoxyl-peptide conjugates to catalyze the regiodivergent oxidation of unsymmetrical diols. Through structural tuning of both the aminoxyl catalytic core and the chiral peptide backbone, we achieved catalyst control that either reinforces or overrides the intrinsic steric bias, leading to oxidation of either the less hindered or the more hindered alcohol in high selectivity.}, archive = {J_JACS}, author = {Samson B. Zacate and Jonas Rein and Soren D. Rozema and Reginald A. Annor and Scott J. Miller and Song Lin}, doi = {10.1021/jacs.5c00330}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8118--8124}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalyst-controlled regiodivergent oxidation of unsymmetrical diols}, volume = {147}, year = {2025}, }
• (2025). Fungal RiPPs side chain macrocyclization catalyzed by copper-dependent DUF3328 enzyme. JACS, 147(10), 8113--8117. (www)

  @article{ , abstract = {Fungal enzymes containing domain of unknown function (DUF) 3328 have been implicated in the oxidative maturation of ribosomally synthesized and post-translationally modified peptides (RiPPs). We report here the functional characterization of one such enzyme, AprY, involved in the biosynthesis of RiPP asperipin-2a. Biochemical reconstitution of AprY showed the enzyme catalyzes two consecutive C–O cross-linking reactions between tyrosines and beta-carbons of residues in the core hexapeptide. The side-chain macrocyclization activities of AprY are copper- and oxygen-dependent and do not require a leader peptide sequence.}, archive = {J_JACS}, author = {Chen-Yu Chiang and Masao Ohashi and Yi Tang}, doi = {10.1021/jacs.4c18770}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8113--8117}, shortjournal = {J. Am. Chem. Soc.}, title = {Fungal RiPPs side chain macrocyclization catalyzed by copper-dependent DUF3328 enzyme}, volume = {147}, year = {2025}, }
• (2025). Asymmetric counteranion-directed halogen bonding catalysis. JACS, 147(10), 8107--8112. (www)

  @article{ , abstract = {Halogen bonding has been established as a promising tool in organocatalysis. Asymmetric processes are nevertheless scarce, and their applications are limited to a few studies applying chiral halogen bond donors. Herein, we combine halogen bonding with asymmetric counteranion-directed catalysis, providing the first highly enantioselective example of such an approach. A strong bidentate iodine(III)-based catalyst with chiral disulfonimides as counteranions is applied in the first asymmetric organocatalysis of the Diels–Alder reaction between cyclopentadiene and trans -β-nitrostyrene, the key step in the synthesis of the drug fencamfamine, which was prepared with high enantioselectivity.}, archive = {J_JACS}, author = {Dominik L. Reinhard and Anna Iniutina and Sven Reese and Tushar Shaw and Christian Merten and Benjamin List and Stefan M. Huber}, doi = {10.1021/jacs.4c18378}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8107--8112}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric counteranion-directed halogen bonding catalysis}, volume = {147}, year = {2025}, }
• (2025). Uncovering the role of direct electron transfer in plasmon-mediated electrochemical reactions. JACS, 147(10), 8101--8106. (www)

  @article{ , abstract = {The mechanism of the charge and energy flow at the metal–molecule interface has attracted much attention, especially with the recent rise of plasmonic nanomaterials for light-to-chemical conversion. Although numerous studies have demonstrated the irreplaceable effects of energetic electrons on accelerating chemical reactions, detangling the direct electron transfer (DET) from indirect electron transfer (IET) and understanding their roles are still challenging. Here, by combining electrochemical dark field scattering spectroscopy, the photoelectrochemical method, and density functional theory calculation, we provided the evidence of DET during chemical reactions, alongside decoupling the contributions of DET and IET, and then established the relationship between chemical reactivity and DET efficiency. Moreover, we discovered that DET is selective for different reactions, e.g., enhancing the oxygen reduction reaction much more than the hydrogen evolution reaction. This work offers the possibility to optimize reaction selectivity via DET and advances mechanistic insights into plasmonic charge transfer.}, archive = {J_JACS}, author = {Shu-Yi Zhu and Feng Xue and Qing-Chen Bai and Yan-Li He and Li-Jun Wang and Lin-Lin Wang and Wei-Jie Liu and Xia-Guang Zhang and Chao Zhan and Zhong-Qun Tian}, doi = {10.1021/jacs.4c17754}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8101--8106}, shortjournal = {J. Am. Chem. Soc.}, title = {Uncovering the role of direct electron transfer in plasmon-mediated electrochemical reactions}, volume = {147}, year = {2025}, }
• (2025). Nickel-catalyzed branched hydroalkylation of alkenes with diazo compounds. JACS, 147(10), 8093--8100. (www)

  @article{ , abstract = {A nickel-catalyzed, branched-selective hydroalkylation of alkenes using diazo compounds has been developed. This protocol enables the functionalization of both activated and unactivated alkenes, in both directed and nondirected manners. Mono-, di-, and trisubstituted alkenes can be effectively transformed. Highly diastereoselective hydroalkylations have also been demonstrated. The method provides a novel approach for introducing an α-carbonyl moiety to alkenes, which is currently inaccessible by existing methods. Preliminary mechanistic investigations suggest a carbene-type mechanism, which is unusual for nickel catalysis.}, archive = {J_JACS}, author = {Nikita Kvasovs and Valeriia Iziumchenko and Alistair J. Sterling and Vladimir Gevorgyan}, doi = {10.1021/jacs.4c17586}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8093--8100}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-catalyzed branched hydroalkylation of alkenes with diazo compounds}, volume = {147}, year = {2025}, }
• (2025). Lignocellulolytic bacterial engineering for tailoring the microstructure of hard carbon as a sodium-ion battery anode with fast plateau kinetics. JACS, 147(10), 8088--8092. (www)

  @article{ , abstract = {Lignocellulosic biomass-derived pyrolysis hard carbon (LCB-HC) shows promising commercial potential as an anode material for sodium-ion batteries (SIBs). LCB compromises multiple biopolymer carbon sources, including cellulose, hemicellulose, and lignin, which influence the formation and microstructure of pyrolysis HC. However, the poor plateau kinetics of LCB-HC is one of the main obstacles that severely limits its energy density with high power density, which could be attributed to the narrow interlayer distance and the lack of abundant closed pores for the intercalation/filling of Na + . Herein, we proposed a bottom-up approach to tailoring the microstructure of LCB-HC by regulating the components of the LCB precursor at the molecular level using bioenzymes secreted by lignocellulolytic bacteria. This mild and efficient enzymatic hydrolysis pathway partially depolymerized the biopolymers of basswood specifically, thereby enabling the construction of a small curved-graphite domain architecture with increased closed pores and an enlarged interlayer distance of LCB-HC, benefiting the low-voltage plateau Na + storage with accelerated kinetics. As a result, the basswood-derived HC delivers a reversible capacity of 366.4 mAh g –1 and performed remarkable plateau capacity retainability with a high proportion of 74.3% even with increased current density to 1000 mA g –1 . Such a microbial-chemistry-assisted approach provided insights into tailoring the microstructure of LCB-HC to construct high-performance SIB anode materials.}, archive = {J_JACS}, author = {Si-Jie Jiang and Yan-Song Xu and Xiao-Wen Sun and Lin Chen and Yun-Nuo Li and Lin Li and Fei-Fei Cao}, doi = {10.1021/jacs.4c15593}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8088--8092}, shortjournal = {J. Am. Chem. Soc.}, title = {Lignocellulolytic bacterial engineering for tailoring the microstructure of hard carbon as a sodium-ion battery anode with fast plateau kinetics}, volume = {147}, year = {2025}, }
• (2025). Surface-enhanced raman spectroscopic study of key intermediates in electrochemical ammonia decomposition. JACS, 147(10), 8083--8087. (www)

  @article{ , abstract = {Ammonia is an alternative hydrogen storage material and a promising source of sustainable clean energy. The lack of a mechanistic understanding of ammonia electrooxidation hinders the efforts to overcome the slow kinetics of the anode reaction in direct ammonia fuel cells. Herein, we use surface-enhanced Raman spectroscopy to study the electro-decomposition of ammonia on the Au surface. We observe three key reaction intermediate species of *NH 2 , *NH and *NNH and thereby disclose a multistage interfacial decomposition mechanism. Among the three, detection of the N-coupled species fills the blank in the mechanistic study of ammonia oxidation. Additionally, we investigated the influence of the reactant concentrations on the different oxidation stages. This spectroscopic evidence opens up promising avenues to overcome the limitations associated with ammonia fuel cells.}, archive = {J_JACS}, author = {Xiaomeng Du and Aoxuan Du and Dan Wang and Yue Mao and Zhao Zhang and Wei Xie}, doi = {10.1021/jacs.4c15489}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8083--8087}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface-enhanced raman spectroscopic study of key intermediates in electrochemical ammonia decomposition}, volume = {147}, year = {2025}, }
• (2025). Industrialization of covalent organic frameworks. JACS, 147(10), 8063--8082. (www)

  @article{ , abstract = {Covalent organic frameworks (COFs) have attracted broad interest because of their well-defined, customizable, highly stable, and porous structures. COFs have shown significant potential for various practical applications, such as gas storage/purification, drug purification, water treatment, catalysis, and battery applications. Scaling up COFs is highly desirable to meet industrial application demands but is hindered by the limitations of synthesis methods and the high cost of reactants. Recently, emerging green synthesis methods, such as mechanochemical synthesis and flux synthesis, have offered promising solutions to these challenges (e.g., ton-scale production of COFs has been achieved by companies recently). This Perspective provides an overview of the state of the art with respect to the industrial production of COFs and discusses factors influencing the large-scale production of COFs. Directions and opportunities for improving the performance and sustainability of COFs toward industrial applications are also emphasized.}, archive = {J_JACS}, author = {Kaiyuan Wang and Xueling Qiao and Hongxia Ren and Yao Chen and Zhenjie Zhang}, doi = {10.1021/jacs.4c16485}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8063--8082}, shortjournal = {J. Am. Chem. Soc.}, title = {Industrialization of covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Not so bioorthogonal chemistry. JACS, 147(10), 8049--8062. (www)

  @article{ , abstract = {The advent of bioorthogonal chemistry has transformed scientific research, offering a powerful tool for selective and noninvasive labeling of (bio)molecules within complex biological environments. This innovative approach has facilitated the study of intricate cellular processes, protein dynamics, and interactions. Nevertheless, a number of challenges remain to be addressed, including the need for improved reaction kinetics, enhanced biocompatibility, and the development of a more diverse and orthogonal set of reactions. While scientists continue to search for veritable solutions, bioorthogonal chemistry remains a transformative tool with a vast potential for advancing our understanding of biology and medicine. This Perspective offers insights into reactions commonly classified as “bioorthogonal”, which, however, may not always demonstrate the desired selectivity regarding the interactions between their components and the additives or catalysts used under the reaction conditions.}, archive = {J_JACS}, author = {Dominik Schauenburg and Tanja Weil}, doi = {10.1021/jacs.4c15986}, journal = {Journal of the American Chemical Society}, month = {3}, number = {10}, pages = {8049--8062}, shortjournal = {J. Am. Chem. Soc.}, title = {Not so bioorthogonal chemistry}, volume = {147}, year = {2025}, }
• (2025). Correction to “Catalytic asymmetric transfer hydrogenation of acylboronates: BMIDA as the privileged directing group”. JACS, 147(9), 8048. (www)

  @article{ , archive = {J_JACS}, author = {Xiangjian Meng and Shouang Lan and Ting Chen and Haotian Luo and Lixuan Zhu and Nanchu Chen and Jinggong Liu and Shuang Yang and Andrej Emanuel Cotman and Qi Zhang and Xinqiang Fang}, doi = {10.1021/jacs.5c02351}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {8048}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Catalytic asymmetric transfer hydrogenation of acylboronates: BMIDA as the privileged directing group”}, volume = {147}, year = {2025}, }
• (2025). Manipulating a thermosalient crystal using selective deuteration. JACS, 147(9), 8032--8047. (www)

  @article{ , abstract = {The thermosalient transformation in nickel(II) bis(diisopropyl)dithiocarbamate has been investigated using selective deuteration. The deuterated crystals undergo a reversible displacive phase transition that is ∼4 K higher in temperature compared to the protonated analogue. Neutron, synchrotron, density-functional theory, and calorimetric techniques were utilized to demonstrate the substantial effect of deuterium. All techniques demonstrated the equivalence of the mechanism on an atomic scale between the protonated and deuterated complexes. The data collected in this study reveal details of the changes of atomic motion that underpin the thermosalience inherent in this system. Deuterium decreased the frequency of atomic vibrations thus increasing the temperature of the observed transformation. This study represents a key advancement in the field of thermosalient molecular systems and provides insights into the control and manipulation of thermosalient materials.}, archive = {J_JACS}, author = {Alexander Angeloski and Pablo Galaviz and Richard A. Mole and Ross O. Piltz and Andrew M. McDonagh and Courtney Ennis and Dominique Appadoo}, doi = {10.1021/jacs.5c01140}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {8032--8047}, shortjournal = {J. Am. Chem. Soc.}, title = {Manipulating a thermosalient crystal using selective deuteration}, volume = {147}, year = {2025}, }
• (2025). Interfacial hydrogen-bond network regulation tuned water dissociation enables selective chlorination of alkenes. JACS, 147(9), 8024--8031. (www)

  @article{ , abstract = {Electrocatalytically selective chlorination of olefins in Cl – -containing solutions is a sustainable method for synthesizing chlorohydrin/vicinal dichloride; however, controlling the selectivity is challenging. Here, aqueous/dimethyl carbonate (DMC) hybrid electrolytes with different H 2 O/DMC ratios are designed to modulate the ·OH formation to increase the corresponding selectivities. The combined results of in/ex situ spectroscopies and molecular dynamics simulations reveal the origin of high selectivity. TFSI – shields the transportation of free H 2 O to provide moderate ·OH formation for the synthesis of chlorohydrin. DMC reconstructs hydrogen bonds with free H 2 O to minimize the interaction between them and the anode, matching the requirements of vicinal dichloride production. Thus, these hybrid electrolytes not only achieve high selectivities of 80% and 76% for chlorohydrin and vicinal dichloride, respectively, but also enable the selective chlorination of other olefins with high isolated yields of up to 74%. This work provides a facile strategy to regulate the selectivity of anodic chlorination via a rational electrolyte design.}, archive = {J_JACS}, author = {Junwei Yao and Chuanqi Cheng and Yongmeng Wu and Cuibo Liu and Shuoshuo Guo and Ying Gao and Bin Zhang}, doi = {10.1021/jacs.5c00818}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {8024--8031}, shortjournal = {J. Am. Chem. Soc.}, title = {Interfacial hydrogen-bond network regulation tuned water dissociation enables selective chlorination of alkenes}, volume = {147}, year = {2025}, }
• (2025). A Copper–Zinc cyanamide solid-solution catalyst with tailored surface electrostatic potentials promotes asymmetric N-intermediate adsorption in nitrite electroreduction. JACS, 147(9), 8012--8023. (www)

  @article{ , abstract = {The electrocatalytic nitrite reduction (NO 2 RR) converts nitrogen-containing pollutants to high-value ammonia (NH 3 ) under ambient conditions. However, its multiple intermediates and multielectron coupled proton transfer process lead to low activity and NH 3 selectivity for the existing electrocatalysts. Herein, we synthesize a solid-solution copper–zinc cyanamide (Cu 0.8 Zn 0.2 NCN) with localized structure distortion and tailored surface electrostatic potential, allowing for the asymmetric binding of NO 2 – . It exhibits outstanding NO 2 RR performance with a Faradaic efficiency of ∼100% and an NH 3 yield of 22 mg h –1 cm –2 , among the best for such a process. Theoretical calculations and in situ spectroscopic measurements demonstrate that Cu–Zn sites coordinated with linear polarized [NCN] 2– could transform symmetric [Cu–O–N–O–Cu] in CuNCN-NO 2 – to a [Cu–N–O–Zn] asymmetric configuration in Cu 0.8 Zn 0.2 NCN-NO 2 – , thus enhancing adsorption and bond cleavage. A paired electro-refinery with the Cu 0.8 Zn 0.2 NCN cathode reaches 2000 mA cm –2 at 2.36 V and remains fully operational at industrial-level 400 mA cm –2 for >140 h with a NH 3 production rate of ∼30 mg NH3 h –1 cm –2 . Our work opens a new avenue of tailoring surface electrostatic potentials using a solid-solution strategy for advanced electrocatalysis.}, archive = {J_JACS}, author = {Jiacheng Jayden Wang and Huong T. D. Bui and Xunlu Wang and Zhuoran Lv and Huashuai Hu and Shuyi Kong and Zhiqiang Wang and Lijia Liu and Wei Chen and Hui Bi and Minghui Yang and Tore Brinck and Jiacheng Wang and Fuqiang Huang}, doi = {10.1021/jacs.5c00837}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {8012--8023}, shortjournal = {J. Am. Chem. Soc.}, title = {A Copper–Zinc cyanamide solid-solution catalyst with tailored surface electrostatic potentials promotes asymmetric N-intermediate adsorption in nitrite electroreduction}, volume = {147}, year = {2025}, }
• (2025). Tailored lattice-matched carbazole self-assembled molecule for efficient and stable perovskite solar cells. JACS, 147(9), 8004--8011. (www)

  @article{ , abstract = {Self-assembled monolayer molecules have been widely employed as interfacial transport materials in inverted perovskite solar cells (PSCs), demonstrating high efficiency and improved device stability. However, self-assembling monolayer (SAM) molecules often suffer from aggregation and weak interactions with the perovskite layer, resulting in inefficient charge transfer and significant energy losses, ultimately limiting the power conversion efficiency and long-term stability of perovskite solar cells. In this work, we developed a series of novel skeleton-matching carbazole isomer SAMs based on the following key design principles: (1) introducing a benzene ring structure to distort the molecular skeleton of the SAM, thereby preventing aggregation and achieving a uniform distribution on fluorine-doped tin oxide (FTO) substrates; (2) strategically incorporating methoxy groups onto the benzene ring at different positions (ortho, meta, and para). These functional groups not only increase anchoring points with the perovskite layer but also fine-tune the molecular dipole moment. Among the SAMs, m-PhPACz exhibits the most favorable properties, with a maximum dipole moment of 2.4 D and an O–O distance that aligns excellently with the diagonal lead ions in the adjacent perovskite lattice, thereby enhancing SAM–perovskite interactions, facilitating efficient charge extraction, and improving interfacial stability. As a result, the new SAM-based PSCs achieved an impressive power conversion efficiency of 26.2%, with 12.9% improvement. Moreover, the devices demonstrated outstanding photothermal stability, retaining 96% of their initial PCE after 1000 h at 85 °C and maintaining 90% of their initial PCE after 300 h of UV-light exposure.}, archive = {J_JACS}, author = {Hongzhuo Wu and Jiaxin Wu and Zuhong Zhang and Xiaoyu Guan and Luyao Wang and Lin-long Deng and Guixiang Li and Antonio Abate and Meng Li}, doi = {10.1021/jacs.5c00629}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {8004--8011}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailored lattice-matched carbazole self-assembled molecule for efficient and stable perovskite solar cells}, volume = {147}, year = {2025}, }
• (2025). Dynamic deprotonation enhancement triggered by accelerated electrochemical delithiation reconstruction during acidic water oxidation. JACS, 147(9), 7993--8003. (www)

  @article{ , abstract = {The structure-dependent transition in reaction pathways during acidic oxygen evolution (OER) is pivotal due to the active site oxidation accompanied by the coordination environment changes. In this work, charge-polarized Ir–O–Co units are constructed in alkali metal cobalt oxides (LiCoO 2 , and Na 0.74 CoO 2 ) to modify the lower Hubbard band. Benefiting from the accelerated delithiation reconstruction induced by the altered band structure, typical Ir-LiCoO 2 produces high-valent Ir sites with unsaturated coordination through the charge compensation during OER. Oxygen atoms shared by trimetallic sites exhibit strong Bro̷nsted acidity, promoting proton migration for unsaturated Ir sites and dynamically enhancing deprotonation. Furthermore, the stable coordination environment, along with electron donation from Co sites, significantly improves the stability of Ir sites. The unique electrochemical activation results in a low overpotential of 190 mV at 10 mA cm –2 during acidic OER and delivers exceptional stability at 1 A cm –2 for 150 h with a slight voltage degradation in a proton exchange membrane electrolyzer. This work provides in-depth insights into the relationship between catalyst reconstruction and reaction mechanisms.}, archive = {J_JACS}, author = {Sheng Zhao and Sung-Fu Hung and Yue Wang and Shaoxiong Li and Juan Yang and Wen-Jing Zeng and Ying Zhang and Hao-Hsiang Chang and Han-Yi Chen and Feng Hu and Linlin Li and Shengjie Peng}, doi = {10.1021/jacs.5c00493}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7993--8003}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic deprotonation enhancement triggered by accelerated electrochemical delithiation reconstruction during acidic water oxidation}, volume = {147}, year = {2025}, }
• (2025). Photodimerization of ferroelectric N,N′-ditetradecyl-stilbenediamide derivative. JACS, 147(9), 7983--7992. (www)

  @article{ , abstract = {A solid state [2 + 2] photodimerization reaction of ─C═C─ bonds in solids has been designed by controlling the molecular arrangement using supramolecular chemistry. Stilbene derivative ( C14SDA ) with alkyl amide chains (─CONHC 14 H 29 ) forms intermolecular amide hydrogen-bonding chains and exhibits reversible successive phase transitions (S1 → S2 → S3 → L) corresponding to the dynamics of the alkyl chains. In the high-temperature solid phase S3, the alkyl chains partially melt, resulting in a one-dimensional (1D) dynamic intermolecular amide hydrogen bond and ferroelectric behavior with hysteresis in the electric field–polarization curve due to polarization reversal of the dipole moment by an external electric field. The S1 phase of C14SDA did not exhibit a photodimerization reaction, while the dynamic S2 and S3 phases exhibited a [2 + 2] photodimerization reaction to form reaction products with cyclobutane rings. In the dynamic ferroelectric S3 phase, trans – cis isomerization of stilbene was observed simultaneously with the formation of the photodimerization product. When the photodimerization reaction was attempted with an electric field applied to the S3 phase, thermal molecular fluctuations were suppressed by the electric field, increasing the distance between ─C═C─ double bonds and reducing the photoreaction yield.}, archive = {J_JACS}, author = {Yunya Zhang and Takashi Takeda and Tomoyuki Akutagawa}, doi = {10.1021/jacs.5c00346}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7983--7992}, shortjournal = {J. Am. Chem. Soc.}, title = {Photodimerization of ferroelectric N,N′-ditetradecyl-stilbenediamide derivative}, volume = {147}, year = {2025}, }
• (2025). Functionalized violet-emitting cd, pb-free quantum dots with thermally activated delayed photoluminescence for efficient photochemical reactions. JACS, 147(9), 7974--7982. (www)

  @article{ , abstract = {Colloidal quantum dots (QDs) are excellent luminescent materials, but their short exciton lifetime, typically in the nanosecond range, restricts their applications in photochemical reactions. By designing QD-molecule conjugates, the exciton energy can be cycled between the QD exciton state and the molecular triplet state through triplet energy transfer, thereby prolonging the exciton lifetime to hundreds of microseconds, which is similar to the mechanism of thermally activated delayed fluorescence in molecules. Currently, QD-molecule-based thermally activated delayed photoluminescence (TADPL) systems have covered the blue to near-infrared spectral range. Here, we extend the reach of TADPL to the violet band, including slight penetration into the ultraviolet, by using Cd, Pb-free ZnSe/ZnS core/shell QDs functionalized with biphenyl ligands, which exhibit the highest TADPL energy (up to 3.0 eV) reported to date for QD-molecule conjugates. The high exciton energy, long lifetime (80 μs), and high TADPL quantum yield (23.7%) of the ZnSe/ZnS-biphenyl system enable very high efficiency in a variety of QD-sensitized photochemical reactions.}, archive = {J_JACS}, author = {Guijie Liang and Lei Wang and Zhaolong Wang and Xin Zhang and Zixiang Zhou and Rongxin Zhang and Ying Liang and Shan He and Kaifeng Wu}, doi = {10.1021/jacs.5c00138}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7974--7982}, shortjournal = {J. Am. Chem. Soc.}, title = {Functionalized violet-emitting cd, pb-free quantum dots with thermally activated delayed photoluminescence for efficient photochemical reactions}, volume = {147}, year = {2025}, }
• (2025). Pressure-modulated energy transfer dynamics in mn2+-doped CdS/ZnS Core/Shell quantum dots. JACS, 147(9), 7965--7973. (www)

  @article{ , abstract = {Transition metal doping in semiconductor quantum dots (QDs) significantly impacts their optical properties, thus expanding the range of their potential optoelectronic applications. This study investigates the pressure-dependent energy transfer dynamics in Mn 2+ -doped CdS/ZnS core/shell QDs, focusing on how external hydrostatic pressure modulates these dynamics and optical properties. By synthesizing Mn 2+ -doped QDs with varying Mn 2+ doping concentrations, we explore the effects of the pressure on photoluminescence (PL) spectra and energy transfer efficiency. Our study reveals that increasing pressure induces a blueshift in the QD host bandgap PL and a redshift in the Mn 2+ dopant PL. The pressure-induced shifts highlight a unique modulation mechanism where the energy transfer efficiency decreases with pressure due to reduced wave function overlap between host excitons and Mn 2+ dopants. Detailed analysis of the PL quantum yields and energy transfer rate constants provides insights into these dynamics, suggesting that the pressure can effectively and reversibly regulate the energy transfer efficiencies and rates. These results have implications for developing pressure-sensitive configurable devices and exploring pressure-induced phenomena in doped nanomaterials.}, archive = {J_JACS}, author = {Na Jin and Yasutaka Nagaoka and Zhenyang Liu and Ruipeng Li and Ou Chen}, doi = {10.1021/jacs.5c00061}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7965--7973}, shortjournal = {J. Am. Chem. Soc.}, title = {Pressure-modulated energy transfer dynamics in mn2+-doped CdS/ZnS Core/Shell quantum dots}, volume = {147}, year = {2025}, }
• (2025). Multimodal precise control over multiselective carbonylation of 1,3-enynes. JACS, 147(9), 7950--7964. (www)

  @article{ , abstract = {Efficiently constructing structurally diverse and complex organic molecules through selective catalytic functionalization is a central goal in synthetic chemistry, yet achieving precise control over multiple reactive centers in multisite substrates remains a formidable challenge. Building on foundational advances in single- and dual-selective transformations, we report a multimodal strategy for the selective carbonylation of 1,3-enynes, a versatile class of multisite substrates. Through meticulous fine-tuning of the catalytic conditions, our approach enables five distinct regio- and stereoselective carbonylative transformations, including direct functionalization (1,2- and 2,1-hydroaminocarbonylation) and tandem cyclization pathways (2,4-, 1,3-, and 2,3-carbonylation). Furthermore, mechanistic studies suggested that multidimensional precise regulation enables the seamless relay of up to three tandem reactions (hydroaminocarbonylation-hydroamination–transamination) with exceptional accuracy. This unified platform not only establishes a robust framework for tackling the enduring challenges of selectivity control in multisite substrates but also broadens the chemical space accessible through 1,3-enyne transformations, exemplifying atom- and step-economic principles and paving the way for transformative advancements in drug discovery, materials science, and beyond.}, archive = {J_JACS}, author = {Chang-Sheng Kuai and Yuanrui Wang and Ting Yang and Xiao-Feng Wu}, doi = {10.1021/jacs.5c00032}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7950--7964}, shortjournal = {J. Am. Chem. Soc.}, title = {Multimodal precise control over multiselective carbonylation of 1,3-enynes}, volume = {147}, year = {2025}, }
• (2025). Fast and massive production of aramid nanofibers via molecule intercalation. JACS, 147(9), 7939--7949. (www)

  @article{ , abstract = {Para-aramid nanofibers, one of the newest high-performance building blocks at the nanoscale, have attracted great attention due to their hard-to-find property sets and ability to form high-porosity solids. However, there are great difficulties in their scalable and sustainable production because the strong intermolecular hydrogen bonds and other interactions of aramid macromolecules lead to lengthy processes with highly corrosive solvents. Taking advantage of uniquely efficient delamination of polymer nanocrystallites, here we show that the preparation time of para-aramid nanofibers can be reduced by 2520 times (from 1 week to four min), while their concentration can be increased by 10 times. Through this molecule intercalation-induced method, novel ribbon-like aramid nanofibers are prepared. The multiscale modeling indicated that delamination of nanofibers occurs via intercalation of alcohols at nanoscale interfaces. 1000 kg nanofiber dispersions were successfully prepared within half an hour in a pilot-scale test. These findings demonstrate the realism of effective aramid recycling into a wide range of multifunctional nanofiber composites.}, archive = {J_JACS}, author = {Zi-Meng Han and YuanZhen Hou and Hao-Cheng Liu and Qing-Fang Guan and Huai-Bin Yang and Kun-Peng Yang and Chong-Han Yin and Zhang-Chi Ling and Yu-Xiang Zhao and Jun Xia and YinBo Zhu and HengAn Wu and Kody Whishant and Nicholas A. Kotov and Shu-Hong Yu}, doi = {10.1021/jacs.4c18620}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7939--7949}, shortjournal = {J. Am. Chem. Soc.}, title = {Fast and massive production of aramid nanofibers via molecule intercalation}, volume = {147}, year = {2025}, }
• (2025). Bro̷nsted acid-catalyzed reduction of furans. JACS, 147(9), 7932--7938. (www)

  @article{ , abstract = {Bioderived furans play a pivotal role in advancing defossilized chemical pathways. The complete reduction of furans currently relies on impractical metal-catalyzed hydrogenations at high pressures and temperatures. In addition, the Birch reduction of unbiased furans to 2,5-dihydrofurans remains an unsolved synthetic challenge. Herein, we report a mild Bro̷nsted acid-catalyzed reduction of furans to 2,5-dihydro- and/or tetrahydrofuran derivatives using silanes as reducing agents. In particular, the first formal Birch reduction of furan itself is achieved. Mechanistic investigations reveal an intricate behavior of HFIP as the crucial solvent, preventing the intrinsic polymerization behavior of furans under acidic conditions and introducing additional driving force by specific product binding.}, archive = {J_JACS}, author = {Nils Frank and Markus Leutzsch and Benjamin List}, doi = {10.1021/jacs.4c18485}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7932--7938}, shortjournal = {J. Am. Chem. Soc.}, title = {Bro̷nsted acid-catalyzed reduction of furans}, volume = {147}, year = {2025}, }
• (2025). Hydrophobic ionic liquid engineering for reversing CO intermediate configuration toward ampere-level CO2 electroreduction to c2+ products. JACS, 147(9), 7921--7931. (www)

  @article{ , abstract = {Hydrophobic ionic liquid (HIL) engineering on the catalyst surface represents a simple yet potent direction for optimizing the CO 2 electroreduction performance. However, the pivotal role of HIL engineering at an industrial current density is still ambiguous due to limited and conflicting research findings. Herein, HIL-engineered oxide-derived Cu porous nanoparticles with electron-delocalized groups and a specific ultramicropore structure are first constructed to facilitate CO 2 -to-C 2+ electroreduction at ampere-level current densities. The uniformly decorated HIL is innovatively demonstrated by positron annihilation lifetime spectroscopy, which offers unparalleled advantages in ultramicropore characterization. Bader charge-dependent performance analyses and theoretical calculations disclose that the N atoms in the HIL lower the adsorption energy of CO on the atop site from −0.38 to −1.42 eV through electron donation, which inverts the most stable adsorption site and favors the energy-efficient dimerization of atop-bound CO. Operando Raman spectra and in situ attenuated total reflection-surface enhanced infrared absorption spectroscopy indicate that the adhered HIL increases *CO coverage and alters the *CO adsorption configuration to an atop-bound state with an abundant high-frequency band. Furthermore, staircase potential electrochemical impedance spectroscopy unravels the specific arrangement structure of HIL enlarges the electrochemical surface charge by about 1.5 times, thereby accelerating CO 2 electroreduction. As a result, the HIL-engineered oxide-derived Cu porous nanoparticles achieve a prominent C 2+ productivity with a Faradaic efficiency of 85.1% and a formation rate up to 2512 μmol h –1 cm –2 , outperforming most reported Cu-based electrocatalysts.}, archive = {J_JACS}, author = {Runhua Chen and Qiong Wu and Juncheng Zhu and Shumin Wang and Zexun Hu and Jun Hu and Junfa Zhu and Hongjun Zhang and Bangjiao Ye and Yongfu Sun and Yi Xie}, doi = {10.1021/jacs.4c18508}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7921--7931}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrophobic ionic liquid engineering for reversing CO intermediate configuration toward ampere-level CO2 electroreduction to c2+ products}, volume = {147}, year = {2025}, }
• (2025). Leveraging immunogenic cell death to enhance the immune response against malignant pleural mesothelioma tumors. JACS, 147(9), 7908--7920. (www)

  @article{ , abstract = {Although various metal-based compounds have exhibited excellent immunogenic cell death (ICD)-inducing properties both in vitro and in vivo, the majority of these compounds have been discovered serendipitously. In this work, we have successfully synthesized and characterized 35 cyclometalated Au(III) complexes containing dithiocarbamate ligands, with 25 of these complexes being previously unreported. Their ability to induce phagocytosis in vitro against immunologically “cold” malignant pleural mesothelioma (MPM) cells was strongly dependent on the cyclometalated scaffold and the overall lipophilicity of the complexes. We elucidated the role of cell death mechanisms in the observed ICD effects and identified correlations between the ability of the complexes to induce necrotic cell death and ICD, both in vitro and in vivo . Complex 2G , with its high phagocytosis rates and low necrosis rates, was recognized as a bona fide ICD inducer, demonstrating a remarkably long-lasting immune response in vaccinated mice. In contrast, complex 1C , characterized by high phagocytosis rates and high necrosis rates, failed to elicit a sustained immune response upon following vaccination; however, it triggered selective activation of calreticulin in tumors upon direct in vivo administration. Overall, this study offers a framework for predicting ICD effects in vivo for structurally similar Au(III) complexes, with the potential for extension to other series of metal complexes.}, archive = {J_JACS}, author = {Meng Rui Chang and Egor M. Matnurov and Chengnan Wu and Jemma Arakelyan and Ho-Jung Choe and Vladimir Kushnarev and Jian Yu Yap and Xiu Xuan Soo and Mun Juinn Chow and Walter Berger and Wee Han Ang and Maria V. Babak}, doi = {10.1021/jacs.4c17966}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7908--7920}, shortjournal = {J. Am. Chem. Soc.}, title = {Leveraging immunogenic cell death to enhance the immune response against malignant pleural mesothelioma tumors}, volume = {147}, year = {2025}, }
• (2025). A dual-targeted molecule for disease-activatable proteolysis targeting chimeras and targeted radionuclide therapy of cancer. JACS, 147(9), 7897--7907. (www)

  @article{ , abstract = {Proteolysis targeting chimeras (PROTACs) represent a cutting-edge approach for targeted protein degradation in cancer therapy, yet they face challenges such as poor pharmacokinetics and specificity issues, leading to undesirable off-target effects and limited antitumor potency. To address these issues, we introduce dual-targeted unimolecular theranostic probes (e.g., radioactive 177 Lu-P-A and its cold counterpart nat Lu-P-A) for disease-activatable PROTACs in combination with targeted radionuclide therapy (TRT) against prostate cancer with high specificity and effectiveness. The probes achieve a cathepsin B (CTSB)-activatable pro-PROTAC moiety for precise degradation of bromodomain-containing protein 4 (BRD4) and a prostate-specific membrane antigen (PSMA)-targeted 177 Lu-based TRT. Owing to the favorable pharmacokinetics and PSMA-mediated excellent targeting efficiency, the probe possesses high tumor imaging specificity and accumulation capacity of therapeutic units for highly effective PROTACs and TRT. In contrast, the free PROTACs unit (e.g., ARV-771) shows no observable therapeutic effect due to its poor targeting ability. Importantly, the BRD4 proteolysis by PROTAC activation can downregulate radiosensitivity-associated RAD51AP1 expression, synergistically enhancing the TRT effect and promoting apoptosis after combined therapy compared to individual treatment regimes. Additionally, the probe demonstrates high renal clearance, underscoring its biosafety for potential clinical translation. This study presents a potential approach for precise PROTACs combined with TRT for effective tumor therapy.}, archive = {J_JACS}, author = {Yuan Zhang and Wei Gu and Wan Chen and Jieli Zhu and Longfei Fan and Liwen Zhang and Liangyou Zhao and Qingqing Miao}, doi = {10.1021/jacs.4c18398}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7897--7907}, shortjournal = {J. Am. Chem. Soc.}, title = {A dual-targeted molecule for disease-activatable proteolysis targeting chimeras and targeted radionuclide therapy of cancer}, volume = {147}, year = {2025}, }
• (2025). Catalytic regio- and enantioselective hydroformylation of trisubstituted alkenes to construct α-quaternary lactams. JACS, 147(9), 7886--7896. (www)

  @article{ , abstract = {Developing novel stereoselective methods for α-quaternary lactams is of significant importance for advancing structure–activity studies, discovering new antibiotics, and synthesizing diverse functional compounds for synthetic and materials research. Herein, we have successfully developed a Rh-catalyzed asymmetric hydroformylation (AHF) of trisubstituted olefins, overcoming both the inherent inertness of trisubstituted olefins in such reactions and Keulemans’ rule, efficiently generating diverse β- and γ-lactams bearing an α-quaternary stereocenter with exceptional regio- and enantioselectivities (up to >20:1 rr, 99% ee). This mild and operationally simple reaction proceeds in an atom-economic manner with a broad substrate scope, along with excellent functional-group tolerance, scalability, and product diversification. Computational studies suggest that the enantio- and/or regioselectivity may originate from the Rh–C bonding along with the noncovalent interactions between the Boc group on the substrate and Ph groups on the ligand.}, archive = {J_JACS}, author = {Dequan Zhang and Jianqiang Zheng and Cai You and Liuting Li and Lung Wa Chung and Qifan Zhou and Shuailong Li and Tianxiang Ren and Yuhong Yang and Xumu Zhang and Xiuxiu Li}, doi = {10.1021/jacs.4c18341}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7886--7896}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic regio- and enantioselective hydroformylation of trisubstituted alkenes to construct α-quaternary lactams}, volume = {147}, year = {2025}, }
• (2025). Enantioselective total synthesis of (−)-rubriflordilactone b by a bioinspired skeletal reorganization approach. JACS, 147(9), 7875--7885. (www)

  @article{ , abstract = {Rubriflordilactone B is a Schisandra bisnortriterpenoid with a unique 5/5/7/6/5/5-hexacyclic framework that includes a characteristic tetrasubstituted aromatic ring. Herein, we report a convergent, enantioselective total synthesis of this natural product by a bioinspired skeletal reorganization approach. Key transformations include a chelation-controlled [2,3]-Wittig–Still rearrangement to assemble the western cyclohexenyl fragment with complete diastereocontrol, a Cu(II)-catalyzed tandem acyloin acylation–Wittig olefin to build the eastern butanolide fragment, a Friedel–Crafts cyclization to construct the seven-membered ring, and an E1cB reaction/transesterification/oxa-Michael addition cascade to forge the pivotal 5/5-fused bicyclic lactone. This work vividly demonstrates that bioinspired skeletal reorganization is a useful strategy for simplifying the retrosynthetic analysis of structurally complex natural products.}, archive = {J_JACS}, author = {Yancheng Xie and Jiajing Bao and Yu Wang and Yi Shen and Zexuan Liang and Hailong Tian and Jinghan Gui}, doi = {10.1021/jacs.4c18292}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7875--7885}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective total synthesis of (−)-rubriflordilactone b by a bioinspired skeletal reorganization approach}, volume = {147}, year = {2025}, }
• (2025). Antifouling spiky nanoelectrodes enhance detection of bacterial mRNA. JACS, 147(9), 7868--7874. (www)

  @article{ , abstract = {Nanomaterials have extensive applications in the development of sensitive biosensors, but the influence of their specific structural properties remains unclear. This work presents a platform that can provide mechanistic insight into how nanostructured electrodes improve the performance of electrochemical biosensors. We designed nanoelectrodes with sub-10 nm spike features through a combination of top-down lithography and solution-based synthesis. These anisotropic structures facilitated rapid electron-transfer, minimized biofouling, and promoted efficient target capture. Using these spiky nanoelectrodes in a biosensor, we detected bacterial mRNA at aM-levels and within 3 min. Our findings reveal the mechanism underlying signal enhancement from high-curvature regions on nanostructured electrodes, highlighting the structure–property relationships of nanostructures in electrochemical sensing.}, archive = {J_JACS}, author = {Yuhao Leo Wu and Jin Jia and Jagotamoy Das and Kimberly T. Riordan and Connor D. Flynn and Yi Wang and Shana O. Kelley and Teri W. Odom}, doi = {10.1021/jacs.4c18175}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7868--7874}, shortjournal = {J. Am. Chem. Soc.}, title = {Antifouling spiky nanoelectrodes enhance detection of bacterial mRNA}, volume = {147}, year = {2025}, }
• (2025). A route toward the on-surface synthesis of organic ferromagnetic quantum spin chains. JACS, 147(9), 7859--7867. (www)

  @article{ , abstract = {Engineering sublattice imbalance is an intuitive way to induce high-spin ground states in bipartite polycyclic conjugated hydrocarbons (PCHs). Such molecules can be employed as building blocks of quantum spin chains, which are outstanding platforms to study fundamental models in quantum magnetism. This is exemplified by recent reports on the bottom-up synthesis of antiferromagnetic spin chains that provided insights into paradigmatic quantum phenomena such as fractionalization. In contrast to antiferromagnetism, demonstration of ferromagnetic coupling between PCHs has been scarce. Previous attempts in this direction were limited by the formation of nonbenzenoid rings leading to spin quenching or the use of spacer motifs that weaken the magnitude of ferromagnetic exchange. Here, we demonstrate the on-surface synthesis of short ferromagnetic spin chains based on dibenzotriangulene, a triplet PCH. Our synthetic strategy centers on the concept of achieving a direct (without spacer motifs) majority–minority sublattice coupling between adjacent molecules. This leads to a global sublattice imbalance in spin chains scaling with the chain length and therefore a ferromagnetic ground state with a strong intermolecular ferromagnetic exchange. Through scanning probe measurements and quantum chemical calculations, we analyze the electronic and magnetic properties of ferromagnetic dimers and trimers of dibenzotriangulene and confirm their quintet and septet ground states, respectively, with an intermolecular ferromagnetic exchange of 7 meV. Furthermore, we elucidate the role of sublattice coupling on magnetism through complementary experiments on antiferromagnetic dibenzotriangulene dimers with majority–majority and minority–minority sublattice couplings. We expect our study to provide impetus for the design of organic ferromagnetic materials.}, archive = {J_JACS}, author = {Fabian Paschke and Ricardo Ortiz and Shantanu Mishra and Manuel Vilas-Varela and Florian Albrecht and Diego Peña and Manuel Melle-Franco and Leo Gross}, doi = {10.1021/jacs.4c18123}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7859--7867}, shortjournal = {J. Am. Chem. Soc.}, title = {A route toward the on-surface synthesis of organic ferromagnetic quantum spin chains}, volume = {147}, year = {2025}, }
• (2025). De novo design of proteins that bind naphthalenediimides, powerful photooxidants with tunable photophysical properties. JACS, 147(9), 7849--7858. (www)

  @article{ , abstract = {De novo protein design provides a framework to test our understanding of protein function and build proteins with cofactors and functions not found in nature. Here, we report the design of proteins designed to bind powerful photooxidants and the evaluation of the use of these proteins to generate diffusible small-molecule reactive species. Because excited-state dynamics are influenced by the dynamics and hydration of a photooxidant’s environment, it was important to not only design a binding site but also to evaluate its dynamic properties. Thus, we used computational design in conjunction with molecular dynamics (MD) simulations to design a protein, designated NBP ( N DI B inding P rotein), that held a naphthalenediimide (NDI), a powerful photooxidant, in a programmable molecular environment. Solution NMR confirmed the structure of the complex. We evaluated two NDI cofactors in this de novo protein using ultrafast pump–probe spectroscopy to evaluate light-triggered intra- and intermolecular electron transfer function. Moreover, we demonstrated the utility of this platform to activate multiple molecular probes for protein labeling.}, archive = {J_JACS}, author = {Samuel I. Mann and Zhi Lin and Sophia K. Tan and Jiaqi Zhu and Zachary X. W. Widel and Ian Bakanas and Jarrett P. Mansergh and Rui Liu and Mark J. S. Kelly and Yibing Wu and James A. Wells and Michael J. Therien and William F. DeGrado}, doi = {10.1021/jacs.4c18151}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7849--7858}, shortjournal = {J. Am. Chem. Soc.}, title = {De novo design of proteins that bind naphthalenediimides, powerful photooxidants with tunable photophysical properties}, volume = {147}, year = {2025}, }
• (2025). The local-scale origin of ferroic properties in BiVO4. JACS, 147(9), 7840--7848. (www)

  @article{ , abstract = {Earth-abundant metal oxides are excellent candidates for photocatalytic applications due to their low cost and high stability in aqueous solutions. Materials that contain a combination of metal cations with an s 2 electron lone pair and a d 0 electronic configuration, such as BiVO 4 , possess favorable band gaps. BiVO 4 has also been reported to possess noncentrosymmetric polar properties, such as flexoelectricity, piezo-photocatalysis, and an anomalous photovoltaic effect, despite its centrosymmetric crystal structure. Here, it is shown how centrosymmetric materials possessing s 2 and d 0 cations can display “hidden” local-scale features, often ignored by conventional crystallography, that influence their physical properties. Anomalous peak shapes are observed in the high-resolution synchrotron X-ray powder diffraction of BiVO 4 , and temperature-dependent local-scale distortions are revealed using neutron total scattering methods. Together, these suggest the polar properties of BiVO 4 are related to local-scale distortions induced by the Bi 3+ 6 s 2 electron lone pairs. This demonstrates the possibility of engineering specific interatomic distances between lone pair-bearing cations and the anion sublattice, creating new opportunities for photocatalytic and polar materials from compounds with long-range centrosymmetric structures.}, archive = {J_JACS}, author = {Bryce G. Mullens and Frederick P. Marlton and Helen E. A. Brand and Helen E. Maynard-Casely and Michelle Everett and Matthew G. Tucker and Emily R. Van Auken and Alicia M. Manjon-Sanz and Gianguido Baldinozzi and Simon M. Vornholt and Karena W. Chapman and Brendan J. Kennedy}, doi = {10.1021/jacs.4c18032}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7840--7848}, shortjournal = {J. Am. Chem. Soc.}, title = {The local-scale origin of ferroic properties in BiVO4}, volume = {147}, year = {2025}, }
• (2025). Taming strong Metal–Support interactions to generalize Gold–Zinc oxide catalysts in oxidative coupling. JACS, 147(9), 7829--7839. (www)

  @article{ , abstract = {Strong metal–support interactions (SMSI) are at the cutting edge of catalysis research, yet their size-dependent nature remains both widespread and subject to ongoing debate. Here, we report the discovery of bell-shaped size-dependent SMSI, and we establish its structure–SMSI–performance relationship in oxidative C–H/O–H coupling reactions. Using Au/ZnO as a prototypical catalyst, we develop a thermodynamic equilibrium model that quantitatively captures the size-dependent surface energy and tension disparities, identifying the particle size ratio as the descriptor for bell-shaped encapsulation dynamics. Larger Au particles with a higher surface energy are prone to wetting by smaller ZnO particles, triggering lattice oxygen spillover to form Au–O species that accelerate the rate-limiting hemiacetal β-H elimination. Simultaneously, residual oxygen vacancies serve as frustrated Lewis pairs, synergizing with Au–O to replenish hemiacetals and complete the catalytic cycle. This dual promotional mechanism overcomes the oxygen activation bottleneck in traditional Au catalysts, achieving state-of-the-art performance of 94.6% aldehyde conversion and 97.0% ester selectivity. The obtained structure–SMSI relationships are applicable to Ir/ZnO and Rh/ZnO catalysts, with similar SMSI–performance relationships extending to various aldehyde substrates, including saturated, unsaturated, and aromatic. These generalizable relationships lay a strong foundation for the strategic design and manipulation of SMSI states.}, archive = {J_JACS}, author = {Yongkai Xie and Xiangxue Zhang and Keng Sang and Wenyao Chen and Zhen Song and Gang Qian and Jing Zhang and De Chen and Xinggui Zhou and Weikang Yuan and Xuezhi Duan}, doi = {10.1021/jacs.4c17968}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7829--7839}, shortjournal = {J. Am. Chem. Soc.}, title = {Taming strong Metal–Support interactions to generalize Gold–Zinc oxide catalysts in oxidative coupling}, volume = {147}, year = {2025}, }
• (2025). Chemoproteomics-enabled de novo proteolysis targeting chimera discovery platform identifies a metallothionein degrader to probe its role in cancer. JACS, 147(9), 7817--7828. (www)

  @article{ , abstract = {Proteolysis targeting chimeras (PROTACs) represent powerful tools to modulate the activity of classically “undruggable” proteins, but their application has been limited to known ligands and a few select protein classes. Herein, we present our chemoproteomic strategy for simultaneous de novo discovery of novel degraders and ligands for challenging and previously “undruggable” targets. Using comparative PROTAC versus ligand global proteomics analyses, we rapidly identify proteins selectively downregulated by several “untargeted” PROTACs containing a VHL E3 ligase recruiter and various covalent and noncovalent ligands. We showcase our approach by identifying a first-in-class PROTAC for metallothionein 2A (MT2A), a small, cysteine-rich, metal-binding protein implicated in heavy metal detoxification, zinc homeostasis, and cellular invasion. Notably, isoform-specific MT overexpression has been shown to augment cellular migration and invasion across several cancer cell lines, although the precise mechanisms are unknown due to insufficient tools to study MTs. We show that optimized PROTAC AA-BR-157 covalently binds conserved C44, degrades overexpressed MT2A with nanomolar potency, and reduces the migration and invasion of MDA-MB-231 cells. We further demonstrate a time-dependent increase in intracellular zinc levels following MT2A degradation as well as downregulation of protein diaphanous homolog 3 (DIAPH3), a positive regulator of actin and cell motility. Super-resolution imaging of MDA-MB-231 cells shows that the downregulation of MT2A and DIAPH3 inhibits cell polarization and thereby migration, suggesting that MT2A may regulate motility via DIAPH3-dependent cytoskeletal remodeling. In summary, our strategy enables the de novo discovery of PROTACs and ligands for novel disease-related targets and lays the groundwork for expansion of the druggable proteome.}, archive = {J_JACS}, author = {Brittney Racioppo and Dany Pechalrieu and Daniel Abegg and Brendan Dwyer and Neal Thomas Ramseier and Ying S. Hu and Alexander Adibekian}, doi = {10.1021/jacs.4c17827}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7817--7828}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemoproteomics-enabled de novo proteolysis targeting chimera discovery platform identifies a metallothionein degrader to probe its role in cancer}, volume = {147}, year = {2025}, }
• (2025). Orthogonal control of transport channels in boron-embedded acenes. JACS, 147(9), 7809--7816. (www)

  @article{ , abstract = {Developing effective structural design strategies for regulating charge transport is a central focus in molecular electronics. The interplay between molecular symmetry and orbital distribution, facilitated by heteroatom substitution, presents opportunities for direct modulation in both resonant and off-resonance tunneling processes. In this study, scanning tunneling microscopy-break junction techniques and the first-principles calculations are employed to investigate the electronic properties of boron-embedded acenes. Compared to the parent acene, boron incorporation shifts the transport-dominating molecular orbital from a centrally localized distribution to a delocalized configuration across the orthogonal molecular backbone. This shift results in a 10-fold increase in conductance in the off-resonance region near zero bias and a 50-fold enhancement in conductance through near-resonant tunneling at high bias voltages. Notably, expanding the central acene fragment increases orbital asymmetry within molecular junctions, thereby compromising transport efficiency. However, applying a bias voltage gradually mitigates the symmetry-breaking effect, leading to through-backbone orbital distribution and a recovery in the near-resonant tunneling conductance. This orthogonal control of electronic transport channels provides a distinct strategy for the effective regulation of molecular conductance.}, archive = {J_JACS}, author = {Boyu Wang and Cheng Chen and Yani Huo and Hongyu Ju and Wanqi Sun and Xiao-Ye Wang and Chuancheng Jia and Jinying Wang and Xuefeng Guo}, doi = {10.1021/jacs.4c17477}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7809--7816}, shortjournal = {J. Am. Chem. Soc.}, title = {Orthogonal control of transport channels in boron-embedded acenes}, volume = {147}, year = {2025}, }
• (2025). Machine-learning-accelerated surface exploration of reconstructed BiVO4(010) and characterization of their aqueous interfaces. JACS, 147(9), 7799--7808. (www)

  @article{ , abstract = {Understanding the semiconductor–electrolyte interface in photoelectrochemical (PEC) systems is crucial for optimizing the stability and reactivity. Despite the challenges in establishing reliable surface structure models during PEC cycles, this study explores the complex surface reconstructions of BiVO 4 (010) by employing a computational workflow integrated with a state-of-the-art active learning protocol for a machine-learning interatomic potential and global optimization techniques. Within this workflow, we identified 494 unique reconstructed surface structures that surpass conventional chemical intuition-driven, bulk-truncated models. After constructing the surface Pourbaix diagram under Bi- and V-rich electrolyte conditions using density functional theory and hybrid functional calculations, we proposed structural models for the experimentally observed Bi-rich BiVO 4 surfaces. By performing hybrid functional molecular dynamics simulations with the explicit treatment of water molecules on selected reconstructed BiVO 4 (010) surfaces, we observed water dissociation from molecular water. Our findings demonstrate significant water dissociation on reconstructed Bi-rich surfaces, highlighting the critical role of bare and undercoordinated Bi sites (only observable in reconstructed surfaces) in driving hydration processes. Our work establishes a foundation for understanding the role of complex, reconstructed Bi surfaces in surface hydration and reactivity. Additionally, our theoretical framework for exploring surface structures and predicting reactivity in multicomponent oxides offers a precise approach to describing complex surface and interface processes in PEC systems.}, archive = {J_JACS}, author = {Yonghyuk Lee and Taehun Lee}, doi = {10.1021/jacs.4c17739}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7799--7808}, shortjournal = {J. Am. Chem. Soc.}, title = {Machine-learning-accelerated surface exploration of reconstructed BiVO4(010) and characterization of their aqueous interfaces}, volume = {147}, year = {2025}, }
• (2025). Ultratough thermoplastic elastomers based on chemically recyclable cycloalkyl-substituted polyhydroxyalkanoates. JACS, 147(9), 7788--7798. (www)

  @article{ , abstract = {It remains a long-standing challenge for chemical recycling of polyhydroxyalkanoates (PHAs) to propiolactone-based monomers due to the high ring strain and many inevitable side reactions. In this contribution, a novel α-spiro-cyclohexyl-propiolactone (SHPL) has been designed with high reactivity toward ring-opening polymerization even at a catalyst loading of <1 ppm. The resulting poly(3-hydroxy-2-spiro-cyclohexylpropionate) (P3HSHP) exhibited high thermal stability with a T d of 364 °C and a high T m of 272 °C. Meanwhile, it could be depolymerized back to SHPL in 86% yield without decarboxylation or elimination side products. Notably, SHPL could be exploited to construct high-performance thermoplastic elastomers (TPEs) via one-pot copolymerization with ε-caprolactone (CL). Particularly, the resulting gradient P(CL 2000 - grad -SHPL 500 ) showcased an ultimate tensile strength of 58.8 ± 4.0 MPa, high stretchability of 1959 ± 53%, a record toughness of 600 MJ/m 3 , and high elastic recovery (>90%). This superior performance of SHPL could advance the development of new sustainable high-performance TPEs.}, archive = {J_JACS}, author = {Hao-Yi Huang and Min Xie and Si-Qi Wang and Yu-Ting Huang and Yong-Hong Luo and Da-Gang Yu and Zhongzheng Cai and Jian-Bo Zhu}, doi = {10.1021/jacs.4c17703}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7788--7798}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultratough thermoplastic elastomers based on chemically recyclable cycloalkyl-substituted polyhydroxyalkanoates}, volume = {147}, year = {2025}, }
• (2025). Combining organic cations of different sizes grants improved control over perovskitoid dimensionality and bandgap. JACS, 147(9), 7777--7787. (www)

  @article{ , abstract = {Because mixed-halide wide-bandgap (1.6–2.0 eV) perovskite solar cells suffer from operating instability related to light-induced halide segregation, it is of interest to study alternative means of bandgap widening. Perovskitoids combine wide bandgaps and structural stability resulting from face- or edge-sharing octahedral connections in their crystal structures. Unfortunately, there existed no prior reports of three-dimensional (3D) perovskitoids having direct bandgaps with optical absorption edges less than 2.2 eV. As the most significant predictor of perovskitoid bandgaps is the fraction of corner-sharing in their crystal structures, we hypothesized that increasing the amount of corner-sharing would access lower bandgaps than previously reported. We accomplished this by mixing a spacer cation within the size range for 3D perovskitoid formation with a smaller perovskite-forming cation. We explored three spacer cations of different sizes: ethylammonium (EA), cyclopropylammonium (c-C3A), and cyclobutylammonium (c-C4A), combining these with methylammonium (MA), and found that the middle cation, c-C3A, pairs with MA to form a 3D perovskitoid with the formula (c-C3A) 3 (MA) 3 Pb 5 I 16 and a direct bandgap with an optical absorption edge at 2.0 eV. Solution-processed films of this perovskitoid showed improved light stability over mixed-halide perovskites, and solar cells based on these films exhibit increased maximum power point operating stability compared to reference mixed-halide devices.}, archive = {J_JACS}, author = {Isaiah W. Gilley and Hyoung Woo Kwon and Cheng Liu and Yi Yang and Chuying Huang and Haoyue Wan and Abdulaziz S. R. Bati and Evan H. Oriel and Mikaël Kepenekian and Badri Vishal and Stefan Zeiske and Khasim Saheb Bayikadi and Taylor E. Wiggins and Eugenia S. Vasileiadou and Bin Chen and Richard D. Schaller and Jacky Even and Stefaan De Wolf and Edward H. Sargent and Mercouri G. Kanatzidis}, doi = {10.1021/jacs.4c17654}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7777--7787}, shortjournal = {J. Am. Chem. Soc.}, title = {Combining organic cations of different sizes grants improved control over perovskitoid dimensionality and bandgap}, volume = {147}, year = {2025}, }
• (2025). Arylsulfonothioates: Thiol-activated donors of hydropersulfides which are excreted to maintain cellular redox homeostasis or retained to counter oxidative stress. JACS, 147(9), 7765--7776. (www)

  @article{ , abstract = {Despite their biological significance, the study of hydropersulfides (RSSH) is often limited due to their inherent instability. Here, we introduce arylsulfonothioates as thiol-activated RSSH donors and provide insight into cellular reactive sulfur species homeostasis. These precursors persulfidate physiologically relevant thiols (RSH) to form the corresponding RSSH. Real-time monitoring of hydrogen sulfide (H 2 S) generation via membrane inlet mass spectrometry (MIMS) was employed to follow RSSH production, revealing that electron-donating aryl substituents marginally slow RSSH release rates, whereas electron-withdrawing substituents slightly accelerate release. Furthermore, arylsulfonothioates with strong electron-withdrawing substituents offer superior protection against doxorubicin (DOX)-induced cardiotoxicity. Experiments using H9c2 cardiomyocytes affirmed the cell-permeability of arylsulfonothioates and their ability to increase intracellular RSSH levels and protein persulfidation levels. Notably, we observe the excretion of RSSH into the extracellular medium. Further investigations revealed the involvement of the cystine/glutamate antiporter SLC7A11, as cotreatment with its inhibitor, sulfasalazine, significantly reduce extracellular RSSH release. H9c2 cells exhibit tolerance to arylsulfonothioate 1g with an electron-withdrawing 4-cyano group at 1 mM; however, inhibition of the cystine antiporter results in a minor decrease in cell viability. Under oxidative stress conditions induced by DOX or hydrogen peroxide (H 2 O 2 ), cotreatment with 1g diminishes the excretion of RSSH and confers cytoprotection against DOX or H 2 O 2 -mediated toxicity. Our findings show adaptive cellular responses to RSSH levels, demonstrating excretion under elevated conditions to maintain redox homeostasis and intracellular retention as a protective response during oxidative stress.}, archive = {J_JACS}, author = {Vinayak S. Khodade and Qi Liu and Chengximeng Zhang and Gizem Keceli and Nazareno Paolocci and John P. Toscano}, doi = {10.1021/jacs.4c17661}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7765--7776}, shortjournal = {J. Am. Chem. Soc.}, title = {Arylsulfonothioates: Thiol-activated donors of hydropersulfides which are excreted to maintain cellular redox homeostasis or retained to counter oxidative stress}, volume = {147}, year = {2025}, }
• (2025). C1-based route for vinyl chloride synthesis with environmental and economic benefits. JACS, 147(9), 7757--7764. (www)

  @article{ , abstract = {Selective coupling of C 1 platform molecules to C 2 olefins is a cornerstone for establishing a sustainable chemical industry based on nonpetroleum sources. Vinyl chloride (C 2 H 3 Cl), one of the top commodity petrochemicals, is commercially produced from coal- or oil-derived C 2 hydrocarbon (acetylene and ethylene) feedstocks with a high carbon footprint. Here, we report a C 1 -based route for vinyl chloride synthesis via the selective oxidative coupling of methyl chloride. This is enabled by a solid catalyst, featuring tungstate nanoclusters embedded in a zirconia matrix, which effectively captures ·CH 2 Cl radicals homogeneously generated in CH 3 Cl oxy-pyrolysis and selectively couples them into C 2 H 3 Cl. In situ synchrotron-based vacuum ultraviolet photoionization mass spectrometry provides direct experimental evidence of the homogeneous-heterogeneous reaction mechanism. The process achieves methyl chloride conversion of 10–65% with a high vinyl chloride selectivity (60–75%) at a reaction temperature of 650–750 °C, which is much lower than the traditional pyrolysis (>850 °C). The catalyst delivers stable performance (at a vinyl chloride yield of ca. 30%) with no deactivation observed during a 50 h test. Furthermore, combining with reaction of methanol and HCl to produce methyl chloride, we establish a methanol-to-vinyl chloride (MTV) route with the potential for significant reductions in climate change impact (24%) and cost (38%) compared to the state-of-the-art ethylene-based balanced process. A more remarkable 237% reduction in climate change impacts can be anticipated in the future-oriented green scenario for the MTV process primarily attributed to the utilization of renewable C 1 feedstocks that results in negative net contributions to the overall impacts.}, archive = {J_JACS}, author = {Yue Wang and Shihui Zou and Abhinandan Nabera and Xutao Chen and Yang Pan and Kunkun Wei and Yunxin Bao and Jingbo Hu and Yilin Zhao and Chengyuan Liu and Juanjuan Liu and Yong Wang and Yutao Ren and Gonzalo Guillén-Gosálbez and Javier Pérez-Ramírez and Jie Fan}, doi = {10.1021/jacs.4c17531}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7757--7764}, shortjournal = {J. Am. Chem. Soc.}, title = {C1-based route for vinyl chloride synthesis with environmental and economic benefits}, volume = {147}, year = {2025}, }
• (2025). Thiophene sulfone single crystal as a reversible thermoelastic linear actuator with an extended stroke and second-harmonic generation switching. JACS, 147(9), 7749--7756. (www)

  @article{ , abstract = {Dynamic organic crystals are becoming recognized as some of the fastest materials for converting light or heat to mechanical work. The degree of deformation and the response time of any actuating material are often exclusive of each other; however, both factors influence the material’s overall performance limits. Unlike polymers, whose disordered structures are not conducive to rapid energy transfer, cooperative phase transitions in dynamic molecular crystals that are amenable to rapid and concerted martensitic-like structure switching could help circumvent that limitation. Here, we report that single crystals of a dibenzothiophene sulfone derivative exhibit extraordinarily large, rapid, and reversible elongation when they undergo a thermally induced phase transition. The value for the linear stroke of ∼15% along the long crystal axis with retention of macroscopic integrity of this material is remarkable and capitalizes on an anisotropic lattice switching with relative changes of 14.8% and −9.5% along its crystallographic a and c axes, respectively, resulting in a visible macroscopic elongation of the crystal. The transitioning crystals deliver forces ranging from 0.19 to 15 μN and a work density of ∼7 × 10 –3 J m –3 . The phase transformation is accompanied by a change in symmetry between centrosymmetric and noncentrosymmetric space groups and a significant change in both the fluorescence and the second-order nonlinear optical (NLO) response. The combination of these properties makes this material a favorable choice for low-power, precise, and small-scale NLO actuation applications.}, archive = {J_JACS}, author = {Zhihua Wang and Rongchao Shi and Ibrahim Tahir and Durga Prasad Karothu and Puxin Cheng and Wenqing Han and Liang Li and Yongshen Zheng and Panče Naumov and Jialiang Xu and Xian-He Bu}, doi = {10.1021/jacs.4c17448}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7749--7756}, shortjournal = {J. Am. Chem. Soc.}, title = {Thiophene sulfone single crystal as a reversible thermoelastic linear actuator with an extended stroke and second-harmonic generation switching}, volume = {147}, year = {2025}, }
• (2025). Synthesis and stabilization of a benzene dianion with a triplet ground state and baird aromaticity. JACS, 147(9), 7741--7748. (www)

  @article{ , abstract = {The triplet benzene dianion is predicted to be aromatic based on Baird’s rule. However, it has remained elusive due to the Jahn–Teller distortion. Herein, we report isolation of a benzene dianion with a triplet ground state in an inverse-sandwich europium benzene complex. Combined experimental and theoretical studies unveil that the strong antiferromagnetic coupling between the benzene dianion and 4f 7 Eu 2+ ions is pivotal to the stabilization of the triplet state of the benzene dianion with Baird aromaticity. In addition, a comparison with analogous ytterbium benzene and europium para -xylene complexes further reveals that the spin state of the benzene dianion depends on the spin–spin interaction and local symmetry. These results accomplish the isolation of the long-sought triplet benzene dianion and illustrate the effectiveness of spin modulation using lanthanide ions.}, archive = {J_JACS}, author = {Yi Wang and Rong Sun and Jiefeng Liang and Yurou Zhang and Bowen Tan and Chong Deng and Yi-Han Wang and Bing-Wu Wang and Song Gao and Wenliang Huang}, doi = {10.1021/jacs.4c17459}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7741--7748}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis and stabilization of a benzene dianion with a triplet ground state and baird aromaticity}, volume = {147}, year = {2025}, }
• (2025). Stereodivergent construction of 3,3′-disubstituted oxindoles via one-pot sequential Allylation/Alkylation and its application to the total synthesis of trigolute b and d. JACS, 147(9), 7729--7740. (www)

  @article{ , abstract = {The absolute and relative configurations of bioactive chiral molecules are typically relevant to their biological properties. It is thus highly important and desirable to construct all possible stereoisomers of a lead candidate or a given bioactive natural compound. Synergistic dual catalysis has been recognized as a reliable synthetic strategy for a variety of predictable stereodivergent transformations. Despite the impressive progress made in this field, stereodivergent carbon–carbon bond-formation reactions involving stabilized nucleophiles remain elusive. Herein, we report an iridium- and magnesium-catalyzed one-pot sequential allylic alkylation/nucleophilic alkylation cascade process for the stereodivergent synthesis of all four stereoisomers of 3,3′-disubstituted oxindoles through a three-component reaction. A diverse array of products is readily prepared with high functional group compatibility in good yields with excellent diastereo- and enantioselectivities. Subsequently, the stereodivergent total synthesis of four stereoisomers of the spirooxindole alkaloid trigolutes B and D has been accomplished through a concise and unified synthetic route using the same set of starting materials.}, archive = {J_JACS}, author = {Bin Qing and Zhuang Yang and Zhenwei Wu and Zichun Zhang and Yuqiao Zhou and Xinlong Yan and Yangbin Liu and Xiaoming Feng}, doi = {10.1021/jacs.4c17425}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7729--7740}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereodivergent construction of 3,3′-disubstituted oxindoles via one-pot sequential Allylation/Alkylation and its application to the total synthesis of trigolute b and d}, volume = {147}, year = {2025}, }
• (2025). Borrowing Hydrogen/Chiral enamine relay catalysis enables diastereo- and enantioselective β-C–H functionalization of alcohols. JACS, 147(9), 7721--7728. (www)

  @article{ , abstract = {We report herein an unprecedented borrowing hydrogen/chiral enamine relay catalysis strategy that enables a highly efficient enantioselective formal β-alkylation of simple alcohols using electron-deficient alkenes and especially nitroalkenes. A variety of 1,4-difunctional products such as nitro alcohols are readily accessible in one waste-free step from feedstock alcohols in excellent levels of stereoselectivity. It is important to note that the products are formed in much higher diastereoselectivity than the enamine catalysis step alone under identical conditions, highlighting the unique advantage of cascade borrowing hydrogen catalysis in achieving high efficiency, economy, and stereoselectivity.}, archive = {J_JACS}, author = {Ming Wai Liaw and Haruka Hirata and Gong-Feng Zou and Jie Wu and Yu Zhao}, doi = {10.1021/jacs.4c17355}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7721--7728}, shortjournal = {J. Am. Chem. Soc.}, title = {Borrowing Hydrogen/Chiral enamine relay catalysis enables diastereo- and enantioselective β-C–H functionalization of alcohols}, volume = {147}, year = {2025}, }
• (2025). Electrochemical lithiation regulates the active hydrogen supply on Ru–Sn nanowires for hydrogen evolution toward the high-performing anion exchange membrane water electrolyzer. JACS, 147(9), 7711--7720. (www)

  @article{ , abstract = {Designing a rational electrocatalyst/electrolyte interface with superb active hydrogen supply is of significant importance for the alkaline hydrogen evolution reaction (HER) and anion exchange membrane water electrolyzers (AEMWEs). Here, we propose a strategy to tune the interfacial active hydrogen supply via inducing dissoluble cation into electrocatalysts to boost HER in alkali, with electrochemical lithiated sub-2 nm RuSn 0.8 nanowires (NWs) as a proof of concept. It is found that a part of Li + could dissolve in situ from lithiated RuSn 0.8 NWs during HER, which tends to affect the interfacial structure and facilitate the proton transport. Among all the Li–Ru–Sn and Ru–Sn NWs, the best-performing Li 3.0 RuSn 0.8 NWs exhibit the lowest initial overpotential of 66 mV at 100 mA cm –2 in 1.0 M KOH, which could be further reduced to 38 mV after the 30 000 cycles accelerated stability test (AST). In situ Raman spectroscopy and operando X-ray adsorption spectroscopy indicate that the pristine Li 3.0 RuSn 0.8 NWs are highly active toward water dissociation and the dissolved Li + during AST could further enhance the flexibility of the hydrogen bond network for proton transportation. Ab initio molecular dynamics simulations and density functional theory calculations disclose that the incorporation of Li into the Ru–Sn lattice is beneficial to lower the water dissociation barrier, while dissolved Li + at the interface significantly increases the population of interfacial water molecules, thereby providing sufficient active hydrogens for H 2 production. The AEMWE equipped with the Li 3.0 RuSn 0.8 NWs cathode delivers an extremely low cell voltage (1.689 V) at an industrial-scale current density (1 A cm –2 ) and outstanding stability (56 μV h –1 loss at 1 A cm –2 after 1000 h galvanostatic test), representing one of the best alkaline HER electrocatalysts ever reported.}, archive = {J_JACS}, author = {Jialun Mao and Jiashun Liang and Yunan Li and Xuan Liu and Feng Ma and Shuxia Liu and Hao Ouyang and Zhao Cai and Tanyuan Wang and Yufei Zhao and Yunhui Huang and Qing Li}, doi = {10.1021/jacs.4c17373}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7711--7720}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical lithiation regulates the active hydrogen supply on Ru–Sn nanowires for hydrogen evolution toward the high-performing anion exchange membrane water electrolyzer}, volume = {147}, year = {2025}, }
• (2025). Analysis of the TiO2 photoanode process using intensity modulated photocurrent spectroscopy and distribution of relaxation times. JACS, 147(9), 7703--7710. (www)

  @article{ , abstract = {Photoelectrochemical water splitting offers a promising pathway for green hydrogen production, but its efficiency is limited by electron−hole recombination. Overcoming this challenge requires detailed analysis of the relationship between charge separation and charge transfer kinetics under operando conditions. Here, we applied intensity-modulated photocurrent spectroscopy (IMPS) combined with distribution of relaxation times (DRT) analysis to the photoanodic process under varying light intensities. This approach revealed three distinct applied potential regions: a high-potential region with constant admittance independent of light intensity; a midpotential region strongly influenced by light intensity; and a low-potential region with back electron−hole recombination (BER). Crucially, our analysis demonstrated that what has traditionally been viewed as a single bulk recombination process can be resolved into distinct mechanisms based on light intensity dependence. Additionally, we identified satellite peaks in the slow kinetic regions for the first time. These peaks, influenced by light intensity and reaction conditions, revealed novel insights into surface-trapped hole dynamics. Based on these insights, we propose tailored band bending models for each kinetic scenario and discuss the implications of satellite peaks for reaction bottlenecks. These results offer new perspectives on understanding and optimizing photoelectrochemical systems.}, archive = {J_JACS}, author = {Yohei Cho and Mengya Yang and Junyi Cui and Yue Yang and Surya Pratap Singh and Salvador Eslava and Daniele Benetti and James R Durrant and Akira Yamaguchi and Masahiro Miyauchi and Fumiaki Amano}, doi = {10.1021/jacs.4c17345}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7703--7710}, shortjournal = {J. Am. Chem. Soc.}, title = {Analysis of the TiO2 photoanode process using intensity modulated photocurrent spectroscopy and distribution of relaxation times}, volume = {147}, year = {2025}, }
• (2025). Light-independent Fe3O4–Methanosarcina acetivorans biohybrid enhances nitrogen fixation and methanogenesis. JACS, 147(9), 7694--7702. (www)

  @article{ , abstract = {Biohybrid systems that integrate microorganisms with nanomaterials have emerged as promising solutions for sustainable nitrogen fixation. However, key challenges, such as the dependence on light and the vulnerability of nitrogenase to oxidative damage, have limited their application. Here, we report a novel, light-independent biohybrid system integrating Fe 3 O 4 nanoparticles with Methanosarcina acetivorans C2A, resulting in a significant enhancement of both nitrogen fixation activity and methane production. Fe 3 O 4 nanoparticles facilitate directional electron transfer, thereby enhancing methanogenesis and nitrogenase function. Furthermore, the biohybrid system enhances adenosine triphosphate (ATP) synthesis through improved electron flow along membrane-bound electron chains, further supporting nitrogenase activity. Our findings provide a new strategy for advancing nitrogen fixation in archaea, offering an efficient and sustainable approach for biological nitrogen fixation without reliance on solar energy.}, archive = {J_JACS}, author = {Xiao-Yu Liu and Jing-Ya Ma and Mei-Yan Liu and Jian-Lu Duan and Yue Wang and Xiao-Dong Sun and Chengcheng Ding and Li-Juan Feng and Zhen Yan and Xian-Zheng Yuan}, doi = {10.1021/jacs.4c17259}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7694--7702}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-independent Fe3O4–Methanosarcina acetivorans biohybrid enhances nitrogen fixation and methanogenesis}, volume = {147}, year = {2025}, }
• (2025). Tuning the crystallinity of a Metal–Organic coordination network at the Liquid–Solid interface. JACS, 147(9), 7682--7693. (www)

  @article{ , abstract = {Single layered metal–organic coordination networks (MOCNs) are gaining attention thanks to their unique electronic and magnetic properties. The presence of coordinatively unsaturated metal sites within their structures provides additional binding locations for substrates in catalytic processes. Consequently, MOCNs fabricated on solid surfaces are emerging as promising candidates for use in solution-based heterogeneous applications. The bottom-up synthesis of such surface-supported MOCNs requires a rigorous design by utilizing two-dimensional (2D) crystal engineering. However, a comprehensive description of the factors governing their synthesis at the liquid–solid interface is still missing, resulting in only a few reported examples. In this work, we use scanning tunneling microscopy (STM) at the liquid–solid interface to reveal the effect of the choice of solvent, concentration, and temperature on the structure of a surface-supported MOCN constituted by a tritopic ligand containing pyridyl moieties and trans -protected Pd(II) cations. A quantitative analysis of the network’s crystallinity is presented. Furthermore, the impact of the synthetic pathway is investigated and a qualitative description of the growth mechanism is provided. Finally, the porosity of the extended honeycomb network is examined by studying the adsorption of guest molecules in its pores.}, archive = {J_JACS}, author = {Antonino Cucinotta and Samuel Eyley and Jack A. Davies and Wim Thielemans and Kunal S. Mali and Steven De Feyter}, doi = {10.1021/jacs.4c17152}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7682--7693}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning the crystallinity of a Metal–Organic coordination network at the Liquid–Solid interface}, volume = {147}, year = {2025}, }
• (2025). Molecular photoelectrodes with enhanced photogenerated charge transport for efficient solar hydrogen evolution. JACS, 147(9), 7671--7681. (www)

  @article{ , abstract = {Photoelectrocatalytic cells for seawater splitting have shown promise toward large-scale deployment; however, challenges remain in operation performances, which outline clear research needs to scale up photoelectrodes with small loss of efficiency. Here, we report an approach for scalable and robust solar H 2 evolution by enhancing photogenerated charge transport in a H 2 -evolving molecular photoelectrode. The photoelectrode is based on p-type conjugated polymers that are homogeneously distributed in a polycarbazole network. With a self-assembled NiS 2 catalyst, the photoelectrode under solar irradiation (100 mW cm –2 , AM 1.5 G) is capable of evolving H 2 from seawater at an external quantum efficiency (EQE) of 34.4% under an applied bias of −0.06 V vs RHE. When scaling up from 1 cm 2 to 25 cm 2 , the photoelectrode generates photocurrents stabilized at 0.4 A and maintains the high EQE at an efficiency loss of less than 1%. Investigation of the photogenerated charge-transport dynamics reveals that the kinetic basis for scaling up lies in the desirable hole diffusion length that far exceeds the spacing between adjacent conjugated-polymer chains due to interchain π–π interactions.}, archive = {J_JACS}, author = {Yifan Gao and Feiqing Sun and Yanjie Fang and Yingke Wen and Feiyang Hong and Bing Shan}, doi = {10.1021/jacs.4c17133}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7671--7681}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular photoelectrodes with enhanced photogenerated charge transport for efficient solar hydrogen evolution}, volume = {147}, year = {2025}, }
• (2025). Manipulating hydrogen-bonding Donor/Acceptor in ultra-robust isoreticular Zr(IV) Metal–Organic frameworks for efficient regulation of water sorption inflection point and steepness. JACS, 147(9), 7663--7670. (www)

  @article{ , abstract = {The development of porous materials exhibiting steep and stepwise adsorption of water vapor at desired humidity is crucial for implementing diverse applications such as humidity control, heat allocation, and atmospheric water harvesting. The precise molecular-level elucidation of structural characteristics and chemical components that dictate the water sorption behaviors in confined nanospaces, metal–organic frameworks (MOFs) in particular, is fundamentally important, but this has yet to be largely explored. In this work, by leveraging the isoreticular principle, we crafted two pairs of isostructural Zr-MOFs with linker backbones of benzene and pyrazine acting as hydrogen-bonding donor and acceptor, respectively. The outstanding water sorption cyclic durability of the four Zr-MOFs permits persuasive investigation of the correlation of the water sorption inflection point and steepness (the two central figures-of-merit for water sorption) with the linker functionality. The two pyrazine-carrying Zr-MOFs both show steep water uptake at lower relative pressure and slightly decreased steepness, which are quantitatively described by the Dubinin-Astakhov relation. We deciphered the privileged water clusters through single-crystal X-ray diffraction studies in which the pyrazine moiety formed stronger hydrogen-bonding interactions with guest water molecules and favored the formation of water pentamers instead of hexamers that are observed in the benzene analog. The hydrogen-bonding donor/acceptor manipulation approach presented in this work may facilitate future research endeavors focusing on molecular attribute engineering in predeterminedly ultrawater-resistant MOF platforms for efficient regulation of water sorption behaviors toward customized applications.}, archive = {J_JACS}, author = {Yuan Geng and Yifei Gao and Pengfu Gao and Jingjing Zhang and Xianhui Tang and Jinqiao Dong and Jingjing Jiao and Helin Niu and Wei Gong and Yong Cui}, doi = {10.1021/jacs.4c17145}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7663--7670}, shortjournal = {J. Am. Chem. Soc.}, title = {Manipulating hydrogen-bonding Donor/Acceptor in ultra-robust isoreticular Zr(IV) Metal–Organic frameworks for efficient regulation of water sorption inflection point and steepness}, volume = {147}, year = {2025}, }
• (2025). Hierarchical reaction logic enables computational design of complex peptide syntheses. JACS, 147(9), 7644--7662. (www)

  @article{ , abstract = {The prevalent assumption in computer-assisted synthesis planning has been to rely on the wealth of reaction data and on the consideration of this vast knowledge base at every stage of route planning. Yet even if equipped with all requisite knowledge of individual reaction transforms and state-of-the-art search algorithms, the existing programs struggle when confronted with advanced targets, such as the complex peptides this work considers. By contrast, when the searches are constrained by hierarchical logic, dictating which subsets of reactions to apply at different stages of synthesis planning, these algorithms are able to plan, within minutes, complete routes to clinically relevant targets as complex as vancomycin and as large as semaglutide. Despite not being trained on any literature precedents, the routes designed by the algorithm mimic the strategies used by human experts. The hierarchical planning we describe incorporates protecting-group strategies and realistic pathway pricing and can be performed in solid-state or solution modes, in the latter case using either C-to-N or N-to-C peptide extension strategies.}, archive = {J_JACS}, author = {Karol Molga and Wiktor Beker and Rafał Roszak and Andrzej Czerwiński and Bartosz A. Grzybowski}, doi = {10.1021/jacs.4c17057}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7644--7662}, shortjournal = {J. Am. Chem. Soc.}, title = {Hierarchical reaction logic enables computational design of complex peptide syntheses}, volume = {147}, year = {2025}, }
• (2025). Temperature-dependent mixed valency in the hexagonal perovskite Cs3NaFe2Cl9. JACS, 147(9), 7634--7643. (www)

  @article{ , abstract = {The hexagonal perovskites Cs 3 NaFe 2 Cl 9 and Cs 3 NaMnFeCl 9 have been synthesized and investigated. Both compounds adopt the 6H perovskite structure with P 6 3 / mmc symmetry. This structure consists of dimers of face-sharing octahedra arranged on the vertices of a triangular network. The transition metal ions occupy sites in these octahedra, leading to Fe 2 Cl 9 4– and FeMnCl 9 4– bioctahedra, respectively. The bioctahedral clusters are sandwiched by layers of corner-sharing octahedra occupied by Na + cations. Diffuse reflectance spectroscopy reveals optical transitions that arise from metal-to-metal charge transfer (Cs 3 NaMnFeCl 9 ) and intervalence charge transfer (Cs 3 NaFe 2 Cl 9 ) excitations. In Cs 3 NaFe 2 Cl 9 , magnetic susceptibility measurements reveal local ferromagnetic coupling (θ CW = 16.7 K), mediated by the rapid exchange of an electron between the iron sites within each dimer. In contrast, the magnetic coupling between Fe 3+ and Mn 2+ in Cs 3 NaMnFeCl 9 is antiferromagnetic (θ CW = −41.4 K). At 100 K, the Mössbauer spectrum is dominated by a single type of iron that corresponds to Fe 2.5+ , signaling electron exchange between iron sites that is faster than the Mössbauer time scale (∼100 ns). Upon further cooling, the Fe 2.5+ signal gives way to a 1:1 ratio of Fe 2+ and Fe 3+ , as the thermally activated hopping slows down.}, archive = {J_JACS}, author = {David Liu and Alexander Milder and Jeremiah Stevens and Cierra Foster and Brendan Beck and Maxim Avdeev and Patrick M. Woodward}, doi = {10.1021/jacs.4c17019}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7634--7643}, shortjournal = {J. Am. Chem. Soc.}, title = {Temperature-dependent mixed valency in the hexagonal perovskite Cs3NaFe2Cl9}, volume = {147}, year = {2025}, }
• (2025). Closed-loop recyclable solid-state polymer electrolytes enabled by reversible lithium salt catalysis. JACS, 147(9), 7624--7633. (www)

  @article{ , abstract = {The rapid expansion in lithium battery production and disposal presents considerable sustainability challenges, emphasizing the critical need for recycling. However, current methods predominantly focus on metals from cathodes, while electrolytes have rarely been recycled. Here, we propose an innovative closed-loop design for solid polymer electrolytes (SPEs), enabled by reversible catalysis of lithium bis(trifluoromethane) sulfonimide (LiTFSI) in both polymerization and depolymerization. The formation of a hydrogen-bonded adduct between TFSI – and alcohol initiates the in situ ring-opening polymerization of Li + -activated trimethylene carbonate (TMC), generating well-defined SPEs. With delicate structural optimization, the SPE achieves an outstanding ionic conductivity of 1.62 × 10 –3 S cm –1 at room temperature with robust high-voltage stability up to 4.7 V. The assembled Li||NCM811 demonstrates promising cycling stability with 88% capacity retention over 100 cycles. Upon end-of-life, LiTFSI facilitates selective depolymerization of the polycarbonate-based SPE at 180 °C without introducing external catalysts, recovering both TMC monomer (>90%) and LiTFSI (>98%) for reuse. This work highlights a significant advance in closed-loop recyclable SPEs and a vital step toward sustainable lithium battery technology.}, archive = {J_JACS}, author = {Pei Chen and Shunjie Liu and Hao Zhou and Shuo Yan and Dongxuan Zhang and Xuan Pang and Xuesi Chen and Xianhong Wang}, doi = {10.1021/jacs.4c17035}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7624--7633}, shortjournal = {J. Am. Chem. Soc.}, title = {Closed-loop recyclable solid-state polymer electrolytes enabled by reversible lithium salt catalysis}, volume = {147}, year = {2025}, }
• (2025). Triggered inversion of dual responsive diblock copolypeptide vesicles. JACS, 147(9), 7617--7623. (www)

  @article{ , abstract = {We report the synthesis of amphiphilic poly( l -methionine sulfoxide) x - b -poly(dehydroalanine) y , diblock copolypeptides, M O x A DH y , and their self-assembly into submicrometer-diameter unilamellar vesicles in aqueous media. The formation of vesicles was observed over an unprecedented range of copolypeptide compositions due to the unique properties and chain conformations of A DH hydrophobic segments. These copolypeptides incorporate two distinct thiol reactive components where each segment can respond differently to a single thiol stimulus. Incubation of M O 35 A DH 30 vesicles with glutathione under intracellular mimetic conditions resulted in vesicle disruption and release of cargo. Further, incubation of M O 35 A DH 30 vesicles with thiolglycolic acid resulted in a reversal of amphipilicity and successful in situ inversion of the vesicle assemblies. This conversion of biomimetic polymer vesicles into stable inverted vesicles using a biologically relevant stimulus at physiological pH and temperature is unprecedented. These results provide insights toward the development of advanced functional synthetic assemblies with potential uses in biology and medicine.}, archive = {J_JACS}, author = {Casey A. Morrison and Ethan P. Chan and Timothy J. Deming}, doi = {10.1021/jacs.4c17033}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7617--7623}, shortjournal = {J. Am. Chem. Soc.}, title = {Triggered inversion of dual responsive diblock copolypeptide vesicles}, volume = {147}, year = {2025}, }
• (2025). Identification of cell receptors responsible for recognition and binding of lipid nanoparticles. JACS, 147(9), 7604--7616. (www)

  @article{ , abstract = {Effective delivery of lipid nanoparticles (LNPs) and their organ- or cell-type targeting are paramount for therapeutic success. Achieving this requires a comprehensive understanding of protein corona dynamics and the identification of cell receptors involved in the recognition and uptake of LNPs. We introduce a simple, fast, and in situ strategy by a biosensor-based “Fishing” method to uncover protein corona formation on LNPs and identify key receptors of human blood cells that are responsible for the recognition and binding of human plasma corona on the surface of LNPs. Unexpectedly, we observed a significant presence of immunoglobulins with high abundance, especially anti-PEG antibodies, within the LNP corona. These antibodies, along with complement opsonization, drive colony-stimulating factor 2 receptor β (CSF2RB)-mediated phagocytosis by human myeloid cells. These compositions of the human plasma corona and their interactions with neighboring proteins are critical for the recognition and binding of LNPs by cell receptors and cellular uptake. Our findings highlight the pivotal role of anti-PEG antibodies in the circulation and phagocytosis of LNPs in vivo . This approach offers profound insights into nanomaterial behavior in vivo , paving the way for the enhanced design and efficacy of LNP-based therapies.}, archive = {J_JACS}, author = {Didar Baimanov and Jing Wang and Yuchen Liu and Pingping Zheng and Shengtao Yu and Fen Liu and Jian Wang and Diana Boraschi and Yuliang Zhao and Chunying Chen and Liming Wang}, doi = {10.1021/jacs.4c16987}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7604--7616}, shortjournal = {J. Am. Chem. Soc.}, title = {Identification of cell receptors responsible for recognition and binding of lipid nanoparticles}, volume = {147}, year = {2025}, }
• (2025). A triangular frustrated Eu(II)–Organic framework for sub-kelvin magnetic refrigeration. JACS, 147(9), 7597--7603. (www)

  @article{ , abstract = {Attaining sub-Kelvin temperatures remains technologically challenging and often relies on the scarce resource 3 He, unless employing adiabatic demagnetization refrigeration. Herein, the active coolant typically consists of weakly coupled paramagnetic ions, whose magnetic interaction strengths are comparable in energy to the relevant temperature regime of cooling. Such interactions depend strongly on inter-ion distances, fundamentally hindering the realization of dense coolants for sub-Kelvin refrigeration. We present a magnetically concentrated triangular coordination network, Eu 0.9 Ba 0.1 I 2 (pyrazine) 3 , featuring the large s = 7/2 moment of Eu(II). Electron paramagnetic resonance, magnetization, and heat capacity measurements reflect antiferromagnetic correlations between the Eu(II) ions and a dominant easy-plane magnetic anisotropy. The ensuing geometric frustration prevents entropy-annihilating magnetic order down to at least 0.17 K. This remarkably low operational temperature for a low-dimensional, molecule-based magnetic refrigerant opens possibilities for on-chip cryogenic refrigeration, especially in scenarios where established inorganic refrigerants cannot be utilized.}, archive = {J_JACS}, author = {Anna S. Manvell and Maja A. Dunstan and David Gracia and Jakub Hrubý and Mariusz Kubus and James N. McPherson and Elias Palacios and Høgni Weihe and Stephen Hill and Jürgen Schnack and Marco Evangelisti and Kasper S. Pedersen}, doi = {10.1021/jacs.4c17003}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7597--7603}, shortjournal = {J. Am. Chem. Soc.}, title = {A triangular frustrated Eu(II)–Organic framework for sub-kelvin magnetic refrigeration}, volume = {147}, year = {2025}, }
• (2025). Red light mediated photoconversion of silicon rhodamines to oxygen rhodamines for single-molecule microscopy. JACS, 147(9), 7588--7596. (www)

  @article{ , abstract = {The rhodamine motif has been modified in myriad ways to produce probes with specific fluorescent and chemical properties optimal for a variety of fluorescence microscopy experiments. Recently, far-red (>640 nm) emitting silicon rhodamines have become popular in single-molecule localization microscopy (SMLM), since these dyes are membrane-permeable and can be used alongside red (570–640 nm) emitting fluorophores for two-color imaging. While this has expanded multicolor SMLM imaging capabilities, we demonstrate that silicon rhodamines can create previously unreported photoproducts with significantly blueshifted emissions, which appear as bright single-molecule crosstalk in the red emission channel. We show that this fluorescence is caused by the replacement of the central silicon group with oxygen after 640 nm illumination, turning far-red silicon rhodamines (JFX650, JF669, etc.) into their red oxygen rhodamine counterparts (JFX554, JF571, etc.). While this blueshifted population can cause artifacts in two-color SMLM data, we demonstrate up to 16-fold reduction in crosstalk using oxygen scavenging systems. We also leverage this far-red photoconversion to demonstrate UV-free photoactivated localization microscopy (PALM) without the need for additives, and with 5-fold higher efficiency than the Cy5 to Cy3 conversion. Finally, we demonstrate multiplexed pseudo two-color PALM in a single emission channel by separating localizations by their photoactivation wavelengths instead of their emission wavelengths.}, archive = {J_JACS}, author = {Jacob M. Ritz and Aset Khakimzhan and Joseph J. Dalluge and Vincent Noireaux and Elias M. Puchner}, doi = {10.1021/jacs.4c16907}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7588--7596}, shortjournal = {J. Am. Chem. Soc.}, title = {Red light mediated photoconversion of silicon rhodamines to oxygen rhodamines for single-molecule microscopy}, volume = {147}, year = {2025}, }
• (2025). Fluorogenic platform for real-time imaging of subcellular payload release in Antibody–Drug conjugates. JACS, 147(9), 7578--7587. (www)

  @article{ , abstract = {Antibody–drug conjugates (ADCs) represent promising therapeutic constructs to enhance the selective delivery of drugs to target cells; however, attaining precise control over the timing and location of payload release remains challenging due to the complex intracellular processes that define ADC internalization, trafficking, and linker cleavage. In this study, we present novel real-time fluorogenic probes to monitor both subcellular dynamics of ADC trafficking and payload release. We optimized a tandem molecular design of sequential pH- and enzyme-activatable naphthalimide fluorophores to (1) track their subcellular localization along the endolysosomal pathway and (2) monitor linker cleavage with OFF-to-ON fluorescence switches. Live-cell imaging microscopy revealed that fluorogenic ADCs can traffic to the lysosomes and yet require residence time in these subcellular compartments for efficient linker cleavage. Notably, the compact size of fluorogenic naphthalimides did not impair the recognition of target cell surface reporters or the kinetics of payload release. This modular platform is applicable to many ADCs and holds promise to inform their rational design for optimal release profiles and therapeutic efficacy.}, archive = {J_JACS}, author = {Ferran Nadal-Bufi and Paulin L. Salomon and Fabio de Moliner and Kathy A. Sarris and Zhi Wang and Rachel D. Wills and Violeta L. Marin and Xiaona Shi and Kuo Zhou and Zhongyuan Wang and Zhou Xu and Michael J. McPherson and Christopher C. Marvin and Adrian D. Hobson and Marc Vendrell}, doi = {10.1021/jacs.4c16842}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7578--7587}, shortjournal = {J. Am. Chem. Soc.}, title = {Fluorogenic platform for real-time imaging of subcellular payload release in Antibody–Drug conjugates}, volume = {147}, year = {2025}, }
• (2025). Alkali cation inhibition of imidazolium-mediated electrochemical CO2 reduction on silver. JACS, 147(9), 7564--7577. (www)

  @article{ , abstract = {Imidazolium-based ionic liquids have led to enhanced CO 2 electroreduction activity due to cation effects at the cathode surface, stabilizing the reaction intermediates and decreasing the activation energy. In aqueous media, alkali cations are also known to improve CO 2 reduction activity on metals such as Ag, with the enhancement attributed to electrical double layer effects and trending with the size of the alkali cation. However, the effect of a mixed catholyte solution of alkali cations in the presence of an imidazolium-based ionic liquid has not been well-explored. Herein, 1-ethyl-3-methylimidazolium tetrafluoroborate, [EMIM][BF 4 ], in water was investigated with alkali salts to unravel the interaction effects for CO 2 electroreduction on Ag. Although both [EMIM] + and alkali cations have individually improved CO 2 to CO conversion on Ag in water, electrochemical results showed that alkali cations hindered imidazolium-mediated CO 2 electroreduction in most conditions. Li + , in particular, was sharply inhibitory compared to other alkali cations and strongly redirected the selectivity to hydrogen evolution. The nature of the alkali cation inhibition was investigated with spectroscopic techniques, including in situ surface-enhanced Raman spectroscopy (SERS) and dynamic electrochemical impedance spectroscopy (DEIS). Along with computational insights from density functional theory (DFT), the electrochemical and spectroscopic data suggest that alkali cations inhibit [EMIM]-mediated CO 2 reduction by competing for surface adsorption sites, preventing the potential-dependent structural reorientation of imidazolium, and promoting hydrogen evolution by bringing solvated water to the cathode surface.}, archive = {J_JACS}, author = {Francois Nkurunziza and Saudagar Dongare and Soumya Chatterjee and Bhavi Shah and Manu Gautam and Baleeswaraiah Muchharla and Bijandra Kumar and Michael J. Janik and Burcu Gurkan and Robert L. Sacci and Joshua M. Spurgeon}, doi = {10.1021/jacs.4c16635}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7564--7577}, shortjournal = {J. Am. Chem. Soc.}, title = {Alkali cation inhibition of imidazolium-mediated electrochemical CO2 reduction on silver}, volume = {147}, year = {2025}, }
• (2025). Tailoring lewis acidity of metal oxides on nickel to boost electrocatalytic hydrogen evolution in neutral electrolyte. JACS, 147(9), 7555--7563. (www)

  @article{ , abstract = {Neutral-pH water splitting for hydrogen production features a benign environment that could alleviate catalyst and electrolyzer corrosion but calls for the corresponding high-efficiency and earth-abundant hydrogen evolution reaction (HER) catalysts. Herein, we first designed a series of metal oxides decorated on Ni as the model catalysts and found a volcano-shaped relationship between the Lewis acidity of Ni/metal oxides and HER activity in neutral media. The Ni/ZnO with the optimum Lewis acidity could balance water dissociation and hydroxyl desorption, thereby greatly boosting the HER. On the basis of this finding, we further in situ grew the Ni/ZnO heterostructure on a three-dimensional conductive support. The resulting catalyst requires overpotentials of merely 34 and 194 mV to deliver the current densities of 10 and 200 mA cm –2 , respectively, and can stably operate at these current densities for 2000 h in 1 M phosphate buffer solution (pH 7), representing the most active and durable HER catalyst in neutral electrolyte reported thus far. Our work provides an effective design scheme for low-cost and high-performance neutral HER catalysts.}, archive = {J_JACS}, author = {Lin-Lin Wang and Xiao-Ran Wang and Hong-Juan Wang and Chong Zhang and Jing-Jing Li and Guo-Jin Feng and Xuan-Xuan Cheng and Xue-Rong Qin and Zi-You Yu and Tong-Bu Lu}, doi = {10.1021/jacs.4c16596}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7555--7563}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailoring lewis acidity of metal oxides on nickel to boost electrocatalytic hydrogen evolution in neutral electrolyte}, volume = {147}, year = {2025}, }
• (2025). DNA framework-enabled ocular barrier penetration for microinvasive antiangiogenic therapy. JACS, 147(9), 7545--7554. (www)

  @article{ , abstract = {Therapeutic aptamers targeting vascular endothelial growth factor A (VEGFA) have advanced the development of antiangiogenic drugs for treating choroidal neovascularization (CNV) diseases. However, despite FDA approval for use in neovascular age-related macular degeneration (nAMD), the effective in vivo delivery of therapeutic aptamers is hindered by ocular barriers and rapid degradation in biofluids. Here, we demonstrated a microinvasive delivery of VEGFA-targeted aptamers to the ocular fundus using tetrahedral framework nucleic acids (tFNAs). Upon incorporating anti-VEGFA aptamers to the tFNAs (apt-tFNA), we interrogated their penetration across the outer blood–retinal barrier (oBRB) to the innermost retinal in the eyeball, while maintaining their structural integrity. In addition, the apt-tFNA showed superior efficacy in inhibiting vascular proliferation and migration by neutralizing VEGFA. Furthermore, in a laser-induced CNV mouse model, subconjunctival injection of apt-tFNA exhibited comparable antiangiogenic efficacy to intravitreal ranibizumab, a monoclonal antibody fragment. These findings suggest that FNAs can effectively deliver therapeutic aptamers to the ocular fundus without compromising their antiangiogenic properties, highlighting their potential for microinvasive and feasible periocular administration in treating neovascular ophthalmic diseases.}, archive = {J_JACS}, author = {Ruobing Wang and Yanhan Liu and Yuelu Zhang and Qiuxue Yi and Wenjuan Xiao and Tianqin Wang and Qi Chen and Jiayang Xiang and Lu Song and Chunhong Li and Fan Li and Lin Liu and Qian Li and Chunhai Fan and Xiuhai Mao and Xiaolei Zuo}, doi = {10.1021/jacs.4c16529}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7545--7554}, shortjournal = {J. Am. Chem. Soc.}, title = {DNA framework-enabled ocular barrier penetration for microinvasive antiangiogenic therapy}, volume = {147}, year = {2025}, }
• (2025). Ligand-enabled selective coupling of MIDA boronates to dehydroalanine-containing peptides and proteins. JACS, 147(9), 7533--7544. (www)

  @article{ , abstract = {α,β-dehydroalanine (ΔAla) is a uniquely reactive nonproteinogenic amino acid often employed for the late-stage functionalization of peptides, natural products ( NP s), and proteins. The modification of ΔAla is a powerful method for the semisynthetic engineering of NPs and for post-translational protein mutagenesis. Numerous enabling ΔAla modification techniques have been developed over the years, but most state-of-the-art approaches furnish product mixtures detrimental in many applications. Here, we report a Pd(II)-mediated coupling reaction between aryl N -methylimidodiacetic acid boronates and ΔAla-containing peptides and proteins which yields Δ z Phe coupling products with high selectivity. The coupling proceeds in water under ambient conditions (37 °C, <24 h) and without the exclusion of oxygen using fully unprotected substrates. The speed and high selectivity of the reaction is enabled by the use of N , N ′-ethylene-bis- L threonine as a Pd(II) ligand. We utilize this chemistry to selectively functionalize a variety of oligopeptides, NP-like compounds, and intact proteins. Finally, we show that the coupling reaction can be readily adapted to modify in vitro translated peptides by devising a platform for the chemoribosomal synthesis of Δ z Phe-containing structures. Altogether, our chemistry provides a powerful tool for the selective late-stage functionalization of ΔAla in peptides and proteins.}, archive = {J_JACS}, author = {Alexander A. Vinogradov and Shih-Yu Pan and Hiroaki Suga}, doi = {10.1021/jacs.4c16525}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7533--7544}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand-enabled selective coupling of MIDA boronates to dehydroalanine-containing peptides and proteins}, volume = {147}, year = {2025}, }
• (2025). Synthesis of non-c2-symmetric biaryldiols via organo-electro catalyzed Aryl–Aryl dehydrogenative cross-coupling. JACS, 147(9), 7524--7532. (www)

  @article{ , abstract = {Despite a few successful examples, controlling the enantioselectivity in the asymmetric synthesis of non- C 2 -symmetric biaryldiols has long been challenging. To address the issues of enantioselectivity and regioselectivity, we introduced a novel organoelectrocatalytic strategy enabling asymmetric aryl–aryl dehydrogenative cross-coupling reactions. Using this approach, valuable non- C 2 -symmetric biaryldiols were obtained in up to 95% yields and 97% enantiomeric excesses ( ee s), and these compounds could be further applied as versatile ligands in asymmetric reactions. Detailed mechanistic studies supported a sequential diradical cross-coupling followed by a central-to-axial chirality conversion pathway.}, archive = {J_JACS}, author = {Dingguo Song and Weiwei Huang and Wenji Zhang and Changdi Zheng and Yuhua Chen and Jiayang Lv and Cunwei Zheng and Weihui Zhong and Fei Ling}, doi = {10.1021/jacs.4c16426}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7524--7532}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of non-c2-symmetric biaryldiols via organo-electro catalyzed Aryl–Aryl dehydrogenative cross-coupling}, volume = {147}, year = {2025}, }
• (2025). Discovery of cysteine carboxyalkylations by real-time isotopic signature targeted profiling. JACS, 147(9), 7513--7523. (www)

  @article{ , abstract = {Data-dependent acquisition (DDA) is widely applied in shotgun proteomics. However, restricted by the scanning speed of mass spectrometry (MS) instruments, it remains challenging for DDA to directly detect peptides with low abundance. Herein, we developed a real-time targeted MS data acquisition method, “isoSTAR”, which identifies target peptides by their unique isotopic signatures during the stage of full-MS scanning and subjects them to targeted MS/MS scans immediately. The method showed dramatic improvement in sensitivity in identifying target peptides with low abundance compared to traditional MS acquisition methods. Using this method, we discovered a series of carboxyalkylations on cysteines during fatty acid metabolism and verified their modification structures using synthetic peptide standards. We envision that isoSTAR will become a powerful and versatile tool to enhance shotgun proteomics applications in profiling protein-centric modifications.}, archive = {J_JACS}, author = {Guogeng Jia and Yicheng Liu and Tianyu Feng and Zixuan Zhang and Huan Tang and Fan Yang and Ziyao Tang and Weidi Xiao and Ying Chen and Jinjun Gao and Chu Wang}, doi = {10.1021/jacs.4c16183}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7513--7523}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of cysteine carboxyalkylations by real-time isotopic signature targeted profiling}, volume = {147}, year = {2025}, }
• (2025). From magic size to atomic precision: Facile synthesis of a CdTe semiconductor nanocluster. JACS, 147(9), 7507--7512. (www)

  @article{ , abstract = {Facile synthesis of atomically precise semiconductor nanoclusters remains an important challenge, especially for those with heavier chalcogens. Combining coordination and colloidal methods, we developed a simple approach for synthesizing an atomically precise CdTe nanocluster with high purity and stability. Specifically, a precise cadmium–thiolate compound, [Cd 4 (SR) 9 ] n , was reacted with a facile phosphine telluride (TePR 3 ) precursor to produce a CdTe magic-sized cluster with a distinct absorption peak at 377 nm and a narrow linewidth of 20 nm. X-ray crystallography reveals the cluster is Cd 32 Te 14 (SR) 36 (PR 3 ) 4 , a homologue of Cd 32 S 14 and Cd 32 Se 14 reported about three decades ago, thus filling the missing link in this family. The cluster features a zincblende core in a truncated tetrahedron shape. While the core is achiral, chirality emerges from the rotational stacking of surface ligands. The left and right enantiomers self-assemble into a highly ordered, atomically coherent cubic superlattice, leading to a rare racemic crystal coined as “kryptoracemate.” This method provides an accessible platform for further atomic engineering of CdTe and related nanoclusters toward their target applications.}, archive = {J_JACS}, author = {Saryvoudh A. Mech and Joshua O. Gibson and Fuyan Ma and Lukasz M. Dobrzycki and Chenjie Zeng}, doi = {10.1021/jacs.4c16188}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7507--7512}, shortjournal = {J. Am. Chem. Soc.}, title = {From magic size to atomic precision: Facile synthesis of a CdTe semiconductor nanocluster}, volume = {147}, year = {2025}, }
• (2025). Excited state covalency, dynamics, and photochemistry of square planar ni-thiolate complexes revealed by ultrafast X-ray absorption. JACS, 147(9), 7496--7506. (www)

  @article{ , abstract = {Highly covalent Ni bis(dithiolene) and related complexes provide an ideal platform for investigating the effects of metal–ligand orbital hybridization on excited state character and dynamics. In particular, we focus on the ligand field excited states that dominate the photophysics of first-row transition metal complexes. We investigate if they can be significantly delocalized off the metal center, possibly yielding photochemical reactivity more similar to charge transfer excited states than metal-centered ligand field excited states. Here, [Ni(mpo) 2 ] (mpo = 2-mercaptopyridine- N -oxide) provides a representative example for the larger chemical class and is an active electro- and photocatalyst for proton reduction. A detailed characterization of the excited state electronic structure, dynamics, and photochemistry of [Ni(mpo) 2 ] is presented based on ultrafast transient X-ray absorption spectroscopy at the Ni and S 1s core absorption K-edges. By comparing the ultrafast Ni K-edge absorption to ab initio calculations, we identify an excited state relaxation mechanism where an initial ligand-to-metal charge transfer excitation results in both excited state electron transfer (generating a catalytically relevant reduced photoproduct [Ni(mpo) 2 ] − ) and relaxation to a pseudotetrahedral triplet ligand field excited state. From the ultrafast S K-edge absorption, the ligand field excited state is found to be highly delocalized onto the thiolate ligands, and a tetrahedral structural distortion is shown to substantially influence the degree of delocalization. The results identify a significant structural coordinate to target when aiming to control the excited state covalency in square planar complexes.}, archive = {J_JACS}, author = {Hyeongtaek Lim and Xinzheng Yang and Christopher B. Larsen and Kathryn Ledbetter and Marija R. Zoric and Sumana L. Raj and Gaurav Kumar and Natalia Powers-Riggs and Matthias C. Hoffmann and Matthieu Chollet and Leland B. Gee and Tim B. van Driel and Roberto Alonso-Mori and Victoria Kabanova and Abdullah Kahraman and Philip J. M. Johnson and Claudio Cirelli and Camila Bacellar and Kelly J. Gaffney and Xiaosong Li and Amy A. Cordones}, doi = {10.1021/jacs.4c16212}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7496--7506}, shortjournal = {J. Am. Chem. Soc.}, title = {Excited state covalency, dynamics, and photochemistry of square planar ni-thiolate complexes revealed by ultrafast X-ray absorption}, volume = {147}, year = {2025}, }
• (2025). Meta-nitration of pyridines and quinolines through oxazino azines. JACS, 147(9), 7485--7495. (www)

  @article{ , abstract = {meta -Nitration of azines (pyridines and quinolines) serves as a powerful method for the prompt construction and derivatization of several pharmaceuticals, agrochemicals, and materials. However, due to the inherent electronic properties of pyridines, achieving direct selective meta –C–H nitration under mild conditions has been a long-standing challenge in synthetic chemistry. Currently, there is no adequate strategy for late-stage meta –C–H nitration of pyridine-containing drugs and drug precursors. To address this void, we introduce a practical protocol for the highly regioselective meta -nitration of pyridines using a dearomatization-rearomatization strategy. The introduced method provides a diversification platform for selective nitration at the meta -position of azines via a radical pathway. This mild, open-air, one-pot, scalable, and catalyst-free process is employed for the late-stage meta -nitration of pyridine containing drugs, drug precursors, and ligands using pyridines as the limiting reagents. Consecutive C3 and C5 difunctionalization of pyridines is also achieved with complete regiocontrol relying on sequential addition, which further highlights the potential of the presented work. Additionally, the obtained products could be transformed into meta -amino azine products and other valuable building blocks. Incorporating N-heterocyclic amine structures through amidation into ibuprofen has significantly improved the drug’s clinical success, highlighting the importance of this work.}, archive = {J_JACS}, author = {Kuruva Balanna and Armido Studer}, doi = {10.1021/jacs.4c16051}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7485--7495}, shortjournal = {J. Am. Chem. Soc.}, title = {Meta-nitration of pyridines and quinolines through oxazino azines}, volume = {147}, year = {2025}, }
• (2025). Designing target-specific data sets for regioselectivity predictions on complex substrates. JACS, 147(9), 7476--7484. (www)

  @article{ , abstract = {The development of machine learning models to predict the regioselectivity of C(sp 3 )–H functionalization reactions is reported. A data set for dioxirane oxidations was curated from the literature and used to generate a model to predict the regioselectivity of C–H oxidation. To assess whether smaller, intentionally designed data sets could provide accuracy on complex targets, a series of acquisition functions were developed to select the most informative molecules for the specific target. Active learning-based acquisition functions that leverage predicted reactivity and model uncertainty were found to outperform those based on molecular and site similarity alone. The use of acquisition functions for data set elaboration significantly reduced the number of data points needed to perform accurate prediction, and it was found that smaller, machine-designed data sets can give accurate predictions when larger, randomly selected data sets fail. Finally, the workflow was experimentally validated on five complex substrates and shown to be applicable to predicting the regioselectivity of arene C–H radical borylation. These studies provide a quantitative alternative to the intuitive extrapolation from “model substrates” that is frequently used to estimate reactivity on complex molecules.}, archive = {J_JACS}, author = {Jules Schleinitz and Alba Carretero-Cerdán and Anjali Gurajapu and Yonatan Harnik and Gina Lee and Amitesh Pandey and Anat Milo and Sarah E. Reisman}, doi = {10.1021/jacs.4c15902}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7476--7484}, shortjournal = {J. Am. Chem. Soc.}, title = {Designing target-specific data sets for regioselectivity predictions on complex substrates}, volume = {147}, year = {2025}, }
• (2025). Identification of covalent cyclic peptide inhibitors targeting Protein–Protein interactions using phage display. JACS, 147(9), 7461--7475. (www)

  @article{ , abstract = {Peptide macrocycles are promising therapeutics for a variety of disease indications due to their overall metabolic stability and potential to make highly selective binding interactions with targets. Recent advances in covalent macrocycle peptide discovery, driven by phage and mRNA display methods, have enabled the rapid identification of highly potent and selective molecules from large libraires of diverse macrocycles. However, there are currently limited examples of macrocycles that can be used to disrupt protein–protein interactions and even fewer examples that function by formation of a covalent bond to a target protein. In this work, we describe a directed counter-selection method that enables identification of covalent macrocyclic ligands targeting a protein–protein interaction using a phage display screening platform. This method utilizes binary and ternary screenings of a chemically modified phage display library, employing the stable and weakly reactive aryl fluorosulfate electrophile. We demonstrate the utility of this approach using the SARS-CoV-2 spike-ACE2 protein–protein interaction and identify multiple covalent macrocyclic inhibitors that disrupt this interaction. The resulting compounds displayed antiviral activity against live virus that was irreversible after washout due to the covalent binding mechanism. These results highlight the potential of this screening platform for developing covalent macrocyclic drugs that disrupt protein–protein interactions with long lasting effects.}, archive = {J_JACS}, author = {Sijie Wang and Franco F. Faucher and Matilde Bertolini and Heeyoung Kim and Bingchen Yu and Li Cao and Katharina Roeltgen and Scott Lovell and Varun Shanker and Scott D. Boyd and Lei Wang and Ralf Bartenschlager and Matthew Bogyo}, doi = {10.1021/jacs.4c15843}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7461--7475}, shortjournal = {J. Am. Chem. Soc.}, title = {Identification of covalent cyclic peptide inhibitors targeting Protein–Protein interactions using phage display}, volume = {147}, year = {2025}, }
• (2025). Photoenolization of α,β-unsaturated esters enables enantioselective contra-thermodynamic positional isomerization to α-tertiary β,γ-alkenyl esters. JACS, 147(9), 7452--7460. (www)

  @article{ , abstract = {The enantioselective protonation of prochiral enolates is an ideal and straightforward platform to synthesize stereodefined α-tertiary esters, which are recurring motifs in a myriad of biorelevant molecules and important intermediates thereof. However, this approach remains onerous, particularly when dealing with α-unactivated esters and related acids, as enantioinduction on the nascent nucleophile necessitates peremptory reaction conditions, thus far only achieved via preformed enolates. A complementary and contra-thermodynamic catalytic strategy is herein described, where a transient photoenol, in the form of a ketene hemiacetal, is enantioselectively protonated with a chiral phosphoric acid (CPA). The prochiral photoketene hemiacetals are procured from excited α,β -unsaturated esters, specifically from the Z -geometric isomer through [1,5]-hydride shift as a chemically productive nonradiative relaxation pathway. Tautomerization via formal 1,3-proton transfer in the photoketene hemiacetal with CPA as a proton shuttle delivers α-branched β,γ -alkenyl esters in good to excellent yields and enantioselectivity under mild conditions. Furthermore, the current protocol was coupled to functional group interconversion experiments, as well as in a formal total synthesis of a known marine γ-butyrolactone-type metabolite. Performing the reaction in a continuous photoflow setup also enabled a gram-scale synthesis of a β,γ -alkenyl ester with up to 92% ee .}, archive = {J_JACS}, author = {Kuei-Chen Chang and Hung-Hsuan Chiu and Pin-Gong Huang and Shinje Miñoza and Wen-Hsuan Lee and Prem Kumar Keerthipati and Sasirome Racochote and Yi-Hua Lee and Chih-Ju Chou and Che-Ming Hsu and Che-Wei Chang and Darunee Soorukram and Cheng-chau Chiu and Hsuan-Hung Liao}, doi = {10.1021/jacs.4c15732}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7452--7460}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoenolization of α,β-unsaturated esters enables enantioselective contra-thermodynamic positional isomerization to α-tertiary β,γ-alkenyl esters}, volume = {147}, year = {2025}, }
• (2025). Laser-induced alignment of nanoparticles and macromolecules for coherent-diffractive-imaging applications. JACS, 147(9), 7445--7451. (www)

  @article{ , abstract = {Laser-induced alignment of particles and molecules was long envisioned to support three-dimensional structure determination using “single-molecule diffraction” with X-ray free-electron lasers [PRL 92, 198102 (2004)]. However, the alignment of isolated macromolecules has not yet been demonstrated also because quantitative modeling is very expensive. We computationally demonstrated that the alignment of nanorods and proteins is possible with a standard laser technology. We performed a comprehensive analysis on the dependence of the degree of alignment on molecular properties and experimental details, e.g., particle temperature and laser-pulse energy. Considering the polarizability anisotropy of about 150,000 proteins, our analysis revealed that most of these proteins can be aligned using realistic experimental parameters.}, archive = {J_JACS}, author = {Muhamed Amin and Jean-Michel Hartmann and Amit K. Samanta and Jochen Küpper}, doi = {10.1021/jacs.4c15679}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7445--7451}, shortjournal = {J. Am. Chem. Soc.}, title = {Laser-induced alignment of nanoparticles and macromolecules for coherent-diffractive-imaging applications}, volume = {147}, year = {2025}, }
• (2025). Pyridinium rotor strategy toward a robust photothermal agent for STING activation and multimodal image-guided immunotherapy for triple-negative breast cancer. JACS, 147(9), 7433--7444. (www)

  @article{ , abstract = {The immunosuppressive tumor microenvironment in triple-negative breast cancer could hinder the response to thorough immunotherapy and diminish the antitumor efficacy. Although the STING pathway emerges as a promising target to remedy defects, uncertain drug delivery might lead to off-target inflammatory reactions. Here, we manifest a novel phototheranostic agent with an aggregation-induced emission property that guided the pharmacological activation of a STING agonist for photothermal immunotherapy to create an immunologically “hot” tumor. A pyridinium rotor strategy is proposed to develop a positively charged TBTP-Bz, which is stably coincorporated with a STING agonist MSA-2 into thermal-responsive exosome-liposome hybrid nanoparticles for tumor-targeting delivery. TBTP-Bz exhibits aggregation-enhanced NIR-II emission and a photoacoustic signal, accomplishing real-time tumor tracking. Its photothermal stimulation induces immunogenic cancer cell death and promotes the precise release of MSA-2, thus boosting STING activation and STING-mediated type I interferon production. Significantly, single-dose photoimmunotherapy effectively suppresses abscopal tumor growth and provokes an immune memory effect to inhibit postsurgical recurrent and rechallenged tumors. This demonstrates promising clinical potential for poorly immunogenic breast cancer.}, archive = {J_JACS}, author = {Shipeng Ning and Ping Shangguan and Xinyan Zhu and Xinwen Ou and Kaiyuan Wang and Meng Suo and Hanchen Shen and Xiuxin Lu and Xianqing Wei and Tianfu Zhang and Xiaoyuan Chen and Ben Zhong Tang}, doi = {10.1021/jacs.4c15534}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7433--7444}, shortjournal = {J. Am. Chem. Soc.}, title = {Pyridinium rotor strategy toward a robust photothermal agent for STING activation and multimodal image-guided immunotherapy for triple-negative breast cancer}, volume = {147}, year = {2025}, }
• (2025). Photoactivated multivariate Metal–Organic frameworks for on-demand drug release: The role of Host–Guest interactions. JACS, 147(9), 7423--7432. (www)

  @article{ , abstract = {The development of smart drug delivery vehicles capable of controlled release upon application of an external stimulus is of paramount interest for the next generation of personalized medicine. Herein, we report a series of six multivariate (MTV) MOFs capable of visible light-activated drug delivery. The drug loading capacity and release rates were systematically tuned through variation of the linker ratio between 4,4′-azobenzene dicarboxylic acid (H 2 ABDA) and 4,4′-(diazene-1,2-diyl)bis(3,5-difluorobenzoic acid) (H 2 ABDA(3,5-F)). The drug loading capacity, dictated by host–guest interactions, was thoroughly explored via a combined experimental and computational approach using two model drug or drug-like molecules, 5-fluorouracil (5-FU) and Nile Red. Notably, the loading capacity for 5-FU follows a “Goldilocks” profile with a maximum loading at 33% H 2 ABDA(3,5-F) content. Computational results confirm the existence of a cooperative ligand environment that promotes strong, preferential binding at the tetrahedral/octahedral pore window formed between two H 2 ABDA and one H 2 ABDA(3,5-F). Thus, the MTV approach enhanced capacity over the native 100% H 2 ABDA(3,5-F) and 0% H 2 ABDA(3,5-F) MOFs. In addition to increased loading, the rate of cargo release upon green light excitation also increased as the percentage of H 2 ABDA(3,5-F) in the MOF was raised, reaching a maximum release rate of 0.9 ± 0.1% of total cargo per minute for the MOF containing 100% H 2 ABDA(3,5-F) MOF. The results highlight the promise of MTV MOF design for optimizing drug delivery vehicles with relevant payloads and patient-dictated dosing.}, archive = {J_JACS}, author = {Hannah D. Cornell and Abhishek T. Sose and Stefan Ilic and Sreenivasulu Chinnabattigalla and Naomei E. Lidman and Colleen M. Oldmixon and Xiaozhou Yang and Sanket A. Deshmukh and Amanda J. Morris}, doi = {10.1021/jacs.4c15222}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7423--7432}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoactivated multivariate Metal–Organic frameworks for on-demand drug release: The role of Host–Guest interactions}, volume = {147}, year = {2025}, }
• (2025). Cambered bipyridyl ligand with extended aryl system enables electrochemical reduction of carbon dioxide and bicarbonate by Mn(bpy)(CO)3Br-type catalyst immobilized on carbon nanotubes. JACS, 147(9), 7411--7422. (www)

  @article{ , abstract = {Heterogeneous materials containing molecular catalytic sites show promise for electrocatalytic reduction of CO 2 to energy-enriched carbon products. Interactions between the catalyst and the heterogeneous support increasingly are recognized as important in governing product selectivity and rate. Recent work on Mn(R-bpy)(CO) 3 Br type catalysts immobilized on multiwalled carbon nanotubes (MWCNT) demonstrated control of electrocatalytic behavior with steric modification of the molecular catalyst. Phenyl groups installed in the 4,4′ positions of the bipyridine ligand (ph-bpy) maximized performance through π–π interactions with the MWCNT support. Herein we report the outcome of extending the ligand π system with Mn(nap-bpy)(CO) 3 Br (nap-bpy = 4,4′-di(naphthalen-1-yl)-2,2′-bipyridine) and Mn(pyr-bpy)(CO) 3 Br (pyr-bpy = 4,4′-di(pyren-1-yl)-2,2′-bipyridine) immobilized on MWCNT. We demonstrate exceptional electrocatalysis with Mn(nap-bpy)(CO) 3 Br/MWCNT (FE CO > 92%; J CO = 16.5 mA/cm 2 ) and find that this catalyst electrochemically reduces bicarbonate in the absence of deliberately added CO 2 at a remarkable overall selectivity of >80% for carbon products (FE HCOO – = 52% and FE CO = 29%). We show diminishing returns to simply adding aromatic character to the bipyridyl ligand with Mn(pyr-bpy)(CO) 3 Br/MWCNT and observe a unique cambering of the Mn(nap-bpy)(CO) 3 Br bipyridyl ligand that we believe enables selective catalysis. Mechanistic studies were carried out on Mn(nap-bpy)(CO) 3 Br/MWCNT using a novel thin-film infrared spectroelectrochemical (IR-SEC) technique. These experiments observe the immobilized Mn(nap-bpy)(CO) 3 Br undergo single electron reduction to a Mn-centered radical that binds CO 2 in a reduction-coupled process.}, archive = {J_JACS}, author = {Adam J. Lee and Emile E. DeLuca and Emma B. Kelly and James M. Taylor and Lydia R. Weddle and Hao Chen and Cheolwoo Park and Colin K. Loeb and Thomas Chan and Clifford P. Kubiak}, doi = {10.1021/jacs.4c15547}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7411--7422}, shortjournal = {J. Am. Chem. Soc.}, title = {Cambered bipyridyl ligand with extended aryl system enables electrochemical reduction of carbon dioxide and bicarbonate by Mn(bpy)(CO)3Br-type catalyst immobilized on carbon nanotubes}, volume = {147}, year = {2025}, }
• (2025). Porous and amorphous MnxMo3S13 chalcogel electrode for high-capacity conversion-based lithium-ion batteries. JACS, 147(9), 7400--7410. (www)

  @article{ , abstract = {While Li-ion batteries (LIBs) are a leading energy storage technology, their energy densities are limited by the low capacity of conventional intercalation cathodes, driving interest in high energy-density Li–S batteries that make use of conversion chemistry. Achieving high capacity, reversibility, and cycle stability, and controlling volume changes in conversion batteries during the charge–discharge process, however, remains challenging. Here, we present a porous, amorphous, sulfide-based Mn x Mo 3 S 13 chalcogel, which concurrently offers high capacity and cycle stability. The solution-processable room temperature synthesized Mn x Mo 3 S 13 ( x = 0.25) chalcogel exhibits a local structure that resembles the Mo 3 S 13 cluster with Mn 2+ distributed across the Mo 3 S 13 matrix, as determined by synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS). Ab initio molecular dynamics (AIMD) simulations reveal that Mn 2+ incorporation shortens the polysulfide chain in the gel matrix compared to the Mo 3 S 13 chalcogel, while forming a coordination environment with disulfide groups, analogous to the experimental findings. A Li/Mn 0.25 Mo 3 S 13 half-cell delivers 897 mAh g –1 capacity during the first discharge and retains 571 mAh g –1 capacity after 100 cycles at a C/3 rate. Distribution of relaxation time (DRT) unveils a stable solid–electrolyte interphase (SEI) formation upon cycling that enables charge–discharge reversibility. Here, the enhanced capacity retention and cycle stability compared to those of the Li/Mo 3 S 13 cell are attributed to the reduced dissolution of active mass into the electrolyte, facilitated by the formation of shorter polysulfide chains within the Mn 0.25 Mo 3 S 13 structure and the strong affinity of Lewis-acidic Mn 2+ for polysulfide anions generated during the charge–discharge process of the Li/Mn 0.25 Mo 3 S 13 cell. Thus, this work illustrates a design principle of material for high-capacity and cycle-stable Li-metal sulfide batteries.}, archive = {J_JACS}, author = {Taohedul Islam and Sahar Bayat and Matthew A. Wright and Subrata Chandra Roy and Conrad Sawicki and Carrie L. Donley and Amar S. Kumbhar and Roman Chernikov and Misganaw Adigo Weret and Kamila M. Wiaderek and Chad Risko and Ruhul Amin and Saiful M. Islam}, doi = {10.1021/jacs.4c15552}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7400--7410}, shortjournal = {J. Am. Chem. Soc.}, title = {Porous and amorphous MnxMo3S13 chalcogel electrode for high-capacity conversion-based lithium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Promoting C–F bond activation for perfluorinated compounds decomposition via atomically synergistic lewis and brønsted acid sites. JACS, 147(9), 7391--7399. (www)

  @article{ , abstract = {Catalytic hydrolysis is a sustainable method for the degradation of perfluorinated compounds (PFCs) but is challenged by the high reaction temperatures required to cleave strong C–F bonds. Herein, we developed an innovative C–F activation strategy by constructing synergistic Lewis and Brønsted acid pairs over atomically dispersed Zn–O–Al sites to promote C–F bond activation for decomposition of typical PFCs, CF 4 . Density functional theory (DFT) calculations demonstrate tricoordinated Al (Al III ) sites and Zn–OH functional, respectively, as Lewis and Brønsted acid sites over Zn–O–Al, synergistically enhancing the adsorption and decomposition of CF 4 . X-ray absorption spectroscopy (XAS), pyridine infrared spectroscopy (Py-IR), and ammonia temperature-programmed desorption (NH 3 -TPD) verified the presence of both Al III and Zn–OH on the atomically dispersed Zn–O–Al sites. CF 4 -TPD and in situ infrared spectroscopy confirmed that the Zn–O–Al sites facilitate CF 4 adsorption and C–F bond activation. As a result, the Zn–O–Al sites with synergistic Lewis and Brønsted acid pairs achieved 100% CF 4 decomposition at a low temperature of 560 °C and demonstrated outstanding stability for more than 250 h.}, archive = {J_JACS}, author = {Wenjie Luo and Kang Liu and Tao Luo and Junwei Fu and Hang Zhang and Chao Ma and Ting-Shan Chan and Cheng-Wei Kao and Zhang Lin and Liyuan Chai and Michelle L. Coote and Min Liu}, doi = {10.1021/jacs.4c15280}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7391--7399}, shortjournal = {J. Am. Chem. Soc.}, title = {Promoting C–F bond activation for perfluorinated compounds decomposition via atomically synergistic lewis and brønsted acid sites}, volume = {147}, year = {2025}, }
• (2025). Weakly bound but strongly interacting: The structures, stabilities, and dynamics of Osmium(II) ethane, propane, and butane complexes. JACS, 147(9), 7377--7390. (www)

  @article{ , abstract = {Low-temperature protonation of the osmium(II) alkyl compounds (C 5 Me 5 )Os(dfmpm)R, where dfmpm = (F 3 C) 2 PCH 2 P(CF 3 ) 2 and R = ethyl, n -propyl, n -butyl, or i -butyl, generates σ-ethane, σ-propane, σ- n -butane, and σ- i -butane complexes. The alkane dissociation barriers are ∼13.2 kcal mol –1 or about 0.5 kcal mol –1 larger than that of the previously described methane complex [(C 5 Me 5 )Os(dfmpm)(CH 4 )] + . The alkane ligands bind to osmium through one methyl group, which exchanges slowly with the unbound terminal methyl group(s). Within the bound methyl group, one bridging hydrogen atom interacts directly with osmium; it exchanges rapidly with the other two methyl C–H bonds at a rate consistent with a slightly hindered C–C bond rotation. The large difference in 1 J CH between the bridging (75 Hz) and terminal (142 Hz) C–H sites is consistent with the view that the 16-electron [(C 5 Me 5 )Os(dfmpm)] + fragment has partially abstracted a hydride group (H – ) from the alkane, which confers carbocation (sp 2 ) character to the CH 2 R portion of the Os–H–CH 2 R unit. The extent of this distortion and the overall strength of the metal-alkane interaction are correlated with the alkane C–H orbital energies in a manner consistent with covalent metal–ligand bonding. Whereas most ligands can bind to metals with little structural reorganization, an alkane must undergo a significant structural change─weakening of a C–H bond─to become a sufficiently good donor and acceptor to bind to a metal. Collectively, these results show that the binding energies of alkane ligands are small not because the constituent metal–ligand interactions are weak but rather because the reorganization energy needed to form them is large.}, archive = {J_JACS}, author = {Nicolas E. Capra and Brian B. Trinh and Gregory S. Girolami}, doi = {10.1021/jacs.4c13921}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7377--7390}, shortjournal = {J. Am. Chem. Soc.}, title = {Weakly bound but strongly interacting: The structures, stabilities, and dynamics of Osmium(II) ethane, propane, and butane complexes}, volume = {147}, year = {2025}, }
• (2025). Ruthenium(II) polypyridyl complexes containing COUBPY ligands as potent photosensitizers for the efficient phototherapy of hypoxic tumors. JACS, 147(9), 7360--7376. (www)

  @article{ , abstract = {Hypoxia, a hallmark of many solid tumors, is linked to increased cancer aggressiveness, metastasis, and resistance to conventional therapies, leading to poor patient outcomes. This challenges the efficiency of photodynamic therapy (PDT), which relies on the generation of cytotoxic reactive oxygen species (ROS) through the irradiation of a photosensitizer (PS), a process partially dependent on oxygen levels. In this work, we introduce a novel family of potent PSs based on ruthenium(II) polypyridyl complexes with 2,2′-bipyridyl ligands derived from COUPY coumarins, termed COUBPYs. Ru-COUBPY complexes exhibit outstanding in vitro cytotoxicity against CT-26 cancer cells when irradiated with light within the phototherapeutic window, achieving nanomolar potency in both normoxic and hypoxic conditions while remaining nontoxic in the dark, leading to impressive phototoxic indices (>30,000). Their ability to generate both Type I and Type II ROS underpins their exceptional PDT efficiency. The lead compound of this study, SCV49 , shows a favorable in vivo pharmacokinetic profile, excellent toxicological tolerability, and potent tumor growth inhibition in mice bearing subcutaneous CT-26 tumors at doses as low as 3 mg/kg upon irradiation with deep-red light (660 nm). These results allow us to propose SCV49 as a strong candidate for further preclinical development, particularly for treating large hypoxic solid tumors.}, archive = {J_JACS}, author = {Diego Abad-Montero and Albert Gandioso and Eduardo Izquierdo-García and Sergi Chumillas and Anna Rovira and Manel Bosch and Mireia Jordà-Redondo and Davor Castaño and Joaquín Bonelli and Valentin V. Novikov and Alba Deyà and José Luis Hernández and Jorge Galino and Marta E. Alberto and Antonio Francés-Monerris and Santi Nonell and Gilles Gasser and Vicente Marchán}, doi = {10.1021/jacs.4c15036}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7360--7376}, shortjournal = {J. Am. Chem. Soc.}, title = {Ruthenium(II) polypyridyl complexes containing COUBPY ligands as potent photosensitizers for the efficient phototherapy of hypoxic tumors}, volume = {147}, year = {2025}, }
• (2025). Differential packing of Cs2Mo6Br14 cluster-based halide in variable diameter carbon nanotubes with elimination and polymerization to 1D [Mo2Br6]x ising model structures by steric confinement. JACS, 147(9), 7345--7359. (www)

  @article{ , abstract = {We present detailed findings on the imaging, structure, and vibrational properties of novel hybrids of the red-emitting octahedral cluster-based compound Cs 2 Mo 6 Br 14 encapsulated within single-walled carbon nanotubes (SWCNTs) of varying diameter. We explore the subtle relationship between the SWCNT internal diameter and Cs 2 Mo 6 Br 14 cluster packing and find a hierarchical relationship between the nature of the cluster packing and a progressive tendency toward formation of one-dimensional (1D) structures as the SWCNT diameter narrows from 24 to 11 Å. As the internal SWCNT van der Waals radius approaches the outside diameter (OD) of the [{Mo 6 II Br 8 i }Br 6 a ] 2– (more simplistically, [Mo 6 III Br 14 ] 2– ) molecular anion species, SWCNT steric confinement causes a compositional elimination and polymerization resulting in the formation of reduced extended [Mo 2 III Br 6 ] x nanoribbons which approximate 1D Ising model structures. Our experimental results, obtained through high-resolution transmission electron microscopy and Raman spectroscopy, are supplemented by density functional theory (DFT) calculations.}, archive = {J_JACS}, author = {Eric Faulques and Victor G. Ivanov and Stéphane Cordier and Reza J. Kashtiban and Yann Molard and Jean-Luc Duvail and Nataliya Kalashnyk and Jeremy Sloan}, doi = {10.1021/jacs.4c14883}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7345--7359}, shortjournal = {J. Am. Chem. Soc.}, title = {Differential packing of Cs2Mo6Br14 cluster-based halide in variable diameter carbon nanotubes with elimination and polymerization to 1D [Mo2Br6]x ising model structures by steric confinement}, volume = {147}, year = {2025}, }
• (2025). High-spin Manganese(V) in an active center analogue of the oxygen-evolving complex. JACS, 147(9), 7336--7344. (www)

  @article{ , abstract = {In a comprehensive investigation of the dinuclear [Mn 2 O 3 ] + cluster, the smallest dimanganese entity with two μ-oxo bridges and a terminal oxo ligand, and a simplified structural model of the active center in the oxygen-evolving complex, we identify antiferromagnetically coupled high-spin manganese centers in very different oxidation states of +2 and +5, but rule out the presence of a manganese(IV)-oxyl species by experimental X-ray absorption and X-ray magnetic circular dichroism spectroscopy combined with multireference calculations. This first identification of a high-spin manganese(V) center in any polynuclear oxidomanganese complex underscores the need for multireference computational methods to describe high-valent oxidomanganese species.}, archive = {J_JACS}, author = {Olesya S. Ablyasova and Mihkel Ugandi and Esma B. Boydas and Mayara da Silva Santos and Max Flach and Vicente Zamudio-Bayer and Michael Roemelt and J. Tobias Lau and Konstantin Hirsch}, doi = {10.1021/jacs.4c14543}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7336--7344}, shortjournal = {J. Am. Chem. Soc.}, title = {High-spin Manganese(V) in an active center analogue of the oxygen-evolving complex}, volume = {147}, year = {2025}, }
• (2025). Engineering helical chirality in metal-coordinated cyclodextrin nanochannels. JACS, 147(9), 7325--7335. (www)

  @article{ , abstract = {Helicates are a defining element of DNAs and proteins, with functions that are critical to a variety of biological processes. Cyclodextrins are promising candidates for forging multiple-stranded helicates with well-defined helicity, but a lack of available tools has precluded the construction of artificial helical nanochannels with a controllable geometry and helicity from these widely available chiral building blocks. Herein, we disclose a family of Ag 6 L 2 helical nanochannels that can be readily assembled from α-cyclodextrin-derived ligands through coordination between pyridinyl groups and Ag + cations. We discovered that the nanochannels exhibit either an M or a P helicity when the Ag + cations adopt a tetrahedral coordination geometry while losing most of their helicity when the Ag + cations are linearly coordinated. Both the geometry and helicity of the nanochannels can be precisely controlled by simply changing the number of methyl groups at the ortho positions of the pyridinyl ligands. The tetracoordinated Ag + cations interconnect the helical nanochannels into an infinite two-dimensional coordinative network characterized by hexagonal tessellation. Theoretical calculations, which reveal lower energies of the helical conformations observed in crystals compared with those of their inverted counterparts, support the experimental results.}, archive = {J_JACS}, author = {Zhiyuan Jiang and Zhi Chen and Xiujun Yu and Shuai Lu and Wenmin Xu and Bo Yu and Charlotte L. Stern and Shu-Yi Li and Yue Zhao and Xinzhi Liu and Yeqiang Han and Shuqi Chen and Kang Cai and Dengke Shen and Kaikai Ma and Xiaopeng Li and Aspen X.-Y. Chen}, doi = {10.1021/jacs.4c14123}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7325--7335}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering helical chirality in metal-coordinated cyclodextrin nanochannels}, volume = {147}, year = {2025}, }
• (2025). Spectroscopic and computational interrogation of a high-valent nickel-dialkyl complex indicates electronic structure asymmetry drives C–C bond formation reactivity. JACS, 147(9), 7317--7324. (www)

  @article{ , abstract = {The study of high-valent organometallic nickel compounds has gained considerable interest recently, primarily driven by the development of nickel-catalyzed alkyl–alkyl cross-coupling reactions that are proposed to employ such high-valent intermediates. In that regard, we have recently reported a formal Ni(III)-dimethyl intermediate supported by the ligand N , N ′, N ″-triisopropyl-1,4,7-triazacyclononane ( i Pr 3 tacn) that can undergo rapid C–C reductive elimination and catalyze alkyl–alkyl Kumada cross-coupling reactions. The bulky nature of this tridentate ligand was suggested to lead to two geometrically and electronically inequivalent alkyl groups bound to the five-coordinate Ni center. Herein, we have employed pulsed electron paramagnetic resonance techniques such as electron nuclear double resonance, hyperfine sublevel correlation, and electron spin echo envelope modulation to provide strong experimental evidence for the geometrically and electronically inequivalent nature of the two methyl groups in which one methyl ligand can be better described as a methyl radical. These experimental results were supported by density functional theory computational methods used to probe the covalent nature of the Ni–C bonds and the formal Ni oxidation state assignment for this catalytically relevant, high-valent Ni intermediate. Moreover, computational investigation of a series of related methyl/alkyl analogs reveals that the radical character of an alkyl group increases for a tertiary vs a secondary vs a primary alkyl group, with direct relevance for alkyl–alkyl cross-coupling catalysis. Overall, this study provides valuable insights into the nature of organometallic Ni-dialkyl species that undergo efficient reductive elimination, likely through an S H 2-type mechanism.}, archive = {J_JACS}, author = {Alina Yerbulekova and Yusuff Moshood and Leonel Griego and Hannah S. Shafaat and Liviu M. Mirica}, doi = {10.1021/jacs.4c14104}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7317--7324}, shortjournal = {J. Am. Chem. Soc.}, title = {Spectroscopic and computational interrogation of a high-valent nickel-dialkyl complex indicates electronic structure asymmetry drives C–C bond formation reactivity}, volume = {147}, year = {2025}, }
• (2025). Profiling proteins involved in peroxynitrite homeostasis using ROS/RNS conditional proteomics. JACS, 147(9), 7305--7316. (www)

  @article{ , abstract = {Peroxynitrite (ONOO – ), the product of the diffusion-controlled reaction of superoxide (O 2 •– ) with nitric oxide (NO • ), plays a crucial role in oxidative and nitrative stress and modulates key physiological processes such as redox signaling. While biological ONOO – is conventionally analyzed using 3-nitrotyrosine antibodies and fluorescent sensors, such probes lack specificity and sensitivity, making high-throughput and comprehensive profiling of ONOO – -associated proteins challenging. In this study, we used a conditional proteomics approach to investigate ONOO – homeostasis by identifying its protein neighbors in cells. We developed Peroxynitrite-responsive protein Labeling reagents ( Porp-L ) and, for the first time, discovered 2,6-dichlorophenol as an ideal moiety that can be selectively and rapidly activated by ONOO – for labeling of proximal proteins. The reaction of Porp-L with ONOO – generated several short-lived reactive intermediates that can modify Tyr, His, and Lys residues on the protein surface. We have demonstrated the Porp-L -based conditional proteomics in immune-stimulated macrophages, which indeed identified proteins known to be involved in the generation and modification of ONOO – and revealed the endoplasmic reticulum (ER) as a ONOO – hot spot. Moreover, we discovered a previously unknown role for Ero1a, an ER-resident protein, in the formation of ONOO – . Overall, Porp-L represent a promising research tool for advancing our understanding of the biological roles of ONOO – .}, archive = {J_JACS}, author = {Hao Zhu and Hiroaki Uno and Kyoichi Matsuba and Itaru Hamachi}, doi = {10.1021/jacs.4c14060}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7305--7316}, shortjournal = {J. Am. Chem. Soc.}, title = {Profiling proteins involved in peroxynitrite homeostasis using ROS/RNS conditional proteomics}, volume = {147}, year = {2025}, }
• (2025). Verdazyl-based radicals for high-field dynamic nuclear polarization NMR. JACS, 147(9), 7293--7304. (www)

  @article{ , abstract = {High-field dynamic nuclear polarization nuclear magnetic resonance (DNP NMR) spectroscopy transfers polarization from unpaired electrons in polarizing agents to nuclei of interest to boost NMR sensitivity. Verdazyl biradicals are a promising choice as polarizing agents because they have been found to generate narrower electron paramagnetic resonance (EPR) signals compared to nitroxide biradicals; an advantageous characteristic for high-field DNP when operating above 400 MHz/263 GHz. The use of verdazyl radicals as DNP polarizing agents has been very limited to date, yet, recent numerical simulations have predicted that verdazyl-nitroxide hybrid biradicals could be more effective polarizing agents than nitroxide-nitroxide biradicals. Herein, the syntheses of a series of verdazyl mono- and biradicals, as well as verdazyl-nitroxide biradicals are described. These radicals were examined in high-field DNP NMR experiments (600 MHz/395 GHz), by measuring 1 H signal enhancements directly and through 13 C{ 1 H} cross-polarization experiments. X-band EPR, 1 H DNP field profiles, and experiments to determine the nuclear build-up times were performed for verdazyl-nitroxide biradicals VerTEMPol and VerTEKol . These hybrid biradicals provide enhancements of up to 100-fold increased signal intensities (i.e., representing >10 4 -fold time savings), approximately four times higher than that of the nitroxide biradical TEKPol , a commonly used polarizing agent in the field.}, archive = {J_JACS}, author = {Jakob A. Meckes and Zachary W. Schroeder and Diganta Sarkar and Riley W. Hooper and Clara E. Faraday-Smith and Alex Brown and Rik R. Tykwinski and Vladimir K. Michaelis}, doi = {10.1021/jacs.4c13374}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7293--7304}, shortjournal = {J. Am. Chem. Soc.}, title = {Verdazyl-based radicals for high-field dynamic nuclear polarization NMR}, volume = {147}, year = {2025}, }
• (2025). Asymmetric radical cyclopropanation of α,β-unsaturated amides with α-boryl and α-silyl dibromomethanes via Cr(II)-based metalloradical catalysis. JACS, 147(9), 7282--7292. (www)

  @article{ , abstract = {Transition-metal-catalyzed asymmetric carbene-transfer reactions represent a powerful strategy for synthesizing chiral cyclopropanes. However, current methods predominantly rely on stabilized carbene-bearing α –π-conjugated groups, restricting access to less stabilized carbenes, such as α -silyl and α -boryl carbenes. Herein, we present an unprecedented Cr(II)-based metalloradical system for the asymmetric cyclopropanation of α , β -unsaturated amides with α -boryl and α -silyl dibromomethanes in the presence of Mn as the reducing agent. Employing a chiral chromium complex, the reaction proceeds under mild conditions, yielding cyclopropanes with three contiguous stereocenters in high diastereo- and enantioselectivities. This method features a Cr-catalyzed radical-based stepwise cyclopropanation mechanism. The broad substrate scope, encompassing various α , β -unsaturated amides, demonstrates the protocol’s versatility and robustness. Mechanistic insights, supported by experimental and computational studies, suggest the formation of α -Cr(III)-alkyl radical intermediates, delineating a pathway distinct from that of classical concerted cyclopropanations. This approach provides a powerful tool for synthesizing highly functionalized cyclopropanes, offering high potential for applications in drug discovery and development.}, archive = {J_JACS}, author = {Xinyu Wang and Zhaoxin Shi and Mingrui Xu and Xiaoyu Lin and Zhaobin Wang}, doi = {10.1021/jacs.4c13269}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7282--7292}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric radical cyclopropanation of α,β-unsaturated amides with α-boryl and α-silyl dibromomethanes via Cr(II)-based metalloradical catalysis}, volume = {147}, year = {2025}, }
• (2025). Intermolecular N–N coupling of a dinitrosyl iron complex induced by hydrogen bond donors in the secondary coordination sphere. JACS, 147(9), 7274--7281. (www)

  @article{ , abstract = {The intermolecular N–N coupling of NO in a dinitrosyl iron complex (DNIC) induced by hydrogen bond donors in the secondary coordination sphere to form N 2 O is reported. A family of complexes containing pendant anilines in the secondary coordination sphere were synthesized and characterized. Reduction of the {Fe(NO) 2 } 9 complex [Fe( PhNH PDI)(NO) 2 ][BPh 4 ] ( 3 ) to the {Fe(NO) 2 } 10 Fe( PhNH PDI)(NO) 2 ( 4 ) results in intermolecular N–N coupling to form N 2 O. Similar reactions of the control {Fe(NO) 2 } 9 complex [Fe( PhNMe PDI)(NO) 2 ][BPh 4 ] ( 7 ), which does not have H-bonding groups in the secondary coordination sphere, do not result in N 2 O formation. The hydrogen bonding capabilities of the complexes were explored spectroscopically and computationally.}, archive = {J_JACS}, author = {Kayla M. Fugami and Gabriel S. Black and Tim Kowalczyk and Takele Seda and John D. Gilbertson}, doi = {10.1021/jacs.4c12787}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7274--7281}, shortjournal = {J. Am. Chem. Soc.}, title = {Intermolecular N–N coupling of a dinitrosyl iron complex induced by hydrogen bond donors in the secondary coordination sphere}, volume = {147}, year = {2025}, }
• (2025). Unraveling hydration shell dynamics and viscosity effects around cyanamide probes via 2D IR spectroscopy. JACS, 147(9), 7264--7273. (www)

  @article{ , abstract = {Hydration dynamics and solvent viscosity play critical roles in the structure and function of biomolecules. An overwhelming body of evidence suggests that protein and membrane fluctuations are closely linked to solvent fluctuations. While extensive research exists on the use of vibrational probes to detect local interactions and solvent dynamics, fewer studies have explored how the behavior of these reporters changes in response to bulk viscosity. To address this gap, two-dimensional infrared spectroscopy (2D IR) was employed in this study to investigate the ultrafast hydration dynamics around a cyanamide (NCN) probe attached to a nucleoside, deoxycytidine, in aqueous solutions with varying glycerol content. The use of a small vibrational probe on a targeted nucleic acid offers the potential to capture more localized hydration dynamics than alternative methods. The time scales for the frequency correlation decays were found to increase linearly with bulk viscosity, ranging from 0.9 to 11.4 ps over viscosities of 0.96–49.1 cP. Additionally, molecular dynamics (MD) simulations were performed to model the local hydration dynamics around the NCN probe. Interestingly, increasing the glycerol content did not significantly alter the hydration of the deoxycytidine. The MD simulations further suggested that the NCN probe’s frequency fluctuations were primarily influenced by the dynamics of water in the second solvation shell. Cage correlation functions, which measure the movement of water molecules in and out of the second solvation shell, exhibited decays that closely matched those of the frequency-fluctuation correlation function (FFCF). These findings offer new insights into hydration dynamics and the impact of viscosity on biological systems.}, archive = {J_JACS}, author = {Christopher J. Mallon and Majid Hassani and Ellia H. Osofsky and Savannah B. Familo and Edward E. Fenlon and Matthew J. Tucker}, doi = {10.1021/jacs.4c12716}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7264--7273}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling hydration shell dynamics and viscosity effects around cyanamide probes via 2D IR spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Non-van-der-waals oriented two-dimensional UiO-66 films by rapid aqueous synthesis at room temperature. JACS, 147(9), 7255--7263. (www)

  @article{ , abstract = {The synthesis of MOFs in a two-dimensional (2D) film morphology is attractive for several applications including molecular and ionic separation. However, 2D MOFs have only been reported from structures that crystallize in lamellar morphology, where layers are held together by van der Waals (vdW) interaction. By comparison, UiO-66, one of the most studied MOFs because of its exceptional chemical stability, has only been reported in three-dimensional (3D) morphology. 2D UiO-66 is challenging to obtain given the robust isotropic bonds in its cubic crystal structure. Herein, we report the first synthesis of non-vdW 2D UiO-66-NH 2 by developing crystal growth conditions that promote in-plane growth over out-of-plane growth. Continuous, oriented UiO-66-NH 2 film with thickness tunable in the range of 0.5 to 2 unit cells could be obtained by sustainable, scalable chemistry, which yielded attractive ion–ion selectivity. The preparation of non-vdW 2D MOF is highly attractive to advance the field of MOF films for diverse applications.}, archive = {J_JACS}, author = {Heng-Yu Chi and Shuqing Song and Kangning Zhao and Kuang-Jung Hsu and Qi Liu and Yueqing Shen and Anne Faustine Sido Belin and Arthur Allaire and Ranadip Goswami and Wendy L. Queen and Kumar Varoon Agrawal}, doi = {10.1021/jacs.4c11134}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7255--7263}, shortjournal = {J. Am. Chem. Soc.}, title = {Non-van-der-waals oriented two-dimensional UiO-66 films by rapid aqueous synthesis at room temperature}, volume = {147}, year = {2025}, }
• (2025). Diastereomeric configuration drives an on-surface specific rearrangement into low bandgap non-benzenoid graphene nanoribbons. JACS, 147(9), 7245--7254. (www)

  @article{ , abstract = {Stereochemistry, usually associated with the three-dimensional arrangement of atoms in molecules, is crucial in processes like life functions, drug action, or molecular reactions. This three-dimensionality typically originates from sp 3 hybridization in organic molecules, but it is also present in out-of-plane sp 2 -based molecules as a consequence of helical structures, twisting processes, and/or the presence of nonbenzenoid rings, the latter significantly influencing their global stereochemistry and leading to the emergence of new exotic properties. In this sense, on-surface synthesis methodologies provide the perfect framework for the precise synthesis and characterization of organic systems at the atomic scale, allowing for the accurate assessment of the associated stereochemical effects. In this work, we demonstrate the importance of the initial diastereomeric configuration in the surface-induced skeletal rearrangement of a substituted cyclooctatetraene (COT) moiety–a historical landmark in the understanding of aromaticity–into a cyclopenta[ c , d ]azulene (CPA) one in a chevron-like graphene nanoribbon (GNR). These findings are evidenced by combining bond-resolved scanning tunneling microscopy with theoretical ab initio calculations. Interestingly, the major well-defined product, a CPA chevron-like GNR, exhibits the lowest bandgap reported to date for an all-carbon chevron-like GNR, as evidenced by scanning tunneling spectroscopy measurements. This work paves the way for the rational application of stereochemistry in the on-surface synthesis of novel graphene-based nanostructures.}, archive = {J_JACS}, author = {Federico Villalobos and Jesús I. Mendieta-Moreno and Jorge Lobo-Checa and Sara P. Morcillo and José I. Martínez and José María Gómez-Fernández and Pedro L. de Andres and José A. Martin-Gago and Juan M. Cuerva and Araceli G. Campaña and Carlos Sánchez-Sánchez}, doi = {10.1021/jacs.4c10478}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7245--7254}, shortjournal = {J. Am. Chem. Soc.}, title = {Diastereomeric configuration drives an on-surface specific rearrangement into low bandgap non-benzenoid graphene nanoribbons}, volume = {147}, year = {2025}, }
• (2025). Enantiocomplementary gut bacterial enzymes metabolize dietary polyphenols. JACS, 147(9), 7231--7244. (www)

  @article{ , abstract = {Molybdenum-dependent catechol dehydroxylases in gut Actinobacteria catalyze the removal of para -hydroxyl groups from catechols, a central reaction in the microbial metabolism of polyphenol compounds. However, the substrates of most putative catechol dehydroxylases remain unidentified due to the challenges of obtaining these enzymes from standard heterologous expression systems. In this work, we establish Gordonibacter urolithinfaciens as a versatile bacterial host to express active catechol dehydroxylases. Using this system, we rapidly deorphanize eight previously uncharacterized gut bacterial catechol dehydroxylases that selectively dehydroxylate intermediates in the gut bacterial metabolism of plant-derived catechins and lignans. Unexpectedly, we discover multiple instances of distinct catechol dehydroxylases that have evolved to selectively metabolize individual substrate enantiomers, setting the stage for future efforts to elucidate their mechanisms and evolution. Altogether, these findings greatly increase our knowledge of these metalloenzymes, illustrating the power of bacterial genetics to accelerate enzyme discovery and providing a more complete understanding of transformations relevant to the health benefits of phytochemicals.}, archive = {J_JACS}, author = {Xueyang Dong and Minwoo Bae and Chi Le and Miguel A. Aguilar Ramos and Emily P. Balskus}, doi = {10.1021/jacs.4c09892}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7231--7244}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantiocomplementary gut bacterial enzymes metabolize dietary polyphenols}, volume = {147}, year = {2025}, }
• (2025). Dynamic in vivo mapping of the methylproteome using a chemoenzymatic approach. JACS, 147(9), 7214--7230. (www)

  @article{ , abstract = {Dynamic protein post-translational methylation is essential for cellular function, highlighted by the essential role of methylation in transcriptional regulation and its aberrant dysregulation in diseases, including cancer. This underscores the importance of cataloging the cellular methylproteome. However, comprehensive analysis of the methylproteome remains elusive due to limitations in current enrichment and analysis pipelines. Here, we employ an l -methionine analogue, ProSeMet, that is chemoenzymatically converted to the SAM analogue ProSeAM in cells and in vivo to tag proteins with a biorthogonal alkyne that can be directly detected via liquid chromatography and tandem mass spectrometry (LC-MS/MS), or functionalized for subsequent selective enrichment and LC-MS/MS identification. Without enrichment, we identify known and novel lysine mono-, di-, and tripargylation, histidine propargylation, and arginine propargylation with site-specific resolution on proteins including heat shock protein HSPA8, the translational elongation factor eEF1A1, and the metabolic enzyme phosphoglycerate mutase 1, or PGAM1, for which methylation has been implicated in human disease. With enrichment, we identify 486 proteins known to be methylated and 221 proteins with novel propargylation sites encompassing diverse cellular functions. Systemic ProSeMet delivery in mice propargylates proteins across organ systems with blood–brain barrier penetrance and identifies site-specific propargylation in vivo with LC-MS/MS. Leveraging these pipelines to define the cellular methylproteome may have broad applications for understanding the methylproteome in the context of disease.}, archive = {J_JACS}, author = {Jonathan Farhi and Benjamin Emenike and Richard S. Lee and Kirti Sad and Dorelle V. Fawwal and Christian M. Beusch and Robert B. Jones and Ashish K. Verma and Celina Y. Jones and Maryam Foroozani and Monica Reeves and Kiran K. Parwani and Pritha Bagchi and Roger B. Deal and David J. Katz and Anita H. Corbett and David E. Gordon and Monika Raj and Jennifer M. Spangle}, doi = {10.1021/jacs.4c08175}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7214--7230}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic in vivo mapping of the methylproteome using a chemoenzymatic approach}, volume = {147}, year = {2025}, }
• (2025). Interplay between Jahn–Teller distortions and structural phase transitions in Ruddlesden–Poppers. JACS, 147(9), 7209--7213. (www)

  @article{ , abstract = {The interplay between crystallographic symmetry, structural distortions, and the tolerance factor derived from the isotropic ionic radii of the constituent cations and anions of inorganic perovskites and related materials is a ubiquitous concept in solid-state and materials chemistry. Here we demonstrate a model for the phase transition temperatures associated with these structural distortions in layered perovskites by considering the anisotropy associated with cations, which are susceptible to first-order Jahn–Teller distortions. These symmetry-lowering phase transitions are known to have a significant interplay with superconductivity in the high- T C layered cuprates, and untangling the chemistry that can effectively control them is of the utmost relevance in the search for similar phenomena in the nickelates, the study of which has been greatly stimulated by recent reports of high-pressure superconductivity.}, archive = {J_JACS}, author = {Anna Herlihy and Wei-Tin Chen and Clemens Ritter and Yu-Chun Chuang and Mark S. Senn}, doi = {10.1021/jacs.5c00459}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7209--7213}, shortjournal = {J. Am. Chem. Soc.}, title = {Interplay between Jahn–Teller distortions and structural phase transitions in Ruddlesden–Poppers}, volume = {147}, year = {2025}, }
• (2025). Synthesis and catalytic activity of thorium nitride complex from dinitrogen reduction. JACS, 147(9), 7203--7208. (www)

  @article{ , abstract = {Metal nitride species are recognized as key intermediates in the conversion of dinitrogen (N 2 ) to ammonia (NH 3 ). In this work, we report the isolation of a multimetallic nitride-bridged thorium complex ( 2 ) by completely cleaving the N≡N triple bond of N 2 . The complex was synthesized through the reduction of a thorium precursor, {N[CH 2 CH 2 N–P i Pr 2 ] 3 ThCl} 2 ( 1 ) and chromium dichloride (CrCl 2 ) using potassium graphite (KC 8 ) under an N 2 atmosphere. Isotopic labeling with 15 N 2 confirms that the nitride in complex 2 originates from N 2 . Under ambient conditions, complex 2 exhibits remarkable catalytic activity, converting N 2 to silylamine with yields of up to 9.9 equiv per thorium molecular catalyst. This work not only represents the first isolation of a thorium nitride complex from N 2 reduction but also provides a rare example of N 2 functionalization promoted by an actinide catalyst.}, archive = {J_JACS}, author = {Weiming Sheng and Thayalan Rajeshkumar and Qianyi Zhao and Jin Xie and Laurent Maron and Congqing Zhu}, doi = {10.1021/jacs.4c18519}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7203--7208}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis and catalytic activity of thorium nitride complex from dinitrogen reduction}, volume = {147}, year = {2025}, }
• (2025). Vinylogous anionic ring-opening polymerization of vinylidenecyclopropanes with native C–H bonds as the dormant species. JACS, 147(9), 7196--7202. (www)

  @article{ , abstract = {Since its inception in 2023, the concept of “C–H bonds as the dormant species” to control chain growth has emerged as a promising, though still evolving, strategy for precision polymer synthesis. Beyond offering a simpler polymerization method, this concept is expected to promote unprecedented reaction pathways. In this study, we report the first vinylogous anionic ring-opening polymerization (ROP) of vinylidenecyclopropanes. Cooperative La(OTf) 3 /DBU catalysis, in conjunction with various sp 3 and sp 2 C–H bonds, has streamlined the synthesis of well-defined alkyne polymers, which are amenable to further chemical modifications. Control experiments and density functional theory (DFT) calculations provide insights into the origin of selectivity and the role of dormant C–H bonds in the reversible-deactivation equilibrium.}, archive = {J_JACS}, author = {Shuai Tang and Xuhui Liang and Yuan Li and Yang-Yang Li and Gen Luo and Jinming Hu and Dian-Feng Chen}, doi = {10.1021/jacs.4c17911}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7196--7202}, shortjournal = {J. Am. Chem. Soc.}, title = {Vinylogous anionic ring-opening polymerization of vinylidenecyclopropanes with native C–H bonds as the dormant species}, volume = {147}, year = {2025}, }
• (2025). Rapid microwave-assisted chemical recycling of poly(p-phenylene terephthalamide). JACS, 147(9), 7191--7195. (www)

  @article{ , abstract = {Back-to-monomer chemical recycling of polymers is crucial in achieving a circular plastics economy. Herein, we report the rapid microwave-assisted depolymerization of poly( p -phenylene terephthalamide) (PPTA), also known as Twaron or Kevlar. The alkaline hydrolysis of PPTA was conducted in a microwave reactor at temperatures ranging from 240 to 260 °C with reaction times of 1–15 min. The highest conversion (96%) was found after 15 min at 260 °C. The resulting monomers terephthalic acid and p -phenylenediamine were successfully purified (>99% purity) in good yields using extraction and precipitation methods. This work presents the fastest depolymerization of PPTA to date under relatively mild conditions, thereby encouraging a circular value chain for PPTA.}, archive = {J_JACS}, author = {Joël Benninga and Bert Gebben and Rudy Folkersma and Vincent S. D. Voet and Katja Loos}, doi = {10.1021/jacs.4c17791}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7191--7195}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid microwave-assisted chemical recycling of poly(p-phenylene terephthalamide)}, volume = {147}, year = {2025}, }
• (2025). Amplifying magnetic field effects on upconversion emission via molecular qubit-driven Triplet–Triplet annihilation. JACS, 147(9), 7187--7190. (www)

  @article{ , abstract = {Triplet–triplet annihilation (TTA) enables photon upconversion by combining two lower-energy triplet excitons to produce a higher-energy singlet exciton. This mechanism enhances light-harvesting efficiency for solar energy conversion and enables the use of lower-energy photons in bioimaging and photoredox catalysis applications. The magnetic modulation of such high-energy excitons presents an exciting opportunity to develop molecular quantum information technologies. While the spin dynamics of triplet exciton pairs are sensitive to external magnetic fields, the magnetic field effects (MFEs) associated with these pairs are generally limited by spin statistics to at most 10% at low fields (<1 T), making them challenging to apply in technological advancements. In contrast, MFEs on spin-correlated radical pairs (SCRPs) can be significantly greater, surpassing those on triplet pairs. By using SCRPs-based molecular qubits as triplet sensitizers in the sensitized TTA scheme, we can magnetically modulate TTA and consequently, the delayed fluorescence of annihilators. In our current system, we have achieved more than 70% magnetic modulation of delayed fluorescence, effectively harnessing and even amplifying magnetic modulation within SCRPs to influence high-energy excitons. This work opens new opportunities for advancing spin-controlled chemical reactions and molecular quantum information technologies.}, archive = {J_JACS}, author = {Neo Lin and Tomoyasu Mani}, doi = {10.1021/jacs.4c16922}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7187--7190}, shortjournal = {J. Am. Chem. Soc.}, title = {Amplifying magnetic field effects on upconversion emission via molecular qubit-driven Triplet–Triplet annihilation}, volume = {147}, year = {2025}, }
• (2025). Irreversible deactivation pathways in Ni(II)-catalyzed nonalternating Ethylene–Carbon monoxide copolymerization. JACS, 147(9), 7182--7186. (www)

  @article{ , abstract = {Endowing polyethylenes with photodegradability via incorporation of low densities of in-chain keto units could reduce the problematic environmental persistency of littered polymer waste. A breakthrough enabling such materials is the recent finding of nickel catalyzed nonalternating copolymerization of ethylene–carbon monoxide. We reveal irreversible catalyst deactivation pathways operative in this reaction. Reductive elimination of the common phosphinephenolate Ni(II) motif occurs with the acyl intermediates formed upon incorporation of carbon monoxide into the growing chain, as observed by low temperature NMR spectroscopy and single crystal X-ray crystallography of the isolated product. Further, we show that such decomposition pathways are generally relevant during ethylene–carbon monoxide copolymerizations under pressure reactor conditions. These findings guide the development of more stable and productive polymerization catalysts to enable the production of environmentally benign polyethylenes.}, archive = {J_JACS}, author = {Lukas Odenwald and Lukas Wursthorn and Stefan Mecking}, doi = {10.1021/jacs.4c16468}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7182--7186}, shortjournal = {J. Am. Chem. Soc.}, title = {Irreversible deactivation pathways in Ni(II)-catalyzed nonalternating Ethylene–Carbon monoxide copolymerization}, volume = {147}, year = {2025}, }
• (2025). Intracellular photocatalytic NADH/NAD(P)H oxidation for cancer drug development. JACS, 147(9), 7161--7181. (www)

  @article{ , abstract = {Photocatalytic cancer therapy (PCT) has emerged as a cutting-edge anticancer mechanism of action, harnessing light energy to mediate the catalytic oxidation of intracellular substrates. PCT is of significant current importance due to its potential to address the limitations of conventional chemotherapy, particularly drug resistance and side effects. This approach offers a noninvasive, targeted cancer treatment option by utilizing metal-based photocatalysts to induce redox and metabolic disorders within cancer cells. The photocatalysts disrupt the cancer cell metabolism by converting NADH/NAD(P)H to NAD + /NAD(P) + via catalytic photoredox processes, altering intracellular NAD + /NADH or NAD(P) + /NAD(P)H ratios, which are crucial for cellular metabolism. Ir(III), Ru(II), Re(I), and Os(II) photocatalysts demonstrated promising PCT efficacy. Despite these developments, gaps remain in the literature for translating this new anticancer mechanism into clinical trials. This Perspective critically examines the developments in this research area and provides future directions for designing efficient photocatalysts for PCT.}, archive = {J_JACS}, author = {Ashish Kumar Yadav and Rajesh Kushwaha and Arif Ali Mandal and Apurba Mandal and Samya Banerjee}, doi = {10.1021/jacs.4c18328}, journal = {Journal of the American Chemical Society}, month = {3}, number = {9}, pages = {7161--7181}, shortjournal = {J. Am. Chem. Soc.}, title = {Intracellular photocatalytic NADH/NAD(P)H oxidation for cancer drug development}, volume = {147}, year = {2025}, }
• (2025). Retraction of “Cooperative Fe/Co-catalyzed remote desaturation for the synthesis of unsaturated amide derivatives”. JACS, 147(8), 7160. (www)

  @article{ , archive = {J_JACS}, author = {Yanjun Wan and Emmanuel Ramírez and Ayzia Ford and Harriet K. Zhang and Jack R. Norton and Gang Li}, doi = {10.1021/jacs.4c18218}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7160}, shortjournal = {J. Am. Chem. Soc.}, title = {Retraction of “Cooperative Fe/Co-catalyzed remote desaturation for the synthesis of unsaturated amide derivatives”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Air and thermally stable cyclic (Alkyl)(amino)carbene ruthenium complexes for efficient ring expansion metathesis polymerization”. JACS, 147(8), 7159. (www)

  @article{ , archive = {J_JACS}, author = {Minjae Jang and Eunsong Jung and Yongkang Yang and Jinkyung Noh and Hayoung Song and Hyunseok Kim and Hoonseok Kang and Solhye Choe and Tae-Lim Choi and Eunsung Lee}, doi = {10.1021/jacs.5c01995}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7159}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Air and thermally stable cyclic (Alkyl)(amino)carbene ruthenium complexes for efficient ring expansion metathesis polymerization”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Dissecting the conformational heterogeneity of stem-loop substructures of the fifth element in the 5′-untranslated region of SARS-CoV-2”. JACS, 147(8), 7158. (www)

  @article{ , archive = {J_JACS}, author = {Klara R. Mertinkus and Andreas Oxenfarth and Christian Richter and Anna Wacker and Carlos P. Mata and Jose Maria Carazo and Andreas Schlundt and Harald Schwalbe}, doi = {10.1021/jacs.5c01923}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7158}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Dissecting the conformational heterogeneity of stem-loop substructures of the fifth element in the 5′-untranslated region of SARS-CoV-2”}, volume = {147}, year = {2025}, }
• (2025). Dual-locked fluorescence probe for monitoring the dynamic transition of pulmonary macrophages. JACS, 147(8), 7148--7157. (www)

  @article{ , abstract = {Pulmonary macrophages undergo dynamic changes in population, proportion, and polarization during respiratory diseases. Monitoring these changes is critical for understanding their roles in pathology, improving the diagnosis, and guiding drug development. However, current analytic methods based on tissue biopsy are invasive and static, limiting their ability to provide such dynamic information. Herein, we report a dual-locked macrophage-specific renal-clearable probe (DMRP NOCas ) for the dynamic monitoring of pulmonary macrophages during influenza A virus (IAV) infection. DMRP NOCas activates fluorescence in the presence of two biomarkers (caspase-1 and NO) only coexpressed by M1 macrophages. To optimize the NO reactivity, the scaffold of DMRP NOCas is screened from the hemicyanine derivatives with an o -phenylenediamine group positioned differently on the indole ring. Notably, the para-substituted o-phenylenediamine demonstrates a higher NO-activated fluorescence compared to its meta-substituted counterpart. This enhancement, as revealed by quantum chemical calculations, is attributed to differential inhibition of twisted intramolecular charge transfer induced by the NO reaction. DMRP NOCas specifically distinguishes M1 macrophages from other leukocytes including T cells, neutrophils, and M2 macrophages, a capability unmatched by single-locked control probes and other reported probes. Consequently, DMRP NOCas enables in vivo dynamic monitoring of pulmonary macrophages, uncovering extensive recruitment and M1 polarization of monocyte-derived macrophages within 48 h of IAV infection. This process is accompanied by a significant reduction in alveolar macrophages. These findings provide new insights into macrophage-mediated pulmonary inflammation and underscore the potential of dual-locked probes for precise diagnosis and monitoring of pathological processes.}, archive = {J_JACS}, author = {Yuxuan Hu and Jing Liu and Mengke Xu and Kanyi Pu}, doi = {10.1021/jacs.5c00506}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7148--7157}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual-locked fluorescence probe for monitoring the dynamic transition of pulmonary macrophages}, volume = {147}, year = {2025}, }
• (2025). Mechanical interlocking of 144 symmetrical 19F and tetraphenylethylene for magnetic resonance-fluorescence dual imaging. JACS, 147(8), 7137--7147. (www)

  @article{ , abstract = {Single-molecule dual 19 F magnetic resonance imaging ( 19 F MRI) and fluorescence imaging (FLI) agents are valuable tools in biomedical research. However, integrating millimolar-sensitivity 19 F MRI and micromolar-sensitivity FLI into a single molecule remains challenging. Here, we report the use of mechanically interlocked [5]rotaxanes to efficiently incorporate 144 symmetrical fluorines ( 19 F) for sensitive 19 F MRI and to control the motion of tetraphenylethylene (TPE) for responsive FLI at the molecular level, yielding a dual imaging agent with micromolar sensitivity. The sensitivity gap between 19 F MRI and FLI is bridged by generating an intense singlet 19 F peak from 144 symmetrical 19 F and modulating their motion through mechanical interlocking. Spectroscopic and imaging studies, in conjunction with molecular dynamics simulations, highlight the critical role of [5]rotaxane formation, wheel “stationing-shuttling”, and the introduction of fluorous bulky perfluoro- tert -butoxymethyl (PFBM) groups as effective strategies to improve 19 F MRI sensitivity and enable responsive FLI. This work not only advances the development of high-performance dual imaging agents but also provides valuable insights into the structure, dynamics, and potential applications of [5]rotaxanes in materials science.}, archive = {J_JACS}, author = {Lan Yang and Fang Wang and Yu Li and Rui Zhou and Anfeng Li and Tingjuan Wu and Maosong Qiu and Lei Zhang and Minghui Yang and Xin Zhou and Zhong-Xing Jiang and Shizhen Chen}, doi = {10.1021/jacs.5c00429}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7137--7147}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanical interlocking of 144 symmetrical 19F and tetraphenylethylene for magnetic resonance-fluorescence dual imaging}, volume = {147}, year = {2025}, }
• (2025). Enhancing selective hydrofluorocarbon greenhouse gas capture via halogenation of Metal–Organic frameworks. JACS, 147(8), 7127--7136. (www)

  @article{ , abstract = {Hydrofluorocarbons (HFCs) are anthropogenically produced greenhouse gases with longer atmospheric lifetimes and higher global warming potentials than those of carbon dioxide. General strategies to abate their emissions from industrial point sources, such as via adsorptive capture, remain scarce. Herein, we uncover the key structure–property relationships that lead to strong binding of HFCs such as fluoroform (CHF 3 ) and difluoromethane (CH 2 F 2 ) in metal–organic frameworks (MOFs) under the low pressures relevant to flue gas scrubbing. Extensive gas sorption and computational studies support that the Zr-based microporous framework MOF-801-Br or HHU-2-Br (HHU = Heinrich-Heine-University Düsseldorf) strongly binds HFCs due to its synergistic combination of Zr-OH sites on the nodes and bromine sites on the linkers. As such, MOF-801-Br demonstrates a record-setting performance for separating CHF 3 from N 2 under dilute conditions. Our work highlights that the combination of multiple hydrogen-bonding sites in microporous MOFs represents a generalizable strategy for HFC capture, enabling their selective removal from industrial waste streams.}, archive = {J_JACS}, author = {Ronald T. Jerozal and Jaehwan Kim and Carolyn Ma and Tristan A. Pitt and Jung-Hoon Lee and Phillip J. Milner}, doi = {10.1021/jacs.5c00393}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7127--7136}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing selective hydrofluorocarbon greenhouse gas capture via halogenation of Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Endogenous HClO-gated cascade MicroRNA imaging for precise diagnosis of atherosclerosis in vivo. JACS, 147(8), 7113--7126. (www)

  @article{ , abstract = {Precise imaging of atherosclerotic plaques using biomarkers could prompt the diagnosis and clinical management of atherosclerosis (AS)-driven cardiovascular diseases. MicroRNA-155 (miR-155) plays a critical role in AS development, with its expression notably upregulated in foam cells within plaques. However, miRNA imaging methods for atherosclerotic plaques face significant challenges, including low specificity, inefficient delivery, and poor cell selectivity. Herein, we develop an endogenous hypochlorous acid (HClO)-gated cascade signal amplification strategy for precise miR-155 imaging in living foam cells, enabling accurate in vivo and ex vivo detection of atherosclerotic plaques. This strategy utilizes a phosphorothioate (PT)-modified hairpin probe that is specifically deprotected by HClO and uncaged by miR-155, triggering a catalytic hairpin assembly (CHA) to amplify fluorescence signals. The PT-CHA probes are encapsulated in lipid nanoparticles (LNs), followed by conjugating with phosphatidylserine (PS)-binding peptide (PBP) for selectively targeting foam cells, enabling in vivo miR-155 imaging in atherosclerotic plaques. The fluorescence intensity of PT-CHA@LN-PBP in the aorta region shows clear differentiation among AS-bearing mice, miR-155 –/– mice, and healthy mice. Moreover, the fluorescence intensity strongly correlates with plaque area and AS progression and can discriminate plaque vulnerability risk with an area under the curve (AUC) of 0.94. Imaging of human aortic tissues further validates the probe’s capacity to distinguish atherosclerotic plaques from normal endarterium. These findings establish PT-CHA@LN-PBP as a noninvasive, reliable diagnostic tool for precise assessment of AS.}, archive = {J_JACS}, author = {Moxuan Ji and Jiantong Dong and Zhuo Ye and Jingjing Kang and Guimei Han and Xiaoqin Hong and Yongchun Wei and Xin Chen and Wei Sun and Dingbin Liu}, doi = {10.1021/jacs.5c00031}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7113--7126}, shortjournal = {J. Am. Chem. Soc.}, title = {Endogenous HClO-gated cascade MicroRNA imaging for precise diagnosis of atherosclerosis in vivo}, volume = {147}, year = {2025}, }
• (2025). Chirality-dependent kinetics of single-walled carbon nanotubes from machine-learning force fields. JACS, 147(8), 7103--7112. (www)

  @article{ , abstract = {The origin of the chirality of single-walled carbon nanotubes (SWCNTs) has been a long-standing dispute. Molecular dynamics (MD) simulations driven by machine-learning force fields (MLFFs), which can study the interface dynamics under near ab initio accuracy, provide a powerful technique to reveal the formation mechanism of SWCNTs. Here, we develop a cobalt–carbon MLFF and perform growth simulations on a cobalt catalyst to investigate the chirality preference of the growth of SWCNTs under the vapor–liquid–solid (VLS) regime. Through microkinetic modeling, we reproduce the observed growth and defect kinetics, demonstrating their dependence on the chirality. It is observed that while the initial chirality assignment is likely related to the configurational degeneracy of the nanotube caps, pentagon defects immediately form and resolve after nucleation. Such processes, which we name diameter control mechanisms, not only control the diameter toward an optimum but also shift the chirality distribution drastically. Our simulation shows a preference toward the (6,5) chirality, which is also widely observed experimentally. Our work offers a microkinetic modeling workflow for the chirality-dependent kinetics of the SWCNTs, highlighting the important contribution of the defect kinetics to the chirality origination.}, archive = {J_JACS}, author = {Sida Sun and Shigeo Maruyama and Yan Li}, doi = {10.1021/jacs.4c18769}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7103--7112}, shortjournal = {J. Am. Chem. Soc.}, title = {Chirality-dependent kinetics of single-walled carbon nanotubes from machine-learning force fields}, volume = {147}, year = {2025}, }
• (2025). Biosynthesis of dothideomins reveals a fungal p450 that constructs the tricyclo[5.2.2.0.4,8]undecane-imbedded core skeleton. JACS, 147(8), 7094--7102. (www)

  @article{ , abstract = {Dothideomins are antibacterial bis(anthraquinone) polyketides isolated from the endophytic fungus Dothideomycetes sp. BMC-101, featuring a unique 6/6/6/5/6/6/6 heptacyclic scaffold imbedded with a tricyclo[5.2.2.0. 4,8 ]undecane core. Although the structures and antibacterial potential are attractive, the biosynthesis process and the formation of a heptacyclic scaffold, especially the tricyclo[5.2.2.0. 4,8 ]undecane cage-like core, are unclear. Here, we elucidated the biosynthesis of dothideomins C and D encoded by a dot gene cluster through heterologous expression, in vivo feeding experiments, and in vitro biochemical assays. Our findings reveal an enzyme cascade involved in the conversion of the precursor emodin into dothideomins. Specifically, the cytochrome P450 monooxygenase DotG is shown to solely catalyze the unprecedented formation of triple C–C bonds and construct the tricyclo[5.2.2.0. 4,8 ]undecane-embedded skeleton. This study enhances the comprehension of the P450 enzyme-controlled formation of complex natural products.}, archive = {J_JACS}, author = {Falei Zhang and Chuanteng Ma and Meilin Zhu and Yinghan Chen and Wenxue Wang and Guojian Zhang and Tianjiao Zhu and Qian Che and Dehai Li}, doi = {10.1021/jacs.4c18595}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7094--7102}, shortjournal = {J. Am. Chem. Soc.}, title = {Biosynthesis of dothideomins reveals a fungal p450 that constructs the tricyclo[5.2.2.0.4,8]undecane-imbedded core skeleton}, volume = {147}, year = {2025}, }
• (2025). Synthesis and reactivity of an Iron–Tin complex with adjacent stannylidyne and ferriostannylene units. JACS, 147(8), 7083--7093. (www)

  @article{ , abstract = {Heavier transition metal carbyne analogs hold significant potential for cooperative activation of small molecules. However, complexes containing more than one heavier tetrylidyne ligand RE (E = Si, Ge, Sn, Pb) are rare due to the high oligomerization tendency of RE ligands. In this study, we describe the complex [Fe(SnAr’) 2 ] ( 1 ; Ar’ = 2,6-Dipp 2 -C 6 H 3 , Dipp = 2,6- i Pr 2 –C 6 H 3 ), which features adjacent Fe–Sn single and double bonds. Complex 1 exhibits versatile reactivity with transition metal and main group compounds. Treatment of complex 1 with Ni(COD) 2 (COD = 1,5-cyclooctadiene) yields the tetranuclear complex [Fe(μ-SnAr’) 2 Ni] ( 2 ), characterized by an unusual “push–pull” interaction between nickel(0) and the two coordinating Sn atoms, as revealed by quantum chemical studies. The reaction of complex 1 with AlBr 3 results in Al–Br bond cleavage and Ar’ migration to aluminum. CH 3 I adds oxidatively to the Sn atom that is singly bonded to Fe, while PMe 3 coordinates to Fe, inducing reversible cleavage of the Fe═Sn double bond. In addition, complex 1 activates inorganic molecules. CO 2 undergoes disproportionation to produce a carbonate-bridged Ar’Sn(μ–OCO 2 )SnAr’ ligand, whereas CS 2 is reductively coupled to form an ethylene tetrathiolate ligand ([C 2 S 4 ] 4– ). The reaction with white phosphorus (P 4 ) generates an unusual Ar’P 4 Sn 2 Ar’ ligand. This multifaceted reactivity illustrates the behavior of the Fe and Sn sites in complex 1 , suggesting that complexes of this type are promising reagents for small molecule activation.}, archive = {J_JACS}, author = {Yang Liu and Franz F. Westermair and Isabelle Becker and Sebastian Hauer and Michael Bodensteiner and Christoph Hennig and Gábor Balázs and Franc Meyer and Ruth M. Gschwind and Robert Wolf}, doi = {10.1021/jacs.4c18423}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7083--7093}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis and reactivity of an Iron–Tin complex with adjacent stannylidyne and ferriostannylene units}, volume = {147}, year = {2025}, }
• (2025). Metal doping activation of anion-mediated electron transfer in catalytic reactions. JACS, 147(8), 7070--7082. (www)

  @article{ , abstract = {Heteroatom-doping has emerged as a transformative approach to producing high-performance catalysts, yet the current trial-and-error approach to optimize these materials remains ineffective. To enable the rational design of more efficient catalysts, models grounded in a deeper understanding of catalytic mechanisms are essential. Existing models, such as d -band center theory, fall short in explaining the role of dopants, particularly when these dopants do not directly interact with reactants. In this study, we synthesize various heteroatom-doped catalysts to explore the correlation between the electronic effects of the dopants and catalyst activity. Using Co-MoS 2 as a model catalyst and the Li–S redox reaction within the cathode of Li–S batteries as a test system, we show the interaction between cobalt sites and adjacent lattice sulfur atoms disrupts the intrinsic structural and electronic symmetry of MoS 2 . This disruption enhances the transfer of spin-polarized electrons from metal centers to lattice sulfur and promotes the adsorption of reactant intermediates. Furthermore, by analyzing 20 different dopant elements, we establish a linear relationship between the electron density in the lattice sulfur and catalyst activity toward the reduction of sulfur species, a relationship that extends to other catalytic systems, such as the hydrogen evolution reaction.}, archive = {J_JACS}, author = {Chao Yue Zhang and Jing Yu and Chen Huang and Guowen Sun and Lluís Balcells and Jiayue Li and Xuede Qi and Cheng Zhu Yi and Javier Herrero-Martín and Laura Simonelli and Francois Fauth and Ren He and Xiaobo Pan and Junshan Li and Jordi Arbiol and Jin Yuan Zhou and Andreu Cabot}, doi = {10.1021/jacs.4c18236}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7070--7082}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal doping activation of anion-mediated electron transfer in catalytic reactions}, volume = {147}, year = {2025}, }
• (2025). Copper-mediated enantioselective C–H thiolation of ferrocenes enabled by the BINOL ligand. JACS, 147(8), 7061--7069. (www)

  @article{ , abstract = {Transition-metal-catalyzed enantioselective C–H activation has transformed the landscape of asymmetric synthesis, enabling the efficient conversion of C–H bonds into C–C and carbon–heteroatom (C–X) bonds. However, the formation of C–S bonds through enantioselective C–H thiolation remains underdeveloped due to challenges such as catalyst deactivation and competitive coordination of sulfur-containing compounds with chiral ligands. Herein, we report an unprecedented approach to constructing sulfur-substituted planar chiral ferrocenes (PCFs) through copper-mediated enantioselective C–H thiolation enabled by only a 2.5 mol % 1,1′-bi-2,2′-naphthol (BINOL) ligand. A variety of sulfur-substituted PCFs were obtained in good yields (up to 83%) with excellent enantioselectivity (up to >99% ee). Mechanistic studies reveal that the irreversible C–H activation serves as both the stereo- and rate-determining step and can be achieved with catalytic amounts of Cu species. Furthermore, the utility of this protocol is illustrated through gram-scale synthesis, removal of the directing group, and the synthesis of N , S -chiral ligands as well as chiral rotaxanes. This significant advancement not only expands the tool kit for constructing chiral organosulfur compounds but also highlights the potential of enantioselective C–H activation in asymmetric synthesis.}, archive = {J_JACS}, author = {Jia-Yi Ma and Qi-Jun Yao and Lu-Chen Jiang and Fan-Rui Huang and Qiang Yue and Bing-Feng Shi}, doi = {10.1021/jacs.4c18255}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7061--7069}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper-mediated enantioselective C–H thiolation of ferrocenes enabled by the BINOL ligand}, volume = {147}, year = {2025}, }
• (2025). Development of a thioetherification of heteroarene electrophiles with broad scope via a proton transfer dual ionization mechanism. JACS, 147(8), 7050--7060. (www)

  @article{ , abstract = {Sulfur-derived functional groups represent prevalent motifs in highly sought-after small molecules, such as active pharmaceutical ingredients (APIs). Thioethers are one such example, being commonly encountered in APIs, prodrugs, and as valuable synthetic “linchpins” to access an array of sulfur-derived functional groups. While nucleophilic aromatic substitution (S N Ar) has traditionally been used to synthesize aryl thioethers, modern approaches leverage transition metals to catalyze thermal or photochemical cross-coupling. While studying photochemical thioetherification reactions, we uncovered a remarkably mild condition that does not require light, transition metals, or exogenous bases. An array of thiols and halogenated heterocycles were coupled to produce >70 diverse products. Reaction progress kinetic analysis (RPKA) and computational studies support a unique mechanism termed proton transfer dual ionization (PTDI) S N Ar. Finally, a predictive statistical model was constructed aided by high-throughput experimentation (HTE) to understand when the PTDI processes are successful, resulting in the completion of ten target-oriented syntheses. This transformation complements modern approaches to thioether synthesis and motivates additional research evaluating PTDI as a general activation mode between reaction partners.}, archive = {J_JACS}, author = {Christian R. Zwick, III and Maike Eckhoff and Jeremy J. Henle and Anna V. Bay and Rafal Swiatowiec and Shashank Shekhar and Cassie Yang and Yong Zhou and Amanda L. Wall and Rodger F. Henry and Jessica N. Hoskins and Matthew S. Sigman}, doi = {10.1021/jacs.4c18304}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7050--7060}, shortjournal = {J. Am. Chem. Soc.}, title = {Development of a thioetherification of heteroarene electrophiles with broad scope via a proton transfer dual ionization mechanism}, volume = {147}, year = {2025}, }
• (2025). Rational design of aqueous na ion batteries toward high energy density and long cycle life. JACS, 147(8), 7039--7049. (www)

  @article{ , abstract = {Prussian blue analogues (PBAs) are promising cathode candidates for aqueous Na ion batteries (ANIBs) considering their low-carbon and cost-effective features. However, it is still a huge challenge to achieve desirable energy density coupled with long cycle life due to inherent Na defects in PBAs and the unstable solid–electrolyte interphase (SEI) layer. Herein, we design Na 2 C 4 O 4 additives as sodium supplements to compensate for Na defects in PBAs, while utilizing the CO 2 products decomposed from Na 2 C 4 O 4 to construct a robust SEI layer containing Na 2 CO 3 species. As proof of concept, our building of full ANIBs using iron-based PBAs and NaTi 2 (PO 4 ) 3 anode with an appropriate amount of Na 2 C 4 O 4 enable a reversible capacity of ∼144 mA h g –1 at 0.2 C and an excellent cycling stability of 15,000 cycles with 85% retention at 10 C. The proposed concept is further extended to the manganese-based PBA ANIBs to deliver an energy density of 92 W h kg –1 with improved cycling stability.}, archive = {J_JACS}, author = {Chunliu Xu and Yuan Liu and Shuai Han and Zhao Chen and Yongzhi Ma and Qiubo Guo and Peng Zhang and Weiqing Yang and Chao Yang and Junmei Zhao and Yong-Sheng Hu}, doi = {10.1021/jacs.4c18168}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7039--7049}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design of aqueous na ion batteries toward high energy density and long cycle life}, volume = {147}, year = {2025}, }
• (2025). Growth of atomically thin metastable β-tungsten in single-walled carbon nanotubes for stable one-dimensional ferromagnets. JACS, 147(8), 7028--7038. (www)

  @article{ , abstract = {Thin-film β tungsten (β-W), a metastable phase of tungsten, holds significant potential in the fabrication of superconducting and spin-memory devices. However, due to the rapid surface passivation of tungsten in oxygen and moisture, the synthesis of nanosized metastable β-W with the intrinsic atomic surface is still difficult, and their magnetic properties remain rather unexplored. Inspired by the strong host–guest interaction-induced stabilization, we reported the synthesis of atomically thin (1.0–1.3 nm) metastable β-W nanowires within single-walled carbon nanotubes (SWCNTs) through an oxygen-assisted transformation of starting W 2 C, with 85% of β-W nanowires along the anisotropic ⟨010⟩ direction. Atomically resolved electron microscopy directly unveils the dynamic evolutions of W 2 C-to-β-W and further β-to-α - W within SWCNTs, depending on the H 2 -annealing time. Detailed mechanistic studies by theoretical calculations and experiments reveal that oxygen diffused within the W 2 C lattice governs the formation and stabilization of ultrathin β-W nanowires within the SWCNTs. Additionally, the nanoconfinement of SWCNTs, restricting the thickness of W nanowires down to 2 nm, also benefits the thermodynamically favorable nucleation of β-W than α-W. With the protection of a single graphene layer against water erosion, β-W@SWCNTs exhibit a ferromagnetic response at ∼130 K, with higher chemical stability than fully exposed thin-film β-W. This work may provide a feasible way to design the ferromagnetic nanowire metamaterials based on aligned SWCNT arrays that have the potential to fabricate microwave and spin devices.}, archive = {J_JACS}, author = {Xin Zhao and Kun Wang and Bowen Li and Quan Xiao and Meihui Song and Wu Wang and Luyao Zhang and Fenfa Yao and Boyuan Yu and Yingbo Li and Xiao Wang and Shu Guo and Chuanhong Jin and Jiaqing He and Feng Yang}, doi = {10.1021/jacs.4c18128}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7028--7038}, shortjournal = {J. Am. Chem. Soc.}, title = {Growth of atomically thin metastable β-tungsten in single-walled carbon nanotubes for stable one-dimensional ferromagnets}, volume = {147}, year = {2025}, }
• (2025). Reconfigured spin-flip process enables efficient and persistent triplet excitons in Organic–Inorganic metal halides. JACS, 147(8), 7017--7027. (www)

  @article{ , abstract = {Triplet excitons, driven by spin-flip processes, play a crucial role in enabling efficient room-temperature phosphorescence across various applications. However, attaining a significant accumulation of long-lived excitons is impeded by the simultaneous influence of nonradiative and radiative decay pathways alongside intersystem crossing efficiencies. Here, we introduce a solvent intercalation approach that leverages the triplet exciton processes in a family of zero-dimensional organic–inorganic halides, A 2 ZnBr 4 (A = organic phosphonium cations). By intercalating phosphorescence inactive molecules into these halides, their spin-flip processes can be reconfigured. This leads to significantly amplified intersystem crossing but attenuated radiative and nonradiative transitions, which give rise to 16- and 6-fold increases in lifetime and quantum yield, respectively. Our single crystal X-ray diffraction, transient absorption, and theoretical calculation results reveal that such dramatic improvement is attributed to the unique spatial effect on both electrons and holes induced by the intercalated molecules. The consequently reduced orbital degeneracy increases the number of spin-allowed channels, promoting intersystem crossing, while the synergistically enhanced electron localization diminishes the triplet exciton decay, leading to high efficiency and enduring phosphorescence. Our findings offer a new pathway for manipulating the spin-flip process to boost the emission of triplet excitons, with potential applications in designing a wide spectrum of phosphorescent materials.}, archive = {J_JACS}, author = {Zi-Ying Li and Rui Feng and Shi-Shuang Huang and Wei Li and Xian-He Bu}, doi = {10.1021/jacs.4c17996}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7017--7027}, shortjournal = {J. Am. Chem. Soc.}, title = {Reconfigured spin-flip process enables efficient and persistent triplet excitons in Organic–Inorganic metal halides}, volume = {147}, year = {2025}, }
• (2025). Achieving higher activity of acidic oxygen evolution reaction using an atomically thin layer of IrOx over Co3O4. JACS, 147(8), 7008--7016. (www)

  @article{ , abstract = {The development of electrocatalysts with reduced iridium (Ir) loading for the oxygen evolution reaction (OER) is essential to produce low-cost green hydrogen from water electrolysis under acidic conditions. Herein, an atomically thin layer of iridium oxide (IrO x ) has been uniformly dispersed onto cobalt oxide (Co 3 O 4 ) nanocrystals to improve the efficient use of Ir for acidic OER. In situ characterization and theoretical calculations reveal that compared to the conventional IrO x cluster, the atomically thin layer of IrO x shows stronger interaction with the Co 3 O 4 and consequently higher OER activity due to the Ir–O–Co bond formation at the interface. Equally important, the facile synthetic method and the promising activity in the proton exchange membrane water electrolyzer, reaching 1 A cm –2 at 1.7 V with remarkable durability, enable potential scale-up applications. These findings provide a mechanistic understanding for designing active, stable and lower-cost electrocatalysts with well-defined structures for acidic OER.}, archive = {J_JACS}, author = {Gengnan Li and Adyasa Priyadarsini and Zhenhua Xie and Sinwoo Kang and Yuzi Liu and Xiaobo Chen and Shyam Kattel and Jingguang G. Chen}, doi = {10.1021/jacs.4c17915}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {7008--7016}, shortjournal = {J. Am. Chem. Soc.}, title = {Achieving higher activity of acidic oxygen evolution reaction using an atomically thin layer of IrOx over Co3O4}, volume = {147}, year = {2025}, }
• (2025). Chemical synthesis reveals pathogenic role of N-glycosylation in microtubule-associated protein tau. JACS, 147(8), 6995--7007. (www)

  @article{ , abstract = {Alzheimer’s disease (AD) is a neurodegenerative disorder characterized by the accumulation of tau protein aggregates. In this study, we investigated the effects of N -glycosylation on tau, focusing on its impact on aggregation and phase behavior. We chemically prepared homogeneous glycoproteins with high-mannose glycans or a single N -acetylglucosamine at the confirmed glycosylation sites in K18 and 2N4R tau. Our findings reveal that N -glycosylation significantly alters biophysical properties and potentially cellular functions of tau. Small glycans promote tau aggregation and liquid–liquid phase separation (LLPS), while larger glycans reduce these effects. High mannose glycans at N410 enhance phosphorylation by GSK3β, suggesting a pathological role in AD. Functional assays demonstrate that N -glycosylation does not impact microtubule polymerization dynamics but modulates aggregation kinetics and morphology. This research underscores the importance of glycosylation in tau pathology and opens new avenues for therapeutic interventions targeting glycan processing.}, archive = {J_JACS}, author = {Wyatt C. Powell and Ruiheng Jing and Morgane Herlory and Patrick Holland and Darya Poliyenko and Christopher C. Ebmeier and Michael H. B. Stowell and Maciej A. Walczak}, doi = {10.1021/jacs.4c17873}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6995--7007}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemical synthesis reveals pathogenic role of N-glycosylation in microtubule-associated protein tau}, volume = {147}, year = {2025}, }
• (2025). Emergence of voronoi-patterned cellular membranes via confinement transformation of self-assembled Metal–Organic frameworks. JACS, 147(8), 6983--6994. (www)

  @article{ , abstract = {The self-assembly of nanoparticles allows the fabrication of complex, nature-inspired architectures. Among these, Voronoi tessellations─intricate patterns found in many natural systems such as insect wings and plant tissues─have broad implications across materials science, biology, and geography. However, replicating these irregular yet organized features at the nanoscale through nanoparticle self-assembly remains challenging. Here, we introduce a confinement transformation method to generate two-dimensional (2D) Voronoi patterns by converting metal–organic frameworks, specifically zeolitic imidazolate framework-8 (ZIF-8), into layered hydroxides. The process begins with the self-assembly of ZIF-8 particles into densely packed monolayers at the liquid–air interface, driven by the Marangoni effect. Subsequent Ni 2+ -induced etching converts the floating ZIF-8 monolayer into a freestanding membrane composed of interconnected polygonal cells, closely resembling the geometric characteristics of Voronoi tessellations. We systematically investigate the parameters affecting the transformation of ZIF-8 particles, shedding light on the mechanism governing Voronoi pattern formation. Mechanical testing and simulations demonstrate that the resulting cellular membranes exhibit enhanced stress distribution and crack resistance, attributed to their Voronoi-patterned architecture. These robust, monolithic membranes composed of Ni-based hydroxides, when serving as catalyst support materials, can synergistically enhance the intrinsic activity of Pt catalysts for alkaline hydrogen evolution reaction by facilitating water dissociation. This work presents a promising approach for creating nature-inspired materials with optimal stress management, superior mechanical properties, and potential catalytic applications.}, archive = {J_JACS}, author = {Xiangyun Xi and Longfei Lv and Xiaoli Gong and Zhebin Zhang and Yifan Gao and Yan Xia and Siyu Wan and Xuesong Wu and Hushui Chen and Dong Yang and Yuwen Zeng and Hongyuan Sheng and Tongtao Li and Angang Dong}, doi = {10.1021/jacs.4c17866}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6983--6994}, shortjournal = {J. Am. Chem. Soc.}, title = {Emergence of voronoi-patterned cellular membranes via confinement transformation of self-assembled Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Host–Guest chemistry-mediated biomimetic chemoenzymatic synthesis of complex glycosphingolipids. JACS, 147(8), 6974--6982. (www)

  @article{ , abstract = {Glycosphingolipids (GSLs) are amphipathic complex biomolecules constituted of hydrophilic glycans covalently linked to hydrophobic lipids via glycosidic bonds. GSLs are widely distributed in cells and tissues, where they play crucial roles in various biological functions and disease processes. However, the heterogeneity and complexity of GSLs make it difficult to explore their precise biofunctions due to obstacles in obtaining well-defined structures. Herein, we report a host–guest-chemistry-mediated biomimetic chemoenzymatic approach for the efficient synthesis of diverse complex GSLs. A key feature of this approach is that the use of methyl-β-cyclodextrin enables amphipathic glycolipids forming water-soluble inclusion complexes to improve their solubility in aqueous media, thereby facilitating enzyme-catalyzed reactions. The power and applicability of our approach are demonstrated by the streamlined synthesis of biologically important globo-, ganglio-, neolacto-, and lacto-series GSLs library containing 20 neutral and acidic glycolipids with different fucosylation and sialylation patterns. The developed method will open new avenues to easily access a wide range of complex GSLs for biomedical applications.}, archive = {J_JACS}, author = {Yuan Ma and Yating Liu and Chang Cao and Jiarong Peng and Yinyu Jiang and Tiehai Li}, doi = {10.1021/jacs.4c17725}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6974--6982}, shortjournal = {J. Am. Chem. Soc.}, title = {Host–Guest chemistry-mediated biomimetic chemoenzymatic synthesis of complex glycosphingolipids}, volume = {147}, year = {2025}, }
• (2025). Impact of grafting density on the assembly and mechanical properties of self-assembled Metal–Organic framework monolayers. JACS, 147(8), 6966--6973. (www)

  @article{ , abstract = {Polymer-grafted metal–organic frameworks (MOFs) can be used to form free-standing self-assembled MOF monolayers (SAMMs). Polymer chains can be introduced onto MOF surfaces through either the ligands or metal nodes using both grafting-to and grafting-from approaches. However, controlling the grafting density of polymer-grafted MOFs has not yet been achieved, because a means to control the density of grafting sites on the MOF surface has not been developed. In this study, the grafting density of polymer-grafted UiO-66 (UiO = University of Oslo) was controlled by functionalizing a portion of the Zr(IV) secondary building units (SBUs) on a UiO-66 surface with a so-called blocking agent. The remaining sites on the UiO-66 SBUs were functionalized with polymerization initiation groups, and polymers were grown from these sites to obtain particles with variable grafting densities and chain lengths that form SAMMs at an air–water interface. Even under conditions of low grafting density, these materials retain the ability to form SAMMs and their free-standing ability. Changes in particle arrangement within the monolayers were investigated using SEM imaging, and the toughness of the monolayers was evaluated using a film-on-water (FOW) method. Furthermore, coarse-grained molecular dynamics simulations were carried out to elucidate the morphology and mechanical properties of the monolayers. Findings from both experiments and simulations indicate that the toughness of SAMMs is more heavily influenced by the chain length of the grafted polymers than by the overall polymer content in the composite.}, archive = {J_JACS}, author = {Minjung Kang and Po-An Lin and Jordan A. Bunch and Darren J. Lipomi and Gaurav Arya and Seth M. Cohen}, doi = {10.1021/jacs.4c17748}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6966--6973}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of grafting density on the assembly and mechanical properties of self-assembled Metal–Organic framework monolayers}, volume = {147}, year = {2025}, }
• (2025). Synergistic effects in low-temperature CO oxidation on cerium oxide surfaces. JACS, 147(8), 6958--6965. (www)

  @article{ , abstract = {The mechanisms underlying the reaction between carbon monoxide (CO) and activated dioxygen on metal oxide substrates to produce CO 2 remain poorly understood, particularly regarding the role of oxygen vacancies and the nature of the activated O 2 adsorbate. In this study, we present experimental findings from infrared reflection–absorption spectroscopy on a model system of bulk monocrystalline CeO 2 (111). Contrary to expectations, exposing the reduced surface to dioxygen (O 2 ) at 80 K does not yield activated oxygen species, such as superoxo or peroxo. Notably, in the presence of adsorbed CO, an unexpected low-temperature oxidation reaction occurs, consuming CO while oxidizing the CeO 2 substrate. Since a direct reaction between impinging O 2 and adsorbed CO is unlikely at these low temperatures, a novel mechanism is proposed. Extensive spin-polarized density functional theory (DFT) calculations reveal that oxygen vacancies play a critical role in this low-temperature CO oxidation. Initially located in the subsurface region (Vss), these vacancies migrate to the surface (Vs) via a concerted interaction with coadsorbed CO and O 2 , leading to O 2 activation and the formation of superoxo or peroxo species. Detailed analysis identifies key reaction intermediates and quantifies their adsorption energies and activation barriers. Our findings suggest that the peroxo-mediated pathway, with its lower activation barrier, is more favorable for CO oxidation at low temperatures compared to the carbonate pathway. This study provides valuable insights into the dynamic role of subsurface oxygen vacancies in the activation of gaseous O 2 and CO oxidation mechanisms on CeO 2 .}, archive = {J_JACS}, author = {Pablo G. Lustemberg and Chengwu Yang and Yuemin Wang and M. Veronica Ganduglia-Pirovano and Christof Wöll}, doi = {10.1021/jacs.4c17658}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6958--6965}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic effects in low-temperature CO oxidation on cerium oxide surfaces}, volume = {147}, year = {2025}, }
• (2025). Superacid in situ protected synthesis of covalent organic frameworks. JACS, 147(8), 6942--6957. (www)

  @article{ , abstract = {Covalent organic frameworks, as a class of fascinating crystalline porous materials, are attracting increasing attention in various fields. Synthesizing these materials to attain crystallinity and porosity is essential; however, it is time-consuming, not cost-effective, and energy-demanding as it involves extensive screenings of reaction conditions and employs undesired aromatic solvents. Despite recent progress in the synthesis, finding an efficient, convenient, low-toxicity, and widely applicable method remains a challenging goal. Here, we report an in situ -protected strategy for synthesizing imine-linked frameworks by exploring triflic acid as the catalyst to replace traditional acetic acid and deploying alcohols as a single-component reaction medium instead of aromatic solvents. We found that the function of triflic acid is threefold: it rapidly protonates amino groups of amine monomers into ammonium cations, protects formyl units of aldehyde monomers by converting them into acetals, and improves the solubilities of both monomers. The in situ -protection scheme greatly changes their concentrations and reactivities, making reactions highly controllable and reversible. This strategy is general for various monomer combinations to develop imine-linked frameworks with different topologies, including tetragonal, rhombic, pentagonal, hexagonal, kagome, dual trigonal, dual rhombic, and dual hexagonal shapes, and various pore sizes from micropores to mesopores, presenting a facile and simple way to synthesize 28 different yet high-quality frameworks in n -butanol/water. Remarkably, nine new imine-linked frameworks are synthesized for the first time, which cannot be prepared by traditional systems. The porphyrin frameworks exhibited exceptional photocatalytic activities in the activation of molecular oxygen to produce highly reactive oxygen species of singlet oxygen.}, archive = {J_JACS}, author = {Xingyao Ye and Ruoyang Liu and Xinyu Mu and Shanshan Tao and Hao Yang and Xuejiao J. Gao and Shuo-Wang Yang and Donglin Jiang}, doi = {10.1021/jacs.4c17548}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6942--6957}, shortjournal = {J. Am. Chem. Soc.}, title = {Superacid in situ protected synthesis of covalent organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Classification and identification of facet- and edge-specific γ-Al2O3 surface sites from 1H/27Al NMR cross-signatures and DFT modeling. JACS, 147(8), 6934--6941. (www)

  @article{ , abstract = {γ-Al 2 O 3 is used as both a catalyst and a support for catalytic active phases. The properties of γ-Al 2 O 3 have been ascribed to specific surface sites, with varying Al coordination number, acidity, and basicity, depending on the morphology of the material. Here, we combine surface-specific 27 Al{ 1 H} 2D high-field NMR (28.2T, 1.2 GHz for 1 H frequency) at fast MAS (50 kHz) to observe four main distinct families of surface Al–OH sites. Comparing the measured NMR signatures ( 27 Al δ iso , C Q , and 1 H δ iso ) to computed values from a large range of structural DFT models enables to identify specific edge and facet Al–OH surface sites in γ-Al 2 O 3 , including a distinct [4] Al–OH site with an unprecedented C Q approaching 18 MHz. This molecular-level description of alumina surfaces opens new opportunities to understand its unique properties, such as the stabilization of small particles down to single atoms, central to catalytic processes.}, archive = {J_JACS}, author = {Domenico Gioffrè and Pierre Florian and Thomas Pigeon and Pascal Raybaud and Céline Chizallet and Christophe Copéret}, doi = {10.1021/jacs.4c17358}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6934--6941}, shortjournal = {J. Am. Chem. Soc.}, title = {Classification and identification of facet- and edge-specific γ-Al2O3 surface sites from 1H/27Al NMR cross-signatures and DFT modeling}, volume = {147}, year = {2025}, }
• (2025). From bis(borylene)-substituted xanthenes as reactive intermediates to diboraoxirane complexes. JACS, 147(8), 6925--6933. (www)

  @article{ , abstract = {The first N -heterocyclic carbene (NHC)-stabilized diboraoxirane complex 4 [NHC = IPr = C{N(iPr)CMe} 2 ] was synthesized through the reduction of the corresponding bis(dichloroboryl-IPr)xanthene 3 with potassium graphite. Intriguingly, its formation stems from a diboron(I)-mediated C–O–C deoxygenation of the xanthene spacer via a bis(borylene)xanthene as a reactive intermediate. Consistent with the proposed pathway, bis(borylene)xanthene 6 with three-coordinate B(I) atoms could be isolated when the sterically less demanding NHC ligand IMe [IMe = C{N(Me)CMe} 2 ] was employed. Due to its ring strain, the B–B bond of the B 2 O ring in 4 undergoes versatile ring-expansion reactions with small molecules to engender new boron-containing heterocycles. In fact, oxidation of 4 with trimethylamine N -oxide, O 2 , and elemental sulfur afforded the unprecedented 1,3-dioxa-2,4-diboretane 7 , 1,3,4-trioxa-2,5-diborolane 8 , and 1-oxa-3,4-dithio-2,5-diborolane 9 , respectively. Moreover, 4 activates isocyanide to produce 1-oxa-2,4-diborete 10 and readily reacts with the C═O groups of benzophenone and CO 2 to generate the ring-expansion products 11 and 12 , respectively.}, archive = {J_JACS}, author = {Jun Fan and Sudip Pan and Shenglai Yao and Chengxiang Ding and Gernot Frenking and Matthias Driess}, doi = {10.1021/jacs.4c17463}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6925--6933}, shortjournal = {J. Am. Chem. Soc.}, title = {From bis(borylene)-substituted xanthenes as reactive intermediates to diboraoxirane complexes}, volume = {147}, year = {2025}, }
• (2025). Engineering the lewis acidity of fe single-atom sites via atomic-level tuning of spatial coordination configuration for enhanced oxygen reduction. JACS, 147(8), 6914--6924. (www)

  @article{ , abstract = {Nitrogen-doped carbon-supported Fe catalysts (Fe-N-C) with Fe-N 4 active sites hold great promise for the oxygen reduction reaction (ORR). However, fine-tuning the structure of Fe-N 4 active sites to enhance their performance remains a grand challenge. Herein, we report an innovative design strategy to promote the ORR activity and kinetics of Fe-N 4 sites by engineering their Lewis acidity, which is achieved by tuning the spatial Fe coordination geometry. Theoretical calculations indicated that Fe 1 -N 4 SO 2 sites (with an axial –SO 2 group bonded to Fe) offered favorable Lewis acidity for the ORR, leading to optimized adsorption energies for the key ORR intermediates. To implement this strategy, we developed a molecular-cage-encapsulated coordination strategy to synthesize a Fe single-atom site catalyst (SAC) with Fe 1 -N 4 SO 2 sites. In agreement with theory, the Fe 1 -N 4 SO 2 /NC catalyst demonstrated outstanding ORR performance in both alkaline ( E 1/2 = 0.910 V in 0.1 M KOH) and acidic media ( E 1/2 = 0.772 V in 0.1 M HClO 4 ), surpassing commercial Pt/C and traditional Fe SACs with Fe 1 -N 4 sites or planar S-coordinated Fe 1 -N 4 -S sites. Moreover, this newly developed catalyst showed great application potential in quasi-solid-state Zn–air batteries, delivering superior performance across a wide temperature range.}, archive = {J_JACS}, author = {Qingyun Qu and Yu Mao and Shufang Ji and Jiangwen Liao and Juncai Dong and Ligang Wang and Qichen Wang and Xiao Liang and Zedong Zhang and Jiarui Yang and Haijing Li and Yongfang Zhou and Ziyun Wang and Geoffrey I. N. Waterhouse and Dingsheng Wang and Yadong Li}, doi = {10.1021/jacs.4c17444}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6914--6924}, shortjournal = {J. Am. Chem. Soc.}, title = {Engineering the lewis acidity of fe single-atom sites via atomic-level tuning of spatial coordination configuration for enhanced oxygen reduction}, volume = {147}, year = {2025}, }
• (2025). Cyclic (Alkenyl)(Amino)Carbene (SMeCAenAC): Introducing a member to the cyclic (Alkyl)(Amino)Carbenes family featuring a narrow energy gap. JACS, 147(8), 6905--6913. (www)

  @article{ , abstract = {Herein, we report the carbene-like activity of a nonisolable, highly ambiphilic cyclic (alkenyl)(amino)carbene ( SMe CA en AC, 3 ), which is stabilized as [( SMe CA en AC)(H)N(SiMe 3 ) 2 ] ( 4 ). This protected form ( 4 ) is stable in air and moisture. Compound 4 can be used as a carbene source through deamination upon heating to 130–140 °C. Moreover, density functional theory (DFT) calculations indicate that SMe CA en AC has the smallest singlet–triplet gap (37.05 kcal/mol) and a narrow highest occupied molecule orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap (3.92 eV) among the cyclic (alkyl)(amino)carbenes (CAACs). The precursor of carbene ( 3 ) can be synthesized on a multigram scale with a good yield. Moreover, the SMe CA en AC-coordinated copper complex showed excellent efficiency in the catalytic addition of phenols to electron-deficient olefins. This study also highlights that [ SMe CA en AC-H]OTf can be used for metal-free catalysis, a property uniquely characteristic of an ambiphilic carbene, even though the formation of free SMe CA en AC ( 3 ) was not achieved.}, archive = {J_JACS}, author = {Chinmoy Majumder and Ankita Sharma and Bindusagar Das and Ritu Yadav and Subrata Kundu}, doi = {10.1021/jacs.4c17319}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6905--6913}, shortjournal = {J. Am. Chem. Soc.}, title = {Cyclic (Alkenyl)(Amino)Carbene (SMeCAenAC): Introducing a member to the cyclic (Alkyl)(Amino)Carbenes family featuring a narrow energy gap}, volume = {147}, year = {2025}, }
• (2025). Three-coordinate iron(0) complex-catalyzed regioselective C–H alkylation of indole derivatives. JACS, 147(8), 6897--6904. (www)

  @article{ , abstract = {The synthesis of alkylated indoles, which are key intermediates for various drugs and bioactive molecules, is of great importance. However, most reports on the synthesis of functionalized indoles use toxic and expensive 4d or 5d metal catalysts, limiting the further application of these methods. Herein, we disclose a versatile regioselective C–H alkylation of indole derivatives using a well-defined three-coordinate iron(0) complex. Neither Grignard reagents nor additional additives are required, making the reaction sustainable, environmentally friendly, and compatible with a broad variety of functional groups to afford C2-alkylated indoles in high yields. In addition, by variation of the aryl substituent on the alkene substrate to the trisubstituted silyl group, the regioselectivity of the C–H alkylation can be altered from Markovnikov to anti -Markovnikov. Detailed mechanistic studies further revealed the catalytic mode of reaction.}, archive = {J_JACS}, author = {Zi-Jing Zhang and Stéphane Golling and Silvia Cattani and Xinran Chen and Lutz Ackermann}, doi = {10.1021/jacs.4c17316}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6897--6904}, shortjournal = {J. Am. Chem. Soc.}, title = {Three-coordinate iron(0) complex-catalyzed regioselective C–H alkylation of indole derivatives}, volume = {147}, year = {2025}, }
• (2025). Ferrocyanide “Skin”-mediated anticatalysis: Mitigating self-discharge in aqueous electrochemical devices. JACS, 147(8), 6886--6896. (www)

  @article{ , abstract = {The interest in aqueous energy storage devices is surging due to their exceptional safety profile. However, in aqueous energy storage systems, interfacial side reactions, predominantly attributed to the oxygen evolution reaction (OER), result in significant self-discharge, which is concomitant with the deterioration of both voltage and capacity. Herein, we propose the construction of a ferrocyanide “skin” on transition metal compounds (TMCs) to mitigate this issue. This engineered “skin” creates Fe–C≡N terminations, initiating a new reaction pathway featured by the bonding process of N–O and N–H bonds. This reaction pathway presents a significant energy barrier, effectively shielding the active sites for the OER from H 2 O molecules and hydroxyl ions. Taking NiO as an example, the ferrocyanide “skin” effectively suppresses the undesired phase transition from NiOOH to Ni(OH) 2 during the idling process of a fully charged electrode, enabling the as-modified electrode to achieve a remarkable voltage retention of 80.0% after 1 week of idling within a device. Furthermore, this concept demonstrates extensive applicability, extending to a range of TMC materials, including but not limited to manganese oxide, vanadium oxide, and nickel cobalt oxide. These findings highlight the efficacy of the ferrocyanide “skin” design strategy as a broadly applicable paradigm for suppressing H 2 O-induced undesirable phase transitions in aqueous energy storage devices.}, archive = {J_JACS}, author = {Jin Li and Shuo Sun and Hao Huang and Teng Zhai and Yanchen Liu and Minghui Gu and Hongye Yang and Mingqing Sun and Tianyi Kou and Shuang Li and Hui Xia}, doi = {10.1021/jacs.4c16996}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6886--6896}, shortjournal = {J. Am. Chem. Soc.}, title = {Ferrocyanide “Skin”-mediated anticatalysis: Mitigating self-discharge in aqueous electrochemical devices}, volume = {147}, year = {2025}, }
• (2025). Strong electron-withdrawing effect activates metal-free carboxylate anion into efficient active sites for electrocatalytic acetylene semihydrogenation. JACS, 147(8), 6880--6885. (www)

  @article{ , abstract = {The exploration of novel and high-performance organo-electrocatalysts with well-defined active sites is vital for understanding catalytic mechanisms and replacing metal-based catalysts, but remains a formidable challenge. Here, we report metal-free trifluoroacetate as a new organo-electrocatalyst, where the strong electron-withdrawing trifluoromethyl (−CF 3 ) group intrinsically transforms the neighboring carboxylate anions (−COO – ) into highly efficient active sites for electrocatalytic acetylene semihydrogenation. The electrophilic acetylene molecule bonds to the negatively charged O – sites of the carboxylate anion via the σ-configuration. Benefiting from precise molecular engineering of electron-withdrawing groups, the ethylene partial current density presents a volcano relationship with the total natural charge of the −COO – anions. In 1 M KOH aqueous solution, trifluoroacetate delivers an ethylene partial current density of 260 mA/cm 2 with an ethylene Faradaic efficiency of 96.8% at −0.9 V versus the reversible hydrogen electrode (RHE) under a pure acetylene atmosphere, outperforming metal-based electrocatalysts. This work presents a new type of high-activity organo-electrocatalysts with −COO – anions as active center and promises its application in electrocatalysis.}, archive = {J_JACS}, author = {Rui Bai and Zhi-Hao Zhao and Mingxuan Liu and Wenxiu Ma and Jin Lin and Siying An and Jiaxin He and Zhenpeng Liu and Lei Zhang and Hui Mei and Jian Zhang}, doi = {10.1021/jacs.4c17260}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6880--6885}, shortjournal = {J. Am. Chem. Soc.}, title = {Strong electron-withdrawing effect activates metal-free carboxylate anion into efficient active sites for electrocatalytic acetylene semihydrogenation}, volume = {147}, year = {2025}, }
• (2025). Molecular principles of proton-coupled quinone reduction in the membrane-bound superoxide oxidase. JACS, 147(8), 6866--6879. (www)

  @article{ , abstract = {Reactive oxygen species (ROS) are physiologically harmful radical species generated as byproducts of aerobic respiration. To detoxify ROS, most cells employ superoxide scavenging enzymes that disproportionate superoxide (O 2 ·– ) to oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ). In contrast, the membrane-bound superoxide oxidase (SOO) is a minimal 4-helical bundle protein that catalyzes the direct oxidation of O 2 ·– to O 2 and drives quinone reduction by mechanistic principles that remain unknown. Here, we combine multiscale hybrid quantum/classical (QM/MM) free energy calculations and microsecond molecular dynamics simulations with functional assays and site-directed mutagenesis experiments to probe the mechanistic principles underlying the charge transfer reactions of the superoxide-driven quinone reduction. We characterize a cluster of charged residues at the periplasmic side of the membrane that functions as a O 2 ·– collecting antenna, initiating electron transfer via two b hemes to the active site for quinone reduction at the cytoplasmic side. Based on multidimensional QM/MM string simulations, we find that a proton-coupled electron transfer (PCET) reaction from the active site heme b and nearby histidine residues (H87, H158) results in quinol (QH 2 ) formation, followed by proton uptake from the cytoplasmic side of the membrane. The functional relevance of the identified residues is supported by site-directed mutagenesis and activity assays, with mutations leading to inhibition of the O 2 ·– -driven quinone reduction activity. We suggest that the charge transfer reactions could build up a proton motive force that supports the bacterial energy transduction machinery, while the PCET machinery provides unique design principles of a minimal oxidoreductase.}, archive = {J_JACS}, author = {Daniel Riepl and Abbas Abou-Hamdan and Jonas Gellner and Olivier Biner and Dan Sjöstrand and Martin Högbom and Christoph von Ballmoos and Ville R. I. Kaila}, doi = {10.1021/jacs.4c17055}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6866--6879}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular principles of proton-coupled quinone reduction in the membrane-bound superoxide oxidase}, volume = {147}, year = {2025}, }
• (2025). Large-scale synthesis of janus nanorods by electrostatics-mediated intramolecular cross-linking of polymeric bottlebrushes. JACS, 147(8), 6857--6865. (www)

  @article{ , abstract = {Nanorods are promising to construct functional superstructures. The currently used nanorods are essentially symmetric, with the same materials at the ends. Theoretical prediction indicates that asymmetric Janus nanorods with varied materials at the ends are advantageous in the synthesis of diversified functional self-assembled materials. Herein, we propose a novel method of electrostatics-mediated intramolecular cross-linking of Janus polymer bottlebrushes to synthesize large-scale asymmetric Janus nanorods at an unprecedentedly high concentration of 300 mg/mL. Compositions of both the nanorod body and ends are broadly tunable in an orthogonal mode to endow the nanorod functional groups for self-assembly, which could be visualized under a STED microscope upon dyeing. The sample amino acid analogous Janus nanorods are achieved by the orthogonal hydrolysis and click reaction at the opposite ends, serving as building blocks to self-organize into superstructures from linear wires, branches, and networks that are highly dependent on the valence states.}, archive = {J_JACS}, author = {Fenglin Li and Zhendong Wen and Yajing Yang and Dayin Sun and Jintao Zhu and Zhihong Nie and Zhenzhong Yang}, doi = {10.1021/jacs.4c16990}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6857--6865}, shortjournal = {J. Am. Chem. Soc.}, title = {Large-scale synthesis of janus nanorods by electrostatics-mediated intramolecular cross-linking of polymeric bottlebrushes}, volume = {147}, year = {2025}, }
• (2025). Neural network potential with multiresolution approach enables accurate prediction of reaction free energies in solution. JACS, 147(8), 6835--6856. (www)

  @article{ , abstract = {We present the design and implementation of a novel neural network potential (NNP) and its combination with an electrostatic embedding scheme, commonly used within the context of hybrid quantum-mechanical/molecular-mechanical (QM/MM) simulations. Substitution of a computationally expensive QM Hamiltonian by an NNP with the same accuracy largely reduces the computational cost and enables efficient sampling in prospective MD simulations, the main limitation faced by traditional QM/MM setups. The model relies on the recently introduced anisotropic message passing (AMP) formalism to compute atomic interactions and encode symmetries found in QM systems. AMP is shown to be highly efficient in terms of both data and computational costs and can be readily scaled to sample systems involving more than 350 solute and 40,000 solvent atoms for hundreds of nanoseconds using umbrella sampling. Most deviations of AMP predictions from the underlying DFT ground truth lie within chemical accuracy (4.184 kJ mol –1 ). The performance and broad applicability of our approach are showcased by calculating the free-energy surface of alanine dipeptide, the preferred ligation states of nickel phosphine complexes, and dissociation free energies of charged pyridine and quinoline dimers. Results with this ML/MM approach show excellent agreement with experimental data and reach chemical accuracy in most cases. In contrast, free energies calculated with static DFT calculations paired with implicit solvent models or QM/MM MD simulations using cheaper semiempirical methods show up to ten times higher deviation from the experimental ground truth and sometimes even fail to reproduce qualitative trends.}, archive = {J_JACS}, author = {Felix Pultar and Moritz Thürlemann and Igor Gordiy and Eva Doloszeski and Sereina Riniker}, doi = {10.1021/jacs.4c17015}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6835--6856}, shortjournal = {J. Am. Chem. Soc.}, title = {Neural network potential with multiresolution approach enables accurate prediction of reaction free energies in solution}, volume = {147}, year = {2025}, }
• (2025). Half-sandwich Ru(II) complexes featuring metal-centered chirality: Configurational stabilization by ligand design, preparation via kinetic resolution, and application in asymmetric catalysis. JACS, 147(8), 6825--6834. (www)

  @article{ , abstract = {While it is well established that half-sandwich Ru(II) complexes possess metal-centered chirality, effective strategies to leverage their metal-centered chirality toward asymmetric synthesis have been challenging due to the configurational lability of the metal stereocenters. The metal-centered chirality is typically mediated by enantiopure ligands, which occupy a relatively narrow chemical space compared to their achiral counterparts. We demonstrate that achiral ligands can be used to access chiral-at-ruthenium half-sandwich complexes with exceptionally high configurational stability. Key to success is the introduction of a rigid bidentate ligand with a minimized dihedral angle between the pyridyl and phenolic moieties, which proved effective for preventing racemization. Computational studies revealed the energetic factors contributing to the exceptional configurational stability enabled by the rigid and planar structure of the successful ligand design. These optically active chiral-at-ruthenium complexes incorporating aldehyde moieties were obtained by NHC-catalyzed kinetic resolution with excellent selectivities ( s -factor up to >200, ee up to 99%). We further demonstrate that they are highly effective chiral aldehyde catalysts for the asymmetric 1,6-conjugate addition of glycine ester and para -quinone methide.}, archive = {J_JACS}, author = {Hui Liang and Gabriel N. Morais and Gang Chen and Wei Tang and Jing Zhao and Chuanyong Wang and K. N. Houk and Shuming Chen and Jiajia Ma}, doi = {10.1021/jacs.4c16928}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6825--6834}, shortjournal = {J. Am. Chem. Soc.}, title = {Half-sandwich Ru(II) complexes featuring metal-centered chirality: Configurational stabilization by ligand design, preparation via kinetic resolution, and application in asymmetric catalysis}, volume = {147}, year = {2025}, }
• (2025). Molecular distinction of cell wall and capsular polysaccharides in encapsulated pathogens by in situ magic-angle spinning NMR techniques. JACS, 147(8), 6813--6824. (www)

  @article{ , abstract = {Pathogenic fungal and bacterial cells are enveloped within a cell wall, a molecular barrier at their cell surface, and a critical architecture that constantly evolves during pathogenesis. Understanding the molecular composition, structural organization, and mobility of polysaccharides constituting this cell envelope is crucial to correlate cell wall organization with its role in pathogenicity and to identify potential antifungal targets. For the fungal pathogen Cryptococcus neoformans , the characterization of the cell envelope has been complexified by the presence of an additional external polysaccharide capsular shell. Here, we investigate how magic-angle spinning (MAS) solid-state NMR techniques increase the analytical capabilities to characterize the structure and dynamics of this encapsulated pathogen. The versatility of proton detection experiments, dynamic-based filters, and relaxation measurements facilitate the discrimination of the highly mobile external capsular structure from the internal rigid cell wall of C. neoformans . In addition, we report the in situ detection of triglyceride molecules from lipid droplets based on NMR dynamic filters. Together, we demonstrate a nondestructive technique to study the cell wall architecture of encapsulated microbes using C. neoformans as a model, an airborne opportunistic fungal pathogen that infects mainly immunocompromised but also competent hosts.}, archive = {J_JACS}, author = {Alons Lends and Gaelle Lamon and Loic Delcourte and Aude Sturny-Leclere and Axelle Grélard and Estelle Morvan and Muhammed Bilal Abdul-Shukkoor and Mélanie Berbon and Alicia Vallet and Birgit Habenstein and Erick J. Dufourc and Paul Schanda and Vishukumar Aimanianda and Antoine Loquet}, doi = {10.1021/jacs.4c16975}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6813--6824}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular distinction of cell wall and capsular polysaccharides in encapsulated pathogens by in situ magic-angle spinning NMR techniques}, volume = {147}, year = {2025}, }
• (2025). Efficient color conversion in Metal–Organic frameworks boosts optical wireless communications beyond 1 GB/s data rate. JACS, 147(8), 6805--6812. (www)

  @article{ , abstract = {Efficient color converters are essential for achieving high −3-dB bandwidths and net data rates in optical wireless communications (OWCs). Here, we emphasize the significance of lanthanide-based metal–organic frameworks (MOFs) combined with an effective energy transfer strategy for developing high-performance color converters in OWC systems. In this approach, we successfully reduced the photoluminescence (PL) lifetime from 1.3 ms of the MOF to 4.6 ns of the MOF–chromophore composite, achieved through an efficient energy transfer process in the cavity and surface of the MOFs. This significant reduction in PL lifetime led to a dramatic increase in the −3-dB bandwidth, rising from less than 0.1 to 65.7 MHz. Most importantly, a net data rate of 1.076 GB/s was achieved, marking the first successful demonstration of lanthanide-based MOFs as color converters that facilitate data transmission rates exceeding 1 GB/s. Notably, both the −3-dB bandwidth and net data rate surpass those of most reported organic and inorganic materials, underscoring the exceptional potential of lanthanide-based MOFs when combined with an efficient energy transfer strategy. We believe this combination paves the way for further innovations in high-speed OWC technologies.}, archive = {J_JACS}, author = {Xin Zhu and Yue Wang and Tengjiao He and Simil Thomas and Hao Jiang and Osama Shekhah and Jian-Xin Wang and Tien Khee Ng and Husam N. Alshareef and Osman M. Bakr and Boon S. Ooi and Mohamed Eddaoudi and Omar F. Mohammed}, doi = {10.1021/jacs.4c16906}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6805--6812}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient color conversion in Metal–Organic frameworks boosts optical wireless communications beyond 1 GB/s data rate}, volume = {147}, year = {2025}, }
• (2025). Highly emissive colloidal nanocrystals of a “2.5-dimensional” monomethylhydrazinium lead bromide. JACS, 147(8), 6795--6804. (www)

  @article{ , abstract = {The ability to control materials at the nanoscale has advanced optoelectronic devices, such as LEDs, displays, and quantum light sources. A new frontier is controlling exciton properties beyond quantum size confinement, achieved through single monolayer heterostructures. In the prototypical example of transition metal dichalcogenide heterostructures and moiré superlattices, excitons with long lifetimes, strong binding energies, and tunable dipole moments have been demonstrated and are ideal for optoelectronics and quantum applications. Expanding this material platform is crucial for further progress. This study introduces colloidal nanocrystals (NCs) of monomethylhydrazinium lead bromide (MMHPbBr 3 ), a novel lead halide perovskite (LHP) with a unique “2.5-dimensional” electronic structure. While the spatial dimensionality of the NC extends in all three dimensions, these NCs exhibit excitonic properties intermediate between 2D and 3D LHPs. Density functional theory (DFT) calculations show that MMHPbBr 3 features spatially separated electron and hole wave functions, with electrons delocalized in 3D and holes confined in 2D monolayers. Synthesized via a rapid colloidal method, these NCs were characterized by using techniques such as 4D-STEM and nuclear magnetic resonance, confirming their monoclinic structure. Optical analysis revealed size-dependent properties and 3D quantum confinement effects, with three distinct photoluminescence (PL) bands at cryogenic temperatures corresponding to excitons with varying interlayer coupling. PL spectroscopy of single MMHPbBr 3 NCs reveals their photon emission statistics, expanding their potential for unconventional quantum material designs.}, archive = {J_JACS}, author = {Viktoriia Morad and Taehee Kim and Sebastian Sabisch and Simon C. Boehme and Simone Delessert and Nadine J. Schrenker and Sara Bals and Gabriele Rainò and Maksym V. Kovalenko}, doi = {10.1021/jacs.4c16698}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6795--6804}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly emissive colloidal nanocrystals of a “2.5-dimensional” monomethylhydrazinium lead bromide}, volume = {147}, year = {2025}, }
• (2025). Harnessing oxidized amines as robust sorbents for carbon capture. JACS, 147(8), 6786--6794. (www)

  @article{ , abstract = {Carbon capture and sequestration (CCS) is imperative to mitigating global climate change, but current implementation falls far short of that needed to reach net-zero global emissions by 2050. Aqueous amine solutions, conceived over a century ago, are the current leading technology for CO 2 separations. However, amines suffer from chemical instability under scrubbing conditions, corrosiveness, and toxicity, hindering their long-term implementation at multiton scales. Herein, we demonstrate for the first time that tertiary amine N-oxides, an oxidative degradation product of amines, can remove CO 2 from dilute streams, including flue gas from a natural gas-fired power plant. Our extensive spectroscopic and computational studies support that the nontoxic, noncorrosive, and inexpensive 4-methylmorpholine N -oxide (MMNO) captures CO 2 under humid conditions via the formation of a hydrogen-bond-stabilized bicarbonate (HCO 3 – ) species, despite being significantly less basic than an amine. Accelerated aging studies show that MMNO exhibits superior oxidative and thermal stability compared to structurally similar amines, highlighting the potential of eco-friendly N -oxides in industrial carbon capture applications.}, archive = {J_JACS}, author = {Sijing Meng and Tristan H. Lambert and Phillip J. Milner}, doi = {10.1021/jacs.4c16764}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6786--6794}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing oxidized amines as robust sorbents for carbon capture}, volume = {147}, year = {2025}, }
• (2025). Synthesis of cationic cyclic oligo(disulfide)s via cyclo-depolymerization: A redox-responsive and potent antibacterial reagent. JACS, 147(8), 6772--6785. (www)

  @article{ , abstract = {Antimicrobial peptides (AMPs) and synthetic topologically defined peptide mimics have been developed as alternatives to traditional small-molecule antibiotics. AMP mimetics arising from linear polymers used widely in preclinical studies have shown promise but have limited stability. Oligomers possessing cyclic topology have been proposed to have increased stability but remain understudied due to synthetic challenges and concerns over cytotoxicity. Herein, we present an efficient approach to prepare cationic, cyclic oligo(disulfide)s ( CCOs ) from lipoic acid derivatives. The CCOs are obtained in a one-pot cascade reaction of ring-opening polymerization preceding an in situ cyclo-depolymerization. CCOs are effective against a broad spectrum of bacteria, exhibiting a 5.43-log reduction in 5 min against Escherichia coli . They did not induce antimicrobial resistance during 24 successive passages in vitro. The cytotoxicity of CCOs is reduced by exploiting glutathione-triggered degradation. Further, fine-tuning of the cationic-to-hydrophilic ratio in CCOs has yielded improved stability in serum and a high selective index (HC 50 /MIC > 1280) against methicillin-resistant Staphylococcus aureus . In an infected wound rodent model, CCOs have shown substantial antibacterial potency against S. aureus , underscoring their therapeutic potential as a new class of antimicrobial agents.}, archive = {J_JACS}, author = {Jia Guo and Siqi Zhang and Yaqi Tao and Wei Zheng and Hao Cheng and Hao Li and Zhibo Wang and Yangqing Gou and Jun Zhu and Linxian Li and Yun Liu and Matthew L. Becker and Wen Tang}, doi = {10.1021/jacs.4c16627}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6772--6785}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of cationic cyclic oligo(disulfide)s via cyclo-depolymerization: A redox-responsive and potent antibacterial reagent}, volume = {147}, year = {2025}, }
• (2025). Surface-emanated vertical organic semiconducting nanobrushes. JACS, 147(8), 6763--6771. (www)

  @article{ , abstract = {Polymer self-assembly offers an important route to construct well-defined nanostructures. However, it remains challenging to assemble polymers into vertically oriented nanostructures. Here, we use a seed-induced confinement self-assembly strategy to construct vertically aligned semiconducting nanobrushes from polyfluorene-based polymers on conductive substrates. Mechanism studies elucidate that the immobilized seeds on the substrate initiate the vertical growth of nanobrushes, and supercritical drying as well as the rigid charged coronas collectively contribute to retaining the vertical architecture. This process enables nanobrushes with ∼40× higher charge mobilities than their bulk film counterparts. Thus, inverted organic solar cells using the nanobrushes as the electron transporting layer (ETL) exhibit a record power conversion efficiency of 18.51% as a result of increased ETL texturing and the ETL-active layer interface favoring electron extraction. Moreover, our approach also enables the uniform growth of nanobrushes on a nanoporous photoanode (bismuth vanadate) for photoelectrochemical water splitting, improving catalyst distribution and electron transfer. Our work presents a feasible approach to fabricating challenging vertical polymer nanostructures, thereby unlocking the tremendous potential of conjugated polymers in optoelectronic applications.}, archive = {J_JACS}, author = {Lei Yang and Congqi Li and Na An and Jinhua Gao and Yanan Wei and Jiawei Qiao and Junpeng Dai and Na Yu and Yan Sun and Qijie Lin and Xin Zhang and Jianqi Zhang and Zheng Tang and Xiaotao Hao and Guanghao Lu and Zhixiang Wei and Ian Manners and Yongbo Kuang and Hui Huang and Antonio Facchetti and Huibin Qiu}, doi = {10.1021/jacs.4c16540}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6763--6771}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface-emanated vertical organic semiconducting nanobrushes}, volume = {147}, year = {2025}, }
• (2025). Charge density wave and superconductivity in BaSbTe2S heterolayer crystal with 2D te square nets. JACS, 147(8), 6753--6762. (www)

  @article{ , abstract = {Low-dimensional materials with charge density waves (CDW) are attractive for their potential to exhibit superconductivity and nontrivial topological electronic features. Here we report the two-dimensional (2D) chalcogenide, BaSbTe 2 S which acts as a new platform hosting these phenomena. The crystal structure of BaSbTe 2 S is composed of alternating atomically thin Te square-net layers and double rock-salt type [(SbTeS) 2 ] 2– slabs separated with Ba 2+ atoms. Due to the electronic instability of the Te square net, an incommensurately modulated structure is triggered and confirmed by both single-crystal X-ray diffraction, electron diffraction, and the presence of an energy bandgap in this compound. Our first-principles electronic structure analysis and investigation of structural dynamical instability suggest that the Te network plays a dominant role in its origin. The incommensurate structure is refined with a modulation vector of q = 0.351(1) b * using an orthorhombic cell of a = 4.4696(5) Å, b = 4.4680(5) Å, and c = 15.999(2) Å under superspace group Pmm 2(0β0)000 at 293 K. The modulation vector q varies as a function of both occupancy of Te in the square net and temperature, indicating the CDW order can be modulated by local distortions. The CDW can be suppressed by pressure, leading to the emergence of superconductivity with a T c up to 7.5 K at 13.6 GPa, suggesting a competition between the CDW order and superconductivity. Furthermore, electrical transport under the magnetic field reveals the existence of compensated high mobility electron- and hole-bands near the Fermi surface (μ ∼600–3500 cm 2 V –1 s –1 ), suggesting Dirac-like band dispersion.}, archive = {J_JACS}, author = {Zhong-Zhen Luo and Hengdi Zhao and Weizhao Cai and Shima Shahabfar and Juncen Li and Songting Cai and Jameson Berg and Tushar Bhowmick and Jin-Ke Bao and Shiqiang Hao and Yihui He and Weiping Guo and Duck Young Chung and Yan Yu and Suchismita Sarker and Matthew Grayson and Christopher Wolverton and Vinayak P. Dravid and Wendan Cheng and Zhigang Zou and Stephan Rosenkranz and Christos D. Malliakas and Shanti Deemyad and Mercouri G. Kanatzidis}, doi = {10.1021/jacs.4c16505}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6753--6762}, shortjournal = {J. Am. Chem. Soc.}, title = {Charge density wave and superconductivity in BaSbTe2S heterolayer crystal with 2D te square nets}, volume = {147}, year = {2025}, }
• (2025). Stability of RbO2 as a discharge product of Metal–O2 batteries. JACS, 147(8), 6747--6752. (www)

  @article{ , abstract = {This study presents evidence that the discharge products of positive electrodes in metal–oxygen batteries using Rb- and Cs-based electrolytes are RbO 2 and CsO 2 , paralleling the findings for Na- and K-based systems. We explored the positive electrode reaction inside alkali metal–oxygen batteries, revealing that the stability of MO 2 compounds (M = Na, K, Rb, Cs) is influenced by the alkali metal ion sizes, achieving maximum reversibility with Rb + ions. Despite the high sensitivity of metal–oxygen batteries to trace amounts of moisture and CO 2 within the cell, we successfully demonstrated stable charge–discharge cycles with a nonaqueous Rb-based electrolyte.}, archive = {J_JACS}, author = {Ryusei Fujimoto and Ryoichi Tatara and Tomooki Hosaka and Daisuke Igarashi and Shinichi Komaba}, doi = {10.1021/jacs.4c16383}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6747--6752}, shortjournal = {J. Am. Chem. Soc.}, title = {Stability of RbO2 as a discharge product of Metal–O2 batteries}, volume = {147}, year = {2025}, }
• (2025). Asymmetric total synthesis of asperones a and b through organocatalyzed quinone [5 + 2] cycloaddition. JACS, 147(8), 6739--6746. (www)

  @article{ , abstract = {The first asymmetric total synthesis of the anti-inflammatory polyketides asperones A ( 1 ) and B ( 2 ) has been accomplished. Key synthetic steps include a Diels–Alder and retro-Diels–Alder cascade to construct the poly substituted phenol, an Al-Salen-catalyzed asymmetric cyanosilylation to form the tertiary alcohol of gregatin A, and an organocatalyzed intermolecular [5 + 2] cycloaddition of p -quinone with electron-deficient alkenes to build the crucial [3.2.1] octane core of asperones A ( 1 ) and B ( 2 ).}, archive = {J_JACS}, author = {Chunlei Qu and Lu Chen and Peng Wang and Jingwei Zhang and Yiming Ding and Xianwen Long and Tingrong Zhang and Yaqiu Zhao and Jun Deng}, doi = {10.1021/jacs.4c16252}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6739--6746}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric total synthesis of asperones a and b through organocatalyzed quinone [5 + 2] cycloaddition}, volume = {147}, year = {2025}, }
• (2025). Water-intercalated and humidity-responsive lamellar materials by self-assembly of sodium acrylate random copolymers. JACS, 147(8), 6727--6738. (www)

  @article{ , abstract = {Herein, we report water-intercalated and humidity-responsive lamellar materials obtained from the self-assembly of sodium acrylate (ANa)/alkyl or oleyl acrylate (RA) random copolymers. The random copolymers efficiently absorbed water into the hydrophilic ANa/main chain phase from the outer environment to form lamellar structures consisting of the water-intercalated hydrophilic segments and the hydrophobic side chains. The lamellar formation involves controlling the weight fraction of hydrophilic segments containing water to 40–70 wt % by the RA content, hydrophobic side chains, and the amount of absorbed water. The domain spacing can be controlled in the range of 2–6 nm. More interestingly, the lamellar materials reversibly afford expansion and contraction of the domain spacing in the sub-1 nm level via the absorption and release of water, in response to relative humidity. The multilayered lamellar formation process via the intercalation of water was analyzed in situ by neutron reflectometry and atomic force microscopy measurements under humid conditions. The polymer film further served as a moisture-sensitive actuator that macroscopically induces deformation responsive to humidity.}, archive = {J_JACS}, author = {Yuki Horiike and Hiroyuki Aoki and Makoto Ouchi and Takaya Terashima}, doi = {10.1021/jacs.4c16219}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6727--6738}, shortjournal = {J. Am. Chem. Soc.}, title = {Water-intercalated and humidity-responsive lamellar materials by self-assembly of sodium acrylate random copolymers}, volume = {147}, year = {2025}, }
• (2025). Origin of pressure-induced nonlinear optical property enhancement in CsGeCl3 perovskite: [GeCl6] octahedron distortion and band gap closing. JACS, 147(8), 6717--6726. (www)

  @article{ , abstract = {Second-harmonic generation (SHG) is the wave–wave nonlinear interaction in doubling wave frequencies, spanning from optics, radio, magnetohydrodynamics, and even the middle atmosphere, and enhancing SHG efficiency has attracted broad interest in both fundamental mechanisms and industrial applications. Laser SHG is characterized by a second-order nonlinear susceptibility tensor in nonlinear optical (NLO) crystals, and its intensity is largely related to the lattice distortion. Halide perovskites demonstrate unique photovoltaic and optoelectronic properties due to their high tunability in crystalline and electronic structures, which provides a great platform to investigate their NLO properties. Here, we report a pressure-driven SHG enhancement in all-inorganic lead-free compound CsGeCl 3 , which exhibits a considerable SHG intensity with 9.1 times (@ 1030 nm) that of KH 2 PO 4 at ambient pressure. Upon compression to 1.07 GPa, the SHG intensity further gains ∼3 times, setting a record-high SHG intensity under high pressure (HP). Concerning the limitations of traditional SHG powder measurements, we developed a new single-crystal angle-resolved polarization strategy to retrieve the intrinsic NLO tensors under HP, confirming pressure-induced SHG enhancement. In situ HP synchrotron X-ray diffraction and Raman scattering reveal a strong correlation between SHG intensity and pressure-induced [GeCl 6 ] octahedral distortion. Optical absorption measurements show significant band gap closing under compression, further favoring SHG enhancement. First-principles calculations corroborate these findings. Our results offer a tunable and clean strategy to enhance the SHG intensity in halide perovskites and establish a reliable approach for probing pressure-dependent NLO mechanism in general.}, archive = {J_JACS}, author = {Jia Qu and Yiming Wang and Zhongyang Li and Mingtao Li and Tianyao Pei and Nana Li and Dequan Jiang and Bin Yang and Bing Li and Meiyan Ye and Pinwen Zhu and Yonggang Wang and Gang Liu and Xin Wang and Wenge Yang}, doi = {10.1021/jacs.4c16182}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6717--6726}, shortjournal = {J. Am. Chem. Soc.}, title = {Origin of pressure-induced nonlinear optical property enhancement in CsGeCl3 perovskite: [GeCl6] octahedron distortion and band gap closing}, volume = {147}, year = {2025}, }
• (2025). Bioorthogonal reaction of β-chloroacroleins with meta-aminothiophenol to develop near-infrared fluorogenic probes for simultaneous two-color imaging. JACS, 147(8), 6707--6716. (www)

  @article{ , abstract = {Highly fluorogenic probe based bioorthogonal chemistry has become a promising tool in biomedical applications. However, the majority of fluorogenic probes are designed by introducing a bioorthogonal partner as a fluorescence quencher into classical fluorophores, and these probes exhibit a deteriorating fluorogenicity as the emission wavelength shifts toward the near-infrared (NIR) region, greatly limiting their applications in vivo. Herein, we report a novel fluorogenic bioorthogonal reaction involving β- chloroacroleins ( β- CAs ) and meta- aminothiophenol ( m- AT 1 ), whose fluorescence increases more than 500-fold upon in situ generating fluorophores. β- CAs are stable under physiological conditions and react rapidly ( β- CA 9 , k 2 = 2.2 × 10 2 M –1 s –1 , in H 2 O) and chemoselectively with m- AT 1 in the presence of biological nucleophiles, and delightfully, the reaction proceeds swiftly even under solvent-free conditions. Furthermore, manipulating the conjugate length of β- CAs enables the emission wavelength of the probes to be fine-tuned from 627 to 778 nm. These probes allow the simultaneous labeling of multiple cellular organelles without washing steps, and two-color tumor visualization is achieved in living mice. We believe this study not only provides new insights for the development of NIR fluorogenic probes with superior turn-on behaviors but also presents a promising fluorogenic bioorthogonal reaction CA-AT with widespread potential applications in biomedical research.}, archive = {J_JACS}, author = {Liping Wang and Yujie Huang and Jing Wang and Yulan Jiang and Bang-Ping Jiang and Hua Chen and Hong Liang and Xing-Can Shen}, doi = {10.1021/jacs.4c16074}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6707--6716}, shortjournal = {J. Am. Chem. Soc.}, title = {Bioorthogonal reaction of β-chloroacroleins with meta-aminothiophenol to develop near-infrared fluorogenic probes for simultaneous two-color imaging}, volume = {147}, year = {2025}, }
• (2025). In situ probing the anion-widened anodic electric double layer for enhanced faradaic efficiency of chlorine-involved reactions. JACS, 147(8), 6698--6706. (www)

  @article{ , abstract = {The electric double layer (EDL), which is directly related to ions, influences the electrocatalytic performance. However, the effects of anions on the anodic EDL and reaction kinetics are unclear, especially in water-mediated electrosynthesis. Here, ClO 4 – anions are discovered to widen the anodic EDL to inhibit the competitive oxygen evolution reaction (OER) for the gram-scale electrosynthesis of 2-chlorocyclohexanol with a 90% Faradaic efficiency (FE) at 100 mA cm –2 . The combined results of molecular dynamics simulations and in situ spectroscopies provide solid evidence for the widened EDL that originates from the repulsion of water molecules from the interface by ClO 4 – . The addition of ClO 4 – has a negligible effect on chlorination kinetics because of the electrostatic interaction between the anode and Cl – but obviously suppresses the interaction between water and the anode, leading to high FEs of anodic electrosynthesis by increasing the energy barrier of the undesirable OER. In addition, this method is suitable for other chlorination reactions with enhanced FEs at 100 mA cm –2 .}, archive = {J_JACS}, author = {Mingming Yan and Rong Yang and Cuibo Liu and Ying Gao and Bin Zhang}, doi = {10.1021/jacs.4c16173}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6698--6706}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ probing the anion-widened anodic electric double layer for enhanced faradaic efficiency of chlorine-involved reactions}, volume = {147}, year = {2025}, }
• (2025). Ultralow coordination copper sites compartmentalized within ordered pores for highly efficient electrosynthesis of n-propanol from CO2. JACS, 147(8), 6688--6697. (www)

  @article{ , abstract = {Coordinatively unsaturated copper (Cu) has been demonstrated to be effective for electrifying CO 2 reduction into C 3 products by adjusting the coupling of C 1 –C 2 intermediates. Nevertheless, the intuitive impacts of ultralow coordination Cu sites on C 3 products are scarcely elucidated due to the lack of synthetic recipes for Cu with low coordination numbers and its vulnerability to aggregation under reductive potentials. Herein, computational predictions revealed that Cu sites with higher levels of coordinative unsaturation favored the adsorption of C 1 and C 2 intermediates. Building upon the correlations, we constructed an ultralow coordination Cu catalyst from the in situ reduction of copper oxide nanoparticles (CuO NPs) compartmentalized within an ordered porous matrix, achieving a remarkable Faradaic efficiency (FE) for n-propanol (n-PrOH) from CO 2 electroreduction, reaching up to 27.4% in the H-cell at −0.8 V RHE and 11.8% at 300 mA cm –2 in the flow cell. The presence and maintenance of ultralow coordination Cu sites during the rigorous electrolysis process contributed to the outstanding performances, as verified by the combination of in situ spectroscopy techniques, disclosing that the formed ultralow coordination Cu sites featured strong adsorption for *C 1 and *C 2 intermediates that lead to n-PrOH.}, archive = {J_JACS}, author = {Qun Li and Jiabin Wu and Caoyu Yang and Siyang Li and Chang Long and Zechao Zhuang and Qian Li and Zhiqing Guo and Xuewei Huang and Zhiyong Tang and Huaiguang Li and Dingsheng Wang and Yadong Li}, doi = {10.1021/jacs.4c16129}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6688--6697}, shortjournal = {J. Am. Chem. Soc.}, title = {Ultralow coordination copper sites compartmentalized within ordered pores for highly efficient electrosynthesis of n-propanol from CO2}, volume = {147}, year = {2025}, }
• (2025). Spatially selective MicroRNA imaging in human colorectal cancer tissues using a multivariate-gated signal amplification nanosensor. JACS, 147(8), 6679--6687. (www)

  @article{ , abstract = {MicroRNA (miRNA) is involved in the genesis in viand development of colorectal cancer. The in vivo imaging of miRNA at the tumor sites is essential for understanding its role in colorectal cancer pathology and therapeutic target identification. However, achieving accurate imaging of miRNA at the tumor sites is hindered by the low abundance of miRNAs in tumor cells and nonspecific signal leakage in normal tissues. Here, we report a multivariate-gated catalytic hairpin assembly (CHA) nanosensor for the specific amplified imaging of microRNA-21 (miR-21) in human colorectal cancer tissues to reveal the underlying miR-21-associated molecular mechanism. The endogenous glutathione and exogenous near-infrared multivariate-gated design in combination with CHA probes improves the signal strength of target miR-21 and reduces the background interference. The nanosensor enables specific amplified imaging of miR-21 in vivo, and the signal-to-background ratios are 1.6-fold compared with traditional CHA methods. With the assistance of the designed nanosensor, we achieve the preliminary identification of tumor tissues and normal tissues from human clinical surgical resection samples. The overexpressed miR-21 is found to suppress the core mismatch repair recognition protein human mutS homologue 2 involved in DNA damage recognition and repair to inhibit the therapeutic efficacy of colorectal cancer. The strategy of probe design, which combines multivariate-gated activation methods with a signal amplification system, is applicable for accurate miRNA imaging and disease-relevant molecular mechanism research.}, archive = {J_JACS}, author = {Xiaoming Zhang and Wenhui Chen and Songlin Wan and Bing Qu and Fei Liao and Di Cheng and Yun Zhang and Zhao Ding and Yanbing Yang and Quan Yuan}, doi = {10.1021/jacs.4c16001}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6679--6687}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatially selective MicroRNA imaging in human colorectal cancer tissues using a multivariate-gated signal amplification nanosensor}, volume = {147}, year = {2025}, }
• (2025). Controlling interlayer disorder toward reversible phase transition in a layered sodium manganese oxide cathode. JACS, 147(8), 6665--6678. (www)

  @article{ , abstract = {Sodium manganese oxides are promising Na-ion battery cathodes but they suffer from irreversible phase transitions during electrochemical reactions. Most strategies to date have aimed to suppress the phase transitions by stabilizing their layered structures through limiting the content of extractable Na + . Here, we conversely increase atomic disorder in the Na-birnessite, a layered sodium manganese oxide, and thereby modulate its phase transition behavior toward improved electrochemical reversibility. Our study reveals that Mn vacancies and Mn migrated into the interlayer affect interlayer local environment of Na + and water molecules consequently enhancing Na + mobility. We observe better capacity retention for disordered “D-Na-birnessite”, which undergoes a reversible phase transition from the birnessite-type structure to an O′3-type α-Na x MnO 2 -like structure through another intermediate metastable birnessite-type phase. This research highlights the positive effects of atomic disorder to regulate phase transition routes for achieving superior electrochemical reversibility, finally paving the way to overcoming the limits of layered oxide cathodes.}, archive = {J_JACS}, author = {Seongkoo Kang and Jihyun Kim and Youngju Choi and Suwon Lee and Leo W. Gordon and Euan N. Bassey and Jean-Claude Badot and Olaf J. Borkiewicz and Olivier Dubrunfaut and Raphaële J. Clément and Yong-Mook Kang}, doi = {10.1021/jacs.4c15913}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6665--6678}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlling interlayer disorder toward reversible phase transition in a layered sodium manganese oxide cathode}, volume = {147}, year = {2025}, }
• (2025). Machine learning-based SERS chemical space for two-way prediction of structures and spectra of untrained molecules. JACS, 147(8), 6654--6664. (www)

  @article{ , abstract = {Identifying unknown molecules beyond existing databases remains challenging in surface-enhanced Raman scattering (SERS) spectroscopy. Conventional SERS analysis relies on matching experimental and cataloged spectra, limiting identification to known molecules in databases. With a vast chemical space of >10 60 molecules, it is impractical to obtain the spectra of every molecule and rely solely on in silico techniques for spectral predictions. Here, we showcase an ML-based SERS chemical space that leverages key spectra–structure correlations to achieve two-way spectra-to-structure and structure-to-spectra predictions for untrained molecules with a >90% average accuracy. Using a SERS chemical space comprising 38 linear molecules from four classes (alcohols, aldehydes, amines, and carboxylic acids), our experimental and in silico studies reveal underlying spectral features that enable the prediction of untrained molecules represented by two molecular descriptors (functional group and carbon chain length). For forward spectra-to-structure predictions, we devise a two-step “classification and regression” ML framework to sequentially predict the functional group and carbon chain length of untrained molecules with 100% accuracy and ≤1 carbon difference, respectively. In addition, using an eXtreme Gradient Boosting (XGBoost) regressor trained on the two molecular descriptors, we attain inverse structure-to-spectra prediction with a high average cosine similarity of 90.4% between the predicted and experimental spectra. Our ML-based SERS chemical space represents a shift in molecular identification from traditional spectral matching to predictive modeling of spectra–structure relationships. These insights could motivate the expansion of SERS chemical spaces and realize demands for present and future SERS technologiesfor accurate unknown identification across diverse fields.}, archive = {J_JACS}, author = {Jaslyn Ru Ting Chen and Emily Xi Tan and Jingxiang Tang and Shi Xuan Leong and Sean Kai Xun Hue and Chi Seng Pun and In Yee Phang and Xing Yi Ling}, doi = {10.1021/jacs.4c15804}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6654--6664}, shortjournal = {J. Am. Chem. Soc.}, title = {Machine learning-based SERS chemical space for two-way prediction of structures and spectra of untrained molecules}, volume = {147}, year = {2025}, }
• (2025). Bioinspired Copper/Amine cooperative catalysis enables asymmetric radical azidation. JACS, 147(8), 6644--6653. (www)

  @article{ , abstract = {Asymmetric radical transformations (ARTs) are vital for constructing chiral drugs and materials, while the highly reactive nature of radicals often imposes a challenge in selectivity control of these processes. Inspired by the principles of enzyme-cofactor cooperation to enhance stereochemical induction in enantioselective radical transformations, we developed an enantioselective asymmetric radical azidation via cooperative organo- and transition metal catalysis. This approach enables the efficient synthesis of heavily functionalized tertiary azides from readily available aldehydes. The key to this enantioselective process is the use of both chiral organocatalysts to transiently convert aldehydes to the corresponding chiral radical cationic species upon oxidation along with a detailed screening of chiral metal-azide catalysts to cooperatively enhance stereoinduction in carbon-azide bond formation. DFT studies suggest a favorable stereocontrol model and validate the crucial roles of chirality pairing of both catalytic schemes. We envision that this copper/amine cooperative catalysis could offer a useful strategy of constructing tetrasubstituted stereogenic carbon in asymmetric radical transformation development.}, archive = {J_JACS}, author = {Rui Wang and Yu-Jie Liang and Kang-Jie Bian and Jie Xu and Si-Yuan Zhou and Ruo-Xing Jin and Wei Guan and Xi-Sheng Wang}, doi = {10.1021/jacs.4c15840}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6644--6653}, shortjournal = {J. Am. Chem. Soc.}, title = {Bioinspired Copper/Amine cooperative catalysis enables asymmetric radical azidation}, volume = {147}, year = {2025}, }
• (2025). Ancient egyptian mummified bodies: Cross-disciplinary analysis of their smell. JACS, 147(8), 6633--6643. (www)

  @article{ , abstract = {Ancient Egyptian mummification was a mortuary practice aimed at preserving the body and soul for the afterlife, achieved through a detailed ritual of embalming using oils, waxes, and balms. While most research on Egyptian mummified bodies has so far been conducted in European collections, our study focuses on the collection of the Egyptian Museum in Cairo. The goal was to evaluate whether contemporary smells reflect the mummification materials and, if so, what information can be of value to collection interpretation and conservation. We combined panel-based sensory analyses with gas chromatography-mass spectrometry-olfactometry (GC-MS-O), microbiological analysis, and historical and conservation research. Apart from differences in odor intensity, the sensory analyses highlighted common olfactory descriptors for all samples: “woody”, “spicy”, and “sweet”. GC-MS-O identified four categories of volatiles based on their origin: (i) original mummification materials; (ii) plant oils used for conservation; (iii) synthetic pesticides; and (iv) microbiological deterioration products. However, the use of insect repellents similar in composition to the original mummification materials makes it challenging to attribute the origin of some compounds. Clusters based on the chemical and olfactory profiles of the smells emerged, suggesting similarities based on the archeological period, conservation treatments, and materiality.}, archive = {J_JACS}, author = {Emma Paolin and Cecilia Bembibre and Fabiana Di Gianvincenzo and Julio Cesar Torres-Elguera and Randa Deraz and Ida Kraševec and Ahmed Abdellah and Asmaa Ahmed and Irena Kralj Cigić and Abdelrazek Elnaggar and Ali Abdelhalim and Tomasz Sawoszczuk and Matija Strlič}, doi = {10.1021/jacs.4c15769}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6633--6643}, shortjournal = {J. Am. Chem. Soc.}, title = {Ancient egyptian mummified bodies: Cross-disciplinary analysis of their smell}, volume = {147}, year = {2025}, }
• (2025). Animal-encoded nonribosomal pathway to bursatellin analogs. JACS, 147(8), 6623--6632. (www)

  @article{ , abstract = {The bursatellin-oxazinin family is a series of tyrosine-derived, nitrile-containing marine natural products from gastropod and bivalve molluscs. Although the first analogs were identified and associated with toxicity 40 years ago, their biosynthetic origins were unknown. During an investigation of published mollusc genomes and transcriptomes, we serendipitously identified a putative bursatellin biosynthetic gene cluster (referred hereafter as the bur-ox pathway). Through biochemical characterization of some bur-ox genes, we provide evidence suggesting that bursatellin-type metabolites are produced by molluscs themselves rather than by their microbial symbionts. We show that the reductive domain from a monomodular nonribosomal peptide synthetase (NRPS) protein FmtATR performs a four-electron reduction to produce tyrosinols from tyrosine derivatives. Moreover, an aminocarboxypropyltransferase enzyme, ACT, uses S -adenosylmethionine (SAM) to transform tyrosinols into their phenolic homoserine ethers, which in bursatellin is further modified to the nitrile. Widespread occurrence of bur-ox in molluscs suggests a common biosynthetic origin for bursatellins and oxazinins as well as an important but currently unidentified physiological role for this metabolite family in molluscs inhabiting diverse ecological niches. The presence of bur-ox pathway homologues in culinary bivalves, such as mussels and geoducks, calls into question the potential of oxazinins as toxins. As one of the few NRPS pathways of animal origin to be characterized, bur-ox sheds light on underappreciated chemical and biochemical diversity in animals.}, archive = {J_JACS}, author = {Aarthi Venugopalan and Eric W. Schmidt}, doi = {10.1021/jacs.4c15714}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6623--6632}, shortjournal = {J. Am. Chem. Soc.}, title = {Animal-encoded nonribosomal pathway to bursatellin analogs}, volume = {147}, year = {2025}, }
• (2025). Helix-guarded molecular clips for cell-free DNA scavenging and treatment of systemic lupus erythematosus. JACS, 147(8), 6612--6622. (www)

  @article{ , abstract = {Immune disorders induced by cell-free DNA (cfDNA) account for the incidence and deterioration of systemic lupus erythematosus (SLE). Scavenging of cfDNA using cationic polymers represents a promising modality for SLE management. However, they bind cfDNA mainly via electrostatic interaction, which would result in an undesired discharge of the captured cfDNA upon competitive replacement by the negatively charged serum/intracellular components. Inspired by the natural recognition mechanism of biomacromolecules via spatial matching, we herein developed a library of dendrimer-templated, spherical, α-helical, and guanidine-rich polypeptides as molecular clips for cfDNA scavenging. Upon optimization of the polypeptide length and density on the dendrimer surface, the top-performing G3-8 was identified, which could tightly confine cfDNA within the cavity between the adjacent, rod-like α-helices. As thus, the helical G3-8 but not the random-coiled analogue D,L -G3-8 enabled robust cfDNA scavenging under serum-rich conditions to inhibit TLR9 activation and inflammation. In SLE mice, i.v. injected G3-8 efficiently prevented organ failure and inhibited inflammation by scavenging cfDNA. This study provides an enlightened strategy to stably bind and scavenge cfDNA and may shift the current paradigm of SLE management.}, archive = {J_JACS}, author = {Yang Zhou and Huan Ye and Yi Yu and Chenglong Ge and Mengyuan Yin and Zhongmin Liu and Jingrui Shen and Renxiang Zhou and Youyong Li and Kam W. Leong and Lichen Yin}, doi = {10.1021/jacs.4c15646}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6612--6622}, shortjournal = {J. Am. Chem. Soc.}, title = {Helix-guarded molecular clips for cell-free DNA scavenging and treatment of systemic lupus erythematosus}, volume = {147}, year = {2025}, }
• (2025). Functionalized docetaxel probes for refined visualization of mitotic spindles by expansion microscopy. JACS, 147(8), 6604--6611. (www)

  @article{ , abstract = {Visualizing the ultrastructure of mitotic spindles, the macromolecular machines that segregate chromosomes during mitosis, by fluorescence imaging remains challenging. Here we introduce an azido- and amino-functionalized docetaxel probe, which upon labeling of microtubules can be fixed, click-labeled and linked into hydrogels. The new probe is particularly useful for super-resolution imaging of dense microtubule structures in mitotic spindles. Multicolor expansion microscopy of mitotic cells allowed us to visualize the different phases of mitosis with unprecedented spatial resolution.}, archive = {J_JACS}, author = {Gang Wen and Xiong Chen and Patrick Eiring and Volker Leen and Johan Hofkens and Markus Sauer}, doi = {10.1021/jacs.4c15608}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6604--6611}, shortjournal = {J. Am. Chem. Soc.}, title = {Functionalized docetaxel probes for refined visualization of mitotic spindles by expansion microscopy}, volume = {147}, year = {2025}, }
• (2025). Atroposelective diverse remote meta-C–H functionalization via kinetic resolution. JACS, 147(8), 6594--6603. (www)

  @article{ , abstract = {A diverse range of Pd(II)-catalyzed enantioselective C–H activation reactions have been developed to construct point, axial, and planar chirality. Despite the importance of chiral biaryl scaffolds in bioactive molecules and chiral ligands, atroposelective functionalization at the meta -position remains a significant challenge. Here, we realized a rare atroposelective remote meta -C–H functionalization with a chiral monoprotected amino acid (MPAA) ligand and a racemic transient norbornene mediator. The reaction starts with enantioselective ortho -C–H activation via kinetic resolution to give a chiral biaryl-palladium intermediate, which subsequently undergoes a Catellani relay to afford chiral meta -functionalized biaryl products ( S -factors up to 458). The obtained diverse enantioenriched quinoline-based atropisomers are ubiquitous in natural products, pharmaceuticals, chiral ligands, and functional materials. Moreover, unprecedented enantioselective meta -alkenylation and alkynylation have also been developed using this approach. A wide range of synthetic applications of the chiral 8-aryl quinolines, including the synthesis of novel P , N -ligand and chiral functional materials with CPL activity, have been demonstrated.}, archive = {J_JACS}, author = {Jian-Jun Li and Xiao-Xuan Zeng and Xin Kuang and Hua-Chen Shen and Peng Wang and Jin-Quan Yu}, doi = {10.1021/jacs.4c15491}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6594--6603}, shortjournal = {J. Am. Chem. Soc.}, title = {Atroposelective diverse remote meta-C–H functionalization via kinetic resolution}, volume = {147}, year = {2025}, }
• (2025). Recombination of autodissociated water ions in a nanoscale pure water droplet. JACS, 147(8), 6583--6593. (www)

  @article{ , abstract = {The recombination of water ions has diverse scientific and practical implications, ranging from acid–base chemistry and biological systems to planetary environments and applications in fuel cell and carbon conversion technologies. While spatial confinement affects the physicochemical properties of water dynamics, its impact on the recombination process has rarely been studied. In this work, we investigate the dynamics of water, the water ion distribution, and the ion recombination process in water droplets as a function of droplet size through molecular dynamics simulations and adaptive quantum mechanical/molecular mechanical calculations. We compare the dynamics of recombination in water droplet sizes ranging from 100 to 18 000 waters, both in their interiors and on their surfaces. We found that the self-diffusion of water dramatically decreases in droplets with a diameter below 2.2 nm. Using a classical RexPoN force-field, we found that the ions in 1000 H 2 O’s spend almost 50% of the time on the surface and 0.5 nm beneath it with a slight preference for OH – ion to reside longer on the surface. We estimate that, on average, recombination in these drops occurs at 400 ps in 1000 H 2 O’s and 1 ns in 3000 H 2 O’s. We also found that recombination is not limited by the local structure of the surface or the size of the droplet but can be influenced by the geometry of the water wire connecting the ions as they approach each other, which can often prevent recombination. Our results provide insights to the reaction microenvironments presented by nanoscopic water droplets.}, archive = {J_JACS}, author = {Soonho Kwon and Prabhat Prakash and Yixiang Cao and Frances A. Houle and William A. Goddard III}, doi = {10.1021/jacs.4c15103}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6583--6593}, shortjournal = {J. Am. Chem. Soc.}, title = {Recombination of autodissociated water ions in a nanoscale pure water droplet}, volume = {147}, year = {2025}, }
• (2025). Reduction-interrupted tandem reaction for general synthesis of functional amino acids by a heterogeneous cobalt catalyst. JACS, 147(8), 6572--6582. (www)

  @article{ , abstract = {Despite their significant importance in numerous fields, the challenges in direct and diverse synthesis of γ-amino-α-hydroxybutyric acids (AHBAs) pose substantial obstacles to explore their functions. Here, by preparation of a N -doped carbon-supported bifunctional cobalt catalyst (Co-DAPhen/C), it was applied to develop a reductive tandem reaction for general synthesis of AHBA derivatives from cheap and abundant nitroarenes, formaldehyde, and acrylates. This catalytic three-component reaction features broad substrate and functionality tolerance, an easily accessible and reusable catalyst, and high step and atom economy. The active Co sites of the catalyst are involved in the mild reduction processes with formic acid, whereas the N-doped carbon support enriches the HCHO and acrylates by physical adsorption, thus favoring the capture of hydroxylamine and nitrone intermediates via condensation and 1,3-dipolar cycloaddition, respectively. Such a metal–support synergy interrupts the conventional reduction of nitroarenes into anilines and results in a novel tandem reaction route. In this work, the concept merging mild reduction and effective intermediate transformations is anticipated to develop more useful tandem reactions by rational catalyst design.}, archive = {J_JACS}, author = {Haotian Hua and Chenggang Ci and Pierre H. Dixneuf and Min Zhang}, doi = {10.1021/jacs.4c15284}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6572--6582}, shortjournal = {J. Am. Chem. Soc.}, title = {Reduction-interrupted tandem reaction for general synthesis of functional amino acids by a heterogeneous cobalt catalyst}, volume = {147}, year = {2025}, }
• (2025). Self-assembled subwavelength nanophotonic structures for spatial object localization and tracking. JACS, 147(8), 6561--6571. (www)

  @article{ , abstract = {Subwavelength resonant nanostructures have facilitated strong light–matter interactions and tunable degrees of freedom of light, such as spectrum, polarization, and direction, thus boosting photonic applications toward light emission, manipulation, and detection. For photodetection, resonant nanostructures have enabled emerging technologies, such as light detection and ranging, spectrometers, and polarimeters, within an ultracompact footprint. However, resonant nanophotonics usually relies on nanofabrication technology, which suffers from the trade-offs between precision and scalability. Here, we first realize the self-assembly of subwavelength resonant nanostructures of metal-halide perovskites for spatial object localization and tracking. By steering crystallization along capillary corner bridges localized at edges, we achieve single crystallinity, subwavelength size, and resonant coupling between perovskite nanowires, thus leading to an angle-resolved photodetector with an angular resolution of 0.523°. Furthermore, we integrate multiple pairs of coupled resonant nanowires along two orthogonal orientations to form angle-resolved photodetector arrays for spatial light localization of both static and moving objects with an error of less than 0.6 cm. These findings create a platform for self-assembled resonant nanostructures, thus paving the way for multifunctional nanophotonic and optoelectronic devices.}, archive = {J_JACS}, author = {Jianpeng Ma and Ziguang Zhao and Yingjie Zhao and Jingyuan Zhang and Jiangang Feng and Hanfei Gao and Junchuan Yang and Meng Yuan and Zhenglian Qin and Ke He and Tenglong Li and Junli Bai and Wei Li and Xiao Wei and Zihao Huang and Fengmian Li and Lei Jiang and Yuchen Wu}, doi = {10.1021/jacs.4c14899}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6561--6571}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-assembled subwavelength nanophotonic structures for spatial object localization and tracking}, volume = {147}, year = {2025}, }
• (2025). Breaking the scaling relationship for oxygen reduction reaction using molecular cobalt complexes. JACS, 147(8), 6549--6560. (www)

  @article{ , abstract = {Developing catalysts that achieve a higher turnover frequency (TOF) with a lower effective overpotential (η eff ) in electrocatalytic reactions is an emerging focus of research. A promising approach to this end is modifying the secondary coordination sphere (SCS) that can facilitate hydrogen bonding interactions or electrostatic effects, thereby lowering the activation energy barrier in the rate-determining step (rds). Herein, we designed and synthesized a series of Co III complexes ( 1 – 8 ) featuring a bis-pyridine-dioxime framework, each with a distinct SCS (−C 6 H 5 ( 1 ), o -NHMe 2 + –C 6 H 4 – ( 2 ), o -OMe–C 6 H 4 – ( 3 ), o -OH–C 6 H 4 – ( 4 ), p -NHMe 2 + –C 6 H 4 – ( 5 ), p -OMe–C 6 H 4 – ( 6 ), pyridine ( 7 ), and pyrimidine ( 8 )). We investigated their electrocatalytic oxygen reduction reaction (ORR) in acetonitrile, both with CF 3 COOH and in a 1:1 CF 3 COOH/CF 3 COO – buffer solution. All complexes demonstrated selective 4e – /4H + reduction of O 2 . A linear free energy relationship (LFER) analysis revealed a trend of increasing the TOF with η eff , aligning with molecular scaling expectations. However, 2 and 3 with the o -NHMe 2 + –C 6 H 4 – and o -OMe–C 6 H 4 – substituents diverged from this trend, exhibiting TOF values over 1000 and 250 times higher than predicted based on their positions in the log(TOF)/η eff correlation within the buffer solution. Kinetic investigations indicate that protonation of the Co III (O 2 • ) adduct is the rds for all catalysts, suggesting that the functional groups in the SCS of 2 and 3 facilitate proton transfer, acting as proton relay sites. We propose that this effect reduces the activation energy barrier in the rds, accounting for the observed deviation from the LFER. This study underscores the critical role of designing an appropriate SCS to enhance catalyst efficiency beyond LFER expectations.}, archive = {J_JACS}, author = {Avijit Das and Aakash Santra and Ankita Kumari and Dibyajyoti Ghosh and Sayantan Paria}, doi = {10.1021/jacs.4c14877}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6549--6560}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking the scaling relationship for oxygen reduction reaction using molecular cobalt complexes}, volume = {147}, year = {2025}, }
• (2025). Structural transformation and degradation of cu oxide nanocatalysts during electrochemical CO2 reduction. JACS, 147(8), 6536--6548. (www)

  @article{ , abstract = {The electrochemical CO 2 reduction reaction (CO 2 RR) holds enormous potential as a carbon-neutral route to the sustainable production of fuels and platform chemicals. The durability for long-term operation is currently inadequate for commercialization, however, and the underlying deactivation process remains elusive. A fundamental understanding of the degradation mechanism of electrocatalysts, which can dictate the overall device performance, is needed. In this work, we report the structural dynamics and degradation pathway of Cu oxide nanoparticles (CuO x NPs) during the CO 2 RR by using in situ small-angle X-ray scattering (SAXS) and X-ray absorption spectroscopy (XAS). The in situ SAXS reveals a reduction in the size of NPs when subjected to a potential at which no reaction products are detected. At potentials where the CO 2 RR starts to occur, CuO x NPs are agglomerated through a particle migration and coalescence process in the early stage of the reaction, followed by Ostwald ripening (OR) as the dominant degradation mechanism for the remainder of the reaction. As the applied potential becomes more negative, the OR process becomes more dominant, and for the most negative applied potential, OR dominates for the entire reaction time. The morphological changes are linked to a gradual decrease in the formation rate for multicarbon products (C 2 H 4 and ethanol). Other reaction parameters, including reaction intermediates and local high pH, induce changes in the agglomeration process and final morphology of the CuO x NPs electrode, supported by post-mortem ex situ microscopic analysis. The in situ XAS analysis suggests that the CuO x NPs reduced into the metallic state before the structural transformation was observed. The introduction of high surface area carbon supports with ionomer coating mitigates the degree of structural transformation and detachment of the CuO x NPs electrode. These findings show the dynamic nature of Cu nanocatalysts during the CO 2 RR and can serve as a rational guideline toward a stable catalyst system under electrochemical conditions.}, archive = {J_JACS}, author = {Soo Hong Lee and Jaime E. Avilés Acosta and Daewon Lee and David M. Larson and Hui Li and Junjie Chen and Jinyoung Lee and Ezgi Erdem and Dong Un Lee and Sarah J. Blair and Alessandro Gallo and Haimei Zheng and Adam C. Nielander and Christopher J. Tassone and Thomas F. Jaramillo and Walter S. Drisdell}, doi = {10.1021/jacs.4c14720}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6536--6548}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural transformation and degradation of cu oxide nanocatalysts during electrochemical CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). Harnessing mn2+ ions and antitumor peptides: A robust hydrogel for enhanced tumor immunotherapy. JACS, 147(8), 6523--6535. (www)

  @article{ , abstract = {Immunotherapy has attracted widespread attention because of its durable and effective antitumor properties. However, systemic delivery strategies often result in immune-related off-target toxicity effects and inadequate drug retention at the tumor site, which limits its broader application. In this research, we designed a dual-functional antitumor peptide (N-Pep) that serves as both a therapeutic agent and metal ions (Mn 2+ ) immunomodulator carrier. The rational designed antitumor peptide self-assembles into a hydrogel through coordination with Mn 2+ ions (referred to as N-Pep-Mn gel). The multiporous hydrogel network allows for efficient loading of antiprogrammed death-1 antibody (αPD-1). The hydrogel served as a depot for the sustained release of Mn 2+ ions and encapsulated αPD-1, effectively activating dendritic cells, polarizing tumor-associated macrophages and enhancing effector T cell infiltration, thereby leading to the effective inhibition of tumor growth through intratumoral and systemic immune responses. Additionally, the hydrogel induces robust immune memory, providing substantial protection against tumor recurrence. These findings underscore the potential of Mn 2+ ion-coordinated antitumor peptide hydrogel as an advanced platform for enhancing antitumor immunotherapy.}, archive = {J_JACS}, author = {Tong Guan and Ziwei Chen and Xin Wang and Susu Gao and Xinyi Lu and Yang Li and Zhichao Wang and Shuhan Zhang and Yuecong Guo and Mengyu Guo and Yanyan Cui and Yaling Wang and Chunying Chen}, doi = {10.1021/jacs.4c14700}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6523--6535}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing mn2+ ions and antitumor peptides: A robust hydrogel for enhanced tumor immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Electrocatalytic ammonia oxidation by pyridyl-substituted ferrocenes. JACS, 147(8), 6514--6522. (www)

  @article{ , abstract = {Ammonia (NH 3 ) is a promising carbon-free fuel when prepared from sustainable resources. First-row transition metal electrocatalysts for ammonia oxidation are an enabling technology for sustainable energy production. We describe electrocatalytic ammonia oxidation using robust molecular complexes based on Earth-abundant iron. Electrochemical studies of ferrocenes with covalently attached pyridine arms reveal facile ammonia oxidation in DMSO (2.4 M NH 3 ) with modest overpotentials (η = 770–820 mV) and turnover frequencies (125–560 h –1 ). Experimental and computational studies indicate that the pendant pyridyl base serves as an H-bond acceptor with an N–H bond of ammonia that transfers a proton to the pyridine following oxidation by the attached ferrocenium moiety in a proton-coupled electron transfer (PCET) step. This generates an amidyl ( • NH 2 ) radical stabilized via H-bonding to a pendant pyridinium moiety that rapidly dimerizes to hydrazine (H 2 N–NH 2 ), which is easily oxidized to nitrogen (N 2 ) at the glassy carbon working electrode. This report identifies a general strategy to oxidize ammonia via H-bonding to a base (B:), thereby activating [B···H-NH 2 ] toward PCET by a proximal oxidant to form [BH···NH 2 ] +/• radical cations, which are susceptible to dimerization to form easily oxidized hydrazine.}, archive = {J_JACS}, author = {Md Estak Ahmed and Richard J. Staples and Thomas R. Cundari and Timothy H. Warren}, doi = {10.1021/jacs.4c14483}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6514--6522}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrocatalytic ammonia oxidation by pyridyl-substituted ferrocenes}, volume = {147}, year = {2025}, }
• (2025). Peptide backbone editing via post-translational o to c acyl shift. JACS, 147(8), 6503--6513. (www)

  @article{ , abstract = {Despite tremendous efforts to engineer translational machinery, replacing the encoded peptide backbone with new-to-nature structures remains a significant challenge. C, H, O, and N are the elements of life, yet ribosomes are capable of forming only C–N bonds as amides, C–O bonds as esters, and C–S bonds as thioesters. There is no current strategy to site-selectively form C–C bonds as ketones embedded in the backbones of ribosomal products. As an alternative to direct ribosomal C–C bond formation, here we report that peptides containing a dehydrolactic acid motif rapidly isomerize to generate backbone-embedded α,γ-diketoamides via a spontaneous formal O to C acyl shift rearrangement. The dehydrolactic acid motif can be introduced into peptides ribosomally or via solid-phase synthesis using α-hydroxyphenylselenocysteine followed by oxidation. Subsequent incubation at physiological pH produces an α,γ-diketoamide that can be diversified using a variety of nucleophiles, including hydrazines and hydroxylamines, to form pyrazoles and oximes, respectively. All of these groups remain embedded directly within the polypeptide backbone. This general strategy for peptide backbone editing, predicated on an intricate cascade of acyl rearrangements, provides the first nonenzymatic example of a C–C bond forming reaction to take place within a peptide backbone. The products so-produced are easily diversified into protein-like materials with backbone-embedded heterocycles. Application of this peptide editing strategy should accelerate the discovery of genetically encoded molecules whose properties more closely resemble those of bioactive natural products.}, archive = {J_JACS}, author = {Carly K. Schissel and Helena Roberts-Mataric and Isaac J. Garcia and Hana Kang and Riaz Mowzoon-Mogharrabi and Matthew B. Francis and Alanna Schepartz}, doi = {10.1021/jacs.4c14103}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6503--6513}, shortjournal = {J. Am. Chem. Soc.}, title = {Peptide backbone editing via post-translational o to c acyl shift}, volume = {147}, year = {2025}, }
• (2025). Precise carboxylic acid-functionalized polyesters in reprocessable vitrimers. JACS, 147(8), 6492--6502. (www)

  @article{ , abstract = {Thermosets are valued for their exceptional dimensional stability, mechanical properties, and resistance to creep and chemicals. Their permanent molecular structures limit reshaping, reprocessing, and recycling. Incorporating exchangeable chemical bonds into cross-linked polymer networks provides materials with thermoset-like properties that are also reprocessable. Here, ring-opening copolymerization (ROCOP) of unpurified, commercially available epoxides and succinic anhydride is employed to synthesize well-defined, low molecular weight polyesters with controlled functionalization. Polymer networks are then formed through the catalyzed reaction of these copolymers with the epoxy-containing cross-linker diglycidyl ether of bisphenol A. Catalyst mixtures of zinc bis(2-ethylhexanoate) and 1,8-diazabicyclo(5.4.0)undec-7-ene are used to assess the role of the catalysts in the curing and dynamic bond exchange reactions. Varying the catalyst ratios results in polymer networks with tunable mechanical properties (90% < ε b < 450%, 0.30 MPa < UTS < 24 MPa), high creep recovery (%recovery > 90% after five creep cycles), and good reprocessability.}, archive = {J_JACS}, author = {Matilde Concilio and Gregory S. Sulley and Fernando Vidal and Steven Brown and Charlotte K. Williams}, doi = {10.1021/jacs.4c14032}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6492--6502}, shortjournal = {J. Am. Chem. Soc.}, title = {Precise carboxylic acid-functionalized polyesters in reprocessable vitrimers}, volume = {147}, year = {2025}, }
• (2025). Ideal bifunctional catalysis for propane dehydrogenation over pt-promoted gallia-alumina and minimized use of precious elements. JACS, 147(8), 6480--6491. (www)

  @article{ , abstract = {Gallia-alumina (Ga x Al 2– x O 3 ), promoted with a trace amount of Pt, exhibits excellent activity and selectivity in propane dehydrogenation (PDH) due to a bifunctional mechanism. Tetrahedrally coordinated Ga (Ga IV ) catalyzes C–H dissociation, while Pt facilitates H recombination into H 2 . To maximize the utilization of precious Pt and Ga, it is crucial to understand the optimal balance between the two catalytic functions or determine the ‘ideal regime.’ Here, we developed techniques to quantify the catalytic functions of Pt and Ga IV sites. H 2 –D 2 exchange rates ( r HD ) and propylene chemisorption ( Q (Ga IV,surf )) were used as effective measures of the catalytic functions of Pt and Ga IV , respectively. When Pt is sufficient relative to Ga IV ( r HD / Q (Ga IV,surf ) ratio >0.3 mol HD mol GaIV,surf –1 s –1 ), the catalysts exhibit ideal catalytic properties. During repeated reaction and regeneration cycles, the catalysts deactivated mainly due to Pt sintering, which leads to an imbalance between the two catalytic functions. Notably, catalysts with higher Pt contents lost catalytic activity faster than those with lower Pt contents, eventually exhibiting reversed activities. This is because increased Pt loading facilitates sintering. Doping a small amount of Ce 3+ onto Ga x Al 2– x O 3 effectively suppresses Pt sintering via strong metal–support interaction. Thus, optimal loadings of Ga and Pt, combined with Ce 3+ doping to stabilize Pt, enabled the minimized use of precious elements while maintaining excellent catalytic properties. Even with 100 ppm Pt and 1 wt % Ga, the catalyst exhibited superior activity, selectivity, and stability compared to the benchmark catalyst, PtSn/γ-Al 2 O 3 , with 7000 ppm (0.7 wt %) Pt.}, archive = {J_JACS}, author = {Susung Lee and Han Chang Kwon and Jaewoo Jeong and Hyeyoung Shin and DongHwan Oh and Jin Seok and Jeong-Chul Kim and Minkee Choi}, doi = {10.1021/jacs.4c13787}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6480--6491}, shortjournal = {J. Am. Chem. Soc.}, title = {Ideal bifunctional catalysis for propane dehydrogenation over pt-promoted gallia-alumina and minimized use of precious elements}, volume = {147}, year = {2025}, }
• (2025). Operando unveiling of hydrogen spillover mechanisms on tungsten oxide surfaces. JACS, 147(8), 6472--6479. (www)

  @article{ , abstract = {Hydrogen spillover is an important process in catalytic hydrogenation reactions, facilitating H 2 activation and modulating surface chemistry of reducible oxide catalysts. This study focuses on the operando unveiling of platinum-induced hydrogen spillover on monoclinic tungsten trioxide (γ-WO 3 ), employing ambient pressure X-ray photoelectron spectroscopy, density functional theory calculations and microkinetic modeling to investigate the dynamic evolution of surface states at varied temperatures. At room temperature, hydrogen spillover results in the formation of W 5+ and hydrogen intermediates (hydroxyl species and adsorbed water), facilitated by Pt metal clusters. With increasing temperature, water desorption, reverse hydrogen spillover and surface-to-bulk diffusion of hydrogen atoms compete with each other, leading initially to reoxidation and then further reduction of W atoms in the near-surface. The combined experimental results and simulations provide a comprehensive understanding of the mechanisms underlying hydrogen interaction with reducible metal oxides, lending insights of relevance to the design of enhanced hydrogenation catalysts.}, archive = {J_JACS}, author = {Haoyi Li and Mona Abdelgaid and Jay R. Paudel and Noah P. Holzapfel and Veronica Augustyn and James R. McKone and Giannis Mpourmpakis and Ethan J. Crumlin}, doi = {10.1021/jacs.4c13711}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6472--6479}, shortjournal = {J. Am. Chem. Soc.}, title = {Operando unveiling of hydrogen spillover mechanisms on tungsten oxide surfaces}, volume = {147}, year = {2025}, }
• (2025). Copper-catalyzed selective amino-alkoxycarbonylation of unactivated alkenes with CO. JACS, 147(8), 6464--6471. (www)

  @article{ , abstract = {1,2-Amino-difunctionalization reactions of alkenes allow the efficient introduction of different functional groups and the rapid construction of valuable functionalized amines. In this respect, we report a copper-catalyzed 1,2-amino-alkoxycarbonylation of unactivated alkenes with CO and alkylamine precursors in the presence of a Lewis acid additive. The novel protocol allows direct access to valuable β-amino acid derivatives from easily available starting materials. The presented methods feature high chemo- and regioselectivities, good functional group tolerance, and substrate scope including diverse bioactive compounds and drug-like molecules. Mechanistic studies indicate that the Lewis acid additive is the key to realizing the efficient umpolung addition of nucleophilic aminyl radicals to electron-rich alkenes, which represents an elegant activation strategy for aminyl radicals.}, archive = {J_JACS}, author = {Si-Shun Yan and Ralf Jackstell and Matthias Beller}, doi = {10.1021/jacs.4c13723}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6464--6471}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper-catalyzed selective amino-alkoxycarbonylation of unactivated alkenes with CO}, volume = {147}, year = {2025}, }
• (2025). Multiple reaction pathways for oxygen evolution as a key factor for the catalytic activity of Nickel–Iron (Oxy)Hydroxides. JACS, 147(8), 6450--6463. (www)

  @article{ , abstract = {We present a comprehensive theoretical study, using state-of-the-art density functional theory simulations, of the structural and electrochemical properties of amorphous pristine and iron-doped nickel–(oxy)hydroxide catalyst films for water oxidation in alkaline solutions, referred to as NiCat and Fe:NiCat. Our simulations accurately capture the structural changes in locally ordered units, as reported by X-ray absorption spectroscopy, when the catalyst films are activated by exposure to a positive potential. We emphasize the critical role of proton-coupled electron transfer in the reversible oxidation of Ni(II) to Ni(III/IV) during this activation. After establishing the structural models of NiCat and Fe:NiCat consistent with experimental data, we used them to explore the atomistic mechanism of the oxygen evolution reaction (OER), which is triggered once the applied potential exceeds the overpotential required for water oxidation and oxygen production. We quantitatively compared seven OER pathways applicable to both the adsorbate evolution mechanism (AEM) and the lattice-oxygen-mediated mechanism (LOM) families, elucidating how iron significantly enhances the catalytic activity of Fe:NiCat compared to NiCat. Our findings suggest that simple metal–oxygen–metal motifs, common on the surface of both crystalline and amorphous metal (oxy)hydroxide films, can promote both AEM and LOM mechanisms under typical OER conditions. Furthermore, we propose that the elusive role of iron lies in the distinct behavior of Ni(IV)–O and Fe(IV)–O bonds in key intermediates preceding the formation of the O–O bond, with Fe ions lowering the potential needed to form these intermediates across the investigated pathways.}, archive = {J_JACS}, author = {Giuseppe Mattioli and Leonardo Guidoni}, doi = {10.1021/jacs.4c12988}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6450--6463}, shortjournal = {J. Am. Chem. Soc.}, title = {Multiple reaction pathways for oxygen evolution as a key factor for the catalytic activity of Nickel–Iron (Oxy)Hydroxides}, volume = {147}, year = {2025}, }
• (2025). Surface lipids in nematodes are influenced by development and species-specific adaptations. JACS, 147(8), 6439--6449. (www)

  @article{ , abstract = {The surface of an organism is a dynamic interface that continually adapts to its environment. In nematodes, the cuticle forms a complex boundary that protects against the physicochemical pressures. However, the precise molecular composition and function of this surface remain largely unexplored. By utilizing 3D-OrbiSIMS, an advanced surface-sensitive mass spectrometry method, we directly characterized the molecular composition of the outermost regions (∼50 nm) of Caenorhabditis elegans and Pristionchus pacificus to improve the understanding of species-specific surface lipid composition and its potential roles in nematode biology. We found that nematode surfaces consist of a lipid-dominated landscape (>81% C. elegans and >69% P. pacificus of all surveyed chemistries) with distinct compositions, which enrich in granularity and complexity through development. The surface lipids are also species-specific, potentially highlighting distinct molecular compositions that are derived from diverging evolutionary paths. By exploring the effect of mutations on lipid production, we found the peroxisomal fatty acid β-oxidation component daf-22 is essential for defining the surface molecular fingerprint. This pathway is conserved across species in producing distinct chemical profiles, indicating its fundamental role in lipid metabolism and maintaining the surface integrity and function. Furthermore, we discovered that variations in surface lipids of C. elegans daf-22 larvae contribute to significantly increased susceptibility to predation by P. pacificus . Therefore, our findings reveal that nematode surface lipids are developmentally dependent, species-specific, and fundamental in interspecies interactions. These insights pave the way for further exploration into the physiological and behavioral significance of surface lipids.}, archive = {J_JACS}, author = {Anna M. Kotowska and Fumie Hiramatsu and Morgan R. Alexander and David J. Scurr and James W. Lightfoot and Veeren M. Chauhan}, doi = {10.1021/jacs.4c12519}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6439--6449}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface lipids in nematodes are influenced by development and species-specific adaptations}, volume = {147}, year = {2025}, }
• (2025). Polyelectrolyte membrane enables highly reversible zinc battery chemistry via immobilizing anion and stabilizing water. JACS, 147(8), 6427--6438. (www)

  @article{ , abstract = {The integration of water-based electrolytes into zinc-ion batteries encounters challenges due to the limited voltage window of water, interfacial side reactions of mobile counterions, and the growth of zinc metal (Zn 0 ) dendrites during charge. In this study, we introduce a nonfluorinated, cation-conducting polyelectrolyte membrane (PEM) designed to alleviate these challenges by suppressing the reactivities of both water and counterions. This PEM forms hydrogen bonds with water molecules through its proton-accepting side chains, thus shifting the lowest unoccupied molecular orbital (LUMO) energy of water from −0.37 to −0.14 eV and inducing a negative shift in the onset potential for hydrogen evolution by 110 mV. Additionally, it immobilizes the counteranions onto the polymer backbones via covalent bonding, hence making the Zn 2+ transference number nearly unity (0.96). Meanwhile, the high modulus PEM establishes a solid-state diffusion barrier to homogenize the interfacial Zn 2+ flux, leading to 3D in-plane interfacial Zn 2+ diffusion and compact Zn 0 plating within the (002) plane. Atomic resolution scanning transmission electron microscopy (STEM) reveals corrosion-free Zn 0 deposition without electrolyte degradation, while operando transition X-ray microscopy (TXM) further illustrates the real-time dendrite-free Zn 0 plating process at 5 mA/cm 2 . Consequently, the unique properties of this water-binding and anion-tethering PEM enable enhanced electrochemical performance without employing highly fluorinated and expensive anions. This PEM demonstrates a durability of 3800 h in Zn 0 –Zn 0 symmetric cells and a lifetime of 6000 cycles in Zn 0 –LiV 3 O 8 full cells.}, archive = {J_JACS}, author = {Yubin He and Rui Zhang and Peichao Zou and Ryan Wonu Chu and Ruoqian Lin and Kang Xu and Huolin L. Xin}, doi = {10.1021/jacs.4c12409}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6427--6438}, shortjournal = {J. Am. Chem. Soc.}, title = {Polyelectrolyte membrane enables highly reversible zinc battery chemistry via immobilizing anion and stabilizing water}, volume = {147}, year = {2025}, }
• (2025). Enabling thermally stimulated delayed phosphorescence in Cu(I) cyclic trinuclear complexes with near-unity quantum yield. JACS, 147(8), 6415--6426. (www)

  @article{ , abstract = {Thermally stimulated delayed phosphorescence (TSDP) emission has recently been discovered in several Au(I)/Au(III) complexes, featuring thermally enhanced emission intensities and notable quantum yields (QYs). Developing earth-abundant metal-based TSDP emitters with further increased QYs holds significant promise for practical applications. Herein, we present a halogen bonding approach to achieve TSDP emission in bromo-substituted Cu(I) cyclic trinuclear complexes (CTCs). Photophysical analysis and theoretical calculations reveal the crucial role of halogen bonding in suppressing the excited-state distortions and reducing energy differences between the first and second triplet excited states (T 1 and T 2 ). This enables efficient spin-allowed reverse internal conversion, leading to the TSDP behavior. Additionally, the low internal reorganization energy and rigid halogen-bonded network in bromo-substituted Cu(I) CTCs result in significantly suppressed nonradiative decay and high QYs, with one approaching near-unity. This work provides an innovative approach to extend the TSDP behavior from Au(I)/Au(III) to Cu(I) complexes with high QYs.}, archive = {J_JACS}, author = {Guo-Quan Huang and Ri-Qin Xia and Xu Chen and Hu Yang and Yong-Liang Huang and Kun Wu and Ji Zheng and Weigang Lu and Dan Li}, doi = {10.1021/jacs.4c09907}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6415--6426}, shortjournal = {J. Am. Chem. Soc.}, title = {Enabling thermally stimulated delayed phosphorescence in Cu(I) cyclic trinuclear complexes with near-unity quantum yield}, volume = {147}, year = {2025}, }
• (2025). Unraveling the stoichiometric interactions and synergism between ligand-protected gold nanoparticles and proteins. JACS, 147(8), 6404--6414. (www)

  @article{ , abstract = {Nanomaterials that engage in well-defined and tunable interactions with proteins are pivotal for the development of advanced applications. Achieving a precise molecular-level understanding of nano-bio interactions is essential for establishing these interactions. However, such an understanding remains challenging and elusive. Here, we identified stoichiometric interactions of water-soluble gold nanoparticles (Au NPs) with bovine serum albumin (BSA), unraveling their synergism in manipulating emission of nano-bio conjugates in the second near-infrared (NIR-II) regime. Using Au 25 ( p -MBS) 18 ( p -MBS = para -mercaptobenzenesulfonic acid) as paradigm particles, we achieved precise binding of Au NPs to BSA with definitive molar ratios of 1:1 and 2:1, which is unambiguously evidenced by high-resolution mass spectrometry and transmission electron microscopy. Molecular dynamics simulations identified well-defined binding sites, mediated by electrostatic interactions and hydrogen bonds between the p -MBS moieties on the Au 25 ( p -MBS) 18 surface and BSA. Particularly, positively charged residues on BSA were found to be pivotal. By careful control of the molar ratio of Au 25 ( p -MBS) 18 to BSA, atomically precise [Au 25 ( p -MBS) 18 ] x –BSA conjugates ( x = 1 or 2) could be formed. Through a comprehensive spectroscopy study, an electron transfer process and synergistic effect were manifested in the Au 25 ( p -MBS) 18 –BSA conjugates, leading to drastically enhanced emission in the NIR-II window. This work offers insights into the precise engineering of nanomaterial–protein interactions and opens new avenues for the development of next-generation nano-bio conjugates for nanotheranostics.}, archive = {J_JACS}, author = {Bihan Zhang and María Francisca Matus and Qiaofeng Yao and Xiaorong Song and Zhennan Wu and Wenping Hu and Hannu Häkkinen and Jianping Xie}, doi = {10.1021/jacs.4c09879}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6404--6414}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the stoichiometric interactions and synergism between ligand-protected gold nanoparticles and proteins}, volume = {147}, year = {2025}, }
• (2025). Non-noble metal single-molecule photocatalysts for the overall photosynthesis of hydrogen peroxide. JACS, 147(8), 6390--6403. (www)

  @article{ , abstract = {Despite the great progress in molecule photocatalytic solar energy conversion, it is particularly challenging to realize a photocatalytic overall reaction in a non-noble metal complex, which represents a new paradigm for photosynthesis. In this study, a class of novel non-noble metal complexes with head-to-tail geometry were designed and readily synthesized via the coordination of triphenylamine-modified 2,2′: 6′,2″-terpyridine ligands with Zn 2+ . As expected, these complexes exhibited the desired through-space charge-transfer transition, generating both long-lived excited states (on the order of microseconds) and separate redox centers under visible-light irradiation. These complexes have particularly low exciton binding energies, which make them excellent heterogeneous single molecular photocatalysts for the overall photosynthetic production of H 2 O 2 . Remarkably, a high H 2 O 2 evolution rate (8862 μmol g –1 h –1 ) was achieved in pure H 2 O under an air atmosphere via precise molecular tailoring, revealing the unparalleled advantages of molecular photocatalysts in improving the catalytic rate of H 2 O 2 production. This is the first time that single-molecule photocatalysts have been used to efficiently complete the photosynthesis of H 2 O 2 . This study presents a new paradigm for photocatalytic energy conversion and provides unique insights into the design of molecular photocatalysts.}, archive = {J_JACS}, author = {Fan Fu and Yongxin Liu and Mingliang Liu and Zhengguang Li and Wanying Zhong and Yaqin Li and Kaixiu Li and Jun Wang and Yongchao Huang and Yiming Li and Wei Liu and Yi Zhang and Kaisong Xiang and Hui Liu and Pingshan Wang and Die Liu}, doi = {10.1021/jacs.4c09445}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6390--6403}, shortjournal = {J. Am. Chem. Soc.}, title = {Non-noble metal single-molecule photocatalysts for the overall photosynthesis of hydrogen peroxide}, volume = {147}, year = {2025}, }
• (2025). Robust heteronuclear correlations for sub-milligram protein in ultrafast magic-angle spinning solid-state NMR. JACS, 147(8), 6384--6389. (www)

  @article{ , abstract = {Proton-detected solid-state nuclear magnetic resonance (ssNMR) under ultrafast magic-angle spinning (MAS) has become a powerful tool for elucidating the structures of proteins with sub-milligram quantities, where establishing 13 C– 15 N correlations is essential. However, traditional 13 C– 15 N cross-polarization (CP), effective at lower MAS frequencies, suffers diminished efficiency under ultrafast MAS conditions. To overcome this limitation, we developed a robust method for selective polarization between insensitive nuclei (SPINE). This approach significantly enhances the heteronuclear 13 C– 15 N correlation efficiency over CP, with gain factors of 1.75 for 13 CA– 15 N and 1.9 and 13 CO– 15 N transfers. SPINE’s efficacy was validated on four diverse proteins: the microcrystalline β1 immunoglobulin binding domain of protein G (GB1), the large-conductance mechanosensitive ion channel from Methanosarcina acetivorans (MaMscL), fibrillar septum-forming protein (SepF), and the vertex protein of the β-carboxysome shell (CcmL). This enhancement can reduce the duration of current multidimensional experiments to about one-third of that using a single 13 C– 15 N CP and to about one-tenth with dual 13 C– 15 N transfers. Our findings underscore the practical utility and versatility of SPINE in ssNMR spectroscopy, making it a valuable approach for advancing structural biology studies of sub-milligram protein.}, archive = {J_JACS}, author = {Hang Xiao and Jian Wang and Huan Tan and Yuefang Gan and Wenjing Liu and Yan Zhang and Zhengfeng Zhang and Jun Yang}, doi = {10.1021/jacs.5c00191}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6384--6389}, shortjournal = {J. Am. Chem. Soc.}, title = {Robust heteronuclear correlations for sub-milligram protein in ultrafast magic-angle spinning solid-state NMR}, volume = {147}, year = {2025}, }
• (2025). Enantioselective ring opening of azetidines via charge recognition in hydrogen-bond-donor catalysis. JACS, 147(8), 6378--6383. (www)

  @article{ , abstract = {We report the highly enantioselective ring-opening of 3-substituted azetidines by alkyl and acyl halides promoted by a chiral squaramide hydrogen-bond donor catalyst. Broad scope is achieved across a variety of substrate combinations possessing disparate steric features. The same catalyst had been identified previously to promote enantioselective opening of oxetanes via both Lewis and Brønsted acid mechanisms. This remarkable generality is interpreted to arise from catalyst recognition of the conserved electrostatic features of the dipolar enantioselectivity-determining transition states in the ring-opening S N 2 mechanisms with simultaneous tolerance of variation of the specific functional group and steric features of the reactions. Specific experimental and computational evidence is provided for a network of electrostatic interactions that forms a shared basis for enantioinduction across these transformations. This work provides a framework for designing catalysts that achieve high enantioselectivity across diverse reactions unified by conserved polar mechanisms.}, archive = {J_JACS}, author = {Joseph J. Gair and Mayuko Isomura and Corin C. Wagen and Daniel A. Strassfeld and Eric N. Jacobsen}, doi = {10.1021/jacs.5c00165}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6378--6383}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective ring opening of azetidines via charge recognition in hydrogen-bond-donor catalysis}, volume = {147}, year = {2025}, }
• (2025). Mechanism-based inhibition of histone deacetylase 6 by a selenocyanate is subject to redox modulation. JACS, 147(8), 6373--6377. (www)

  @article{ , abstract = {Organoselenocyanates have attracted considerable attention in recent years due to their therapeutic potential and versatility in medicinal chemistry. Here, we report on the mechanism of inhibition by 5-phenylcarbamoylpentyl selenocyanide (SelSA-2), an analogue of the well-characterized histone deacetylase inhibitor suberoylanilide hydroxamic acid (SAHA, a.k.a. Vorinostat). We show that histone deacetylases 6 and 10 promote selenocyanate hydrolysis to generate a selenolate anion, and we explore the redox chemistry of selenium as it modulates inhibitory activity through reversible formation of the diselenide. The 2.15 Å-resolution crystal structure of histone deacetylase 6 cocrystallized with SelSA-2 conclusively demonstrates that it is not the selenocyanate, but instead a zinc-bound selenolate anion, that is the active pharmacophore responsible for enzyme inhibition.}, archive = {J_JACS}, author = {Juana Goulart Stollmaier and Briana Abigail R. Czarnecki and David W. Christianson}, doi = {10.1021/jacs.5c00157}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6373--6377}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanism-based inhibition of histone deacetylase 6 by a selenocyanate is subject to redox modulation}, volume = {147}, year = {2025}, }
• (2025). Isomeric azulene-based carbon-centered radicals derived from N-heterocyclic carbenes. JACS, 147(8), 6367--6372. (www)

  @article{ , abstract = {Azulene (isomer with naphthalene), a representative nonalternant hydrocarbon, has attracted significant attention as a building block for π-extended molecules owing to its distinctive electronic structure and physicochemical properties that differ from those of conventional alternant hydrocarbons. Nevertheless, the development of stable carbon-centered radicals utilizing an azulene moiety remains relatively scarce. Herein, we report the electronic structures and optical properties of azulene-based carbon-centered radical isomers, 1 and 2 , which were designed and synthesized by attaching N-heterocyclic carbenes (NHCs) to the 6-position of the seven-membered ring or 2-position of the five-membered ring of azulene, respectively. Density functional theory calculations reveal that the spin density in 1 is primarily localized on the five-membered ring of the azulene, indicating it as π-extended cyclopentadienyl radicals, whereas the spin density is predominantly distributed in the seven-membered ring of azulene for 2 , serving as an example of π-extended cycloheptatrienyl radicals. Furthermore, although both radicals 1 and 2 exhibit anti-Kasha emission, the emission wavelength of 2 ( λ em ∼ 495 nm) is significantly red-shifted compared to that of 1 ( λ em ∼ 396 nm).}, archive = {J_JACS}, author = {Xin Li and Zhao-Wang Gao and Can Chen and Xu-Ning Wang and Ying-Feng Han}, doi = {10.1021/jacs.4c18599}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6367--6372}, shortjournal = {J. Am. Chem. Soc.}, title = {Isomeric azulene-based carbon-centered radicals derived from N-heterocyclic carbenes}, volume = {147}, year = {2025}, }
• (2025). Hydrophobized Metal–Organic frameworks as versatile building blocks for tailored nanocrystal superlattices. JACS, 147(8), 6361--6366. (www)

  @article{ , abstract = {This study introduces an effective strategy for hydrophobizing metal–organic frameworks (MOFs) using oleyl phosphate (OP) ligands. This modification makes MOF particles dispersible in nonpolar solvents and provides them with colloidal stability akin to traditional colloidal nanocrystals (NCs). The resulting OP-capped MOF particles can then be employed as building blocks for constructing various two-dimensional (2D) and 3D superlattices through self-assembly methods typically used for NCs. Additionally, binary superlattices with tailored structures can be achieved by coassembling OP-capped MOF particles with different NCs. This robust surface hydrophobization approach is adaptable to various MOFs, facilitating the rational design and creation of complex MOF-based superstructures.}, archive = {J_JACS}, author = {Xuesong Wu and Yutong Gao and Hao Wang and Zhebin Zhang and Xiangyun Xi and Dong Yang and Tongtao Li and Angang Dong}, doi = {10.1021/jacs.4c17724}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6361--6366}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrophobized Metal–Organic frameworks as versatile building blocks for tailored nanocrystal superlattices}, volume = {147}, year = {2025}, }
• (2025). A dynamic covalent organic framework with entangled 2D layers. JACS, 147(8), 6355--6360. (www)

  @article{ , abstract = {Dynamic covalent organic frameworks (COFs) represent an emerging class of porous materials with an inherent structural flexibility. However, due to the challenges in their synthesis and structural characterization, research on dynamic COFs remains at an early stage and requires further exploration. Herein, we report the designed synthesis of a novel COF with entangled 2D layers that exhibits interesting dynamic behavior in response to organic vapor exposure. By employing the continuous rotation electron diffraction technique, we precisely resolved the crystal structures of the COF before and after vapor adsorption. Structural analysis revealed that the vapor-induced conformational changes, such as anthracene unit rotation, triggered layer adjustments and reduced entanglement angles, leading to significant pore structure alterations. This study not only introduces a new class of dynamic COFs but also provides a foundation for the rational design of entangled frameworks with structural flexibility for diverse applications.}, archive = {J_JACS}, author = {Yuanpeng Cheng and Honglin Du and Yongyong Wang and Junjie Xin and Yulong Dong and Xuejiao Wang and Xu Zhou and Bo Gui and Junliang Sun and Cheng Wang}, doi = {10.1021/jacs.4c17962}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6355--6360}, shortjournal = {J. Am. Chem. Soc.}, title = {A dynamic covalent organic framework with entangled 2D layers}, volume = {147}, year = {2025}, }
• (2025). Catalytic phosphorylation of tyrosine via a radical arbuzov reaction. JACS, 147(8), 6349--6354. (www)

  @article{ , abstract = {Synthetic protein/peptide modification is a powerful strategy for the development of new therapeutics and tools for chemical biology. Accordingly, the development of a synthetic variant of biological tyrosine phosphorylation, a cornerstone of the post-translational modification landscape, could find widespread application in the study of this fundamental biochemical signal. This work describes the development of a mechanistically novel, redox-neutral, photocatalytic tyrosine phosphorylation reaction via a radical Arbuzov-type mechanism. The reaction proceeds with good tyrosine selectivity in di-, tri-, and oligopeptides under mild conditions near neutral pH, tolerating potentially problematic functionality. As the first photocatalytic tyrosine phosphorylation reaction, this work represents a major advance toward the goal of synthetic tyrosine phosphorylation.}, archive = {J_JACS}, author = {Benjamin D. A. Shennan and Tomoyuki Fukuta and Mina Yamane and Takashi Koyama and Harunobu Mitsunuma and Motomu Kanai}, doi = {10.1021/jacs.4c17637}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6349--6354}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic phosphorylation of tyrosine via a radical arbuzov reaction}, volume = {147}, year = {2025}, }
• (2025). Vancomycin–Teixobactin conjugates. JACS, 147(8), 6343--6348. (www)

  @article{ , abstract = {Vancomycin continues to be a widely used antibiotic of last resort in treating drug-resistant pathogens despite the emergence of vancomycin-resistant strains such as vancomycin-resistant Enterococci (VRE). This communication reports that conjugation of vancomycin to a second antibiotic that targets a different region of lipid II enhances and rescues its antibiotic activity. Conjugation of vancomycin to a minimal teixobactin pharmacophore in which residues 1–6 are replaced with an aromatic amide results in substantial enhancement in activity over the individual components or mixtures thereof. Three conjugates with minimum inhibitory concentrations (MICs) of 0.5 μg/mL against methicillin-resistant Staphylococcus aureus (MRSA) and 0.063–0.125 μg/mL against methicillin-susceptible Staphylococcus aureus (MSSA) were identified. Each of these conjugates is also active against VRE, even though the individual components are inactive, with the most active conjugate (Cbp-Lys 10 -teixo 7–11 -vanco) having an MIC of 2–4 μg/mL. These findings demonstrate that conjugation of vancomycin to a minimal teixobactin pharmacophore is an effective strategy for enhancing the activity of vancomycin against important Gram-positive pathogens.}, archive = {J_JACS}, author = {Maria Sophia Teresa Lee Padilla and James S. Nowick}, doi = {10.1021/jacs.4c17175}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6343--6348}, shortjournal = {J. Am. Chem. Soc.}, title = {Vancomycin–Teixobactin conjugates}, volume = {147}, year = {2025}, }
• (2025). One-step HF-free synthesis of alkali metal fluorides from fluorspar. JACS, 147(8), 6338--6342. (www)

  @article{ , abstract = {Alkali metal fluorides (MF) are commodity chemicals currently synthesized from naturally occurring fluorite (fluorspar, CaF 2 ) in two steps: conversion of acid grade fluorspar (AGF) into highly hazardous hydrogen fluoride (HF) followed by neutralization with alkali metal hydroxides/carbonates. Herein, we report a one-step mechanochemical reaction that converts AGF into alkali metal fluorides under basic conditions, bypassing HF. The method consists of reacting AGF with alkali metal (hydr)oxides and titanium dioxide (TiO 2 ) under mechanical energy for MF formation and in situ sequestration of calcium (hydr)oxide byproducts as calcium titanate (CaTiO 3 ). Ca 2+ sequestration prevents reversible CaF 2 formation upon aqueous extraction, thus enabling the isolation of alkali metal fluorides. We also demonstrate that alkali metal titanates (M 2 TiO 3 ) are suitable reagents for both CaF 2 activation and Ca 2+ sequestration, with K 2 TiO 3 being optimal for KF synthesis.}, archive = {J_JACS}, author = {Thomas Schlatzer and Christopher A. Goult and Michael A. Hayward and Véronique Gouverneur}, doi = {10.1021/jacs.4c16608}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6338--6342}, shortjournal = {J. Am. Chem. Soc.}, title = {One-step HF-free synthesis of alkali metal fluorides from fluorspar}, volume = {147}, year = {2025}, }
• (2025). Aligning the induced anisotropy of isotropic nanoparticles with liquid crystals. JACS, 147(8), 6332--6337. (www)

  @article{ , abstract = {Thermotropic liquid crystals (LCs) present opportunities for synergistic interactions with ligand-functionalized nanoparticles (NPs). Understanding the dynamics and structures of ligand-coated NPs in an anisotropic LC environment allows for better design and control of versatile LC-NP hybrid materials. Here, simulations and experiments yield direct evidence that cyanobiphenyl LCs induce anisotropy in the biphenylalkyl ligand shells of spherical NPs. The ellipsoidal NP aligns with the LC director. Magnetic fields can dictate the directional ordering of mesogens and consequently allow control of the orientation of the nonmagnetic NPs. Controlling the alignment and deformation advances the design and engineering of these hybrid nanomaterials.}, archive = {J_JACS}, author = {Yifan Ning and Dai-Bei Yang and Shengsong Yang and Yugang Zhang and Jeffery G. Saven and Christopher B. Murray}, doi = {10.1021/jacs.4c16332}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6332--6337}, shortjournal = {J. Am. Chem. Soc.}, title = {Aligning the induced anisotropy of isotropic nanoparticles with liquid crystals}, volume = {147}, year = {2025}, }
• (2025). Single-enzyme conversion of tryptophan to skatole and cyanide expands the mechanistic competence of diiron oxidases. JACS, 147(8), 6326--6331. (www)

  @article{ , abstract = {Skatole is a pungent heterocyclic compound derived from the essential amino acid l -tryptophan by bacteria in the mammalian digestive tract. The four-step anaerobic conversion of tryptophan to skatole is well-established; though, to date, no aerobic counterpart has been reported. Herein, we report the discovery of the oxygen-dependent skatole synthase SktA that single-handedly converts 5-bromo- l -tryptophan to 5-bromoskatole, obviating the need for a multienzyme process. SktA is part of a three-gene biosynthetic gene cluster (BGC) in the cyanobacterium Nostoc punctiforme NIES-2108 and functions as a nonheme diiron enzyme belonging to the heme oxygenase-like domain-containing oxidase (HDO) superfamily. Our detailed biochemical analyses revealed cyanide and bicarbonate as biosynthetic coproducts, while stopped-flow experiments showed the hallmark formation of a substrate-triggered peroxo Fe 2 (III) intermediate. Overall, this work unravels an alternative pathway for converting tryptophan to skatole while also expanding the functional repertoire of HDO enzymes.}, archive = {J_JACS}, author = {Sanjoy Adak and Logan A. Calderone and August Krueger and Maria-Eirini Pandelia and Bradley S. Moore}, doi = {10.1021/jacs.4c14573}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6326--6331}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-enzyme conversion of tryptophan to skatole and cyanide expands the mechanistic competence of diiron oxidases}, volume = {147}, year = {2025}, }
• (2025). Facile synthesis of housanes by an unexpected strategy. JACS, 147(8), 6318--6325. (www)

  @article{ , abstract = {Rigid bicyclic hydrocarbons have emerged as important building blocks in the drug discovery industry. Despite progress in this general area, bicyclo[2.1.0]pentanes (housanes) are an understudied class of molecules. Herein we report an unconventional synthesis of borylated housanes. Our method features a broad scope and high diastereoselectivities in the synthesis of versatile intermediates. The route involves a strain-release diboration of bicyclo[1.1.0]butane and intramolecular deborylative alkylation. The versatility of the bridgehead boronic ester was demonstrated in several functionalizations. Lastly, the mechanism of the reaction was investigated, and an unusual stereospecific and diastereoselective ring expansion was uncovered.}, archive = {J_JACS}, author = {Yanyao Liu and Somanea Tranin and Yu-Che Chang and Evan B. Piper and Thomas Fessard and Ryan Van Hoveln and Christophe Salome and M. Kevin Brown}, doi = {10.1021/jacs.4c13298}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6318--6325}, shortjournal = {J. Am. Chem. Soc.}, title = {Facile synthesis of housanes by an unexpected strategy}, volume = {147}, year = {2025}, }
• (2025). The role of interfaces and charge for chemical reactivity in microdroplets. JACS, 147(8), 6299--6317. (www)

  @article{ , abstract = {A wide variety of reactions are reported to be dramatically accelerated in aqueous microdroplets, making them a promising platform for environmentally clean chemical synthesis. However, to fully utilize the microdroplets for accelerating chemical reactions requires a fundamental understanding of how microdroplet chemistry differs from that of a homogeneous phase. Here we provide our perspective on recent progress to this end, both experimentally and theoretically. We begin by reviewing the many ways in which microdroplets can be prepared, creating water/hydrophobic interfaces that have been frequently implicated in microdroplet reactivity due to preferential surface adsorption of solutes, persistent electric fields, and their acidity or basicity. These features of the interface interplay with specific mechanisms proposed for microdroplet reactivity, including partial solvation, possible gas phase channels, and the presence of highly reactive intermediates. We especially highlight the role of droplet charge and associated electric fields, which appears to be key to understanding how certain reactions, like the formation of hydrogen peroxide and reduced transition metal complexes, are thermodynamically possible in microdroplets. Lastly, we emphasize opportunities for theoretical advances and suggest experiments that would greatly enhance our understanding of this fascinating subject.}, archive = {J_JACS}, author = {R. Allen LaCour and Joseph P. Heindel and Ruoqi Zhao and Teresa Head-Gordon}, doi = {10.1021/jacs.4c15493}, journal = {Journal of the American Chemical Society}, month = {2}, number = {8}, pages = {6299--6317}, shortjournal = {J. Am. Chem. Soc.}, title = {The role of interfaces and charge for chemical reactivity in microdroplets}, volume = {147}, year = {2025}, }
• (2025). Retraction of “Hydrogen atom transfer (HAT)-mediated remote desaturation enabled by Fe/Cr–H cooperative catalysis”. JACS, 147(7), 6298. (www)

  @article{ , archive = {J_JACS}, author = {Yanjun Wan and Augustine K. Adda and Jin Qian and David A. Vaccaro and Peixian He and Gang Li and Jack R. Norton}, doi = {10.1021/jacs.4c18216}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6298}, shortjournal = {J. Am. Chem. Soc.}, title = {Retraction of “Hydrogen atom transfer (HAT)-mediated remote desaturation enabled by Fe/Cr–H cooperative catalysis”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Synthesis and stability of biomolecules in C–H–O–N fluids under earth’s upper mantle conditions”. JACS, 147(7), 6297. (www)

  @article{ , archive = {J_JACS}, author = {Tao Li and Nore Stolte and Renbiao Tao and Dimitri A. Sverjensky and Isabelle Daniel and Ding Pan}, doi = {10.1021/jacs.5c01671}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6297}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Synthesis and stability of biomolecules in C–H–O–N fluids under earth’s upper mantle conditions”}, volume = {147}, year = {2025}, }
• (2025). Sequencing of d/l-DNA and XNA by templated-synthesis. JACS, 147(7), 6288--6296. (www)

  @article{ , abstract = {Progress in oligonucleotide sequencing has transformed modern biology and medicine. Here we report a fast and efficient enzyme-free primer extension of PNA with reversible chain termination and its application to DNA and XNA sequencing. The approach leverages activated 4-mer PNAs that react in a templated ligation reaction at μM concentrations within minutes. We demonstrate that the fidelity of this enzyme-free primer extension benefits from reactions performed with a mixture of activated PNAs where every 4-mer has its self-complementary 4-mer. The reactions can be performed using the whole repertoire of 4-mers (256 permutations) in a parallelized manner. Using a primer in combination with its −1, −2, and −3 deletion allows for sequencing by MALDI analysis, using the increment in mass for each nucleobase assignment. Given the enzyme-free nature of this sequencing and the achiral nature of PNA, we further demonstrate that the technology can be used to sequence d - or l -DNA as well as LNA and PNA (XNA).}, archive = {J_JACS}, author = {Saurabh Joshi and Patrick Romanens and Nicolas Winssinger}, doi = {10.1021/jacs.5c00708}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6288--6296}, shortjournal = {J. Am. Chem. Soc.}, title = {Sequencing of d/l-DNA and XNA by templated-synthesis}, volume = {147}, year = {2025}, }
• (2025). Visible light-promoted deracemization of α-amino aldehyde by synergistic chiral primary amine and hypervalent iodine catalysis. JACS, 147(7), 6280--6287. (www)

  @article{ , abstract = {α-Amino aldehydes, as versatile chiral synthons, are easily racemized under normal acid or base conditions, seriously limiting their synthetic potentials. We report herein an effective deracemization of α-amino aldehydes by a synergistic chiral primary amine and hypervalent iodine catalysis under visible light. The developed catalytic system allows for the on-demand production of α-Boc- or Cbz-protected amino aldehydes with high enantioselectivity. Mechanistic studies verified a photochemical Z – E isomerization mechanism that drives the deracemization process.}, archive = {J_JACS}, author = {Tianrun Pan and Xieyang Jiang and Mouxin Huang and Long Zhang and Sanzhong Luo}, doi = {10.1021/jacs.4c18407}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6280--6287}, shortjournal = {J. Am. Chem. Soc.}, title = {Visible light-promoted deracemization of α-amino aldehyde by synergistic chiral primary amine and hypervalent iodine catalysis}, volume = {147}, year = {2025}, }
• (2025). Luminescent Cerium(III) complexes with poly(mercaptoimidazolyl)borate: A new emitter based on S-coordinating ligands. JACS, 147(7), 6268--6279. (www)

  @article{ , abstract = {Lanthanide ions are hard Lewis acids and usually form weak bonds with soft sulfur donors, which result in the supposed instability of their complexes with S-coordinating ligands. Compared with luminescent lanthanide complexes with hard nitrogen or oxygen donor ligands, the development of luminescent lanthanide complexes based on sulfur-donor ligands currently lags behind. In this work, two types of poly(mercaptoimidazolyl)borate ligands, one is tridentate and the other is tetradentate, were used for the design and synthesis of two series of novel S-coordinating cerium(III) (Ce(III)) complexes, which were found to be not only luminescent but also with moderate to surprisingly good stability in air. By tuning the ligand type and substituents, blue- and yellow-green-emitting Ce(III) complexes with different emission mechanisms of d–f transition, delayed d–f transition, and ligand-centered fluorescence/phosphorescence were obtained, among which the highest photoluminescence quantum yield (PLQY) was 97%, and the most stable one can still maintain 74% of the initial PLQY even after exposure to air for 1 month. Furthermore, we investigated the degradation mechanism of these complexes in air, revealing the oxidation of low-valence sulfur(II) to high-valence sulfur-containing S═O bonds. This work shows the potential of S-coordinating ligands in luminescent Ce(III) complexes and provides new perspectives for designing Ce(III) complexes with soft donors.}, archive = {J_JACS}, author = {Jiayin Zheng and Ruoyao Guo and Hao Qi and Huanyu Liu and Yanxin Zha and Rubing Bai and Yujia Li and Zuqiang Bian and Zhiwei Liu}, doi = {10.1021/jacs.4c18459}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6268--6279}, shortjournal = {J. Am. Chem. Soc.}, title = {Luminescent Cerium(III) complexes with poly(mercaptoimidazolyl)borate: A new emitter based on S-coordinating ligands}, volume = {147}, year = {2025}, }
• (2025). Enantioselective decarboxylative hydrogen-atom transfer reaction. JACS, 147(7), 6259--6267. (www)

  @article{ , abstract = {Direct enantioselective decarboxylative transformations of carboxylic acids have become powerful tools for constructing structurally and functionally diverse molecules. Herein, an unprecedented organocatalyzed protocol for enantioconvergent decarboxylative reduction was established by leveraging dual catalysis of photoredox-mediated radical generation and a thiol-catalyzed asymmetric hydrogen-atom transfer process. With this hydrodecarboxylation, a variety of chiral 3-substituted indolines were attained from the acids in moderate to excellent yields with high enantioselectivities.}, archive = {J_JACS}, author = {Yugui Xu and Chaoren Shen and Kaiwu Dong}, doi = {10.1021/jacs.4c18464}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6259--6267}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective decarboxylative hydrogen-atom transfer reaction}, volume = {147}, year = {2025}, }
• (2025). Light-induced increase in bond strength─from chalcogen bond to three-electron σ bond upon excitation. JACS, 147(7), 6249--6258. (www)

  @article{ , abstract = {Chalcogen bonds are σ hole interactions between a chalcogen center and a Lewis base center and have been applied in recent years as an alternative to hydrogen bonds in supramolecular chemistry and catalysis. While the electronic interactions of chalcogen bonds in the ground state have been intensively analyzed, there is barely any knowledge about the electron structure in the excited state. This is despite the fact that in some cases photoswitches containing chalcogen bonds exhibit exceptional switching behavior. Here, we investigate the effect of light absorption on chalcogen bonds containing divalent chalcogen centers. Quantum chemical calculations reveal that in the excited S 1 state the noncovalent chalcogen bond converts to a covalent three-electron σ bond. The bond between the chalcogen center and the Lewis base center is thus significantly reinforced by light excitation. This change in bond type explains the previously experimentally observed nonswitchability of some tellurium-containing azo compounds. Furthermore, we were able to demonstrate that the switchability of certain selenium-containing compounds is temperature-dependent, whereby the ratio of the less stable cis compound is higher for higher temperatures. These results highlight the potential for designing responsive materials and dynamic molecular systems based on light-induced chalcogen bond modulation.}, archive = {J_JACS}, author = {Zoe Nonie Scheller and Saber Mehrparvar and Gebhard Haberhauer}, doi = {10.1021/jacs.4c18435}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6249--6258}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-induced increase in bond strength─from chalcogen bond to three-electron σ bond upon excitation}, volume = {147}, year = {2025}, }
• (2025). Development of a highly durable photocatalytic CO2 reduction using a mn-complex catalyst: Application of selective photosplitting of a Mn(0)–Mn(0) bond. JACS, 147(7), 6236--6248. (www)

  @article{ , abstract = {fac -[Mn I (diimine)(CO) 3 (L)] 0/+ has attracted significant attention as a catalyst for the photocatalytic reduction of CO 2 . However, in such photocatalytic systems, the photoexcitation of Mn complexes and reaction intermediates induces their decomposition, which lowers the durability of these systems. In this study, we clarified the primary process whereby the Mn complex catalyst decomposes during the photocatalytic reaction. Based thereupon, we successfully constructed a highly durable photocatalytic system, of which the turnover number of formate (TON HCOO– ) exceeded 1700 when fac -[Mn I (bpy)(CO) 3 ((OC(O)OC 2 H 5 N(C 2 H 5 OH) 2 ) ( Mn-CO 2 -TEOA ) as the catalyst, [Os II (4,4′-dimethyl-bpy)(5,5′-dimethyl-bpy) 2 ] 2+ ( Os ) as the photosensitizer, and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole ( BIH ) as the reductant were used in conjunction with irradiation at λ ex ≥ 620 nm. In contrast, for the same photocatalytic system, irradiation at λ ex ≥ 480 nm lowered the TON HCOO– to less than 60. The significant difference in the durability of the photocatalytic system arises from the dependence of the Mn(0)–Mn(0) dimer [Mn 0 2 (bpy) 2 (CO) 6 ] ( Dim-Mn ), an intermediate produced during the photocatalytic reaction, on the wavelength of the irradiated light for its photoreactivity. That is, the irradiation of Dim-Mn at λ ex ≥ 620 nm selectively induces splitting of the Mn–Mn bond to produce [Mn 0 (bpy)(CO) 3 ] ( Mn • ) and, contrary to this, splitting of the Mn(0)–CO bonds and further decomposition processes are induced by irradiation at λ ex ≥ 480 nm.}, archive = {J_JACS}, author = {Hiroki Koizumi and Yusuke Tamaki and Kei Kamogawa and Marco Nicaso and Yutaka Suzuki and Yasuomi Yamazaki and Hiroyuki Takeda and Osamu Ishitani}, doi = {10.1021/jacs.4c18366}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6236--6248}, shortjournal = {J. Am. Chem. Soc.}, title = {Development of a highly durable photocatalytic CO2 reduction using a mn-complex catalyst: Application of selective photosplitting of a Mn(0)–Mn(0) bond}, volume = {147}, year = {2025}, }
• (2025). Beyond the vibrational stark effect: Unraveling the large redshifts of alkyne C–H bond in solvation environments. JACS, 147(7), 6227--6235. (www)

  @article{ , abstract = {C–H···O hydrogen bonds are formed in systems ranging from biomolecular complexes to small-molecule structures. Previous work has focused on the blueshifts in the C–H stretching frequency ( 𝜈 ¯ CH ν ¯ CH ν¯CH ) induced by these hydrogen bonds and their chemical and biological roles. Here, we show that, in contrast, terminal alkyne C–H hydrogen bonds exhibit large redshifts (50–100 cm –1 ) upon hydrogen bonding with oxygen-containing solvents. Using spectroscopic and computational approaches, we elucidate and compare the roles of the vibrational Stark effect, bond polarization, and charge transfer in driving the C–H redshift. We show that the redshifts of alkyne’s terminal C–H upon the formation of hydrogen bonds correlate with the Lewis basicity of the solvent and are significantly larger than those arising solely from solvent electric fields (vibrational Stark effect), differing from the well-studied redshift of carbonyl vibrations induced by hydrogen bonds. Through a decomposition of vibrational frequency shifts based on DFT calculations using absolutely localized molecular orbitals, we demonstrate that including the effects of bond polarization and charge transfer, in addition to the vibrational Stark effect, results in quantitative agreement between experimentally observed C–H frequency shifts and the theoretically predicted values in various oxygen-containing solvents. Our results highlight the significance of effects beyond pure electrostatics in accounting for the large redshifts in C–H···O hydrogen bonds and exemplify our approach to quantifying the contributions from different physical effects.}, archive = {J_JACS}, author = {Chu Zheng and Yuezhi Mao and Thomas E. Markland and Steven G. Boxer}, doi = {10.1021/jacs.4c18102}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6227--6235}, shortjournal = {J. Am. Chem. Soc.}, title = {Beyond the vibrational stark effect: Unraveling the large redshifts of alkyne C–H bond in solvation environments}, volume = {147}, year = {2025}, }
• (2025). Ligand-governed regio- and enantioselective [2 + 2 + 2] cycloaddition of 1,7-enynes: Assembly of the benzo[c]chromen-1-ol backbone and access to enantioenriched cannabinol bioisostere. JACS, 147(7), 6214--6226. (www)

  @article{ , abstract = {We herein report a regioselective synthesis of the benzo[ c ]chromenol core via cationic rhodium-catalyzed [2 + 2 + 2] cycloaddition of 1,7-enynes with tetrolic acid derivatives. With the selection of an appropriate ligand, both regioisomers could be obtained in excellent regiomeric ratio and enantiomeric excess. The regioselectivity was governed by different factors, which was suggested by computational studies. Furthermore, the asymmetric synthesis of an axially chiral cannabinol bioisostere candidate was achieved by the transformation from central chirality to axial chirality. Demonstration of the synthesis of a natural compound was also depicted.}, archive = {J_JACS}, author = {King Hung Nigel Tang and Taichi Kishi and Natsuhiko Sugimura and Yuto Horio and Takanori Shibata}, doi = {10.1021/jacs.4c18319}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6214--6226}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand-governed regio- and enantioselective [2 + 2 + 2] cycloaddition of 1,7-enynes: Assembly of the benzo[c]chromen-1-ol backbone and access to enantioenriched cannabinol bioisostere}, volume = {147}, year = {2025}, }
• (2025). Single-electron catalysis of reversible cycloadditions under nanoconfinement. JACS, 147(7), 6203--6213. (www)

  @article{ , abstract = {Electron transfer (ET) is crucial in many chemical reactions, but its mechanism and role are hardly understood in nanobiotechnology due to the complexity of reaction species and pathways involved. By modulating and monitoring electron behavior at the single-molecule level, we can better understand the fundamental mechanisms and ways to control them for technological use. Here, we unravel a mechanism of single-electron catalysis under positively charged nanoconfinement. We demonstrate that both (2 + 2) and (4 + 4) cycloadditions can be catalyzed reversibly by a single electron. Key reaction pathways are discovered by monitoring sequential electrical signals in the cycloadditions through advanced single-molecule detection platforms. Experimental and theoretical results consistently demonstrate that combining single ET processes with nanoconfinement involving cucurbit[8]uril can lower the reaction energy barrier and promote reversible cycloaddition. Moreover, we show that the bias voltage can fine-tune ET processes and chemical equilibria in bond formation and cleavage. Our results provide a novel approach to elucidate, modulate, and design electron-involved reactions and functionalized devices.}, archive = {J_JACS}, author = {Xin Zhu and Hongliang Chen and Jinying Wang and Agostino Migliore and Xingxing Li and Yanwei Li and Boyu Wang and Chen Yang and Yang Jiao and Jiawen Cao and Caiyao Yang and Chunyan Gao and Suhang He and Kendall N. Houk and Jinlong Yang and J. Fraser Stoddart and Chuancheng Jia and Xuefeng Guo}, doi = {10.1021/jacs.4c18064}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6203--6213}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-electron catalysis of reversible cycloadditions under nanoconfinement}, volume = {147}, year = {2025}, }
• (2025). Mechanism of hydrogen generation catalyzed by a single atom and its spin regulation. JACS, 147(7), 6193--6202. (www)

  @article{ , abstract = {Single-atom catalysts exhibit the excellent catalytic activity and selectivity, making them widely applicable in the fields of advanced materials, environmental science, and chemical synthesis. However, understanding the mechanism of single-atom catalytic reactions, such as the hydrogen generation reaction, is still challenging, which notably hampers the optimization and precise control of the reaction. Here, we immobilize a single-metal atom model catalyst into a single-molecule electrical detection platform for in situ monitoring of the catalytic hydrogen generation process at the single-event level. In combination with theoretical and experimental studies, the catalytic mechanisms of the hydrogen generation reaction, especially the selection of the catalytic center through charge, spin, and orbital quantum control, are elucidated. In addition, a hydrogen generation process via quantum spin-induced catalysis is observed, in which the turnover frequency increases by about 65 times at a magnetic field of 50 mT. This study provides valuable insights into the intrinsic mechanism of single-metal atom catalysis and opens up unique avenues for their precise control, thus offering a useful strategy for efficiently developing clean energy.}, archive = {J_JACS}, author = {Mingyao Li and Weilin Hu and Boyu Wang and Yusen Li and Wenyuan Jian and Jie Hao and Long Chen and Chuancheng Jia and Xuefeng Guo}, doi = {10.1021/jacs.4c17722}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6193--6202}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanism of hydrogen generation catalyzed by a single atom and its spin regulation}, volume = {147}, year = {2025}, }
• (2025). High-energy, high-power sodium-ion batteries from a layered organic cathode. JACS, 147(7), 6181--6192. (www)

  @article{ , abstract = {Sodium-ion batteries (SIBs) attract significant attention due to their potential as an alternative energy storage solution, yet challenges persist due to the limited energy density of existing cathode materials. In principle, redox-active organic materials can tackle this challenge because of their high theoretical energy densities. However, electrode-level energy densities of organic electrodes are compromised due to their poor electron/ion transport and severe dissolution. Here, we report the use of a low-bandgap, conductive, and highly insoluble layered metal-free cathode material for SIBs. It exhibits a high theoretical capacity of 355 mAh g –1 per formula unit, enabled by a four-electron redox process, and achieves an electrode-level energy density of 606 Wh kg –1 electrode (90 wt % active material) along with excellent cycling stability. It allows for facile two-dimensional Na + diffusion, which enables a high intrinsic rate capability. Growth of the active cathode material in the presence of as little as 2 wt % carboxyl-functionalized carbon nanotubes improves charge transport and charge transfer kinetics and further enhances the power performance. Altogether, these allow the construction of SIB cells built from an affordable, sustainable organic small molecule, which provide a cathode energy density of 472 Wh kg –1 electrode when charging/discharging in 90 s and a top specific power of 31.6 kW kg –1 electrode .}, archive = {J_JACS}, author = {Tianyang Chen and Jiande Wang and Bowen Tan and Kimberly J. Zhang and Harish Banda and Yugang Zhang and Dong-Ha Kim and Mircea Dincă}, doi = {10.1021/jacs.4c17713}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6181--6192}, shortjournal = {J. Am. Chem. Soc.}, title = {High-energy, high-power sodium-ion batteries from a layered organic cathode}, volume = {147}, year = {2025}, }
• (2025). Linear dichroism microscopy resolves competing structural models of a synthetic light-harvesting complex. JACS, 147(7), 6171--6180. (www)

  @article{ , abstract = {The initial stages of photosynthesis in light-harvesting antennae, driven by excitonic energy transport, have inspired the design of artificial light-harvesting complexes. Double-walled nanotubes (DWNTs) formed from the cyanine dye C8S3 provide a robust, self-assembled system that mimics natural chlorosomes in both structure and optical properties. Two competing molecular packing models─bricklayer (BL) and herringbone (HB)─have been proposed to explain the structural and optical characteristics of these DWNTs. This study resolves the debate by combining theoretical analysis with advanced polarization-resolved wide-field photoluminescence microscopy. Quantum-classical simulations reveal reduced linear dichroism (LDr) as a decisive parameter for distinguishing between the models. Experimental measurements of single DWNTs yielded LDr values as high as 0.93, strongly favoring the BL model. The BL model’s unique excitonic patterns, dominated by negative couplings among individual chromophores, generate superradiant exciton states with transition dipoles preferentially aligned along the nanotube axis. In contrast, the HB model’s mixed positive and negative couplings produce destructive interference, leading to a weaker alignment of transition dipoles. Our approach deepens the understanding of the structure–property relationships in self-assembled systems and demonstrates the potential of slip-stacking engineering to fine-tune excitonic properties for artificial light-harvesting applications.}, archive = {J_JACS}, author = {Alexey V. Kuevda and Mónica K. Espinoza Cangahuala and Richard Hildner and Thomas L. C. Jansen and Maxim S. Pshenichnikov}, doi = {10.1021/jacs.4c17708}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6171--6180}, shortjournal = {J. Am. Chem. Soc.}, title = {Linear dichroism microscopy resolves competing structural models of a synthetic light-harvesting complex}, volume = {147}, year = {2025}, }
• (2025). Comparison of a nonheme iron cyclopropanase with a homologous hydroxylase reveals mechanistic features associated with distinct reaction outcomes. JACS, 147(7), 6162--6170. (www)

  @article{ , abstract = {Despite the diversity of reactions catalyzed by mononuclear iron and 2-oxoglutarate-dependent enzymes, the factors that lead to diverse reaction outcomes beyond canonical hydroxylation remain elusive. Cyclopropanation reactions are of particular interest not only due to the prevalence of cyclopropane moieties in pharmaceuticals but also due to the chemistry that allows cyclopropanation to outcompete oxygen rebound. HrmJ is one such cyclopropanase from the biosynthetic pathway of hormaomycin; however, a homologue is herein discovered that instead catalyzes C -hydroxylation of the same nitro enolate substrate. These enzymes were reconstituted with Mn(II) and V(IV)═O as mimics of the resting (Fe(II)) and reactive (Fe(IV)═O) intermediate states, respectively. Corresponding crystal structures of the cyclopropanase bound with a substrate imply H atom transfer via an offline π-pathway. In contrast, analogous structural analysis of the hydroxylase implies H atom abstraction likely proceeds through a σ-pathway. Preparation of isotopically labeled substrates and stopped-flow kinetic analyses indicate that while the pro-S hydrogen of C4 is abstracted in both enzymes, the Fe(IV)═O intermediate reacts ca. 17-fold faster in the active site of the hydroxylase, consistent with the mechanistic assignments. These results also support a correlation between the mechanism of H atom transfer and the subsequent fate of the substrate radical once generated. A subtle difference in substrate positioning not only affects the H atom abstraction pathway but also allows the nitro enolate moiety to intercept the resulting substrate radical in the active site of the cyclopropase, thereby facilitating intramolecular C–C bond formation in a stereoselective manner.}, archive = {J_JACS}, author = {Yu-Cong Zheng and Xiaojun Li and Lide Cha and Jared C. Paris and Charalambos Michael and Richiro Ushimaru and Yasushi Ogasawara and Ikuro Abe and Yisong Guo and Wei-chen Chang}, doi = {10.1021/jacs.4c17741}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6162--6170}, shortjournal = {J. Am. Chem. Soc.}, title = {Comparison of a nonheme iron cyclopropanase with a homologous hydroxylase reveals mechanistic features associated with distinct reaction outcomes}, volume = {147}, year = {2025}, }
• (2025). Regio- and stereoselective hydroalkynylation of internal alkynes with terminal alkynes by half-sandwich rare-earth catalysts. JACS, 147(7), 6149--6161. (www)

  @article{ , abstract = {The regio- and stereoselective hydroalkynylation of internal alkynes with terminal alkynes is of great interest and importance as a straightforward route for synthesizing multisubstituted 1,3-enynes. However, this transformation often suffers from regio- and stereoselectivity issues when working with unsymmetrical internal alkynes. Herein, we report for the first time the regio- and syn -stereoselective hydroalkynylation of a variety of heteroatom-functionalized unsymmetrical internal alkynes including homopropargyl ethers, thioethers, and tertiary amines with terminal alkynes by half-sandwich rare-earth catalysts. This protocol provides an atom-efficient and straightforward route for the synthesis of a new family of heteroatom (O, S, or N)-functionalized 1,3-enynes, featuring 100% atom-efficiency, broad substrate scope, and high regio- and syn -stereoselectivity (>19:1 r.r. and >19:1 syn / anti ). The mechanistic details have been elucidated by deuterium-labeling experiments, control experiments, and isolation and transformations of key reaction intermediates, revealing that the reaction proceeded through the C(sp)–H deprotonation of a terminal alkyne by a half-sandwich scandium alkyl species to form a catalytically active dimeric half-sandwich scandium tetraalkynyl species followed by heteroatom-assisted insertion of internal alkyne into the Sc–alkynyl bond and the subsequent protonolysis of the resulting Sc–alkenyl bond with another terminal alkyne molecule. The coordination of the heteroatom (O, S, or N) of internal alkynes to the catalyst metal center plays a critically important role in achieving a high level of reactivity and regio- and stereoselectivity. Remarkably, the catalytically active dimeric half-sandwich scandium tetraalkynyl species can be recovered and reused, constituting the first example of a recyclable catalyst system for the hydroalkynylation of internal alkynes.}, archive = {J_JACS}, author = {Na Hao and Tenggang Jiao and Zhou Sun and Aniket Mishra and Qingde Zhuo and Masayoshi Nishiura and Zhaomin Hou and Xuefeng Cong}, doi = {10.1021/jacs.4c17210}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6149--6161}, shortjournal = {J. Am. Chem. Soc.}, title = {Regio- and stereoselective hydroalkynylation of internal alkynes with terminal alkynes by half-sandwich rare-earth catalysts}, volume = {147}, year = {2025}, }
• (2025). High-pressure effects on an octa-hydrated curium complex: An experimental and theoretical investigation. JACS, 147(7), 6137--6148. (www)

  @article{ , abstract = {An octa-hydrated curium compound [Cm(H 2 O) 8 ](Hdtp)(dtp)·H 2 O ( Cm1 , H 2 dtp = 2,3-di(tetrazol-5-yl)pyrazine) along with its lanthanide analogues [Ln(H 2 O) 8 ](Hdtp)(dtp)·H 2 O ( Ln1 , Ln 3+ = La 3+ –Nd 3+ , Sm 3+ –Lu 3+ ) were synthesized and characterized using single crystal X-ray diffraction and spectroscopic methods. Bond length analysis of VIII Cm(III)–OH 2 (where VIII refers to the coordination number) was compared to VIII Ln(III)–OH 2 (Ln 3+ = Nd 3+ and Sm 3+ ), indicating similar VIII M(III)–OH 2 bond lengths because of their similar eight-coordinate ionic radii of these VIII M(III) cations. Owing to the reduced coordination number, the VIII Cm(III)–OH 2 bond lengths were shorter than previously reported IX Cm(III)–OH 2 bonds in [Cm(H 2 O) 9 ](CF 3 SO 3 ) 3 . The octa-aquo complexes were also characterized by solid-state UV-vis-NIR spectroscopy in addition to variable-temperature and variable-pressure photoluminescence. Variable-pressure absorption spectra of Cm1 were compared with Ln1 and show that the Cm(III) f → f transitions have a stronger dependence on pressure than that observed in Ln1 (Ln 3+ = Nd 3+ and Sm 3+ ). The experimental and computational analyses reveal that the monotonic decrease in the computed energy difference between the ground state and the first excited state corresponds to the observed red shift of the photoluminescence peak. This is accompanied by a gradual reduction in the average Cm(III)–OH 2 bond length and a delocalization of spin densities, alongside an intensified interaction involving the 5f orbitals under increasing pressure. These changes accommodate the new geometry and collectively modify the energy landscape, resulting in peak broadening and quenching.}, archive = {J_JACS}, author = {Zhuanling Bai and Morgan Redington and Soumi Haldar and Nicholas B. Beck and Joseph M. Sperling and Benjamin Scheibe and Jacob P. Brannon and Eva Zurek and Laura Gagliardi and Thomas E. Albrecht}, doi = {10.1021/jacs.4c17589}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6137--6148}, shortjournal = {J. Am. Chem. Soc.}, title = {High-pressure effects on an octa-hydrated curium complex: An experimental and theoretical investigation}, volume = {147}, year = {2025}, }
• (2025). Molecular self-gating inside a zeolite catalyst. JACS, 147(7), 6126--6136. (www)

  @article{ , abstract = {Diffusion is a ubiquitous process that is strongly correlated with concentration. Based on developed three-dimensional free energy and a continuous-time random-walk coarse-graining method, we found the optimal diffusion pathway under confinement, determined all diffusional energy barriers, and identified the major units of zeolite where molecular diffusion is limited. Interestingly, a novel diffusion mechanism was determined in the nanopore of a zeolite catalyst by molecular dynamics simulation, pulsed field gradient, and 2D exchange spectroscopy (EXSY) NMR experiments. We describe a “molecular self-gating effect” that effectively predominates the diffusion process in cage-type (e.g., RHO and MER) zeolites through a “traffic jam” and a “smooth traffic” process. Initially, transport is hindered by molecules forming a gate (traffic jam); then, as the number of molecules reaches a certain threshold, diffusion increases rapidly due to the synergistic collisions of aggregated molecules upon the gate (smooth traffic). This unique diffusion behavior is observed here for the first time and illustrates a microscopic mechanism dictated by the molecular self-gating effect in a confined space. The exploitable diffusion disclosed herein should shed new light on the fundamental understanding of transport, as well as enrich diffusion behavior under confinement.}, archive = {J_JACS}, author = {Zhiqiang Liu and Caiyi Lou and Jiamin Yuan and Xiaomin Tang and Yuzhou Fan and Ji Qi and Rui Zhang and Peng Peng and Guoliang Liu and Shutao Xu and Anmin Zheng}, doi = {10.1021/jacs.4c17510}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6126--6136}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular self-gating inside a zeolite catalyst}, volume = {147}, year = {2025}, }
• (2025). A holistic data-driven approach to synthesis predictions of colloidal nanocrystal shapes. JACS, 147(7), 6116--6125. (www)

  @article{ , abstract = {The ability to precisely design colloidal nanocrystals (NCs) has far-reaching implications in optoelectronics, catalysis, biomedicine, and beyond. Achieving such control is generally based on a trial-and-error approach. Data-driven synthesis holds promise to advance both discovery and mechanistic knowledge. Herein, we contribute to advancing the current state of the art in the chemical synthesis of colloidal NCs by proposing a machine-learning toolbox that operates in a low-data regime, yet comprehensive of the most typical parameters relevant for colloidal NC synthesis. The developed toolbox predicts the NC shape given the reaction conditions and proposes reaction conditions given a target NC shape using Cu NCs as the model system. By classifying NC shapes on a continuous energy scale, we synthesize an unreported shape, which is the Cu rhombic dodecahedron. This holistic approach integrates data-driven and computational tools with materials chemistry. Such development is promising to greatly accelerate materials discovery and mechanistic understanding, thus advancing the field of tailored materials with atomic-scale precision tunability.}, archive = {J_JACS}, author = {Ludovic Zaza and Bojana Ranković and Philippe Schwaller and Raffaella Buonsanti}, doi = {10.1021/jacs.4c17283}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6116--6125}, shortjournal = {J. Am. Chem. Soc.}, title = {A holistic data-driven approach to synthesis predictions of colloidal nanocrystal shapes}, volume = {147}, year = {2025}, }
• (2025). Harnessing the FBXW7 somatic mutant R465C for targeted protein degradation. JACS, 147(7), 6108--6115. (www)

  @article{ , abstract = {Targeted protein degradation (TPD) is a pharmacological strategy that eliminates specific proteins from cells by harnessing cellular proteolytic degradation machinery. In proteasome-dependent TPD, expanding the repertoire of E3 ligases compatible with this approach could enhance the applicability of this strategy across various biological contexts. In this study, we discovered that a somatic mutant of FBXW7, R465C, can be exploited by heterobifunctional compounds for targeted protein degradation. This work demonstrates the potential of utilizing mutant E3 ligases that occur exclusively in diseased cells for TPD applications.}, archive = {J_JACS}, author = {Ananya A. Basu and Chenlu Zhang and Milad Rouhimoghadam and Anil Vasudevan and Justin M. Reitsma and Xiaoyu Zhang}, doi = {10.1021/jacs.4c17331}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6108--6115}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing the FBXW7 somatic mutant R465C for targeted protein degradation}, volume = {147}, year = {2025}, }
• (2025). Tailoring CO2 adsorption configuration with spatial confinement switches electroreduction product from formate to acetate. JACS, 147(7), 6095--6107. (www)

  @article{ , abstract = {Multi-proton-coupled electron transfer, multitudinous intermediates, and unavoidable competing hydrogen evolution reaction during CO 2 electroreduction make it tricky to control high selectivity for specific products. Here, we present spatial confinement of Fe single atoms (FeN 2 S 2 ) by adjacent FeS clusters (Fe 4 S 4 ) to orientate the transition of CO 2 adsorption configuration from C,O-side to O-end, which triggers a shift of activated CO 2 from first-step protonation to C–C coupling, thus switching the target product from HCOOH in high Faraday efficiency (FE: 90.6%) on FeN 2 S 2 to CH 3 COOH (FE: 82.3%) on Fe 4 S 4 /FeN 2 S 2 . The adsorption strength of *OCHO upon the solitary FeN 2 S 2 site is linearly related to the coordination number of Fe–S, with HCOOH predominantly produced over single-atom FeN 2 S 2 (ortho-substituted S atoms). Fe 4 S 4 cluster functions as a switch for a specific reduction product, which can not only optimize the spatial and electronic structure of the neighboring FeN 2 S 2 but also impel complete reduction of CO 2 to the hydrocarbon intermediate *CH 3 , followed by coupling of CO 2 * and *CH 3 via the single-atom cluster synergistic catalysis of Fe 4 S 4 /FeN 2 S 2 . This spatial confinement strategy provides a new avenue to modulate the reactant adsorption model for desirable reaction pathways, with potential applications in diverse multistep electrochemical processes of controlled selectivity.}, archive = {J_JACS}, author = {Huaqin Wang and Heyu Sui and Yalong Ding and Ying Yang and Yaqiong Su and Hu Li}, doi = {10.1021/jacs.4c17295}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6095--6107}, shortjournal = {J. Am. Chem. Soc.}, title = {Tailoring CO2 adsorption configuration with spatial confinement switches electroreduction product from formate to acetate}, volume = {147}, year = {2025}, }
• (2025). Ketenimines as aza-dienophiles. JACS, 147(7), 6087--6094. (www)

  @article{ , abstract = {N -Aryl ketenimines have been established as highly reactive aza-dienophiles. Intermolecular cycloadditions are achieved upon heating in the presence of 2,5-bis(silyloxy)furans and proceed with high levels of peri-, regio-, chemo- and diastereo-selectivity. Spontaneous C–O cleavage yields oxygenated pyridone derivatives in a highly convergent and redox-neutral manner. Combined experimental and computational studies demonstrate N -aryl ketenimines to be significantly more reactive than imino dienophiles, as a consequence of less distorted transition states. Derivatization studies include the development of isocyanate and cyclic ketenimine equivalents as aza-dienophiles, while extension to a one-pot aza-Diels–Alder/oxa-Diels–Alder sequence provides a three-component approach to complex fused pyridone/pyran systems.}, archive = {J_JACS}, author = {Christopher J. DeAngelis and Geeta Goyal and Marshall J. Liss and Jessica E. Budwitz and Mary Stuart Herlihy and Audrey V. Conner and Steven E. Wheeler and Pengchen Ma and Miranda Li and K. N. Houk and Christopher G. Newton}, doi = {10.1021/jacs.4c17174}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6087--6094}, shortjournal = {J. Am. Chem. Soc.}, title = {Ketenimines as aza-dienophiles}, volume = {147}, year = {2025}, }
• (2025). Why do weak-binding M–N–C single-atom catalysts possess anomalously high oxygen reduction activity?. JACS, 147(7), 6076--6086. (www)

  @article{ , abstract = {Single-atom catalysts (SACs) with metal–nitrogen–carbon (M–N–C) structures are widely recognized as promising candidates in oxygen reduction reactions (ORR). According to the classical Sabatier principle, optimal 3 d metal catalysts, such as Fe/Co–N–C, achieve superior catalytic performance due to the moderate binding strength. However, the substantial ORR activity demonstrated by weakly binding M–N–C catalysts such as Ni/Cu–N–C challenges current understandings, emphasizing the need to explore new underlying mechanisms. In this work, we integrated a pH-field coupled microkinetic model with detailed experimental electron state analyses to verify a novel key step in the ORR reaction pathway of weak-binding SACs─the oxygen adsorption at the metal–nitrogen bridge site. This step significantly altered the adsorption scaling relations, electric field responses, and solvation effects, further impacting the key kinetic reaction barrier from HOO * to O * and pH-dependent performance. Synchrotron spectra analysis further provides evidence for the new weak-binding M–N–C model, showing an increase in electron density on the antibonding π orbitals of N atoms in weak-binding M–N–C catalysts and confirming the presence of N–O bonds. These findings redefine the understanding of weak-binding M–N–C catalyst behavior, opening up new perspectives for their application in clean energy.}, archive = {J_JACS}, author = {Di Zhang and Fangxin She and Jiaxiang Chen and Li Wei and Hao Li}, doi = {10.1021/jacs.4c16733}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6076--6086}, shortjournal = {J. Am. Chem. Soc.}, title = {Why do weak-binding M–N–C single-atom catalysts possess anomalously high oxygen reduction activity?}, volume = {147}, year = {2025}, }
• (2025). Stereoselective chemoenzymatic cascades for the synthesis of densely functionalized iminosugars. JACS, 147(7), 6067--6075. (www)

  @article{ , abstract = {1,4-Dicarbonyls are versatile synthons for the construction of diverse pharmacophores and natural products. However, the stereoselective synthesis of densely functionalized 1,4-dicarbonyls is challenging. Here, we report a versatile biocatalytic route to access chiral 2,3-dihydroxy-1,4-diketones in high yields and up to gram scale using d -fructose-6-phosphate aldolase ( Ec FSA). The utility of these compounds as synthons is exemplified in enzyme cascades with subsequent regio- and stereoselective enzymatic transamination to form densely functionalized homochiral 1-pyrrolines followed by chemical or enzymatic reduction to tetrasubstituted pyrrolidines.}, archive = {J_JACS}, author = {Christopher R. B. Swanson and Léa Gourbeyre and Grayson J. Ford and Pere Clapés and Sabine L. Flitsch}, doi = {10.1021/jacs.4c16732}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6067--6075}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereoselective chemoenzymatic cascades for the synthesis of densely functionalized iminosugars}, volume = {147}, year = {2025}, }
• (2025). Fluorination: Simple change but complex impact on ferroelectric nematic and smectic liquid crystal phases. JACS, 147(7), 6058--6066. (www)

  @article{ , abstract = {A series of liquid crystal (LC) materials are reported, which form a variety of ferroelectric nematic and smectic phases. The relationship between the number and position of lateral fluorine substituents and the formation of ferroelectric LC phases is investigated. While the addition of fluorine substituents increases the temperature at which ferroelectric order appears, the relationship between fluorination and the LC phase sequence is more complicated. Introducing lateral fluorine substituents can either suppress or promote the formation of ferroelectric smectic phases, depending on their position within the molecule, and the interplay between these trends allows for more exotic ferroelectric phases to appear.}, archive = {J_JACS}, author = {Grant J. Strachan and Ewa Górecka and Jordan Hobbs and Damian Pociecha}, doi = {10.1021/jacs.4c16802}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6058--6066}, shortjournal = {J. Am. Chem. Soc.}, title = {Fluorination: Simple change but complex impact on ferroelectric nematic and smectic liquid crystal phases}, volume = {147}, year = {2025}, }
• (2025). Lattice oxygen-driven co-adsorption of carbon dioxide and nitrate on copper: A pathway to efficient urea electrosynthesis. JACS, 147(7), 6049--6057. (www)

  @article{ , abstract = {The electrochemical coupling of CO 2 and NO 3 – on copper-based catalysts presents a sustainable strategy for urea production while simultaneously addressing wastewater denitrification. However, the inefficient random adsorption of CO 2 and NO 3 – on the copper surface limits the interaction of the key carbon and nitrogen intermediates, thereby impeding efficient C–N coupling. In this study, we demonstrate that the residual lattice oxygen in oxide-derived copper nanosheets (O L -Cu) can effectively tune the electron distribution, thus activating neighboring copper atoms and generating electron-deficient copper (Cu δ+ ) sites. These Cu δ+ sites enhance CO 2 adsorption and stabilize *CO intermediates, which enables the directional NO 3 – adsorption at adjacent Cu δ+ sites. This mechanism shortens the C–N coupling pathway and achieves a urea yield of up to 298.67 mmol h –1 g –1 at −0.7 V versus RHE, with an average Faradaic efficiency of 31.71% at a high current density of ∼95 mA cm –2 . In situ spectroscopic measurements confirmed the formation of Cu δ+ sites and tracked the evolution of the key intermediates (i.e., *CO, *NO, *OCNO, and *NOCONO) during urea synthesis. Density functional theory calculations revealed that Cu δ+ sites promote adjacent coadsorption of *CO and *NO 3 , as well as *OCNO and *NO 3 , significantly improving C–N coupling kinetics. This study underscores the critical role of lattice oxygen in facilitating adjacent coadsorption and improving C–N coupling selectivity.}, archive = {J_JACS}, author = {Xiaoxiao Wei and Shao-Qing Liu and Hengjie Liu and Yutian Ding and Peng-Xia Lei and Shuwen Wu and Li Song and Xian-Zhu Fu and Jing-Li Luo}, doi = {10.1021/jacs.4c16801}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6049--6057}, shortjournal = {J. Am. Chem. Soc.}, title = {Lattice oxygen-driven co-adsorption of carbon dioxide and nitrate on copper: A pathway to efficient urea electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Red-light-active N,C,N-pincer bismuthinidene: Excited state dynamics and mechanism of oxidative addition into aryl iodides. JACS, 147(7), 6037--6048. (www)

  @article{ , abstract = {Despite the progress made in the field of synthetic organic photocatalysis over the past decade, the use of higher wavelengths, especially those in the deep-red portion of the electromagnetic spectrum, remains comparatively rare. We have previously disclosed that a well-defined N,C,N -pincer bismuthinidene ( 1a ) can undergo formal oxidative addition into a wide range of aryl electrophiles upon absorption of low-energy red light. In this study, we map out the photophysical dynamics of 1a and glean insights into the nature of the excited state responsible for the activation of aryl electrophiles. Transient absorption and emission techniques reveal that, upon irradiation with red light, the complex undergoes a direct S 0 → S 1 metal-to-ligand charge transfer (MLCT) transition, followed by rapid intersystem crossing (ISC) to a highly reducing emissive triplet state (−2.61 V vs Fc +/0 in MeCN). The low dissipative losses incurred during ISC (∼6% of the incident light energy) help rationalize the ability of the bismuthinidene to convert low-energy light into useful chemical energy. Spectroelectrochemical and computational data support a charge-separated excited-state structure with radical-anion character on the ligand and radical-cation character on bismuth. Kinetic studies and competition experiments afford insights into the mechanism of oxidative addition into aryl iodides; concerted and inner-sphere processes from the triplet excited state are ruled out, with the data strongly supporting a pathway that proceeds via outer-sphere dissociative electron transfer.}, archive = {J_JACS}, author = {Alexios Stamoulis and Mauro Mato and Paolo Cleto Bruzzese and Markus Leutzsch and Alejandro Cadranel and Marcos Gil-Sepulcre and Frank Neese and Josep Cornella}, doi = {10.1021/jacs.4c16815}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6037--6048}, shortjournal = {J. Am. Chem. Soc.}, title = {Red-light-active N,C,N-pincer bismuthinidene: Excited state dynamics and mechanism of oxidative addition into aryl iodides}, volume = {147}, year = {2025}, }
• (2025). Multi-dimensional, multi-scale analysis of interphase chemistry for enhanced fast-charging of lithium-ion batteries with ion mass spectrometry. JACS, 147(7), 6023--6036. (www)

  @article{ , abstract = {Understanding the fundamental properties of electrode–electrolyte interphases (EEIs) is essential for designing electrolytes that support stable operation under high charging rates. In this study, we benchmark our fast-charging electrolyte (FCE) against the commercial LP57 electrolyte to identify the EEI characteristics that enhance fast-charging performance. By utilizing the latest advances in time-of-flight secondary ion mass spectrometry (TOF-SIMS) and focused-ion beam (FIB) techniques, we reveal the complex chemical architecture of the cathode–electrolyte interphase (CEI). Our findings indicate that stable battery operation under fast-charging conditions requires reduced surface reactivity rather than stabilizing the bulk integrity of the cathode. While inorganic species are often cited as beneficial for EEI composition, their distribution within the EEI is equally critical. Additionally, dynamic interactions between the cathode material and conductive carbon significantly affect CEI formation and alter the passivation layer chemistry. A chemically homogeneous distribution of CEI components passivating preferentially the active material particles is desired for enhanced performance. Notably, the amount of electrolyte decomposition species in the solid-electrolyte interphase (SEI) far outweighs their distribution within the SEI in determining better electrochemical performance. An inorganic-rich SEI effectively protects graphite particles, suppresses the accumulation of metallic lithium, and prevents the formation of lithium dendrites. Overall, an enhanced fast-charging performance can be achieved by tuning the interphase chemistry and architecture on both the cathode and anode sides.}, archive = {J_JACS}, author = {Chen Liu and Andrei Dolocan and Zehao Cui and Arumugam Manthiram}, doi = {10.1021/jacs.4c16561}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6023--6036}, shortjournal = {J. Am. Chem. Soc.}, title = {Multi-dimensional, multi-scale analysis of interphase chemistry for enhanced fast-charging of lithium-ion batteries with ion mass spectrometry}, volume = {147}, year = {2025}, }
• (2025). Three-dimensional covalent organic frameworks with lil topology. JACS, 147(7), 6016--6022. (www)

  @article{ , abstract = {The diversity of covalent organic frameworks (COFs) is continuously expanding, providing various materials with tailor-made structures and properties. However, the development of crystalline three-dimensional (3D) COFs with new topologies is an essential but arduous challenge. In this study, we first developed one kind of 3D COFs with the lil topological structure, which were assembled by D 4h - and C 2h -symmetric building blocks. The 3D COFs were determined in a space group of Imma , in which each D 4h -symmetric unit is connected with four C 2h -symmetric units, forming a noninterpenetrated network. The densely packed copper phthalocyanine and stable polyimide linkage render these COFs as a polymeric material with high dielectric constant and low dielectric loss at high frequencies (>1 kHz). Significantly, the dielectric constant was determined as high as 63, which constitutes a new record value among phthalocyanine-based and polyimide polymers. Therefore, this study not only provides important guidance for the design of 3D lil -net COFs but also supplies promising materials for application in high-energy-density and pulsed capacitors.}, archive = {J_JACS}, author = {Xinyu Wu and Hanwen Wang and Ning Huang}, doi = {10.1021/jacs.4c16422}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6016--6022}, shortjournal = {J. Am. Chem. Soc.}, title = {Three-dimensional covalent organic frameworks with lil topology}, volume = {147}, year = {2025}, }
• (2025). Enabling selective mechanochemical scission of network crosslinks by exchanging single carbon atoms for silicon. JACS, 147(7), 6006--6015. (www)

  @article{ , abstract = {The tearing of a polymer network arises from mechanochemically coupled bond-breaking events in the backbone of a polymer chain. An emerging research area is the identification of molecular strategies for network toughening, such as the strategic placement of mechanochemically reactive groups (e.g., scissile mechanophores) in the crosslinks of a network instead of in the load-bearing primary strands. These mechanically labile crosslinkers have typically relied on release of ring strain or weak covalent bonds for selective covalent bond scission. Here, we report a novel chemical design for accelerated mechanochemical bond scission based on replacing a single carbon atom in a crosslinker with a silicon atom. This single-atom replacement affords up to a two-fold increase in the tearing energy. We suggest a mechanism, validated by computational modeling, for accelerated mechanochemical Si–C bond scission based on minimizing the energy required to distort the starting material toward the transition-state geometry. We demonstrated the seamless incorporation of these scissile carbosilanes to toughen 3D-printed networks, which demonstrates their suitability for additive manufacturing processes.}, archive = {J_JACS}, author = {Sophia J. Melvin and Yunxin Yao and Xiao Huang and Rowina C. Bell and Ryann E. Kemmerling and Ilia Kevlishvili and Angus C. Berg and Ana Paula Kitos Vasconcelos and Alshakim Nelson and Heather J. Kulik and Stephen L. Craig and Rebekka S. Klausen}, doi = {10.1021/jacs.4c16323}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {6006--6015}, shortjournal = {J. Am. Chem. Soc.}, title = {Enabling selective mechanochemical scission of network crosslinks by exchanging single carbon atoms for silicon}, volume = {147}, year = {2025}, }
• (2025). Indoloindolizines: The complete story of a polycyclic aromatic scaffold from theoretical design to organic field-effect transistor applications. JACS, 147(7), 5996--6005. (www)

  @article{ , abstract = {The development of stable and tunable polycyclic aromatic compounds (PACs) is crucial for the advancement of organic optoelectronics. Conventional PACs, such as acenes, often suffer from poor stability due to photooxidation and oligomerization, which are linked to their frontier molecular orbital energy levels. To address these limitations, we designed and synthesized a new class of π-expanded indoloindolizines by merging indole and indolizine moieties into a single polycyclic framework. We developed a scalable synthetic protocol to produce a wide range of π-expanded derivatives. The structural, electronic, and optical properties of these compounds were extensively characterized. We achieved precise modulation of the electronic structure by controlling the aromaticity of specific rings. Benzannulation at targeted positions allowed fine-tuning of the HOMO–LUMO gap, leading to distinct shifts in the optoelectronic properties. Single-crystal X-ray diffraction confirmed their molecular structures, while theoretical calculations provided insights into the observed experimental trends. These indoloindolizines exhibit vivid colors and fluorescence across the visible spectrum and enhanced stability against photooxidation. Reactivity studies demonstrated high regioselectivity in electrophilic substitutions, highlighting the indole-like behavior of these compounds and opening avenues for further functionalization. To showcase the practical utility of our design rules, we fabricated organic field-effect transistors (OFETs) using the newly developed indoloindolizines, which revealed remarkable performance with ambipolar charge transport properties. Overall, our work establishes indoloindolizines as a promising platform for the development of stable, tunable organic materials for optoelectronic applications. Through rational molecular design, we have provided a new pathway for molecular innovation in organic electronics.}, archive = {J_JACS}, author = {Abhishek Pareek and Muhammad Yasir Mehboob and Maciej Cieplak and Maciej Majdecki and Hubert Szabat and Krzysztof Noworyta and Piotr Połczyński and Maja Morawiak and Piyush Sindhu Sharma and Cina Foroutan-Nejad and Przemysław Gaweł}, doi = {10.1021/jacs.4c16189}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5996--6005}, shortjournal = {J. Am. Chem. Soc.}, title = {Indoloindolizines: The complete story of a polycyclic aromatic scaffold from theoretical design to organic field-effect transistor applications}, volume = {147}, year = {2025}, }
• (2025). Small ligand-involved pickering droplet interface controls reaction selectivity of metal catalysts. JACS, 147(7), 5984--5995. (www)

  @article{ , abstract = {Developing efficient methods to improve catalytic selectivity, particularly without sacrificing catalytic activity, is of paramount significance for chemical synthesis. In this work, we report a small ligand-involved Pickering droplet interface as a brand-new strategy to effectively regulate reaction selectivity of metal catalysts. It was found that small ligands such as polar arenes could engineer the surface structure of Pt catalysts that were assembled at Pickering droplet interfaces. Due to the strong hydrogen-bonding interactions with water, the polar arenes preferentially adsorbed with the water adlayer that covered Pt surfaces, forming water-mediated metal–organic interfaces on the Pickering emulsion droplets. Such an interface system displayed a significantly enhanced p -vinylaniline selectivity from 8.7 to 94.2% with an unreduced conversion in p -nitrostyrene hydrogenation. The selectivity was found to follow a negatively linear correlation with the bond length of the interfacial hydrogen bonds. Theoretical calculations revealed that the small arene ligands could closely array at the interface, which modulated the adsorption patterns of reactant/product molecules to prevent the C═C group from approaching Pt surfaces without suppressing their accessibility toward reactant molecules. Such a remarkable interfacial steric effect contributed to the efficient control of the hydrogenation selectivity. Our work provides an innovative strategy to modulate the surface structure of metal catalysts, opening a new venue to tune catalytic selectivity.}, archive = {J_JACS}, author = {Jie Yang and Yue Sun and Hu Shi and Houbing Zou and Yabin Zhang and Xinxin Tian and Hengquan Yang}, doi = {10.1021/jacs.4c16128}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5984--5995}, shortjournal = {J. Am. Chem. Soc.}, title = {Small ligand-involved pickering droplet interface controls reaction selectivity of metal catalysts}, volume = {147}, year = {2025}, }
• (2025). Vibrationally assisted tunneling through the bread of a proton Sandwich─Connections to dynamic matching. JACS, 147(7), 5971--5983. (www)

  @article{ , abstract = {Proton sandwiches are unusual nonclassical carbocations characterized by a five-center, four-electron bonding array which rapidly isomerize to lower energy isomers with three-center, two-electron bonding arrays via hydrogen migration transition states. These reactions are suspected to involve significant contributions from tunneling, even at relatively high temperatures, where tunneling effects are usually minimal. Machine-learning-accelerated ring-polymer, quasiclassical, and classical ab initio molecular dynamics simulations were used to investigate the effects of a flavor of dynamic matching that involves coupling of vibrational modes of the reactant to the transition structure mode with an imaginary frequency, and how quantum mechanical tunneling affects this coupling. These nonstatistical dynamic effects were quantified by analysis of momentum in the molecular dynamics simulations. We show the importance of momentum for reactivity with and without tunneling, how tunneling amplifies these benefits, and that vibrational modes can be leveraged to generate beneficial momentum.}, archive = {J_JACS}, author = {Yusef G. Ahmed and Gabe Gomes and Dean J. Tantillo}, doi = {10.1021/jacs.4c16135}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5971--5983}, shortjournal = {J. Am. Chem. Soc.}, title = {Vibrationally assisted tunneling through the bread of a proton Sandwich─Connections to dynamic matching}, volume = {147}, year = {2025}, }
• (2025). Topological design of highly conductive weakly solvating electrolytes for ultrastable sodium metal batteries operating at −60 °C and below. JACS, 147(7), 5962--5970. (www)

  @article{ , abstract = {Weakly solvating electrolytes (WSE) can favor reversible Na batteries at −40 °C for some extreme applications because of the low desolvation energy. However, it is challenging to enable reversible Na batteries at lower temperatures. Herein, we uncover that the low ionic conductivity of WSE reduces reaction kinetics at −60 °C. Accordingly, a highly conductive weakly solvating electrolyte (HCWSE) is designed by introducing additives of strongly solvating solvents and the dilution of NaPF 6 . The additive can dominate the solvation sheath, increase the dissociation of NaPF 6 and the fluidity of the electrolyte, and thus greatly improve the ionic conductivity. Furthermore, the binding energy between Na + and solvents is proposed as a descriptor to determine the solvating power of solvents, based on which a series of ultralow-temperature HCWSEs have been topologically designed by facilely introducing strong-solvation ether additives into the weak-solvation solvents. As a demonstration, the HCWSE showcases the long cycling of Na||Na cell at −60 °C with an overpotential of 42 mV under 1 mA cm –2 for 1200 h. The Na||NNFM (Na 0.75 Ni 0.25 Fe 0.25 Mn 0.5 O 2 ) cell exhibits a reversible capacity of 79.2 mAh g –1 after 160 cycles. The cells also achieve impressive performances at −70 °C.}, archive = {J_JACS}, author = {Zhiling Wang and Tao Zheng and Shuzhan Wang and Xia-Guang Zhang and Yu Gu and Shuai Tang and Yongzhu Fu}, doi = {10.1021/jacs.4c16076}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5962--5970}, shortjournal = {J. Am. Chem. Soc.}, title = {Topological design of highly conductive weakly solvating electrolytes for ultrastable sodium metal batteries operating at −60 °C and below}, volume = {147}, year = {2025}, }
• (2025). Unravelling size-dependent upconversion luminescence in ytterbium and erbium codoped NaYF4 nanocrystals. JACS, 147(7), 5955--5961. (www)

  @article{ , abstract = {The size of the lanthanide upconversion nanocrystals significantly impacts their luminescence properties, yet the underlying mechanisms remain unclear. In this work, we undertake a systematic examination of the size effects in the commonly studied hexagonal phase sodium yttrium fluoride (β-NaYF 4 ) nanocrystals codoped with ytterbium and erbium ions and their core–shell structure. We demonstrate the coexistence of surface quenching and finite-size-dependent energy transfer mechanisms, quantify the effects of size-dependent surface quenching and finite-size-dependent energy transfer, and determine an interaction energy transfer distance limit of ∼8.8 nm. A proposed theoretical model for the interplay between the two underlying mechanisms is shown to predict the experimental observations of size-dependent upconversion luminescence. Our findings provide a clear and fundamental understanding of the size effects on lanthanide upconversion luminescence at the nanoscale, thereby giving important implications for a variety of applications ranging from bioimaging and nanothermometry.}, archive = {J_JACS}, author = {Xingxu Liu and Langping Tu and Feng Li and Dingxin Huang and Hans Ågren and Guanying Chen}, doi = {10.1021/jacs.4c15683}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5955--5961}, shortjournal = {J. Am. Chem. Soc.}, title = {Unravelling size-dependent upconversion luminescence in ytterbium and erbium codoped NaYF4 nanocrystals}, volume = {147}, year = {2025}, }
• (2025). Accelerating ion desolvation via bioinspired ion channel design in nonconcentrated aqueous electrolytes. JACS, 147(7), 5943--5954. (www)

  @article{ , abstract = {In aqueous-based electrochemical energy storage devices, uncontrolled hydrolysis of water at the electrochemical interfaces limits the application of such aqueous batteries or supercapacitors in business. The “water-in-salt” design is a valid strategy to broaden the electrochemical stability window in aqueous electrolytes, but drawbacks such as high manufacturing cost, high electrolyte viscosity, etc., also hinder its development. Here, inspired by biological ion channels in cell membranes, we propose an effective approach to engineer the electrode surface, inducing the desolvation of hydrated ions at the electrochemical interface and inhibiting water decomposition in nonconcentrated electrolytes. The biological engineering strategy enables the induction of controlled desolvation and accelerates the transportation of hydrated ions, e.g., potassium. The subnanometer design (0.8 nm) forces the hydrated potassium ions to shed their solvation shell with a hydration number of only 0.3, while the electrostatic interactions between the pore groups and the potassium ions facilitate their transport. The Zn||Zn cells demonstrate a stable cycling lifespan of over 1000 h at 1 mA cm –2 /10 mAh cm –2 . This work sheds new light on regulating the electrochemical interfaces in low-concentration aqueous electrolytes for designing aqueous-based energy storage devices.}, archive = {J_JACS}, author = {Jiangbin Deng and Guanfeng Xue and Chen Li and Shuang Zhao and Yujie Zheng and Yuting He and Ruduan Yuan and Kaixin Wang and Tangming Mo and Yuxuan Xiang and Yu Chen and Yang Geng and Luda Wang and Guang Feng and Xu Hou and Meng Li}, doi = {10.1021/jacs.4c15443}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5943--5954}, shortjournal = {J. Am. Chem. Soc.}, title = {Accelerating ion desolvation via bioinspired ion channel design in nonconcentrated aqueous electrolytes}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of DMOA-derived meroterpenoids: Achieving selectivity in the synthesis of (+)-berkeleyacetal d and (+)-peniciacetal i. JACS, 147(7), 5933--5942. (www)

  @article{ , abstract = {The synthesis of complex natural products requires efficient control over chemoselectivity, stereoselectivity, and regioselectivity. Berkeleyacetals, a subfamily of 3,5-dimethylorsellinic acid (DMOA)-derived meroterpenoids, pose substantial synthetic challenges due to their densely functionalized and highly oxidized architectures, which have constrained synthetic efforts. Here, we present the first total synthesis of this class of DMOA-derived meroterpenoids, specifically (+)-berkeleyacetal D and (+)-peniciacetal I. Our approach features a chemoselective deprotonation followed by an intramolecular single-electron transfer (SET) from an enolate to an alkyl bromide, enabling the construction of the 2,3-dihydrofuran ring in berkeleyacetal D. Additional selective transformations include an endo -selective intramolecular Diels–Alder reaction, chemoselective methylations and semihydrogenation of [3]dendralene, and a solvent-controlled diastereoselective epoxidation. Beyond providing a synthetic route to these densely congested natural products, our study offers mechanistic insights into achieving selectivity in the assembly of architecturally demanding molecules.}, archive = {J_JACS}, author = {Jianpeng Zhang and Xiaotong Luo and Jingfu Zhang and Chao Li}, doi = {10.1021/jacs.4c15205}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5933--5942}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of DMOA-derived meroterpenoids: Achieving selectivity in the synthesis of (+)-berkeleyacetal d and (+)-peniciacetal i}, volume = {147}, year = {2025}, }
• (2025). 1H NMR trajectories for analyzing the growth and purification of 2D polyaramids. JACS, 147(7), 5921--5932. (www)

  @article{ , abstract = {The recent synthesis of two-dimensional (2D) polyaramid (PA) polymers has shown that they exhibit remarkable mechanical and gas barrier properties. However, new methods are necessary to enable the efficient measurement of discoidal sizes of 2D polyaramids and tracking of their growth over time during reaction. Herein, we employ 1 H NMR peak analysis of the aromatic and proton end group regions to characterize 2D-PA growth from monomeric precursors, alongside purification using two-stage filtration and washing steps. The ratio of aromatic to end group protons yields the molecular weight and discoidal size, while the skewness of the NMR peaks in the aromatic region provides a relative weighting between dendritic, small, and larger polycyclic domains. These two metrics delineate a distinct two-dimensional 1 H NMR trajectory that we show to be valuable for analyzing the results of differing synthetic and processing conditions. Theoretical bounds corresponding to dendrimer and polycyclic limits as a function of repeat unit size are derived as an aid in trajectory analysis. These results establish an analytical framework for evaluating 2D-PA and its variants, facilitating the exploration of the synthetic landscape.}, archive = {J_JACS}, author = {Zitang Wei and Yu-Ming Tu and Wonjun Yim and Michelle Quien and Ali A. Alizadehmojarad and Xun Gong and Michael S. Strano}, doi = {10.1021/jacs.4c15053}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5921--5932}, shortjournal = {J. Am. Chem. Soc.}, title = {1H NMR trajectories for analyzing the growth and purification of 2D polyaramids}, volume = {147}, year = {2025}, }
• (2025). Pushing an altermagnet to the ultimate 2D limit: Symmetry breaking in monolayers of GdAlSi. JACS, 147(7), 5911--5920. (www)

  @article{ , abstract = {Altermagnets have emerged as a class of materials combining ferromagnetic properties with vanishing net magnetization. This combination is highly promising for spintronics, especially if a material can be brought to the nanoscale. However, experimental studies of the 2D limit of the altermagnets are lacking. Here, we study epitaxial films on silicon of the Weyl altermagnet GdAlSi ranging from more than a hundred unit cells to a single unit cell. The films do not show any discernible net magnetic moments. Electron transport studies reveal a remarkable transformation. Thick films exhibit the chiral anomaly, whereas symmetry restrictions prevent observation of the anomalous Hall effect in our electron transport measurements. In ultrathin films, a spontaneous anomalous Hall effect manifests itself, indicating a nonrelativistic spin splitting. The transformation is associated with crystal symmetry breaking accompanying the 3D-to-2D crossover. The work highlights the role of dimensionality in altermagnetism and provides a platform for studies aiming at ultracompact spintronics.}, archive = {J_JACS}, author = {Oleg E. Parfenov and Dmitry V. Averyanov and Ivan S. Sokolov and Alexey N. Mihalyuk and Oleg A. Kondratev and Alexander N. Taldenkov and Andrey M. Tokmachev and Vyacheslav G. Storchak}, doi = {10.1021/jacs.4c14891}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5911--5920}, shortjournal = {J. Am. Chem. Soc.}, title = {Pushing an altermagnet to the ultimate 2D limit: Symmetry breaking in monolayers of GdAlSi}, volume = {147}, year = {2025}, }
• (2025). Ion-specific effects under electric fields on ice nucleation at the mica surface. JACS, 147(7), 5904--5910. (www)

  @article{ , abstract = {Applying external electric fields to mineral surfaces can have a substantial impact on ice nucleation, influencing both climate and atmospheric systems. While earlier studies have demonstrated that electric fields can enhance ice nucleation on nonmineral surfaces, the mechanisms driving heterogeneous ice nucleation (HIN) on mineral surfaces under electric fields with different surface ions remain unclear. In this study, we investigate the ion-specific effects under electric fields on HIN efficiency using mica surfaces containing various cations. Our findings reveal that an upward electric field significantly boosts HIN of water droplets atop Na-mica surfaces, raising the nucleation temperature by approximately 6 °C. In contrast, mica surfaces with other cations or those exposed to a downward electric field show no change in nucleation temperature or HIN efficiency. Molecular dynamics simulations suggest that Na + ions detach more easily from the mica surface under an electric field, exposing more of the flat mica lattice and thus possibly promoting ice nucleation. This study offers new insights into the ion-specific effects of electric fields on HIN, providing a deeper understanding of the role of cations and electric fields in ice nucleation processes.}, archive = {J_JACS}, author = {Zhanhui Wang and Ziqi Huang and Zhiyuan He and Dan Wang and Xin Zhou and Jianjun Wang}, doi = {10.1021/jacs.4c14879}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5904--5910}, shortjournal = {J. Am. Chem. Soc.}, title = {Ion-specific effects under electric fields on ice nucleation at the mica surface}, volume = {147}, year = {2025}, }
• (2025). Low-temperature exsolution of rh from mixed ZnFeRh oxides toward stable and selective catalysts in liquid-phase hydroformylation. JACS, 147(7), 5887--5903. (www)

  @article{ , abstract = {The exsolution of metal nanoparticles offers a promising strategy to enhance catalyst stability and fine-tune metal–support interactions. Expanding the use of exsolved nanoparticles in heterogeneous catalysis requires the development of low-temperature ( T < 400 °C) exsolution processes. In this study, we report the synthesis of phase-pure ZnFe 2– x Rh x O 4 metal oxide precursors with a spinel-type crystal structure. The isomorphic substitution of Fe 3+ in the host lattice by Rh 3+ was confirmed by X-ray diffraction and Raman spectroscopy combined with DFT calculations. The hydrothermal synthesis method of the oxide precursors was specifically chosen so that very small oxide particles of 10–20 nm were obtained, which enabled the exsolution of Rh nanoparticles with a particle size of about 1 to 2 nm at temperatures below 200 °C in a hydrogen-containing atmosphere. Compared to a Rh catalyst prepared by conventional wet impregnation of ZnFe 2 O 4 , the catalysts obtained by low-temperature exsolution show superior properties in terms of selectivity toward aldehydes in the hydroformylation of 1-hexene in the liquid phase. In addition, there is no Rh loss due to leaching, which is the main challenge for heterogeneous Rh catalysts used in liquid phase reactions. The exceptionally strong metal–support interaction imparts unique nanostructures and electronic properties to the exsolved metal nanoparticles, as revealed by electron energy loss spectroscopy (EELS) and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The specific adsorption sites on the exsolved Rh particles lead to stronger metal–hydride and weaker metal–carbonyl bonds on the surface, steering the reaction pathway toward hydroformylation rather than olefin isomerization.}, archive = {J_JACS}, author = {Daniel Delgado and Gregor Koch and Shan Jiang and Jinhu Dong and Jutta Kröhnert and Franz-Philipp Schmidt and Thomas Lunkenbein and Carmen Galdeano Ruano and José Gaona-Miguélez and Diego Troya and Pascual Oña-Burgos and Annette Trunschke}, doi = {10.1021/jacs.4c14839}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5887--5903}, shortjournal = {J. Am. Chem. Soc.}, title = {Low-temperature exsolution of rh from mixed ZnFeRh oxides toward stable and selective catalysts in liquid-phase hydroformylation}, volume = {147}, year = {2025}, }
• (2025). Supramolecular diodes with Donor–Acceptor interactions. JACS, 147(7), 5879--5886. (www)

  @article{ , abstract = {Inspired by the initial proposal of σ-bridged donor–acceptor (D-σ-A) single-molecule diodes in 1974, extensive studies over the past 50 years have explored various designs for π-conjugated D-π–A single-molecule diodes due to their feasible chemical synthesis and effective charge transfer. However, the rectification ratio of π-conjugated single-molecule diodes has been long-term limited by the challenge of asymmetric electronic coupling to induce the rectification effect. Here, we present a supramolecular diode constructed through an intramolecular π–π interaction-driven assembly strategy. The asymmetric transmission in this system is tunable via subangström mechanical control, resulting in a rectification ratio of up to 16. Electron transport studies reveal that this through-space D-π–π–A system constructed by the π–π stacking between pyrene ( Py ) and naphthalenediimide ( NDI ) is crucial for achieving asymmetric currents under different bias polarization. Theoretical calculations suggest that the intermolecular destructive quantum interference not only enables a sharp variation in electron transmission but also facilitates asymmetric electronic energy shifts through mechanical stretching, significantly improving the rectification ratio. Our work provides a general approach to fabricating and modulating asymmetric molecular architectures through noncovalent supramolecular interactions, showcasing the potential of high-performance single-molecule rectifiers.}, archive = {J_JACS}, author = {Wei Xu and Hua Zhang and Yu Zhou and Taige Lu and Yuting Li and Yixuan Zhu and Caiyun Wei and Jueting Zheng and Ruihao Li and Jing Li and Lijue Chen and Guanxin Zhang and Jia Shi and Junyang Liu and Deqing Zhang and Wenjing Hong}, doi = {10.1021/jacs.4c14656}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5879--5886}, shortjournal = {J. Am. Chem. Soc.}, title = {Supramolecular diodes with Donor–Acceptor interactions}, volume = {147}, year = {2025}, }
• (2025). Rh(II) and chiral phosphoric acid co-catalyzed selective O–H insertions for stereodivergent O-alkylation of glycosides. JACS, 147(7), 5871--5878. (www)

  @article{ , abstract = {Carbohydrates are synthetically challenging molecules with essential biological functions in all living systems. The selective synthesis and modification of carbohydrates are crucial for investigating their biological functions. Controlling chemo-, regio-, and stereoselectivity is a central theme in carbohydrate synthesis. Achieving the full set of stereoisomers of carbohydrate derivatives would significantly enhance the efficiency of building compound libraries for biological studies and drug discovery. However, the selective functionalization of seemingly identical hydroxyl groups in carbohydrates remains a long-standing challenge in organic chemistry. In carbohydrate synthesis, achieving precise control of both relative configurations in catalyst-controlled reactions that create a new stereocenter presents a significant synthetic challenge. Herein, we developed an efficient method for the stereodivergent O -alkylation of carbohydrate hydroxyl groups via Rh(II)/chiral phosphoric acid-cocatalyzed insertion of metal carbenoids. This system is mild and robust, offering excellent selectivity across a broad range of substrates with high regio- and stereoselectivity. Furthermore, this strategy opens up vast opportunities for stereodivergent synthesis.}, archive = {J_JACS}, author = {Jicheng Wu and Peijing Jia and Hua Tang and Deqin Cai and Weiping Tang}, doi = {10.1021/jacs.4c14614}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5871--5878}, shortjournal = {J. Am. Chem. Soc.}, title = {Rh(II) and chiral phosphoric acid co-catalyzed selective O–H insertions for stereodivergent O-alkylation of glycosides}, volume = {147}, year = {2025}, }
• (2025). Constraining interlayer slipping in p2-type layered oxides with oxygen redox by constructing strong covalent bonds. JACS, 147(7), 5860--5870. (www)

  @article{ , abstract = {Lattice oxygen redox (LOR) in P2-type layered oxides is an effective strategy to break through the limit of energy density of conventional cathodes due to its high redox potential (>4 V vs Na + /Na) as well as extra capacity. Nevertheless, LOR-induced local structure distortion and irreversible phase transitions cause serious electrochemical performance degradation, hindering practical applications. Herein, we propose that the generation of the OP4 phase can be replaced with the Z phase by introducing the Sb element with a higher ionic potential and strong covalent bonds within the TMO 6 octahedron. Z phase transition is realized by constraining interlayer slipping between adjacent transition metal (TM) layers compared to OP4, which reduces the strain in the layered structure, lowers the Na + diffusion energy barrier, and creates more efficient Na + diffusion channels. Consequently, Sb-substituted oxides demonstrate excellent kinetics, rate capability (79 mAh g –1 at 1 A g –1 ) in half cells, and a high energy density of 487 Wh kg –1 (on cathode) in full cells.}, archive = {J_JACS}, author = {Xinyin Cai and Zulipiya Shadike and Nan Wang and Xun-Lu Li and Yong Wang and Qinfeng Zheng and Yixiao Zhang and Weixiao Lin and Linsen Li and Liwei Chen and Shuiyun Shen and Enyuan Hu and Yong-Ning Zhou and Junliang Zhang}, doi = {10.1021/jacs.4c14587}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5860--5870}, shortjournal = {J. Am. Chem. Soc.}, title = {Constraining interlayer slipping in p2-type layered oxides with oxygen redox by constructing strong covalent bonds}, volume = {147}, year = {2025}, }
• (2025). Synthesis, characterization, and catalytic activity of ni(0) (DQ)dtbbpy, an air-stable, bifunctional red-light-sensitive precatalyst. JACS, 147(7), 5851--5859. (www)

  @article{ , abstract = {Despite a well-established and growing body of work on nickel(0) precatalysts, the potential of nickel(0) complexes as bifunctional precatalysts remains underexplored. In this study, we synthesized, characterized, and evaluated the catalytic activity of (Ni(0)(DQ)dtbbpy), a bifunctional, red-light-sensitive, and air-stable nickel(0) complex. Owing to its unique photophysical properties, it effectively catalyzed the etherification and amination of aryl bromides under 620–630 nm light irradiation, functioning as both a photocatalyst and an active metal catalyst. Mechanistic studies and density functional theory (DFT) calculations further confirmed the exceptional absorption properties of Ni(0)(DQ)dtbbpy in the red-light region, as well as the electron transfer process triggered by red-light irradiation.}, archive = {J_JACS}, author = {Jingsheng Li and Pengpeng Wang and Baoyu Bai and Yulin Xiao and Ya-Fei Wan and Yonggang Yan and Fei Li and Geyang Song and Gang Li and Chao Wang and Xue-Peng Zhang and Jianyang Dong and Tengfei Kang and Dong Xue}, doi = {10.1021/jacs.4c14533}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5851--5859}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis, characterization, and catalytic activity of ni(0) (DQ)dtbbpy, an air-stable, bifunctional red-light-sensitive precatalyst}, volume = {147}, year = {2025}, }
• (2025). Photosensitized gold-catalyzed cross-couplings of aryl bromides. JACS, 147(7), 5839--5850. (www)

  @article{ , abstract = {Recently, ligand-promoted Au(I)/Au(III)-catalyzed cross-coupling reactions with aryl iodides have garnered considerable attention. Here, we report the first visible-light-driven gold-catalyzed cross-couplings of challenging aryl bromides. In the presence of a (P, N)-gold(I) catalyst and an acridinium photocatalyst under blue LED irradiation, C–O coupling of aryl bromides with carboxylic acids was achieved, and soon it was found that this photoinduced gold-catalyzed cross-coupling of aryl bromides was appliable for other C–C, C–N, and C–S bond formation. Experimental and computational studies suggest that this visible-light-driven gold-catalyzed cross-couplings of aryl bromides involves two discrete photoinduced energy transfer (EnT) events: first, energy transfer (EnT) from a photosensitizer produces an excited-state gold(I) complex that allows the bottleneck oxidative addition of aryl bromides to form an aryl Au(III) complex and second, the reductive elimination of aryl-Au(III) complex to regenerate Au(I). Collectively, the new synergistic catalytic method developed here highlights the tremendous potential of photochemical gold catalysis via excited-state organogold complexes, as well as its potential to facilitate drug discovery due to the biocompatibility and mildness of the reaction conditions.}, archive = {J_JACS}, author = {Jiawen Wu and Fusheng Guo and Chenju Yi and Rongjie Yang and Xiaoguang Lei and Zhonghua Xia}, doi = {10.1021/jacs.4c14501}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5839--5850}, shortjournal = {J. Am. Chem. Soc.}, title = {Photosensitized gold-catalyzed cross-couplings of aryl bromides}, volume = {147}, year = {2025}, }
• (2025). Sialylation shields glycoproteins from oxidative stress: Mechanistic insights into sialic acid oxidation and structural stability. JACS, 147(7), 5828--5838. (www)

  @article{ , abstract = {Sialylation, a crucial yet labile protein modification, is increasingly recognized for its role in modulating protein structure, function, and stability. While the impact of oxidative stress on protein integrity is well-established, the protective role of sialylation against such damage remains poorly understood. This study employs a microscale low-temperature plasma device to generate a controlled, deep radical oxidation environment mimicking cellular oxidative stress. By subjecting free sialic acids (Neu5Ac and Neu5Gc) to time-resolved deep radical exposure, high-resolution mass spectrometry, and high-fidelity density functional theory calculations, we establish an unprecedented oxidation pathway, revealing unique stepwise side chain oxidation prior to ring opening. Comprehensive radical oxidation maps comprising over 100 oxidative intermediates provide a molecular basis for the higher propensity of Neu5Gc over Neu5Ac in resisting radical oxidation. Further, using human transferrin as a model glycoprotein, we demonstrate the protective role of sialylation against oxidative unfolding. Through a combination of site mapping, enzymatic treatments, and all-ion unfolding ion mobility-mass spectrometry, we identify specific protein sialylation patterns and structural motifs that are crucial for maintaining structural stability under oxidative stress. Our findings provide unprecedented insights into the intricate interplay between sialylation and oxidative stress, highlighting the importance of sialylation in stabilizing protein conformations under various oxidative stresses.}, archive = {J_JACS}, author = {Yamei Wang and Dongbei Jin and Lifang Ren and Ning Wang and Yifei Jia and Zhen Zheng and Wensheng Cai and Haohao Fu and Gongyu Li}, doi = {10.1021/jacs.4c14454}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5828--5838}, shortjournal = {J. Am. Chem. Soc.}, title = {Sialylation shields glycoproteins from oxidative stress: Mechanistic insights into sialic acid oxidation and structural stability}, volume = {147}, year = {2025}, }
• (2025). Reversible angle distortion-dependent electrochemical CO2 reduction on cobalt phthalocyanine. JACS, 147(7), 5819--5827. (www)

  @article{ , abstract = {Deducing the local electronic and atomic structural changes in active sites during electrochemical carbon dioxide reduction is essential for elucidating the intrinsic mechanisms and developing highly active catalysts that are stable for a long duration. Herein, utilizing operando valence-to-core X-ray emission spectroscopy and high energy-resolution fluorescence detected X-ray absorption near-edge structure, combined with spectroscopic calculations, the atomic and electronic structure evolutions of the model cobalt phthalocyanine (CoPc) were quantitatively elucidated. Under real reaction conditions, CoPc undergoes reversible angle distortion while maintaining a constant metal–ligand bond length, causing changes in the energy levels of split d orbitals and electron density of molecular orbitals. The angle distortion further influences intrinsic interactions among the ligands, intermediates, and metal centers. The reversible change in the bond angle with the CO Faraday efficiency was also determined, demonstrating the robustness. The demonstrated findings serve as an important contribution to determine the structure–performance relationship of CoPc which enlightens the further rational design of atomically dispersed site catalysts with high activity and to emphasize the capabilities of the high energy resolution X-ray spectroscopy toward analyzing metal–implanted N-doped carbon catalysts.}, archive = {J_JACS}, author = {Bingbao Mei and Jianing Mao and Zhaofeng Liang and Fanfei Sun and Shuai Yang and Ji Li and Jingyuan Ma and Fei Song and Zheng Jiang}, doi = {10.1021/jacs.4c14409}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5819--5827}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible angle distortion-dependent electrochemical CO2 reduction on cobalt phthalocyanine}, volume = {147}, year = {2025}, }
• (2025). The stereoselectivity of neighboring group-directed glycosylation is concentration-dependent. JACS, 147(7), 5808--5818. (www)

  @article{ , abstract = {The formation of 1,2- trans -glycosides taking advantage of neighboring group participation by stereodirecting esters at the 2-position of glycosyl donors is widely held to be a robust and reliable protocol. Examples abound, however, of cases in which less-than-perfect selectivity is obtained, causing practitioners to survey different esters or resort to alternative strategies in the quest for optimal selectivities and yields. Consideration of the mechanism of neighboring group participation and in particular of the competing process of S N 2-like glycosylation with activated covalent donors leads to the hypothesis that in cases of imperfect selectivity, more careful attention to reaction concentration and stoichiometry may be beneficial. Three case studies are presented to demonstrate the concentration dependence of neighboring group-directed glycosylation reactions targeting the formation of both 1,2- trans -equatorial and 1,2- trans -axial glycosides. Higher concentrations, whether achieved through increased acceptor:donor stoichiometry or through increased concentration at a fixed stoichiometry, mostly lead to erosion of 1,2- trans -selectivity as the competing S N 2-like reaction with the covalent donors becomes increasingly important. These observations underline the importance of a rational, mechanism-based approach to glycosylation in general and more importantly suggest a simple approach to enhancing 1,2- trans -selectivity in neighboring group-directed glycosylation reactions displaying less-than-perfect 1,2- trans -selectivity, namely, moving to a different concentration regime.}, archive = {J_JACS}, author = {Pallabita Basu and David Crich}, doi = {10.1021/jacs.4c14402}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5808--5818}, shortjournal = {J. Am. Chem. Soc.}, title = {The stereoselectivity of neighboring group-directed glycosylation is concentration-dependent}, volume = {147}, year = {2025}, }
• (2025). Copper chelate targeting externalized phosphatidylserine inhibits PD-l1 expression and enhances cancer immunotherapy. JACS, 147(7), 5796--5807. (www)

  @article{ , abstract = {Inhibitors of the PD-1/PD-L1 immune checkpoint have revolutionized cancer treatment. However, the clinical response remains limited, with only 20% of patients benefiting from treatment and approximately 60% of PD-L1-positive patients exhibiting resistance. One key factor contributing to resistance is the externalization of phosphatidylserine (PS) on the surface of cancer cells, which suppresses immune responses and promotes PD-L1 expression, further hindering the efficacy of PD-L1 blockade therapies. Here, we introduce a copper chelate composed of a terpyridine–Cu complex with a farnesol tail designed to selectively target and cap the externalized PS on cancer cells. This approach not only promotes dendritic cell maturation and effector T-cell proliferation and tumor infiltration but also significantly inhibits PD-L1 expression, thereby amplifying T-cell-mediated immune responses. Our results demonstrate that this strategy induces robust immunological memory and leads to the eradication of tumors in over 70% of mice with colorectal and melanoma cancers. These findings highlight a promising, antibody-independent strategy for cancer immunotherapy where targeting externalized PS could overcome current limitations of checkpoint blockade therapies.}, archive = {J_JACS}, author = {Fan Gao and Wei You and Lei Zhang and Ai-Zong Shen and Guang Chen and Ze Zhang and Xuan Nie and Lei Xia and Wei-Qiang Huang and Long-Hai Wang and Chun-Yan Hong and Da-Long Yin and Ye-Zi You}, doi = {10.1021/jacs.4c14394}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5796--5807}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper chelate targeting externalized phosphatidylserine inhibits PD-l1 expression and enhances cancer immunotherapy}, volume = {147}, year = {2025}, }
• (2025). Electrocatalytic alkene Hydrogenation/Deuteration. JACS, 147(7), 5785--5795. (www)

  @article{ , abstract = {Traditional reductions of alkenes, such as using stoichiometric reductants with waste generation and catalytic hydrogenation with high-pressure H 2 , are accompanied by environmental or safety issues. Herein, we demonstrated a universal method for the electrocatalytic hydrogenation and deuteration of alkenes with modified electrodes under ambient temperature. The key M-H/M-D species for alkene reduction were generated from the electrolysis of H 2 O/D 2 O on modified electrodes, which avoided the usage of H 2 and D 2 . Mono-, di-, tri-, and tetra-substituted alkenes were successfully reduced in this electrocatalytic system using H 2 O and D 2 O as hydrogen and deuterium sources. Electron-donating/-withdrawing alkenes, alkenes with other easily reducible functional groups, and complicated natural products and drugs were all reductive hydrogenated and deuterated with excellent yields (85 examples, yields up to 99%). Faraday efficiency of this efficient method could reach 84%. Moreover, the catalytic amount of metal could decrease to less than 0.01 mol %.}, archive = {J_JACS}, author = {Faxiang Bu and Yuqi Deng and Lijun Lu and Yan Li and Wenxu Song and Zhaoliang Yang and Xu Luo and Xin Dong and Ruijie Yi and Dali Yang and Shengchun Wang and Aiwen Lei and Wu Li}, doi = {10.1021/jacs.4c14320}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5785--5795}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrocatalytic alkene Hydrogenation/Deuteration}, volume = {147}, year = {2025}, }
• (2025). Activation of electrophilic reactivity by protonation and oxidation of a peroxo CoIIICoIII complex: Reactivity and molecular structures of hydroperoxo, superoxo, and peroxo CoIIICoIII complexes. JACS, 147(7), 5775--5784. (www)

  @article{ , abstract = {In nature, oxidizing metalloenzymes usually bind O 2 in the form of peroxo intermediates that frequently requires for activation a further protonation, for which the formation of hydroperoxo species is proposed. In dinuclear metalloenzymes, which typically feature Fe, Mn, and Cu, structures and electrophilic reactivity of peroxo, superoxo, and hydroperoxo intermediates are generally difficult to study due to their reactive and transient nature, which is why more stable peroxo Co III Co III complexes might be helpful models. Here, we present the molecular structures of a series of μ-1,2-peroxo, μ-1,2-superoxo, and μ-1,1-hydroperoxo Co III Co III complexes and the variation of their electrophilic hydrogen-atom-transfer (HAT) and oxygen-atom-transfer (OAT) reactivity. The μ-1,2-peroxo complex exhibits no electrophilic reactivity, whereas oxidation to the μ-1,2-superoxo complex activates electrophilic HAT reactivity, while protonation to the μ-1,1-hydroperoxo complex activates electrophilic OAT reactivity. The latter occurs by an associated mechanism with the μ-1,1-hydroperoxo ligand being the electrophilic OAT agent. Protonation to the μ-1,1-hydroperoxo elongates the O–O bond, while oxidation to the μ-1,2-superoxo shortens it relative to the μ-1,2-peroxo. The protonation of the μ-1,2-peroxo complex could be made accessible by the introduction of remote electron-donating substituents into a recently reported μ-1,2-peroxo Co III Co III complex that increases the μ-1,2-peroxo basicity by more than five p K a units. Hence, the initially counterintuitive increase of electron donation by the ligand environment increases the μ-1,2-peroxo basicity allowing its protonation to a more electrophilic μ-1,1-hydroperoxo ligand. More generally, HAT and OAT reactivity is correlated with accessibility of the following intermediate.}, archive = {J_JACS}, author = {Felix Depenbrock and Eckhard Bill and Maurice van Gastel and Daniel J. SantaLucia and Stephan Walleck and Jan Oldengott and Anja Stammler and Thorsten Glaser}, doi = {10.1021/jacs.4c14045}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5775--5784}, shortjournal = {J. Am. Chem. Soc.}, title = {Activation of electrophilic reactivity by protonation and oxidation of a peroxo CoIIICoIII complex: Reactivity and molecular structures of hydroperoxo, superoxo, and peroxo CoIIICoIII complexes}, volume = {147}, year = {2025}, }
• (2025). Cryogenic organometallic Carbon–Fluoride bond functionalization with broad functional group tolerance. JACS, 147(7), 5764--5774. (www)

  @article{ , abstract = {The unique properties of fluorinated organic compounds have received intense interest and have conquered a myriad of applications in the chemical and pharmaceutical sciences. Today, an impressive range of alkyl fluorides are commercially available, and there are many practical methods to make them exist. However, the unmatched stability and inertness of the C–F bond have largely limited its synthetic value, which is very different from the widely accepted utility of alkyl chlorides, bromides, and iodides that serve everyday as “workhorse” building blocks in countless carbon–carbon bond forming reactions. This study demonstrates practical and high-yielding functionalization of the C–F bond under mild conditions, i.e., at temperatures as low as −78 °C, in short reaction times and with unconventional chemoselectivity. Cryogenic Csp 3 –F bond cleavage using fluorophilic organoaluminum compounds together with fast nucleophile transfer of intermediate ate complexes forge carbon–carbon bonds with unactivated primary, secondary, and tertiary alkyl fluorides alike. This method, which exploits the stability of the Al–F bond as the thermodynamic driving force, is highly selective toward Csp 3 –F bond functionalization, whereas many other functional groups including alkyl chloride, bromide, iodide, aryl halide, alkenyl, alkynyl, difluoroalkyl, trifluoromethyl, ether, ester, hydroxyl, acetal, heteroaryl, nitrile, nitro, and amide groups are tolerated, which is an unexpected reversal of long-standing main group organometallic and alkyl halide cross-coupling reactivity and compatibility patterns. As a result, the strongest single bond in organic chemistry can now be selectively targeted in high-yielding arylation, alkylation, alkenylation, and alkynylation reactions and used in late-stage functionalization applications that are complementary to currently available methods.}, archive = {J_JACS}, author = {D. Lucas Kane and Bryan C. Figula and Kaluvu Balaraman and Jeffery A. Bertke and Christian Wolf}, doi = {10.1021/jacs.4c13956}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5764--5774}, shortjournal = {J. Am. Chem. Soc.}, title = {Cryogenic organometallic Carbon–Fluoride bond functionalization with broad functional group tolerance}, volume = {147}, year = {2025}, }
• (2025). Covalent dynamic DNA networks to translate multiple inputs into programmable outputs. JACS, 147(7), 5755--5763. (www)

  @article{ , abstract = {Inspired by naturally occurring protein dimerization networks, in which a set of proteins interact with each other to achieve highly complex input-output behaviors, we demonstrate here a fully synthetic DNA-based dimerization network that enables highly programmable input-output computations. Our DNA-based dimerization network consists of DNA oligonucleotide monomers modified with reactive moieties that can covalently bond with each other to form dimer outputs in an all-to-all or many-to-many fashion. By designing DNA-based input strands that can specifically sequester DNA monomers, we can control the size of the reaction network and thus fine-tune the yield of each DNA dimer output in a predictable manner. Thanks to the programmability and specificity of DNA–DNA interactions, we show that this approach can be used to control the yield of different dimer outputs using different inputs. The approach is also versatile and we demonstrate dimerization networks based on two distinct covalent reactions: thiol–disulfide and strain-promoted azide–alkyne cycloaddition (SPAAC) reactions. Finally, we show here that the DNA-based dimerization network can be used to control the yield of a functional dimer output, ultimately controlling the assembly and disassembly of DNA nanostructures. The covalent dynamic DNA networks shown here provide a way to convert multiple inputs into programmable outputs that can control a broader range of functions, including ones that mimic those of living cells.}, archive = {J_JACS}, author = {Simone Brannetti and Serena Gentile and Erica Del Grosso and Sijbren Otto and Francesco Ricci}, doi = {10.1021/jacs.4c13854}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5755--5763}, shortjournal = {J. Am. Chem. Soc.}, title = {Covalent dynamic DNA networks to translate multiple inputs into programmable outputs}, volume = {147}, year = {2025}, }
• (2025). Activating the basal plane of 2D transition metal dichalcogenides via high-entropy alloying. JACS, 147(7), 5743--5754. (www)

  @article{ , abstract = {Two-dimensional materials, such as transition metal dichalcogenides (TMDCs) in the 2H or 1T crystal phases, are promising (electro)catalyst candidates due to their high surface-to-volume ratio and composition of low-cost, abundant elements. While the edges of elemental TMDC nanoparticles, such as MoS 2 , can show significant catalytic activity, the basal plane of the pristine materials is notoriously inert, which limits their normalized activity. Here, we show that high densities of catalytically active sites can be formed on the TMDC basal plane by alloying elements that prefer the 2H (1T) phase into a 1T (2H) structure. The global stability of the alloy, in particular, whether it crystallizes in the 2H or 1T phase, can be controlled by ensuring a majority of elements prefer the target phase. We further show that the mixing entropy plays a decisive role in stabilizing the alloy, implying that high-entropy alloying becomes essential. Our calculations point to a number of interesting nonprecious hydrogen evolution catalysts, including (CrTaVHfZr)S 2 and (CrNbVTiZr)S 2 in the 1T-phase and (MoNbTaVTi)S 2 in the 2H-phase. Our work opens new directions for designing catalytic sites via high-entropy alloy stabilization of locally unstable structures.}, archive = {J_JACS}, author = {Mohammad Amin Akhound and Karsten Wedel Jacobsen and Kristian Sommer Thygesen}, doi = {10.1021/jacs.4c13863}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5743--5754}, shortjournal = {J. Am. Chem. Soc.}, title = {Activating the basal plane of 2D transition metal dichalcogenides via high-entropy alloying}, volume = {147}, year = {2025}, }
• (2025). Convergent total synthesis of aleutianamine. JACS, 147(7), 5736--5742. (www)

  @article{ , abstract = {Herein, we describe a convergent total synthesis of the pyrroloiminoquinone natural product aleutianamine that exemplifies a novel paradigm for pyrroloiminoquinone synthesis by hinging upon a convergent intermolecular carbon–carbon bond forming event. Specifically, the coupling of a pyrroloquinone monoketal and a siloxythiophene fragment, each prepared in seven steps from commercially available materials, allows for access to the entire carbon framework of aleutianamine in only eight steps. A variety of intriguing skeletal rearrangements, minimal late-stage redox adjustments, and a carefully choreographed sequence of carbon–nitrogen bond formations then deliver the natural product.}, archive = {J_JACS}, author = {Joseph P. Tuccinardi and John L. Wood}, doi = {10.1021/jacs.4c12946}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5736--5742}, shortjournal = {J. Am. Chem. Soc.}, title = {Convergent total synthesis of aleutianamine}, volume = {147}, year = {2025}, }
• (2025). Enantioselective synthesis of chiral 1,4-dihydroquinolines via iridium-catalyzed asymmetric partial hydrogenation of quinolines. JACS, 147(7), 5725--5735. (www)

  @article{ , abstract = {Chiral 1,4-dihydroquinolines are frequently found in natural products and pharmaceuticals, yet a generally useful route for their synthesis remains elusive. Here, we present an asymmetric partial hydrogenation strategy to access enantioenriched 1,4-dihydroquinolines from quinolines. Our strategy involves incorporating an ester group at position 3 of the quinoline ring, thereby enhancing the electronic deficiency and polarity of the C3–C4 double bond. Employing a chiral Ir-SpiroPAP catalyst facilitated the hydrogenation of a wide variety of 4-substituted 3-ethoxycarbonylquinolines, yielding chiral 1,4-dihydroquinolines in high yields (up to 95%) with exceptional enantioselectivity and efficiency (up to 99% ee and 1840 TONs). Noteworthy for its scalability and practicality, the method provides a robust avenue for the synthesis of valuable compounds such as 9-aryl aza-podophyllotoxins and melatonin MT 2 receptor modulators. Density functional theory calculations were performed to gain insights into the reaction mechanism and the origins of the enantioselectivity.}, archive = {J_JACS}, author = {Chang-Liang Zhu and Xueyuan Yan and Huai-Yu Bin and Xiong Wu and Zheng-Yan Huang and Pu-Cha Yan and Genping Huang and Jian-Hua Xie and Qi-Lin Zhou}, doi = {10.1021/jacs.4c13618}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5725--5735}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective synthesis of chiral 1,4-dihydroquinolines via iridium-catalyzed asymmetric partial hydrogenation of quinolines}, volume = {147}, year = {2025}, }
• (2025). Proline cis/trans conformational selection controls 14–3–3 binding. JACS, 147(7), 5714--5724. (www)

  @article{ , abstract = {Intrinsically disordered protein regions (IDRs) are structurally dynamic yet functional, often interacting with other proteins through short linear motifs (SLiMs). Proline residues in IDRs introduce conformational heterogeneity on a uniquely slow time scale arising from cis / trans isomerization of the Xaa-Pro peptide bond. Here, we explore the role of proline isomerization in the interaction between the prolactin receptor (PRLR) and 14–3–3. Using NMR spectroscopy, thermodynamic profiling, and molecular dynamics (MD) simulations, we uncover a unique proline isomer-dependent binding, with a cis conformation affinity 3 orders of magnitude higher than the trans . MD simulations identify structural constraints in the narrow 14–3–3 binding groove that provide an explanation for the observed isomer selectivity. The cis preference of WT PRLR introduces a slow kinetic component relevant to signal propagation and a steric component that impacts chain direction. Proline isomerization constitutes a previously unrecognized selective component relevant to the ubiquitous 14–3–3 interactome. Given the prevalence of prolines in IDRs and SLiMs, our study highlights the importance of considering the distinct properties of proline isomers in experimental design and data interpretation to fully comprehend IDR functionality.}, archive = {J_JACS}, author = {Frederik F. Theisen and Andreas Prestel and Nina L. Jacobsen and Oline K. Nyhegn-Eriksen and Johan G. Olsen and Birthe B. Kragelund}, doi = {10.1021/jacs.4c13462}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5714--5724}, shortjournal = {J. Am. Chem. Soc.}, title = {Proline cis/trans conformational selection controls 14–3–3 binding}, volume = {147}, year = {2025}, }
• (2025). Ion irradiation-induced coordinatively unsaturated zn sites for enhanced CO hydrogenation. JACS, 147(7), 5703--5713. (www)

  @article{ , abstract = {Defect engineering critically influences metal oxide catalysis, yet controlling coordinatively unsaturated metal sites remains challenging due to their inherent instability under reaction conditions. Here, we demonstrate that high-flux argon ion (Ar + ) irradiation above recrystallization temperatures generated well-defined coordinatively unsaturated Zn (CUZ) sites on ZnO(101̅0) surfaces that exhibited enhanced stability and activity for CO hydrogenation. Combining low-temperature scanning probe microscopy, ambient pressure X-ray photoelectron spectroscopy, and surface–ligand infrared spectroscopy with density functional theory calculations, we identified <12̅10> step edges exposing CUZ sites as the dominant active sites. These sites facilitate hydrogen-assisted CO dissociation through a mechanism distinct from formate-mediated pathways on stoichiometric ZnO. The ion-irradiation approach effectively addressed instability of Zn species, a major problem in ZnO catalysis, enabling stable performance in syngas conversion when combined with zeolites. Our atomic scale investigation provided spectroscopic fingerprints for active sites on the ZnO catalyst and insights into the structure–activity relationships of ZnO for CO hydrogenation. Our approach for engineering thermally stable defect sites in oxide catalysts provided opportunities for rational catalyst design beyond traditional preparation methods.}, archive = {J_JACS}, author = {Wei-Peng Shao and Yunjian Ling and Hongru Peng and Jie Luo and Yunjun Cao and Yihua Ran and Jun Cai and Jiayu Lv and Bowen Zhu and Yun Liu and Yuxiang Chen and Na Li and Feng Jiao and Huiqi Chen and Yifeng Zhu and Xin Ou and Yuemin Wang and Christof Wöll and Qiang Fu and Xiulian Pan and Peijun Hu and Wei-Xue Li and Zhi Liu and Xinhe Bao and Fan Yang}, doi = {10.1021/jacs.4c13234}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5703--5713}, shortjournal = {J. Am. Chem. Soc.}, title = {Ion irradiation-induced coordinatively unsaturated zn sites for enhanced CO hydrogenation}, volume = {147}, year = {2025}, }
• (2025). Pyrochlore NaYbO2: A potential quantum spin liquid candidate. JACS, 147(7), 5693--5702. (www)

  @article{ , abstract = {The search for quantum spin liquids (QSL) and chemical doping in such materials to explore superconductivity have continuously attracted intense interest. Here, we report the discovery of a potential QSL candidate, pyrochlore-lattice β-NaYbO 2 . Colorless and transparent NaYbO 2 single crystals, layered α-NaYbO 2 (∼250 μm on edge) and octahedral β-NaYbO 2 (∼50 μm on edge), were grown for the first time. Synchrotron X-ray single-crystal diffraction unambiguously determined that the newfound β-NaYbO 2 belongs to the three-dimensional pyrochlore structure characterized by the R 3̅ m space group, corroborated by synchrotron X-ray and neutron powder diffraction and pair distribution function. Magnetic measurements revealed no long-range magnetic order or spin glass behavior down to 0.4 K with a low boundary spin frustration factor of 17.5, suggesting a potential QSL ground state. Under high magnetic fields, the potential QSL state was broken and spins order. Our findings reveal that NaYbO 2 is a fertile playground for studying novel quantum states.}, archive = {J_JACS}, author = {Chuanyan Fan and Tieyan Chang and Longlong Fan and Simon J. Teat and Feiyu Li and Xiaoran Feng and Chao Liu and Shilei Wang and Huifen Ren and Jiazheng Hao and Zhaohui Dong and Lunhua He and Shanpeng Wang and Chengwang Niu and Yu-Sheng Chen and Xutang Tao and Junjie Zhang}, doi = {10.1021/jacs.4c13166}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5693--5702}, shortjournal = {J. Am. Chem. Soc.}, title = {Pyrochlore NaYbO2: A potential quantum spin liquid candidate}, volume = {147}, year = {2025}, }
• (2025). Acrolein-mediated conversion of lysine to electrophilic heterocycles for protein diversification and toxicity profiling. JACS, 147(7), 5679--5692. (www)

  @article{ , abstract = {Understanding protein interactions in the presence of biological metabolites is critical for unraveling biological processes and advancing therapeutic interventions. This study focuses on α,β-unsaturated carbonyls, particularly acrolein-derived protein modifications, unveiling a one-pot, four-step, selective chemistry that results in the formation of a heterocyclic α,β-unsaturated carbonyl, termed 3-formyl-3,4-dehydropiperidino (FDP), exclusively on lysine residues. Remarkably, this chemistry transforms lysine, a nucleophile, into an electrophilic warhead. We demonstrate its versatility in late-stage peptide diversification, precision protein engineering, and homogeneous protein labeling with diverse payloads. Additionally, FDP-lysine smoothly transforms into another heterocycle, 3-methylpyridinium (3-MP) lysine via deoxygenation and aromatization in reagentless conditions. This transformation facilitates late-stage peptide functionalization and homogeneous engineering of proteins, with MP-lysine acting as a mass booster. Leveraging this chemistry, we discovered hyperreactive sites responsible for acrolein-induced modification through chemoproteomic profiling of FDP- and MP-modified proteins. Our findings revealed changes in protein–protein interactions mediated by FDP-modified proteins and uncovered ∼1548 novel cross-linking partners of an FDP-modified protein.}, archive = {J_JACS}, author = {Zachary E. Paikin and Benjamin Emenike and Rajendra Shirke and Christian Michel Beusch and David Ezra Gordon and Monika Raj}, doi = {10.1021/jacs.4c12928}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5679--5692}, shortjournal = {J. Am. Chem. Soc.}, title = {Acrolein-mediated conversion of lysine to electrophilic heterocycles for protein diversification and toxicity profiling}, volume = {147}, year = {2025}, }
• (2025). 3D electron diffraction structure of an organic semiconductor reveals conformational polymorphism. JACS, 147(7), 5669--5678. (www)

  @article{ , abstract = {Crystal and conformational polymorphisms play crucial roles in the physical and chemical properties of materials, impacting their stability, solubility, and bioavailability, which are essential for various applications in pharmaceuticals, materials science, and chemistry. Despite their significance, the structural analysis of these polymorphisms, particularly conformational polymorphisms, remains challenging due to the limited methodology that provides sufficient resolution for microcrystalline variants of polymorphs. Three-dimensional electron diffraction (3D ED) is an emerging technique with significant potential for elucidating the microcrystal structures of functional organic molecules, pharmaceuticals, and biomolecules. Despite this potential, there are limited instances of 3D ED structures for small molecules exhibiting the lowest crystallographic symmetry with a preferred orientation and possibly conformational variations of constituent molecules. A novel organic semiconductor, Ph-anti-benzothieno[5,6- b ]benzothieno[3,2- b ]thiophene-C10 (antiC10), is one of such examples. We successfully determined the 3D ED structure of this challenging molecule. The antiC10 crystal exhibited the lowest symmetry (space group P 1), and the preferred orientations against the grid resulted in a missing cone. These challenges were surmounted by employing a sequential molecular replacement approach with an ab initio -generated search model. The resulting octameric antiC10 structure reveals a two-monolayer architecture and an antiparallel alkyl-interdigitated herringbone configuration in contrast to the all-parallel associations observed in its previously reported isomer. Concurrently, the alkyl chains are intricately interdigitated with each other and positioned between the adjacent π-core strata. Detailed analysis has elucidated the conformational polymorphism in herringbone packing between the two monolayers as well as in intramolecular conformations among monomers. The structure with conformational polymorphism is presumably in a metastable intermediate state, stabilized by twinning. These findings may provide critical insights into the crystallization mechanisms and rational design of organic semiconductors. This research demonstrates that advancements in 3D ED technology and sequential phasing methodologies have enabled the study of previously unreachable structures.}, archive = {J_JACS}, author = {Hirofumi Kurokawa and Saori Maki-Yonekura and Kiyofumi Takaba and Toshiki Higashino and Satoru Inoue and Tatsuo Hasegawa and Koji Yonekura}, doi = {10.1021/jacs.4c12734}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5669--5678}, shortjournal = {J. Am. Chem. Soc.}, title = {3D electron diffraction structure of an organic semiconductor reveals conformational polymorphism}, volume = {147}, year = {2025}, }
• (2025). 2D quantum spin-liquid candidate including a chiral anion: κ-(BEDT-TTF)2[BR/S(salicylate)2]. JACS, 147(7), 5658--5668. (www)

  @article{ , abstract = {The quantum spin-liquid state was first theorized by Anderson 50 years ago and the challenge remains to realize a quantum spin-liquid material. A handful of two-dimensional molecular candidates have attracted huge attention over the past 30 years owing to their triangular lattice possessing S = 1/2 spin systems. We present a new quantum spin-liquid candidate in 2D Mott insulator κ-(BEDT-TTF) 2 [B R / S (salicylate)] 2 . The structure has a double-width anion layer giving it a strong 2D character. The spiroborate anion is chiral and the salt is an inversion twin, having no inversion symmetry center and crystallizing in space group P 2 1 . This offers the possibility of novel behavior owing to the low symmetry not previously seen in molecular spin-liquid candidates. The peak height of the 6K anomaly of κ-(BEDT-TTF) 2 [B R / S (salicylate) 2 ] is 2 or 3 times larger than that of κ-(BEDT-TTF) 2 Cu 2 (CN) 3 and EtMe 3 Sb[Pd(dmit) 2 ] 2 . The structure presents many opportunities for crystal engineering through atom-by-atom changes to the ligands on the spiroborate anion to produce a family of materials which lie in and around the QSL region of the phase diagram for these salts. This gives the prospect of an experimental playground to deepen understanding of the QSL state. Electrical resistivity, SQUID magnetometry, band calculations, heat capacity, Infrared and Raman spectroscopy are reported for κ-(BEDT-TTF) 2 [B R / S (salicylate) 2 ].}, archive = {J_JACS}, author = {Toby J. Blundell and Kathryn Sneade and Joseph O. Ogar and Satoshi Yamashita and Hiroki Akutsu and Yasuhiro Nakazawa and Takashi Yamamoto and Lee Martin}, doi = {10.1021/jacs.4c12386}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5658--5668}, shortjournal = {J. Am. Chem. Soc.}, title = {2D quantum spin-liquid candidate including a chiral anion: κ-(BEDT-TTF)2[BR/S(salicylate)2]}, volume = {147}, year = {2025}, }
• (2025). Cathode design based on nitrogen redox and linear coordination of cu center for all-solid-state fluoride-ion batteries. JACS, 147(7), 5649--5657. (www)

  @article{ , abstract = {All-solid-state fluoride-ion batteries (FIBs) have attracted extensive attention as candidates for next-generation energy storage devices; however, promising cathodes with high energy density are still lacking. In this study, Cu 3 N is investigated as a cathode material for all-solid-state fluoride-ion batteries, which offers enough anionic vacancies around the 2-fold coordinated Cu center for F – intercalation, thereby enabling a multielectron-transferred fluorination process. The contribution of both cationic and anionic redox to charge compensation, in particular, the generation of molecular nitrogen species in highly charged states, has been proved by several synchrotron-radiation-based spectroscopic technologies. As a result, Cu 3 N exhibits a high reversible capacity of ∼550 mAh g –1 , exceeding many conventional fluoride-ion cathodes. It is believed that the new charge compensation chemistry as well as the unique intercalation behaviors of novel mixed-anion Cu–N/F local structures could bring new insights into energy storage materials.}, archive = {J_JACS}, author = {Datong Zhang and Kentaro Yamamoto and Zulai Cao and Yanchang Wang and Zhuoyan Zhong and Hisao Kiuchi and Toshiki Watanabe and Toshiyuki Matsunaga and Koji Nakanishi and Hidenori Miki and Hideki Iba and Yoshihisa Harada and Koji Amezawa and Kazuhiko Maeda and Hiroshi Kageyama and Yoshiharu Uchimoto}, doi = {10.1021/jacs.4c12391}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5649--5657}, shortjournal = {J. Am. Chem. Soc.}, title = {Cathode design based on nitrogen redox and linear coordination of cu center for all-solid-state fluoride-ion batteries}, volume = {147}, year = {2025}, }
• (2025). In-situ thermometry reveals fragmentation behavior based on local temperature in α-olefin polymerization catalysts. JACS, 147(7), 5642--5648. (www)

  @article{ , abstract = {Typical industrial olefin polymerization processes to produce both commodity and specialty polyolefin grades are mainly based on spherical, heterogeneous catalyst particles. During α-polymerization, heat from the exothermic reaction and pressure induced by the growing polymer chains on the catalyst particle lead to fragmentation, revealing active sites for further polymerization. To study these phenomena precisely and in-depth, we utilized a Nd-doped LaOCl-supported metallocene model system. This model catalyst can accurately display fluctuations in temperature with luminescence thermometry. During mild gas phase prepolymerization conditions, we observed a temperature difference of +43 °C and link this to the exothermicity of the ethylene polymerization reaction. In addition, the fragmentation behavior of the model catalyst was accurately monitored. The shell feature of the catalyst ruptured layer-by-layer, while the inner core fragmented via a bisectional fragmentation mechanism. We demonstrated that it is possible to probe the individual temperatures of multiple catalyst support particles within the field-of-view of the probe. This was correlated to structural changes and kinetics in an α-olefin polymerization catalyst. This powerful toolbox could be applied to different heterogeneous catalytic systems to correlate the temperature profile with morphological evolution.}, archive = {J_JACS}, author = {Joren M. Dorresteijn and Bas Terlingen and Koen W. Bossers and Thimo S. Jacobs and Yevkeni Wisse and Peter de Peinder and Virginie Cirriez and Alexandre Welle and Eelco T. C. Vogt and Florian Meirer and Bert M. Weckhuysen}, doi = {10.1021/jacs.4c11357}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5642--5648}, shortjournal = {J. Am. Chem. Soc.}, title = {In-situ thermometry reveals fragmentation behavior based on local temperature in α-olefin polymerization catalysts}, volume = {147}, year = {2025}, }
• (2025). Bio-orthogonal labeling of chitin in native pathogenic candida species via the chitin scavenge pathway. JACS, 147(7), 5632--5641. (www)

  @article{ , abstract = {The fungal cell wall is essential for the integrity of the cell, providing strength and shape, as well as protection against environmental stimuli. For pathogenic fungi, the cell wall is also the initial point of contact with the host. Specific cell wall features such as hypha tails and smaller glycan components modulate a wide range of fungal interactions with the immune defenses. Here, a bio-orthogonal labeling method utilizing N -acetyl-glucosamine (NAG) probes is developed to fluorescently label native, pathogenic yeast via the chitin scavenging pathway. A panel of NAG probes was assembled, synthesized, and characterized for the ability to label the chitin in pathogenic yeast. Enzymatic data show that the native scavenging biosynthetic enzyme, Hxk1, is promiscuous, permitting the labeling of the native chitin biopolymer. This chitin labeling method was validated via the development of mass spectrometry protocols. When compared to the current available labeling systems for chitin, the probes do not affect the integrity of the cell wall and do not interrupt cell growth. Furthermore, the NAG probes enabled multiple “click” platforms across pathogenic Candida species including Candida albicans and Candida tropicalis . Budding and filamentous hyphal states were observed. The results indicate the probes’ utility for in vivo study of the morphological, pathogenic switch, and visualization of growth patterns. Thus, the use of these probes in pathogenic Candida strains is ideal for a variety of future applications including strain specific antifungals, diagnostic tools, and immunomodulators.}, archive = {J_JACS}, author = {Caroline Williams and Bella R. Carnahan and Stephen N. Hyland and Kristen E. DeMeester and Catherine L. Grimes}, doi = {10.1021/jacs.4c11554}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5632--5641}, shortjournal = {J. Am. Chem. Soc.}, title = {Bio-orthogonal labeling of chitin in native pathogenic candida species via the chitin scavenge pathway}, volume = {147}, year = {2025}, }
• (2025). Self-assembled monolayers of triazolylidenes on gold and mixed Gold/Dielectric substrates. JACS, 147(7), 5624--5631. (www)

  @article{ , abstract = {N -Heterocyclic carbenes (NHCs) have emerged as valuable ligands for surface chemistry. They can be used to prepare robust self-assembled monolayers (SAMs) for a variety of applications, including as small-molecule inhibitors (SMIs) for metal surfaces in the fabrication of next-generation integrated circuits with angstrom precision. However, little work has been performed to assess the effect of structural and electronic modifications to the basic NHC structure. Herein, we report the design and deposition of a series of 1,2,3-triazolylidene (Tz)-type carbenes on gold (Au) and Au/SiO 2 patterned substrates. Triazolylidenes are an important class of stable carbenes that can be prepared with ease by using click chemistry. In this work, we studied the selective deposition of 1,2,3-triazolium hydrogen carbonate salts. The thermal properties of these precursors were measured and shown to be appropriate for either solution or vapor phase deposition. Tz-SAM stability was studied by time-of-flight secondary-ion mass spectrometry (ToF-SIMS) of Tz SAMs before and after exposure to various conditions, leading to the conclusion that Tz SAMs have thermal stabilities greater than that of NHC SAMs reported to date. Tz SAMs were analyzed by using X-ray and ultraviolet photoelectron spectroscopy (XPS, UPS) and contact angle measurements. High selectivity for deposition on metal regions over dielectric regions on patterned Au/SiO 2 substrates enabled the use of Tzs as an entirely new class of SMIs on preventing ZnO deposition, providing considerable potential utility in microelectronics fabrication methods. Structure–property relationships were studied and provided key insight into the effectiveness of the SAM as a blocking agent.}, archive = {J_JACS}, author = {Dana A.R. Nanan and Justin T. Lomax and Jordan Bentley and Lindsay Misener and Alex. J. Veinot and Wai-Tung Shiu and Lijia Liu and Paul J. Ragogna and Cathleen M. Crudden}, doi = {10.1021/jacs.4c11125}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5624--5631}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-assembled monolayers of triazolylidenes on gold and mixed Gold/Dielectric substrates}, volume = {147}, year = {2025}, }
• (2025). Recycling sulfur-poisoned pd catalysts via thermal atomization for semi-hydrogenation of acetylene. JACS, 147(7), 5615--5623. (www)

  @article{ , abstract = {Palladium catalysts are highly efficient for a variety of chemical industrial processes but are prone to being affected by poisons during practical application. Sulfur is one of the major poisons in Pd-based catalysts. The recycling of deeply poisoned Pd species like Pd sulfides is challenging due to the strong Pd–S bond. Herein, we proposed a top-down strategy to degrade Pd sulfides and create Pd single-atom sites simultaneously by one-step thermal atomization. Pd 4 S model nanoparticles were successfully converted to Pd single-atom sites supported on nitrogen and sulfur-codoped carbon (Pd 1 /N, S–C) after loading them on ZIF-8 and thermal treatment. PdZn intermediates were formed during the atomization process. Density functional theory revealed that the formation of PdZn helped the generation of vacancies adjacent to metal nanoparticles, which prompted the atomization process. This strategy can be facilely applied to the atomization of sulfur-poisoned commercial Pd/C, which shows the potential for recycling commercial catalysts. The optimal Pd 1 /N, S–C catalyst showed good activity and much enhanced selectivity than Pd 4 S for the semi-hydrogenation of acetylene.}, archive = {J_JACS}, author = {Qiheng Li and Shoujie Liu and Jin-Cheng Liu and Zhi Li and Yadong Li}, doi = {10.1021/jacs.4c11305}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5615--5623}, shortjournal = {J. Am. Chem. Soc.}, title = {Recycling sulfur-poisoned pd catalysts via thermal atomization for semi-hydrogenation of acetylene}, volume = {147}, year = {2025}, }
• (2025). Viologen-radical-driven hydrogen evolution from water catalyzed by co-NHC catalysts: Radical scavenging by nitrate and volmer-heyrovsky-like CPET pathway. JACS, 147(7), 5602--5614. (www)

  @article{ , abstract = {The factors controlling the catalytic activity in photochemical hydrogen evolution reaction (HER) are studied in detail for two macrocyclic cobalt compounds bearing two N-heterocyclic carbenes and two pyridyl donors ( Co-NHC1 and Co-NHC2 , where Co-NHC2 has a methoxy substituent on each pyridyl ligand). The present study adopts an aqueous photosystem consisting of EDTA, [Ru(bpy) 3 ] 2+ (bpy = 2,2′-bipyridine), and MV 2+ (MV 2+ = methylviologen) at pH = 5. Both catalysts are shown to promote HER in a similar efficiency (TON = 12–13 in 6 h), revealing a minor contribution of the electron-donating methoxy substituents. The catalyst degradation is shown to proceed during the photocatalysis, leading to afford [Co(edta)] − (EDTA = H 4 edta) as a dead-end species. The lack of any heterogeneous species was evidenced by DLS (dynamic light scattering). It was also found that nitrate involved as a counteranion in the photocatalysis components substantially inhibits the photocatalytic HER, giving rise to a large diminishment in TON from 12.7 to 7.2. The Griess test was used to confirm that NO 3 – serves as a scavenger deactivating the reduced form of MV 2+ (i.e., MV + ·). The detailed spectroscopic study reveals that the radical dimer (MV + ·) 2 plays a key role in promoting the one-step two-electron process: (MV + ·) 2 + NO 3 – + 2H + → 2MV 2+ + NO 2 – + H 2 O. Experimental and DFT results also reveal that a unique double CPET (concerted proton–electron transfer) pathway is taken to evolve H 2 by the Co-NHC catalysts with substantially minimized reorganization energies: Co(II)-NHC − → − CPET → CPET →CPET Co(III)(H)-NHC − → − CPET → CPET →CPET Co(II)-NHC + H 2 . This pathway can be viewed as related to the so-called Volmer-Heyrovsky mechanism adopted by some metals and is quite unique to the Co-NHC catalysts.}, archive = {J_JACS}, author = {Kosei Yamauchi and Ken Kawano and Koichi Yatsuzuka and Kaori Kawamura and Masanori Kan and Ken Sakai}, doi = {10.1021/jacs.4c10246}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5602--5614}, shortjournal = {J. Am. Chem. Soc.}, title = {Viologen-radical-driven hydrogen evolution from water catalyzed by co-NHC catalysts: Radical scavenging by nitrate and volmer-heyrovsky-like CPET pathway}, volume = {147}, year = {2025}, }
• (2025). A stereoselective decarboxylative Aromatase/Cyclase directs the biosynthesis of an axially chiral biphenyl framework in fasamycin. JACS, 147(7), 5596--5601. (www)

  @article{ , abstract = {Aromatic polyketides are an important class of natural products with various bioactivities, and their structural diversity arises from modifications to their aromatic frameworks. In this study, we identify a stereoselective aromatase/cyclase (ARO/CYC) FasU, which is responsible for forming the axial chiral biphenyl framework in fasamycin. FasU catalyzes sequential decarboxylation and cyclization/aromatization with strict S -stereospecificity on a previously unidentified biosynthetic intermediate. Through crystal structure analysis and site-directed mutagenesis, we reveal the enzyme’s substrate binding mode, stereospecificity, and the key residues involved in catalysis. This discovery introduces a novel class of ARO/CYC enzymes in type II polyketide biosynthesis, advancing the development of biocatalysts for chiral aromatic polyketides.}, archive = {J_JACS}, author = {Kai Jiang and Cheng Zhu and Xiaoli Yan and Guangjun Li and Zhi Lin and Zixin Deng and Shukun Luo and Xudong Qu}, doi = {10.1021/jacs.4c18376}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5596--5601}, shortjournal = {J. Am. Chem. Soc.}, title = {A stereoselective decarboxylative Aromatase/Cyclase directs the biosynthesis of an axially chiral biphenyl framework in fasamycin}, volume = {147}, year = {2025}, }
• (2025). In crystallo wolff rearrangement of a metalated diazoester: Structural confirmation of the singlet carbene wolff-intermediate. JACS, 147(7), 5590--5595. (www)

  @article{ , abstract = {The Wolff rearrangement (WR) is widely used for the synthesis of ketenes from diazoketones and -esters. Stepwise WR reactions are proposed to proceed through transient carbonylcarbene (R–C–C(O)–R′) intermediates, which so far have evaded structural characterization. Here, a Wolff metallocarbene (Pt II –C–C(O)–OEt) is reported as a fleeting intermediate in the photoinitiated fragmentation of a diazoester ligand. Frozen solution and crystal matrix isolation experiments enabled the spectroscopic, magnetic, crystallographic, and computational characterization of this highly reactive species. All methods confirmed a singlet ground state for the WR metallocarbene, which is stabilized by π interactions with the carboxyl substituent, thus complementing computational and transient spectroscopy studies for classic organic WR reactions.}, archive = {J_JACS}, author = {Ze-Jie Lv and Arnd Fitterer and Regine Herbst-Irmer and Serhiy Demeshko and Hendrik Verplancke and Max C. Holthausen and Sven Schneider}, doi = {10.1021/jacs.4c18289}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5590--5595}, shortjournal = {J. Am. Chem. Soc.}, title = {In crystallo wolff rearrangement of a metalated diazoester: Structural confirmation of the singlet carbene wolff-intermediate}, volume = {147}, year = {2025}, }
• (2025). Iridium-catalyzed stereocontrolled C(sp3)–C(sp3) cross-coupling of boronic esters and allylic carbonates enabled by boron-to-zinc transmetalation. JACS, 147(7), 5583--5589. (www)

  @article{ , abstract = {The stereocontrolled C(sp 3 )–C(sp 3 ) cross-coupling represents a considerable challenge of great contemporary interest. While this has been achieved through the reactions of boronate complexes with π-allyl iridium complexes, such reactions suffered from a limited substrate scope. We now report that following transmetalation from boronate complexes to organozinc reagents enables previously unreactive substrates to engage in stereocontrolled C(sp 3 )–C(sp 3 ) cross-coupling. The broader substrate scope has enabled their application to the synthesis of biologically active molecules. The organozinc reagents react through a stereoinvertive coupling pathway with π-allyl iridium complexes, in contrast to reactions with other electrophiles that occur with retention of stereochemistry. The reaction uniquely combines the enantiospecific reactivity of an enantioenriched organometallic nucleophile with the enantioselective engagement of a racemic electrophile, enabling access to all stereoisomers.}, archive = {J_JACS}, author = {Hong-Cheng Shen and Varinder K. Aggarwal}, doi = {10.1021/jacs.4c17931}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5583--5589}, shortjournal = {J. Am. Chem. Soc.}, title = {Iridium-catalyzed stereocontrolled C(sp3)–C(sp3) cross-coupling of boronic esters and allylic carbonates enabled by boron-to-zinc transmetalation}, volume = {147}, year = {2025}, }
• (2025). Catalysis of free C–C bond rotation: C–F---H–X H-bonds find a catalytic role. JACS, 147(7), 5577--5582. (www)

  @article{ , abstract = {There are few dynamic processes in organic chemistry that are more central to the molecular structure than C–C bond rotation. It is notable, however, that there exist few (if any) cases in which its hindered variants can actually be catalyzed. In this communication, we report a unique model system for the clear documentation of the catalysis of 360° C–C bond rotation that employs a transient but key N–H---F–C hydrogen bond as a linchpin and secondary “dual” charge-induced n → π* interactions and ion pairing effects that bolster catalysis.}, archive = {J_JACS}, author = {Muyuan Wang and Aarush Prasad and Nathaniel G. Garrison and Prabodh Rao and Hyeok-Kyu Kwon and Maxime A. Siegler and Thomas Lectka}, doi = {10.1021/jacs.4c17384}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5577--5582}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalysis of free C–C bond rotation: C–F---H–X H-bonds find a catalytic role}, volume = {147}, year = {2025}, }
• (2025). Anion-guided hierarchical assembly of heterometallic clusters. JACS, 147(7), 5572--5576. (www)

  @article{ , abstract = {Anions are important as templates for the construction of many structurally sophisticated and functional supramolecular architectures. Deciphering the specific role of such templates remains a great challenge due to the unique characteristics of anions. Herein, three heterometallic Ce–Ni clusters, namely, [Ce 24 Ni 36 L 36 ( μ 4 - OAc ) 6 (OH) 52 (Cl) 8 ]Cl 6 ·110H 2 O ( Ce 24 Ni 36 , OAc = acetate ion, L = N -methyliminodiacetate), [Ce 17 Ni 27 L 27 ( μ 6 - C 2 O 4 ) 6 (OH) 15 (Cl) 16 (H 2 O) 19 ](ClO 4 ) 2 Cl 6 ·45H 2 O ( Ce 17 Ni 27 ), and [Ce 21 Ni 30 L 30 ( μ 6 - C 2 O 4 ) 2 ( μ 4 - OAc )(OH) 32 (Cl) 15 (H 2 O) 14 ](ClO 4 ) 4 Cl 7 ·55H 2 O ( Ce 21 Ni 30 ), were obtained and structurally characterized; the formation of these cage-like clusters was assisted, respectively, by acetate, oxalate, and a combination of the two as templates. Structural analyses generate key information on the anion-directed hierarchical assembly, starting from a primary building block of {CeNi 3 } to two anion-specific secondary building blocks (SBUs)─the tetragonal {Ce 4 Ni 8 ( OAc )} and the pentagonal {Ce 5 Ni 9 ( C 2 O 4 )}. Further assembly steps are guided by these curved SBUs, affording a truncated octahedral Ce 24 Ni 36 and a lantern-like Ce 17 Ni 27 , with acetate and oxalate being the sole template, respectively. The combined use of acetate and oxalate produced Ce 21 Ni 30 , a cluster with an unprecedented structure viewable as a hybrid of a truncated octahedron and a dodecahedron.}, archive = {J_JACS}, author = {Weiming Huang and Qingsong Yang and Wanmin Chen and Zhiping Zheng}, doi = {10.1021/jacs.4c16564}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5572--5576}, shortjournal = {J. Am. Chem. Soc.}, title = {Anion-guided hierarchical assembly of heterometallic clusters}, volume = {147}, year = {2025}, }
• (2025). Designed synthesis of covalent organic multicycles. JACS, 147(7), 5566--5571. (www)

  @article{ , abstract = {Covalent organic multicycles (COMs) have been designed and synthesized via the covalent assembly of rigid three-arm Y-shaped and U-shaped building blocks. These COMs have a precise tricyclic structure and exhibit remarkable solubility in a range of common solvents. Featuring well-defined cavities with electron-rich structures, these COMs displayed good adsorption capabilities for iodine in both its vapor and liquid states. Moreover, the solution processability allows for the facile fabrication of these COMs as uniform films on different substrates via the spin coating methods.}, archive = {J_JACS}, author = {Tong Yang and Qian Gao and Xue-Hui Liu and Jin-Min Wu and Wei Wang and San-Yuan Ding}, doi = {10.1021/jacs.4c16320}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5566--5571}, shortjournal = {J. Am. Chem. Soc.}, title = {Designed synthesis of covalent organic multicycles}, volume = {147}, year = {2025}, }
• (2025). Palladium-catalyzed enantioselective stereodivergent desymmetrization of cyclic 1,4-allyldiboronates. JACS, 147(7), 5560--5565. (www)

  @article{ , abstract = {In the presence of a chiral palladium-based catalyst, 1,4-diboryl-2-alkenes undergo enantioselective cross-coupling that results in desymmetrization of the substrate structure. Depending on the reaction conditions and the choice of ligand, the reaction can occur with cis or trans selectivity, allowing the construction of an array of different substituted chiral carbocycles in an enantiomerically enriched fashion.}, archive = {J_JACS}, author = {Hao Liang and Lorenzo D. Battistoni and Sergei Tcyrulnikov and Christophe Allais and Robert A. Singer and James P. Morken}, doi = {10.1021/jacs.4c16020}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5560--5565}, shortjournal = {J. Am. Chem. Soc.}, title = {Palladium-catalyzed enantioselective stereodivergent desymmetrization of cyclic 1,4-allyldiboronates}, volume = {147}, year = {2025}, }
• (2025). Streamlining sulfated oligosaccharide and glycan synthesis with engineered mutant 6-SulfoGlcNAcases. JACS, 147(7), 5554--5559. (www)

  @article{ , abstract = {Sulfation is a common, but poorly understood, post-glycosylational modification (PGM) used to modulate biological function. To deepen our understanding of the roles of various sulfated glycoforms and their relevant binding proteins, we must expand our enzymatic toolkit for their synthesis. Here, we bypass the need for both sulfotransferases and glycosyltransferases by engineering a series of mutants of a 6-SulfoGlcNAcase, from Streptococcus pneumoniae , to directly and efficiently synthesize not only the ubiquitous 6S-GlcNAc-β-1,3-Gal linkage prevalent within host glycans, but also the 6S-GlcNAc-β-1,6-GalNAc commonly observed within core-6 O-glycans, and the more exotic 6S-GlcNAc-β-1,4-GalNAc linkage. We further elaborate these into complex sulfated N-glycan and O-glycan structures of biological relevance. By utilizing the cost-effective activated donor pNP-6S-GlcNAc in conjunction with mutant GH185 6-SulfoGlcNAcases we demonstrate a simple yet powerful in vitro method for generating well-defined sulfated oligosaccharides and glycoforms for use in a variety of applications including glycan arrays, glycan remodeling, and specificity studies with carbohydrate binding proteins such as lectins.}, archive = {J_JACS}, author = {Rajneesh K. Bains and Feng Liu and Seyed A. Nasseri and Jacob F. Wardman and Stephen G. Withers}, doi = {10.1021/jacs.4c14102}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5554--5559}, shortjournal = {J. Am. Chem. Soc.}, title = {Streamlining sulfated oligosaccharide and glycan synthesis with engineered mutant 6-SulfoGlcNAcases}, volume = {147}, year = {2025}, }
• (2025). Anhydrous solid-state proton conduction in crystalline MOFs, COFs, HOFs, and POMs. JACS, 147(7), 5515--5553. (www)

  @article{ , abstract = {Strategic design of solid-state proton-conducting electrolytes for application in anhydrous proton-exchange membrane fuel cells (PEMFCs) has gained burgeoning interest due to a spectrum of advantageous features, including higher CO tolerance and ease in the water management systems. Toward this direction, crystalline materials like metal–organic frameworks (MOFs), covalent organic frameworks (COFs), hydrogen-bonded organic frameworks (HOFs), and polyoxometalates (POMs) are emerging PEM materials, offering strategic structural engineering through crystallography, thus enabling ultrahigh anhydrous proton conductivity up to 10 –2 –10 –1 S/cm. This Perspective highlights significant progress achieved thus far with such crystalline platforms in the domain of anhydrous proton conduction across a wide temperature window (sub-zero to above 100 °C). Based on their structural backgrounds, these platforms are categorized into four classes (viz. MOFs, COFs, HOFs, and POMs) with a detailed evolutionary timeline since their emergence early in 2009. Insightful discussions with a key focus on the strategies undertaken to attain anhydrous proton conductivity along with implementation in fuel cell technology through membrane electrode assembly are presented. A section on “Critical Analysis and Future Prospects” provides decisive key viewpoints on those overlooked issues with future endorsement (e.g., performance assessment with CO tolerance analysis and fuel cell test stand) for further development while comparing them with other anhydrous platforms from both academic and industrial perspectives.}, archive = {J_JACS}, author = {Debolina Mukherjee and Apu Saha and Subhodeep Moni and Dirk Volkmer and Madhab C. Das}, doi = {10.1021/jacs.4c14029}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5515--5553}, shortjournal = {J. Am. Chem. Soc.}, title = {Anhydrous solid-state proton conduction in crystalline MOFs, COFs, HOFs, and POMs}, volume = {147}, year = {2025}, }
• (2025). Architecting Metal–Organic frameworks at molecular level toward direct air capture. JACS, 147(7), 5495--5514. (www)

  @article{ , abstract = {Escalating carbon dioxide (CO 2 ) emissions have intensified the greenhouse effect, posing a significant long-term threat to environmental sustainability. Direct air capture (DAC) has emerged as a promising approach to achieving a net-zero carbon future, which offers several practical advantages, such as independence from specific CO 2 emission sources, economic feasibility, flexible deployment, and minimal risk of CO 2 leakage. The design and optimization of DAC sorbents are crucial for accelerating industrial adoption. Metal–organic frameworks (MOFs), with high structural order and tunable pore sizes, present an ideal solution for achieving strong guest–host interactions under trace CO 2 conditions. This perspective highlights recent advancements in using MOFs for DAC, examines the molecular-level effects of water vapor on trace CO 2 capture, reviews data-driven computational screening methods to develop a molecularly programmable MOF platform for identifying optimal DAC sorbents, and discusses scale-up and cost of MOFs for DAC.}, archive = {J_JACS}, author = {Zi-Ming Ye and Yi Xie and Kent O. Kirlikovali and Shengchang Xiang and Omar K. Farha and Banglin Chen}, doi = {10.1021/jacs.4c12200}, journal = {Journal of the American Chemical Society}, month = {2}, number = {7}, pages = {5495--5514}, shortjournal = {J. Am. Chem. Soc.}, title = {Architecting Metal–Organic frameworks at molecular level toward direct air capture}, volume = {147}, year = {2025}, }
• (2025). Vintages for new fashion: Red-shifted photoswitching via the triplet-photoreaction channel with charge-transfer complex sensitizers. JACS, 147(6), 5486--5494. (www)

  @article{ , abstract = {Triplet-sensitization has been proven invaluable for creating photoswitches operated over a full visible-light spectrum. While designing efficient triplet-sensitizers is crucial for establishing visible-light photochromism, it remains an appealing yet challenging task. In this work, we propose a versatile strategy to fabricate triplet-sensitizers with intermolecular charge-transfer complexes (CTCs). Through fine-tuning interactions between various donor and acceptor units, a series of CTC sensitizers were prepared with intensified visible-light absorption and a distinctive narrow Δ E ST feature. By virtue of this, a bidirectional visible-light photochromism (475 nm/605 nm) was achieved via integrating CTC sensitizers with classic diarylethene (DAE) photoswitches in various substrates upon triplet photoreaction pathways. Proof-of-concept applications, such as photoresponsive printing and mechanic-facilitated inkpad, were subsequently presented. The flexible accessibility and tunability of CTC sensitizers facilitate both generalized and customized production of photoresponsive systems that operate within the visible-light region.}, archive = {J_JACS}, author = {Wenhui Wang and Jinghong Dai and Zhiwei Zhang and Junji Zhang and He Tian}, doi = {10.1021/jacs.4c18682}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5486--5494}, shortjournal = {J. Am. Chem. Soc.}, title = {Vintages for new fashion: Red-shifted photoswitching via the triplet-photoreaction channel with charge-transfer complex sensitizers}, volume = {147}, year = {2025}, }
• (2025). Bias dependence of the transition state of the hydrogen evolution reaction. JACS, 147(6), 5472--5485. (www)

  @article{ , abstract = {The hydrogen evolution reaction (HER) is one of the most prominent electrocatalytic reactions of green energy transition. However, the kinetics across materials and electrolyte pH and the impact of hydrogen coverage at high current densities remain poorly understood. Here, we study the HER kinetics over a large set of nanoparticle catalysts in industrially relevant acidic and alkaline membrane electrode assemblies that are only operated with pure water humidified gases. We discover distinct kinetic fingerprints between the iron triad (Fe, Ni, Co), coinage (Au, Cu, Ag), and platinum group metals (Ir, Pt, Pd, Rh). Importantly, the applied bias changes not only the activation energy ( E A ) but also the pre-exponential factor ( A ). We interpret these changes as entropic changes in the interfacial solvent that differ between acid and base and entropic changes on the surface due to a changing hydrogen coverage. Finally, we observe that anions can induce Butler–Volmer behavior for the coinage metals in acid. Our results provide a new foundation to understand HER kinetics and, more broadly, highlight the pressing need to update common understanding of basic concepts in the field of electrocatalysis.}, archive = {J_JACS}, author = {José M. Gisbert-González and Carlos G. Rodellar and Jody Druce and Eduardo Ortega and Beatriz Roldan Cuenya and Sebastian Z. Oener}, doi = {10.1021/jacs.4c18638}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5472--5485}, shortjournal = {J. Am. Chem. Soc.}, title = {Bias dependence of the transition state of the hydrogen evolution reaction}, volume = {147}, year = {2025}, }
• (2025). Dual pathways of photorelease carbon monoxide via photosensitization for tumor treatment. JACS, 147(6), 5459--5471. (www)

  @article{ , abstract = {Carbon monoxide (CO) gas therapy, as an emerging therapeutic strategy, is promising in tumor treatment. However, the development of a red or near-infrared light-driven efficient CO release strategy is still challenging due to the limited physicochemical characteristics of the photoactivated carbon monoxide-releasing molecules (photoCORMs). Here, we discovered a novel photorelease CO mechanism that involved dual pathways of CO release via photosensitization. Specifically, the photosensitizer Chlorin e6 (Ce6) sensitized oxygen to produce singlet oxygen ( 1 O 2 ) and oxidized photoCORM Mn 2 (CO) 10 to release CO in an air-saturated solvent under red light (655 nm, 50 mW/cm 2 ) irradiation. Furthermore, Ce6 and Mn 2 (CO) 10 could undergo multistep photochemical reactions to release CO, as well as the degradation of the photosensitizer Ce6 in an oxygen-depleted solution. As a proof of concept, we demonstrated the feasibility and tumor inhibition of this CO release strategy both in vitro and in vivo . These results provide a robust platform for the development of new approaches to CO-mediated modulation of signaling pathways and further facilitate the practical use of gas therapeutic methods in tumor therapy in vivo .}, archive = {J_JACS}, author = {Juan-Mei Wang and Jia-Yao Li and Xue-Hui Shi and Zhi-Gang Wang and Le Zeng and Dai-Wen Pang and Ling Huang and Shu-Lin Liu}, doi = {10.1021/jacs.4c18400}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5459--5471}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual pathways of photorelease carbon monoxide via photosensitization for tumor treatment}, volume = {147}, year = {2025}, }
• (2025). Atomistic origin of microsecond carrier lifetimes at perovskite grain boundaries: Machine learning-assisted nonadiabatic molecular dynamics. JACS, 147(6), 5449--5458. (www)

  @article{ , abstract = {The polycrystalline nature of perovskites, stemming from their facile solution-based fabrication, leads to a high density of grain boundaries (GBs) and point defects. However, the impact of GBs on perovskite performance remains uncertain, with contradictory statements found in the literature. We developed a machine learning force field, sampled GB structures on a nanosecond time scale, and performed nonadiabatic (NA) molecular dynamics simulations of charge carrier trapping and recombination in stoichiometric and doped GBs. The simulations reveal long, microsecond carrier lifetimes, approaching experimental data, stemming from charge separation at the GBs and small NA coupling, 0.01–0.1 meV. Stoichiometric GBs exhibit transient trap states, which, however, are not particularly detrimental to the carrier lifetime. Halide dopants form interstitial defects in the bulk, but have a stabilizing influence on the GB structure by passivating undersaturated Pb atoms and reducing the transient trap state formation. On the contrary, excess Pb destabilizes GBs, allowing formation of persistent midgap states that trap charges. Still, the charge carrier lifetime reduces relatively little, because the midgap states decouple from the bands, and charges are more likely to escape back into bands upon a GB structural fluctuation. The atomistic study into the structural dynamics of perovskite GBs and its influence on charge carrier trapping and recombination provides valuable insights into the complex properties of perovskites and the intricate role of GBs in the material performance.}, archive = {J_JACS}, author = {Yifan Wu and Weibin Chu and Bipeng Wang and Oleg V. Prezhdo}, doi = {10.1021/jacs.4c18223}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5449--5458}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomistic origin of microsecond carrier lifetimes at perovskite grain boundaries: Machine learning-assisted nonadiabatic molecular dynamics}, volume = {147}, year = {2025}, }
• (2025). DNL-17: A small-pore aluminophosphate in ABC-6 family with 24 stacking layers unraveled by three-dimensional electron diffraction. JACS, 147(6), 5440--5448. (www)

  @article{ , abstract = {Small-pore aluminophosphate (AlPO) molecular sieves (MSs), particularly those in the ABC-6 family, have gained significant attention for their unique capabilities in selective adsorption and energy storage. However, developing new synthesis strategies for designing AlPOs with three-dimensional (3D) channel systems and determining the structures of nanosized novel AlPO MSs remain challenging tasks. In this study, we introduce a new small-pore AlPO with a 3D channel system, named DNL-17, synthesized by using a diquaternary ammonium compound as an organic structure-directing agent (OSDA). Its crystallographic structure was determined through advanced 3D electron diffraction (ED) techniques and further confirmed by emerging integrated differential phase contrast imaging. DNL-17 exhibits a remarkable 24-layer stacking sequence along the c -axis and features a variety of composite building units (CBUs), including d 6 r , can , cha , and eri . Significantly, a combination of 3D ED, theoretical calculations, and solid-state 13 C NMR reveals that the employed OSDA adopts distinct conformations to stabilize different cages. This finding highlights a novel strategy for constructing AlPO MSs with diverse cage-based CBUs. Furthermore, DNL-17 demonstrates unique selective adsorption properties, particularly in the separation of n -butane and isobutane.}, archive = {J_JACS}, author = {Chenyang Nie and Yuanhao Li and Xiaona Liu and Nana Yan and Chao Ma and Jiahui Zhu and Linlin Hao and Peng Guo and Zhongmin Liu}, doi = {10.1021/jacs.4c18190}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5440--5448}, shortjournal = {J. Am. Chem. Soc.}, title = {DNL-17: A small-pore aluminophosphate in ABC-6 family with 24 stacking layers unraveled by three-dimensional electron diffraction}, volume = {147}, year = {2025}, }
• (2025). Sulfur lone pairs open avenues for π* → n orange-to-red TADF and OLEDs. JACS, 147(6), 5432--5439. (www)

  @article{ , abstract = {It is always important and fascinating to explore new organic emitters that exploit unconventional pathways to unveil their emission with unique properties, such as thermally activated delayed fluorescence (TADF). In this study, we report that the rarely explored sulfur lone pair (n) is a promising alternative, where the correlated π* → n emission can be used to attain strong TADF and thus practical OLEDs. The designed strategy incorporates several key concepts (Figure 1a), in which the persulfide aromatic spirocycle enhances spin–orbit coupling, thereby increasing the intersystem crossing rate. Next, molecules with a twisted donor–acceptor configuration bridged by spiro[4.4]nonane as well as spatially orthogonal sulfur lone pairs and π* features significantly reduce the singlet–triplet gap. Finally, the rigid spirocyclic backbone inhibits nonradiative transitions. The proof-of-concept is given by compound 1 , which achieves nπ* thermally activated delayed fluorescence (TADF) maximized at 635 nm with photoluminescence quantum yields as high as 52% in CH 2 Cl 2 . Wet-processed OLEDs containing 1 achieved a maximum external quantum efficiency of 6.4% at a brightness of 189 cd m –2 (∼600 nm), opening an alternative 1 nπ* route for practical π* → n TADF OLEDs.}, archive = {J_JACS}, author = {Hao Sun and Xuping Li and Chao-Hsien Hsu and Chieh-Ming Hung and Bin Wu and Zhe-Hong Su and Glib V. Baryshnikov and Chenzi Li and Hans Ågren and Zhiyun Zhang and Wei Huang and Dayu Wu and Pi-Tai Chou and Liangliang Zhu}, doi = {10.1021/jacs.4c18235}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5432--5439}, shortjournal = {J. Am. Chem. Soc.}, title = {Sulfur lone pairs open avenues for π* → n orange-to-red TADF and OLEDs}, volume = {147}, year = {2025}, }
• (2025). Ionic remote α-C–H allenylation of silyl ethers involving a [1,5]-hydride shift promoted by silylium-ion regeneration. JACS, 147(6), 5426--5431. (www)

  @article{ , abstract = {A silylium-ion-promoted α-C–H allenylation of silyl ethers tethered to an internal alkyne is described. The actual intermolecular allenylation event occurs after the trans -selective hydrosilylation of the alkyne, where an in situ-generated β-silicon-stabilized vinyl cation engages in an intramolecular [1,5]-hydride shift. This process transforms the silyl ether into a silylcarboxonium ion, which reacts with propargylsilanes as nucleophiles, formed by the rapid silylium-ion-catalyzed isomerization of allenylsilanes. As part of the allenylation step, the propagating silylium-ion electrophile is regenerated, thereby closing the catalytic cycle. An allylsilane is also applicable in this transformation, producing the corresponding α-C–H allylation product in high yield.}, archive = {J_JACS}, author = {Honghua Zuo and Sebastian Kemper and Hendrik F. T. Klare and Martin Oestreich}, doi = {10.1021/jacs.4c18137}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5426--5431}, shortjournal = {J. Am. Chem. Soc.}, title = {Ionic remote α-C–H allenylation of silyl ethers involving a [1,5]-hydride shift promoted by silylium-ion regeneration}, volume = {147}, year = {2025}, }
• (2025). Harnessing organopotassium reagents for cross-coupling with YPhos-pd catalysts: Opportunities, applications, and challenges. JACS, 147(6), 5417--5425. (www)

  @article{ , abstract = {With advances in the applications of earth-abundant organopotassium reagents in C–C bond forming processes, this study pioneers Pd-catalyzed cross coupling reactions between aryl halides and a range of aryl and benzylpotassium species generated by direct C–H metalation. Key for the success of this approach is the use of electron-rich ylide-substituted phosphine (YPhos) ligands, which enable fast conversion of the potassium species in solution. This protocol can be carried out in a one-pot manner at room temperature, without the need for purification of the in situ prepared organopotassium compounds or any additional additives, enabling the isolation of a broad scope of coupling products even on a gram-scale.}, archive = {J_JACS}, author = {Daniel Knyszek and Julian Löffler and David E. Anderson and Eva Hevia and Viktoria H. Gessner}, doi = {10.1021/jacs.4c18073}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5417--5425}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing organopotassium reagents for cross-coupling with YPhos-pd catalysts: Opportunities, applications, and challenges}, volume = {147}, year = {2025}, }
• (2025). Macroscopic gold cluster helical tendrils. JACS, 147(6), 5408--5416. (www)

  @article{ , abstract = {Handedness-controllable macroscopic helices are needed for understanding the chirality transfer through scales and design of high-performance devices. Bottom-up self-assembly rarely affords macroscopic helical superstructures because of accumulating disorder that is difficult to avoid during hierarchical self-assembly. Here, we demonstrate that tetragold Au 4 clusters can assemble into macroscopic helices at the centimeter scale. Halogen-bond induces hierarchical self-assembly from nanotubes to aslant stacked nanotubes and finally to macrohelices. Sacrificial template synthesis via solvent-corrosion sufficiently removes the embedded 1,3,5-trifluoro-2,4,6-triiodobenzene to produce helical skeletons. Homochiral macroscopic tendrils are controllably synthesized by chiral halogen bonding donors, allowing high-fidelity chiral amplification. This work contributes to the development of macroscopic helical superstructures by hierarchical assembly.}, archive = {J_JACS}, author = {Ya-Jie Wang and Xiao-Yan Shi and Yu Guo and Xing-Nan Wang and Ke-Xin Zheng and Xue-Wen Yang and Pengyao Xing and Shuang-Quan Zang}, doi = {10.1021/jacs.4c17800}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5408--5416}, shortjournal = {J. Am. Chem. Soc.}, title = {Macroscopic gold cluster helical tendrils}, volume = {147}, year = {2025}, }
• (2025). Pd1Ni2 trimer sites drive efficient and durable hydrogen oxidation in alkaline media. JACS, 147(6), 5398--5407. (www)

  @article{ , abstract = {Anion-exchange membrane fuel cell (AEMFC) is a cost-effective hydrogen-to-electricity conversion technology under a zero-emission scenario. However, the sluggish kinetics of the anodic hydrogen oxidation reaction (HOR) impedes the commercial implementation of AEMFCs. Here, we develop a Pd single-atom-embedded Ni 3 N catalyst (Pd 1 /Ni 3 N) with unconventional Pd 1 Ni 2 trimer sites to drive efficient and durable HOR in alkaline media. Integrating theoretical and experimental analyses, we demonstrate that dual Pd 1 Ni 2 sites achieve a “*H on Pd 1 Ni 2 –H V + *OH on Pd 1 Ni 2 –H N ” adsorption mode, effectively weakening the overstrong *H and *OH adsorptions on pristine Ni 3 N. Owing to the unique coordination mode and atomically dispersed catalytic sites, the resulting Pd 1 /Ni 3 N catalyst delivers a high intrinsic and mass activity together with excellent antioxidation capability and CO tolerance. Specifically, the HOR mass activity of Pd 1 /Ni 3 N reaches 7.54 A mg Pd –1 at the overpotential of 50 mV. The AEMFC employing Pd 1 /Ni 3 N as the anode catalyst displays a high power density of 31.7 W mg Pd –1 with an ultralow anode precious metal loading of only 0.023 mg Pd cm –2 . This study provides guidance for the design of high-performance alkaline HOR catalytic sites at the atomic level.}, archive = {J_JACS}, author = {Shu-Qi Wang and Ze-Cheng Yao and Zhuo-Qi Shi and Xuerui Liu and Tang Tang and Hai-Rui Pan and Lirong Zheng and Qinghua Zhang and Dong Su and Zhongbin Zhuang and Lu Zhao and Qi An and Jin-Song Hu}, doi = {10.1021/jacs.4c17605}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5398--5407}, shortjournal = {J. Am. Chem. Soc.}, title = {Pd1Ni2 trimer sites drive efficient and durable hydrogen oxidation in alkaline media}, volume = {147}, year = {2025}, }
• (2025). Modulation of Protein–Protein interactions with molecular glues in a synthetic condensate platform. JACS, 147(6), 5386--5397. (www)

  @article{ , abstract = {Misregulation of protein–protein interactions (PPIs) underlies many diseases; hence, molecules that stabilize PPIs, known as molecular glues, are promising drug candidates. Identification of novel molecular glues is highly challenging among others because classical biochemical assays in dilute aqueous conditions have limitations for evaluating weak PPIs and their stabilization by molecular glues. This hampers the systematic discovery and evaluation of molecular glues. Here, we present a synthetic condensate platform for the study of PPIs and molecular glues in a crowded macromolecular environment that more closely resembles the dense cellular milieu. With this platform, weak PPIs can be enhanced by sequestration. The condensates, based on amylose derivatives, recruit the hub protein 14-3-3 via affinity-based uptake, which results in high local protein concentrations ideal for the efficient screening of molecular glues. Clients of 14-3-3 are sequestered in the condensates based on their enhanced affinity upon treatment with molecular glues. Fine control over the condensate environment is illustrated by modulating the reactivity of dynamic covalent molecular glues by the adjustment of pH and the redox environment. General applicability of the system for screening of molecular glues is highlighted by using the nuclear receptor PPARγ, which recruits coregulators via an allosteric PPI stabilization mechanism. The condensate environment thus provides a unique dense molecular environment to enhance weak PPIs and enable subsequent evaluation of small-molecule stabilization in a molecular setting chemically en route to the cellular interior.}, archive = {J_JACS}, author = {Thijs W. van Veldhuisen and Renske M. J. Dijkstra and Auke A. Koops and Peter J. Cossar and Jan C. M. van Hest and Luc Brunsveld}, doi = {10.1021/jacs.4c17567}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5386--5397}, shortjournal = {J. Am. Chem. Soc.}, title = {Modulation of Protein–Protein interactions with molecular glues in a synthetic condensate platform}, volume = {147}, year = {2025}, }
• (2025). Cuδ+ site-enhanced adsorption and crown ether-reconfigured interfacial D2O promote electrocatalytic dehalogenative deuteration. JACS, 147(6), 5377--5385. (www)

  @article{ , abstract = {Electrocatalytic dehalogenative deuteration is a sustainable method for precise deuteration, whereas its Faradaic efficiency (FE) is limited by a high overpotential and severe D 2 evolution reaction (DER). Here, Cu δ+ site-adjusted adsorption and crown ether-reconfigured interfacial D 2 O are reported to cooperatively increase the FE of dehalogenative deuteration up to 84% at −100 mA cm –2 . Cu δ+ sites strengthen the adsorption of aryl iodides, promoting interfacial mass transfer and thus accelerating the kinetics toward dehalogenative deuteration. The crown ethers disrupt the hydration effect of K·D 2 O and reconstruct the hydrogen bond with the interfacial D 2 O, lowering the content K·D 2 O of the electric double layer and hindering the interaction between D 2 O and the cathode, thus inhibiting the kinetics of the competitive DER. A linear relationship between the matched sizes of crown ethers and alkali metal cations is demonstrated for universally increasing FEs. This method is also suitable for the deuteration of various halides with high easily reducible functional group compatibility and improved FEs at −100 mA cm –2 .}, archive = {J_JACS}, author = {Meng He and Haotian Wang and Chuanqi Cheng and Rui Li and Cuibo Liu and Ying Gao and Bin Zhang}, doi = {10.1021/jacs.4c17432}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5377--5385}, shortjournal = {J. Am. Chem. Soc.}, title = {Cuδ+ site-enhanced adsorption and crown ether-reconfigured interfacial D2O promote electrocatalytic dehalogenative deuteration}, volume = {147}, year = {2025}, }
• (2025). Dimerization of hexaphyrin with an appendant pyrrole possessing a reactive site to alleviate the steric hindrance. JACS, 147(6), 5368--5376. (www)

  @article{ , abstract = {Oxidative dimerization of π-conjugated molecules is a straightforward approach for effectively extending π-conjugation and absorption features. However, it is challenging to construct dimeric species of bulky π-conjugated frameworks because of the steric hindrances and/or poor regioselectivity. To address these issues, a pyrrole unit has been regioselectively appended to the α position of N-confused hexaphyrin (1.1.1.1.1.0) 1 by a facile acid-catalyzed condensation reaction, leading to the formation of pyrrole-appendant 2 . Subsequent oxidation of 2 yielded an inner-fused monomer 2F and two fused dimeric species, namely, (2F) 2 a and (2F) 2 b . In contrast, oxidation of the corresponding Ni(II) complex 2Ni generated dimer (2Ni) 2 . Subsequent demetalation resulted in the formation of bipyrrole-linked freebase dimer (2) 2 , which could chelate Ni(II) and Cu(II) ions to furnish complexes (2Ni) 2 and (2Cu) 2 , respectively. In comparison to the fused dimeric species (2F) 2 a and (2F) 2 b , the nonfused dimer (2) 2 and its complexes (2Ni) 2 and (2Cu) 2 exhibit diminished local aromaticity, narrowed HOMO–LUMO gaps, and a red-shifted absorption profile that extends up to 2200 nm. These findings underscore a potent strategy for creating expanded porphyrin dimers, wherein the aromaticity and near-infrared absorption can be fine-tuned by incorporating an appendant pyrrole unit.}, archive = {J_JACS}, author = {Yongshu Xie and Guangxian Su and Masatoshi Ishida and Bin Zhu and Glib Baryshnikov and Feng Sha and Chengjie Li and Xinyan Wu and Hans Ågren and Hiroyuki Furuta and Qizhao Li}, doi = {10.1021/jacs.4c17052}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5368--5376}, shortjournal = {J. Am. Chem. Soc.}, title = {Dimerization of hexaphyrin with an appendant pyrrole possessing a reactive site to alleviate the steric hindrance}, volume = {147}, year = {2025}, }
• (2025). Sequential and time-controlled Sol–Gel transitions by mechanical switching of molecular tweezers. JACS, 147(6), 5360--5367. (www)

  @article{ , abstract = {Controlling the motion of molecular machines to influence higher-order structures is well-established in biological systems but remains a significant challenge for synthetic analogs. Herein, we aim to harness the mechanical switching of switchable molecular tweezers to modulate their self-assembly and produce stimuli-responsive organogels. We report a series of terpy(Pt-salphen) 2 molecular tweezers functionalized with alkyl chains that act as low-molecular-weight gelators (LMWGs) in their open conformation. The resulting organogels were thoroughly characterized by SEM, cryo-TEM, SAXS, and rheology. The macroscopic transition from gel to solution was achieved by the cation-induced closing of the tweezers, which triggers their substantial structural reorganization. Reversible sol–gel transitions were achieved through the sequential addition of chemical stimuli or by a decomposable acid in a time-controlled operation. Such transient disassembly process regulated by a chemical fuel enables multiple gelation cycles with minimal waste while maintaining stable rheological properties. These results underscore the potential of switchable molecular tweezers in creating advanced stimuli-responsive materials.}, archive = {J_JACS}, author = {Pablo Msellem and Geoffrey Groslambert and Louise Miton and Mickaël Pomes-Hadda and Nathan J. Van Zee and Clément Guibert and Guillaume Vives}, doi = {10.1021/jacs.4c17146}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5360--5367}, shortjournal = {J. Am. Chem. Soc.}, title = {Sequential and time-controlled Sol–Gel transitions by mechanical switching of molecular tweezers}, volume = {147}, year = {2025}, }
• (2025). P–P coupling with and without terminal Metal–Phosphorus intermediates. JACS, 147(6), 5350--5359. (www)

  @article{ , abstract = {Terminal metal–phosphorus (M–P) complexes are of significant contemporary interest as potential platforms for P-atom transfer (PAT) chemistry. Decarbonylation of metal–phosphaethynolate (M–PCO) complexes has emerged as a general synthetic approach to terminal M–P complexes. M–P complexes that are stabilized by strong M–P multiple bonds are kinetically persistent and isolable. In the absence of strong M–P stabilization, the formation of diphosphorus-bridged complexes (i.e., M–P–P–M species) is often interpreted as evidence for the intermediacy of reactive, unobserved M–P species. Here, we demonstrate that while diphosphorus complexes can arise from reactive M–P species, P–P coupling can also proceed directly from M–PCO species without the intermediacy of M–P complexes. Photochemical decarbonylations of a pincer-supported Ni (II)–PCO complex at 77 K afford a spectroscopically observed terminal Ni–P complex, which is best described as a triplet, Ni(II)-metallophosphinidene with two unpaired electrons localized on the atomic phosphorus ligand. Thermal annealing of this transient Ni–P complex results in rapid dimerization to afford the corresponding P 2 2– -bridged dinickel complex. Unexpectedly, the same P 2 2– -bridged dinickel complex can also be accessed via a thermally promoted process in the absence of light. The analysis of reaction kinetics, isotope-labeling studies, and computational results indicate that the thermal P–P coupling process proceeds via a noncanonical mechanism that avoids terminal M–P intermediates. Together, these results represent the first observation of P–P coupling from characterized terminal M–P species and demonstrate that terminal M–P intermediates are not required to obtain P–P coupling products. These observations provide critical mechanistic understanding of the activation modes relevant to P-atom transfer.}, archive = {J_JACS}, author = {Richard R. Thompson and Matthew T. Figgins and Duleeka C. Wannipurage and Angel Renteria-Gomez and Achyut Ranjan Gogoi and Joshua Telser and David L. Tierney and Marc C. Neben and Serhiy Demeshko and Osvaldo Gutierrez and David C. Powers}, doi = {10.1021/jacs.4c16833}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5350--5359}, shortjournal = {J. Am. Chem. Soc.}, title = {P–P coupling with and without terminal Metal–Phosphorus intermediates}, volume = {147}, year = {2025}, }
• (2025). Efficient methanol oxidation kinetics enabled by an ordered heterocatalyst with dual electric fields. JACS, 147(6), 5340--5349. (www)

  @article{ , abstract = {Induced by a sharp-tip-enhanced electric field, periodical nanoassemblies can regulate the reactant flux on the electrode surface, efficiently optimizing the mass transfer kinetics in electrocatalysis. However, when the nanoscale building blocks in homoassemblies are arranged densely, it results in the overlap and reduction of the local electric field. Herein, we present a comprehensive kinetic heteromodel that simultaneously couples the sharp-tip-enhanced electric field and charge transfer electric field between different building blocks with any arrangement densities. The dual electric fields drive the diffusion of reactants from the bulk solution to the electrode surface, significantly enhancing mass transfer kinetics along the horizontal and longitudinal directions, which promotes the electrocatalytic activity significantly. Moreover, the wide generality of the model is further confirmed by electrochemical experiments involving various electrocatalytic systems and catalysts. Therefore, this work highlights the significant role of dual electric fields in electrocatalysis, which is expected to facilitate the development of customized and outstanding catalysts in the future.}, archive = {J_JACS}, author = {Tian Liu and Qing-Xia Chen and Zhen He and Jin-Long Wang and Si-Zhe Sheng and Jian-Wei Liu and Shu-Hong Yu}, doi = {10.1021/jacs.4c16885}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5340--5349}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient methanol oxidation kinetics enabled by an ordered heterocatalyst with dual electric fields}, volume = {147}, year = {2025}, }
• (2025). Transient triplet metallopnictinidenes M–Pn (M = PdII, PtII; pn = p, as, sb): Characterization and dimerization. JACS, 147(6), 5330--5339. (www)

  @article{ , abstract = {Nitrenes (R–N) have been subject to a large body of experimental and theoretical studies. The fundamental reactivity of this important class of transient intermediates has been attributed to their electronic structures, particularly the accessibility of triplet vs singlet states. In contrast, electronic structure trends along the heavier pnictinidene analogues (R–Pn; Pn = P–Bi) are much less systematically explored. We here report the synthesis of a series of metallodipnictenes, {M–Pn═Pn–M} (M = Pd II , Pt II ; Pn = P, As, Sb, Bi) and the characterization of the transient metallopnictinidene intermediates, {M–Pn} for Pn = P, As, Sb. Structural, spectroscopic, and computational analysis revealed spin triplet ground states for the metallopnictinidenes with characteristic electronic structure trends along the series. In comparison to the nitrene, the heavier pnictinidenes exhibit lower-lying ground state SOMOs and singlet excited states, thus suggesting increased electrophilic reactivity. Furthermore, the splitting of the triplet magnetic microstates is beyond the phosphinidenes {M–P} dominated by heavy pnictogen atom induced spin–orbit coupling.}, archive = {J_JACS}, author = {Marc C. Neben and Nils Wegerich and Tarek A. Al Said and Richard R. Thompson and Serhiy Demeshko and Kevin Dollberg and Igor Tkach and Gerard P. Van Trieste, III and Hendrik Verplancke and Carsten von Hänisch and Max C. Holthausen and David C. Powers and Alexander Schnegg and Sven Schneider}, doi = {10.1021/jacs.4c16830}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5330--5339}, shortjournal = {J. Am. Chem. Soc.}, title = {Transient triplet metallopnictinidenes M–Pn (M = PdII, PtII; pn = p, as, sb): Characterization and dimerization}, volume = {147}, year = {2025}, }
• (2025). Chiral primary amine-catalyzed asymmetric photochemical reactions of pyridotriazoles with boronic acids to access triarylmethanes. JACS, 147(6), 5320--5329. (www)

  @article{ , abstract = {Imine-containing azaarene-based triarylmethanes are vital molecular motifs that are prevalent in a wide array of bioactive compounds. Recognizing the limitations of current synthetic methodologies─marked by a scarcity of examples and difficulties in flexible functional group modulation─we have developed an efficient and modular asymmetric photochemical strategy employing pyridotriazoles and boronic acids as substrates. Utilizing novel chiral diamine-derived pyrroles and primary amines as catalysts, we successfully synthesized a diverse range of triarylmethanes with high yields and excellent enantioselectivities. This method not only exhibits a broad substrate scope and outstanding functional group tolerance but also enables the precise synthesis of deuterated derivatives using inexpensive D 2 O as the deuterium source. Mechanistic studies reveal that an unusual 1,4-boron shift is a critical step in generating the boronated enamine intermediate, while also shedding light on the potential enantiocontrol mechanisms facilitated by the chiral catalyst.}, archive = {J_JACS}, author = {Chenyang Jiang and Youlan Meng and Yinwa Huang and Chan Liu and Yanli Yin and Xiaowei Zhao and Shanshan Cao and Zhiyong Jiang}, doi = {10.1021/jacs.4c16811}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5320--5329}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral primary amine-catalyzed asymmetric photochemical reactions of pyridotriazoles with boronic acids to access triarylmethanes}, volume = {147}, year = {2025}, }
• (2025). Synthetically relevant post-transition state bifurcation leading to diradical and zwitterionic intermediates: Controlling nonstatistical kinetic selectivity through solvent effects. JACS, 147(6), 5310--5319. (www)

  @article{ , abstract = {A post-transition state surface intersection (PTSSI) between radical and zwitterionic states that causes a bifurcation in the reaction pathway was discovered through density functional theory calculations on potential energy surfaces and ab initio molecular dynamics simulations of cycloadditions between a bicyclobutane and a triazolinedione (BCB-TAD). It was predicted that changes to the solvent polarity would enable control over the dynamic selectivity in this system; indeed, experimental evidence supported this prediction. This work not only provides new insights into an unusual type of post-transition state bifurcation, but also demonstrates how the nonstatistical dynamic effects that control selectivity for such reactions can be manipulated rationally to increase the yields of synthetically useful reactions.}, archive = {J_JACS}, author = {Wang-Yeuk Kong and Yun Hu and Wentao Guo and Abhay Potluri and Jennifer M. Schomaker and Dean J. Tantillo}, doi = {10.1021/jacs.4c16760}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5310--5319}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthetically relevant post-transition state bifurcation leading to diradical and zwitterionic intermediates: Controlling nonstatistical kinetic selectivity through solvent effects}, volume = {147}, year = {2025}, }
• (2025). Antagonistic effects of distance and overlap toward anomalous pressure-induced blueshift of π–π excimer fluorescence in 9-(2,2-diphenylvinyl)anthracene crystals. JACS, 147(6), 5300--5309. (www)

  @article{ , abstract = {Piezochromic materials usually exhibit a gradual redshift of emission as pressure increases due to the formation of a low-energy “dark” state, e.g., excimer. However, our study presents an anomalous excimer-based pressure-induced emission blueshift. A crystal was investigated here with a discrete π–π anthracene dimer stacking and excimer emission, and the dimer is characterized by an overshifted off-center stacking pattern. Intriguingly, under isotropic hydrostatic pressure, this crystal exhibits negative linear compressibility almost along the c -axis of the unit cell. Furthermore, an antagonistic effect between overlap ratio (S π–π ) and interplanar distance (D π–π ) within the dimer on emission was identified: reduced D π–π typically dominates the emission redshift, while decreasing S π–π can cause emission blueshift. When the pressure reaches around 5.00 GPa, the π–π excimer fluorescence exhibits an unexpected blueshift, indicating the reign of decreasing S π–π . This study not only sheds light on the modulation of fluorescence properties by noncovalent interactions but also introduces an innovative approach to anomalous piezochromism.}, archive = {J_JACS}, author = {Xinqi Yang and Yuxiang Dai and Haichao Liu and Kai Wang and Hai-Le Yan and Xihan Yu and Zhou-An Xia and Min Wu and Shitong Zhang and Guanjun Xiao and Bo Zou and Bing Yang}, doi = {10.1021/jacs.4c16582}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5300--5309}, shortjournal = {J. Am. Chem. Soc.}, title = {Antagonistic effects of distance and overlap toward anomalous pressure-induced blueshift of π–π excimer fluorescence in 9-(2,2-diphenylvinyl)anthracene crystals}, volume = {147}, year = {2025}, }
• (2025). Chemically triggered reactive coacervates show life-like budding and membrane formation. JACS, 147(6), 5293--5299. (www)

  @article{ , abstract = {Phase-separated coacervates can enhance reaction kinetics and guide multilevel self-assembly, mimicking early cellular evolution. In this work, we introduce “reactive” complex coacervates that undergo chemically triggered self-immolative transformations, directing the self-assembly of the reaction products within their matrix. These self-assemblies then evolve to show life-like properties such as budding and membrane formation. We find that the coacervate composition critically influences reaction rates and product distribution and guides the hierarchical self-assembly. This work showcases “reactive” coacervates as a versatile platform to influence reaction and self-assembly pathways for controlled supramolecular synthesis and hierarchical self-organization in confined spaces.}, archive = {J_JACS}, author = {Sudeep Koppayithodi and Nishant Singh}, doi = {10.1021/jacs.4c16416}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5293--5299}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemically triggered reactive coacervates show life-like budding and membrane formation}, volume = {147}, year = {2025}, }
• (2025). Stability frontiers in the AM6X6 kagome metals: The LnNb6Sn6 (Ln:Ce–Lu,Y) family and density-wave transition in LuNb6Sn6. JACS, 147(6), 5279--5292. (www)

  @article{ , abstract = {The kagome motif is a versatile platform for condensed matter physics, hosting rich interactions between magnetic, electronic, and structural degrees of freedom. In recent years, the discovery of a charge density wave (CDW) in the AV 3 Sb 5 superconductors and structurally-derived bond density waves (BDW) in FeGe and ScV 6 Sn 6 have stoked the search for new kagome platforms broadly exhibiting density wave (DW) transitions. In this work, we evaluate the known AM 6 X 6 chemistries and construct a stability diagram that summarizes the structural relationships among the >125 member family. Subsequently, we introduce our discovery of the broader Ln Nb 6 Sn 6 ( Ln :Ce–Nd,Sm,Gd–Tm,Lu,Y) family of kagome metals and an analogous DW transition in LuNb 6 Sn 6 . Our X-ray scattering measurements clearly indicate a (1/3, 1/3, 1/3) ordering wave vector ( 3 ‾ √ × 3 ‾ √ × 3 3 × 3 × 3 3×3×3 superlattice) and diffuse scattering on half-integer L -planes. Our analysis of the structural data supports the “rattling mode” DW model proposed for ScV 6 Sn 6 and paints a detailed picture of the steric interactions between the rare-earth filler element and the host Nb–Sn kagome scaffolding. We also provide a broad survey of the magnetic properties within the HfFe 6 Ge 6 -type Ln Nb 6 Sn 6 members, revealing a number of complex antiferromagnetic and metamagnetic transitions throughout the family. This work integrates our new Ln Nb 6 Sn 6 series of compounds into the broader AM 6 X 6 family, providing new material platforms and forging a new route forward at the frontier of kagome metal research.}, archive = {J_JACS}, author = {Brenden R. Ortiz and William R. Meier and Ganesh Pokharel and Juan Chamorro and Fazhi Yang and Shirin Mozaffari and Alex Thaler and Steven J. Gomez Alvarado and Heda Zhang and David S. Parker and German D. Samolyuk and Joseph A. M. Paddison and Jiaqiang Yan and Feng Ye and Suchismita Sarker and Stephen D. Wilson and Hu Miao and David Mandrus and Michael A. McGuire}, doi = {10.1021/jacs.4c16347}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5279--5292}, shortjournal = {J. Am. Chem. Soc.}, title = {Stability frontiers in the AM6X6 kagome metals: The LnNb6Sn6 (Ln:Ce–Lu,Y) family and density-wave transition in LuNb6Sn6}, volume = {147}, year = {2025}, }
• (2025). Electrochemically driven selective olefin epoxidation by Cobalt–TAML catalyst. JACS, 147(6), 5269--5278. (www)

  @article{ , abstract = {Epoxides are versatile chemical intermediates that are used in the manufacture of diversified industrial products. For decades, thermochemical conversion has long been employed as the primary synthetic route. However, it has several drawbacks, such as harsh and explosive operating conditions, as well as a significant greenhouse gas emissions problem. In this study, we propose an alternative electrocatalytic epoxidation reaction, using [Co III (TAML)] − (TAML = tetraamido macrocyclic ligand) as a molecular catalyst. Under ambient conditions, the catalyst selectively epoxidized olefin substrates using water as the oxygen atom source, affording an efficient catalytic epoxidation of olefins with a broad substrate scope. Notably, [Co III (TAML)] − achieved >60% Faradaic efficiency (FE) with >90% selectivity for cyclohexene epoxidation, which other heterogeneous electrocatalysts have never attained. Electrokinetic studies shed further light on the detailed mechanism of olefin epoxidation, which involved a rate-limiting proton-coupled electron transfer process, forming reactive cobalt oxygen active species embedded in 2e - oxidized TAML. Operando voltammetry-electrospray ionization mass spectrometry (VESI-MS) and electron paramagnetic resonance (EPR) analyses were utilized to identify a cobalt oxygen active intermediate during an electrocatalytic epoxidation by [Co III (TAML)] − . Our findings offer a new possibility for sustainable chemical feedstock production using electrochemical methods.}, archive = {J_JACS}, author = {Suyeon S. Kim and Sugyeong Hong and Adarsh Koovakattil Surendran and Avishek Roy and Deesha D. Malik and Dohyun Chun and Sojin Kim and Yumin Kim and Yong-Min Lee and Yong Ho Lee and Xiaoyan Lu and Jana Roithová and Sun Hee Kim and Wonwoo Nam and Kyoungsuk Jin}, doi = {10.1021/jacs.4c16243}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5269--5278}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemically driven selective olefin epoxidation by Cobalt–TAML catalyst}, volume = {147}, year = {2025}, }
• (2025). Precision molecular engineering of compact near-infrared fluorophores. JACS, 147(6), 5258--5268. (www)

  @article{ , abstract = {Organic fluorophores with near-infrared (NIR) emission and reduced molecular size are crucial for advancing bioimaging and biosensing technologies. Traditional methods, such as conjugation expansion and heteroatom engineering, often fail to reduce fluorophore size without sacrificing NIR emission properties. Addressing this challenge, our study utilized quantum chemical calculations and structure–property relationship analysis to establish an iterative design approach and enable precision engineering for compact, single-benzene-based NIR fluorophores. These newly developed fluorophores exhibit emissions up to 759 nm and maintain molecular weights as low as 192 g/mol, approximately 50% of that of Cy7. Additionally, they display unique environmental sensitivity─nonemissive in aqueous solutions but highly emissive in lipid environments. This property significantly enhances their utility in wash-free imaging of live cells. Our findings mark a substantial breakthrough in fluorophore engineering, paving the way for more efficient and adaptable imaging methodologies.}, archive = {J_JACS}, author = {Rongrong Huang and Qinglong Qiao and Deborah Seah and Tianruo Shen and Xia Wu and Fabio de Moliner and Chao Wang and Nannan Ding and Weijie Chi and Huaming Sun and Marc Vendrell and Zhaochao Xu and Yu Fang and Xiaogang Liu}, doi = {10.1021/jacs.4c16087}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5258--5268}, shortjournal = {J. Am. Chem. Soc.}, title = {Precision molecular engineering of compact near-infrared fluorophores}, volume = {147}, year = {2025}, }
• (2025). Facile, reversible hydrogen activation by low-coordinate magnesium oxide complexes. JACS, 147(6), 5247--5257. (www)

  @article{ , abstract = {New approaches to achieve facile and reversible dihydrogen activation are of importance for synthesis, catalysis, and hydrogen storage. Here we show that low-coordinate magnesium oxide complexes [{( RDip nacnac)Mg} 2 (μ-O)] 1 , with RDip nacnac = HC(RCNDip) 2 , Dip = 2,6- i Pr 2 C 6 H 3 , R = Me ( 1a ), Et ( 1b ), i Pr ( 1c ), readily react with dihydrogen under mild conditions to afford mixed hydride-hydroxide complexes [{( RDip nacnac)Mg} 2 (μ-H)(μ-OH)] 4 . Dehydrogenation of complexes 4 is strongly dependent on remote ligand substitution and can be achieved by simple vacuum-degassing of 4c (R = i Pr) to regain 1c . Donor addition to complexes 4 also releases hydrogen and affords donor adducts of magnesium oxide complexes. Computational studies suggest that the hydrogen activation mechanism involves nucleophilic attack of an oxide lone pair at a weakly bound H 2 ···Mg complex in an S N 2-like manner that induces a heterolytic dihydrogen cleavage to yield an MgOH and an MgH unit. Alternative synthetic routes into complex 4b from a magnesium hydride complex have been investigated and the ability of complexes 1 or 4 to act as catalysts for the hydrogenation of 1,1-diphenylethene (DPE) has been tested.}, archive = {J_JACS}, author = {Samuel Thompson and Stuart Burnett and Rochelle Ferns and Tanja van Mourik and Aidan P. McKay and Alexandra M. Z. Slawin and David B. Cordes and Andreas Stasch}, doi = {10.1021/jacs.4c16041}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5247--5257}, shortjournal = {J. Am. Chem. Soc.}, title = {Facile, reversible hydrogen activation by low-coordinate magnesium oxide complexes}, volume = {147}, year = {2025}, }
• (2025). Co-catalytic coupling of alkyl halides and alkenes: The curious role of lutidine. JACS, 147(6), 5238--5246. (www)

  @article{ , abstract = {Continuous pressure to shorten synthetic sequences along with the concomitant expansion of scope makes the use of alkyl bromides, chlorides, and oxygen based leaving groups- which are abundant and readily available feedstocks, highly attractive for C–C bond synthesis. However, selective activation of these bonds to generate radical intermediates remains challenging and is generally unfeasible using traditional activation strategies. Herein, we report a dual catalytic activation strategy to access primary, secondary, and tertiary alkyl radicals from respective alkyl chlorides and bromides, as well as primary tosylates and trifluoroacetates. While the method relies on visible light and a photocatalyst to facilitate electron transfer, based on reduction potentials, the substrates are not expected to be reduceable, and yet they are reduced in the presence of lutidine. Ultimately, our investigation revealed that lutidine was a precatalyst and ultimately led to the use of lutidinium iodide salt which served as a critical cocatalyst that resulted in improved reaction profiles. Our studies revealed two critical roles that lutidinium iodide salts play which made it possible to engage otherwise unreactive substrates: nucleophilic exchange and halogen atom transfer by the lutidinium radical. In short, this work converts unactivated alkyl chlorides, bromides, tosylates, and trifluoroacetates to radicals that can be used for C–C bond formation without the need for preactivation─effectively expediting synthesis}, archive = {J_JACS}, author = {Roshini Hanumanthu and Parul Sharma and Avery Ethridge and Jimmie D. Weaver, III}, doi = {10.1021/jacs.4c15812}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5238--5246}, shortjournal = {J. Am. Chem. Soc.}, title = {Co-catalytic coupling of alkyl halides and alkenes: The curious role of lutidine}, volume = {147}, year = {2025}, }
• (2025). Selective liquid chemical production in waste polyolefin photorefinery by controlling reactive species. JACS, 147(6), 5228--5237. (www)

  @article{ , abstract = {Photocatalytic upcycling of waste polyolefins into value-added chemicals provides promise in plastic waste management and resource utilization. Previous works demonstrate that polyolefins can be converted into carboxylic acids, with CO 2 as the final oxidation product. It is still challenging to explore more transformation products, particularly mild-oxidation products such as alcohols, because of their instability compared with polymer substrates, which are prone to oxidation during catalytic reactions. In this work, we propose an efficient strategy to regulate the product type through precise control of radicals, intermediates, and reaction paths. Taking the commonly used photocatalyst C 3 N 4 as an example, its major products are carboxylic acids and CO 2 . When MoS 2 is introduced to construct a Z -scheme heterostructure, gas products are significantly reduced and alcohols appear with a high yield of 1358.8 μmol g cat –1 and a high selectivity up to 80.3%. This is primarily attributed to the presence of •OH radicals from oxygen reduction, acting a key role in alcohol formation while simultaneously suppressing the competing pathways oxygen to •O 2 – and 1 O 2 , thus reducing the overoxidation products. The β-scission of the C–C bonds in the polymer chains generates intermediate alkyl species, followed by the combination with •OH to produce methanol, which is more energetically favorable for MoS 2 /C 3 N 4 . In contrast, alkyl species couple with oxygen species to form formic acid, which is favorable for C 3 N 4 . This work provides new approaches for controlling the product types and offers new insights into the reaction pathways involved in polyolefin photorefinery.}, archive = {J_JACS}, author = {Xinlin Liu and Xianpeng Wang and Mingyu Chu and Wenjing Zhang and Jie Fu and Shengming Li and Lu Wang and Jinxing Chen and Qiao Zhang and Muhan Cao}, doi = {10.1021/jacs.4c15718}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5228--5237}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective liquid chemical production in waste polyolefin photorefinery by controlling reactive species}, volume = {147}, year = {2025}, }
• (2025). Selective depolymerization for sculpting polymethacrylate molecular weight distributions. JACS, 147(6), 5220--5227. (www)

  @article{ , abstract = {Chain-end reactivation of polymethacrylates generated by reversible-deactivation radical polymerization (RDRP) has emerged as a powerful tool for triggering depolymerization at significantly milder temperatures than those traditionally employed. In this study, we demonstrate how the facile depolymerization of poly(butyl methacrylate) (PBMA) can be leveraged to selectively skew the molecular weight distribution (MWD) and predictably alter the viscoelastic properties of blended PBMA mixtures. By mixing polymers with thermally active chain ends with polymers of different molecular weights and inactive chain ends, the MWD of the blends can be skewed to be high or low by selective depolymerization. This approach leads to the counterintuitive principle of the “destructive strengthening” of a material. Finally, we demonstrate, as a proof of concept, the encryption of information within polymer mixtures by linking Morse code with the MWDs before and after selective depolymerization, allowing for the encoding of data within blends of synthetic macromolecules.}, archive = {J_JACS}, author = {Ariana M. Tamura and Kevin A. Stewart and James B. Young and Nathan B. Wei and Alexander J. Cantor and Brent S. Sumerlin}, doi = {10.1021/jacs.4c15553}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5220--5227}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective depolymerization for sculpting polymethacrylate molecular weight distributions}, volume = {147}, year = {2025}, }
• (2025). Toughening poly(lactic acid) without compromise – Statistical copolymerization with a bioderived bicyclic lactone. JACS, 147(6), 5212--5219. (www)

  @article{ , abstract = {Poly(lactic acid) (PLA) offers a renewable and degradable alternative to petroleum-based plastic, but its mechanical properties are not ideal for many applications. Herein, we describe the synthesis and polymerization of 2-oxo-3,8-dioxabicyclo[3.2.1]octane (ODO), a bioderived bicyclic lactone, and show that copolymers of l -lactide (LA) with small amounts of ODO have improved mechanical properties over PLA. Homopolymerization of ODO to poly(oxo-3,8-dioxabicyclo[3.2.1]octane) (PODO) is optimized for both solution-phase, organocatalytic and melt-phase, metal-catalyzed conditions. In comparison to the monocyclic analog, ε-caprolactone (CL), ODO has a lower enthalpy of polymerization and faster rate of polymerization. PODO is an amorphous, elastomeric polyester that has a T g 90 °C higher than poly(ε-caprolactone) (PCL). Statistical copolymerization of LA with small fractions of ODO yields tough and transparent thermoplastics that have over 12× elongation at break compared to native PLA, while maintaining T g , Young’s modulus ( E ), and yield strength. Together, these results describe how the incorporation of the tetrahydrofuran ring alters lactone polymerizability and the thermomechanical properties of the homopolymer and copolymer materials.}, archive = {J_JACS}, author = {Lucas A. H. Sanchez and Cristian P. Woroch and David M. Dumas and Robert M. Waymouth and Matthew W. Kanan}, doi = {10.1021/jacs.4c15697}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5212--5219}, shortjournal = {J. Am. Chem. Soc.}, title = {Toughening poly(lactic acid) without compromise – Statistical copolymerization with a bioderived bicyclic lactone}, volume = {147}, year = {2025}, }
• (2025). Rhodium-catalyzed homogeneous asymmetric hydrogenation of naphthol derivatives. JACS, 147(6), 5197--5211. (www)

  @article{ , abstract = {Due to their strong aromaticity and difficulties in chemo-, regio-, and enantioselectivity control, asymmetric hydrogenation of naphthol derivatives to 1,2,3,4-tetrahydronaphthols has remained a long-standing challenge. Herein, we report the first example of homogeneous asymmetric hydrogenation of naphthol derivatives catalyzed by tethered rhodium–diamine catalysts, affording a wide array of optically pure 1,2,3,4-tetrahydronaphthols in high yields with excellent regio-, chemo-, and enantioselectivities (up to 98% yield and >99% ee). Mechanistic studies with experimental and computational approaches reveal that fluorinated solvent 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) plays vital roles in the control of reactivity and selectivity, and 1-naphthol is reduced via a cascade reaction pathway, including dearomative tautomerization, 1,4-hydride addition, and 1,2-hydride addition in sequence. A novel synergistic activation mode was proposed in which HFIP assists a synergistic activation of both the hydrogen molecule and naphthol in the presence of a base, and the in situ-generated fleeting keto tautomer is immediately trapped and reduced by the Rh(III)–H species before it escapes from the solvent cage. This protocol provides a straightforward and practical pathway for the synthesis of key intermediates for several chiral drugs. Particularly, optically pure Nadolol, a drug for the treatment of hypertension, angina pectoris, congestive heart failure, and certain arrhythmias, is enantioselectively synthesized for the first time.}, archive = {J_JACS}, author = {Shu-Xin Zhang and Linhong Long and Zeyu Li and Yan-Mei He and Shan Li and Hui Chen and Wei Hao and Qing-Hua Fan}, doi = {10.1021/jacs.4c15673}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5197--5211}, shortjournal = {J. Am. Chem. Soc.}, title = {Rhodium-catalyzed homogeneous asymmetric hydrogenation of naphthol derivatives}, volume = {147}, year = {2025}, }
• (2025). Acidity reversal enables site-specific ring-opening polymerization of epoxides from biprotonic compounds. JACS, 147(6), 5189--5196. (www)

  @article{ , abstract = {Polyethers are versatile materials extensively used in advanced as well as everyday applications. The incorporation of primary amine functionality into polyethers is particularly attractive due to its well-established coupling chemistries. However, the inherent nucleophilicity of amine group poses a challenge in the anionic ring-opening polymerization (ROP) of epoxides and requires the use of robust protecting groups that can withstand the harsh conditions of ROP without triggering undesirable side reactions. In this work, we present streamlined synthesis of amino-functionalized polyethers using classic N -carbamate-protected aminoalcohols as initiators for the ROP of epoxides. A Lewis acid-excess two-component organocatalytic system is found to trigger efficient anionic ROP of epoxides while preserving the integrity of the carbamate protection. Despite the higher intrinsic acidity of the carbamate group compared to the hydroxyl group, it is noncompetitive in both the deprotonation and ring-opening steps. This is due to an intriguing acidity-reversing effect of the catalyst, which allows site-specific ethoxylation to proceed exclusively from the hydroxyl group. The resulting poly(propylene oxide) and poly(ethylene oxide) exhibit the targeted molar mass, low dispersity, and well-defined end groups. The fidelity of the amino functionalities is further corroborated and utilized in construction of polypeptoide-based hybrid block copolymers using the synthesized polyethers as macroinitiators.}, archive = {J_JACS}, author = {Urška Češarek and Lijun Liu and Qiyi Chen and Tianyuan Wen and Ema Žagar and Junpeng Zhao and David Pahovnik}, doi = {10.1021/jacs.4c15676}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5189--5196}, shortjournal = {J. Am. Chem. Soc.}, title = {Acidity reversal enables site-specific ring-opening polymerization of epoxides from biprotonic compounds}, volume = {147}, year = {2025}, }
• (2025). Chiral locomotion transitions of an active gel and their chemomechanical origin. JACS, 147(6), 5182--5188. (www)

  @article{ , abstract = {Transitions between chiral rotational locomotion modes occur in a variety of active individuals and populations, such as sidewinders, self-propelled chiral droplets, and dense bacterial suspensions. Despite recent progress in the study of active matter, general principles governing rotational chiral transition remain elusive. Here, we study, experimentally and theoretically, rotational locomotion and its chiral transition in a 2D polyacrylamide (PAAm)-based BZ gel driven by Belousov–Zhabotinsky reaction–diffusion waves. Analysis reveals that the phase difference (Δφ) between orthogonal components of kinematic quantities, such as chemomechanical force, displacement, and velocity, determines rotational chirality, i.e., chiral locomotion transition occurs when Δφ changes sign. This criterion is illustrated with a kinematic equation, which can be applied to biological and physical systems, including super-rotational/superhelical locomotion reported recently during E. gracilis swimming and sperm navigation. This work has potential applications for the design of functional materials and intelligent robots.}, archive = {J_JACS}, author = {Haodi Yu and Lin Ren and Yunjie Wang and Hui Wang and Meng Zhang and Changwei Pan and Ling Yuan and Jiujun Zhang and Irving R. Epstein and Qingyu Gao}, doi = {10.1021/jacs.4c15550}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5182--5188}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral locomotion transitions of an active gel and their chemomechanical origin}, volume = {147}, year = {2025}, }
• (2025). Creation of segmented platelets with diverse crystalline cores using double crystalline triblock copolymers. JACS, 147(6), 5172--5181. (www)

  @article{ , abstract = {Two-dimensional (2D) platelet structures with uniform dimensions and spatially defined diverse cores are highly sought but are still challenging to access. Living crystallization-driven self-assembly (CDSA)-seeded growth enables the creation of uniform 2D core–shell nanomaterials with diverse core compositions via sequential epitaxial crystallization of block copolymers. Nevertheless, general limitation of the growth process to strict requirements of heteroepitaxial crystallization is a major obstacle to the formation of segmented nanoparticles with extended diverse core chemistries. Herein, we introduce a strategy of using double-crystalline triblock copolymers, such as poly(ε-caprolactone)- block -poly( p -dioxanone)- block -poly( N,N -dimethyl acrylamide) (PCL- b -PPDO- b -PDMA), as bridges to create segmented platelets with compositionally distinct cores. The epitaxial crystallization of the PCL block excludes the PPDO block, forming out-of-plane PPDO crystals that seed subsequent epitaxial crystallization of the added PPDO unimer, producing flat-on quasi-square PPDO crystals. Meanwhile, the less-defined orientation of PPDO crystals has confirmed the presence of flat-on epitaxy between PCL and PPDO. For comparison, PCL- b -PHL (PHL = poly(ζ-heptalactone)) forms in-plane crystals with a strictly defined orientation via edge-on epitaxy due to the cocrystallization of PCL and PHL. Therefore, this approach provides a novel route to construct precisely controlled segmented 2D platelet structures with chemically distinct cores and tunable functionalities, an extension to expand the precise design of complex nanoparticles.}, archive = {J_JACS}, author = {Zhiqiang Gao and Xu Zhang and Bowen Zheng and Jingyuan Gu and Zaizai Tong}, doi = {10.1021/jacs.4c15602}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5172--5181}, shortjournal = {J. Am. Chem. Soc.}, title = {Creation of segmented platelets with diverse crystalline cores using double crystalline triblock copolymers}, volume = {147}, year = {2025}, }
• (2025). Temperature-robust solvation enabled by solvent interactions for low-temperature sodium metal batteries. JACS, 147(6), 5162--5171. (www)

  @article{ , abstract = {The broad temperature adaptability associated with the desolvation process remains a formidable challenge for organic electrolytes in rechargeable metal batteries, especially under low-temperature (LT) conditions. Although a traditional approach involves utilizing electrolytes with a high degree of anion participation in the solvation structure, known as weakly solvation electrolytes (WSEs), the solvation structure of these electrolytes is highly susceptible to temperature fluctuations, potentially undermining their LT performance. To address this limitation, we have devised an innovative electrolyte that harnesses the interplay between solvent molecules, effectively blending strong and weak solvents while incorporating anion participation in a solvation structure that remains mostly unchanged by temperature variations. Remarkably, the competitive coordination between the two solvent molecules introduces local disorder, which not only boosts ionic conductivity but also prevents salt precipitation and solidification. Therefore, this electrolyte has a conductivity of 3.12 mS cm –1 at −40 °C. Na 3 V 2 (PO 4 ) 3 ||Na cells demonstrated a high reversible capacity of 95.9 mAh g –1 at −40 °C, which is 87.6% of that at room temperature, as well as stable cycling for 3400 cycles with capacity retention of 98.2% at −20 °C and 5 C and 600 cycles with capacity retention of 96.1% at −40 °C and 1 C. This study provides a new perspective on designing LT electrolytes by regulating temperature-robust solvation structures.}, archive = {J_JACS}, author = {Zhenxin Huang and Zichun Xiao and Haihan Zhang and Qianyu Zhang and Jiawu Cui and Jintian Luo and Wei Tang and Yuping Wu}, doi = {10.1021/jacs.4c15478}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5162--5171}, shortjournal = {J. Am. Chem. Soc.}, title = {Temperature-robust solvation enabled by solvent interactions for low-temperature sodium metal batteries}, volume = {147}, year = {2025}, }
• (2025). Spatial control of CAR t cell activation using tumor-homing polymers. JACS, 147(6), 5149--5161. (www)

  @article{ , abstract = {CAR T cell therapies often lack specificity, leading to issues ranging from inadequate antigen targeting to off-tumor toxicities. To counter that lack of specificity, we expanded tumor targeting capabilities with universal CAR and spatially defined CAR T cell engagement with targets through a combination of synthetic biology and biomaterial approaches. We developed a novel framework, called “ In situ Mobilization: Polymer Activated Cell Therapies” (IMPACT) for polymer-mediated, anatomical control of IF-THEN gated CAR T cells. With IMPACT, a regulated payload such as a BiTE or tumor-targeting CAR will only be expressed after engineered cells engage a tumor-localizing polymer (“IF” condition). In this first demonstration of IMPACT, we engineered CAR T cells to respond to fluorescein that is displayed by an injectable polymer that binds to and is retained in fibrin deposits in tumor microenvironments. This interaction then drives selective and conditional expression of a protein within tumors (“THEN” condition). Here, we develop the polymer and CAR T cell infrastructure of IMPACT and demonstrate tumor-localized CAR T cell activation in a murine tumor model after the intravenous administration of polymer and engineered T cells.}, archive = {J_JACS}, author = {Clinton M. Heinze and Trey J. Pichon and Abe Y. Wu and Michael Baldwin and James Matthaei and Kefan Song and Meilyn Sylvestre and Joshua Gustafson and Nathan J. White and Michael C. Jensen and Suzie H. Pun}, doi = {10.1021/jacs.4c15442}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5149--5161}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatial control of CAR t cell activation using tumor-homing polymers}, volume = {147}, year = {2025}, }
• (2025). Binary phase diagrams of coordination polymers with eutectic behaviors. JACS, 147(6), 5140--5148. (www)

  @article{ , abstract = {We demonstrated the construction of binary phase diagrams of coordination polymer crystals by using their reversible solid–liquid transition (melting and crystallization) behaviors. Three types of binary phase diagrams of Ag + -based coordination polymers were made and the origins of each diagram formation were investigated. All diagrams showed eutectic phenomena induced by ligand exchange reactions at the interface of the two constituents. Solid solution formation was observed when we used two crystals with similar structures and coordination geometries, and the reaction was driven by both the anion and ligand exchange processes. The optimal binary compounds found in the phase diagrams were applicable as a latent heat storage material working at 100 °C with high energy recovery efficiency, stability in phase-transition cycles, and large hysteresis of melting/crystallization.}, archive = {J_JACS}, author = {Karnjana Atthawilai and Hiroyasu Tabe and Kotaro Ohara and Kanokwan Kongpatpanich and Satoshi Horike}, doi = {10.1021/jacs.4c15317}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5140--5148}, shortjournal = {J. Am. Chem. Soc.}, title = {Binary phase diagrams of coordination polymers with eutectic behaviors}, volume = {147}, year = {2025}, }
• (2025). Unveiling new reactivities in complex mixtures: Synthesis of tricyclic pyridinium derivatives. JACS, 147(6), 5132--5139. (www)

  @article{ , abstract = {The discovery of new transformations drives the development of synthetic organic chemistry. While the main goal of synthetic chemists is to obtain the maximum yield of a desired product with minimal side product formation, meticulous characterization of the latter offers an opportunity for discovering new reaction pathways, alternative mechanisms, and new products. Herein, we present a case study on the discovery and development of a new chemical transformation using online mass spectrometry. This highly sensitive method enabled the discovery of a new reaction pathway in a catalyst-free cross-dehydrogenative coupling of 1,2,3,4-tetrahydroisoquinoline with acetone via peroxide intermediate, ultimately yielding a tricyclic pyridinium compound. Mass spectrometry was instrumental in detecting and identifying the structure of the pyridinium compound, initially formed as a trace byproduct, which allowed us to develop a general methodology for its exclusive formation.}, archive = {J_JACS}, author = {Johanan Kootstra and Jaya Mehara and Marieke J. Veenstra and Maëlle Le Cacheux and Luca E. Oddone and Aleksandr Y. Pereverzev and Janaa Roithová and Syuzanna R. Harutyunyan}, doi = {10.1021/jacs.4c15196}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5132--5139}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling new reactivities in complex mixtures: Synthesis of tricyclic pyridinium derivatives}, volume = {147}, year = {2025}, }
• (2025). Exploring the maximum potential of initiating ability in metal-free primary explosives. JACS, 147(6), 5125--5131. (www)

  @article{ , abstract = {Lead azide (LA) is a widely utilized primary explosive, serving as the initiating charge in blasting caps or detonators to start the detonation process of secondary explosives. The toxicity and environmental concerns associated with LA have led to regulatory restrictions and increased scrutiny, prompting the search for lead-free alternatives. LA is highly sensitive toward heat, shock, or friction, which poses safety challenges during manufacturing, handling, and storage. Developing lead-free, environmentally friendly, thermostable, and safe next-generation primary explosives with high initiating ability is a significant challenge and an important goal. Herein, 1,8-diazido-bis([1,2,4]triazolo)[4,3- b :3′,4′- f ][1,2,4,5]tetrazine (DATTY) was synthesized and studied. It is important to highlight that DATTY has a high nitrogen content of 80.3%, and a lower friction sensitivity (5 N) than that of LA (0.3 N), while being stable under ambient conditions. DATTY is a highly endothermic primary explosive with a heat of formation of 6.533 kJ g –1 . It demonstrates exceptional initiating ability, with a minimum primary charge (MPC) of just 1 mg, markedly lower than the MPC of LA, which is 10 mg, as well as other previously reported primary explosives. The detonation velocity of DATTY ( v D = 8835 m s –1 ) is exceptional, surpassing that of all other primary explosives. The development of DATTY represents significant progress in the field of primary explosives, setting a new benchmark for safety and efficiency.}, archive = {J_JACS}, author = {Qiong Yu and Zhiyuan Zheng and Zhenxin Yi and Wenbin Yi and Jean’ne M. Shreeve}, doi = {10.1021/jacs.4c14967}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5125--5131}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploring the maximum potential of initiating ability in metal-free primary explosives}, volume = {147}, year = {2025}, }
• (2025). Chemospecific heterostructure and heteromaterial assembly of Metal–Organic framework nanoparticles. JACS, 147(6), 5114--5124. (www)

  @article{ , abstract = {Nanoparticles of highly porous metal–organic frameworks (MOFs) are some of the most exciting nanomaterials under development, with potential applications that range from biomedicine and catalysis to adsorption technologies. However, our synthetic methodologies to functionalize and manipulate MOF nanoparticles (NPs) are less well developed than they might be. Here we create MOF NPs derivatized with hydrazone units on their exterior, enabling chemospecific reversible dynamic covalent modification of structures on the external surface. Pairwise combinations of nanometer-sized building blocks with complementary dynamic covalent surface units can be used to prepare heterostructure assemblies (i.e., two MOFs with different structures and morphologies) and heteromaterial assemblies (a MOF with a nanoparticle of another kind, in this case gold) in which the directional molecular-level dynamic covalent links demand intimate mixing of the two nanoscale components. Crucially, the defining characteristic of the MOF components─their porosity─is minimally affected by the external functionalization and interparticle linking. The development of atomically precise dynamic covalent functionalization on the external surface of MOF NPs opens up new avenues for programmable frameworks with responsive behaviors and modular assembly of porous materials with precise control over the spatial organization of multiple nanoscale building blocks.}, archive = {J_JACS}, author = {Ailsa K. Edward and Romy Ettlinger and Zuzanna Z. Janczuk and Guoxiong Hua and Russell E. Morris and Euan R. Kay}, doi = {10.1021/jacs.4c15261}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5114--5124}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemospecific heterostructure and heteromaterial assembly of Metal–Organic framework nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Molecular and electronic structures at electrochemical interfaces from in situ resonant X-ray diffraction. JACS, 147(6), 5106--5113. (www)

  @article{ , abstract = {An original approach to characterize electrochemical interfaces at the atomic level, a challenging topic toward the understanding of electrochemical reactivity, is reported. We employed in situ surface resonant X-ray diffraction experiments combined with their simulation using first-principle density functional theory calculations and were thus able to determine the molecular and electronic structures of the partially ionic layer facing the electrode surface, as well as the charge distribution in the surface metal layers. Pt(111) in an acidic medium at an applied potential excluding specific adsorption was studied. The presence of a positively charged counter layer composed of 1.60 water and 0.15 hydronium molecules per platinum surface unit cell at 2.8 Å from the oppositely charged Pt(111) surface was found. Our results give a unique insight into the water–metal interaction at the electrochemical interfaces.}, archive = {J_JACS}, author = {Yvonne Soldo-Olivier and Yves Joly and Maurizio De Santis and Yvonne Gründer and Nils Blanc and Eric Sibert}, doi = {10.1021/jacs.4c15282}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5106--5113}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular and electronic structures at electrochemical interfaces from in situ resonant X-ray diffraction}, volume = {147}, year = {2025}, }
• (2025). Impact of secondary sphere hydrogen bonds on o2 reactivity within a nonheme iron complex. JACS, 147(6), 5099--5105. (www)

  @article{ , abstract = {A nonheme iron complex bearing the tris(6-phenylamino-pyridyl)methylamine (TPA NHPh ) ligand with appended hydrogen bond (H-bond) groups displays facile O 2 reactivity to form a monomeric Fe(III)OH complex, which can release •OH via rebound to a carbon radical. An analogous compound without H-bonds, based on tris(6-methylpyridyl)methylamine (TPA Me ), exhibits minimal O 2 reactivity, forming a Fe(III) 2 (μ-O)(μ–OH) dimer, which also reacts with carbon-based radicals. The H-bonding system enables O 2 binding and activation at weakly reducing nonheme iron complexes, highlighting a cooperative role of secondary sphere units to facilitate reactions at atypical redox environments.}, archive = {J_JACS}, author = {Andrew R. LaDuca and Jessica R. Wilson and Writhabrata Sarkar and Matthias Zeller and Nathaniel K. Szymczak}, doi = {10.1021/jacs.4c15153}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5099--5105}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of secondary sphere hydrogen bonds on o2 reactivity within a nonheme iron complex}, volume = {147}, year = {2025}, }
• (2025). Molecular evolution of target organosulfur enables high-performance aqueous zinc batteries. JACS, 147(6), 5089--5098. (www)

  @article{ , abstract = {Organic cathode materials for aqueous zinc-ion batteries (AZIBs) have garnered significant attention due to their environmental friendliness and structurally customizable nature. However, the low voltage, sluggish redox kinetics, and high solubility of most n-type cathode materials hinder their wide deployment. To overcome these challenges, through molecular evolution, we rationally select a cheap industrial material, organodisulfide 2,2′-dithiobis (benzothiazole) (MBTS), as an n-type cathode material for AZIBs. Due to the presence of N-containing benzothiazole rings, the dissociation energy of the sulfur−sulfur (S–S) bond is reduced, substantially enhancing the discharge voltage and improving the reaction kinetics. They regulate the π-conjugated plane to achieve a low solubility and fast charge transfer. Moreover, density functional theory (DFT) calculations elucidate the synergistic effect between adjacent active sites and Zn 2+ storage reactions, revealing that the formation of weak coordination bonds between N and Zn atoms (N–Zn–S bond) reduces the solubility of the discharge product. Molecular evolution has led to the fast reaction kinetics of zinc ion storage, thus achieving a high performance under high mass loading. At a current density of 0.05 A g –1 , MBTS exhibits an average discharge voltage of 1.02 V, with a mere overpotential of 100 mV, and delivers a high specific capacity of 153.6 mAh g –1 . The assembled pouch cell demonstrates an excellent rate capability of 124.4 mAh g –1 at 1 A g –1 and displays a stable cycle life after 200 cycles with 96.8% capacity retention. Remarkably, MBTS maintains high specific capacity and favorable cycle stability under various ultrahigh loadings, up to 18.2 mg cm –2 . The findings provide substantial guidance for practical applications of organic electrode materials in AZIBs.}, archive = {J_JACS}, author = {Wenxuan Sun and Fulong Zhu and Wei Guo and Yongzhu Fu}, doi = {10.1021/jacs.4c14751}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5089--5098}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular evolution of target organosulfur enables high-performance aqueous zinc batteries}, volume = {147}, year = {2025}, }
• (2025). Conformationally adaptable extractant flexes strong lanthanide reverse-size selectivity. JACS, 147(6), 5080--5088. (www)

  @article{ , abstract = {Chemical selectivity is traditionally understood in the context of rigid molecular scaffolds with precisely defined local coordination and chemical environments that ultimately facilitate a given transformation of interest. By contrast, nature leverages dynamic structures and strong coupling to enable specific interactions with target species in otherwise complex media. Taking inspiration from nature, we demonstrate unconventional selectivity in the solvent extraction of light over heavy lanthanides using a conformationally flexible ligand called octadecyl acyclopa (ODA). This novel ligand forms pseudocyclic molecular complexes with lanthanide ions at organic/aqueous interfaces, revealed by vibrational sum frequency generation spectroscopy. These complexes are extracted into the organic phase, where femtosecond structural dynamics are probed by two-dimensional infrared spectroscopy and ab initio molecular dynamics simulations to mechanistically frame the macroscopic selectivity trends. We find larger-than-expected structural fluctuations and bond lengths for heavy Ln–ODA complexes that arise from an inability of ODA to contort around the smaller ions to satisfy all would-be bonding interactions, despite forming some individually strong bonds. This finding contrasts with the binding of ODA with lighter lanthanides where, despite individually weaker bonds, collective interactions manifest that minimize structural fluctuations and give rise to enhanced thermodynamic stability. These results point to a new paradigm where conformational dynamics and cumulative bonding interactions can be used to facilitate unconventional chemical transformations.}, archive = {J_JACS}, author = {Md Faizul Islam and Lu Lin and Debmalya Ray and Uvinduni I. Premadasa and Ying-Zhong Ma and Robert L. Sacci and Vilmos Kertesz and Radu Custelcean and Vyacheslav S. Bryantsev and Benjamin Doughty and Nikki A. Thiele}, doi = {10.1021/jacs.4c15074}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5080--5088}, shortjournal = {J. Am. Chem. Soc.}, title = {Conformationally adaptable extractant flexes strong lanthanide reverse-size selectivity}, volume = {147}, year = {2025}, }
• (2025). Highly water-soluble polyether-based viologen negolytes for aqueous redox-flow batteries. JACS, 147(6), 5071--5079. (www)

  @article{ , abstract = {Aqueous redox-flow batteries employing polymeric active materials and size-exclusion membranes can potentially offer sustainable energy storage at a much lower cost. However, redox-active polymers that are soluble in water are scarce. Herein, we develop a series of water-soluble viologen-bearing homopolymers based on a highly hydrophilic polyether backbone─the first of its kind─through a one-step postpolymerization modification of poly(epibromohydrin). These new functional polymers exhibit relatively high solubility values upward of 0.5 M and display the stable and reversible redox processes associated with small molecule viologens. In preliminary redox flow battery tests at neutral pH, the polyethers cycle well with no observable interference from the backbone and can deliver 4.04 Ah l –1 at 20 mA cm –2 . Overall, these prototypes represent a key addition to the small library of active materials for aqueous polymer redox-flow batteries.}, archive = {J_JACS}, author = {Eloi Grignon and Jiang Tian Liu and Ye Fun Tan and Yang Cao and Alán Aspuru-Guzik and Dwight S. Seferos}, doi = {10.1021/jacs.4c14969}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5071--5079}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly water-soluble polyether-based viologen negolytes for aqueous redox-flow batteries}, volume = {147}, year = {2025}, }
• (2025). Reactions of SleC, its structure and inhibition in mitigation of spore germination in clostridioides difficile. JACS, 147(6), 5060--5070. (www)

  @article{ , abstract = {Spore germination in Clostridioides difficile is initiated by a cascade of activities of several proteins that culminates in the activation of SleC, a cell-wall-processing enzyme. We report herein the details of the enzymatic activities of SleC by the use of synthetic peptidoglycan fragments and of spore sacculi. The reactions include the formation of 1,6-anhydromuramate─a hallmark of lytic transglycosylase activity─as well as a muramate hydrolytic product, both of which proceed through the same transient oxocarbenium species. Furthermore, we report the first X-ray structure of zymogenic prepro-SleC at 2.1 Å resolution. Additionally, the structure provides insights into the YabG and CspB cleavage sites necessary for the activation of the zymogen. The active site of SleC presents relevant differences in contrast to SpoIID, a homologous lytic transglycosylase involved in the sporulation Clostridioides species, explaining the ability of SleC to turn over the spore sacculus, a prerequisite for the germination event. A screening of an in-house library of compounds led to the discovery of an oxadiazole that binds to the mature (activated) form of SleC, whereby it shuts down the ability of spores to germinate in the presence of germinants. This is consistent with the SleC activity as an end-point for the germination cascade. The mechanistic knowledge and the inhibitor hold the promise in addressing an unmet medical need in intervention of recurrent infections by C. difficile .}, archive = {J_JACS}, author = {Choon Kim and Rafael Molina and Mijoon Lee and Alba Garay-Alvarez and Jingdong Yang and Yuanyuan Qian and Biruk T. Birhanu and Dusan Hesek and Juan A. Hermoso and Mayland Chang and Shahriar Mobashery}, doi = {10.1021/jacs.4c14976}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5060--5070}, shortjournal = {J. Am. Chem. Soc.}, title = {Reactions of SleC, its structure and inhibition in mitigation of spore germination in clostridioides difficile}, volume = {147}, year = {2025}, }
• (2025). Polarization switching from valence trapping in an oxo-bridged trinuclear iron complex. JACS, 147(6), 5051--5059. (www)

  @article{ , abstract = {Switching electric polarization by external stimuli constitutes a technical foundation for various applications. Here, we reported the observation of polarization-switching behavior in an oxo-bridged mixed-valence complex [Fe 3 O(piv) 6 (py) 3 ] (piv = pivalate, py = pyridine). Detailed variable-temperature Mössbauer spectral analyses unambiguously confirm the occurrence of an electron localization–delocalization transition between two inequivalent Fe sites. Given that the compound crystallizes in a polar space group, the change in the molecular dipole moments leads to a pyroelectric effect observed during this transition, indicating thermally induced polarization switching behavior. As the complex exhibits asymmetry in the valence-active sites and antiferromagnetic interaction between them, the possibility of magnetoelectric coupling in this compound is also discussed on the basis of the recent prediction of polarization switching through modulating the degree of electron delocalization by magnetic fields in the mixed-valence systems.}, archive = {J_JACS}, author = {Wen-Huang Xu and Shu-Qi Wu and Sheng-Qun Su and Yu-Bo Huang and Wenwei Zheng and Xiaopeng Zhang and Tianchi Ji and Kaige Gao and Xu-Guang Zhou and Shiyue Peng and Qian Chen and Masashi Tokunaga and Yasuhiro H. Matsuda and Atsushi Okazawa and Osamu Sato}, doi = {10.1021/jacs.4c14954}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5051--5059}, shortjournal = {J. Am. Chem. Soc.}, title = {Polarization switching from valence trapping in an oxo-bridged trinuclear iron complex}, volume = {147}, year = {2025}, }
• (2025). Highly nucleophilic pyridinamide anions in apolar organic solvents due to asymmetric ion pair association. JACS, 147(6), 5043--5050. (www)

  @article{ , abstract = {Free ions in organic solvents of low polarity would be valuable tools for the activation of low-reactivity substrates. However, the formation of unreactive ion pairs at concentrations relevant for synthesis has prevented the success of this concept so far. On the example of highly nucleophilic pyridinamide phosphonium salts in dichloromethane, we show that asymmetric aggregation offers a solution to this general problem. A combination of conductivity, diffusion-ordered NMR (DOSY), and kinetic measurements utilizing a refined ionic strength-controlled benzhydrylium ion methodology enables unique insight into the aggregation/association state of the ions and the nucleophilicity of the involved anions. This approach reveals that pyridinamide tetraphenylphosphonium salts aggregate in dichloromethane solution asymmetrically to form sandwich-type cations and anions together with their free counterions. The nucleophilicity of free pyridinamide ions exceeds that of the neutral reference nucleophile 9-azajulolidine (TCAP) by up to 2 orders of magnitude. Based on these results, we suggest that asymmetric aggregation in organic solvents of low polarity might be a general pathway to boost the reactivity of anionic nucleophiles.}, archive = {J_JACS}, author = {Veronika Burger and Maximilian Franta and Armin R. Ofial and Ruth M. Gschwind and Hendrik Zipse}, doi = {10.1021/jacs.4c14825}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5043--5050}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly nucleophilic pyridinamide anions in apolar organic solvents due to asymmetric ion pair association}, volume = {147}, year = {2025}, }
• (2025). Bis-cycloruthenated complexes in visible light-induced C–H alkylation with epoxides. JACS, 147(6), 5035--5042. (www)

  @article{ , abstract = {Bis-cycloruthenated complexes (BCRCs) of the type [Ru(N^C) 2 L 2 ] are proposed to be key reactive intermediates in the Ru(II)-catalyzed directed C–H functionalization of arenes. While the exceptional ground state reactivity of BCRCs toward a number of electrophiles has been explored, their reactivity upon photoexcitation is still unknown. Herein, we report studies on the photoexcitation of BCRCs that establish their capability to access chemically useful excited states. Remarkably, photoexcited BCRCs demonstrate greatly increased reactivity toward the electron transfer processes required for alkyl halide activation, overcoming current limitations of their ground-state reactivity. We have demonstrated this reactivity by expanding upon the current chemical space occupied by Ru-catalyzed C–H functionalization to include ortho -alkylation with epoxides.}, archive = {J_JACS}, author = {Kurt Bentley and Mishra Deepak Hareram and Gang-Wei Wang and Alexander A. V. Millman and Ignacio Perez-Ortega and Luke M. Nichols and Cassandre C. Bories and Lauren E. Walker and Adam W. Woodward and Alexander P. Golovanov and Louise S. Natrajan and Igor Larrosa}, doi = {10.1021/jacs.4c14835}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5035--5042}, shortjournal = {J. Am. Chem. Soc.}, title = {Bis-cycloruthenated complexes in visible light-induced C–H alkylation with epoxides}, volume = {147}, year = {2025}, }
• (2025). A supramolecular fluorescent chemosensor enabling specific and rapid quantification of norepinephrine dynamics. JACS, 147(6), 5025--5034. (www)

  @article{ , abstract = {Host–guest supramolecular fluorescence probes have garnered significant attention in the detection and sensing of bioactive molecules due to their functionalization potential, adjustable physical properties, and high specificity. However, such probes that reliably, rapidly, and specifically measure neurotransmitter dynamics at the cellular and in vivo level have yet to be reported. Herein, we present a supramolecular fluorescent chemosensor designed for norepinephrine (NE) detection, showing an exceptional response and specificity through host–guest complexation. Multiple covalent/noncovalent interactions, molecular-folding, and confinement effect in the system synergistically enhance selectivity and accelerate reaction kinetics down to 190 ms. Our chemosensor enables real-time quantification and imaging of NE across various models including neuronal cytomembranes, brain tissues, and zebrafish. Notably, we successfully monitored NE levels in 26 brain regions of freely moving mice under fear-induced stress, revealing elevated concentrations of NE in these regions associated with emotional processing. Thus, our chemosensor is a robust tool for measuring neurotransmitter dynamics in diverse model organisms.}, archive = {J_JACS}, author = {Yudan Zhao and Yuxiao Mei and Jing Sun and Yang Tian}, doi = {10.1021/jacs.4c14727}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5025--5034}, shortjournal = {J. Am. Chem. Soc.}, title = {A supramolecular fluorescent chemosensor enabling specific and rapid quantification of norepinephrine dynamics}, volume = {147}, year = {2025}, }
• (2025). Asymmetric relay catalysis enables unreactive allylic alcohols to participate in 1,3-dipolar cycloaddition of azomethine ylides. JACS, 147(6), 5014--5024. (www)

  @article{ , abstract = {Current synthetic transformations occur readily with starting materials that possess both innate reactivity and steric accessibility or functional-group-oriented reactivity. However, achieving reactions with inactive feedstock substrates remains significantly challenging and normally requires cumbersome prior functional group manipulations. Herein, we report an unprecedented example of catalytic asymmetric 1,3-dipolar cycloaddition of azomethine ylides with nonactivated alkenes enabled by copper/ruthenium relay catalysis. Key to the success is the temporary activation strategy initiated by oxidative dehydrogenation of inert allylic alcohols into electron-demanding reversed highly reactive enones, which triggers the ensuing Cu-catalyzed asymmetric 1,3-dipolar cycloaddition followed by reductive hydrogenation to deliver highly functionalized chiral pyrrolidines with the construction of two C–C bonds and four well-defined stereogenic centers in an atom-/step-economical and redox-neutral manner. This method features mild reaction conditions, operational simplicity, and broad substrate scope and is also characterized by formal dynamic kinetic resolution. Mechanistic studies and control experiments supported a typical borrowing-hydrogen cascade orthogonally merged with 1,3-dipolar cycloaddition and revealed that the superiority and reliability of relay catalysis are enabled by the controlled release of highly reactive but unstable enones to impede the undesired polymerization. It should be noted that up to four stereoisomers of the challenging and otherwise inaccessible pyrrolidines and cyclobutanes could be readily prepared through concise late-stage elaborations.}, archive = {J_JACS}, author = {Xiang Cheng and Cong Fu and Bo-Bin Chen and Xin Chang and Xiu-Qin Dong and Chun-Jiang Wang}, doi = {10.1021/jacs.4c14761}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5014--5024}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric relay catalysis enables unreactive allylic alcohols to participate in 1,3-dipolar cycloaddition of azomethine ylides}, volume = {147}, year = {2025}, }
• (2025). Fractional spinon quasiparticles in open-shell triangulene spin-1/2 chains. JACS, 147(6), 5004--5013. (www)

  @article{ , abstract = {The emergence of spinon quasiparticles, which carry spin but lack charge, is a hallmark of collective quantum phenomena in low-dimensional quantum spin systems. While the existence of spinons has been demonstrated through scattering spectroscopy in ensemble samples, real-space imaging of these quasiparticles within individual spin chains has remained elusive. In this study, we construct individual Heisenberg antiferromagnetic spin-1/2 chains using open-shell [2]triangulene molecules as building blocks. Each [2]triangulene unit, owing to its sublattice imbalance, hosts a net spin-1/2 in accordance with Lieb’s theorem, and these spins are antiferromagnetically coupled within covalent chains with a coupling strength of J = 45 meV. Through scanning tunneling microscopy and spectroscopy, we probe the spin states, excitation gaps, and their spatial excitation weights within covalent spin chains of varying lengths with atomic precision. Our investigation reveals that the excitation gap decreases as the chain length increases, extrapolating to zero for long chains, consistent with Haldane’s gapless prediction. Moreover, inelastic tunneling spectroscopy reveals an m -shaped energy dispersion characteristic of confined spinon quasiparticles in a one-dimensional quantum box. These findings establish a promising strategy for exploring the unique properties of excitation quasiparticles and their broad implications for quantum information.}, archive = {J_JACS}, author = {Zhangyu Yuan and Xin-Yu Zhang and Yashi Jiang and Xiangjian Qian and Ying Wang and Yufeng Liu and Liang Liu and Xiaoxue Liu and Dandan Guan and Yaoyi Li and Hao Zheng and Canhua Liu and Jinfeng Jia and Mingpu Qin and Pei-Nian Liu and Deng-Yuan Li and Shiyong Wang}, doi = {10.1021/jacs.4c14712}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {5004--5013}, shortjournal = {J. Am. Chem. Soc.}, title = {Fractional spinon quasiparticles in open-shell triangulene spin-1/2 chains}, volume = {147}, year = {2025}, }
• (2025). Activating redox chemistry of quinones for high energy density aqueous sodium-ion batteries. JACS, 147(6), 4993--5003. (www)

  @article{ , abstract = {Anode materials with high capacity and suitable redox potential are crucial for improving the energy density of aqueous sodium-ion batteries (ASIBs). And organic anode materials play a promising role due to their tunable electrochemical performance. However, the insufficient electroactive sites lead to a low capacity, hindering the elevation of energy density. Thus, it is essential to design organic molecules with multiple redox-active sites. Herein, we propose a strategy to activate redox sites by regulating the spatial distribution of delocalized electrons within the conjugation system, and the quinone rings are successfully activated as new reversible Na-ion storage sites via enhancing the electron density. The obtained 2,5-dihydroxy-1,4-benzoquinonatocobalt (Co-DHBQ) with electroactive quinone rings exhibits a superior capacity of 183 mA h g –1 accompanied by a multiple-electron transfer. Benefiting from the high capacity, the Co-DHBQ||Na 2 Mn[Fe(CN) 6 ]·2H 2 O (MnHCF) full cell outputs a ultrahigh energy density of 110 W h kg –1 (based on the total active material mass of the anode and cathode) with a lifespan of 3000 cycles. This work proposes a strategy to activate new redox sites, providing a new impetus for designing high-performance organic electrode materials and developing high energy density ASIBs.}, archive = {J_JACS}, author = {Yizhong Gou and Nini Liu and Peng Yu and Jingwen Zhang and Jian Peng and Jiantao Han and Yunhui Huang and Chun Fang}, doi = {10.1021/jacs.4c14676}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4993--5003}, shortjournal = {J. Am. Chem. Soc.}, title = {Activating redox chemistry of quinones for high energy density aqueous sodium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Aerolysin nanopore structures revealed at high resolution in a lipid environment. JACS, 147(6), 4984--4992. (www)

  @article{ , abstract = {Aerolysin is a β-pore-forming toxin produced by most Aeromonas bacteria, which has attracted large attention in the field of nanopore sensing due to its narrow and charged pore lumen. Structurally similar proteins, belonging to the aerolysin-like family, are present throughout all kingdoms of life, but very few of them have been structurally characterized in a lipid environment. Here, we present the first high-resolution atomic cryo-EM structures of aerolysin prepore and pore in a membrane-like environment. These structures allow the identification of key interactions, which are relevant for understanding the pore formation mechanism and for correctly positioning the pore β-barrel and its anchoring β-turn motif in the membrane. Moreover, we elucidate at high resolution the architecture of key pore mutations and precisely identify four constriction rings in the pore lumen that are highly relevant for nanopore sensing experiments.}, archive = {J_JACS}, author = {Jana S. Anton and Ioan Iacovache and Juan F. Bada Juarez and Luciano A. Abriata and Louis W. Perrin and Chan Cao and Maria J. Marcaida and Benoît Zuber and Matteo Dal Peraro}, doi = {10.1021/jacs.4c14288}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4984--4992}, shortjournal = {J. Am. Chem. Soc.}, title = {Aerolysin nanopore structures revealed at high resolution in a lipid environment}, volume = {147}, year = {2025}, }
• (2025). Sustained, selective, and efficient photochemical CO2 reduction to formate by electron-deficient ruthenium polypyridyl complexes. JACS, 147(6), 4972--4983. (www)

  @article{ , abstract = {Metal hydrides play a significant role in a variety of reactions, including chemical, electrochemical, and photochemical CO 2 reduction. Molecular metal hydrides have the distinct advantage of allowing tunability of their hydricities by rational ligand modifications, with more electron-rich metal hydrides being in general more hydridic. We report here a new approach to generate highly hydridic metal hydrides of the type [Ru(tpy)(LL)(H)] n + by introducing electron-withdrawing substituents into the backbone of the bidentate LL ligand. This strategy enables the generation of the metal hydride [Ru(tpy)(LL)(H)] + at mild negative potentials and further one-electron reduction to the more hydridic [Ru(tpy)(LL)(H)] 0 at a potential window that is redox silent for the more electron-rich metal hydride analogue [Ru(tpy)(bpy)(H)] + . In addition, formate release takes place from the hydride transfer adducts [Ru---HCOO)(tpy)(LL)] 0 rather than from the corresponding formato complexes [Ru(tpy)(LL)(OCHO)] 0 , which would require further reduction to [Ru(tpy)(LL)(OCHO)] − as demonstrated by IR spectroelectrochemistry. The parent [Ru(tpy)(LL)(CH 3 CN)] n + solvento complexes were then tested as catalysts for the reduction of CO 2 to formate in a four-component homogeneous photochemical approach driven by a Ru(II) sensitizer. The results showed selective (>88%) formate production with a record turnover number of ∼50,000 and record turnover frequency of 4.4 s –1 when compared to other molecular catalysts.}, archive = {J_JACS}, author = {Sai Puneet Desai and Lei Zhang and Chiara Cappuccino and Andressa V. Müller and David C. Grills and Dmitry E. Polyansky and Renato N. Sampaio and Javier J. Concepcion}, doi = {10.1021/jacs.4c14099}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4972--4983}, shortjournal = {J. Am. Chem. Soc.}, title = {Sustained, selective, and efficient photochemical CO2 reduction to formate by electron-deficient ruthenium polypyridyl complexes}, volume = {147}, year = {2025}, }
• (2025). Understanding the dynamics governing electrocatalytic hydrodeoxygenation of lignin bio-oil to hydrocarbons. JACS, 147(6), 4962--4971. (www)

  @article{ , abstract = {Electrocatalytic hydrodeoxygenation (EHDO) is a promising approach for upgrading biomass-derived bio-oils to sustainable fuels without the use of high-pressure hydrogen gas and elevated temperatures. However, direct EHDO for realistic hydrophobic lignin-based oil production remains challenging. Herein, we discuss the molecular dynamics that govern the EHDO of lignin bio-oil over Pt/C in an acidic electrolyte added with 2-propanol or a surfactant. Excellent conversion (98.1%) and a high yield (79.0%) of hydrogenated products, including 40.5% propyl-cyclohexane, are achieved under ambient temperature and pressure. Experimental results and various investigations on molecular dynamics suggest that EHDO occurs at the water-solvent-catalyst three-phase boundary. Proton transfer significantly influences the current density of EHDO. Factors such as cluster size and vector of lignin-based oil to electrode govern the selectivity and Faradaic efficiency of EHDO. This work advances the understanding of dynamics for EHDO and suggests governing factors to improve it.}, archive = {J_JACS}, author = {Jialu Wang and Man Ho Han and Kezia Megagita Gerby Langie and Da Hye Won and Mi-Young Lee and Cheoulwoo Oh and Hyo Sang Jeon and Jai Hyun Koh and Hyung-Suk Oh and Dong Ki Lee and Woong Hee Lee}, doi = {10.1021/jacs.4c14254}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4962--4971}, shortjournal = {J. Am. Chem. Soc.}, title = {Understanding the dynamics governing electrocatalytic hydrodeoxygenation of lignin bio-oil to hydrocarbons}, volume = {147}, year = {2025}, }
• (2025). Semisynthesis of isomerized histone h4 reveals robustness and vulnerability of chromatin toward molecular aging. JACS, 147(6), 4952--4961. (www)

  @article{ , abstract = {Proteins are subject to aging in the form of spontaneous, nonenzymatic post-translational modifications (PTMs). One such PTM is the formation of the β-linked isomer l -isoaspartic acid (isoAsp) from aspartic acid (Asp) or asparagine residues, which tends to occur in long-lived proteins. Histones can exhibit half-lives on the order of 100 days, and unsurprisingly, isoAsp formation has been observed in nearly every histone family. Delineating the molecular consequences of isoAsp formation in histones is challenging due to the multitude of processes that occur on such time scales. To isolate the effects of a specific isoAsp modification thus necessitates precise in vitro characterization with well-defined substrates. Here, we adapt a protein semisynthesis approach to generate full-length variants of histone H4 in which the canonical Asp at position 24 is replaced by its isoAsp isomer (H4isoD24). This variant was incorporated into chromatin templates, and the resulting constructs were used to interrogate key parameters of chromatin integrity and maintenance in vitro : compaction, nucleosome remodeling, and methylation of H4 lysine 20 (H4K20). Remarkably, despite its disruptive changes to the backbone’s spacing and direction, isoD24 did not dramatically disrupt Mg 2+ -mediated chromatin self-association or nucleosome repositioning by the remodeler Chd1. In contrast, H4isoD24 significantly inhibited both Set8- and Suv4-20h1-catalyzed methylation at H4K20. These results suggest that H4isoD24 gives rise to a complex reorganization of the chromatin functional landscape, in which macroscopic processes show robustness and local mechanisms exhibit vulnerability to the presence of this mark.}, archive = {J_JACS}, author = {Tianze Zhang and Luis F. Guerra and Yana Berlina and Jon R. Wilson and Beat Fierz and Manuel M. Müller}, doi = {10.1021/jacs.4c14136}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4952--4961}, shortjournal = {J. Am. Chem. Soc.}, title = {Semisynthesis of isomerized histone h4 reveals robustness and vulnerability of chromatin toward molecular aging}, volume = {147}, year = {2025}, }
• (2025). Pressure-induced engineering of surface oxygen vacancies on metal oxides for heterogeneous photocatalysis. JACS, 147(6), 4945--4951. (www)

  @article{ , abstract = {Oxygen vacancies (OVs) spatially confined on the surface of metal oxide semiconductors are advantageous for photocatalysis, in particular, for O 2 -involved redox reactions. However, the thermal annealing process used to generate surface OVs often results in undesired bulk OVs within the metal oxides. Herein, a high pressure-assisted thermal annealing strategy has been developed for selectively confining desirable amounts of OVs on the surface of metal oxides, such as tungsten oxide (WO 3 ). Applying a pressure of 1.2 gigapascal (GPa) on WO 3 induces significant lattice compression, which would strengthen the W–O bonds and increase the diffusion activation energy for the migration of the O migration. This pressure-induced compression effectively inhibits the formation of bulk OVs, resulting in a high density of surface-confined OVs on WO 3 . These well-defined surface OVs significantly enhance the photocatalytic activation of O 2 , facilitating H 2 O 2 production and aerobic oxidative coupling of amines. This strategy holds promise for the defect engineering of other metal oxides, enabling abundant surface OVs for a range of emerged applications.}, archive = {J_JACS}, author = {Xiaoyi Wang and Sikang Xue and Meirong Huang and Wei Lin and Yidong Hou and Zhiyang Yu and Masakazu Anpo and Jimmy C. Yu and Jinshui Zhang and Xinchen Wang}, doi = {10.1021/jacs.4c14073}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4945--4951}, shortjournal = {J. Am. Chem. Soc.}, title = {Pressure-induced engineering of surface oxygen vacancies on metal oxides for heterogeneous photocatalysis}, volume = {147}, year = {2025}, }
• (2025). Theoretical insights into the selectivity of single-atom Fe–N–C catalysts for electrochemical NOx reduction. JACS, 147(6), 4937--4944. (www)

  @article{ , abstract = {Single-atom Fe–N–C catalysts have attracted significant attention in the NO x reduction reaction (NO x RR). However, the origin of their selectivity in the NO x RR remains unclear, impeding further advancements in application. Herein, we investigate the potential-driven competitive mechanism for NH 3 and NH 2 OH production in the NO x RR over single-atom pyridinic-FeN 4 and pyrrolic-FeN 4 sites using constant-potential density functional theory calculations. The origin of selectivity in the NO x RR is linked to the switching of Fe 3 d orbitals as they interact with intermediates. The selectivity between NH 3 and NH 2 OH is determined by the applied potentials. The pyridinic-FeN 4 predominantly generates NH 3 at higher reduction potentials (−0.6 to −1.2 V, vs SHE), while NH 2 OH is favored at lower reduction potentials (0.6 to −0.6 V). The pyrrolic-FeN 4 shows a similar potential-dependent product distribution, with a crossover potential of −1.0 V. The selectivity-determining intermediates (SDIs) in the NO x RR are *NH 2 OH and *NH 2 + *OH. The potential-dependent selectivity is governed by the switching of Fe 3 d orbitals interacting with SDIs, from dumbbell-shaped Fe 3 dz 2 to four-leaf clover-like Fe 3 dxz , 3 dyz , and 3 dx 2 -y 2 , which plays a crucial role in controlling product distribution based on applied potentials. These findings offer new insights into the product selectivity of single-atom catalysts for the NO x RR.}, archive = {J_JACS}, author = {Yao Tan and Junwei Fu and Tao Luo and Kang Liu and Min Liu}, doi = {10.1021/jacs.4c14021}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4937--4944}, shortjournal = {J. Am. Chem. Soc.}, title = {Theoretical insights into the selectivity of single-atom Fe–N–C catalysts for electrochemical NOx reduction}, volume = {147}, year = {2025}, }
• (2025). Enhancing chemoselectivity of on-surface reactions on reconstructed au(110): The case of a pentalene-bridged polyacene analogue. JACS, 147(6), 4930--4936. (www)

  @article{ , abstract = {Polyacene analogues, consisting of short acene segments separated by nonbenzenoid rings, offer intriguing electronic properties and magnetic interactions. Pentalene-bridged polyacenes (PPs), in particular, hold promise for enhancing the electrical conductivity and potential open-shell ground states. However, PPs have remained elusive in solution chemistry due to poor solubility and limited synthetic protocols. Here, we report the on-surface synthesis of PPs through the annulation between ortho-xylene groups. Scanning tunneling microscopy and atomic force microscopy reveal that the reconstructed Au(110) surface significantly enhances the chemoselectivity of the annulation process. Scanning tunneling spectroscopy combined with density functional theory suggests that PP exhibits a narrow direct band gap, similar to long acenes. This work demonstrates the potential for band structure engineering in polyacene analogues by incorporating nonbenzenoid rings, paving the way to advancements in organic electronics and spintronics.}, archive = {J_JACS}, author = {Feifei Xiang and Amogh Kinikar and Markus Mühlinghaus and Nicolò Bassi and Carlo A. Pignedoli and Klaus Müllen and Roman Fasel and Pascal Ruffieux}, doi = {10.1021/jacs.4c13944}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4930--4936}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing chemoselectivity of on-surface reactions on reconstructed au(110): The case of a pentalene-bridged polyacene analogue}, volume = {147}, year = {2025}, }
• (2025). Spatial scale matters: Hydrolysis of aryl methyl ethers over zeolites. JACS, 147(6), 4915--4929. (www)

  @article{ , abstract = {The local environment of the active site, such as the confinement of hydronium ions within zeolite pores, significantly influences catalytic turnover, similar to enzyme functionality. This study explores these effects in the hydrolysis of guaiacols─lignin-derived compounds─over zeolites in water. In addition to the interesting catechol products, this reaction is advantageous for study due to its bimolecular hydrolysis pathway, which involves a single energy barrier and no intermediates, simplifying kinetic studies and result interpretation. As in alcohol dehydration, hydronium ions show enhanced activity in ether hydrolysis due to undercoordination and increased electrophilicity when confined within zeolite pores, compared to bulk water. In addition, a volcano-shaped relationship between hydronium ion activity and Brønsted acid density was observed. However, unlike alcohol dehydration, this activity distribution cannot be attributed to variations in ionic strength within the pores, as the rate-determining step in the hydrolysis of guaiacols involves the attack of a neutral water molecule, unaffected by ionic strength. Instead, a detailed transition state analysis revealed a significant thermodynamic energy compensation effect, driven by the spatial organization of the transition state. This organization is influenced by the available reaction space, the interaction between the reacting species and the zeolite environment, leading to the volcano-shaped dependence. This phenomenon also explains the unusual reactivity order of the 4-R-guaiacol derivatives (R = H, Me, Et, Pr) with zeolite catalysis, extending beyond the traditional steric and electronic effects to provide a deeper understanding of reactant reactivity. The work concludes that the critical spatial parameters for fast ether hydrolysis─resulting in the highest hydronium activity─are determined by a combination of zeolite properties (topology and acid density) and reactant size.}, archive = {J_JACS}, author = {Xian Wu and Mathias Bal and Qiang Zhang and Shao-Tao Bai and Ivan Scodeller and Walter Vermandel and Jihong Yu and Bert U. W. Maes and Bert F. Sels}, doi = {10.1021/jacs.4c13729}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4915--4929}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatial scale matters: Hydrolysis of aryl methyl ethers over zeolites}, volume = {147}, year = {2025}, }
• (2025). Breaking barcode limits: Metal nanoparticle lego brick self-assembly for high-throughput screening. JACS, 147(6), 4904--4914. (www)

  @article{ , abstract = {As precision medicine increasingly reveals the biological diversity among individuals, the demand for higher-throughput screening techniques, particularly suspension array technologies capable of more multiplexing from smaller samples in a single run, is intensifying. However, advancements in the multiplexing capability of current suspension platforms have lagged with limited alleviation, necessitating breakthroughs for innovative solutions that enable larger-scale measurements. Here, we introduce such a breakthrough with a novel mass-cytometric barcode engineering by metal nanoparticle-based “Lego Brick”-like self-assembly for high-throughput barcode design and capacity amplification. The suspension array capacity can be expanded to over 20,500 unique barcodes by flexibly assembling just 10 types of barcoding units (metal nanoparticles) onto the surface of the barcoding center (magnetic spheres) through a universal biotin–streptavidin binding template, significantly enhancing both throughput and versatility. Further multiplexed immunoassay, termed MassMAP, demonstrates high-throughput profiling of cancer biomarkers, highlighting the revolutionary potential of Lego Brick self-assembly in massive cytometric screening for higher-throughput applications.}, archive = {J_JACS}, author = {Zili Huang and Xiaobo Xie and Yi Wu and Rui Liu and Yi Lv}, doi = {10.1021/jacs.4c13706}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4904--4914}, shortjournal = {J. Am. Chem. Soc.}, title = {Breaking barcode limits: Metal nanoparticle lego brick self-assembly for high-throughput screening}, volume = {147}, year = {2025}, }
• (2025). Structural modulation and enhanced magnetic ordering in incommensurate K1–xCrSe2 crystals. JACS, 147(6), 4896--4903. (www)

  @article{ , abstract = {Layered delafossite-type compounds and related transition metal dichalcogenides, characterized by their triangular net structures, serve as prototypical systems for exploring the intricate interplay between crystal structure and magnetic behavior. Herein, we report on the discovery of the compound K 1– x CrSe 2 ( x ≈ 0.13), an incommensurately modulated phase. Single crystals of this compound were grown for the first time using a K/Se self-flux. We find a monoclinic crystal structure with incommensurate modulation that can be rationalized by a 3 + 1-dimensional model. This modulation compensates for the under-stoichiometry of K cations, creating pronounced undulations in the CrSe 2 layers. Our anisotropic magnetization measurements reveal that K 1– x CrSe 2 undergoes a transition to a long-range magnetically ordered state below T N = 133 K, a temperature 1.6 to 3.3 times higher than in earlier reported KCrSe 2 compounds. Our findings open new avenues for tuning the magnetic properties of these layered materials through structural modulation.}, archive = {J_JACS}, author = {Felix Eder and Catherine Witteveen and Enrico Giannini and Fabian O. von Rohr}, doi = {10.1021/jacs.4c13545}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4896--4903}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural modulation and enhanced magnetic ordering in incommensurate K1–xCrSe2 crystals}, volume = {147}, year = {2025}, }
• (2025). "Suspended" single rhenium atoms on nickel oxide for efficient electrochemical oxidation of glucose. JACS, 147(6), 4886--4895. (www)

  @article{ , abstract = {Well-defined single-atom catalysts (SACs) serve as ideal model systems for directly comparing experimental results with theoretical calculations, offering profound insights into heterogeneous catalytic processes. However, precisely designing and controllably synthesizing SACs remain challenging due to the unpredictable structure evolution of active sites and generation of embedded active sites, which may bring about steric hindrance during chemical reactions. Herein, we present the precious nonpyrolysis synthesis of Re SACs with a well-defined phenanthroline coordination supported by NiO (Re 1 -phen/NiO). Multiple experimental characterizations together with theoretical calculations unravel the idea that the isolated Re atoms are suspended on the NiO surface, connected by phenanthroline ligands standing perpendicular to the surface. This unique structure provides the Re 1 -phen/NiO SAC with a strong capability to activate glucose molecules, enabling fully exposed Re=O double bonds in an open-ended reaction environment to simultaneously react with hydroxyl and aldehyde groups at both ends of the glucose molecule, rapidly forming glucaric acid.}, archive = {J_JACS}, author = {Xunzhu Jiang and Xianhong Wu and Mingyue Lv and Xiaoli Pan and Hua Wang and Chenyang Li and Meixin Chen and Wei Chen and Bo Zhang and Guangtao Yu and Zhong-Shuai Wu and Botao Qiao and Bin Liu and Fritz E. Kühn and Tao Zhang}, doi = {10.1021/jacs.4c13368}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4886--4895}, shortjournal = {J. Am. Chem. Soc.}, title = {"Suspended" single rhenium atoms on nickel oxide for efficient electrochemical oxidation of glucose}, volume = {147}, year = {2025}, }
• (2025). A second near-infrared window-responsive Metal–Organic-framework-based photosensitizer for tumor immunotherapy via synergistic ferroptosis and STING activation. JACS, 147(6), 4871--4885. (www)

  @article{ , abstract = {Photodynamic therapy (PDT) holds promise as a cancer treatment modality due to its potential for enhanced therapy precision and safety. To enhance deep tissue penetration and minimize tissue adsorption and phototoxicity, developing photosensitizers activated by second near-infrared window (NIR-II) light shows significant potential. However, the efficacy of PDT is often impeded by tumor microenvironment hypoxia, primarily caused by irregular tumor vasculature. Fortunately, the stimulator of interferon genes (STING) pathway, known for immune activation, has been linked to vasculature normalization. In this study, we developed a nanoplatform (Fe-THBQ/SR) by loading a STING agonist (SR-717) into an iron-tetrahydroxy-1,4-benzoquinone (Fe-THBQ) metal–organic framework. Fe-THBQ was proven to be an effective NIR-II photosensitizer, generating numerous reactive oxygen species (ROS) under 1064 nm laser irradiation. These ROS downregulated heat shock protein expression, consequently promoting mild-photothermal therapy (mild-PTT), and facilitated ferroptosis by depleting glutathione (GSH)/glutathione peroxidase 4. Moreover, Fe-THBQ/SR released SR-717 upon GSH stimulation, synergizing with the ROS-mediated double-stranded DNA leakage to enhance STING activation. This process contributed to tumor vasculature normalization and hypoxia alleviation, thereby enhancing the PDT efficacy. Overall, we presented a versatile single-laser-triggered nanoplatform (Fe-THBQ/SR) for NIR-II PDT and NIR-II mild-PTT and simultaneously coupled it with the effective activation of STING to form a reinforcing cycle. These synergistic enhancements increased the immunogenicity of tumor cells, remodeled the immunosuppressive tumor microenvironment, increased T lymphocyte infiltration, and improved therapeutic outcomes.}, archive = {J_JACS}, author = {Huan Zhao and Shujuan Jin and Yang Liu and Qian Wang and Brynne Shu Ni Tan and Shihuai Wang and Wang-Kang Han and Xuping Niu and Yanli Zhao}, doi = {10.1021/jacs.4c13241}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4871--4885}, shortjournal = {J. Am. Chem. Soc.}, title = {A second near-infrared window-responsive Metal–Organic-framework-based photosensitizer for tumor immunotherapy via synergistic ferroptosis and STING activation}, volume = {147}, year = {2025}, }
• (2025). On-surface synthesis and characterization of pentadecacene and its gold complexes. JACS, 147(6), 4862--4870. (www)

  @article{ , abstract = {Acenes are an important class of polycyclic aromatic hydrocarbons that have gained considerable attention from chemists, physicists, and material scientists, due to their exceptional potential for organic electronics. They serve as an ideal platform for studying the physical and chemical properties of sp 2 carbon frameworks in the one-dimensional limit and also provide a fertile playground to explore magnetism in graphenic nanostructures due to their zigzag edge topology. While higher acenes up to tridecacene have been successfully generated by means of on-surface synthesis, it is imperative to extend their synthesis toward even longer homologues to comprehensively understand the evolution of their electronic ground state. Here, we demonstrate the on-surface synthesis of pentadecacene ( 15ac ) from a trietheno-bridged precursor via the atom-manipulation-induced dissociation of protecting groups or the elimination of adatoms in a gold-pentadecacene complex. The generated 15ac was investigated by scanning tunneling microscopy (STM)/spectroscopy (STS) and noncontact atomic force microscopy (nc-AFM), in combination with first-principles spin-polarized density functional theory (DFT) calculations. We found that 15ac exhibits an open-shell singlet ground state with an experimental singlet–triplet gap of 124 meV and an STS transport gap of ∼1.12 eV. The formation of Au-pentadecacene complexes suggested a considerable contribution of polyradical character to the electronic ground state of 15ac . Our work contributes to a fundamental understanding of the electronic properties of long acenes and to the development of a versatile STM tip-assisted methodology for the synthesis of elusive compounds.}, archive = {J_JACS}, author = {Zilin Ruan and Jakob Schramm and John B. Bauer and Tim Naumann and Laurentia V. Müller and Felix Sättele and Holger F. Bettinger and Ralf Tonner-Zech and J. Michael Gottfried}, doi = {10.1021/jacs.4c13296}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4862--4870}, shortjournal = {J. Am. Chem. Soc.}, title = {On-surface synthesis and characterization of pentadecacene and its gold complexes}, volume = {147}, year = {2025}, }
• (2025). Intermolecular misfolding captured in parallelly organized titin. JACS, 147(6), 4853--4861. (www)

  @article{ , abstract = {The giant muscle protein titin is largely responsible for the passive elasticity of the muscles. The I-band part of titin is elastic, and its constitutive immunoglobulin (Ig) domains undergo force-induced unfolding and refolding when the muscle is stretched toward or beyond the end of the physiological range of sarcomere length. Correct folding of the titin Ig domains is essential to the structure and functions of titin. Although our knowledge of titin elasticity at the molecular level has been largely obtained from single molecule experiments, titin does not exist as an isolated molecule. Instead, six titins are parallelly organized in the muscle sarcomeres. It remains unknown what impact such a parallel organization brings on the folding of titin Ig domains and titin elasticity. Using the two-molecule force spectroscopy technique, here, we report the direct observation of the intermolecular misfolding of titin Ig domains that are arranged in parallel. Our results reveal that when parallelly arranged, two I94 domains can misfold into an intermolecular domain-swapped state that is thermally and mechanically stable. Such intermolecular misfolding may play important structural and functional roles in titin organization and elasticity.}, archive = {J_JACS}, author = {Jiacheng Zuo and Hongbin Li}, doi = {10.1021/jacs.4c13008}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4853--4861}, shortjournal = {J. Am. Chem. Soc.}, title = {Intermolecular misfolding captured in parallelly organized titin}, volume = {147}, year = {2025}, }
• (2025). Reticular synthesis of covalent organic frameworks with kgd-v topology and trirhombic pores. JACS, 147(6), 4844--4852. (www)

  @article{ , abstract = {Two-dimensional (2D) covalent organic frameworks (COFs) with designable pore structures can be synthesized under the guidance of topology diagrams. Among the five existing edge-transitive topological nets, kgd topology is considered a fine candidate for constructing COFs with ultramicropores. However, all of the reported COFs with kgd topology need the use of C 6 -symmetric monomers, which are limited in compound type and difficult to synthesize. Here, we first develop a new approach to construct 2D COFs (clv-COFs) with a similar geometrical shape of kgd topology, named kgd-v topology, through the combination of C 2 v - and C 3 -symmetric monomers. The size of micropores in these clv-COFs is consistent with the rhombic pores in kgd topology and can be easily tuned by varying the length of C 2 v - and C 3 -symmetric monomers. These clv-COFs exhibit excellent atmospheric water harvesting (AWH) ability due to regular small micropores. An efficient water harvester based on clv-COF-1 can produce 1.73 L kg –1 day –1 at 45% relative humidity under solar illumination. Our approach enriches the reticular chemistry and can facilitate the research of COF-based AWH systems.}, archive = {J_JACS}, author = {Yuan-Zhe Cheng and Hui-Yuan Kong and Peng-Yuan Hao and Kang Huang and Xuesong Ding and Xinghua Shi and Yujian He and Bao-Hang Han}, doi = {10.1021/jacs.4c12973}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4844--4852}, shortjournal = {J. Am. Chem. Soc.}, title = {Reticular synthesis of covalent organic frameworks with kgd-v topology and trirhombic pores}, volume = {147}, year = {2025}, }
• (2025). Atomic-level tin regulation for high-performance Zinc–Air batteries. JACS, 147(6), 4833--4843. (www)

  @article{ , abstract = {The trade-off between the performances of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) presents a challenge in designing high-performance aqueous rechargeable zinc–air batteries (a-r-ZABs) due to sluggish kinetics and differing reaction requirements. Accurate control of the atomic and electronic structures is crucial for the rational design of efficient bifunctional oxygen electrocatalysts. Herein, we designed a Sn–Co/RuO 2 trimetallic oxide utilizing dual-active sites and tin (Sn) regulation strategy by dispersing Co (for ORR) and auxiliary Sn into the near-surface and surface of RuO 2 (for OER) to enhance both ORR and OER performances. Both theoretical calculations and advanced dynamic monitoring experiments revealed that the auxiliary Sn effectively regulated the atomic/electronic environment of Ru and Co dual-active sites, which optimized the *OOH/*OH adsorption behavior and promoted the release of the final products, thus breaking the reaction limits. Therefore, the as-designed Sn–Co/RuO 2 catalysts exhibited superb bifunctional performance with an oxygen potential difference (Δ E ) of 0.628 V and negligible activity degradation after 200,000 (ORR) or 20,000 (OER) CV cycles. The a-r-ZABs based on the Sn–Co/RuO 2 catalyst exhibited a higher performance at a wide temperature range of −30 to 65 °C. They demonstrated an ultralong lifespan of 138 days (20,000 cycles) at 5 mA cm –2 , 39.7 times higher than that of Pt/C + IrO 2 coupled catalysts at a low temperature of −20 °C. Additionally, they maintained an initial power density of 85.8% after long-term tests, significantly outperforming previously reported catalysts. More importantly, the a-r-ZABs also showed excellent stability of 766.45 h (about 4598 cycles) at a high current density of 10 mA cm –2 .}, archive = {J_JACS}, author = {Yunrui Li and Jiaqi Xu and Fan Lan and Yao Wang and Hairong Jiang and Ping Zhu and Xueke Wu and Ya Huang and Run Li and Qinyuan Jiang and Yanlong Zhao and Ruina Liu and Longgui Zhang and Rufan Zhang}, doi = {10.1021/jacs.4c12601}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4833--4843}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic-level tin regulation for high-performance Zinc–Air batteries}, volume = {147}, year = {2025}, }
• (2025). Disulfide-directed multicyclic peptides with N-terminally extendable α-helices for recognition and activation of g protein-coupled receptors. JACS, 147(6), 4821--4832. (www)

  @article{ , abstract = {Many peptide hormones adopt long α-helical structures upon interacting with their cognate receptors but often exhibit flexible conformations when unbound. Strategies that can stabilize long α-helices without disrupting their binding to receptors are still lacking, which hinders progress in their biological applications and drug development. Here, we present an approach that combines rational design with library screening to create and identify a unique disulfide-directed multicyclic peptide (DDMP) scaffold, which could effectively stabilize N-terminally extendable α-helices while displaying exceptional efficiency in disulfide pairing and oxidative folding. This DDMP scaffold was then utilized for stabilizing the α-helical structure of glucagon-like peptide-1 (GLP-1), resulting in a potent GLP-1 receptor (GLP-1R) agonist with a significantly improved α-helicity and proteolytic stability. By incorporating external α-helices into the DDMP scaffold, we can effectively preserve the native N-terminal α-helical structures while allowing for extensive evolution of the C-terminal disulfide-rich domain for enhancing target binding, as demonstrated by the generation of the DDMP-stabilized GLP-1 (g1:Ox). The cryo-electron microscopy structure of the g1:Ox–GLP-1R in complex with heterotrimeric G s reveals the molecular basis for the potent binding between g1:Ox and GLP-1R. Specifically, the DDMP moiety establishes additional interactions with the extracellular domain of GLP-1R, which are absent in the case of GLP-1. Thus, this work offers a novel and effective approach for engineering therapeutic peptides and other peptide α-helices, ensuring that both the N- and C-terminal regions remain essential for target recognition and activation.}, archive = {J_JACS}, author = {Shihui Fan and Jie Li and Jie Zhuang and Qingtong Zhou and Yiting Mai and Bingni Lin and Ming-Wei Wang and Chuanliu Wu}, doi = {10.1021/jacs.4c12808}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4821--4832}, shortjournal = {J. Am. Chem. Soc.}, title = {Disulfide-directed multicyclic peptides with N-terminally extendable α-helices for recognition and activation of g protein-coupled receptors}, volume = {147}, year = {2025}, }
• (2025). Entropy-tailored fast-charging sodium layered cathodes. JACS, 147(6), 4810--4820. (www)

  @article{ , abstract = {O3-type layered transition metal (TM) oxides are widely used as cathode materials for Na-ion batteries due to their high energy density potential, enabled by the state of charge (SoC)-dependent transition from octahedral (O-type) to prismatic (P-type) structures during Na-ion (de)sodiation. However, the O–P transition is often criticized for compromising the Na-ion mobility and limiting the cycle life. Herein, we reveal the intrinsic correlation between O–P transitions, oxygen behaviors, and Na-ion kinetics. We demonstrate that a compositionally versatile, entropy-tailored approach can promote preferred transitions (characterized by large lattice parameter deviations in the O-type region and rapid O–P biphasic reactions), enhancing Na-ion migration, as revealed by in situ high-energy synchrotron X-ray diffraction (HEXRD). Additionally, irreversible oxygen loss at high SoC is effectively mitigated, while TM migration and surface reconstruction are greatly suppressed, further accelerating Na-ion transport and stabilizing the structure, as confirmed by X-ray absorption spectroscopy (XAS) and theoretical analyses. The result is an exceptionally high rate capability of 88.7 mAh g –1 at 20 C (2.4 A g –1 ) with a superior normalized retention of 72.6%, accompanied by a prolonged lifetime with 74.3% retention after 1000 cycles. This work advances the understanding of the chemistry–property relationships in O3-type layered cathodes and broadens the prospects for fabricating high-power-density electrodes.}, archive = {J_JACS}, author = {Haoji Wang and Yu Mei and Jinqiang Gao and Lianshan Ni and Ningyun Hong and Lu Ma and Gihan Kwon and Jiangnan Huang and Yi He and Wentao Deng and Guoqiang Zou and Hongshuai Hou and Chaoping Liang and Tongchao Liu and Xiaobo Ji and Khalil Amine}, doi = {10.1021/jacs.4c12733}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4810--4820}, shortjournal = {J. Am. Chem. Soc.}, title = {Entropy-tailored fast-charging sodium layered cathodes}, volume = {147}, year = {2025}, }
• (2025). HydE catalytic mechanism is powered by a radical relay with redox-active Fe(I)-containing intermediates. JACS, 147(6), 4800--4809. (www)

  @article{ , abstract = {[FeFe]-hydrogenases are enzymes that catalyze the redox interconversion of H + and H 2 using a six-iron active site, known as the H-cluster, which consists of a structurally unique [2Fe] H subcluster linked to a [4Fe–4S] H subcluster. A set of enzymes, HydG, HydE, and HydF, are responsible for the biosynthesis of the [2Fe] H subcluster. Among them, it is well established that HydG cleaves tyrosine into CO and CN – and forms a mononuclear [Fe(II)(Cys)(CO) 2 (CN)] complex. Recent work using EPR spectroscopy and X-ray crystallography show that HydE uses this organometallic Fe complex as its native substrate. The low spin Fe(II) center is reduced into an adenosylated Fe(I) species, which is proposed to form an Fe(I)Fe(I) dimer within HydE. The highly unusual transformation catalyzed by HydE draws interest in both biochemistry and organometallic chemistry. Due to the instability of the substrate, the intermediates, and the proposed product, experimental characterization of the detailed HydE mechanism and its final product is challenging. Herein, the catalytic mechanism of HydE is studied using hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations. A radical relay mechanism was found for the cleavage of the cysteine S–Cβ bond that is energetically favored with respect to a closed-shell mechanism involving unconventional proton transfer. In addition, we propose a pathway for the dimerization of two Fe(I) complexes within the HydE hydrophobic cavity, which is consistent with the recent experimental result that HydF can perform [FeFe]-hydrogenase maturation with a synthetic dimer complex as the substrate. These simulation results take us further down the path to a more complete understanding of these enzymes that synthesize one of Nature’s most efficient energy conversion catalysts.}, archive = {J_JACS}, author = {Nanhao Chen and Guodong Rao and Lizhi Tao and R. David Britt and Lee-Ping Wang}, doi = {10.1021/jacs.4c12668}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4800--4809}, shortjournal = {J. Am. Chem. Soc.}, title = {HydE catalytic mechanism is powered by a radical relay with redox-active Fe(I)-containing intermediates}, volume = {147}, year = {2025}, }
• (2025). Four-electron-transferred pyrene-4,5,9,10-tetraone derivatives enabled high-energy-density aqueous organic flow batteries. JACS, 147(6), 4790--4799. (www)

  @article{ , abstract = {Multielectron-transferred molecules hold great potential to enhance the energy density and reduce the cost for aqueous organic flow batteries (AOFBs). However, the extended conjugated units required for increasing redox-active sites and stabilizing the multielectron reaction always decrease the molecular polarity, limiting the solubility in the electrolyte. Herein, we presented an asymmetrical pyrene-4,5,9,10-tetraone-1-sulfonate (PTO–PTS) monomer which not only could reversibly store four electrons but also exhibited a high theoretical electron concentration of 4.0 M and the strongly heat-resistant intermediate semiquinone free radical. As a result, PTO–PTS-based AOFBs demonstrated a high energy density of 59.6 Wh L catholyte –1 (89 Ah L –1 ) with an ultrastable capacity retention of nearly 100% for above 5200 cycles (60 days). Moreover, the heat-stable PTO–PTS structure further enabled both symmetric and full cells to achieve remarkable cycling durability for over a thousand cycles at 60 °C. The outstanding cell performance and high thermal stability suggest its promising application in large-scale energy storage.}, archive = {J_JACS}, author = {Guangxu Ge and Chenkai Mu and Yonggang Wang and Changkun Zhang and Xianfeng Li}, doi = {10.1021/jacs.4c12506}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4790--4799}, shortjournal = {J. Am. Chem. Soc.}, title = {Four-electron-transferred pyrene-4,5,9,10-tetraone derivatives enabled high-energy-density aqueous organic flow batteries}, volume = {147}, year = {2025}, }
• (2025). Surface copassivation strategy for developing water-soluble InP colloidal quantum dots with high luminescence and suppressed blinking. JACS, 147(6), 4778--4789. (www)

  @article{ , abstract = {Colloidal quantum dots (QDs) are promising emitters for biological applications because of their excellent fluorescence, convenient surface modification, and photostability. However, the toxic cadmium composition in the state-of-the-art QDs and their inferior properties in the aqueous phase greatly restrict further use. The performance of water-soluble indium phosphide (InP) QDs lags far behind those of Cd-containing counterparts due to the lack of effective surface protection. Here, we present an efficient copassivation strategy via dual hydrophilic ligands to achieve water-soluble InP-based QDs with ideal optical properties. A record photoluminescence quantum yield of near-unity and monoexponential decay dynamics for water-soluble InP-based QDs are achieved. For the first time, we realize a single water-soluble InP-based QD with significantly suppressed blinking. Furthermore, the novel QDs exhibit superior cellular imaging capabilities and high resistance to photobleaching compared with commonly used organic dyes. The results presented here will inspire the development of environmentally friendly water-soluble QDs as a promising class of fluorescence labels for biological applications.}, archive = {J_JACS}, author = {Zhe Liu and Xiaoqi Hou and Huangpeng You and Zheng Wang and Kaijie Zhu and Xingyu Hu and Peixian Li and Xingchang Lu and Qingyu Wang and Zifeng Liu and Dongliang Hu and Jiangtong Su and Ning Dai and Yang Li}, doi = {10.1021/jacs.4c10731}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4778--4789}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface copassivation strategy for developing water-soluble InP colloidal quantum dots with high luminescence and suppressed blinking}, volume = {147}, year = {2025}, }
• (2025). Disentangling driving force effects, polar effects, e–/H+ imbalance, and other influences on H-atom transfer reactions. JACS, 147(6), 4766--4777. (www)

  @article{ , abstract = {Hydrogen atom transfer (HAT) reactions and their kinetic barriers Δ G HAT ‡ are important in organic and inorganic chemistry. This study examines factors that influence Δ G HAT ‡ , reporting the kinetics and thermodynamics of HAT from various ruthenium bis(acetylacetonate) pyridine-imidazole complexes to nitroxyl radicals. Across these 36 reactions, the Δ G PT ° and Δ G HAT ° can be independently varied, with different sets of Ru complexes primarily tuning either their p K a s or their E °s. The ΔΔ G HAT ‡ are analyzed using multiple linear free energy relationships (LFERs), the first largely experimental study of its kind. The barriers vary most strongly with the overall driving force, ΔΔ G HAT ‡ = 0.28 × ΔΔ G HAT ° , but are also affected by HAT intrinsic barriers (λ), sterics, and the thermochemical e – /H + imbalance of the reactions, |Δ G PT ° – Δ G ET ° |. The latter is a small but significant effect, revealed only by comparing LFERs. The imbalance analysis is closely related to traditional explanations of polar effects, but it is quantitative: Δ G HAT ‡ shifts by ∼4% with changes in |Δ G PT ° – Δ G ET ° |. This is the same dependence as was observed for purely organic HAT from toluenes─a remarkable result because traditional explanations of organic polar effects, e.g., using X–H bond polarities, do not apply to the Ru complexes in which the e – and H + are spatially separated. This work demonstrates the strong similarities between different kinds of HAT reactions when viewed through the lens of H + / e – (PCET) free energies. This lens also shows that Δ G HAT ‡ are ∼10-fold more sensitive to changes in Δ G HAT ° and λ than to the e – /H + free-energy imbalance.}, archive = {J_JACS}, author = {Benjamin D. Groff and Mauricio Cattaneo and Katheryn C. Rinaolo and Brandon Q. Mercado and James M. Mayer}, doi = {10.1021/jacs.4c10596}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4766--4777}, shortjournal = {J. Am. Chem. Soc.}, title = {Disentangling driving force effects, polar effects, e–/H+ imbalance, and other influences on H-atom transfer reactions}, volume = {147}, year = {2025}, }
• (2025). Energizing robust Sulfur/Lithium electrochemistry via nanoscale-asymmetric-size synergism. JACS, 147(6), 4752--4765. (www)

  @article{ , abstract = {Sluggish redox kinetics and dendrite growth perplex the fulfillment of efficient electrochemistry in lithium–sulfur (Li–S) batteries. The complicated sulfur phase transformation and sulfur/lithium diversity kinetics necessitate an all-inclusive approach in catalyst design. Herein, a compatible mediator with nanoscale-asymmetric-size configuration by integrating Co single atoms and defective CoTe 2– x (Co SA -CoTe 2– x @NHCF) is elaborately developed for regulating sulfur/lithium electrochemistry synchronously. Substantial electrochemistry and theoretical analyses reveal that CoTe 2– x exhibits higher catalytic activity in long-chain polysulfide transformation and Li 2 S decomposition, while monodispersed Co sites are more effective in boosting sulfur reduction kinetics to regulate Li 2 S deposition. Such cascade catalysis endows Co SA -CoTe 2– x @NHCF with the all-around service of “trapping-conversion-recuperation” for sulfur species during the whole redox reaction. Furthermore, it is demonstrated by in situ transmission electron microscopy that initially formed electronic-conductive Co and ionic-conductive Li 2 Te provide sufficient lithiophilic sites to regulate homogeneous Li plating and stripping with markedly suppressed dendrite growth. Consequently, by coupling the Co SA -CoTe 2– x @NHCF interlayer and Li@Co SA -CoTe 2– x @NHCF anode, the constructed Li–S full batteries deliver superior cycling stability and rate performance, and the flexible pouch cell exhibits stable cycling performance at 0.3 C. The gained insights into the synergistic effect of asymmetric-size structures pave the way for the integrated catalyst design in advanced Li–S systems.}, archive = {J_JACS}, author = {Youzhang Huang and Jiantao Li and Yinggan Zhang and Liang Lin and Zhefei Sun and Guiyang Gao and Baisheng Sa and Laisen Wang and Lu Ma and Sungsik Lee and Ming-Sheng Wang and Dong-Liang Peng and Khalil Amine and Qingshui Xie}, doi = {10.1021/jacs.4c10238}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4752--4765}, shortjournal = {J. Am. Chem. Soc.}, title = {Energizing robust Sulfur/Lithium electrochemistry via nanoscale-asymmetric-size synergism}, volume = {147}, year = {2025}, }
• (2025). Single-molecule oxidoreductase activity analysis for activity-based diagnosis based on proteoform alterations. JACS, 147(6), 4743--4751. (www)

  @article{ , abstract = {We developed a single-molecule enzyme activity assay platform for NAD(P) + -dependent oxidoreductases, leveraging a new NAD(P)H-responsive fluorogenic probe optimized for microdevice-based fluorometric detection. This platform enabled the detection of enzyme activities in blood and cerebrospinal fluid (CSF), including lactate dehydrogenase, glucose-6-phosphate dehydrogenase, and hexokinases. We demonstrate its potential for activity-based diagnosis by detecting altered populations of enzyme activity species in blood and CSF from liver damage in brain tumor patients.}, archive = {J_JACS}, author = {Mayano Minoda and Junpei Hatakeyama and Norimichi Nagano and Tadahaya Mizuno and Takumi Iwasaka and Sho Shiga and Kazuki Takahashi and Hideto Hiraide and Shingo Sakamoto and Yu Kagami and Ayumi Kashiro and Kazufumi Honda and Yuki Sugiura and Kazuhiko Mishima and Masayo Kaneko Mishima and Hiroyuki Kusuhara and Yasuteru Urano and Toru Komatsu}, doi = {10.1021/jacs.4c07624}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4743--4751}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-molecule oxidoreductase activity analysis for activity-based diagnosis based on proteoform alterations}, volume = {147}, year = {2025}, }
• (2025). N-protonated acridinium catalyst enables anti-markovnikov hydration of unconjugated tri- and disubstituted olefins. JACS, 147(6), 4736--4742. (www)

  @article{ , abstract = {The preparation of alcohols with anti-Markovnikov selectivity directly from olefins and water is a sought-after reaction due to its atom-economy and potential cost-effectiveness. Herein, we present the first general method for direct, catalytic anti-Markovnikov hydration of unconjugated tri- and disubstituted olefins. The key advancement is made possible by an oxidative ( E * red = 2.15 V) N -H acridinium catalyst, which allowed for the functionalization of alkenes that were previously unreactive in such transformations due to their high oxidation potential. The developed protocol is not limited to hydration but also enables other hydrofunctionalizations, such as hydroetherifications, following the same mechanistic pathway.}, archive = {J_JACS}, author = {Boris Alexander van der Worp and Tobias Ritter}, doi = {10.1021/jacs.4c18185}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4736--4742}, shortjournal = {J. Am. Chem. Soc.}, title = {N-protonated acridinium catalyst enables anti-markovnikov hydration of unconjugated tri- and disubstituted olefins}, volume = {147}, year = {2025}, }
• (2025). Asymmetric total synthesis of janthinoid a. JACS, 147(6), 4731--4735. (www)

  @article{ , abstract = {The asymmetric total synthesis of janthinoid A has been accomplished for the first time in 14 steps without using a protecting group. The trans -decalin subunit and the rigid oxabicyclo[3.2.1]octane motif were constructed via an epoxide-initiated cationic π-cyclization reaction and a Fe(ClO 4 ) 3 -mediated oxidative cascade cyclization reaction, respectively.}, archive = {J_JACS}, author = {Fu Tang and Zhong-Chao Zhang and Zhi-Lin Song and Yuan-He Li and Zi-Hao Zhou and Jia-Jun Chen and Zhen Yang}, doi = {10.1021/jacs.4c17480}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4731--4735}, shortjournal = {J. Am. Chem. Soc.}, title = {Asymmetric total synthesis of janthinoid a}, volume = {147}, year = {2025}, }
• (2025). Molecular uranium dioxide-mediated CO2 photoreduction. JACS, 147(6), 4726--4730. (www)

  @article{ , abstract = {The reduction of CO 2 mediated by transition metals has garnered significant interest, yet little is known about the reduction of CO 2 using f-element compounds. Herein, the reduction of CO 2 to CO by tetravalent uranium (U IV ) compound UO 2 is investigated via matrix isolation infrared spectroscopy and quantum chemical study. Our results reveal that a stable carbonate intermediate OU IV CO 3 ( A ) can be prepared at low temperatures (4–12 K). Through photolytic reactions of A under visible-light irradiations (495 nm < λ < 580 nm), the charge-separated pentavalent U V isomer [U V O 2 ] + [(η 2 -O 2 C)] − ( B ) is produced through electron transfer from the quasi-atomic U-7s orbital to the CO 2 moiety. Sequentially, one C═O bond in CO 2 breaks by successive UV–visible irradiation (250 nm < λ < 580 nm), and the photolysis generates the products CO and hexavalent U VI compound U VI O 3 following two intermediates U VI O 3 (CO) ( C ) and U VI O 3 (OC) ( D ) with a physiosorbed carbonyl group. Moreover, the evolution of oxidation states from electron-rich U IV to U VI on multiple potential energy surfaces of different electronic states involving configurations U(f 1 s 1 → f 2 → f 1 → f 0 ) is further demonstrated. Our findings unveil a mechanism for the photoreduction of CO 2 by a UO 2 molecule. This strategy can be used to design molecular and solid-state catalysts for depleted uranium for CO 2 reduction reactions.}, archive = {J_JACS}, author = {Xue-Lian Jiang and Jia Zhuang and Guohai Deng and Jun-Bo Lu and Chongyang Zhao and Ning Jiang and Han-Shi Hu and Mingfei Zhou and Jun Li}, doi = {10.1021/jacs.4c17188}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4726--4730}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular uranium dioxide-mediated CO2 photoreduction}, volume = {147}, year = {2025}, }
• (2025). Photolytic and thermal reactions of [C6H4(PPh2)2(μ-n2)] and its lewis acid adducts: N–N bond cleavage and liberation of n2. JACS, 147(6), 4720--4725. (www)

  @article{ , abstract = {The known species (Ph 3 P) 2 N 2 was previously described as two phosphine donors associated with a doubly Lewis acidic N 2 -unit based on its thermal liberation of N 2 . Herein, we prepare the related species [C 6 H 4 (PPh 2 ) 2 (μ-N 2 )] 4 , where the cisoid chelation of the N 2 fragment facilitates both N 2 liberation and N–N bond cleavage reactions. In addition, these reactions can be achieved selectively via thermolysis of a Lewis acid adduct of 4 or by direct photolysis, respectively. These findings provide insights on avenues to P(V) reduction, photochemical N–C bond formation, and the design of donor–acceptor combinations for N 2 capture and functionalization.}, archive = {J_JACS}, author = {Linkun Miao and Jason Yeung and Amir Yeganeh-Salman and Zheng-wang Qu and Stefan Grimme and Douglas W. Stephan}, doi = {10.1021/jacs.4c16123}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4720--4725}, shortjournal = {J. Am. Chem. Soc.}, title = {Photolytic and thermal reactions of [C6H4(PPh2)2(μ-n2)] and its lewis acid adducts: N–N bond cleavage and liberation of n2}, volume = {147}, year = {2025}, }
• (2025). In-cell mass spectrometry and ultraviolet photodissociation navigates the intracellular protein heterogeneity. JACS, 147(6), 4714--4719. (www)

  @article{ , abstract = {Directly probing the heterogeneous conformations of intracellular proteins within their native cellular environment remains a significant challenge in mass spectrometry (MS). Here, we establish an in-cell MS and ultraviolet photodissociation (UVPD) strategy that directly ejects proteins from living cells into a mass spectrometer, followed by 193 nm UVPD for structural analysis. Applying this approach to calmodulin (CaM), we reveal that it adopts more extended conformations within living cells compared with purified samples in vitro , highlighting the unique influence of intracellular environments on protein folding. Furthermore, UVPD analysis of calcium ion (Ca 2+ )-binding variants of CaM unveils not only the conformational heterogeneity induced by multiple Ca 2+ modulations but also reveals distinct preferences of Ca 2+ binding sites across different conformations. This strategy provides a powerful tool for interrogating the structure–function relationships of intracellular protein variants with sophisticated metal ion binding, paving the way for a deeper understanding of protein conformations within their native cellular context.}, archive = {J_JACS}, author = {Shirui Yang and Zhuanghao Hou and Zheyi Liu and Zhixiong Jin and Heng Zhao and Kaiming Cao and Shan Zhao and Weiqing Zhang and Chunlei Xiao and Xueming Yang and Guangming Huang and Fangjun Wang}, doi = {10.1021/jacs.4c16376}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4714--4719}, shortjournal = {J. Am. Chem. Soc.}, title = {In-cell mass spectrometry and ultraviolet photodissociation navigates the intracellular protein heterogeneity}, volume = {147}, year = {2025}, }
• (2025). Facilitated channeling of fixed carbon and energy into chemicals in artificial phototrophic communities. JACS, 147(6), 4707--4713. (www)

  @article{ , abstract = {Light-driven CO 2 biovalorization offers a promising route for coupling carbon mitigation with petrochemical replacement. Synthetic phototrophic communities that mimic lichens can reduce the metabolic burden with improved CO 2 utilization. However, inefficient channeling of carbon and energy between species seriously hinders the collaborative CO 2 -to-molecule route. Herein, we report a universal carbon sequestration (UCS) module based on photosynthetic microbes that provides a high-speed tunnel for channeling carbon and energy to heterotrophs. Compared to that of the traditional CO 2 -to-sucrose module, the UCS module sequestered 30% more carbon into glycerol, a generally available carbon source with high energy density. We demonstrated that the UCS module can be highly compatible with various industrial chassis and genetically recalcitrant microbes, enabling the rapid development of synthetic phototrophic communities without additional genetic manipulation. Notably, the accelerated electron transport and nutrient recycling systems may facilitate carbon and energy communications between cooperative partners. These UCS module-based communities efficiently channeled CO 2 into a wide range of chemicals, with a negative carbon footprint of −25.04 to −440.74 kgCO 2 e/kg of products. This strategy widens the boundaries of artificial photosynthetic communities and may boost carbon-negative biomanufacturing.}, archive = {J_JACS}, author = {Chaofeng Li and Haotian Zheng and Yuhang Li and Liangxu Liu and Jiawei Wang and Hengrun Li and Yaoyue Zhang and Chao Liao and Jun Ni}, doi = {10.1021/jacs.4c15940}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4707--4713}, shortjournal = {J. Am. Chem. Soc.}, title = {Facilitated channeling of fixed carbon and energy into chemicals in artificial phototrophic communities}, volume = {147}, year = {2025}, }
• (2025). Serine hydrolase-catalyzed polyol lipids are necessary for rodlet layer formation on the cell wall of entomopathogenic fungi. JACS, 147(6), 4701--4706. (www)

  @article{ , abstract = {Some key secondary metabolism genes are important for driving the infection process of entomopathogenic fungi; however, their chemical substance basis has not been well investigated. Here, mixtures of polyol lipids are discovered, which are synthesized through iterative chain transfer–esterification–hydrolysis cycles catalyzed by serine hydrolase during the release of online highly reducing polyketide intermediates. Importantly, an in vivo gene knockout experiment revealed that the synthesis of polyol lipids is necessary for rodlet layer formation on the cell wall of Beauveria bassiana . Our work uncovers an unexpected way for the synthesis of polyol lipids and illuminates a new perspective on their part in significant physiological processes in entomopathogenic fungi.}, archive = {J_JACS}, author = {Dekun Kong and Qian He and Dong-Mei Lin and Huaran Zhang and Lin Chen and Yanhua Fan and Man-Cheng Tang and Yi Zou}, doi = {10.1021/jacs.4c15577}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4701--4706}, shortjournal = {J. Am. Chem. Soc.}, title = {Serine hydrolase-catalyzed polyol lipids are necessary for rodlet layer formation on the cell wall of entomopathogenic fungi}, volume = {147}, year = {2025}, }
• (2025). Samarium as a catalytic electron-transfer mediator in electrocatalytic nitrogen reduction to ammonia. JACS, 147(6), 4695--4700. (www)

  @article{ , abstract = {Samarium diiodide (SmI 2 ) exhibits high selectivity for N 2 R catalyzed by molybdenum complexes; however, it has so far been employed only as a stoichiometric reagent (0.3 equiv of NH 3 per Sm) combined with coordinating proton sources (e.g., H 2 O, ROH). The latter inhibit catalytic turnover of Sm III owing to buildup of stable hydroxide/alkoxide sinks. Here, we report a tandem Sm/Mo-catalyzed e N 2 R system that achieves the lowest overpotential and highest Faradaic efficiency (82%) reported to date for nonaqueous e N 2 R at ambient pressure. Up to 8.4 equiv of NH 3 is produced per Sm, representing a 25-fold increase over N 2 R with stoichiometric SmI 2 . A noncoordinating proton source enables electrochemical SmI 3 /SmI 2 cycling at the applied potential of −1.45 V vs Fc +/0 .}, archive = {J_JACS}, author = {Emily A. Boyd and Hoimin Jung and Jonas C. Peters}, doi = {10.1021/jacs.4c14845}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4695--4700}, shortjournal = {J. Am. Chem. Soc.}, title = {Samarium as a catalytic electron-transfer mediator in electrocatalytic nitrogen reduction to ammonia}, volume = {147}, year = {2025}, }
• (2025). Deciphering the role of vinylene carbonate in shaping CO2 cluster growth and stability via wavelet-enhanced microwave spectroscopy. JACS, 147(6), 4689--4694. (www)

  @article{ , abstract = {This study presents the first integration of wavelet denoising with resonator-enhanced microwave spectroscopy to explore the formation and characteristics of gas-phase heterogeneous vinylene carbonate-(CO 2 ) 1–5 clusters. Through this innovative approach, faint spectral lines were detected with efficiency, enhancing our understanding of complex interaction patterns that govern the growth and stability of these molecular clusters. It was found that CO 2 aggregates preferentially around the vinylene carbonate molecule through C···O tetrel bonds at the carbonyl and ether groups, altering the typical self-aggregation topology of free CO 2 clusters. This leads to more symmetrical growth around the vinylene carbonate monomer. Our findings provide insights into the solvation mechanisms of compounds in supercritical CO 2 thereby advancing the understanding of subnanoscale CO 2 aggregation patterns.}, archive = {J_JACS}, author = {Chenxu Wang and Junlin Lan and Meiyue Li and Hao Wang and Fan Xie and Xiao Tian and Tianyue Gao and Junhua Chen and Zhenhong Yu and Melanie Schnell and Jens-Uwe Grabow and Qian Gou}, doi = {10.1021/jacs.4c14584}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4689--4694}, shortjournal = {J. Am. Chem. Soc.}, title = {Deciphering the role of vinylene carbonate in shaping CO2 cluster growth and stability via wavelet-enhanced microwave spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Assessing the robustness of the clock transition in a mononuclear s = 1 Ni(II) complex spin qubit. JACS, 147(6), 4685--4688. (www)

  @article{ , abstract = {Ni(II) complexes with an integer spin S = 1 that behave as clock transition spin qubits at zero magnetic field are resilient to magnetic fluctuations of the spin bath, while Co(II) complexes with a half-integer spin ( S = 3/2) lose their coherence when they are subject to the same fluctuating magnetic field as the Ni(II) ones. These findings demonstrate that adequately designed Ni(II) complexes are excellent candidates for spin qubits.}, archive = {J_JACS}, author = {Idris Tlemsani and François Lambert and Nicolas Suaud and Christian Herrero and Régis Guillot and Anne-Laure Barra and Serge Gambarelli and Talal Mallah}, doi = {10.1021/jacs.4c14367}, journal = {Journal of the American Chemical Society}, month = {2}, number = {6}, pages = {4685--4688}, shortjournal = {J. Am. Chem. Soc.}, title = {Assessing the robustness of the clock transition in a mononuclear s = 1 Ni(II) complex spin qubit}, volume = {147}, year = {2025}, }
• (2025). Correction to “One-step electrochemical ethylene-to-ethylene glycol conversion over a multitasking molecular catalyst”. JACS, 147(5), 4684. (www)

  @article{ , archive = {J_JACS}, author = {An-Zhen Li and Bo-Jun Yuan and Ming Xu and Ye Wang and Chunyu Zhang and Xiongbo Wang and Xi Wang and Jing Li and Lirong Zheng and Bi-Jie Li and Haohong Duan}, doi = {10.1021/jacs.5c00293}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4684}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “One-step electrochemical ethylene-to-ethylene glycol conversion over a multitasking molecular catalyst”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Directing nanoparticle organization in response to diverse chemical inputs”. JACS, 147(5), 4683. (www)

  @article{ , archive = {J_JACS}, author = {Yan Xiong and Colin Yancey and Heon-Joon Lee and Dayoung Gloria Lee and Emily Helm and Byunghwa Kang and Alison Grinthal and Daniel McKeen and Oleg Gang and Rebecca Schulman}, doi = {10.1021/jacs.5c00023}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4683}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Directing nanoparticle organization in response to diverse chemical inputs”}, volume = {147}, year = {2025}, }
• (2025). Superconductor–Insulator transition induced by precise subtripled vapor chemical gating. JACS, 147(5), 4675--4682. (www)

  @article{ , abstract = {Recent progress in superconductor–insulator transition has shed light on the intermediate metallic state with unique electronic inhomogeneity. The microscopic model, suggesting that carrier spatial distribution plays a decisive role in the intermediate state, has been instrumental in understanding the quantum transition. However, the narrow carrier density window in which the intermediate state exists necessitates precise control of the gate dielectric layer, presenting a challenge to in situ map the carrier spatial distribution. Herein, a subtripled vapor chemical gating strategy has been proposed to precisely control carrier density and map spatial distribution in the Li x ZrNCl system. The chemical gating strategy utilizes subtripled vapor to quasi-continuously reduce the Li doping level, driving the ground-state transition from superconductor to quantum metal to quantum Griffiths singularity (QGS) to insulator. In situ optical mapping demonstrates an inhomogeneous electronic state in the intermediate metallic state and an evolution to a stripe-like pattern at 4 K, offering new insights into the nature of the intermediate metallic state.}, archive = {J_JACS}, author = {Haodong Zhou and Ziren Wang and Junchi Wu and Yuqiao Guo and Taishen Li and Yongzhi She and Nan Pan and Yi Xie and Changzheng Wu}, doi = {10.1021/jacs.4c17794}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4675--4682}, shortjournal = {J. Am. Chem. Soc.}, title = {Superconductor–Insulator transition induced by precise subtripled vapor chemical gating}, volume = {147}, year = {2025}, }
• (2025). Cation effect on the electrochemical platinum dissolution. JACS, 147(5), 4667--4674. (www)

  @article{ , abstract = {Ensuring the stability of electrocatalysts is paramount to the success of electrochemical energy conversion devices. Degradation is a fundamental process involving the release of positively charged metal ions into the electric double layer (EDL) and their subsequent diffusion into the bulk electrolyte. However, despite its vital importance in achieving prolonged electrocatalysis, the underlying causality of catalyst dissolution with the EDL structure remains largely unknown. Here, we show that electrochemical Pt dissolution is strongly influenced by the identity of the alkali metal cation (AM + ) in the electrolyte. By monitoring Pt dissolution in real-time, we found a trend of reduced Pt leaching in the sequence Li + > Na + > K + > Cs + . Our computational predictions suggest that interfacial OH – concentration plays a pivotal role in Pt dissolution, where OH – facilitates the outward diffusion of dissolved Pt ions into the bulk electrolyte by neutralizing the Pt z + species, thereby screening the migration force for their redeposition. Combined with this theoretical result, we verify a strong correlation between the amount of dissolved Pt and the hydrolysis p K a or acidity of AM + , indicating that the AM + identity determines the local OH – concentration and thereby modifies the amount of Pt dissolution. Our results underscore the need to tune the EDL structure to achieve durable electrocatalysis, a promising area for future research.}, archive = {J_JACS}, author = {Haesol Kim and Minho M. Kim and Junsic Cho and Seunghoon Lee and Dong Hyun Kim and Seung-Jae Shin and Tomohiko Utsunomiya and William A. Goddard, III and Yu Katayama and Hyungjun Kim and Chang Hyuck Choi}, doi = {10.1021/jacs.4c17833}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4667--4674}, shortjournal = {J. Am. Chem. Soc.}, title = {Cation effect on the electrochemical platinum dissolution}, volume = {147}, year = {2025}, }
• (2025). Probing the influence of the protein scaffold on H-cluster reactivity via gain-of-function Studies─Improved h2 evolution and o2 tolerance through rational design of [FeFe] hydrogenase. JACS, 147(5), 4654--4666. (www)

  @article{ , abstract = {[FeFe] hydrogenases make up a structurally diverse family of metalloenzymes that catalyze proton/dihydrogen interconversion. They can be classified into phylogenetically distinct groups denoted A–G, which differ in structure and reactivity. Prototypical Group A hydrogenases have high turnover rates and remarkable energy efficiency. As compared to Group A enzymes, the putatively sensory Group D hydrogenase from Thermoanaerobacter mathranii ( Tam HydS) has a thousand-fold lower H 2 evolution rate and a high overpotential requirement to drive catalysis (irreversible) but shows increased inhibitor tolerance. This divergence in structure and activity between hydrogenases makes them ideal models for studying second (active-site environment) and outer ( e.g. , substrate transport) coordination sphere effects on metal cofactors. Herein, we generated three Tam HydS-based variants, each mimicking proposed key structural features of Group A hydrogenase: the “active site” ( AS ), “proton-transfer pathway” ( PTP ), and “combined” ( CM = AS + PTP ) variant. A fourth single-point variant, A137C , which introduces a proposed critical cysteine in the active site, was characterized as a reference. No change in isolation resulted in Group A-like behavior; i.e ., no positive impact on catalytic performance was observed. The CM variant, however, showed increased H 2 evolution activity but retained the overpotential requirement. Additionally, the CM variant improved the already relatively high stability of Tam HydS against O 2 and CO inhibition. These findings show that activity rates, (ir)reversibility, and susceptibility to gaseous inhibitors are decoupled. Moreover, the results highlight the importance of exploring hydrogenase diversity as a path toward understanding the structural factors that enable the outstanding catalytic properties of [FeFe] hydrogenases.}, archive = {J_JACS}, author = {Princess R. Cabotaje and Alina Sekretareva and Moritz Senger and Ping Huang and Kaija Walter and Holly J. Redman and Nicholas Croy and Sven T. Stripp and Henrik Land and Gustav Berggren}, doi = {10.1021/jacs.4c17364}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4654--4666}, shortjournal = {J. Am. Chem. Soc.}, title = {Probing the influence of the protein scaffold on H-cluster reactivity via gain-of-function Studies─Improved h2 evolution and o2 tolerance through rational design of [FeFe] hydrogenase}, volume = {147}, year = {2025}, }
• (2025). Step edge defects have nanoscale impact on the electronic structure in semiconducting transition metal dichalcogenide electrocatalysts. JACS, 147(5), 4643--4653. (www)

  @article{ , abstract = {This work uses MoTe 2 single crystals to address the challenge in heterogeneous catalysis of identifying active sites and determining the electronic factors responsible for catalytic activity. We find that for semiconducting MoTe 2 , spots that fall along step edges show more catalytic activity than spots that fall solely on the basal plane. In contrast, for a semimetallic phase of MoTe 2 , there is no measurable difference between the H 2 evolution activity at the step edges and at the basal plane, indicating that the active sites for H 2 evolution catalysis on transition metal dichalcogenides are phase dependent. We additionally find that the local H 2 evolution activity correlates with local potential differences, higher conductance, and faster rates of outer-sphere electron transfer to a redox-active probe in solution. Interestingly, in the semiconducting phase of MoTe 2 , these local electronic structure differences were measured both at the edge sites and at basal plane sites next to the edge, extending >50 nm away from the edge. These results indicate that for MoTe 2 , basal plane sites near the edge may have stronger free energies of H adsorption, Δ G H,ads , than basal plane sites farther from the edge. Thus, we propose that edge sites in semiconducting transition metal dichalcogenides are better thought of as defect sites that substantially modulate the electronic structure in the surrounding region rather than solely as undercoordinated active sites. These results provide exciting opportunities to use defects to alter the electronic structure at existing active sites in semiconductor electrocatalysts.}, archive = {J_JACS}, author = {Kenneth Ortiz Chua and Megan N. Jackson}, doi = {10.1021/jacs.4c17263}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4643--4653}, shortjournal = {J. Am. Chem. Soc.}, title = {Step edge defects have nanoscale impact on the electronic structure in semiconducting transition metal dichalcogenide electrocatalysts}, volume = {147}, year = {2025}, }
• (2025). Modulation of molecular quadrupole moments by phenyl side-chain fluorination for high-voltage and high-performance organic solar cells. JACS, 147(5), 4631--4642. (www)

  @article{ , abstract = {The ground-state charge generation (GSCG) in photoactive layers determines whether the photogenerated carriers occupy the deep trap energy levels, which, in turn, affects the device performance of organic solar cells (OSCs). In this work, charge-quadrupole electrostatic interactions are modulated to achieve GSCG through a molecular strategy of introducing different numbers of F atom substitutions on the BTA3 side chain. The results show that 8F substitution (BTA3–8F) and 16F substitution (BTA3–16F) lead to different patterns of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy level changes. The perfluorination of the phenyl side chain endows BTA3–16F with a LUMO energy level similar to that of BTA3, ensuring a high V OC . Besides, BTA3–16F features a large charge-quadrupole moment, promoting strong electrostatic interactions between neighboring molecules along the π–π stacking direction, which then induces the GSCG in photoactive components. This efficient GSCG directly makes a significant impact on the subsequent kinetics of photogenerated exciton dissociation, recombination, and transport over longer time periods, as well as on nonradiative recombination over larger spatial scales. Benefiting from the favorable GSCG and suitable energy level arrangement, PTQ10/BTA3–16F achieves a V OC of 1.302 V and a PCE of 11.14%, setting the world record for OSCs performance with a V OC greater than 1.3 V. In addition, BTA3–16F is an effective guest molecule to improve the performance of ternary OSCs, and PM6/L8-BO/BTA3–16F-based ternary device achieves the highest PCE of 19.82%. This result emphasizes the important role of GSCG between photoactive components in OSC performance and demonstrates that modulation of molecular quadrupole moments is an effective means of designing efficient acceptors.}, archive = {J_JACS}, author = {Tingting Dai and Yuhan Meng and Zongtao Wang and Jiahao Lu and Zhi Zheng and Mengzhen Du and Qing Guo and Erjun Zhou}, doi = {10.1021/jacs.4c17140}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4631--4642}, shortjournal = {J. Am. Chem. Soc.}, title = {Modulation of molecular quadrupole moments by phenyl side-chain fluorination for high-voltage and high-performance organic solar cells}, volume = {147}, year = {2025}, }
• (2025). Enantiocontrolled cyclization to form chiral 7- and 8-membered rings unified by the same catalyst operating with different mechanisms. JACS, 147(5), 4624--4630. (www)

  @article{ , abstract = {Chiral medium-sized rings, albeit displaying attractive properties for drug development, suffer from numerous synthetic challenges due to difficult cyclization steps that must take place to form these unusually strained, atropisomeric rings from sterically crowded precursors. In fact, catalytic enantioselective cyclization methods for the formation of chiral seven-membered rings are unknown, and the corresponding eight-membered variants are also sparse. In this work, we present a substrate preorganization-based, enantioselective, organocatalytic strategy to construct seven- and eight-membered rings featuring chirality that is intrinsic to the ring in the absence of singular stereogenic atoms or single bond axes of chirality. The reactions proceed under mild conditions and with high levels of stereocontrol. Notably, the same bifunctional iminophosphorane chiral catalyst orchestrates the cyclization of substrates of two different ring sizes, under two different mechanistic paradigms. We envision that the mechanistic and ring size versatility of this method could guide further applications of asymmetric catalysis to other challenging cyclization reactions.}, archive = {J_JACS}, author = {Nicolò Tampellini and Brandon Q. Mercado and Scott J. Miller}, doi = {10.1021/jacs.4c17080}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4624--4630}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantiocontrolled cyclization to form chiral 7- and 8-membered rings unified by the same catalyst operating with different mechanisms}, volume = {147}, year = {2025}, }
• (2025). Enantioselective total syntheses of vallesamidine and schizozygane alkaloids. JACS, 147(5), 4613--4623. (www)

  @article{ , abstract = {A general streamlined strategy for the enantioselective total syntheses of the schizozygane family of natural products and related alkaloid vallesamidine is described. Specifically, a catalytic enantioconvergent cross-coupling sets the quaternary stereogenic center in a pluripotent intermediate adorned with an olefin and three orthogonal carboxylate groups, upon which the modularity of the synthesis relies. A late-stage catalytic oxidative lactamization of an alkyne is instrumental in the first-generation synthesis of the schizozygane alkaloids. In the second-generation approach, a novel application of the van Leusen reaction for the generation of lactams is pivotal to accessing the schizozygane alkaloids from a common intermediate. The strategies outlined here are expected to enable detailed biological investigations as well as facilitate access to and provide solutions for the late-stage modification of bioactive alkaloids.}, archive = {J_JACS}, author = {Gujjula V. Ramakrishna and Zurwa Latif and Filippo Romiti}, doi = {10.1021/jacs.4c16900}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4613--4623}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective total syntheses of vallesamidine and schizozygane alkaloids}, volume = {147}, year = {2025}, }
• (2025). Directed evolution and unusual protonation mechanism of pyridoxal radical C–C coupling enzymes for the enantiodivergent photobiocatalytic synthesis of noncanonical amino acids. JACS, 147(5), 4602--4612. (www)

  @article{ , abstract = {Visible light-driven pyridoxal radical biocatalysis has emerged as a new strategy for the stereoselective synthesis of valuable noncanonical amino acids in a protecting-group-free fashion. In our previously developed dehydroxylative C–C coupling using engineered PLP-dependent tryptophan synthases, an enzyme-controlled unusual α-stereochemistry reversal and pH-controlled enantiopreference were observed. Herein, through high-throughput photobiocatalysis, we evolved a set of stereochemically complementary PLP radical enzymes, allowing the synthesis of both l - and d -amino acids with enhanced enantiocontrol across a broad pH window. These newly engineered l - and d -amino acid synthases permitted the use of a broad range of organoboron substrates, including boronates, trifluoroborates, and boronic acids, with excellent efficiency. Mechanistic studies unveiled unexpected PLP racemase activity with our earlier PLP enzyme variants. This promiscuous racemase activity was abolished in our evolved amino acid synthases, shedding light on the origin of enhanced enantiocontrol. Further mechanistic investigations suggest a switch of proton donor to account for the stereoinvertive formation of d -amino acids, highlighting an unusual stereoinversion mechanism that is rare in conventional two-electron PLP enzymology.}, archive = {J_JACS}, author = {Lei Cheng and Zhiyu Bo and Benjamin Krohn-Hansen and Yang Yang}, doi = {10.1021/jacs.4c16716}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4602--4612}, shortjournal = {J. Am. Chem. Soc.}, title = {Directed evolution and unusual protonation mechanism of pyridoxal radical C–C coupling enzymes for the enantiodivergent photobiocatalytic synthesis of noncanonical amino acids}, volume = {147}, year = {2025}, }
• (2025). Observation of o2 molecules inserting into Fe–H bonds in a ferrous Metal–Organic framework. JACS, 147(5), 4595--4601. (www)

  @article{ , abstract = {Exploring the interactions between oxygen molecules and metal sites has been a significant topic. Most previous studies concentrated on enzyme-mimicking metal sites interacting with O 2 to form M–OO species, leaving the development of new types of O 2 -activating metal sites and novel adsorption mechanisms largely overlooked. In this study, we reported an Fe(II)-doped metal–organic framework (MOF) [Fe 3 Zn 2 H 4 (bibtz) 3 ] ( MAF-203 , H 2 bibtz = 1 H ,1’ H -5,5′-bibenzo[ d ][1,2,3]triazole), featuring an unprecedented tetrahedral Fe(II)HN 3 site. This MOF exhibits selective adsorption behavior for O 2 from air, achieving an O 2 /N 2 separation selectivity of up to 67.1. Breakthrough experiments confirmed that MAF-203 can effectively capture O 2 from the air even under a high relative humidity of 60%. X-ray absorption spectroscopy, in situ diffuse reflectance infrared Fourier transform spectra, and ab initio molecular dynamics simulations were utilized to monitor the O 2 loading process on the Fe(II)HN 3 site. Interestingly, O 2 molecules could insert into the Fe–H bonds of the tetrahedral Fe II HN 3 sites, forming Fe III –OOH species (instead of the commonly observed Fe–OO species) with an ultrahigh adsorption enthalpy of −99.2 kJ mol –1 . Consequently, the O 2 capture behavior of MAF-203 enables efficient electrochemical 2e – oxygen reduction for the production of H 2 O 2 with air as the feedstock. Specifically, in a solid-state electrolyte electrolyzer without any liquid electrolyte, MAF-203 achieved selective O 2 capture and continuous production of medical-grade H 2 O 2 (3.2 wt %) solution without salts for 70 h, with performance comparable to that under pure O 2 conditions. The O 2 adsorption and activation mechanisms inaugurate a fresh chapter in grasping the interaction between O 2 molecules and metal sites.}, archive = {J_JACS}, author = {Hao-Lin Zhu and Jia-Run Huang and Feifei Zhang and Pei-Qin Liao and Xiao-Ming Chen}, doi = {10.1021/jacs.4c16736}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4595--4601}, shortjournal = {J. Am. Chem. Soc.}, title = {Observation of o2 molecules inserting into Fe–H bonds in a ferrous Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Making mo(0) a competitive alternative to Ir(III) in phosphors and photocatalysts. JACS, 147(5), 4587--4594. (www)

  @article{ , abstract = {Iridium is used in commercial light-emitting devices and in photocatalysis but is among the rarest stable chemical elements. Therefore, replacing iridium(III) in photoactive molecular complexes with abundant metals is of great interest. First-row transition metals generally tend to yield poorer luminescence behavior, and it remains difficult to obtain excited states with redox properties that exceed those of noble-metal-based photocatalysts. Here, we overcome these challenges with a nonprecious second-row transition metal. Tailored coordination spheres for molybdenum(0) lead to photoluminescence quantum yields that rival those of iridium(III) complexes and photochemical reduction reactions not normally achievable with iridium(III) become possible. These developments open new perspectives for replacing noble metals in lighting applications with Earth-abundant metals and for advancing metal-based photocatalysis beyond current limits.}, archive = {J_JACS}, author = {Tao Jin and Narayan Sinha and Dorothee S. Wagner and Alessandro Prescimone and Daniel Häussinger and Oliver S. Wenger}, doi = {10.1021/jacs.4c16672}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4587--4594}, shortjournal = {J. Am. Chem. Soc.}, title = {Making mo(0) a competitive alternative to Ir(III) in phosphors and photocatalysts}, volume = {147}, year = {2025}, }
• (2025). Atomically dispersed Ta–O–Co sites capable of mitigating side reaction occurrence for stable Lithium–Oxygen batteries. JACS, 147(5), 4578--4586. (www)

  @article{ , abstract = {The side reactions accompanying the charging and discharging process, as well as the difficulty in decomposing the discharge product lithium peroxide, have been important issues in the research field of lithium–oxygen batteries for a long time. Here, single atom Ta supported by Co 3 O 4 hollow sphere was designed and synthesized as a cathode catalyst. The single atom Ta forms an electron transport channel through the Ta–O–Co structure to stabilize octahedral Co sites, forming strong adsorption with reaction intermediates and ultimately forming a film-like lithium peroxide that is highly dispersed. More importantly, the formation of the Ta–O–Co structure can reduce the vacancy formation energy on the catalyst surface, accelerate oxygen activation and conversion into superoxide anions, promote the rapid conversion of strong oxidizing intermediate lithium superoxide into lithium peroxide, avoid the oxidation of lithium superoxide to the electrode and electrolyte, reduce the occurrence of side reactions, and mitigate the production of byproduct lithium carbonate. The overpotential of the battery is reduced significantly, and the reversibility and cycling stability of the battery are improved. This study provides a practical and feasible direction for mitigating the side reaction and improving the performance of the battery.}, archive = {J_JACS}, author = {Yu Zhang and Chang Chen and Chang He and Qi Yang and Xin Tan and Zhiyuan Xu and Yanying Jiang and Mengwei Yuan and Caiyun Nan and Chen Chen}, doi = {10.1021/jacs.4c16544}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4578--4586}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomically dispersed Ta–O–Co sites capable of mitigating side reaction occurrence for stable Lithium–Oxygen batteries}, volume = {147}, year = {2025}, }
• (2025). Systematic fluorination is a powerful design strategy toward fluid molecular ferroelectrics. JACS, 147(5), 4571--4577. (www)

  @article{ , abstract = {Ferroelectric nematic (N F ) liquid crystals combine liquid-like fluidity and orientational order of conventional nematics with macroscopic electric polarization comparable in magnitude to solid-state ferroelectric materials. Here, we present a systematic study of twenty-seven homologous materials with various fluorination patterns, giving new insight into the molecular origins of spontaneous polar ordering in fluid ferroelectric nematics. Beyond our initial expectations, we find the highest stability of the N F phase to be in materials with specific fluorination patterns rather than the maximal fluorination, which might be expected based on simple models. We find a delicate balance between polar and apolar nematics, which is entirely dictated by the substitution of the fluorine atoms. Aided by electronic structure calculations, we show this to have its origins in the radial distribution of charge across the molecular surface, with molecules possessing a more oscillatory distribution of electrons across their surfaces and possessing a higher propensity to form polar nematic phases. This work provides a new set of ground rules and design principles that can inform the synthesis of future ferroelectric nematogens.}, archive = {J_JACS}, author = {Calum J. Gibb and Jordan Hobbs and Richard J. Mandle}, doi = {10.1021/jacs.4c16555}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4571--4577}, shortjournal = {J. Am. Chem. Soc.}, title = {Systematic fluorination is a powerful design strategy toward fluid molecular ferroelectrics}, volume = {147}, year = {2025}, }
• (2025). Image-based phenotypic profiling enables rapid and accurate assessment of EGFR-activating mutations in tissues from lung cancer patients. JACS, 147(5), 4552--4570. (www)

  @article{ , abstract = {Determining mutations in the kinase domain of the epidermal growth factor receptor (EGFR) is critical for the effectiveness of EGFR tyrosine kinase inhibitors (TKIs) in lung cancer. Yet, DNA-based sequencing analysis of tumor samples is time-consuming and only provides gene mutation information on EGFR, making it challenging to design effective EGFR-TKI therapeutic strategies. Here, we present a new image-based method involving the rational design of a quenched probe based on EGFR-TKI to identify mutant proteins, which permits specific and “no-wash” real-time imaging of EGFR in living cells only upon covalent targeting of the EGFR kinase. We also show that the probe enables distinguishing EGFR mutant tumor-bearing mice from wild-type tumor-bearing mice via fluorescence-intensity-based imaging with high signal contrast. More interestingly, the image-based phenotypic approach can be used to predict EGFR mutations in tumors from lung cancer patients with an accuracy of 94%. Notably, when immunohistochemistry analysis is integrated, an improved accuracy of 98% is achieved. These data delineate a drug-based phenotypic imaging approach for in-biopsy visualization and define functional groups of EGFR mutants that can effectively guide EGFR-TKI therapeutic decision-making besides gene mutation analysis.}, archive = {J_JACS}, author = {Qian Lei and Xinglong Zhou and Ying Li and Shuang Zhao and Na Yang and Zhaolin Xiao and Chao Song and Quanwei Yu and Hui Deng}, doi = {10.1021/jacs.4c16528}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4552--4570}, shortjournal = {J. Am. Chem. Soc.}, title = {Image-based phenotypic profiling enables rapid and accurate assessment of EGFR-activating mutations in tissues from lung cancer patients}, volume = {147}, year = {2025}, }
• (2025). Steering energy transfer pathways through mn-doping in perovskite nanocrystals. JACS, 147(5), 4541--4551. (www)

  @article{ , abstract = {Modulation of singlet and triplet energy transfer from excited semiconductor nanocrystals to attached dye molecules remains an important criterion for the design of light-harvesting assemblies. Whereas one can consider the selection of donor and acceptor with favorable energetics, spectral overlap, and kinetics of energy transfer as a means to direct the singlet and triplet energy transfer pathways, it is not obvious how to control the singlet and triplet characteristics of the donor semiconductor nanocrystal itself. By doping CsPb(Cl 0.7 Br 0.3 ) 3 nanocrystals with Mn 2+ , we have now succeeded in increasing the triplet characteristics of semiconductor nanocrystals. The singlet and triplet energy transfer between excited Mn-CsPb(Cl 0.7 Br 0.3 ) 3 nanocrystals and a cyanine dye (4,5-benzoindotricarbocyanine) show the participation of band gap states in singlet energy transfer and Mn 2+ -activated states in triplet energy transfer. By tracking donor and acceptor emission as well as transient absorption spectral features, we were able to distinguish the two independent energy transfer pathways. Whereas singlet energy transfer from the exciton emission band remains unchanged (2%), increasing the concentration of Mn 2+ in perovskite nanocrystals results in an increase of triplet energy transfer yield up to 17.5%. The ability to enhance the triplet transfer yield in CsPb(Cl 0.7 Br 0.3 ) 3 nanocrystals through Mn-doping opens up new opportunities to develop optoelectronic and display devices.}, archive = {J_JACS}, author = {Akshaya Chemmangat and Sara Murray and Prashant V. Kamat}, doi = {10.1021/jacs.4c16567}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4541--4551}, shortjournal = {J. Am. Chem. Soc.}, title = {Steering energy transfer pathways through mn-doping in perovskite nanocrystals}, volume = {147}, year = {2025}, }
• (2025). Proton-controlled electron injection in MoS2 during hydrogen evolution revealed by time-resolved spectroelectrochemistry. JACS, 147(5), 4531--4540. (www)

  @article{ , abstract = {Monolayer MoS 2 is an effective electrocatalyst for the hydrogen evolution reaction (HER). Despite significant efforts to optimize the active sites, its catalytic performance still falls short of theoretical predictions. One key factor that has often been overlooked is the electron injection from the conductive substrate into the MoS 2 . The charge transfer behavior at the substrate-MoS 2 interface is nonclassical, exhibiting a liquid-gated electron injection behavior, the underlying mechanism of which remain under debate. To investigate this, we employ nanosecond time-resolved spectroelectrochemistry to probe the electron injection dynamics into monolayer MoS 2 under operando HER conditions. Simultaneously, transient current measurements provide insights into the electron density at the substrate. By combining the electron density obtained from the MoS 2 through spectroelectrochemical analysis with the electron density at the conductive substrate derived from transient current measurements, we explore the electron injection dynamics and characterize the current density potential (J-E) behavior at the substrate-MoS 2 interface. Our findings show that the electron injection barrier and capability correlate strongly with proton concentration in the electrolyte. This relationship likely reflects the electron concentration-dependent conductivity of MoS 2 , where higher proton concentrations lead to fewer stray electrons before injection begins.}, archive = {J_JACS}, author = {Tao Yang and Boning Wu and Chunmei Ding and Xianchang Yan and Wenming Tian and Shengye Jin}, doi = {10.1021/jacs.4c16536}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4531--4540}, shortjournal = {J. Am. Chem. Soc.}, title = {Proton-controlled electron injection in MoS2 during hydrogen evolution revealed by time-resolved spectroelectrochemistry}, volume = {147}, year = {2025}, }
• (2025). Nearly barrierless four-hole water oxidation catalysis on semiconductor photoanodes with high density of accumulated surface holes. JACS, 147(5), 4520--4530. (www)

  @article{ , abstract = {The sluggish water oxidation reaction (WOR) is considered the kinetic bottleneck of artificial photosynthesis due to the complicated four-electron and four-proton transfer process. Herein, we find that the WOR can be kinetically nearly barrierless on four representative photoanodes (i.e., α-Fe 2 O 3 , TiO 2 , WO 3 , and BiVO 4 ) under concentrated light irradiation, wherein the rate-limiting O–O bond formation step is driven by accumulated surface photogenerated holes that exhibit a superior fourth-order kinetics. The activation energy is about 0.03 eV for the fourth-order kinetic pathway, which is quantitatively estimated by combining the Population model and Butler–Volmer model with the Eyring-like equation and is further confirmed by density functional theory calculations. The WOR rate under this condition shows more than 1 order of magnitude enhancement compared with that of first-, second-, or third-order kinetics. Focusing on α-Fe 2 O 3 , the accumulated high-density surface holes form adjacent Fe V ═O intermediates that effectively activate surface-adsorbed H 2 O molecules via the hydrogen-bonding effect, as revealed by operando Raman measurements and ab initio molecular dynamics simulations. This work discloses a systematic understanding of the internal relations between activation energy and reaction orders of surface holes for future WOR study.}, archive = {J_JACS}, author = {Siqin Liu and Kun Dang and Lei Wu and Shuming Bai and Yuchao Zhang and Jincai Zhao}, doi = {10.1021/jacs.4c16443}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4520--4530}, shortjournal = {J. Am. Chem. Soc.}, title = {Nearly barrierless four-hole water oxidation catalysis on semiconductor photoanodes with high density of accumulated surface holes}, volume = {147}, year = {2025}, }
• (2025). Circular polymer designed by regulating entropy: Spiro-valerolactone-based polyesters with high gas barriers and adhesion strength. JACS, 147(5), 4511--4519. (www)

  @article{ , abstract = {Enthalpy is often the focal point when designing monomers for polymer circularity, but much less is explored on how entropy can be exploited to create polymers with synergistic circularity and properties. Here, we design a series of spiro-lactones (SLs) with closed-chain cycloalk(en)yl substituents at the α,α-position of δ-valerolactone (δVL), which, when combined with the parent δVL and gem -α,α-dialkyl-substituted δVL with open-chain alkyl groups, provide a desired platform for exploring the circular polymer design by focusing on the entropy change of polymerization. These SLs exhibit finely balanced (de)polymerizability that is regulated chiefly by entropy differentiation, allowing both the facile synthesis of polyester PSLs ( M n up to 1000 kg mol –1 ) in a living fashion and selective depolymerization of the PSLs to completely recover monomers under mild conditions (using a recyclable catalyst at 100 °C). One such PSL is semicrystalline ( T m = 134 °C), strong (ultimate strength = 43 MPa), hard (modulus = 1.85 GPa), and modestly flexible. These notable mechanical properties are bolstered by its superior barriers to oxygen and moisture permeation compared to common packaging materials. In addition, this PSL can be postfunctionalized to a recyclable OH-containing PSL that shows higher adhesion strength than the comparative commercial adhesives.}, archive = {J_JACS}, author = {Cui-Ting Han and Kai Ma and Zhen Zhang and Ryan W. Clarke and Ravikumar R. Gowda and Tie-Qi Xu and Eugene Y.-X. Chen}, doi = {10.1021/jacs.4c16260}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4511--4519}, shortjournal = {J. Am. Chem. Soc.}, title = {Circular polymer designed by regulating entropy: Spiro-valerolactone-based polyesters with high gas barriers and adhesion strength}, volume = {147}, year = {2025}, }
• (2025). Nanoscale manipulation of single-molecule conformational transition through vibrational excitation. JACS, 147(5), 4504--4510. (www)

  @article{ , abstract = {Controlling molecular actions on demand is a critical step toward developing single-molecule functional devices. Such control can be achieved by manipulating the interactions between individual molecules and their nanoscale environment. In this study, we demonstrate the conformational transition of a single pyrrolidine molecule adsorbed on a Cu(100) surface, driven by vibrational excitation through tunneling electrons using scanning tunneling microscopy. We identify multiple transition pathways between two structural states, each governed by distinct vibrational modes. The nuclear motions corresponding to these modes are elucidated through density functional theory calculations. By leveraging fundamental forces, including van der Waals interactions, dipole–dipole interactions, and steric hindrance, we precisely tune the molecule-environment coupling. This tuning enables the modulation of vibrational energies, adjustment of transition probabilities, and selection of the lowest-energy transition pathway. Our findings highlight how tunable force fields in a nanoscale cavity can govern molecular conformational transitions, providing a pathway to engineer molecule-environment interactions for targeted molecular functionalities.}, archive = {J_JACS}, author = {Weike Quan and Zihao Wang and Yueqing Shi and Kangkai Liang and Liya Bi and Hao Zhou and Zhiyuan Yin and Wan-Lu Li and Shaowei Li}, doi = {10.1021/jacs.4c16218}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4504--4510}, shortjournal = {J. Am. Chem. Soc.}, title = {Nanoscale manipulation of single-molecule conformational transition through vibrational excitation}, volume = {147}, year = {2025}, }
• (2025). Functionalized terthiophene as an ambipolar redox system: Structure, spectroscopy, and switchable proton-coupled electron transfer. JACS, 147(5), 4493--4503. (www)

  @article{ , abstract = {Organic redox systems that can undergo oxidative and reductive (ambipolar) electron transfer are elusive yet attractive for applications across synthetic chemistry and energy science. Specifically, the use of ambipolar redox systems in proton-coupled electron transfer (PCET) reactions is largely unexplored but could enable “switchable” reactivity wherein the uptake and release of hydrogen atoms are controlled using a redox stimulus. Here, we describe the synthesis and characterization of an ambipolar functionalized terthiophene (TTH) bearing methyl thioether and phosphine oxide groups that exhibits switchable PCET reactivity. Electrochemical studies established that the functionalized TTH can be reversibly oxidized and reduced, prompting the synthesis and characterization of cationic and anionic radicals on a single TTH platform. Combined structural, spectroscopic, and computational investigations revealed the influence of the methyl thioether and phosphine oxide moieties on the TTH electronic structure that results in the stabilization of both cationic and anionic radicals. Upon single-electron oxidation, the functionalized TTH serves as a hydrogen atom acceptor and undergoes PCET with 1,4-dihydroquinone to generate a TTH hydroxyphosphonium species. The process was found to be reversible upon single-electron reduction, with functionalized TTH acting as a hydrogen atom donor in a PCET reaction with 2,3-dimethylanthraquinone. The thermochemistry of the O–H bond formed and cleaved in functionalized TTH during the reaction sequence was investigated, revealing that a bond weakening of 30 kcal/mol underpins the switchable PCET reactivity. Overall, these studies provide an electrochemical, structural, spectroscopic, and thermochemical foundation for the use of ambipolarity to control PCET reactions in organic redox systems.}, archive = {J_JACS}, author = {Daniel Käch and Daniel Klose and Lionel Wettstein and Máté J. Bezdek}, doi = {10.1021/jacs.4c16003}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4493--4503}, shortjournal = {J. Am. Chem. Soc.}, title = {Functionalized terthiophene as an ambipolar redox system: Structure, spectroscopy, and switchable proton-coupled electron transfer}, volume = {147}, year = {2025}, }
• (2025). Synergistic enhancement of ferroptosis via mitochondrial accumulation and photodynamic-controlled release of an Organogold(I) cluster prodrug. JACS, 147(5), 4482--4492. (www)

  @article{ , abstract = {Effective delivery and controlled release of metallo-prodrugs with sustained activation and rapid response feed the needs of precise medicine in metal chemotherapeutics. However, gold-based anticancer drugs often suffer from detoxification binding and extracellular transfer by sulfur-containing peptides. To address this challenge, we integrate a thiol-activated prodrug strategy of newly prepared hypercoordinated carbon-centered gold(I) clusters (HCGCs) with their photosensitization character to augment the mitochondrial release of Au(I) in tumors. In contrast to the distorted [CAu 4 ] kernel of a pentanuclear HCGC compound [ A5 ], its dimeric congener [ A9 ] exhibits a symmetrical [{CAu 4 }–Au–{CAu 4 }] structure with a remarkable hypercarbon-to-Au 4 electron donation. This unique arrangement results in a microsecond long metal–metal-to-ligand charge transfer excited state relative to the nanosecond intraligand excited state of [ A5 ]. Upon light irradiation at 560 nm, [ A9 ] generates active 1 O 2 to oxidize glutathione (GSH) into poorly coordinating GSSG in the cytoplasm and finally promotes subcellular delivery of HCGCs to mitochondria. Moreover, GSH further triggers consecutive release of active [AuPPh 3 ] + ions to inhibit cytoplasmic glutathione peroxidase GPX4 and mitochondrial thioredoxin reductase TrxR2, which collectively result in accelerated ferroptosis of human bladder cancer EJ cells and show excellent antitumor performance in mouse bladder tumor models.}, archive = {J_JACS}, author = {Kui Xiao and Da-Yong Hou and Ni-Yuan Zhang and Wan Wang and Ming-Yi Leung and Wing-Kei Kwok and Ziyong Chen and Cong Jin and Wanhai Xu and Hao Wang and Vivian Wing-Wah Yam and Liang Zhao}, doi = {10.1021/jacs.4c15820}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4482--4492}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic enhancement of ferroptosis via mitochondrial accumulation and photodynamic-controlled release of an Organogold(I) cluster prodrug}, volume = {147}, year = {2025}, }
• (2025). Gold(I)-catalyzed 2-deoxy-β-glycosylation via 1,2-Alkyl/Arylthio migration: Synthesis of velutinoside a pentasaccharide. JACS, 147(5), 4469--4481. (www)

  @article{ , abstract = {2-Deoxy-β-glycosides are essential components of natural products and pharmaceuticals; however, the corresponding 2-deoxy-β-glycosidic bonds are challenging to chemically construct. Herein, we describe an efficient catalytic protocol for synthesizing 2-deoxy-β-glycosides via either IPrAuNTf 2 -catalyzed activation of a unique 1,2- trans -positioned C2- S -propargyl xanthate (OSPX) leaving group or (PhO) 3 PAuNTf 2 -catalyzed activation of a 1,2- trans -C2- ortho -alkynylbenzoate (OABz) substituent of the corresponding thioglycosides. These activation processes trigger 1,2-alkyl/arylthio-migration glycosylation, enabling the synthesis of structurally diverse 2-deoxy-β-glycosides under mild reaction conditions. The power of this strategy is demonstrated by the first synthesis of the pentasaccharide chain corresponding to velutinoside A, which features gold(I)-catalyzed construction of four successive β- l -oleandrosidic bonds in both a convergent and a one-pot glycosylation manner. Mechanistic studies, including control experiments and deuterium-labeling experiments, emphasize the crucial role of the OSPX and the involvement of the gold(I)-activated C≡C triple bond during the glycosylation process. The low-temperature NMR experiments unveiled a unique dual-coordination pattern of the gold(I) catalyst to the thiocarbonyl group and the alkynyl group of the OSPX, initiating a 5- exo -dig cyclization process. Furthermore, density functional theory (DFT) simulations reveal the ligand-induced match-mismatch effect between leaving groups OSPX and OABz and gold catalysts IPrAuNTf 2 and (PhO) 3 PAuNTf 2 . The DFT simulations also suggest that the formation of 2-deoxy-β-glycosidic bonds occurs via the bottom-face attack of the acceptor to the oxocarbenium intermediate, which adopts a 4 H 3 half-chair conformation, leading to an energetically favored, 4 C 1 -conformed intermediate Dβ that is stabilized by a hydrogen bonding interaction.}, archive = {J_JACS}, author = {Xianyang Wang and Han Ding and Aoxin Guo and Xiaofei Song and Peng Wang and Ni Song and Biao Yu and Peng Xu and Xue-Wei Liu and Ming Li}, doi = {10.1021/jacs.4c15805}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4469--4481}, shortjournal = {J. Am. Chem. Soc.}, title = {Gold(I)-catalyzed 2-deoxy-β-glycosylation via 1,2-Alkyl/Arylthio migration: Synthesis of velutinoside a pentasaccharide}, volume = {147}, year = {2025}, }
• (2025). Hydrogen tunneling and conformational motions in nonadiabatic proton-coupled electron transfer between interfacial tyrosines in ribonucleotide reductase. JACS, 147(5), 4459--4468. (www)

  @article{ , abstract = {Ribonucleotide reductase (RNR) is essential for DNA synthesis and repair in all living organisms. The mechanism of E. coli RNR requires long-range radical transport through a proton-coupled electron transfer (PCET) pathway spanning two different protein subunits. Herein, the direct PCET reaction between the interfacial tyrosine residues, Y356 and Y731, is investigated with a vibronically nonadiabatic theory that treats the transferring proton and all electrons quantum mechanically. The input quantities to the PCET rate constant expression are computed with a combination of density functional theory and molecular dynamics simulations. The calculations highlight the importance of hydrogen tunneling in this PCET reaction. Compression of the distance between the proton donor and acceptor oxygen atoms of the interfacial tyrosine residues is essential to facilitate hydrogen tunneling by increasing the overlap between the reactant and product proton vibrational wave functions. This compression occurs by thermal conformational fluctuations of these interfacial tyrosine residues. N733 and R411 are identified as key residues that can hydrogen bond to Y731 and Y356, respectively, and thereby compete with the hydrogen-bonding interaction between Y731 and Y356 required for direct PCET. Understanding the roles of hydrogen tunneling and conformational motions in this interfacial PCET reaction, as well as identifying other residues that may impact the kinetics, is important for targeted protein engineering efforts to modulate RNR activity.}, archive = {J_JACS}, author = {Jiayun Zhong and Qiwen Zhu and Alexander V. Soudackov and Sharon Hammes-Schiffer}, doi = {10.1021/jacs.4c15756}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4459--4468}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydrogen tunneling and conformational motions in nonadiabatic proton-coupled electron transfer between interfacial tyrosines in ribonucleotide reductase}, volume = {147}, year = {2025}, }
• (2025). A dual-pathway responsive mechanophore for intelligent luminescent polymer materials. JACS, 147(5), 4450--4458. (www)

  @article{ , abstract = {Mechanoluminescent units, when integrated into polymer matrices, undergo structural transformations in response to mechanical force, resulting in changes in fluorescence. This phenomenon holds considerable promise for the development of stress-sensing materials. Despite the high demand for robust, tunable mechanoluminescent mechanophores for force assessment and smart force-responsive materials, strategies for their design and synthesis remain underdeveloped. In an attempt to address this challenge, we have introduced a novel dual-pathway responsive mechanophore, bis(2-(2-( tert -butyldimethylsilanyloxy)benzylidene)amino)aryl disulfides ( SSTBS ), which, when incorporated into polymer chains, exhibits fluorescence upon the combined application of force and chemical stimulus, irrespective of their sequence. This property is facilitated by the disulfide bond’s sensitivity to mechanical force and the fluoride anion-induced desilylation and deprotonation. Notably, the force-responsive threshold of the SSTBS mechanophore can be finely tuned by TBAF treatment, as supported by both experimental and computational studies, providing a simple, yet effective means, to regulate polymer force responsiveness on demand. We believe that the strategy developed in this investigation will shed light on the design of mechanophores for the fabrication of intelligent luminescent polymer materials and advance the development of smart force-reporting systems.}, archive = {J_JACS}, author = {Dejing Xu and Maolin Wang and Ruozhou Huang and J. Fraser Stoddart and Yuping Wang}, doi = {10.1021/jacs.4c15655}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4450--4458}, shortjournal = {J. Am. Chem. Soc.}, title = {A dual-pathway responsive mechanophore for intelligent luminescent polymer materials}, volume = {147}, year = {2025}, }
• (2025). Tetrahedral lithium stuffing in disordered rocksalt cathodes for high-power-density and energy-density batteries. JACS, 147(5), 4438--4449. (www)

  @article{ , abstract = {Li-rich cation-disordered rocksalt (DRX) materials introduce new paradigms in the design of high-capacity Li-ion battery cathode materials. However, DRX materials show strikingly sluggish kinetics due to random Li percolation with poor rate performance. Here, we demonstrate that Li stuffing into the tetrahedral sites of the Mn-based rocksalt skeleton injects a novel tetrahedron-octahedron-tetrahedron diffusion path, which acts as a low-energy-barrier hub to facilitate high-speed Li transport. Moreover, the enhanced stability of lattice oxygen and the suppression of transition metal migration preserve the efficacy of the Li percolation network during cycling. Overall, the tetrahedral Li stuffing DRX material exhibits high energy density (311 mAh g –1 , 923 Wh kg –1 ) and high power density (251 mAh g –1 , 697 Wh kg –1 at 1000 mA g –1 ). Our results highlight the potential to develop high-performance and earth-abundant cathode materials within the extensive range of rocksalt compounds.}, archive = {J_JACS}, author = {Yu Mei and Yujin Li and Haoji Wang and Jinqiang Gao and Lianshan Ni and Debbie S. Silvester and Craig E. Banks and Wentao Deng and Baishan Chen and Guoqiang Zou and Hongshuai Hou and Tongchao Liu and Xiaobo Ji and Chaoping Liang and Khalil Amine}, doi = {10.1021/jacs.4c15631}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4438--4449}, shortjournal = {J. Am. Chem. Soc.}, title = {Tetrahedral lithium stuffing in disordered rocksalt cathodes for high-power-density and energy-density batteries}, volume = {147}, year = {2025}, }
• (2025). Dipnictogen radical chemistry: A dithorium-supported distibene radical trianion. JACS, 147(5), 4430--4437. (www)

  @article{ , abstract = {Although two examples of σ-bonded trans -bent [RSbSbR] •– (R = bulky organo- or Ga-groups) that formally contain the Sb 2 •3– radical trianion moiety are known in p-block chemistry, d- or f-element Sb 2 •3– radical trianion complexes, with or without R-substituents, have remained elusive. Here, we report that reduction of a 77:23 mix of [{Th(Tren TIPS )} 2 (μ-η 2 :η 2 -Sb 2 )] ( 3a , Tren TIPS = {N(CH 2 CH 2 NSiPr i 3 ) 3 } 3– ):[{Th(Tren TIPS )} 2 (μ-SbH)] ( 3b ) with 1.5 equiv of KC 8 in the presence of 1.1 equiv of 2.2.2-cryptand yields the emerald green Sb 2 •3– radical complex [K(2.2.2-cryptand)][{Th(Tren TIPS )} 2 (μ-η 2 :η 2 -Sb 2 )] ( 4 ), providing an f-block Sb 2 •3– radical trianion complex, and the heaviest actinide-N 2 radical analogue. When the recrystallization conditions are modified, a small crop of red crystals determined to be [K(2.2.2-cryptand)] 3 [{Th(Tren TIPS )(μ-η 3 :η 3 -Sb 3 )} 2 (μ-K)] ( 5 ) were also isolated, highlighting the complexity of heavy group 15 homodiatomic reduction chemistry. SQUID magnetometry and EPR spectroscopy suggest that the Sb 2 •3– radical trianion in 4 is fairly well isolated, due to electrostatic binding to Th, with pseudoaxial g -values reflecting the distinctive Sb 2 •3– radical trianion side-on bridging π-bonded coordination mode. Spectroscopically validated computational analysis of 3a and 4 confirms the stronger donating capability, and weaker Sb–Sb bond, of Sb 2 •3– radical trianion compared to the Sb 2 2– dianion form.}, archive = {J_JACS}, author = {Jingzhen Du and Kevin Dollberg and John A. Seed and Floriana Tuna and Ashley J. Wooles and Carsten von Hänisch and Stephen T. Liddle}, doi = {10.1021/jacs.4c15431}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4430--4437}, shortjournal = {J. Am. Chem. Soc.}, title = {Dipnictogen radical chemistry: A dithorium-supported distibene radical trianion}, volume = {147}, year = {2025}, }
• (2025). Basin-size mapping: Prediction of metastable polymorph synthesizability across TaC–TaN alloys. JACS, 147(5), 4419--4429. (www)

  @article{ , abstract = {The sizes of the basins of attraction on the potential energy surface are helpful indicators in determining the experimental synthesizability of metastable phases. In principle, these basins can be controlled with changes in thermodynamic conditions such as composition, pressure, and surface energy. Herein, we use random structure sampling to computationally study how alloying smoothly perturbs basin of attraction sizes. The TaC 1– x N x pseudobinary is an ideal test system given the structural and polymorphic contrast of its parent compounds and their technological relevance as epitaxial substrates for Al 1– x Ga x N. While we find limited thermodynamic stability across all computationally observed phases, random structure sampling shows a significant composition region where the rocksalt basin dominates. As such, we predict the potential for the nonequilibrium synthesis of metastable rocksalt TaC 1– x N x alloys as substrates for Al 1– x Ga x N. At higher nitrogen concentrations, other low-energy metastable polymorphs emerge that continue to retain the hexagonal close packing suitable for III–N growth. Confidence in these trends was established through uncertainty quantification of the basin sizes and energy distributions; such analysis utilized the Beta and Dirichlet distributions. We also find (a) polymorph basin sizes can be rationalized in terms of energetic preferences for different coordination environments; and (b) basin sizes universally shrink with increasing nitrogen content, making the system more prone to amorphous growth.}, archive = {J_JACS}, author = {Andrew Novick and Quan Nguyen and Matthew Jankousky and M. Brooks Tellekamp and Eric S. Toberer and Vladan Stevanović}, doi = {10.1021/jacs.4c15441}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4419--4429}, shortjournal = {J. Am. Chem. Soc.}, title = {Basin-size mapping: Prediction of metastable polymorph synthesizability across TaC–TaN alloys}, volume = {147}, year = {2025}, }
• (2025). Fully atomistic molecular dynamics simulation of ice nucleation near an antifreeze protein. JACS, 147(5), 4411--4418. (www)

  @article{ , abstract = {Heterogeneous ice nucleation is a widespread phenomenon in nature. Despite extensive research on ice nucleation near biological antifreeze proteins, a probe for ice nucleation and growth processes at the atomic level is still lacking. Herein, we present simulation evidence of the heterogeneous ice nucleation process on the ice-binding surface (IBS) of the Tenebrio molitor antifreeze protein (TmAFP). Our all-atomistic molecular dynamics simulations reveal detailed steps toward precritical nucleus formation from one-dimensional (1D) channel water to a 2D ice nanolayer and, finally, a 3D ice nucleus. Compared with homogeneous ice nucleation under the same supercooling conditions, the IBS of TmAFP can markedly reduce the critical size of the ice embryo and lower the nucleation free energy barrier, thereby favoring ice nucleation. Additionally, through artificial mutation of selected functional groups on the IBS, we gain deeper insights into how the specific functional groups of the IBS affect ice nucleation. We highlight that the carbonyl groups in the backbone play a crucial role by providing fixed locations for channel water. This function is essential for ensuring alignment between the 2D ice nanolayer and the ice lattice structure.}, archive = {J_JACS}, author = {Yue Zhang and Ning Wei and Liwen Li and Yuan Liu and Changxiong Huang and Zhen Li and Yujie Huang and Dengsong Zhang and Joseph S. Francisco and Junhua Zhao and Chunlei Wang and Xiao Cheng Zeng}, doi = {10.1021/jacs.4c15210}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4411--4418}, shortjournal = {J. Am. Chem. Soc.}, title = {Fully atomistic molecular dynamics simulation of ice nucleation near an antifreeze protein}, volume = {147}, year = {2025}, }
• (2025). Observation of robust compressed CuO6 octahedra and exotic spin structure in CaCuFe2O5. JACS, 147(5), 4403--4410. (www)

  @article{ , abstract = {CuO 6 octahedra usually show elongated distortion, leading to active d x 2 −y 2 orbitals and planar exchange interactions, while compressed CuO 6 octahedra with active d 3 z 2 − r 2 orbitals and unidirectional exchange interactions are exceptionally rare. Here, we design and synthesize a new frustrated antiferromagnet CaCuFe 2 O 5 through a high-pressure and high-temperature approach, in which robust compressed CuO 6 octahedra are realized, separating the Fe 2 O 5 sheets that comprise zigzag spin ladders. Magnetic susceptibility and specific heat measurements exhibit a long-range antiferromagnetic order below the Néel temperature of 165 K, which is further confirmed by neutron diffraction. Detailed magnetic refinement reveals a C-type spin structure, with its spin arrangement and orientation distinct from that of the isostructural CaFe 3 O 5 . By constructing a Heisenberg model, we find that this is due to the exchange redistribution between the CuO 6 octahedra and Fe 2 O 5 sheets, during which some of the exchange interactions are selectively annihilated due to the specific orientation of the Cu d 3 z 2 − r 2 orbitals in the compressed CuO 6 octahedra. Our results provide a unique example of robust compressed CuO 6 octahedra and show that it can selectively annihilate some of the exchange interactions and completely modify the spin structure and magnetic frustration accordingly.}, archive = {J_JACS}, author = {Maocai Pi and Junye Yang and Jie Zhang and Xubin Ye and Xiao Wang and Lunhua He and Zhiwei Hu and Chien-Te Chen and ChangYang Kuo and Zhao Pan and Yao Shen and Youwen Long}, doi = {10.1021/jacs.4c15326}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4403--4410}, shortjournal = {J. Am. Chem. Soc.}, title = {Observation of robust compressed CuO6 octahedra and exotic spin structure in CaCuFe2O5}, volume = {147}, year = {2025}, }
• (2025). Beyond polymerization: In situ coupled fluorination enables more stable interfaces for solid-state lithium batteries. JACS, 147(5), 4393--4402. (www)

  @article{ , abstract = {In situ polymerization strategies hold great promise for enhancing the physical interfacial stability in solid-state batteries, yet (electro)chemical degradation of polymerized interfaces, especially at high voltages, remains a critical challenge. Herein, we find interphase engineering is crucial for the polymerization process and polymer stability and pioneer an in situ polymerization-fluorination (Poly-FR) strategy to create durable interfaces with excellent physical and (electro)chemical stabilities, achieved by designing a bifunctional initiator for both polymerization and on-surface lithium donor reactions. The integrated in situ fluorination converts Li 2 CO 3 impurities on LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) surfaces into LiF-rich interphases, effectively inhibiting the aggressive (de)lithiation intermediates and protecting the interface from underlying chemical degradation, thereby surpassing the stability limitations of polymerization alone. Furthermore, the Poly-FR mediated symmetric Li|Li cells achieve an impressive cycling stability of up to 12,000 h. Solid-state cells with NCM811 cathodes and Li metal anodes realize an ultrastable cycling performance of 400 cycles with 83.4% retention at a high voltage of 4.5 V. This work points toward advanced in situ polymerization and beyond.}, archive = {J_JACS}, author = {Xunjie Yin and Yong Guo and Sijia Chi and Yiran Jia and Fangbing Li and Jiangshan Qi and Xuerui Yi and Shichao Wu and Quan-Hong Yang}, doi = {10.1021/jacs.4c15079}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4393--4402}, shortjournal = {J. Am. Chem. Soc.}, title = {Beyond polymerization: In situ coupled fluorination enables more stable interfaces for solid-state lithium batteries}, volume = {147}, year = {2025}, }
• (2025). From radical coupling to enantioselective controlled protonation: Advancing precise construction of stereocenters. JACS, 147(5), 4382--4392. (www)

  @article{ , abstract = {Recent advancements in green and sustainable platforms, particularly visible light-driven photocatalysis, have spurred significant progress in radical chemistry, enabling the efficient synthesis of important molecules from simple and readily available feedstocks under mild conditions. However, the rapid orbital flipping and high reactivity of radicals pose substantial challenges for achieving precise enantiocontrol in stereocenter formation via radical coupling. In this study, we present a generic and efficient strategy that modulates this elusive approach, facilitating enantiocontrollable protonation through 1,3-boron migration. We successfully developed two previously elusive photocatalytic asymmetric transformations: the de Mayo reaction utilizing energy transfer and three-component reactions of cyanoazaarenes initiated by single-electron transfer. Moreover, the incorporation of cost-effective D 2 O as a deuterium source enhances the synthetic and pharmaceutical significance of this method, offering a valuable tool for future applications.}, archive = {J_JACS}, author = {Xin Sun and Wenle Zhu and Yanli Yin and Xiaowei Zhao and Zhiyong Jiang}, doi = {10.1021/jacs.4c15276}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4382--4392}, shortjournal = {J. Am. Chem. Soc.}, title = {From radical coupling to enantioselective controlled protonation: Advancing precise construction of stereocenters}, volume = {147}, year = {2025}, }
• (2025). Molecular hydride superconductor BiH4 with tc up to 91 k at 170 GPa. JACS, 147(5), 4375--4381. (www)

  @article{ , abstract = {In pursuit of high- T c hydride superconductors, the molecular hydrides have attracted less attention because the hydrogen quasimolecules are usually inactive for superconductivity. Here, we report on the successful synthesis of a novel bismuth hydride superconductor C 2/ c -BiH 4 at pressures around 170–180 GPa. Its structure comprises bismuth atoms and elongated hydrogen molecules with a H–H bond length of 0.81 Å at 170 GPa, characterizing it as a typical molecular hydride. Transport measurements revealed the occurrence of superconductivity with T c up to 91 K at 170 GPa, as evidenced by a sharp drop of resistivity to zero and a characteristic downward shift of T c under magnetic fields. Calculations by density functional theory elucidate that both midfrequency H-derived phonons and low-frequency vibrations from Bi atoms are important for the strong electron–phonon coupling in BiH 4 , differentiating it from most high- T c superconducting hydrides. Our work not only places C 2/ c -BiH 4 among the molecular hydride superconductors with the highest T c but also offers new directions for designing and synthesizing more high- T c hydride superconductors.}, archive = {J_JACS}, author = {Pengfei Shan and Liang Ma and Xin Yang and Mei Li and Ziyi Liu and Jun Hou and Sheng Jiang and LiLi Zhang and Lifen Shi and Pengtao Yang and Chuanlong Lin and Bosen Wang and Jianping Sun and Haizhong Guo and Yang Ding and Huiyang Gou and Zhongxian Zhao and Jinguang Cheng}, doi = {10.1021/jacs.4c15137}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4375--4381}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular hydride superconductor BiH4 with tc up to 91 k at 170 GPa}, volume = {147}, year = {2025}, }
• (2025). Light-harvesting spin hyperpolarization of organic radicals in a Metal–Organic framework. JACS, 147(5), 4365--4374. (www)

  @article{ , abstract = {Light-driven spin hyperpolarization of organic molecules is a crucial technique for spin-based applications such as quantum information science (QIS) and dynamic nuclear polarization (DNP). Synthetic chemistry provides the design of spins with atomic precision and enables the scale-up of individual spins to hierarchical structures. The high designability and extended pore structure of metal–organic frameworks (MOFs) can control interactions between spins and guest molecules. However, the effective design of polarizing radical electron spins by photoexcitation in MOFs has been unexplored. Here, we show that it is possible to effectively hyperpolarize radical electron spins by harvesting mobile excitons in MOFs. As a proof of concept, we introduce 4-carboxy TEMPO molecules as electron spins into MOF-525, which contains an array of porphyrin chromophores, and demonstrate that this light-harvesting MOF system generates a spin-polarized excited quartet state and doublet ground state even by doping a small amount of electron spins. The current material design leads to the creation of highly spin-polarized nanospaces that can be used for quantum sensing and DNP by efficiently generating high-spin polarization in MOFs doped with small amounts of electron spins to prevent spin relaxation.}, archive = {J_JACS}, author = {Tomoyuki Hamachi and Miku Inoue and Masaaki Fuki and Teruyuki Honda and Reiya Yabuki and Bhavesh Parmar and Kiyoshi Miyata and Ken Onda and Takuma Ito and Yuki Kurashige and Yasuhiro Kobori and Nobuhiro Yanai}, doi = {10.1021/jacs.4c14916}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4365--4374}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-harvesting spin hyperpolarization of organic radicals in a Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Weak covalent bonds and mechanochemistry for synergistic self-strengthening of elastomers. JACS, 147(5), 4357--4364. (www)

  @article{ , abstract = {The macroscopic properties of elastomers are intimately linked to their molecular reactivity and mechanisms. Here, we propose a new strategy for designing strengthening materials based on the synergy of weak covalent bonds and mechanochemistry. After mechanical treatment, the failure strength and toughness of the elastomer increased from 2.37 ± 0.05 MPa and 11.34 ± 0.30 MJ/m 3 to 6.02 ± 0.04 MPa and 18.40 ± 0.30 MJ/m 3 , respectively, while maintaining excellent tensile properties. Notably, experimental tests, theoretical calculations, and small-molecule reaction model results show that the sulfur–carbon bond is more prone to homolysis, and the reactive sites are between sulfur radicals and the end-positioned carbon of the vinyl. The C–S weak bond of spirothiopyran (STP) first undergoes homolysis to dissipate energy suffering from external stress, and the radical-mediated click reaction leads to the interchain cross-linking, thus enhancing the mechanical strength. In the end, the prepared elastomer is further used to construct a photonic elastomer, which exhibits not only mechanical force-enhanced strength but also mechanochromism. The present work provides an opportunity for innovative design of self-strengthening materials, and the prepared novel self-strengthening elastomer has broad applications in visualized strain monitoring, electronic skin, soft robots, and other fields.}, archive = {J_JACS}, author = {Xuefen Li and Wensheng Zou and Wenshuai Zhao and Yudong Sun and Anyang Tang and Shufen Zhang and Wenbin Niu}, doi = {10.1021/jacs.4c14796}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4357--4364}, shortjournal = {J. Am. Chem. Soc.}, title = {Weak covalent bonds and mechanochemistry for synergistic self-strengthening of elastomers}, volume = {147}, year = {2025}, }
• (2025). High entropy: A general strategy for broadening the operating temperature of magnetic refrigeration. JACS, 147(5), 4349--4356. (www)

  @article{ , abstract = {Lattice distortion and disorder in the chemical environment of magnetic atoms within high-entropy compounds present intriguing issues in the modulation of magnetic functional compounds. However, the complexity inherent in high-entropy disordered systems has resulted in a relative scarcity of comprehensive investigations exploring the magnetic functional mechanisms of these alloys. Herein, we investigate the magnetocaloric effect (MCE) of the high-entropy intermetallic compound Gd 0.2 Tb 0.2 Dy 0.2 Ho 0.2 Er 0.2 Co 2 . Notably, the operating temperature range of the MCE broadens by an order of magnitude from 9 to 83 K while maintaining the refrigeration capacity compared to ErCo 2 . Atomic-scale microstructure analysis and atomic pair distribution function measurements reveal that lattice distortion stabilizes the cubic structure and induces disorder in the chemical environment of magnetic atoms. First-principles calculations point out that the enhanced average correlation energy raises the Curie temperature. The random distribution of elements across these sites induces local magnetic disorder around magnetic atoms with lower correlation energy, broadening the operating temperature range of MCE. This study not only significantly advances the understanding of the magnetic behavior of high-entropy alloys but also promotes the research progress of high-entropy functional compounds.}, archive = {J_JACS}, author = {Feixiang Long and Yuzhu Song and Hengchao Li and Yuanji Xu and Fuyang Tian and Yuanpeng Zhang and Tianyu Li and Hui Liu and Jiazheng Hao and Lunhua He and Xianran Xing and Fengxia Hu and Jun Chen}, doi = {10.1021/jacs.4c14759}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4349--4356}, shortjournal = {J. Am. Chem. Soc.}, title = {High entropy: A general strategy for broadening the operating temperature of magnetic refrigeration}, volume = {147}, year = {2025}, }
• (2025). Palladium-catalyzed oxidative Allene–Allene cross-coupling. JACS, 147(5), 4338--4348. (www)

  @article{ , abstract = {Direct cross-coupling reactions between two similar unactivated partners are challenging but constitute a powerful strategy for the creation of new carbon–carbon bonds in organic synthesis. [4]Dendralenes are a class of acyclic branched conjugated oligoenes with great synthetic potential for the rapid generation of structural complexity, yet the chemistry of [4]dendralenes remains an unexplored field due to their limited accessibility. Herein, we report a highly selective palladium-catalyzed oxidative cross-coupling of two allenes with the presence of a directing olefin in one of the allenes, enabling the facile synthesis of a broad range of functionalized [4]dendralenes in a convergent modular manner. Specifically, the selective allenic C–H activation of an allene with an allyl substituent as the assisting group gives rise to a vinylpalladium intermediate, which reacts with a less substituted allene in a carbopalladation, followed by a β-hydride elimination. The reaction sequence leads to a new C(sp 2 )–C(sp 2 ) bond between two diene units. Remarkably, this protocol provides an unconventional strategy for the site-selective and stereoselective construction of C(vinyl)–C(vinyl) bonds without using any halogenated and organometallics olefin precursors. Furthermore, the practical transformations of the synthesized [4]dendralenes and late-stage modifications of biorelevant molecules demonstrate their potential in the total synthesis of natural products and drug discovery.}, archive = {J_JACS}, author = {Haibo Wu and Qi Pan and Judith Grill and Magnus J. Johansson and Youai Qiu and Jan-E. Bäckvall}, doi = {10.1021/jacs.4c14607}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4338--4348}, shortjournal = {J. Am. Chem. Soc.}, title = {Palladium-catalyzed oxidative Allene–Allene cross-coupling}, volume = {147}, year = {2025}, }
• (2025). Vitamin b2 operates by dual thermodynamic and kinetic mechanisms to selectively tailor urate crystallization. JACS, 147(5), 4324--4337. (www)

  @article{ , abstract = {Here we demonstrate how a biologically relevant molecule, riboflavin (vitamin B2), operates by a dual mode of action to effectively control crystallization of ammonium urate (NH 4 HU), which is associated with cetacean kidney stones. In situ microfluidics and atomic force microscopy experiments confirm a strong interaction between riboflavin and NH 4 HU crystal surfaces that substantially inhibits layer nucleation and spreading by kinetic mechanisms of step pinning and kink blocking. Riboflavin does not alter the distribution of tautomeric urate isomers, but its adsorption on NH 4 HU crystal surfaces does interfere with the effects of minor urate tautomer by limiting its ability to induce NH 4 HU crystal defects while also suppressing NH 4 HU nucleation and inhibiting crystal growth by 80% at an uncharacteristically low modifier concentration. Time-resolved spectroscopy measurements, ab initio calculations, and molecular dynamics simulations confirm that each riboflavin molecule forms a complex with six or more urate molecules to lower supersaturation, thereby reducing the rate of NH 4 HU crystallization by a thermodynamically driven mechanism. The degree of complexation observed for riboflavin far exceeds that of common chelating agents, and results in crystal dissolution when the free urate concentration falls below NH 4 HU solubility. The synergism that is created by riboflavin’s dual kinetic and thermodynamic mechanisms is rarely achieved by more conventional crystal growth inhibitors. These insights offer new approaches that could be influential for the design of molecular modifiers in crystal engineering applications, the development of therapeutics for pathological conditions, and establishing broader understanding of the roles played by foreign agents in natural and biological crystallization.}, archive = {J_JACS}, author = {Si Li and Sungil Hong and Qizan Chen and Jenny Meegan and Celeste B. Parry and Jeetain Mittal and Giannis Mpourmpakis and Jeffrey D. Rimer}, doi = {10.1021/jacs.4c14629}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4324--4337}, shortjournal = {J. Am. Chem. Soc.}, title = {Vitamin b2 operates by dual thermodynamic and kinetic mechanisms to selectively tailor urate crystallization}, volume = {147}, year = {2025}, }
• (2025). Probing london dispersion in proton-bound onium ions: Are Alkyl–Alkyl steric interactions reliably modeled?. JACS, 147(5), 4308--4323. (www)

  @article{ , abstract = {We report spectroscopic and spectrometric experiments that probe the London dispersion interaction between tert -butyl substituents in three series of covalently linked, protonated bis -pyridines in the gas phase. Molecular ions in the three test series, along with several reference molecules for control, were electrosprayed from solution into the gas phase and then probed by infrared multiphoton dissociation spectroscopy and trapped ion mobility spectrometry. The observed N–H stretching frequencies provided an experimental readout diagnostic of the ground-state geometry of each ion, which could be furthermore compared to a second, independent structural readout via the collision cross section. In each of the three series, the strength of a London dispersion interaction could be modulated systematically by a progressive increase in the size of substituents from H to Me to tert -Bu. Parallel to the experimental study, extensive dispersion-corrected density functional theory (DFT-D3BJ) calculations were performed with a range of exchange correlation functionals. A full analysis of the conformational space for the flexible members of the series, and an analysis of the vibrational spectra in the context of a general double-well potential, finds that DFT-D3BJ appears to significantly overbind alkyl–alkyl interactions, specifically interactions between tert -Bu groups, even failing to predict the minimum energy structures reliably in the case of molecules in which London dispersion competes with other noncovalent interactions such as hydrogen bonding.}, archive = {J_JACS}, author = {Vladimir Gorbachev and Adélaïde Savoy and Alexandra Tsybizova and Robert Pollice and Lara van Tetering and Jonathan Martens and Jos Oomens and Giel Berden and Peter Chen}, doi = {10.1021/jacs.4c14525}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4308--4323}, shortjournal = {J. Am. Chem. Soc.}, title = {Probing london dispersion in proton-bound onium ions: Are Alkyl–Alkyl steric interactions reliably modeled?}, volume = {147}, year = {2025}, }
• (2025). Molecular processes that control organic electrosynthesis in near-electrode microenvironments. JACS, 147(5), 4296--4307. (www)

  @article{ , abstract = {Electrosynthesis at an industrial scale offers an opportunity to use renewable electricity in chemical manufacturing, accelerating the decarbonization of large-scale chemical processes. Organic electrosynthesis can improve product selectivity, reduce reaction steps, and minimize waste byproducts. Electrochemical synthesis of adiponitrile (ADN) via hydrodimerization of acrylonitrile (AN) is a prominent example of industrial organic electrochemical processes, with annual production reaching 0.3 MMT. It circumvents the drawbacks of thermochemical synthesis by reducing toxicity and leveraging clean electricity as an energy source. Despite its industrial importance, mechanistic understanding and experimental insights on the near-electrode molecular processes of AN electrohydrodimerization remain insufficient. Here we show, using in situ ATR-FTIR spectroscopy, that tetraalkylammonium ions populate the electrical double layer (EDL), creating a microenvironment that favors interactions with organic molecules and enhances AN concentration while expelling water molecules. Our results provide experimental evidence supporting long-standing mechanistic hypotheses. Kinetic isotope effect studies reveal that propionitrile (PN) formation is rate-limited by proton transfer, while ADN formation likely is not. Electron paramagnetic resonance spectroscopy confirms the presence of free radicals during AN electroreduction, suggesting that coupling of PN radicals occurs primarily in the electrolyte. These insights highlight the importance of carefully controlling the EDL composition for selective organic electrosynthesis and provide fundamental engineering guidance for designing high-performing electro-organic reactions. We anticipate these findings will guide the optimization of electrolyte formulations and electrode interfaces for ADN synthesis and other emerging electro-organic processes.}, archive = {J_JACS}, author = {Ricardo Mathison and Rasha Atwi and Hannah B. McConnell and Emilio Ochoa and Elina Rani and Toshihiro Akashige and Jason A. Röhr and André D. Taylor and Claudia E. Avalos and Eray S. Aydil and Nav Nidhi Rajput and Miguel A. Modestino}, doi = {10.1021/jacs.4c14420}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4296--4307}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular processes that control organic electrosynthesis in near-electrode microenvironments}, volume = {147}, year = {2025}, }
• (2025). Peptide-based complex coacervates stabilized by cation−π interactions for cell engineering. JACS, 147(5), 4284--4295. (www)

  @article{ , abstract = {Complex coacervation is a form of liquid–liquid phase separation, whereby two types of macromolecules, usually bearing opposite net charges, self-assemble into dense microdroplets driven by weak molecular interactions. Peptide-based coacervates have recently emerged as promising carriers to deliver large macromolecules (nucleic acids, proteins and complex thereof) inside cells. Thus, it is essential to understand their assembly/disassembly mechanisms at the molecular level in order to tune the thermodynamics of coacervates formation and the kinetics of cargo release upon entering the cell. In this study, we designed histidine-rich peptides consisting of modular sequences in which we systematically incorporate cationic, anionic, or aromatic residues at specific positions along the sequence in order to modulate intermolecular interactions and the resulting coacervation stability. We show that cation−π interactions between arginine and aromatic side chains are particularly efficient in stabilizing complex coacervates, and these interactions can be disrupted in the protein-rich intracellular environment, triggering the disassembly of complex coacervates followed by cargo release. With the additional grafting of a disulfide-based self-immolative side chain, these complex coacervates exhibited enhanced stability and could deliver proteins, mRNA, and CRISPR/Cas9 genome editing tools with tunable release kinetics into cells. This capability extends to challenging cell types, such as macrophages. Our study highlights the critical role of cation−π interactions in the design of peptide-based coacervates, expanding the biomedical and biotechnology potential of this emerging intracellular delivery platform.}, archive = {J_JACS}, author = {Yue Sun and Xi Wu and Jianguo Li and Chandra Shekhar Verma and Jing Yu and Ali Miserez}, doi = {10.1021/jacs.4c14469}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4284--4295}, shortjournal = {J. Am. Chem. Soc.}, title = {Peptide-based complex coacervates stabilized by cation−π interactions for cell engineering}, volume = {147}, year = {2025}, }
• (2025). Standardized approach for diversification of complex small molecules via aryl thianthrenium salts. JACS, 147(5), 4268--4283. (www)

  @article{ , abstract = {Thianthrenation is a useful strategy for the late-stage diversification of complex small molecules owing to the positional selectivity and the synthetic versatility of thianthrenium salts as electrophilic linchpins. However, substrate-dependent identification of suitable reaction conditions for thianthrenation can be difficult. Reported reaction conditions for the functionalization of thianthrenium salts vary significantly and, in some instances, lack robustness and practicality. Herein, we report a generalized approach for the preparation of thianthrenium salts and two reaction manifolds for practical, robust, and parallel diversification of thianthrenium salts.}, archive = {J_JACS}, author = {Dilgam Ahmadli and Sven Müller and Yuanhao Xie and Tomas Smejkal and Simon Jaeckh and Andrei V. Iosub and Simon R. Williams and Tobias Ritter}, doi = {10.1021/jacs.4c14391}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4268--4283}, shortjournal = {J. Am. Chem. Soc.}, title = {Standardized approach for diversification of complex small molecules via aryl thianthrenium salts}, volume = {147}, year = {2025}, }
• (2025). Intrinsic mechanical effects on the activation of carbon catalysts. JACS, 147(5), 4258--4267. (www)

  @article{ , abstract = {The mechanical effects on carbon-based metal-free catalysts (C-MFCs) have rarely been explored, despite the global interest in C-MFCs as substitutes for noble metal catalysts. Stress is ubiquitous, whereas its dedicated study is severely restricted due to its frequent entanglement with other structural variables, such as dopants, defects, and interfaces in catalysis. Herein, we report a proof-of-concept study by establishing a platform to continuously apply strain to a highly oriented pyrolytic graphite (HOPG) lamina, simultaneously collecting electrochemical signals. Notably, we establish, for the first time, the correlation between the surface strain of graphitic carbon and its activation effect on the oxygen reduction reaction (ORR). Our results indicate that while in-plane and edge carbon sites in HOPG could not be further activated by applying tensile strain, a strong and repeatable dependence of catalytic activity on tensile strain was observed when the structure incorporated in-plane defects, leading to a significant ∼35.0% improvement in ORR current density with the application of ∼0.6% tensile strain. Density functional theory (DFT) simulations reveal that appropriate strain on specific defects can optimize the adsorption of reaction intermediates, and the Stone–Wales defect on graphene is correlated with the observed mechanical effect. This work elucidates fundamental principles of strain effects on the catalytic activity of graphitic carbon toward ORR and may lay the groundwork for the development of carbon-based mechano-electrocatalysis.}, archive = {J_JACS}, author = {Bowen Liu and Shuaishuai Xu and Yang Gao and Xinying Luo and Junjie Xiong and Huihui Li and Zhongliang Yu and Lipeng Zhang and Qinghua Zhang and Shenlong Zhao and Binwei Zhang and Zhenhai Xia and Lan Chen and Baojie Feng and Liming Dai and Bin Wang}, doi = {10.1021/jacs.4c14372}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4258--4267}, shortjournal = {J. Am. Chem. Soc.}, title = {Intrinsic mechanical effects on the activation of carbon catalysts}, volume = {147}, year = {2025}, }
• (2025). Enantioselective synthesis of tetrahydro-1H-1,3-methanocarbazoles by formal (3 + 3)-cycloaddition using bicyclo[1.1.0]butanes. JACS, 147(5), 4249--4257. (www)

  @article{ , abstract = {Asymmetric synthesis presents many challenges, with the selective formation of chiral bridged polyheterocycles being a notable example. Cycloadditions using bicyclo[1.1.0]butanes (BCB) offer a promising solution along those lines, yet, despite significant advances in that emerging area, asymmetric control has remained limited thus far. Here, we describe an organocatalytic, enantioselective formal (3 + 3)-cycloaddition of BCBs with 1 H -indol-3-yl((hetero)aryl)methanol derivatives. This approach enables the rapid and efficient synthesis of chiral tetrahydro-1 H -1,3-methanocarbazole derivatives (34 examples) from readily available starting materials, with very good stereochemical control (up to 98:2 er ). Successful scale-up experiments and product modification demonstrated the potential of this methodology. Control experiments and DFT calculations provide insights into the mechanistic pathway.}, archive = {J_JACS}, author = {Shubham Dutta and Constantin G. Daniliuc and Christian Mück-Lichtenfeld and Armido Studer}, doi = {10.1021/jacs.4c14276}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4249--4257}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective synthesis of tetrahydro-1H-1,3-methanocarbazoles by formal (3 + 3)-cycloaddition using bicyclo[1.1.0]butanes}, volume = {147}, year = {2025}, }
• (2025). Dynamic kinetic resolution-based asymmetric transfer hydrogenation of racemic 2-substituted quinolines. JACS, 147(5), 4239--4248. (www)

  @article{ , abstract = {The synthesis of chiral tetrahydroquinolines (THQs) has garnered significant interest from medicinal chemists due to their frequent presence as pharmacophores in bioactive compounds. While existing synthetic methods have primarily focused on THQs with single or multiple endocyclic chiral centers, the selective construction of THQs with both endo- and exo- cyclic chiral centers remains a significant challenge that requires further development. This study introduces a dynamic kinetic resolution (DKR)-based transfer hydrogenation of racemic 2-substituted quinolines, which yields structurally novel chiral THQs with consecutive endo- and exo- cyclic chiral centers in excellent yields and stereoselectivities (59 examples, with generally >20:1 dr and >90% ee, up to three consecutive stereocenters). Our approach offers a mechanistically novel method for the asymmetric transformation of electron-deficient aromatic N-heterocycles and presents an innovative way to expand the chiral N-heterocycle chemical space for medicinal chemistry.}, archive = {J_JACS}, author = {Ming-Rong Liang and Xian Du and Jian Lin and Nianxin Rong and Xiaohang Zhan and Xinyue Mao and Haokun Zhuang and Tianyu Niu and Qin Yin}, doi = {10.1021/jacs.4c14200}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4239--4248}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic kinetic resolution-based asymmetric transfer hydrogenation of racemic 2-substituted quinolines}, volume = {147}, year = {2025}, }
• (2025). Diving into unknown waters: Water-soluble clickable au13 nanoclusters protected with N-heterocyclic carbenes for bio-medical applications. JACS, 147(5), 4230--4238. (www)

  @article{ , abstract = {The use of gold nanoclusters in biomedical applications has been steadily increasing in recent years. However, water solubility is a key factor for these applications, and water-soluble gold nanoclusters are often difficult to isolate and susceptible to exchange or oxidation in vivo. Herein, we report the isolation of N-heterocyclic carbene (NHC)-protected atomically precise gold nanoclusters functionalized with triethylene glycol monomethyl ether groups. These clusters are highly luminescent and water soluble and are shown to be stable in biological media. Importantly, the core structure, stability, and high quantum yield of the nanoclusters were conserved after backbone modification. Depending on the nature of the halide group, clusters have high stability in simulated biofluids and resist attack by glutathione. In vivo studies show that no abnormal cellular morphology is introduced in the kidney, liver, or spleen of mice treated with [Au 13 (NHC) 5 Br 2 ]Br 3 nanoclusters protected by 1,8-dimethylnaphthyl-linked NHCs. This cluster has a blood elimination half-life of 0.68 h. Functionalization of the wingtip groups of the cluster with azide groups is demonstrated, and complete reaction of all 10 azide groups with strained alkynes is shown, highlighting the potential of these clusters in biological settings.}, archive = {J_JACS}, author = {Angus I. Sullivan and Emily A. Steele and Shinjiro Takano and Elham Zeinizade and Juan Chen and Sami Malola and Kumar Siddhant and Hannu Häkkinen and Kevin G. Stamplecoskie and Tatsuya Tsukuda and Gang Zheng and Cathleen M. Crudden}, doi = {10.1021/jacs.4c14240}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4230--4238}, shortjournal = {J. Am. Chem. Soc.}, title = {Diving into unknown waters: Water-soluble clickable au13 nanoclusters protected with N-heterocyclic carbenes for bio-medical applications}, volume = {147}, year = {2025}, }
• (2025). Steering the absorption configuration of intermediates over pd-based electrocatalysts toward efficient and stable CO2 reduction. JACS, 147(5), 4219--4229. (www)

  @article{ , abstract = {Palladium (Pd) catalysts are promising for electrochemical reduction of CO 2 to CO but often can be deactivated by poisoning owing to the strong affinity of *CO on Pd sites. Theoretical investigations reveal that different configurations of *CO endow specific adsorption energies, thereby dictating the final performances. Here, a regulatory strategy toward *CO absorption configurations is proposed to alleviate CO poisoning by simultaneously incorporating Cu and Zn atoms into ultrathin Pd nanosheets (NSs). As-prepared PdCuZn NSs can catalyze CO production at a wide potential window (−0.28 to −0.78 V vs RHE) and achieve a maximum FE CO of 96% at −0.35 V. Impressively, it exhibits stable CO production of 100 h under ∼95% FE CO with no decay. Combined results from X-ray analysis, in situ spectroscopy, and theoretical simulations suggest that the codoping strategy not only optimizes the electronic structure of Pd but also weakens the binding strengths of *CO and increases the proportion of weak-binding linear *CO absorption configuration on catalysts’ surfaces. Such targeted adoption of weakly bound configurations abates the energy barrier of *CO desorption and facilitates CO production. This work confers a useful design tactic toward Pd-based electrocatalysts, codoping for steering adsorption configuration to achieve highly selective and stable CO 2 -to-CO conversion.}, archive = {J_JACS}, author = {Shuting Wei and Yanchao Xu and Tao Song and Hao Dai and Fan Li and Xin Gao and Yanjie Zhai and Shanhe Gong and Rui Li and Xiao Zhang and Kangcheung Chan}, doi = {10.1021/jacs.4c14253}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4219--4229}, shortjournal = {J. Am. Chem. Soc.}, title = {Steering the absorption configuration of intermediates over pd-based electrocatalysts toward efficient and stable CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). Superhydrophobic and self-healing porous organic macrocycle crystals for methane purification under humid conditions. JACS, 147(5), 4210--4218. (www)

  @article{ , abstract = {Purifying methane from natural gas using adsorbents not only requires the adsorbents to possess excellent separation performance but also to overcome additional daunting challenges such as humidity interference and durability requirements for sustainable use. Herein, porous organic crystals of a new macrocycle ( CaC9 ) with superhydrophobic and self-healing features are prepared and employed for the purification of methane (>99.99% purity) from ternary methane/ethane/propane mixtures under 97% relative humidity. The high selectivity for methane and water-resistance are attributed to the unique chemical structure of CaC9 , possessing an intrinsic 4.2 Å pore along with a pore environment modified with saturated alkyl chains. Besides, CaC9 crystals exhibit a self-healing capacity to realize in situ reconstruction of porosity within 15 min. The transformation of CaC9 crystals from a nonporous state to a porous state can be easily achieved upon treatment with n -hexane vapor, thereby presenting a novel solution to enhance the sustainable separation processes of porous materials. This work introduces a novel molecular-level porous adsorbent for natural gas separation, providing a valuable impetus for designing novel adsorbents with unexpected functions.}, archive = {J_JACS}, author = {Zeju Wang and Li Zhao and Zhenguo Zhang and Xinru Sheng and Hanlin Yue and Rui Liu and Zhongwen Liu and Yating Li and Li Shao and Yun−Lei Peng and Bin Hua and Feihe Huang}, doi = {10.1021/jacs.4c14130}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4210--4218}, shortjournal = {J. Am. Chem. Soc.}, title = {Superhydrophobic and self-healing porous organic macrocycle crystals for methane purification under humid conditions}, volume = {147}, year = {2025}, }
• (2025). Dual-ligand assisted anisotropic assembly for the construction of NIR-II light-propelled mesoporous nanomotors. JACS, 147(5), 4198--4209. (www)

  @article{ , abstract = {The advent of autonomous nanomotors presents exciting opportunities for nanodrug delivery. However, significant potential remains for enhancing the asymmetry of nanomotors and advancing the development of second near-infrared (NIR-II) light-propelled nanomotors capable of operating within deep tissues. Herein, we developed a dual-ligand assisted anisotropic assembly strategy that enables precise regulation of the interfacial energy between selenium (Se) nanoparticle and periodic mesoporous organosilica (PMO). This strategy facilitates the controllable anisotropic growth of PMO on the Se nanoparticle, leading to the formation of Se&PMO Janus nanohybrids. The exposure ratio of the Se subunit within the Janus nanohybrids can be finely tuned from 0% to 75%. Leveraging the transformability of the Se subunit, a variety of functional M x Se&PMO Janus nanocomposites (M x Se denotes metal selenide) were further derived. As a proof of concept, CuSe&PMO Janus nanohybrids, with NIR-II photothermal properties, were employed as NIR-II light-driven nanomotors. By precisely controlling the exposure ratio of the CuSe subunit within the Janus nanostructure, these CuSe&PMO nanomotors achieved optimal self-propulsion, thus enhancing cellular uptake and promoting deep tumor penetration. Furthermore, the high loading capacity and hydrophobic framework of the PMO subunit enabled the incorporation of hydrophobic disulfiram, thereby significantly boosting the efficacy of synergistic active-motion photothermal therapy.}, archive = {J_JACS}, author = {Jia Jia and Runfeng Lin and Minchao Liu and Mengmeng Hou and Hongyue Yu and Qianqian Lu and Yuzhu Ma and Tiancong Zhao and Fan Zhang and Mohamed F. Mady and Ahmed A. Elzatahry and Jiawen Wang and Yujin Ji and Dongyuan Zhao and Xiaomin Li}, doi = {10.1021/jacs.4c14011}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4198--4209}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual-ligand assisted anisotropic assembly for the construction of NIR-II light-propelled mesoporous nanomotors}, volume = {147}, year = {2025}, }
• (2025). Automated flow synthesis of artificial heme enzymes for enantiodivergent biocatalysis. JACS, 147(5), 4188--4197. (www)

  @article{ , abstract = {The remarkable efficiency with which enzymes catalyze small-molecule reactions has driven their widespread application in organic chemistry. Here, we employ automated fast-flow solid-phase synthesis to access catalytically active full-length enzymes without restrictions on the number and structure of noncanonical amino acids incorporated. We demonstrate the total syntheses of iron-dependent Bacillus subtilis myoglobin (BsMb) and sperm whale myoglobin (SwMb). The synthetic enzymes displayed excellent enantioselectivity and yield in carbene transfer reactions. Absolute control over enantioselectivity in styrene cyclopropanation was achieved using synthetic L- and D-BsMb mutants, which delivered each enantiomer of cyclopropane product in identical and opposite enantiomeric enrichment. BsMb mutants outfitted with noncanonical amino acids were used to facilitate detailed structure–activity relationship studies, revealing a previously unrecognized hydrogen-bonding interaction as the primary driver of enantioselectivity in styrene cyclopropanation. We anticipate that our approach will advance biocatalysis by providing reliable and rapid access to fully synthetic enzymes possessing noncanonical amino acids.}, archive = {J_JACS}, author = {Giulio Fittolani and Dennis A. Kutateladze and Andrei Loas and Stephen L. Buchwald and Bradley L. Pentelute}, doi = {10.1021/jacs.4c13832}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4188--4197}, shortjournal = {J. Am. Chem. Soc.}, title = {Automated flow synthesis of artificial heme enzymes for enantiodivergent biocatalysis}, volume = {147}, year = {2025}, }
• (2025). Radical S-adenosylmethionine sulfurtransferase MybB catalyzed formation of the 4-thiazolidinone core in mycobacidin represents an intersection between primary and secondary metabolism. JACS, 147(5), 4180--4187. (www)

  @article{ , abstract = {Mycobacidin is an antitubercular antibiotic structurally composed of a sulfur-containing 4-thiazolidinone ring, yet its biosynthesis including the mechanism of sulfur incorporation has remained an open question since its discovery in 1952. In this study, the mycobacidin biosynthetic gene cluster is identified from soil-dwelling Streptomyces , and the corresponding biosynthetic pathway starting with 7-oxoheptanoate is characterized. The radical SAM enzyme MybB catalyzes two sulfur insertion reactions, thereby bridging C 7 and C 10 to complete the 4-thiazolidinone heterocycle as the final step in mycobacidin maturation. MybB is a homologue of biotin synthase, and in both biosynthetic pathways, the bridging sulfur originates from the degradation of an enzymatic auxiliary [Fe 2 S 2 ] cluster. Introduction of the two C–S bonds during 4-thiazolidinone cyclization is shown to take place in a fixed sequence with the terminal C 10 –S bond generated first followed by the C 7 –S bond. MybB thus represents a generalization of biotin synthase activity that contributes to the maturation of not only primary but also secondary metabolites via sequential sulfur insertion reactions to yield sulfur containing heterocycles.}, archive = {J_JACS}, author = {Houyuan Zhao and Junling Bu and Hung-wen Liu}, doi = {10.1021/jacs.4c13760}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4180--4187}, shortjournal = {J. Am. Chem. Soc.}, title = {Radical S-adenosylmethionine sulfurtransferase MybB catalyzed formation of the 4-thiazolidinone core in mycobacidin represents an intersection between primary and secondary metabolism}, volume = {147}, year = {2025}, }
• (2025). A granzyme B-cleavable t cell-targeted bispecific cell vesicle connector for reversing new-onset type 1 diabetes. JACS, 147(5), 4167--4179. (www)

  @article{ , abstract = {Type 1 diabetes (T1D) is an autoimmune disorder in which pancreatic β-cells are destroyed by CD8 + T cells. Anti-CD3 antibody effectively treats early-stage T1D when β-cell autoantibodies are detected but before symptoms appear. However, it impairs the immune system temporarily, exposing individuals to infection. A therapeutic that can reverse new-onset T1D without harming the immune system remains urgently needed. Herein, we have constructed cellular vesicles presenting granzyme B-responsive fusion proteins (designated aCD8-GrzBcs-IL2) composed of a single-chain variable fragment of anti-CD8 antibodies and a mutein interleukin-2 (IL2). aCD8-GrzBcs-IL2 is designed to simultaneously inhibit CD8 + T cells and promote Treg cells, especially when CD8 + T cells are attacking β-cells. In vitro , these cellular vesicles can inhibit the cell-killing effect of CD8 + T cells and enhance the expansion of Treg cells. Notably, intravenous administration of aCD8-GrzBcs-IL2-expressed cellular vesicles reversed newly onset diabetes in 77.8% of nonobese diabetic (NOD) mice without reducing blood CD3 + T cells and CD8 + T cells, indicating a favorable safety profile.}, archive = {J_JACS}, author = {Yanfang Wang and Yanping Sun and Xiuwen Zhang and Shenqiang Wang and Xuehui Huang and Kairui Xu and Yun Liu and Yingqi Huang and Jianchang Xu and Xinwei Wei and Hao Cheng and Liqiang Pan and Jinqiang Wang and Zhen Gu}, doi = {10.1021/jacs.4c13644}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4167--4179}, shortjournal = {J. Am. Chem. Soc.}, title = {A granzyme B-cleavable t cell-targeted bispecific cell vesicle connector for reversing new-onset type 1 diabetes}, volume = {147}, year = {2025}, }
• (2025). Switchable acidic oxygen evolution mechanisms on atomic skin of ruthenium metallene oxides. JACS, 147(5), 4159--4166. (www)

  @article{ , abstract = {RuO 2 has been considered as a promising, low-cost, and highly efficient catalyst in the acidic oxygen evolution reaction (OER). However, it suffers from poor stability due to the inevitable involvement of the lattice oxygen mechanism (LOM). Here, we construct a unique metallene-based core-skin structure and unveil that the OER pathway of atomic RuO 2 skin can be regulated from the LOM to an adsorbate evolution mechanism by altering the core species from metallene oxides to metallenes. This switch is achieved without sacrificing the number of active sites, enabling Pd@RuO 2 metallenes to exhibit outstanding acidic OER activity with a low overpotential of 189 mV at 10 mA cm –2 , which is 54 mV lower than that of the counterpart PdO@RuO 2 metallenes. Additionally, they also exhibit robust stability with negligible activity decay over 100 h at 50 mA cm –2 , outperforming most reported RuO 2 -based catalysts. Multiple spectroscopic analyses and theoretical calculations demonstrate that the Pd-metallene core, acting as an electron donor, increases the migration energy of subsurface oxygen atoms and optimizes the adsorption energy of intermediates on the active Ru sites, enabling a switch in the reaction mechanism. Such a unique metallene-based core-skin structure offers a novel way for tuning the catalytic behaviors of electrocatalysts.}, archive = {J_JACS}, author = {Tianyi Gao and Dongxu Jiao and Lina Wang and Xin Ge and Xin Wen and Lei Zhang and Lirong Zheng and Xiaoxin Zou and Wei Zhang and Weitao Zheng and Jinchang Fan and Xiaoqiang Cui}, doi = {10.1021/jacs.4c13656}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4159--4166}, shortjournal = {J. Am. Chem. Soc.}, title = {Switchable acidic oxygen evolution mechanisms on atomic skin of ruthenium metallene oxides}, volume = {147}, year = {2025}, }
• (2025). Lipophilicity modulation of fluorescent probes for in situ imaging of cellular microvesicle dynamics. JACS, 147(5), 4147--4158. (www)

  @article{ , abstract = {Real-time monitoring of dynamic microvesicles (MVs), vesicles associated with living cells, is of great significance in deeply understanding their origin, transport, and function. However, specific labeling MVs poses a challenge due to the lack of unique biomarkers that differentiate them from other cellular compartments. Here, we present a strategy to selectively label MVs by evaluating a series of lipid layer-sensitive cationic indolium-coumarin fluorescent probes (designated as IC-C n , with n ranging from 1 to 18) that feature varying aliphatic side chains (C n H 2 n +1 ). Through in situ cell imaging and analysis, we found that IC-C n location is highly related to their lipophilicities and the phospholipid layer hydrophobic microenvironments in cellular compartments. In detail, IC-C1 and IC-C2 specifically localize MVs both inside and outside cells. In contrast, IC-C3, IC-C4, and IC-C5 label cellular MVs and mitochondria but with distinct fluorescence lifetimes. Using these probes strategically, we have discovered that, in addition to the biogenesis of MVs from plasma membranes and damaged mitochondria, newly formed MVs can undergo fusion and fission processes. Moreover, mitochondria-derived MVs, beyond being released from parent cells, can fuse with lysosomes to facilitate the removal of dysfunctional mitochondria. The work not only provides new insights into MV physiology but also inspires the design strategies for probes used in specific labeling in cell studies.}, archive = {J_JACS}, author = {Wei Huang and Guangmei Han and Dong Wang and Yingzhong Zhu and Hui Wang and Zhengjie Liu and Kajsa Uvdal and Junlong Geng and Zhangjun Hu and Ruilong Zhang and Zhongping Zhang}, doi = {10.1021/jacs.4c13516}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4147--4158}, shortjournal = {J. Am. Chem. Soc.}, title = {Lipophilicity modulation of fluorescent probes for in situ imaging of cellular microvesicle dynamics}, volume = {147}, year = {2025}, }
• (2025). Mechanically triggered protein desulfurization. JACS, 147(5), 4135--4146. (www)

  @article{ , abstract = {The technology of native chemical ligation and postligation desulfurization has greatly expanded the scope of modern chemical protein synthesis. Here, we report that ultrasonic energy can trigger robust and clean protein desulfurization, and we developed an ultrasound-induced desulfurization (USID) strategy that is simple to use and generally applicable to peptides and proteins. The USID strategy involves a simple ultrasonic cleaning bath and an easy-to-use and easy-to-remove sonosensitizer, titanium dioxide. It features mild and convenient reaction conditions and excellent functional group compatibility, e.g., with thiazolidine (Thz) and serotonin, which are sensitive to other desulfurization strategies. The USID strategy is robust: without reoptimizing the reaction conditions, the same USID procedure can be used for the clean desulfurization of a broad range of proteins with one or more sulfhydryl groups, even in multi-hundred-milligram scale reactions. The utility of USID was demonstrated by the one-pot synthesis of bioactive cyclopeptides such as Cycloleonuripeptide E and Segetalin F, as well as convergent chemical synthesis of functionally important proteins such as histone H3.5 using Thz as a temporary protecting group. A mechanistic investigation indicated that USID proceeds via a radical-based mechanism promoted by low-frequency and low-intensity ultrasonication. Overall, our work introduces a mechanically triggered approach with the potential to become a robust desulfurization method for general use in chemical protein synthesis by both academic and industrial laboratories.}, archive = {J_JACS}, author = {Dongyang Han and Yan Cui and Xiangyu Deng and Chuntong Li and Xianglai Zhu and Bingji Wang and Guo-Chao Chu and Zhipeng A. Wang and Shan Tang and Ji-Shen Zheng and Lu-Jun Liang and Lei Liu}, doi = {10.1021/jacs.4c13464}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4135--4146}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanically triggered protein desulfurization}, volume = {147}, year = {2025}, }
• (2025). Operando characterization of fe in doped Nix(Fe1–x)OyHz catalysts for electrochemical oxygen evolution. JACS, 147(5), 4120--4134. (www)

  @article{ , abstract = {Iron-doped nickel oxyhydroxides, Ni x (Fe 1– x )O y H z , are among the most promising oxygen evolution reaction (OER) electrocatalysts in alkaline environments. Although iron (Fe) significantly enhances the catalytic activity, there is still no clear consensus on whether Fe directly participates in the reaction or merely acts as a promoter. To elucidate the Fe’s role, we performed operando X-ray spectroscopy studies supported by DFT on Ni x (Fe 1– x )O y H z electrocatalysts. We probed the reversible changes in the structure and electronic character of Ni x (Fe 1– x )O y H z as the electrode potential is cycled between the resting (here at 1.10 V RHE ) and operational states (1.66 V RHE ). DFT calculations and XAS simulations on a library of Fe structures in various NiO y H z environments are in favor of a distorted local octahedral Fe(III)O 3 (OH) 3 configuration at the resting state with the NiO y H z scaffold going from α-Ni(OH) 2 to γ-NiOOH as the potential is increased. Under catalytic conditions, EXAFS and HERFD spectra reveal changes in p - d mixing (covalency) relative to the resting state between O/OH ligands and Fe leading to a shift from octahedral to square pyramidal coordination at the Fe site. XES measurements and theoretical simulations further support that the Fe equilibrium structure remains in a formal Fe(III) state under both resting and operational conditions. These spectral changes are attributed to potential dependent structural rearrangements around Fe. The results suggest that ligand dissociation leads to the C 4v symmetry as the most stable intermediate of the Fe during OER. This implies that Fe has a weakly coordinated or easily dissociable ligand that could serve to coordinate the O–O bond formation and, tentatively, play an active role in the Ni x (Fe 1– x )O y H z electrocatalyst.}, archive = {J_JACS}, author = {Joakim Halldin Stenlid and Mikaela Görlin and Oscar Diaz-Morales and Bernadette Davies and Vladimir Grigorev and David Degerman and Aleksandr Kalinko and Mia Börner and Mikhail Shipilin and Matthias Bauer and Alessandro Gallo and Frank Abild-Pedersen and Michal Bajdich and Anders Nilsson and Sergey Koroidov}, doi = {10.1021/jacs.4c13417}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4120--4134}, shortjournal = {J. Am. Chem. Soc.}, title = {Operando characterization of fe in doped Nix(Fe1–x)OyHz catalysts for electrochemical oxygen evolution}, volume = {147}, year = {2025}, }
• (2025). EPR characterization of the BlsE substrate radical offers insight into the determinants of reaction outcome that distinguish radical SAM dioldehydratases from dehydrogenases. JACS, 147(5), 4111--4119. (www)

  @article{ , abstract = {A small but growing set of radical SAM ( S -adenosyl- l -methionine) enzymes catalyze the radical mediated dehydration or dehydrogenation of 1,2-diol substrates. In some cases, these activities can be interchanged via minor structural perturbations to the reacting components raising questions regarding the relative importance of hyperconjugation, proton circulation and leaving group stability in determining the reaction outcome. The present work describes trapping and electron paramagnetic resonance (EPR) characterization of an α-hydroxyalkyl radical intermediate during dehydration and dehydrogenation of cytosylglucuronic acid and its derivatives catalyzed by the radical SAM enzyme BlsE and its Glu189Ala mutant from the blasticidin S biosynthetic pathway. The substrate radical is found to have a dihedral angle between the electron spin carrier p-orbital and the C–O bond to be cleaved that appears to be sufficient to support elimination despite lying outside the strictly periplanar region. A more significant contributor to the gating of dehydration activity, however, appears to be establishment of a proper hydrogen bonding configuration in order to stabilize the accumulation of negative charge on the eliminated hydroxyl group.}, archive = {J_JACS}, author = {Baixu Ma and Yu-Hsuan Lee and Mark W. Ruszczycky and Daan Ren and Amelia Engstrom and Hung-wen Liu and Lizhi Tao}, doi = {10.1021/jacs.4c13307}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4111--4119}, shortjournal = {J. Am. Chem. Soc.}, title = {EPR characterization of the BlsE substrate radical offers insight into the determinants of reaction outcome that distinguish radical SAM dioldehydratases from dehydrogenases}, volume = {147}, year = {2025}, }
• (2025). Two-photon-driven photoprotection mechanism in echinenone-functionalized orange carotenoid protein. JACS, 147(5), 4100--4110. (www)

  @article{ , abstract = {Orange carotenoid protein (OCP) is a photoactive protein that mediates photoprotection in cyanobacteria. OCP binds different ketocarotenoid chromophores such as echinenone (ECN), 3′- hydroxyechinenone (hECN), and canthaxanthin (CAN). In the dark, OCP is in an inactive orange form known as OCP O ; upon illumination, a red active state is formed, referred to as OCP R , that can interact with the phycobilisome. Large gaps still exist in the mechanistic understanding of the events between photon absorption and formation of the OCP R state. Recent studies suggested that more than one photon may be absorbed during the photocycle. Using a two-pulse excitation setup with variable time delays between the pulses, we demonstrate that canthaxanthin-functionalized OCP O forms the OCP R signature after absorption of a single photon. By contrast, OCP O complexed with hECN or ECN does not photoconvert to OCP R upon single photon absorption. Instead, OCP R is formed only upon absorption of a second photon arriving roughly one second after the first one, implying the existence of a metastable light-sensitive OCP 1hv intermediate. To the best of our knowledge, a sequential 2-photon absorption mechanism in a single biological photoreceptor chromophore is unique. It results in a nonlinear response function with respect to light intensity, effectively generating a threshold switch. In the case of OCP, this prevents down regulation of photosynthesis at low light irradiance.}, archive = {J_JACS}, author = {Stanisław Niziński and Elisabeth Hartmann and Robert L. Shoeman and Mirosław Tarnawski and Adjélé Wilson and Jochen Reinstein and Diana Kirilovsky and Michel Sliwa and Gotard Burdziński and Ilme Schlichting}, doi = {10.1021/jacs.4c13341}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4100--4110}, shortjournal = {J. Am. Chem. Soc.}, title = {Two-photon-driven photoprotection mechanism in echinenone-functionalized orange carotenoid protein}, volume = {147}, year = {2025}, }
• (2025). Anion-modulated solvation sheath and electric double layer enabling lithium-ion storage from −60 to 80 °C. JACS, 147(5), 4089--4099. (www)

  @article{ , abstract = {Current lithium batteries experience significant performance degradation under extreme temperature conditions, both high and low. Traditional wide-temperature electrolyte designs typically addressed these challenges by manipulating the solvation sheath and selecting solvents with extreme melting/boiling points. However, these solvent-mediated solutions, while effective at one temperature extreme, invariably fail at the opposite end due to the inherent difficulties in maintaining solvent stability across wide temperatures. Herein, we report the use of the main lithium salt to simultaneously address interfacial challenges at both extremely high and low temperatures. This approach is different from the conventional solvent-mediated strategies. As a proof of concept, we utilized lithium nitrate (LiNO 3 ) to establish an anion-controlled solvation structure and electric double layer. The formulated electrolytes exhibited remarkable performance across temperature extremes, retaining 56.1% capacity at −60 °C and sustaining 400 stable cycles at 80 °C. In contrast, electrolytes based on current solvent-mediated strategies failed to operate at −60 °C and could not exceed 50 cycles at 80 °C. By shifting the focus to the main salt rather than the solvent, our work offers the possibility of addressing the enduring challenges of electrolyte stability across a broad temperature range.}, archive = {J_JACS}, author = {Song Yuan and Shengkai Cao and Xi Chen and Jiaqi Wei and Zhisheng Lv and Huarong Xia and Lixun Chen and Rayner Bao Feng Ng and Fu Lun Tan and Haicheng Li and Xian Jun Loh and Shuzhou Li and Xue Feng and Xiaodong Chen}, doi = {10.1021/jacs.4c13011}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4089--4099}, shortjournal = {J. Am. Chem. Soc.}, title = {Anion-modulated solvation sheath and electric double layer enabling lithium-ion storage from −60 to 80 °C}, volume = {147}, year = {2025}, }
• (2025). On-line inductively coupled plasma mass spectrometry reveals material degradation dynamics of au and cu catalysts during electrochemical CO2 reduction. JACS, 147(5), 4079--4088. (www)

  @article{ , abstract = {A significant challenge in commercializing electrochemical CO 2 reduction (CO 2 R) is achieving catalyst durability. In this study, online inductively coupled mass spectrometry (ICP–MS) was used to investigate catalyst degradation via nanoparticle detachment and/or dissolution into metal ions under CO 2 R operating conditions in 0.1 M KHCO 3 . We developed an experimental framework with ex situ characterization to validate the online ICP–MS method for in situ evaluation of degradation from metal foils. By varying the applied potential and microenvironment (CO 2 vs N 2 -saturated electrolyte), we gained insights into the degradation of Au and Cu foils under CO 2 R and hydrogen evolution reaction (HER) conditions. While both Au and Cu foils were observed to be stable to dissolution in these regimes, degradation via nanoparticle detachment from the foil surface at the femtogram scale was observed as a function of reaction conditions, providing new insights into material degradation mechanisms. When applying potential steps at −0.1 and −1.0 V vs the reversible hydrogen electrode (RHE), Au was found to degrade via nanoparticle detachment under CO 2 R operating conditions more than under HER conditions, while Cu was found to degrade via nanoparticle detachment in similar amounts during both reactions. Au lost ∼1.8× more mass and ∼7.5× more nanoparticles than Cu under CO 2 R operating conditions. This study demonstrates the use of online ICP–MS to gain insight into the degradation of Au and Cu, the importance of studying unconventional degradation mechanisms such as nanoparticle detachment, and that online ICP–MS can be further utilized to gain fundamental understanding of catalyst durability for a variety of reaction systems.}, archive = {J_JACS}, author = {Katherine Yan and Sang-Won Lee and Kyra M. K. Yap and Aniket S. Mule and Ryan T. Hannagan and Jesse E. Matthews and Gaurav A. Kamat and Dong Un Lee and Michaela Burke Stevens and Adam C. Nielander and Thomas F. Jaramillo}, doi = {10.1021/jacs.4c13233}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4079--4088}, shortjournal = {J. Am. Chem. Soc.}, title = {On-line inductively coupled plasma mass spectrometry reveals material degradation dynamics of au and cu catalysts during electrochemical CO2 reduction}, volume = {147}, year = {2025}, }
• (2025). Temperature-adaptive organic scintillators for X-ray radiography. JACS, 147(5), 4069--4078. (www)

  @article{ , abstract = {Organic phosphorescence or thermally activated delayed fluorescence (TADF) scintillators, while effective in utilizing triplet excitons, are sensitive to temperature changes, which can impact radioluminescence performance. In this study, we have developed a type of temperature-adaptive organic scintillator with phosphorescence and TADF dual emission. These scintillators can automatically switch modes with temperature changes, enabling efficient radioluminescence from 77 to 400 K. The highest photoluminescence quantum yield and light yield are 83.2% and 78,229 ± 562 photons MeV –1 excited by a UV lamp and X-ray, respectively. Their detection limit is 51 and 23 nGy·s –1 at room temperature and 77 K, respectively, which is lower than the standard dosage of 5.5 μGy s –1 for X-ray diagnostics. Moreover, given the high spatial resolution of 21.7 l p mm –1 , we demonstrate their potential application in multiple-temperature X-ray radiography, offering promising new possibilities. This work opens a new route for developing organic scintillators to adapt to ambient temperature change and paves the way for their use in various temperature-sensitive radiography applications.}, archive = {J_JACS}, author = {Mengyang Dong and Ziyang Wang and Zhenyi Lin and Yushan Zhang and Zhengkang Chen and Yiming Wu and Huili Ma and Zhongfu An and Long Gu and Wei Huang}, doi = {10.1021/jacs.4c12872}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4069--4078}, shortjournal = {J. Am. Chem. Soc.}, title = {Temperature-adaptive organic scintillators for X-ray radiography}, volume = {147}, year = {2025}, }
• (2025). Structural basis of ultralow capacitances at Metal–Nonaqueous solution interfaces. JACS, 147(5), 4060--4068. (www)

  @article{ , abstract = {Metal–nonaqueous solution interfaces, a key to many electrochemical technologies, including lithium metal batteries, are much less understood than their aqueous counterparts. Herein, on several metal–nonaqueous solution interfaces, we observe capacitances that are 2 orders of magnitude lower than the usual double-layer capacitance. Combining electrochemical impedance spectroscopy, atomic force microscopy, and physical modeling, we ascribe the ultralow capacitance to an interfacial layer of 10–100 nm above the metal surface. This nanometric layer has a Young’s modulus around 2 MPa, which is much softer than typical solid-electrolyte interphase films. In addition, its AC ionic conductivity is 4-to-5 orders of magnitude lower than that of the bulk electrolyte. The temperature dependencies of the AC ionic conductivity and thickness suggest that the soft layer is formed from metal-mediated, dipole–dipole interactions of the nonaqueous solvent molecules. The observed soft layer opens new avenues of modulating battery performance via rational design of ion transport, (de)solvation, and charge transfer in this interfacial region.}, archive = {J_JACS}, author = {Juan Chen and Zengming Zhang and Xiaoting Yin and Chenkun Li and Fengjiao Yu and Yuping Wu and Jiawei Yan and Jun Huang and Yuhui Chen}, doi = {10.1021/jacs.4c12443}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4060--4068}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural basis of ultralow capacitances at Metal–Nonaqueous solution interfaces}, volume = {147}, year = {2025}, }
• (2025). Length-dependent conduction of polyynes: Searching for the limit of the tunneling regime. JACS, 147(5), 4052--4059. (www)

  @article{ , abstract = {Rigid, conjugated molecules are excellent candidates as molecular wires since they can achieve full extension between electrodes while maintaining conjugation. Molecular design can be used to minimize the accessible pi surface and interactions between the bridging wire and the electrode. Polyynes are archetypal molecular wires that feature a rigid molecular framework with a cross-section of a single carbon atom. Understanding the behavior of polyynes in molecular junctions is essential for testing models of length versus electron transport. We report the construction of molecular junctions using polyynes with a well-defined length up to ca. 5 nm in devices characterized by scanning tunneling microscopy break junctions. The polyynes, Py**[ n ] ( n = 4, 6, 8, 10, 12, 16), are end-capped with pyridyl groups, and we demonstrate good agreement between the length of the molecular junction and the calculated molecular length, with an average discrepancy of just 0.1 nm. This highlights the power of STM-BJ experiments to accurately determine the molecular length. The range of molecular lengths, from 1.8 to 4.8 nm, mark this as the most accurate determination of β in polyynes to date (β = 2.2 ± 0.1 nm –1 ). We have applied a model based on the single and triple bond lengths to interpret β-values, which predicts β = 1.9 nm –1 , consistent with the experimental value. This model also confirms that electronic coupling in polyynes is unaffected by the rotation about the single bonds. At all molecular lengths, we observe conductance in the tunneling regime due to the long effective conjugation length of polyynes.}, archive = {J_JACS}, author = {Yueze Gao and Edmund Leary and Lucía Palomino-Ruiz and José M. Malagón and M. Teresa González and Maximilian Krempe and Matthew Johnson and Rik R. Tykwinski}, doi = {10.1021/jacs.4c12895}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4052--4059}, shortjournal = {J. Am. Chem. Soc.}, title = {Length-dependent conduction of polyynes: Searching for the limit of the tunneling regime}, volume = {147}, year = {2025}, }
• (2025). Hydride formation and decomposition on cu(111) in HClO4. JACS, 147(5), 4038--4051. (www)

  @article{ , abstract = {Cu electrodeposition and the electrocatalysis of hydrogenation reactions thereupon involve significant interactions with adsorbed hydrogen. Electrochemical mass spectrometry (EC-MS) is used to explore the formation and decomposition of surface hydride on Cu(111) in 0.1 mol L –1 HClO 4 . Hydride formation is associated with two reduction waves that reflect the potential-dependent H ads coverage and its reconstruction. Voltammetric cycling reveals an additional oxidative and reductive feature at ≈ −0.05 V versus the reversible hydrogen electrode (RHE) that reflects the state of the 2D surface hydride. Extending the voltammetric window to more negative potentials results in an increase in H ads coverage and surface reconstruction that subsequently leads to accelerated hydride decomposition at positive potentials. Voltammetric and chronoamperometric analysis of hydride formation indicates a H ads coverage of ≈0.75 monolayers (ML) between −0.225 V vs RHE and −0.275 V vs RHE with further increases in H ads observed with the onset and acceleration of the HER at more negative potentials. Returning to more positive potentials, hydride decomposition begins above −0.05 V vs RHE. Recombination of H ads to form H 2 accounts for desorption of ≈0.5 ML of H ads while its oxidation to H 3 O + consumes between ≈0.15 and ≈0.4 ML of H ads , depending on the specific electrochemical conditions. The potential-dependent H ads coverage and surface reconstruction are congruent with trends identified in recent computational and electrochemical scanning tunneling microscopy studies. In contrast to perchloric acid, the presence of strongly adsorbing anions, such as sulfate or halides, favors hydride decomposition via the recombination pathway.}, archive = {J_JACS}, author = {David Raciti and Thomas P. Moffat}, doi = {10.1021/jacs.4c12782}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4038--4051}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydride formation and decomposition on cu(111) in HClO4}, volume = {147}, year = {2025}, }
• (2025). Gas–Liquid interface of aqueous solutions of surface active aromatic molecules studied using extreme ultraviolet laser photoelectron spectroscopy and molecular dynamics simulation. JACS, 147(5), 4026--4037. (www)

  @article{ , abstract = {We investigated the gas–liquid interface of aqueous solutions containing phenol and related aromatic compounds using extreme ultraviolet laser photoelectron spectroscopy and molecular dynamics simulations. The interfacial densities of protonated and deprotonated forms of phenol, aniline, and 4-nitrophenol were found to be primarily determined by their surface affinities and exhibit similar concentration dependences to their respective bulk densities. Despite the distinct interfacial orientations of their permanent dipole moments, these compounds monotonically decreased the surface potential at higher concentrations. The exception was sodium phenolate, whose surface potential first increased and then decreased with increasing concentration. This behavior is attributed to the opposing effects of the electric double layer formed by Na + and phenolate ions at the gas–liquid interface and the induced electronic polarization of phenolate.}, archive = {J_JACS}, author = {Yo-ichi Yamamoto and Tomonori Hirano and Tatsuya Ishiyama and Akihiro Morita and Toshinori Suzuki}, doi = {10.1021/jacs.4c12310}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4026--4037}, shortjournal = {J. Am. Chem. Soc.}, title = {Gas–Liquid interface of aqueous solutions of surface active aromatic molecules studied using extreme ultraviolet laser photoelectron spectroscopy and molecular dynamics simulation}, volume = {147}, year = {2025}, }
• (2025). Impact of ligand structure on biological activity and photophysical properties of NHC-protected au13 nanoclusters. JACS, 147(5), 4017--4025. (www)

  @article{ , abstract = {N-heterocyclic carbene (NHC)-protected gold nanoclusters display high stability and high photoluminescence, making them well-suited for fluorescence imaging and photodynamic therapeutic applications. We report herein the synthesis of two bisNHC-protected Au 13 nanoclusters with π-extended aromatic systems. Depending on the position of the π-extended aromatic system, changes to the structure of the ligand shell in the cluster are observed, with the ability to correlate increases in rigidity with increases in fluorescence quantum yield. Density functional theory analysis reveals that both synthesized Au 13 nanoclusters are 8-electron superatoms but have distinct differences in the characteristics of the lowest unoccupied single-electron states. Qualitatively, this implies different mechanisms for excitations and their decay over the fundamental energy gap. Stability and photophysical studies were carried out to provide the emission lifetime and optical purity of the two clusters. Active intracellular uptake of the nanoclusters was confirmed in vitro using confocal microscopy in human epithelial carcinoma cells. Reactive oxygen species production was measured at 7% efficiency. The high cluster stability, photoluminescence quantum yields, and efficient cellular uptake in cancer cells suggest potential for these nanoclusters as highly efficient and tunable nanomedical platforms.}, archive = {J_JACS}, author = {Viveka K. Kulkarni and Emily L. Albright and Elham Zeinizade and Emily Steele and Juan Chen and Lili Ding and Sami Malola and Shinjiro Takano and Kristen Harrington and Nahyun Kwon and Tetyana I. Levchenko and Masakazu Nambo and Tatsuya Tsukuda and Hannu Häkkinen and Kevin Stamplecoskie and Gang Zheng and Cathleen M. Crudden}, doi = {10.1021/jacs.4c12072}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4017--4025}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of ligand structure on biological activity and photophysical properties of NHC-protected au13 nanoclusters}, volume = {147}, year = {2025}, }
• (2025). High-pressure neutron diffraction study on ε-FeOOH: The spin-reorientation transition and hydrogen-bond symmetrization. JACS, 147(5), 4005--4016. (www)

  @article{ , abstract = {The compression behavior of iron oxyhydroxide ε-FeOOH is complex, with variations in its magnetic property and bonding character. In this study, in situ powder neutron diffraction experiments were conducted on ε-FeOOH and ε-FeOOD up to pressures exceeding 20 GPa to investigate a spin-reorientation (spin-flop) transition, hydrogen-bond (H-bond) symmetrization, and their correlation. The magnetic transition was observed at 8 GPa in both ε-FeOOH and ε-FeOOD. The Fe-spins aligned in an A-type antiferromagnetic order and reoriented from the c -direction to the b -direction above 8 GPa. The crystal symmetry and H-bonds of ε-FeOOH transitioned from P 2 1 nm with asymmetric H-bonds to Pnnm with disordered H-bonds at 17.90 GPa, while ε-FeOOD remained asymmetric. The pressure evolution of the interatomic angles and distances indicates that the coordinate geometry of Fe transitioned toward H-bond symmetrization and would have affected the magnetic anisotropy. This study provides insights into the pressure effect of the magnetic transition on compounds containing hydrogen bonds.}, archive = {J_JACS}, author = {Osamu Ikeda and Hajime Yamamoto and Asami Sano-Furukawa and Tatsuya Sakamaki and Takahiro Kuribayashi and Yukio Noda and Akio Suzuki}, doi = {10.1021/jacs.4c11982}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {4005--4016}, shortjournal = {J. Am. Chem. Soc.}, title = {High-pressure neutron diffraction study on ε-FeOOH: The spin-reorientation transition and hydrogen-bond symmetrization}, volume = {147}, year = {2025}, }
• (2025). Atomically dispersed Co–P moieties via direct thermal exfoliation for alkaline hydrogen electrosynthesis. JACS, 147(5), 3994--4004. (www)

  @article{ , abstract = {The development of highly active and stable cathodes in alkaline solutions is crucial for promoting the commercialization of anion exchange membrane (AEM) electrolyzers, yet it remains a significant challenge. Herein, we synthesized atomically dispersed CoP 4 moieties (CoP 4 –SSC) immobilized on ultrathin carbon nanosheets via a phosphidation exfoliation strategy at medium temperature. The thermodynamic formation process of the Co–P moieties was elucidated using X-ray absorption spectroscopy (XAS) and theoretical calculations. Remarkably, the resulting CoP 4 –SSC electrocatalyst exhibited outstanding activity for alkaline hydrogen evolution, with a low overpotential of 52 mV at 10 mA cm –2 and a turnover frequency of up to 23.83 s –1 . Moreover, the AEM electrolyzer fabricated with CoP 4 –SSC achieved a current density of 1 A cm –2 under an applied voltage of only 1.94 V, showing negligible degradation after 500 h of continuous electrocatalysis. A series of operando characterizations and density functional theory calculations revealed that the atomically dispersed Co–P moieties formed a nanointerface of [P-*H···H 2 O*-Co], which facilitates water dissociation during the Volmer–Heyrovsky pathway.}, archive = {J_JACS}, author = {Zheng Zhou and Yixin Su and Hao Tan and Yang Wang and Qianwei Huang and Haozhu Wang and Jingyang Wang and Momoji Kubo and Zitao Ni and Yuan Kong and Shenlong Zhao}, doi = {10.1021/jacs.4c11788}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {3994--4004}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomically dispersed Co–P moieties via direct thermal exfoliation for alkaline hydrogen electrosynthesis}, volume = {147}, year = {2025}, }
• (2025). Synthesis, structure, and redox reactivity of ni complexes bearing a redox and Acid–Base non-innocent ligand with NiII, NiIII, and NiIV formal oxidation states. JACS, 147(5), 3981--3993. (www)

  @article{ , abstract = {A series of Ni complexes bearing a redox and acid–base noninnocent tetraamido macrocyclic ligand, H 4 -(TAML-4) {H 4 -(TAML-4) = 15,15-dimethyl-5,8,13,17-tetrahydro-5,8,13,17-tetraaza-dibenzo[ a,g ]cyclotridecene-6,7,14,16-tetraone}, with formal oxidation states of Ni II , Ni III , and Ni IV were synthesized and characterized structurally and spectroscopically. The X-ray crystallographic analysis of the Ni complexes revealed a square planar geometry, and the [Ni(TAML-4)] complex with the formal oxidation state of Ni IV was characterized to be [Ni III (TAML-4 •+ )] with the oxidation state of the Ni III ion and the one-electron oxidized TAML-4 ligand, TAML-4 •+ . The Ni III oxidation state and the TAML-4 radical cation ligand, TAML-4 •+ , were supported by X-ray absorption spectroscopy and density functional theory calculations. The reversible interconversions between [Ni II (TAML-4)] 2– and [Ni III (TAML-4)] − and between [Ni III (TAML-4)] − and [Ni III (TAML-4 •+ )] were demonstrated in spectroelectrochemical measurements as well as in chemical oxidation and reduction reactions. The reactivities of [Ni III (TAML-4)] − and [Ni III (TAML-4 •+ )] were then investigated in hydride transfer reactions using NADH analogs. Hydride transfer from 9,10-dihydro-10-methylacridine (AcrH 2 ) to [Ni III (TAML-4 •+ )] was found to proceed via electron transfer (ET) from AcrH 2 to [Ni III (TAML-4 •+ )] with no deuterium kinetic isotope effect ( k H / k D = 1.0(2)). In contrast, hydride transfer from AcrH 2 to [Ni III (TAML-4)] − proceeded much more slowly via a concerted proton-coupled electron transfer (PCET) process with k H / k D = 7.0(5). In the latter reaction, an electron and a proton were transferred to the Ni III center and the TAML-4 ligand, respectively. The mechanisms of the ET by [Ni III (TAML-4 •+ )] and the concerted PCET by [Ni III (TAML-4)] − were ascribed to the different redox potentials of the Ni complexes.}, archive = {J_JACS}, author = {Deepika G. Karmalkar and Hyeongtaek Lim and Mahesh Sundararajan and Yong-Min Lee and Mi Sook Seo and Dae Young Bae and Xiaoyan Lu and Britt Hedman and Keith O. Hodgson and Won-Suk Kim and Eunsung Lee and Edward I. Solomon and Shunichi Fukuzumi and Wonwoo Nam}, doi = {10.1021/jacs.4c11751}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {3981--3993}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis, structure, and redox reactivity of ni complexes bearing a redox and Acid–Base non-innocent ligand with NiII, NiIII, and NiIV formal oxidation states}, volume = {147}, year = {2025}, }
• (2025). Coherent strain-inhibiting phase construction of lithium-rich manganese-based oxide toward high mechanochemical stability. JACS, 147(5), 3967--3980. (www)

  @article{ , abstract = {A layered lithium-rich manganese-based oxide cathode, containing R 3̅ m (LiTMO 2 , TM = Mn, Ni, Co) and C 2/ m (Li 2 MnO 3 ) nanodomains, utilizes both transition metals and oxygen redox to yield substantial energy density. However, the inherent heterogeneous nature and distinct nanodomain redox chemistries of layered lithium-rich oxides will inevitably cause pernicious lattice strain and structural displacement, which can hardly be eliminated by conventional doping or coating strategies and result in accelerated performance decay. Herein, we incorporate a strain-inhibiting perovskite phase coherently grown within the layered structure to effectively restrain the displacement and lattice strain during uneven Li-ion extraction. The enhanced mechanochemical stability of the designed cathode benefits the persistent structure and reversible oxygen redox, thereby achieving high initial Coulombic efficiency and stable cycling and voltage profiles. Our approach of lattice engineering alleviates the strain and displacement caused by inhomogeneous reactivity between heterogeneous nanodomains and promotes the development of advanced cathode materials with long durability.}, archive = {J_JACS}, author = {Zhou Xu and Xingzhong Guo and Xuemei Zeng and Junxiang Liu and Jingran Yin and Minglu Ren and Junzhang Wang and Tengteng Qin and Zhizhen Zhang and Luxi Li and Khalil Amine and Yifei Yuan and Tongchao Liu}, doi = {10.1021/jacs.4c11385}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {3967--3980}, shortjournal = {J. Am. Chem. Soc.}, title = {Coherent strain-inhibiting phase construction of lithium-rich manganese-based oxide toward high mechanochemical stability}, volume = {147}, year = {2025}, }
• (2025). Electron microscopy reveals inhomogeneous adsorption of iodine and concurrent defect formation in a Metal–Organic framework. JACS, 147(5), 3959--3966. (www)

  @article{ , abstract = {Adsorption behaviors are typically examined through adsorption isotherms, which measure the average adsorption amount as a function of partial pressure or time. However, this method is incapable of identifying inhomogeneities across the adsorbent, which may occur in the presence of strong intermolecular interactions of the adsorbate. In this study, we visualize the adsorption of molecular iodine (I 2 ) in the metal–organic framework material MFM-300(Sc) using high-resolution scanning transmission electron microscopy (STEM). Our observations demonstrate that, counterintuitively, I 2 adsorption in MFM-300(Sc) occurs in an inhomogeneous manner, regardless of the I 2 uptake level. Even at adsorption saturation, corresponding to an average of 23 iodine atoms per unit cell, MOF channels with significantly varying iodine contents─from nearly empty to densely filled─coexist. Image simulations suggest that the most densely packed I 2 may locally form the previously proposed triple-helix structure, corresponding to up to 142 iodine atoms per unit cell. Furthermore, STEM imaging reveals that I 2 adsorption can induce the formation of structural defects, such as edge dislocations and stacking faults, within the MOF framework. These defects persist even after the complete removal of I 2 molecules. Additionally, we have developed a surfactant-capping strategy to minimize the release of adsorbed I 2 from MFM-300(Sc) and validated its effectiveness using STEM imaging.}, archive = {J_JACS}, author = {Ying Liu and Dong Liu and Zhaohui Liu and Min Mao and Daliang Zhang and Jun Tao and Hui Zhang and Kepeng Song and Lingmei Liu and Yu Han}, doi = {10.1021/jacs.4c11304}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {3959--3966}, shortjournal = {J. Am. Chem. Soc.}, title = {Electron microscopy reveals inhomogeneous adsorption of iodine and concurrent defect formation in a Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Harnessing large language models to collect and analyze Metal–Organic framework property data set. JACS, 147(5), 3943--3958. (www)

  @article{ , abstract = {This research focused on the efficient collection of experimental metal–organic framework (MOF) data from scientific literature to address the challenges of accessing hard-to-find data and improving the quality of information available for machine learning studies in materials science. Utilizing a chain of advanced large language models (LLMs), we developed a systematic approach to extract and organize MOF data into a structured format. Our methodology successfully compiled information from more than 40,000 research articles, creating a comprehensive and ready-to-use data set. Specifically, data regarding MOF synthesis conditions and properties were extracted from both tables and text and then analyzed. Subsequently, we utilized the curated database to analyze the relationships between synthesis conditions, properties, and structure. Through machine learning, we identified the existence of a gap between simulation data and experimental data, and further analysis revealed the factors contributing to this discrepancy. Additionally, we leveraged the extracted synthesis condition data to develop a synthesis condition recommender system. This system suggests optimal synthesis conditions based on the provided precursors, offering a practical tool to refine synthesis strategies. This underscores the importance of experimental datasets in advancing MOF research.}, archive = {J_JACS}, author = {Yeonghun Kang and Wonseok Lee and Taeun Bae and Seunghee Han and Huiwon Jang and Jihan Kim}, doi = {10.1021/jacs.4c11085}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {3943--3958}, shortjournal = {J. Am. Chem. Soc.}, title = {Harnessing large language models to collect and analyze Metal–Organic framework property data set}, volume = {147}, year = {2025}, }
• (2025). Activation of primary C–H bonds in oxidative cyclizations of tambjamines catalyzed by rieske oxygenases TamC and PtTamC. JACS, 147(5), 3937--3942. (www)

  @article{ , abstract = {Tambjamines are complex bipyrrole-containing natural products that possess promising bioactive properties. Although Pseudoalteromonas citrea is known to produce both cyclic tambjamine MYP1 and the linear precursor (YP1), the biosynthetic machinery used to catalyze the site-selective oxidative carbocyclization at the unactivated 1° carbon of YP1 has remained unclear. Here, we demonstrate that a three-component Rieske system consisting of an oxygenase (TamC) and two redox partner proteins is responsible for this unprecedented activity on YP1 and potentially, a non-native substrate (BE-18591). We also show that a homologous oxidase from Pseudoalteromonas tunicata ( Pt TamC) can function together with the partner proteins from P. citrea to process both YP1 and BE-18591. These reactions represent the first Rieske oxygenase-catalyzed activations of C–H bonds at 1° carbons, resulting in carbon–carbon bond formation. The use of TamC and Pt TamC to potentially generate the new-to-nature cyclic analogue of BE-18591 suggests the enormous biocatalytic potential of these Rieske systems to facilitate late-stage oxidative cyclizations at terminal C(sp3)–H bonds.}, archive = {J_JACS}, author = {Manasa Ramachandra and Joshua L. M. Innis and Jian Yu and Graeme W. Howe and Françoise Sauriol and Richard D. Oleschuk and Avena C. Ross}, doi = {10.1021/jacs.4c17468}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {3937--3942}, shortjournal = {J. Am. Chem. Soc.}, title = {Activation of primary C–H bonds in oxidative cyclizations of tambjamines catalyzed by rieske oxygenases TamC and PtTamC}, volume = {147}, year = {2025}, }
• (2025). Synthesis of telechelic isotactic polypropylenes for circular polypropylene-like materials via chain transfer polymerization. JACS, 147(5), 3931--3936. (www)

  @article{ , abstract = {While synthesizing circular polymers with telechelic polyolefin building blocks recently emerged as a promising strategy for addressing conventional polyethylenes’ sustainability challenges, the lack of telechelic i PP ( t PP) with sufficient difunctional purity for polycondensation has been limiting the development of circular polypropylenes with i PP-like structures and properties. Here we described a combined approach of coordinative chain transfer polymerization and transition-metal-catalyzed quenching reaction with various acyl chlorides, affording t PPs with a high difunctional ratio (up to ∼99%) and broad end functional group scope. The steric effect of polymeryl-Zn species and the role of Pd catalyst were revealed by DFT. This method also solved the low difunctional ratio challenge for telechelic polyethylenes. Ester-linked i PPs with i PP-like structure and thermomechanical properties and PE/ i PP multiblock copolymers were synthesized by the resulting t PPs.}, archive = {J_JACS}, author = {Zonglun Yu and Xing-Wang Han and Peizhi Li and Yanan Zhao and Xun Zhang and Xiu-Li Sun and Yanshan Gao and You-Yun Zhou and Yong Tang}, doi = {10.1021/jacs.4c15910}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {3931--3936}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of telechelic isotactic polypropylenes for circular polypropylene-like materials via chain transfer polymerization}, volume = {147}, year = {2025}, }
• (2025). Effects of iron impurities and content on electrochemical performance and oxygen evolution selectivity of nickel catalysts for ethanol oxidation. JACS, 147(5), 3925--3930. (www)

  @article{ , abstract = {Although performance enhancements due to trace Fe incorporation into Ni catalysts for the oxygen evolution reaction (OER) have been well documented, the effects of trace versus bulk Fe incorporation into Ni catalysts for the ethanol oxidation reaction (EOR)─a promising anodic alternative to OER─are unclear. Herein, we perform extensive cyclic voltammetry experiments on Ni-based thin films to show that trace Fe incorporation from electrolyte impurities has a minimal impact on EOR performance, while codeposited Fe significantly suppresses catalytic current (by half at 1.5 V RHE ). Additionally, we apply operando electrochemical mass spectrometry (EC-MS) and directly observe the otherwise concealed onset potential of OER during EOR on the thin films, which surprisingly shows that the presence or absence of ethanol does not significantly impact OER, suggesting the reactions are catalyzed on different active sites. We also show that the previously observed low Faradaic efficiency of Ni for OER is time dependent─an important insight for the general interpretation of EC-MS data. Overall, our results further demonstrate the catalytic distinction between trace and bulk Fe incorporation in Ni and provide new insights into selectivity between EOR and OER.}, archive = {J_JACS}, author = {Colin F. Crago and Simon Li and Ashton M. Aleman and Tana Siboonruang and Milenia Rojas Mendoza and Thomas F. Jaramillo and Michaela Burke Stevens}, doi = {10.1021/jacs.4c15365}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {3925--3930}, shortjournal = {J. Am. Chem. Soc.}, title = {Effects of iron impurities and content on electrochemical performance and oxygen evolution selectivity of nickel catalysts for ethanol oxidation}, volume = {147}, year = {2025}, }
• (2025). Folding and functionalizing DNA origami: A versatile approach using a reactive polyamine. JACS, 147(5), 3919--3924. (www)

  @article{ , abstract = {DNA nanotechnology is a powerful synthetic approach to crafting diverse nanostructures through self-assembly. Chemical decoration of such nanostructures is often required to tailor their properties for specific applications. In this Letter, we introduce a pioneering method to direct the assembly and enable the functionalization of DNA nanostructures using an azide-bearing functional polyamine. We first demonstrate the successful polyamine-assisted folding of a scaffolded DNA origami nanostructure equipped with reactive azide groups. Leveraging this reactivity, we next showcase the decoration of the DNA origami via strain-promoted azide–alkyne cycloaddition with dibenzocyclooctyne-containing functional molecules. Specifically, we incorporate a fluorophore (Cy5), polyethylene glycol (PEG), and a hydrophobic phosphatidylethanolamine (PE) tag to tailor the properties of our DNA origami nanostructures. Our approach is expected to streamline and reduce the cost of chemical customization of intricate DNA nanostructures, paving the way for enhanced versatility and applicability.}, archive = {J_JACS}, author = {Alejandro Postigo and Carlos Marcuello and William Verstraeten and Santiago Sarasa and Tobias Walther and Anabel Lostao and Kerstin Göpfrich and Jesús del Barrio and Silvia Hernández-Ainsa}, doi = {10.1021/jacs.4c12637}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {3919--3924}, shortjournal = {J. Am. Chem. Soc.}, title = {Folding and functionalizing DNA origami: A versatile approach using a reactive polyamine}, volume = {147}, year = {2025}, }
• (2025). Using classifiers to predict catalyst design for polyketone microstructure. JACS, 147(5), 3913--3918. (www)

  @article{ , abstract = {We applied a classifier method to predict palladium catalysts for the formation of nonalternating polyketones via the copolymerization of CO and ethylene; current examples are limited to using phosphine sulfonate and diphosphazane monoxide supporting ligands. With the reported workflow, we discovered two new classes of palladium complexes capable of achieving the synthesis of nonalternating polyketones with a lower CO content than those made by known palladium catalysts. Our results show that we doubled the number of classes of palladium compounds that can catalyze the formation of this type of polymer. We envision that this methodology can be applied to accelerate catalyst discovery when selectivity is an important outcome.}, archive = {J_JACS}, author = {Yin-Pok Wong and Hyuk-Joon Jung and Shiyun Lin and Matthew A. Shammami and Hootan Roshandel and Henry M. Dodge and Scott M. Chapp and Lorenzo C. Ruiz De Castilla and Dunwei Wang and Loi H. Do and Chong Liu and Alexander J. M. Miller and Paula L. Diaconescu}, doi = {10.1021/jacs.4c11666}, journal = {Journal of the American Chemical Society}, month = {2}, number = {5}, pages = {3913--3918}, shortjournal = {J. Am. Chem. Soc.}, title = {Using classifiers to predict catalyst design for polyketone microstructure}, volume = {147}, year = {2025}, }
• (2025). Correction to “Dioxane bridge formation during the biosynthesis of spectinomycin involves a twitch radical S-adenosyl methionine dehydrogenase that may have evolved from an epimerase”. JACS, 147(4), 3912. (www)

  @article{ , archive = {J_JACS}, author = {Jiawei Zhang and Xueli Hou and Zhang Chen and Yeonjin Ko and Mark W. Ruszczycky and Yutian Chen and Jiahai Zhou and Hung-wen Liu}, doi = {10.1021/jacs.4c18639}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3912}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Dioxane bridge formation during the biosynthesis of spectinomycin involves a twitch radical S-adenosyl methionine dehydrogenase that may have evolved from an epimerase”}, volume = {147}, year = {2025}, }
• (2025). The role of torsion on the force-coupled reactivity of a fluorenyl naphthopyran mechanophore. JACS, 147(4), 3904--3911. (www)

  @article{ , abstract = {The unique reactivity of molecules under force commands an understanding of structure–mechanochemical activity relationships. While conceptual frameworks for understanding force transduction in many systems are established, systematic investigations into force-coupled molecular torsions are limited. Here, we describe a novel fluorenyl naphthopyran mechanophore for which mechanical force is uniquely coupled to the torsional motions associated with the overall chemical transformation as a result of the conformational rigidity imposed by the fluorene group. Using a combined experimental and theoretical approach, we demonstrate that variation in the pulling geometry on the fluorene subunit results in significant differences in mechanochemical activity due to pronounced changes in how force is coupled to distinct torsional motions and their coherence with the nuclear motions that accompany the force-free ring-opening reaction. Notably, subtle changes in polymer attachment position lead to a >50% difference in the rate of mechanochemical activation in ultrasonication experiments. Our results offer new insights into the structural and geometric factors that influence mechanochemical reactivity by describing how mechanical force is coupled to a reaction that principally involves torsional motions.}, archive = {J_JACS}, author = {Skylar K. Osler and Nathan A. Ballinger and Maxwell J. Robb}, doi = {10.1021/jacs.4c18395}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3904--3911}, shortjournal = {J. Am. Chem. Soc.}, title = {The role of torsion on the force-coupled reactivity of a fluorenyl naphthopyran mechanophore}, volume = {147}, year = {2025}, }
• (2025). Unraveling various stacking modes and local structures in poly(triazine imide) materials via low-dose electron microscopy. JACS, 147(4), 3896--3903. (www)

  @article{ , abstract = {Poly(triazine imide) (PTI) materials, a class of layered graphitic carbon nitrides, have garnered significant attention for their unique electronic, thermal, and catalytic properties. These properties can be adjusted through postsynthesis treatments. However, the influence of these treatments on the layer stacking modes and local structures within PTI remains largely unexplored. Herein, we demonstrate that low-dose electron microscopy can provide crucial insights into these previously unanswered questions. Utilizing integrated differential phase-contrast scanning transmission electron microscopy (iDPC-STEM) with carefully controlled electron doses, we achieved subangstrom resolution imaging of PTI materials. The obtained images reveal that acid treatments promote the transformation from AA’-stacking to AB- and ABC-stacking, with the latter being identified for the first time. Density functional theory calculations indicate that the replacement of intercalated cations is the primary driver of stacking mode transformation, while interlayer electrostatic interactions dictate the overall layer stacking. In addition, iDPC-STEM reveals the presence of Cl on the zigzag side surfaces of pristine PTI and its absence in acid-treated PTI. It also uncovers a Cl-deficient transition zone between AA’-stacking and AB-stacking regions, suggesting that the transformation of stacking modes is accompanied by the extraction and reintercalation of Cl ions.}, archive = {J_JACS}, author = {Guanxing Li and Cailing Chen and Hui Zhang and Zhen-Hua Li and Chenghua Sun and Zhan Shi and Yu Han}, doi = {10.1021/jacs.4c17928}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3896--3903}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling various stacking modes and local structures in poly(triazine imide) materials via low-dose electron microscopy}, volume = {147}, year = {2025}, }
• (2025). TiOx(OH)4–2x nanosheets with catalytic antioxidative activity alleviate oxidative injury in diabetic cardiomyopathy. JACS, 147(4), 3885--3895. (www)

  @article{ , abstract = {Diabetic cardiomyopathy (DCM) is one of the most lethal complications of diabetes and is induced by the overproduction of reactive oxygen species (ROS) in cardiomyocytes due to sustained high glucose levels, leading to cardiac oxidative damage and final sudden death. Drugs and antioxidants currently applied to the clinical therapy of DCM fail to scavenge ROS efficiently, resulting in compromised therapeutic efficacy. Herein, a nanocatalytic antioxidative therapeutic strategy is proposed for DCM treatment. A two-dimensional TiO x (OH) 4–2 x nanosheet platform has been constructed with efficient ROS-scavenging activity, which can catalyze antioxidation reaction through redox cycling between Ti IV /Ti III accompanied by inner-sphere two-electron transfer. Cellular experiments demonstrate that the TiO x (OH) 4–2 x nanosheet can not only protect cardiomyocytes from oxidative damage induced by a high glucose environment but also alleviate inflammation to further protect cardiomyocytes from inflammatory injury. The in vivo animal model confirms that the nanosheet alleviates myocardial oxidative injury and recovers cardiac function. Such a nanocatalytic antioxidation strategy is expected to provide a feasible approach for treating DCM and other cardiovascular diseases.}, archive = {J_JACS}, author = {Yufan Yao and Bowen Yang and Jianlin Shi}, doi = {10.1021/jacs.4c18026}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3885--3895}, shortjournal = {J. Am. Chem. Soc.}, title = {TiOx(OH)4–2x nanosheets with catalytic antioxidative activity alleviate oxidative injury in diabetic cardiomyopathy}, volume = {147}, year = {2025}, }
• (2025). Identifying the bifunctional mechanism in alkaline water electrolysis by lewis pairs at the single-atom scale. JACS, 147(4), 3874--3884. (www)

  @article{ , abstract = {The bifunctional mechanism, involving multiactive compositions to simultaneously dissociate water molecules and optimize intermediate adsorption, has been widely used in the design of catalysts to boost water electrolysis for sustainable hydrogen energy production but remains debatable due to difficulties in accurately identifying the reaction process. Here, we proposed the concept of well-defined Lewis pairs in single-atom catalysts, with a unique acid–base nature, to comprehensively understand the exact role of multiactive compositions in an alkaline hydrogen evolution reaction. By facilely adjusting active moieties, the induced synergistic effect between Lewis pairs (M–P/S/Cr pairs, M = Ru, Ir, Pt) can significantly facilitate the cleavage of the H–OH bond and accelerate the removal of intermediates, thereby switching the rate-determining step from the Volmer step to the Heyrovsky step. Moreover, the representative Ru–P Lewis pairs deliver an impressive 266 h durability at a high industrial current density of 2 A cm –2 without activity decay in anion-exchange membrane water electrolysis, and the concept can be extended to modify commercial noble-metal-based catalysts for performance enhancement. This work not only sheds light on the important effect of the bifunctional mechanism in alkaline water electrolysis at the single-atom scale but also offers a universal descriptor for the rational design of advanced catalysts.}, archive = {J_JACS}, author = {Hongqiang Jin and Xiang Chen and Yumin Da and Lei Fan and Rui Jiang and Yukun Xiao and Bingqing Yao and Qian He and Yu Yu and Wei Chen}, doi = {10.1021/jacs.4c18040}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3874--3884}, shortjournal = {J. Am. Chem. Soc.}, title = {Identifying the bifunctional mechanism in alkaline water electrolysis by lewis pairs at the single-atom scale}, volume = {147}, year = {2025}, }
• (2025). Modular construction of multivariate Metal–Organic frameworks for luminescent sensing. JACS, 147(4), 3866--3873. (www)

  @article{ , abstract = {Metal–organic frameworks (MOFs) have played a pivotal role as rapid and effective luminescent sensing materials. Numerous MOFs with diverse characteristics have been meticulously designed for target analytes. Previous studies have highlighted the factors of spectral characteristics, energy levels, interaction forces, and sensor stabilities for the luminescent sensing performance in response to a specific analyte. This conventional “point-to-point” approach necessitates the matching of sensing materials to a specific analyte. Herein, we develop a modular MOF-based luminescent sensing platform by using a mixed-ligand strategy. A luminescent MOF Eu-FDA with 2,5-furandicarboxylic acid can serve as the foundational platform, with partial replacement by nine distinct hexacyclic isophthalic acids as the modules, respectively, to specifically accommodate different analytes with particular structures and properties. This substitution has been meticulously confirmed through single-crystal X-ray diffraction. Confronted with analytes possessing diverse structural or property characteristics, modular isophthalic acid derivatives can enhance the sensing capability to achieve heightened sensitivity.}, archive = {J_JACS}, author = {Zongsu Han and Kun-Yu Wang and Rong-Ran Liang and Yifan Guo and Yihao Yang and Mengmeng Wang and Yue Mao and Jiatong Huo and Wei Shi and Hong-Cai Zhou}, doi = {10.1021/jacs.4c17248}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3866--3873}, shortjournal = {J. Am. Chem. Soc.}, title = {Modular construction of multivariate Metal–Organic frameworks for luminescent sensing}, volume = {147}, year = {2025}, }
• (2025). ROMP of macromonomers prepared by ROMP: Expanding access to complex, functional bottlebrush polymers. JACS, 147(4), 3855--3865. (www)

  @article{ , abstract = {Graft-through ring-opening metathesis polymerization (ROMP) of norbornene-terminated macromonomers (MMs) prepared using various polymerization methods has been extensively used for the synthesis of bottlebrush (co)polymers, yet the potential of ROMP for the synthesis of MMs that can subsequently be polymerized by graft-through ROMP to produce new bottlebrush compositions remains untapped. Here, we report an efficient “ROMP-of-ROMP” method that involves the synthesis of norbornene-terminated poly(norbornene imide) (PNI)-based MMs that, following ROMP, provide new families of bottlebrush (co)polymers and “brush-on-brush” hierarchical architectures. In the bulk state, the organization of the PNI pendants drives bottlebrush backbone extension to enable rapid assembly of asymmetric lamellar morphologies with large asymmetry factors. Overall, this work expands the scope of complex macromolecular architectures and provides insights into the interplay of backbone rigidity and self-assembly that will guide future nanolithography applications.}, archive = {J_JACS}, author = {Zehao Sun and Bin Liu and Mingchao Ma and Alfredo Alexander-Katz and Caroline A. Ross and Jeremiah A. Johnson}, doi = {10.1021/jacs.4c17151}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3855--3865}, shortjournal = {J. Am. Chem. Soc.}, title = {ROMP of macromonomers prepared by ROMP: Expanding access to complex, functional bottlebrush polymers}, volume = {147}, year = {2025}, }
• (2025). B, n codoped defective reduced graphene oxide as a highly efficient frustrated lewis pairs catalyst for the selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols. JACS, 147(4), 3840--3854. (www)

  @article{ , abstract = {The development of all-solid-state frustrated Lewis pairs (FLPs) metal-free hydrogenation catalysts with excellent activity and stability remains a significant challenge. In this work, B, N codoped FLPs catalysts (De-rGO-N x B y ) were prepared by the strategy of fabricating carbon defects and heteroatom doping on the surface of reduced graphene oxide and applied in the selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols. It was found that electron-rich pyridine-N (Lewis base) and adjacent electron-deficient B–N (Lewis acid) sites could be constructed on the surface of reduced graphene oxide using dicyandiamide and metaboric acid as N and B sources, thus forming FLPs sites. More importantly, the constructed carbon defects could facilitate the formation of pyridinic-N/B–N FLPs sites, thereby improving the catalytic hydrogenation activity and the selectivity to unsaturated alcohols. Furthermore, in situ DRIFTS and DFT calculations show that the pyridinic-N/B–N FLPs sites can efficiently activate the C═O of aldehydes and H 2 molecules with only 0.53 eV dissociation energy of the H–H bond. Also, the catalyst presents excellent catalytic performance in the transfer hydrogenation reactions with cyclohexanol and its derivatives as hydrogen sources. This study provides new ideas for the design and preparation of all-solid-state FLPs metal-free catalysts and promotes the green synthesis of unsaturated alcohols.}, archive = {J_JACS}, author = {Linhao Zhong and Xiaoqing Liao and Huaquan Huang and Haishuai Cui and Jinmei Huang and He’an Luo and Yong Pei and Yang Lv and Pingle Liu}, doi = {10.1021/jacs.4c17103}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3840--3854}, shortjournal = {J. Am. Chem. Soc.}, title = {B, n codoped defective reduced graphene oxide as a highly efficient frustrated lewis pairs catalyst for the selective hydrogenation of α,β-unsaturated aldehydes to unsaturated alcohols}, volume = {147}, year = {2025}, }
• (2025). Staudinger reaction-responsive coacervates for cytosolic antibody delivery and TRIM21-mediated protein degradation. JACS, 147(4), 3830--3839. (www)

  @article{ , abstract = {A low-molecular-weight compound whose structure strikes a fine balance between hydrophobicity and hydrophilicity may form coacervates via liquid–liquid phase separation in an aqueous solution. These coacervates may encapsulate and convoy proteins across the plasma membrane into the cell. However, releasing the cargo from the vehicle to the cytosol is challenging. Here, we address this issue by designing phase-separating coacervates, which are disassembled by the bioorthogonal Staudinger reaction. We constructed and selected triphenylphosphine-based compounds that formed phase-separated coacervates in an aqueous solution. Reacting the coacervates with azides resulted in microdroplet dissolution, so they received the name S taudinger Reaction- R esponsive Coa cervates, SR-Coa . SR-Coa could encapsulate proteins, including antibodies, and translocate them across the plasma membrane into the cell. Further treatment of the cell with ethyl azidoacetate induced the cargo dispersion from the puncta to the cytosolic distribution. We showcased an application of the SR-Coa /ethyl azidoacetate system in facilitating the translocation of the EGFR/antibody complex into the cell, which induced EGFR degradation via the TRIM21-dependent pathway both in vitro and in vivo. Besides the membrane protein EGFR, this system could also degrade endogenous protein EZH2. Taken together, here we report a strategy of controlling molecular coacervates by a bioorthogonal reaction in the cell for cytosolic protein delivery and demonstrate its use in promoting targeted protein degradation via the proteasome-dependent pathway.}, archive = {J_JACS}, author = {Yishu Bao and Zhiyi Xu and Kai Cheng and Xiaojing Li and Fangke Chen and Dingdong Yuan and Fang Zhang and Audrey Run-Yu Che and Xiangze Zeng and Yuan-Di Zhao and Jiang Xia}, doi = {10.1021/jacs.4c17054}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3830--3839}, shortjournal = {J. Am. Chem. Soc.}, title = {Staudinger reaction-responsive coacervates for cytosolic antibody delivery and TRIM21-mediated protein degradation}, volume = {147}, year = {2025}, }
• (2025). Guest segregation in heteromeric multicage systems. JACS, 147(4), 3823--3829. (www)

  @article{ , abstract = {Dynamically interconvertible metallo-supramolecular multicomponent assemblies, coexisting orthogonally in solution, serve as simplified mimics for complex networks found in biological systems. Building on recent advances in controlling the nonstatistical self-assembly of heteroleptic coordination cages and heteromeric completive self-sorting, i.e., the coformation of multiple low-symmetry assemblies, we herein describe the first instance of emerging functionality from a heteromeric multicage system. In particular, one heteroleptic cage coexists in equilibrium with one or two different homoleptic cages, each capable of preferentially encapsulating one out of three guests within their cavities. Guest segregation occurs under thermodynamic control and can be reached following several distinct paths. Each pathway involves different sequential transformations, eventually leading to the same outcome. We found that the most complex mixture of components (three ligands, three guests, plus palladium cations) always yields an ordered, pathway-independent final state of three coexisting host–guest species, thus representing a case of simplexity in self-sorted systems. This study forms a basis for expanding the scope of dynamic transformation processes implemented in multicage host–guest systems. Together with the incorporation of stimuli-responsive elements and other functionality, complex cage populations with bioinspired applications in controllable compound separation schemes, compartmentalized cascade reactions, and multistep (even bifurcated) molecular information processing will become accessible.}, archive = {J_JACS}, author = {Elie Benchimol and Andrea Rivoli and Michele Kabiri and Bo Zhang and Julian J. Holstein and Pablo Ballester and Guido H. Clever}, doi = {10.1021/jacs.4c16971}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3823--3829}, shortjournal = {J. Am. Chem. Soc.}, title = {Guest segregation in heteromeric multicage systems}, volume = {147}, year = {2025}, }
• (2025). Small CAG repeat RNA forms a duplex structure with sticky ends that promote RNA condensation. JACS, 147(4), 3813--3822. (www)

  @article{ , abstract = {Biomolecular condensation lays the foundation of forming biologically important membraneless organelles, but abnormal condensation processes are often associated with human diseases. Ribonucleic acid (RNA) plays a critical role in the formation of biomolecular condensates by mediating the phase transition through its interactions with proteins and other RNAs. However, the physicochemical principles governing RNA phase transitions, especially for short RNAs, remain inadequately understood. Here, we report that small CAG repeat (sCAG) RNAs composed of six to seven CAG repeats, which are pathogenic factors in Huntington’s disease, undergo phase transition in vitro and in cells. Leveraging solution nuclear magnetic resonance spectroscopy and advanced coarse-grained molecular dynamic simulations, we reveal that sCAG RNAs form duplex structures with 3′-sticky ends, where the GC stickers initiate intermolecular crosslinking and promote the formation of RNA condensates. Furthermore, we demonstrate that sCAG RNAs can form cellular condensates within nuclear speckles. Our work suggests that the RNA phase transition can be promoted by specific structural motifs, reducing the reliance on sequence length and multivalence. This opens avenues for exploring new functions of RNA in biomolecular condensates and designing novel biomaterials based on RNA condensation.}, archive = {J_JACS}, author = {Liqi Wan and Chengwei Zhang and Yu Liu and Jiacheng Zhang and Lei He and Yuchao Zhang and Guangyong Chen and Pei Guo and Da Han}, doi = {10.1021/jacs.4c16886}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3813--3822}, shortjournal = {J. Am. Chem. Soc.}, title = {Small CAG repeat RNA forms a duplex structure with sticky ends that promote RNA condensation}, volume = {147}, year = {2025}, }
• (2025). Molecule-based Proton–Electron mixed conductor with the highest ambipolar conductivity. JACS, 147(4), 3804--3812. (www)

  @article{ , abstract = {Proton–electron mixed conductors (PEMCs) are an essential component for potential applications in hydrogen separation and energy conversion devices. However, the exploration of PEMCs with excellent mixed conduction, which is quantified by the ambipolar conductivity, σ amb = σ e σ H /(σ e + σ H ) (σ e : electronic conductivity; σ H : proton conductivity), is still a great challenge, largely due to the lack of structural characterization of both conducting mechanisms. In this study, we prepared a molecule-based proton–electron mixed-conducting cation radical salt, (ET) 4 [Pt 2 (pop) 2 (Hpop) 2 ]·PhCN (ET: bis(ethylenedithio)tetrathiafulvalene, pop 2– : P 2 H 2 O 5 2– ), by electrocrystallization. The salt shows metallic electronic conduction, which arises from the (ET) 2 •+ layers, with a high σ e value (1–2 S cm –1 at room temperature). The metallic state was corroborated by magnetic susceptibility measurement and band structure calculation. The salt also shows superprotonic conduction (σ H = 2.1 × 10 –2 S cm –1 at room temperature under dried conditions), which relies on the one-dimensional (1D) hydrogen-bonding network of protonated paddlewheel-type Pt-dimer complex anions, [Pt 2 (pop) 2 (Hpop) 2 ] 2– . Crystallographic and computational studies revealed the presence of infinite intra- and intermolecular O–H···O hydrogen bonds, which show a double-well-like potential energy curve with a negligible energy barrier in the 1D chain, facilitating Grotthuss-type proton hopping via Lewis basic sites. Among the structurally defined PEMCs, the present salt displays the highest room temperature σ amb value of 2.1 × 10 –2 S cm –1 even under dried conditions. The σ amb value has the same order as those of reported perovskites-type metal oxides at high temperatures and achieves a level that is beneficial for the practical applications.}, archive = {J_JACS}, author = {Peng-Hao Wang and Yukihiro Yoshida and Soichiro Yasaka and Mitsuhiko Maesato and Yoshiaki Nakano and Hiroshi Kitagawa}, doi = {10.1021/jacs.4c16779}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3804--3812}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecule-based Proton–Electron mixed conductor with the highest ambipolar conductivity}, volume = {147}, year = {2025}, }
• (2025). Confinement and catalysis within de novo designed peptide barrels. JACS, 147(4), 3796--3803. (www)

  @article{ , abstract = {De novo protein design has advanced such that many peptide assemblies and protein structures can be generated predictably and quickly. The drive now is to bring functions to these structures, for example, small-molecule binding and catalysis. The formidable challenge of binding and orienting multiple small molecules to direct chemistry is particularly important for paving the way to new functionalities. To address this, here we describe the design, characterization, and application of small-molecule:peptide ternary complexes in aqueous solution. This uses α-helical barrel (αHB) peptide assemblies, which comprise 5 or more α helices arranged around central channels. These channels are solvent accessible, and their internal dimensions and chemistries can be altered predictably. Thus, αHBs are analogous to “molecular flasks” made in supramolecular, polymer, and materials chemistry. Using Förster resonance energy transfer as a readout, we demonstrate that specific αHBs can accept two different organic dyes, 1,6-diphenyl-1,3,5-hexatriene and Nile red, in close proximity. In addition, two anthracene molecules can be accommodated within an αHB to promote anthracene photodimerization. However, not all ternary complexes are productive, either in energy transfer or photodimerization, illustrating the control that can be exerted by judicious choice and design of the αHB.}, archive = {J_JACS}, author = {Rokas Petrenas and Olivia A. Hawkins and Jacob F. Jones and D. Arne Scott and Jordan M. Fletcher and Ulrike Obst and Lucia Lombardi and Fabio Pirro and Graham J. Leggett and Thomas A.A. Oliver and Derek N. Woolfson}, doi = {10.1021/jacs.4c16633}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3796--3803}, shortjournal = {J. Am. Chem. Soc.}, title = {Confinement and catalysis within de novo designed peptide barrels}, volume = {147}, year = {2025}, }
• (2025). Molecular strain accelerates electron transfer for enhanced oxygen reduction. JACS, 147(4), 3786--3795. (www)

  @article{ , abstract = {Fe–N–C materials are emerging catalysts for replacing precious platinum in the oxygen reduction reaction (ORR) for renewable energy conversion. However, their potential is hindered by sluggish ORR kinetics, leading to a high overpotential and impeding efficient energy conversion. Using iron phthalocyanine (FePc) as a model catalyst, we elucidate how the local strain can enhance the ORR performance of Fe–N–Cs. We use density functional theory to predict the reaction mechanism for the four-electron reduction of oxygen to water. Several key differences between the reaction mechanisms for curved and flat FePc suggest that molecular strain accelerates the reductive desorption of *OH by decreasing the energy barrier by ∼60 meV. Our theoretical predictions are substantiated by experimental validation; we find that strained FePc on single-walled carbon nanotubes attains a half-wave potential ( E 1/2 ) of 0.952 V versus the reversible hydrogen electrode and a Tafel slope of 35.7 mV dec –1 , which is competitive with the best-reported Fe–N–C values. We also observe a 70 mV change in E 1/2 and dramatically different Tafel slopes for the flat and curved configurations, which agree well with the calculated energies. When integrated into a zinc–air battery, our device affords a maximum power density of 350.6 mW cm –2 and a mass activity of 810 mAh g Zn –1 at 10 mA cm –2 . Our results indicate that molecular strain provides a compelling tool for modulating the ORR activities of Fe–N–C materials.}, archive = {J_JACS}, author = {Charles B. Musgrave III and Jianjun Su and Pei Xiong and Yun Song and Libei Huang and Yong Liu and Geng Li and Qiang Zhang and Yinger Xin and Molly Meng-Jung Li and Ryan Tsz Kin Kwok and Jacky W. Y. Lam and Ben Zhong Tang and William A. Goddard III and Ruquan Ye}, doi = {10.1021/jacs.4c16637}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3786--3795}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular strain accelerates electron transfer for enhanced oxygen reduction}, volume = {147}, year = {2025}, }
• (2025). Supramolecularly built local electric field microenvironment around cobalt phthalocyanine in covalent organic frameworks for enhanced photocatalysis. JACS, 147(4), 3776--3785. (www)

  @article{ , abstract = {The local electric field (LEF) plays an important role in the catalytic process; however, the precise construction and manipulation of the electric field microenvironment around the active site remains a significant challenge. Here, we have developed a supramolecular strategy for the implementation of a LEF by introducing the host macrocycle 18-crown-6 (18C6) into a cobalt phthalocyanine (CoPc)-containing covalent organic framework (COF). Utilizing the supramolecular interaction between 18C6 and potassium ion (K + ), a locally enhanced K + concentration around CoPc can be built to generate a LEF microenvironment around the catalytically active Co site. The COF with this supramolecularly built LEF realizes an activity of up to 7.79 mmol mmol Co –1 h –1 in the photocatalytic CO 2 reduction reaction (CO 2 RR), which is a 180% improvement compared to its counterpart without 18C6 units. The effect of LEF can be subtly controlled by fully harnessing the K + @18C6 interaction by changing the potassium salts with different counterions. In situ spectroscopy and density functional theory calculations show that the complexation of K + by 18C6 creates a positive electric field that stabilizes the critical intermediate *COOH involved in CO 2 RR, which can be tuned by the halide ion-mediated K + @18C6 interaction and hydrogen-bonding interaction, consequently leading to improved catalytic performance to varying degrees.}, archive = {J_JACS}, author = {Yi Zhang and Xinyu Guan and Zheng Meng and Hai-Long Jiang}, doi = {10.1021/jacs.4c16538}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3776--3785}, shortjournal = {J. Am. Chem. Soc.}, title = {Supramolecularly built local electric field microenvironment around cobalt phthalocyanine in covalent organic frameworks for enhanced photocatalysis}, volume = {147}, year = {2025}, }
• (2025). Readily accessible, versatile, and adaptive biaxially chiral chromophores. JACS, 147(4), 3769--3775. (www)

  @article{ , abstract = {Precisely controlling quantum states is relevant in next-generation quantum computing, encryption, and sensing. Chiral organic chromophores host unique light–matter interactions, which allow them to manipulate the quantized circular polarization of photons. Axially chiral organic scaffolds, such as helicenes or twisted acenes, are powerful motifs in chiral light manipulation. However, these systems usually require complex syntheses and small-scale (10 mg) enantiomer separations, typically complicating systematic investigations of their structure–property relationships. We report here the straightforward synthesis of both enantiomers ( R / S ) of 10 different axially chiral chromophores. This protocol relies on a readily accessible, enantiomerically pure, and axially chiral contorting element, benzodinaptho[1,4]dioxicine-2,3-diamine (DODA), that we synthesize in two steps with high purity and good yield at gram scale. Subsequent derivation of DODA transfers the chirality from one axis to twist the dominant chromophore around a second, orthogonal axis. Using this biaxial contortion design element, we produce 10 enantiopure biaxial chromophores, without the need for chromatographic separations, and no observable compromise to chiroptical integrity. These chromophores exhibit broadband single-handed absorption without Cotton effects from 265 to 485 nm, indicating chiral excitonic character that forms between the DODA and twisted core chromophore. This platform is responsive to solvent polarity in the excited state, displaying >50 nm bathochromic shifts in the photoluminescence spectra. In addition, this scaffold intensely interacts with changes in pH, which allows us to ultimately access monosignate circular dichroism absorption over a 300 nm range.}, archive = {J_JACS}, author = {Summer J. Brown and Jiaoyan Zhao and Ellen Forehand and Lukasz Dobrzycki and Rupam Roy and A M Mahmudul Hasan and Wendu Ding and Cedric Schaack and Austin M. Evans}, doi = {10.1021/jacs.4c16566}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3769--3775}, shortjournal = {J. Am. Chem. Soc.}, title = {Readily accessible, versatile, and adaptive biaxially chiral chromophores}, volume = {147}, year = {2025}, }
• (2025). S-d coupling-induced dynamic off-centering of cu drives high thermoelectric performance in TlCuS. JACS, 147(4), 3758--3768. (www)

  @article{ , abstract = {Seeking new and efficient thermoelectric materials requires a detailed comprehension of chemical bonding and structure in solids at microscopic levels, which dictates their intriguing physical and chemical properties. Herein, we investigate the influence of local structural distortion on the thermoelectric properties of TlCuS, a layered metal sulfide featuring edge-shared Cu–S tetrahedra within Cu 2 S 2 layers. While powder X-ray diffraction suggests average crystallographic symmetry with no distortion in CuS 4 tetrahedra, the synchrotron X-ray pair distribution function experiment exposes concealed local symmetry breaking, with dynamic off-centering distortions of the CuS 4 tetrahedra. The Cu off-centering is driven by the on-site coupling of filled 3 d and unoccupied 4 s orbitals ( s - d ) of Cu through a second-order Jahn–Teller mechanism. Bond softening by the p - d* (S-3 p and Cu-3 d ) antibonding interaction coupled with dynamic off-centering distortions causes significant anharmonicity in the lattice, which acts as a phonon-blocking mechanism conducive to ultralow lattice thermal conductivity (κ lat ) (∼0.35–0.23 W m –1 K –1 in the ∼296–573 K temperature range) in TlCuS. The synergy between low κ lat and multiband electronic structure leads to thermoelectric figure-of-merits (zT) of ∼1 and ∼1.3 at 573 K for pristine TlCuS and TlCu 0.98 S, respectively, underscoring the potential of metal sulfides as promising high-performance thermoelectrics.}, archive = {J_JACS}, author = {Animesh Bhui and Prasad V. D. Matukumilli and Shuva Biswas and Abdul Ahad and Anupama Ghata and Divya Rawat and Moinak Dutta and Ajay Soni and Umesh V. Waghmare and Kanishka Biswas}, doi = {10.1021/jacs.4c16394}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3758--3768}, shortjournal = {J. Am. Chem. Soc.}, title = {S-d coupling-induced dynamic off-centering of cu drives high thermoelectric performance in TlCuS}, volume = {147}, year = {2025}, }
• (2025). Diverse behaviors of n2 on mo centers bearing POCOP-pincer ligands and the role of π-electron configuration in regulating the pathway of n2 activation. JACS, 147(4), 3747--3757. (www)

  @article{ , abstract = {Activation of N 2 through transition-metal complexes has emerged as a powerful strategy for N 2 fixation under mild conditions. Dissociative route and associative route are considered as two major routes for N 2 transformation on transition-metal complexes. Homolysis of N 2 between two metal fragments is the crucial step of the dissociative route and has been proven to be an efficient approach to the terminal metal nitride, which is the key intermediate for both routes. Hence, the conditions for N 2 cleavage have attracted much interest and discussion. Herein, we investigated the reactivity of N 2 when coordinated on Mo centers bearing POCOP-pincer ligands and isolated and characterized many novel N 2 -related intermediates such as [(POCOP Cy )MoI] 2 (μ-N 2 ) ( 2 Cy ), (POCOP Cy )Mo(N)(μ-N)MoI ( 5 Cy ), {[(POCOP Cy )Mo(N 2 ) 2 ] 2 (μ-N 2 )}[Na(crypt-222)] ( 6 Cy -crypt ), and [(POCOP Cy )Mo(N 2 ) 2 (μ-N 2 )Mo(N)]Na ( 8 Cy ). The influences of the oxidation state of the metal centers, π electrons, reaction conditions, etc., on the N 2 -reactivity were also studied both experimentally and theoretically. Accordingly, some fundamental understanding of the regulation of N 2 activation pathways was proposed: an N 2 -bridged Mo dimer without ligand trans to the bridging N 2 is a preferred structure for N 2 cleavage; having adequate electrons to be transferred into the σ–σ*−σ related orbital in the {MoNNMo} manifold is the key; and heating or electron excitation is advantageous to the dissociative route.}, archive = {J_JACS}, author = {Guoqiang Zhang and Qijun Li and Xinchao Wang and Li Jin and Qian Liao}, doi = {10.1021/jacs.4c16240}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3747--3757}, shortjournal = {J. Am. Chem. Soc.}, title = {Diverse behaviors of n2 on mo centers bearing POCOP-pincer ligands and the role of π-electron configuration in regulating the pathway of n2 activation}, volume = {147}, year = {2025}, }
• (2025). Manganese(I)-catalyzed enantioselective alkylation to access P-stereogenic phosphines. JACS, 147(4), 3740--3746. (www)

  @article{ , abstract = {This work introduces a novel Mn(I)-catalyzed enantioselective alkylation methodology that efficiently produces a wide array of P-chiral phosphines with outstanding yields and enantioselectivities. Notably, the exceptional reactivity of Mn(I) complexes in these reactions is demonstrated by their effective catalysis with both typically reactive alkyl iodides and bromides, as well as with less reactive alkyl chlorides. This approach broadens the accessibility to various P-chiral phosphines and simplifies the synthesis of chiral tridentate pincer phosphines to a concise 1–2 step process, contrary to conventional, labor-intensive multistep procedures. Importantly, the development significantly expands the applicability of earth-abundant Mn(I)-based complexes beyond their recently established roles in catalytic hydrogenative and conjugate addition reactions, emphasizing the catalytic potential of Mn(I) complexes as a viable alternative to noble metal chemistry and, in some cases, even surpassing their performance.}, archive = {J_JACS}, author = {Bin Wan and Marta Castiñeira Reis and Tizian-Frank Ramspoth and Syuzanna R. Harutyunyan}, doi = {10.1021/jacs.4c16130}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3740--3746}, shortjournal = {J. Am. Chem. Soc.}, title = {Manganese(I)-catalyzed enantioselective alkylation to access P-stereogenic phosphines}, volume = {147}, year = {2025}, }
• (2025). Dual activation modes enable bifunctional catalysis of aldol reactions by flexible dihydrazides. JACS, 147(4), 3731--3739. (www)

  @article{ , abstract = {Hydrazides are known to catalyze reactions of α,β-unsaturated aldehydes via transient iminium formation. The iminium intermediate displays enhanced electrophilicity, which facilitates conjugate additions and cycloadditions. We observed that a hydrazide embedded in a seven-membered ring catalyzes homoaldol condensation of a simple aldehyde in a process that displays an approximate second-order dependence on the hydrazide. This finding suggests a dual activation mechanism involving both iminium and enamine intermediates. The unexpected nucleophilic activation mode led us to examine a series of simple dihydrazides for bifunctional catalysis of the aldol condensation. The two cyclic hydrazide units were connected via linear polymethylene linkers, which are inherently flexible. Substantial increases in initial reaction rate, relative to a monohydrazide, were observed for polymethylene linkers of sufficient length, with a maximum at 10 methylenes. Reactions promoted by this dihydrazide displayed an approximate first-order dependence on catalyst concentration, which suggested a bifunctional catalytic mechanism. Even for a dihydrazide with an 18-methylene linker, a substantial increase in relative initial rate was observed. These observations show that significant coordination can be achieved between two catalytically active moieties even when these moieties are connected via many flexible bonds.}, archive = {J_JACS}, author = {Philip P. Lampkin and Samuel H. Gellman}, doi = {10.1021/jacs.4c16143}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3731--3739}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual activation modes enable bifunctional catalysis of aldol reactions by flexible dihydrazides}, volume = {147}, year = {2025}, }
• (2025). Revealing the potential-dependent rate-determining step of oxygen reduction reaction on single-atom catalysts. JACS, 147(4), 3724--3730. (www)

  @article{ , abstract = {Single-atom catalysts (SACs) have attracted widespread attention due to their potential to replace platinum-based catalysts in achieving efficient oxygen reduction reaction (ORR), yet the rational optimization of SACs remains challenging due to their elusive reaction mechanisms. Herein, by employing ab initio molecular dynamics simulations and a thermodynamic integration method, we have constructed the potential-dependent free energetics of ORR on a single iron atom catalyst dispersed on nitrogen-doped graphene (Fe–N 4 /C) and further integrated these parameters into a microkinetic model. We demonstrate that the rate-determining step (RDS) of the ORR on SACs is potential-dependent rather than invariant within the operative potential range. Specifically, under the charge-neutral condition, the RDS is calculated to be water desorption with the highest barrier, while as the potential increases, it gradually transitions to the protonation of *OH species, O 2 * species, and O* species, regardless of the protonation of *OH species as the potential-determining step. Moreover, we reveal the critical role of the dynamic adsorption of axially adsorbed water in facilitating the release of the single-atom site, thus enhancing the ORR rate. Our work has resolved the long-standing controversies over the RDS of ORR on SACs and implies that the step with the lowest exothermicity is not always synonymous with the RDS, highlighting the importance of examining the kinetic barriers under realistic potential conditions for understanding the electrocatalytic performance.}, archive = {J_JACS}, author = {Hui-Min Yan and Gang Wang and Xin-Mao Lv and Hao Cao and Gang-Qiang Qin and Yang-Gang Wang}, doi = {10.1021/jacs.4c16098}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3724--3730}, shortjournal = {J. Am. Chem. Soc.}, title = {Revealing the potential-dependent rate-determining step of oxygen reduction reaction on single-atom catalysts}, volume = {147}, year = {2025}, }
• (2025). 3D covalent organic framework membrane with interactive ion nanochannels for hydroxide conduction. JACS, 147(4), 3714--3723. (www)

  @article{ , abstract = {Crystalline porous materials, known for their ordered structures, hold promise for efficient hydroxide conductivity in alkaline fuel cells with limited ionic densities. However, the rigid cross-linking of porous materials precludes their processing into membranes, while composite membranes diminish materials’ conductivity advantage due to the interrupted phases. Here, we report a self-standing three-dimensional covalent organic framework (3D COF) membrane with efficient OH-transport through its interconnected 3D ionic nanochannels. The large-area, homogeneously connected COF membrane, with an 8 cm diameter and 20 μm thickness, was prepared using an interface polymerization strategy assisted by sacrificial templates of a polyacrylonitrile membrane. At the microscopic level, the introduction of imidazolium salt-building units resulted in a noninterpenetrated structure of 3D COF, creating a 3D interactive continuous hydrophilic channel for OH – -conduction. The 3D COF membrane demonstrated high conductivity (169 mS/cm at 80 °C, 100% humidity) and achieved a peak power density of 160 mW/cm 2 in H 2 /O 2 single-cell tests. This COF interface polymerization strategy brings new possibilities to address the challenges of porous material membrane formation and is expected to advance their practical applications in the field of ion transport.}, archive = {J_JACS}, author = {Jia Chen and Zhuozhuo Tang and Li Sheng and Zonglong Li and Da Zhu and Jianlong Wang and Yaping Tang and Xiangming He and Hong Xu}, doi = {10.1021/jacs.4c16029}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3714--3723}, shortjournal = {J. Am. Chem. Soc.}, title = {3D covalent organic framework membrane with interactive ion nanochannels for hydroxide conduction}, volume = {147}, year = {2025}, }
• (2025). Rational design of prussian blue analogues for ultralong and wide-temperature-range sodium-ion batteries. JACS, 147(4), 3702--3713. (www)

  @article{ , abstract = {Architecting Prussian blue analogue (PBA) cathodes with optimized synergistic bimetallic reaction centers is a paradigmatic strategy for devising high-energy sodium-ion batteries (SIBs); however, these cathodes usually suffer from fast capacity fading and sluggish reaction kinetics. To alleviate the above problems, herein, a series of early transition metal (ETM)–late transition metal (LTM)-based PBA (Fe-VO, Fe-TiO, Fe-ZrO, Co-VO, and Fe-Co-VO) cathode materials have been conveniently fabricated via an “acid-assisted synthesis” strategy. As a paradigm, the FeVO-PBA (FV) delivers a superb rate capability (148.9 and 56.1 mAh/g under 0.5 and 100 C, respectively), remarkable cycling stability over 30,000 cycles, high energy density (259.7 Wh/kg for the full cell), and a wide operation-temperature range (−60–80 °C). In situ / ex situ techniques and density functional theory calculations reveal the quasi-zero-strain and multielectron redox mechanisms of the FeVO-PBA cathode during cycling, supporting its higher specific capacity and stable cycling. It is considered that the d–d electron compensation effect between Fe and V enhanced the reversibility and kinetics of redox reactions and simultaneously improved the electronic conductivity and structural stability of the FeVO-PBA cathode. This work may pave a new way for the rational design of high-performance cathode materials with bimetallic reaction centers for SIBs.}, archive = {J_JACS}, author = {Zhongxin Jing and Lingtong Kong and Muhammad Mamoor and Lu Wang and Bo Zhang and Bin Wang and Yanjun Zhai and Fengbo Wang and Guangmeng Qu and Yueyue Kong and Dedong Wang and Liqiang Xu}, doi = {10.1021/jacs.4c16031}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3702--3713}, shortjournal = {J. Am. Chem. Soc.}, title = {Rational design of prussian blue analogues for ultralong and wide-temperature-range sodium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Organocatalytic asymmetric synthesis of o-carboranyl amines. JACS, 147(4), 3692--3701. (www)

  @article{ , abstract = {Carboranyl amines are distinct from typical organic amines. Due to the electronic influence of the carborane cage, they have low nucleophilicity and are reluctant to alkylate. Moreover, asymmetric synthesis of chiral carboranes is still in its infancy. Herein we have achieved the first catalytic asymmetric N -alkylation of o -carboranyl amine, providing general access to diverse secondary o -carboranyl amines with high efficiency and enantioselectivity under mild conditions. For the first time, asymmetric organocatalysis was introduced to carborane chemistry. Key to the success is the use of in situ generated (naphtho-)quinone methides as the alkylating reagents and suitable chiral acid catalysts. This protocol is also applicable to the asymmetric S -alkylation of 1-SH- o -C 2 B 10 H 11 . Control experiments and kinetic studies provided important insights into the reaction mechanism, which likely involves rate-determining generation of the quinone methide followed by fast and enantio-determining nucleophilic addition.}, archive = {J_JACS}, author = {Hong-Lei Xu and Minghui Zhu and Herman H. Y. Sung and Ian D. Williams and Zhenyang Lin and Chaoshen Zhang and Jianwei Sun}, doi = {10.1021/jacs.4c16062}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3692--3701}, shortjournal = {J. Am. Chem. Soc.}, title = {Organocatalytic asymmetric synthesis of o-carboranyl amines}, volume = {147}, year = {2025}, }
• (2025). Nucleation and growth of monodisperse and monocrystalline wurtzite CdSe nanocrystals: Zinc alkanoates as neutral ligands. JACS, 147(4), 3679--3691. (www)

  @article{ , abstract = {Here, we demonstrate that monocrystalline (free of stacking faults) wurtzite CdSe nanocrystals with monodisperse size, shape (dots, rods, or wires), and facet structure are synthesized in both strongly confined and weakly confined size regimes. Considering the unique c -axis of wurtzite CdSe, we introduce a new type of neutral ligand (e.g., zinc-alkanoate ones) to pair with their dominating nonpolar low-index facets. Nucleation of the stacking fault-free wurtzite seeds instead of zinc-blende tetrahedrons is identified as the key step, which is optimized by a set of conditions matching the neutral zinc-alkanoate ligands. In the following growth stage, conditions are much less stringent, although the neutral zinc-alkanoate ligands are still critical in achieving nearly atomically flat facets of those monocrystalline nanocrystals. In the strongly confined size regime, the ensemble photoluminescence (PL) full-width-at-half-maximum (FWHM) of wurtzite CdSe nanocrystals reaches a record low (59 meV). In the weakly confined size regime, dual-peak PL caused by thermal population is observed. Monodisperse and monocrystalline wurtzite CdSe nanocrystals show distinctively size-dependent optical properties, in comparison with their zinc-blende counterparts. Results here suggest that the atomically precise synthesis of colloidal semiconductor nanocrystals is feasible, implying an advanced class of nanomaterials for exploring various optical and optoelectronic applications.}, archive = {J_JACS}, author = {Xu Cao and Jiongzhao Li and Xudong Qian and Chuyue Li and Xiaogang Peng}, doi = {10.1021/jacs.4c15987}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3679--3691}, shortjournal = {J. Am. Chem. Soc.}, title = {Nucleation and growth of monodisperse and monocrystalline wurtzite CdSe nanocrystals: Zinc alkanoates as neutral ligands}, volume = {147}, year = {2025}, }
• (2025). Secondary alkylation of arenes via the Borono–Catellani strategy. JACS, 147(4), 3670--3678. (www)

  @article{ , abstract = {A modular platform technology for the synthesis of α-aryl carbonyl derivatives via Borono–Catellani-type secondary alkylation of arenes is presented. This practical method features a broad substrate scope regarding aryl boronic acid catechol esters, secondary alkyl bromides, and diversified terminating reagents (e.g., olefins, alkynes, and Zn(CN) 2 ), mild reaction conditions, and good functional-group tolerance. Importantly, the asymmetric version based on a dynamic kinetic asymmetric transformation (DyKAT) has also been realized by introducing the 1:1 diastereomeric mixture of α-bromo carboxamides bearing an Evans chiral auxiliary as the electrophiles, and constantly excellent diastereoselectivities (>20:1 d.r. ) are obtained. Notably, the obtained chiral products can be readily transformed into diversified enantioenriched α-aryl propionic acid derivatives, laying a solid foundation for the discovery of new NSAIDs. Through mechanistic studies and DFT calculations, a critical stereoretentive oxidative addition step is revealed in this Borono–Catellani secondary alkylation reaction, and the origins of stereodiscrimination of this DyKAT are well explained.}, archive = {J_JACS}, author = {Haiyun Peng and Dandan Wang and Jinxiang Ye and Ze-Shui Liu and Zewen Zhu and Xuepeng Fu and Chang Liu and Hengjiang Cong and Hong-Gang Cheng and Qianghui Zhou}, doi = {10.1021/jacs.4c15956}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3670--3678}, shortjournal = {J. Am. Chem. Soc.}, title = {Secondary alkylation of arenes via the Borono–Catellani strategy}, volume = {147}, year = {2025}, }
• (2025). Oxygen-driven atom transfer radical polymerization. JACS, 147(4), 3662--3669. (www)

  @article{ , abstract = {In traditional atom transfer radical polymerization (ATRP), oxygen must be meticulously eliminated due to its propensity to quench radical species and halt the polymerization process. Additionally, oxygen oxidizes the lower-valent Cu catalyst, compromising its ability to activate alkyl halides and propagate polymerization. In this study, we present an oxygen-driven ATRP utilizing alkylborane compounds, a method that not only circumvents the need for stringent oxygen removal but also exploits oxygen as an essential cofactor to promote polymerization. This approach exhibits broad compatibility in organic or aqueous media, yielding well-defined polymers with low dispersity ( Đ as low as 1.11) and molecular weights closely aligned with theoretical values. Triethylborane (Et 3 B) and its air-stable triethylborane-amine complex (Et 3 B-DMAP) facilitate controlled polymerization under open-to-air conditions, demonstrating efficiency across a wide range of monomers. Moreover, the technique enables the successful synthesis of protein–polymer conjugates and supports surface modifications of nanoparticles and silicon wafers under aerobic conditions. This oxygen-driven ATRP represents a robust and versatile platform for precision polymerization with far-reaching implications in materials science, biomedicine, and advanced surface engineering.}, archive = {J_JACS}, author = {Yuxuan Du and Zhe Chen and Zhikang Xie and Siyu Yi and Krzysztof Matyjaszewski and Xiangcheng Pan}, doi = {10.1021/jacs.4c15952}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3662--3669}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxygen-driven atom transfer radical polymerization}, volume = {147}, year = {2025}, }
• (2025). Hyperconjugation engineering of π-extended azaphosphinines for designing tunable thermally activated delayed fluorescence emitters. JACS, 147(4), 3650--3661. (www)

  @article{ , abstract = {Implanting heteroatoms into organic π-conjugated molecules (OCMS) offered a great opportunity to fine-tune the chemical structures and optoelectronic properties. This work describes a new family of 1,4-azaphosphinines with extended σ–π hyperconjugations. The photophysical studies revealed that azaphosphinines exhibited narrow-band thermally activated delayed fluorescence (TADF) ( full width at half-maximum: 26–40 nm). According to the orbital localization analysis and natural bond orbital analysis, the effective σ*−π* hyperconjugation is believed to induce the multiple-resonance (MR) TADF, which is distinct from the p−π conjugation-induced MR-TADF in BN systems. Although having the large Δ E S1–T1 s (>3.0 ev), the study suggested that σ*−π hyperconjugation endowed the system with the structural vibration favorable for the spin-vibronic-assisted RISC. Having the tunable p-centers (lp, O, S, Se, and Me + ), azaphosphinines showed a fine-tuned TADF. Generally, azaphosphinines with strong σ*−π* hyperconjugations showed small Δ E S1–T1 s, efficient RISCs, and high PLQYs. Leveraging on the efficient hyperconjugations, TADF emission of the system spanned from UV-blue to green. Particularly, extended azaphosphinines exhibited the high photoluminescence quantum yields (74% in toluene and 92% in the 10% doped PMMA). As a proof of concept, two azaphosphinines with a PO center were applied as the light-emitting materials in organic lighting-emitting diodes. The devices showed the narrow-band UV- and deep-blue emission with EQE as high as 10.3%. The current study offered us a new strategy, namely, σ–π hyperconjugation-induced MR-TADF, for designing OCMs with tunable light-emitting properties.}, archive = {J_JACS}, author = {Zhaoxin Liu and Lingqiang Meng and Yanrong Jiang and Chao Li and Huanchao Gu and Kexuan Zhao and Ji Zhang and Hong Meng and Yi Ren}, doi = {10.1021/jacs.4c15651}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3650--3661}, shortjournal = {J. Am. Chem. Soc.}, title = {Hyperconjugation engineering of π-extended azaphosphinines for designing tunable thermally activated delayed fluorescence emitters}, volume = {147}, year = {2025}, }
• (2025). Unlocking the key to photocatalytic hydrogen production using electronic mediators for Z-scheme water splitting. JACS, 147(4), 3641--3649. (www)

  @article{ , abstract = {A prevalent challenge in particulate photocatalytic water splitting lies in the fact that while numerous photocatalysts exhibit outstanding hydrogen evolution reaction (HER) activity in organic sacrificial reagents, their performance diminishes markedly in a Z-scheme water splitting system using electronic mediators. This underlying reason remains undefined, posing a long-standing issue in photocatalytic water splitting. Herein, we unveiled that the primary reason for the decreased HER activity in electronic mediators is due to the strong adsorption of shuttle ions on cocatalyst surfaces, which inhibits the initial proton reduction and results in a severe backward reaction of the oxidized shuttle ions. To address this, taking typical visible-light-responsive photocatalysts, BaTaO 2 N and SrTiO 3 :Rh, as examples, we have developed a strategy via selective surface modification of metal cocatalysts (such as Pt, Ru) with chromium oxide species (CrO x ) to prevent the adsorption of shuttle ions. It is demonstrated that the photocatalytic HER activities of BaTaO 2 N and SrTiO 3 :Rh can be improved by one to two orders of magnitude in diverse shuttle ions. The introduced CrO x substantially weakens the interaction between the metal cocatalysts and shuttle ions, promotes proton adsorption for the HER reaction, and also suppresses the backward reaction between shuttle ions. Owing to the improved HER activity, the photocatalytic performance of Z-scheme water splitting is significantly enhanced, providing a feasible strategy for constructing efficient Z-scheme systems in heterogeneous photocatalysis.}, archive = {J_JACS}, author = {Ming Shi and Xuan Wu and Yue Zhao and Rengui Li and Can Li}, doi = {10.1021/jacs.4c15540}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3641--3649}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking the key to photocatalytic hydrogen production using electronic mediators for Z-scheme water splitting}, volume = {147}, year = {2025}, }
• (2025). Spontaneous formation of single-crystalline spherulites in a chiral 2D hybrid perovskite. JACS, 147(4), 3631--3640. (www)

  @article{ , abstract = {In two-dimensional (2D) chiral metal-halide perovskites (MHPs), chiral organic spacers induce structural chirality and chiroptical properties in the metal-halide sublattice. This structural chirality enables reversible crystalline-glass phase transitions in ( S -NEA) 2 PbBr 4 , a prototypical chiral 2D MHP where NEA + represents 1-(1-naphthyl)ethylammonium. Here, we investigate two distinct spherulite states of ( S -NEA) 2 PbBr 4 , exhibiting either radial-like or stripe-like banded patterns depending on the annealing conditions of the amorphous film. Despite similarities in optical absorption and photoluminescence, the stripe-like, banded spherulite exhibits higher crystallinity and improved optical transparency compared to those of radial-like spherulite. X-ray nanoprobe measurements reveal tilting-angle modulations in the octahedral plane of stripe-like spherulites, correlating with the film’s surface geometry. Transfer matrix calculations indicate that the optical contrast in stripe-like patterns, seen in bright-field optical microscopy, arises from optical interference effects, differing from the contrast mechanism observed in polymer spherulites. Ultrafast carrier dynamics experiments suggest that the stripe-like spherulites resemble single crystals more closely than radial-like spherulites, while electrical conductivity measurements show enhanced charge carrier transport in stripe-like spherulites. These findings offer insights into MHP spherulite states with a single composition but different morphologies, previously observed only in polymers, highlighting their potential for optoelectronic applications.}, archive = {J_JACS}, author = {Shunran Li and Du Chen and Bowen Li and Hanfei Yan and Benjamin J. Lawrie and Bongjun Choi and Dongjoon Rhee and Yanyan Li and Huan Zhao and Linqi Chen and Ajith Pattammattel and Suchismita Sarker and Deep Jariwala and Peijun Guo}, doi = {10.1021/jacs.4c15471}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3631--3640}, shortjournal = {J. Am. Chem. Soc.}, title = {Spontaneous formation of single-crystalline spherulites in a chiral 2D hybrid perovskite}, volume = {147}, year = {2025}, }
• (2025). Ab initio predictions of adsorption in flexible Metal–Organic frameworks for water harvesting applications. JACS, 147(4), 3615--3630. (www)

  @article{ , abstract = {Metal–organic frameworks such as MOF-303 and MOF-LA2–1 have demonstrated exceptional performance for water harvesting applications. To enable a reticular design of such materials, an accurate prediction of the adsorption properties with chemical accuracy and fully accounting for the flexibility is crucial. The computational prediction of water adsorption properties in MOFs has become standard practice, but current methods lack the predictive power needed to design new materials. Limitations stem from the way the interatomic potential is described and the inadequate consideration of the framework flexibility. Herein, we showcase a methodology to obtain chemically accurate adsorption isotherms that fully account for framework flexibility. The method relies on very accurate and efficiently trained machine learning potentials and transition matrix Monte Carlo simulations to account for framework flexibility. For MOF-303, quantitatively accurate adsorption isotherms are obtained, provided an accurately benchmarked electronic structure method is used to train the machine learning potential, and local and global framework flexibility is accounted for. The broader applicability is shown through the study of MOF-333 and MOF-LA2–1. Analysis of the water density profiles in the MOFs gives insight into the factors governing the shape and origin of the isotherm. An optimal water harvester should have initial seeding sites with intermediate adsorption strength to prevent detrimental low-pressure water uptake. To increase the working capacity, linker extension strategies can be used while maintaining the initial seeding sites, as was done in MOF-LA2–1. The methodology can be applied to other guest molecules and MOFs, enabling the future design of MOFs with specific adsorption properties.}, archive = {J_JACS}, author = {Ruben Goeminne and Veronique Van Speybroeck}, doi = {10.1021/jacs.4c15287}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3615--3630}, shortjournal = {J. Am. Chem. Soc.}, title = {Ab initio predictions of adsorption in flexible Metal–Organic frameworks for water harvesting applications}, volume = {147}, year = {2025}, }
• (2025). Chain shuttling enantioselective polymerization: An effective strategy for synthesizing stereoblock polythioethers. JACS, 147(4), 3607--3614. (www)

  @article{ , abstract = {Herein, we propose to synthesize stereoblock polythioethers through the chain shuttling enantioselective ring-opening polymerization (ROP) of thiiranes. The use of diastereoisomeric dinuclear Cr complexes with optimized steric hindrance allowed the production of polythioethers with both a head-to-tail content and isotacticity of >99%. In particular, the introduction of dithiols enabled the synthesis of stereoblock polythioethers via a chain shuttling process, thus producing sulfhydryl-telechelic polythioethers with tunable thermal properties. Experimental results and density functional theory calculations indicate that the configuration of the chiral axle of the dinuclear Cr complex determines the enantioselectivity of the asymmetric ROP of thiiranes.}, archive = {J_JACS}, author = {Tian-Jun Yue and Yu Xiao and Bai-Hao Ren and Xiao-Bing Lu and Wei-Min Ren}, doi = {10.1021/jacs.4c15343}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3607--3614}, shortjournal = {J. Am. Chem. Soc.}, title = {Chain shuttling enantioselective polymerization: An effective strategy for synthesizing stereoblock polythioethers}, volume = {147}, year = {2025}, }
• (2025). Electrostatic and electronic effects on doped nickel oxide nanofilms for water oxidation. JACS, 147(4), 3593--3606. (www)

  @article{ , abstract = {An ideal water-splitting electrocatalyst is inexpensive, abundant, highly active, stable, selective, and durable. The anodic oxygen evolution reaction (OER) is the main bottleneck for H 2 production with a complex and not fully resolved mechanism, slow kinetics, and high overpotential. Nickel oxide-based catalysts (NiO x ) are highly active and cheaper than precious metal catalysts. However, rigorous catalyst tests and DFT calculations are still needed to rationally optimize NiO x catalysts. In this work, we combine plasma-enhanced atomic layer deposition (PE-ALD) and density functional theory (DFT) to address the role of dopants in promoting NiO x OER activity. Ultrathin films of NiO x doped with Zn 2+ , Al 3+ , and Sn 4+ presented improved intrinsic activity, stability, and durability for the OER. The results show a low to high catalytic performance of ZnNiO x < NiO x < AlNiO x < SnNiO x , which we attribute to an increase in the concentration of valence band (VB) holes combined with conduction band (CB) electron conductivity, characterized by electrochemical impedance spectroscopy (EIS). The influence of doping on the electronic structure and catalytic activity was investigated using advanced characterization techniques and density functional theory (DFT) calculations (PEB0/pob-TZVP). DFT complements the experimental results, showing that the dopant charge states and orbital hybridization enhance the OER by improving the charge carrier concentration and mobility, thus allowing optimal binding energies and charge dynamics and delocalization. Our findings demonstrate the potential of PE-ALD-doped nanofilms NiO x and DFT to rationally design and develop catalysts for sustainable energy applications.}, archive = {J_JACS}, author = {Ina Østrøm and Marco Favaro and Moein Seyfouri and Patrick Burr and Bram Hoex}, doi = {10.1021/jacs.4c14493}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3593--3606}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrostatic and electronic effects on doped nickel oxide nanofilms for water oxidation}, volume = {147}, year = {2025}, }
• (2025). ThCTi@Cs(6)-c82: Th═C double bond in a mixed actinide-transition metal cluster. JACS, 147(4), 3584--3592. (www)

  @article{ , abstract = {A thorium–carbon double bond that corresponds to the sum of theoretical covalent double bond radii has long been sought after in the study of actinide-ligand multiple bonding as a synthetic target. However, the stabilization of this chemical bond remains a great challenge to date, in part because of a relatively poor energetic matching between 5f-/6d- orbitals of thorium and the 2s-/2p- frontier orbitals of carbon. Herein, we report the successful synthesis of a thorium–carbon double bond in a carbon-bridged actinide-transition metal cluster, i.e., [Th═C═Ti], encapsulated inside a fullerene cage of C 82 . ThCTi@ C s (6)-C 82 was successfully synthesized by a modified arc discharging method and characterized by mass spectrometry, single-crystal X-ray crystallography, various spectroscopy, and theoretical calculations. X-ray crystallographic analysis reveals a bent μ 2 -bridged carbide cluster with a Th–C distance of 2.123(18) Å, which is the shortest reported to date in an isolable compound and is comparable to the sum of the covalent Th═C double bond radii (2.10 Å). In addition, Th═C═Ti takes an unexpected nonlinear configuration with a bond angle of 133.0(10)°. The combined experimental and theoretical investigation further revealed the bonding nature of Th═C, which is polarized toward the bridged carbon but has a notably higher covalency than the Th–C bonds reported previously for organometallic compounds. Moreover, pronounced cage-to-metal donation appears to be stabilizing the encapsulated Th═C═Ti cluster. This work offers a deeper understanding of the bonding behavior of thorium and features the unique ability of fullerene cages to stabilize bonding motifs containing different types of metal–ligand multiple bonds.}, archive = {J_JACS}, author = {Zhengkai Cao and Xiaojuan Yu and Yang-Rong Yao and Jochen Autschbach and Ning Chen}, doi = {10.1021/jacs.4c15253}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3584--3592}, shortjournal = {J. Am. Chem. Soc.}, title = {ThCTi@Cs(6)-c82: Th═C double bond in a mixed actinide-transition metal cluster}, volume = {147}, year = {2025}, }
• (2025). Integration of motion and stillness: A paradigm shift in constructing nearly planar NIR-II AIEgen with ultrahigh molar absorptivity and photothermal effect for multimodal phototheranostics. JACS, 147(4), 3570--3583. (www)

  @article{ , abstract = {The two contradictory entities in nature often follow the principle of unity of opposites, leading to optimal overall performance. Particularly, aggregation-induced emission luminogens (AIEgens) with donor–acceptor (D–A) structures exhibit tunable optical properties and versatile functionalities, offering significant potential to revolutionize cancer treatment. However, trapped by low molar absorptivity (ε) owing to the distorted configurations, the ceilings of their photon-harvesting capability and the corresponding phototheranostic performance still fall short. Therefore, a research paradigm from twisted configuration to near-planar structure featuring a high ε is urgently needed for AIEgens development. Herein, by introducing the strategy of “motion and stillness” into a highly planar A–D–A skeleton, we successfully developed a near-infrared (NIR)-II AIEgen of Y5-2BO-2BTF, which boasts an impressive ε of 1.06 × 10 5 M –1 cm –1 and a photothermal conversion efficiency (PCE) of 77.8%. The modification of steric hindrance on the benzene ring in the acceptor unit of the aggregation-caused quenching counterpart Y5-2BO, to a meta -CF 3 -substituted naphthyl, leads to reversely staggered packing and various intermolecular noncovalent conformational locks in Y5-2BO-2BTF (“stillness”). Furthermore, the −CF 3 moiety acted as a flexible motion unit with an ultralow energy barrier, significantly facilitating the photothermal process in loose Y5-2BO-2BTF aggregates (“motion”). Accordingly, Y5-2BO-2BTF nanoparticles enabled tumor eradication and pulmonary metastasis inhibition through NIR-II fluorescence-photoacoustic-photothermal imaging-navigated type I photodynamic-photothermal therapy. This work provides the first evidence that the highly planar conformation with a reversely staggered stacking arrangement could serve as a novel molecular design direction for AIEgens, shedding new light on constructing superior phototheranostic agents for bioimaging and cancer therapy.}, archive = {J_JACS}, author = {Shiping Yang and Qian Jia and Xinwen Ou and Fang Sun and Chaoqi Song and Tingxing Zhao and Ryan T. K. Kwok and Jianwei Sun and Zheng Zhao and Jacky W. Y. Lam and Zhongliang Wang and Ben Zhong Tang}, doi = {10.1021/jacs.4c15216}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3570--3583}, shortjournal = {J. Am. Chem. Soc.}, title = {Integration of motion and stillness: A paradigm shift in constructing nearly planar NIR-II AIEgen with ultrahigh molar absorptivity and photothermal effect for multimodal phototheranostics}, volume = {147}, year = {2025}, }
• (2025). In situ conversion of atherosclerotic plaques’ iron into nanotheranostics. JACS, 147(4), 3553--3569. (www)

  @article{ , abstract = {The presence of a substantial necrotic core in atherosclerotic plaques markedly heightens the risk of rupture, a consequence of elevated iron levels that exacerbate oxidative stress and lipid peroxidation, thereby sustaining a detrimental cycle of ferroptosis and inflammation. Concurrently targeting both ferroptosis and inflammation is crucial for the effective treatment of vulnerable plaques. In this study, we introduce gallium hexacyanoferrate nanoabsorption catalysts (GaHCF NACs) designed to disrupt this pathological cycle. GaHCF NACs function as highly efficient iron chelators with robust antiferroptosis properties. Through in situ capture of iron within atherosclerotic plaques, these catalysts enhance reactive oxygen species scavenging, initiating an amplified therapeutic response. GaHCF NACs significantly advance plaque regression, stabilization, and vascular functional recovery by inhibiting MAPK13 (p38-δ MAPK) signaling, a key mediator of inflammation and cell death. Importantly, the in situ iron capture process generates a detectable photoacoustic signal, offering a notable diagnostic advantage that allows real-time monitoring of plague status. This multifunctional nanocatalytic platform in situ transforms toxic iron within atherosclerotic plaques into both a therapeutic and diagnostic agent, adapting dynamically to the microenvironment and representing a promising strategy for reducing plaque vulnerability and preventing rupture.}, archive = {J_JACS}, author = {Wenqi Pan and Sihui Shao and Xinyue Cao and Xinyue Dai and Yi Zheng and Jingyun Cheng and Wei Feng and Rong Wu and Yu Chen}, doi = {10.1021/jacs.4c15068}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3553--3569}, shortjournal = {J. Am. Chem. Soc.}, title = {In situ conversion of atherosclerotic plaques’ iron into nanotheranostics}, volume = {147}, year = {2025}, }
• (2025). Key interaction changes determine the activation process of human parathyroid hormone type 1 receptor. JACS, 147(4), 3539--3552. (www)

  @article{ , abstract = {The parathyroid hormone type 1 receptor (PTH1R) plays a crucial role in modulating various physiological functions and is considered an effective therapeutic target for osteoporosis. However, a lack of detailed molecular and energetic information about PTH1R limits our comprehensive understanding of its activation process. In this study, we performed computational simulations to explore key events in the activation process, such as conformational changes in PTH1R, Gs protein coupling, and the release of guanosine diphosphate (GDP). Our analysis identified kinetic information, including the rate-determining step, transition state, and energy barriers. Free-energy and structural analyses revealed that GDP could be released from the Gs protein when the binding cavity is partially open. Additionally, we predicted important residues, including potential pathogenic mutations, and verified their significance through site-directed mutations. These findings enhance our understanding of class B GPCR activation mechanisms. Furthermore, the methodology employed in this study can be applied to other biophysical systems.}, archive = {J_JACS}, author = {Yue Zhang and Qingchuan Zheng and Arieh Warshel and Chen Bai}, doi = {10.1021/jacs.4c15025}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3539--3552}, shortjournal = {J. Am. Chem. Soc.}, title = {Key interaction changes determine the activation process of human parathyroid hormone type 1 receptor}, volume = {147}, year = {2025}, }
• (2025). Scale-up of microdroplet reactors for efficient CO2 resource utilization. JACS, 147(4), 3529--3538. (www)

  @article{ , abstract = {Two-phase reactions involving microdroplets have gained significant attention in recent years due to their unique ability to catalyze and accelerate reactions that typically do not occur under standard conditions by leveraging chemical and physical effects at the micrometer-scale interface. In this work we have innovatively developed a scaled-up microdroplet reactor for the efficient resource utilization of CO 2 . The reaction liquid is sprayed in the form of mist ( d 32 < 20 μm), facilitating complete contact and reaction with gaseous CO 2 . We explored the effects of spray properties and reactor parameters on the continuous production of organic carbonates from CO 2 . Remarkably, the microdroplet reactor enhanced the reaction efficiency by at least 10-fold compared to conventional high-pressure reactor setups. Additionally, we used computational fluid dynamics (CFD) simulations to optimize the process conditions and continuous production parameters, systematically studying the effects of scaling up the device. Here, we present insights into the utilization of microdroplet reactors for CO 2 conversion in scaled-up applications, supported by robust data.}, archive = {J_JACS}, author = {Xiemin Liu and Xinyao Li and Xinrong Wang and Yanan Li and Xingbang Hu and Zheng Zhou and Feng Zhang and Zhibing Zhang and Yi Chen}, doi = {10.1021/jacs.4c14733}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3529--3538}, shortjournal = {J. Am. Chem. Soc.}, title = {Scale-up of microdroplet reactors for efficient CO2 resource utilization}, volume = {147}, year = {2025}, }
• (2025). Be aware of transient dissolution processes in Co3O4 acidic oxygen evolution reaction electrocatalysts. JACS, 147(4), 3517--3528. (www)

  @article{ , abstract = {Recently, cobalt-based oxides have received considerable attention as an alternative to expensive and scarce iridium for catalyzing the oxygen evolution reaction (OER) under acidic conditions. Although the reported materials demonstrate promising durability, they are not entirely intact, calling for fundamental research efforts to understand the processes governing the degradation of such catalysts. To this end, this work studies the dissolution mechanism of a model Co 3 O 4 porous catalyst under different electrochemical conditions using online inductively coupled plasma mass spectrometry (online ICP-MS), identical location scanning transmission electron microscopy (IL-STEM), and differential electrochemical mass spectrometry (DEMS). Despite the high thermodynamics tendency reflected in the Pourbaix diagram, it is shown that the cobalt dissolution kinetics is sluggish and can be lowered further by modifying the electrochemical protocol. For the latter, identified in this study, several (electro)chemical reaction pathways that lead to the dissolution of Co 3 O 4 must be considered. Hence, this work uncovers the transient character of cobalt dissolution and provides valuable insights that can help to understand the promising stability of cobalt-based materials in already published works and facilitate the knowledge-driven design of novel, stable, abundant catalysts toward the OER in an acidic environment.}, archive = {J_JACS}, author = {Tatiana Priamushko and Evanie Franz and Anja Logar and Lazar Bijelić and Patrick Guggenberger and Daniel Escalera-López and Matej Zlatar and Jörg Libuda and Freddy Kleitz and Nejc Hodnik and Olaf Brummel and Serhiy Cherevko}, doi = {10.1021/jacs.4c14952}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3517--3528}, shortjournal = {J. Am. Chem. Soc.}, title = {Be aware of transient dissolution processes in Co3O4 acidic oxygen evolution reaction electrocatalysts}, volume = {147}, year = {2025}, }
• (2025). Ordered interfacial water generated at poly(ionic liquid) membrane surface imparts ultrafast water transport and superoleophobicity. JACS, 147(4), 3507--3516. (www)

  @article{ , abstract = {Achieving ultrahigh permeance and superoleophobicity is crucial for membrane application. Here, we demonstrated that a poly(ionic liquid)/PES hydrogel membrane can achieve dual goals. The high polarity of the ionic liquids induces the water molecules on the membrane surface to be arranged more ordered, as verified by molecular dynamics (MD) simulation and advanced femtosecond sum frequency generation (SFG) vibrational spectroscopy. Meanwhile, a large amount of water exists in membrane pores, demonstrated by water absorption, low-field nuclear magnetic resonance, and SFG spectroscopy. The interfacial water layer endows the membrane with superior anti-oil-fouling properties, and the large amount of water in membrane pores imparts membrane with ultrahigh permeability. The positive charge on the channel surface and moderate channel size confer a high rejection of metal ions. The optimal membrane exhibited a permeance of 35.1 L m –2 h –1 bar –1 , 5–10 times that of conventional hydrogel membranes with similar rejection. Moreover, the membrane exhibited excellent antibacterial properties. It can be expected that highly polar poly(ionic liquid) membranes will find promising applications in the water treatment field.}, archive = {J_JACS}, author = {Luqi Xiao and Xiaoxuan Zheng and Ju Bai and Junjun Tan and Dujuan Meng and Zhen Zhang and Hongyan Liu and Lili Gong and Shuangjiang Luo and Shuji Ye and Zhongyi Jiang and Linglong Shan and Suojiang Zhang}, doi = {10.1021/jacs.4c14897}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3507--3516}, shortjournal = {J. Am. Chem. Soc.}, title = {Ordered interfacial water generated at poly(ionic liquid) membrane surface imparts ultrafast water transport and superoleophobicity}, volume = {147}, year = {2025}, }
• (2025). Ambient temperature isolation of a monatomic boron(0) complex. JACS, 147(4), 3500--3506. (www)

  @article{ , abstract = {The first bottleable example of a neutral Group 13 atom bound only by neutral donor ligands (L) has been fully characterized by spectroscopic methods and its structure determined by a single-crystal X-ray diffraction study. A two-coordinate paramagnetic L 2 B 0 complex can readily be accessed through a facile reduction reaction and is stabilized by π-accepting cyclic (alkyl)(amino)carbene (CAAC) ligands. Further reduction of (CAAC) 2 B leads to the isolation of a stable diamagnetic boride anion. In turn, oxidation leads to the putative formation of a transient two-coordinate cationic borylene, which has been trapped to form a stable boron(I) complex. Density functional theory calculations support the formulation of (CAAC) 2 B as a boron(0) complex stabilized by strong multiple bonding.}, archive = {J_JACS}, author = {William Kennedy and Vignesh Pattathil and YuXiang Wei and Felipe Fantuzzi and Conor Pranckevicius}, doi = {10.1021/jacs.4c14915}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3500--3506}, shortjournal = {J. Am. Chem. Soc.}, title = {Ambient temperature isolation of a monatomic boron(0) complex}, volume = {147}, year = {2025}, }
• (2025). Hypoxia-initiated supramolecular free radicals induce intracellular polymerization for precision tumor therapy. JACS, 147(4), 3488--3499. (www)

  @article{ , abstract = {Despite the development of various controlled release systems for antitumor therapies, off-target side effects remain a persistent challenge. In situ therapeutic synthesis from biocompatible substances offers a safer and more precise alternative. This study presents a hypoxia-initiated supramolecular free radical system capable of inducing intracellular polymerization, thereby disrupting the cytoskeleton and organelles within 4T1 cells. The system utilizes a 2:1 supramolecular host–guest complex of cucurbit[7]uril (CB[7]) and perylene diimide derivative (PDI), termed PDI+2CB[7], which is selectively reduced by the tumor’s hypoxic and reducing environment to generate delocalized free radical anions. CB[7] effectively stabilizes these anions, enabling the PDI+2CB[7] complex to initiate free radical polymerization with 2-hydroxyethyl methacrylate (HEMA) inside the 4T1 cells. The resulting in situ polymerization significantly disrupts tumor metabolism, leading to a strong antitumor response without systemic toxicity. This study demonstrates that stable, endogenous stimulus-induced supramolecular free radicals can trigger intracellular polymerization reactions, achieving a selective and effective antitumor therapy without conventional chemotherapeutic agents.}, archive = {J_JACS}, author = {Mian Tang and Zhiqing Yang and Xingchen Tang and He Ma and Beibei Xie and Jiang-Fei Xu and Cheng Gao and David Bardelang and Ruibing Wang}, doi = {10.1021/jacs.4c14847}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3488--3499}, shortjournal = {J. Am. Chem. Soc.}, title = {Hypoxia-initiated supramolecular free radicals induce intracellular polymerization for precision tumor therapy}, volume = {147}, year = {2025}, }
• (2025). Crafting hollow spheres via bulk ice melting with ppb-level gas sensing performance. JACS, 147(4), 3478--3487. (www)

  @article{ , abstract = {Ice melting, a common yet complex phenomenon, remains incompletely understood. While theoretical studies suggest that preexisting defects in ice generate “off-lattice” water molecules, triggering bulk ice melting, direct experimental evidence of their form has been lacking as the transparent and transient nature of ice poses significant challenges for observation with current techniques. Here, we introduce an ice-melting-induced lyophilization (IMIL) technique that employs graphene-based nanoprobes to replicate and track liquid evolution within melting bulk ice. Our experimental data and theoretical calculations indicate that “off-lattice” water molecules form spherical droplets that enlarge and coalesce as the melting progresses. Notably, the IMIL technique represents a novel nanotechnology for crafting high-quality hollow spheres by leveraging naturally occurring droplets as templates, offering advantages in simplicity, environmental friendliness, scalability, and size adjustability over traditional methods. Additionally, platinum-loaded graphene-based hollow spheres fabricated via the IMIL technique demonstrate ultrasensitive formaldehyde detection with a 5 parts per billion detection limit, rapid response and recovery times (∼4.9 s), and room-temperature operation without auxiliary technology, outperforming WHO standards and current detection methods. These findings highlight the potential of the IMIL technique for creating versatile hollow spheres for diverse applications.}, archive = {J_JACS}, author = {Zhuo Chen and Jinrong Wang and Xing Liu and Yao Wang and Jie Shen and Jiaqiang Li and Xianda Liu and Xueyan Li and Wenle Pei and Ying Guo and Guosheng Shi and Hao Li and Ahmad M. U. Siddiqui and Nicolaas F. de Rooij and Lei Jiang and Guofu Zhou}, doi = {10.1021/jacs.4c14808}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3478--3487}, shortjournal = {J. Am. Chem. Soc.}, title = {Crafting hollow spheres via bulk ice melting with ppb-level gas sensing performance}, volume = {147}, year = {2025}, }
• (2025). Ni-catalyzed enantioselective desymmetrization: Development of divergent acyl and decarbonylative cross-coupling reactions. JACS, 147(4), 3468--3477. (www)

  @article{ , abstract = {Ni-catalyzed asymmetric reductive cross-coupling reactions provide rapid and modular access to enantioenriched building blocks from simple electrophile precursors. Reductive coupling reactions that can diverge through a common organometallic intermediate to two distinct families of enantioenriched products are particularly versatile but underdeveloped. Here, we describe the development of a bis(oxazoline) ligand that enables the desymmetrization of meso -anhydrides. When secondary benzylic electrophiles are employed, doubly stereoselective acyl cross-coupling proceeds to give ketone products with catalyst control over three newly formed stereogenic centers. Alternatively, the use of primary alkyl halides in the presence of an additional halogen atom transfer catalyst results in decarbonylative alkylation to give enantioenriched β-alkyl acids. Analysis of reaction rates for a range of both catalysts and substrates supports the notion that tuning the different electrophile activation steps with the two catalysts is required for enhanced reaction performance. These studies illustrate how reaction design can diverge a common Ni-acyl intermediate to either acyl or decarbonylative coupling products and highlight how dual ligand systems can be used to engage unactivated alkyl halides in Ni-catalyzed asymmetric reductive coupling.}, archive = {J_JACS}, author = {Ángel D. Hernández-Mejías and Alexander M. Shimozono and Avijit Hazra and Sven Richter and Zhengjia Tong and Neil F. Langille and Kyle Quasdorf and Andrew T. Parsons and Matthew S. Sigman and Sarah E. Reisman}, doi = {10.1021/jacs.4c14767}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3468--3477}, shortjournal = {J. Am. Chem. Soc.}, title = {Ni-catalyzed enantioselective desymmetrization: Development of divergent acyl and decarbonylative cross-coupling reactions}, volume = {147}, year = {2025}, }
• (2025). Molecular orbital tuning of pentacene-based organic semiconductors through N-ethynylation of dihydrodiazapentacene. JACS, 147(4), 3459--3467. (www)

  @article{ , abstract = {This study explores the concept of molecular orbital tuning for organic semiconductors through the use of N,N ′-diethynylated derivatives of 6,13-dihydro-6,13-diazapentacene ( 2a and 2b ). These novel molecules maintain the same molecular geometry and π–π stacking as their parent pentacene derivatives ( 1a and 1b ), as confirmed by X-ray crystallography. However, they exhibit altered frontier molecular orbitals in terms of the phase, nodal properties, and energy levels. Theoretical calculations based on crystal structures indicate that 2a and 2b could significantly enhance the hole mobilities of the parent compounds by improving the hole transfer integral. Organic field-effect transistors (OFETs) of 1a and 2a were fabricated by using dip-coating and bar-coating methods. Both types of devices for 2a demonstrated a hole mobility exceeding 1 cm 2 V –1 s –1 , more than twice that of the respective devices for 1a . Additionally, unlike its pentacene parent, 2a is transparent to visible light and exhibits significantly enhanced environmental stability against light and air, making it a promising candidate for broader applications in organic electronic devices.}, archive = {J_JACS}, author = {Li Zhang and Yujie Zhao and Jiasheng Li and Yuang Fu and Boyu Peng and Jun Yang and Xinhui Lu and Qian Miao}, doi = {10.1021/jacs.4c14775}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3459--3467}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular orbital tuning of pentacene-based organic semiconductors through N-ethynylation of dihydrodiazapentacene}, volume = {147}, year = {2025}, }
• (2025). Organocatalytic activation of alkynes enabled remote control of atroposelectivity via vinylidene para-quinone methides. JACS, 147(4), 3450--3458. (www)

  @article{ , abstract = {Axially chiral o -VQMs have been extensively investigated as key intermediates to approach miscellaneous chiral structures. By sharp contrast, their structural isomers p -VQMs have not been previously documented. The major reason, which results in the significant delay, may ascribe to the inherent challenges in the enantioselective activation of alkynes in a remote manner. Herein, we demonstrate that the remote activation mechanism of para -hydroxyl-substituted arylacetylenes enables significant stereochemical induction, resulting in axially chiral aryl-alkenes with excellent enantiopurities. A series of control experiments are performed to elucidate the insights of this asymmetric transformation and to verify the involvement of multimolecular CPAs in the reaction process. These findings are expected to unlock a new feature for VQM chemistry and inspire investigation into the organocatalytic remote control of stereoselectivity.}, archive = {J_JACS}, author = {Yuan Cui and Yong-Bin Wang and Huan-Huan Liu and Shao-Hua Xiang and Bin Tan}, doi = {10.1021/jacs.4c14589}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3450--3458}, shortjournal = {J. Am. Chem. Soc.}, title = {Organocatalytic activation of alkynes enabled remote control of atroposelectivity via vinylidene para-quinone methides}, volume = {147}, year = {2025}, }
• (2025). Can low structural anisotropy produce high optical anisotropy? anomalous giant optical birefringent effect in PI4AlI4 in focus. JACS, 147(4), 3438--3449. (www)

  @article{ , abstract = {Tetrahedral halides with broad transparency and large second harmonic effects have the potential to serve as mid-infrared wide-bandgap materials with balanced nonlinear-optical (NLO) properties. However, their regular tetrahedral motifs tend to exhibit low optical birefringence (Δ n < 0.03) due to limited structural anisotropy, which constrains their practical phase-matched capability. A significant challenge in halide structural chemistry and material exploration is to enhance the Δ n of tetrahedral halides while maintaining their balanced properties. The question of whether tetrahedra with low structural anisotropy can produce high optical anisotropy remains unanswered. In this study, in addition to the conventional strategy of enhancing Δ n by increasing structural anisotropy, we identify a previously unreported strategy of enhancing Δ n by increasing electronic anisotropy. This novel strategy model unprecedentedly enhances the Δ n of an existing tetrahedral halide, PI 4 AlI 4 , to a degree not achievable by conventional techniques, with the value reaching up to 0.31@1 μm. The anomalous increase in Δ n is achieved by anisotropic charge redistribution resulting from a unique charge transfer effect between the anionic and cationic tetrahedral motifs. First-principles analysis provides further corroboration of the detailed chemical bonding electronic distributions and charge transfer illustrations. It is predicted that analogous AsI 4 AlI 4 and TeI 4 ZnI 4 will exhibit a greater propensity for giant Δ n (> 0.5@1 μm). This finding will greatly enrich the structural chemistry of sp 3 -hybridized tetrahedra and provide seminal ideas for the design and modulation of highly birefringent structures.}, archive = {J_JACS}, author = {Huige Chen and Pifu Gong and Zheshuai Lin and Lei Kang}, doi = {10.1021/jacs.4c14624}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3438--3449}, shortjournal = {J. Am. Chem. Soc.}, title = {Can low structural anisotropy produce high optical anisotropy? anomalous giant optical birefringent effect in PI4AlI4 in focus}, volume = {147}, year = {2025}, }
• (2025). Photocatalytic methanol dehydrogenation with switchable selectivity. JACS, 147(4), 3428--3437. (www)

  @article{ , abstract = {Switchable selectivity achieved by altering reaction conditions within the same photocatalytic system offers great advantages for sustainable chemical transformations and renewable energy conversion. In this study, we investigate an efficient photocatalytic methanol dehydrogenation with controlled selectivity by varying the concentration of nickel cocatalyst, using zinc indium sulfide nanocrystals as a semiconductor photocatalyst, which enables the production of either formaldehyde or ethylene glycol with high selectivity. Control experiments revealed that formaldehyde is initially generated and can either serve as a terminal product or intermediate in producing ethylene glycol, depending on the nickel concentration in the solution. Mechanistic studies suggest a unique role of ionic nickel as an additional photoelectron competitor that can significantly influence selectivity, alongside its well-established function as a hydrogen evolution reaction cocatalyst under photocatalytic conditions. The demonstrated switchable selectivity provides a new tool for producing diverse products from methanol, while advancing the understanding of cocatalyst behavior for versatile catalytic performance.}, archive = {J_JACS}, author = {Jie Luo and Cheng Zhu and Jialu Li and Jianbo Jin and Nathan E. Soland and Patrick W. Smith and Yu Shan and Alexander M. Oddo and Arifin Luthfi Maulana and Lihini Jayasinghe and Xinyu Chen and Tianle Wang and Jia-An Lin and Emily Lu and Bernd Schaefer and Matthias Schmalzbauer and Rui Zhang and Fabian Seeler and Carlos Lizandara-Pueyo and Jinghua Guo and Peidong Yang}, doi = {10.1021/jacs.4c14413}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3428--3437}, shortjournal = {J. Am. Chem. Soc.}, title = {Photocatalytic methanol dehydrogenation with switchable selectivity}, volume = {147}, year = {2025}, }
• (2025). Permanent nanobubbles in water: Liquefied hollow carbon spheres break the limiting diffusion current of oxygen reduction reaction. JACS, 147(4), 3421--3427. (www)

  @article{ , abstract = {Porous liquids have traditionally been designed with sterically hindered solvents. Alternatively, recent efforts rely on dispersing microporous frameworks in simpler solvents like water. Here we report a unique strategy to construct macroporous water by selectively incorporating hydrophilicity on the surfaces of hydrophobic hollow carbon spheres (HCS). Specifically, we show that the stable dispersion surface ionized HCS in water while retaining the inherent porosity. The electrocatalytic conversion of small gas molecules in aqueous electrolytes is limited by the concentration and diffusion rates of gas molecules in water. In this case, macroporous water exhibited 6 times gas uptake compared to nonporous (pure) water. By leveraging the high gas capacity and enhanced diffusion kinetics, the limiting diffusion current of oxygen reduction reaction (ORR) in macroporous water is 2 times that in nonporous water, offering promising prospects for sustainable energy conversion technologies.}, archive = {J_JACS}, author = {Debabrata Moitra and Arvind Ganesan and Fan Wang and Liqi Qiu and Kevin Siniard and Zhenzhen Yang and Shannon M. Mahurin and Lilin He and Kai Li and Hongjun Liu and De-en Jiang and Tao Wang and Sheng Dai}, doi = {10.1021/jacs.4c13875}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3421--3427}, shortjournal = {J. Am. Chem. Soc.}, title = {Permanent nanobubbles in water: Liquefied hollow carbon spheres break the limiting diffusion current of oxygen reduction reaction}, volume = {147}, year = {2025}, }
• (2025). Temperature induced unfolding and compaction of cytochrome c in the same aqueous solutions. JACS, 147(4), 3412--3420. (www)

  @article{ , abstract = {Most conventional methods used to measure protein melting temperatures reflect changes in structure between different conformational states and are typically fit to a two-state model. Population abundances of distinct conformations were measured using variable-temperature electrospray ionization ion mobility mass spectrometry to investigate the thermally induced unfolding of the model protein cytochrome c . Nineteen conformers formed at high temperature have elongated structures, consistent with unfolded forms of this protein. However, one conformer that is more compact than the native state of the protein is also formed from this same solution upon heating. The abundance of this compact conformer increases with temperatures up to 90 °C. Rapid mixing and collision-induced gas-phase unfolding experiments demonstrate that formation of this compact conformer is not an artifact of rapid refolding during the ESI process or structural rearrangement in the gas-phase, and therefore the compact conformer must be formed in bulk solution at higher temperatures. The main folded conformer at 90 °C has a cross section that is ∼30 Å 2 larger than that at 27 °C. Results from collision-induced unfolding experiments indicate that they have different gas-phase stabilities that are not directly related to differences in their initial internal energies upon transitioning into the gas phase and therefore have different structures. These results demonstrate the advantage of mass and ion mobility measurements for investigating protein conformational landscapes and provide the first evidence for formation of both unfolded and more compact conformations of a protein from the same solution upon heating.}, archive = {J_JACS}, author = {Jacob S. Jordan and Casey J. Chen and Katherine J. Lee and Evan R. Williams}, doi = {10.1021/jacs.4c14267}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3412--3420}, shortjournal = {J. Am. Chem. Soc.}, title = {Temperature induced unfolding and compaction of cytochrome c in the same aqueous solutions}, volume = {147}, year = {2025}, }
• (2025). Silicate-confined hydrogen on nanoscale zerovalent iron for efficient defluorination reactions. JACS, 147(4), 3402--3411. (www)

  @article{ , abstract = {Defluorination reactions are increasingly vital due to the extensive use of organofluorine compounds with robust carbon–fluorine (C–F) bonds; particularly, the efficient defluorination of widespread and persistent per- and polyfluoroalkyl substances under mild conditions is crucial due to their accumulation in the environment and human body. Herein, we demonstrate that surface-modified silicate of pronounced proton affinity can confine active hydrogen (•H) onto nanoscale zerovalent iron (nZVI) by withdrawing electrons from nZVI to react with bound protons, generating confined active hydrogen (•H * ) for efficient defluorination under ambient conditions. The exposed silicon cation (Si σ+ ) of silicate functions as a Lewis acid site to activate the C–F bond by forming Si σ+ ...F – –C and substantially lowers the energy barrier of nucleophilic •H * attack, thereby facilitating selective C–F hydrodefluorination and subsequent fluorine immobilization. In a column flow reactor, silicate-modified nZVI efficiently removes perfluorooctanoic acid (PFOA) of concentrations ranging from 0.24 to 24 μmol/L with 75–92% defluorination efficiencies, 8 times higher than those of nZVI, generating environmentally friendly alkyl carboxylic acids as the primary products. Besides PFOA, this novel nZVI also realizes deep defluorination of other organofluorine compounds, including perfluorooctanesulfonates and fluoroquinolones, demonstrating its superior defluorination potential.}, archive = {J_JACS}, author = {Minzi Liao and Shengxi Zhao and Guangming Zhan and Jiajie Liang and Zhilin Li and Fengfeng Dong and Yitao Pan and Hao Li and Lizhi Zhang}, doi = {10.1021/jacs.4c14261}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3402--3411}, shortjournal = {J. Am. Chem. Soc.}, title = {Silicate-confined hydrogen on nanoscale zerovalent iron for efficient defluorination reactions}, volume = {147}, year = {2025}, }
• (2025). Trapping anions within stacks of tetra-urea macrocycles. JACS, 147(4), 3392--3401. (www)

  @article{ , abstract = {Designing molecular receptors that bind anions in water is a significant challenge, and an even greater difficulty lies in using these receptors to remove anions from water without resorting to the hazardous liquid–liquid extraction approach. We here demonstrate an effective and synthetically simple strategy toward these goals by exploiting ion-pair assembly of macrocycles. Our anion binding ensemble consists of an octa-chloro tetra-urea macrocyclic anion receptor (ClTU), which forms water-dispersible aggregates, and a tetra-cationic fluorescent dye 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin (TMPyP4), which provides Coulombic stabilization and fluorescence reporting of anion binding in an ion-pair assembly. The ability of ClTU to form oligomeric/polymeric stacks with chloride ions and countercations was demonstrated by X-ray crystallographic and 1 H NMR studies in DMSO. In water, the addition of anions to a mixture of ClTU and TMPyP4 led to the formation of ion-pair assemblies showing quenched fluorescence from TMPyP4 and apparent selectivity in the order of CrO 4 2– ≈ SO 4 2– > Cl – > ClO 4 – ≈ NO 3 – > AcO – > F – > H 2 PO 4 – . The assembly can be applied to remove traces of toxic CrO 4 2– anions from tap water simply by using syringe filters to separate large aggregates from water. Molecular dynamics studies support the formation of columnar stacks of ClTU in solution, which allow for insertion of both anionic guests and cationic TMPyP4 dyes.}, archive = {J_JACS}, author = {Junhong Li and Osman Catal and Igor Marques and Daniel A. McNaughton and Raed M. Maklad and William G. Ryder and Max J. S. Hill and Annela Seddon and William Lewis and Dave J. Adams and Vítor Félix and Xin Wu and Philip A. Gale}, doi = {10.1021/jacs.4c14194}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3392--3401}, shortjournal = {J. Am. Chem. Soc.}, title = {Trapping anions within stacks of tetra-urea macrocycles}, volume = {147}, year = {2025}, }
• (2025). Multidimensional resonance controlled by critical size in printed binary colloidal crystals for high-contrast imaging. JACS, 147(4), 3383--3391. (www)

  @article{ , abstract = {Colloidal crystal engineering enables the precise construction of structures with remarkable properties. However, the flexible and synergistic regulation of multiple properties of colloidal crystals remains a significant challenge. Here, we inspire from Brazilian opals to self-assemble polymer nanoparticles in the gaps of a single-layer opal substrate to fabricate large-scale binary colloidal crystals (BCCs). These BCCs have well-defined sizes, compositions, and dimensions, of which the crystallization process is finely controlled by the Marangoni flow. Notably, we find a critical size for the simultaneous and independent regulation of their lattice resonance wavelength and intensity, forming a full-color palette. Moreover, these BCCs as optical coatings allow for high-contrast imaging of microbials, benefiting from strong spatial confinement. Compared to glass in clinical smearing, they have an order of magnitude improvement in chromatism without dyeing. This work demonstrates that BCCs hold great potential in creating multifunctional devices for various applications including information display, biological detection, and optical imaging.}, archive = {J_JACS}, author = {Xu Yang and Zeying Zhang and Hongyu Sun and Yang Yun and Hongfei Xie and Zhiyu Tan and Huadong Wang and Yaqi Yang and Bingda Chen and Haoran Teng and Xiangyu Pan and Mingtong Yang and Yali Sun and Yanlin Song and Meng Su}, doi = {10.1021/jacs.4c14185}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3383--3391}, shortjournal = {J. Am. Chem. Soc.}, title = {Multidimensional resonance controlled by critical size in printed binary colloidal crystals for high-contrast imaging}, volume = {147}, year = {2025}, }
• (2025). Atmospheric hydroxyl radical route revealed: Interface-mediated effects of mineral-bearing microdroplet aerosol. JACS, 147(4), 3371--3382. (www)

  @article{ , abstract = {Hydroxyl radical (·OH) plays a crucial role in atmospheric chemistry, regulating the oxidative potential and aerosol composition. This study reveals an unprecedented source of ·OH in the atmosphere: mineral dust-bearing microdroplet aerosols. We demonstrate that Kaolin clay particles in microdroplet aerosols trigger rapid ·OH production upon solar irradiation, with rates reaching an order of at least 10 –3 M s –1 . This production rate is several orders of magnitude higher than that of the bulk phase (2.4 × 10 –11 M s –1 ) and previously known pathways. On this basis, the surface-based interfacial ·OH production rate is estimated to be 8.9 × 10 –5 mol m –2 s –1 at the air–water–solid interface of 1 μm sized aerosol particles. The enhanced ·OH formation is attributed to the unique features of air–water–solid interfaces, where the lifespan of photoinduced holes was significantly increased due to the presence of strong electric fields at the air–water interface. We further investigated the impacts of various environmental factors and aerosol properties on ·OH production, including light intensity, relative humidity, particle size, and pH. Our findings provide new insights into atmospheric photochemical processes mediated by mineral dust-bearing microdroplet aerosols, which are important contributors to ·OH source in the atmosphere. This work advances our understanding of atmospheric interfacial chemistry and its profound and lasting implications for air quality and climate.}, archive = {J_JACS}, author = {Le Yang and Yangyang Liu and Qiuyue Ge and Jilun Wang and Runbo Wang and Wenbo You and Wei Wang and Tao Wang and Liwu Zhang}, doi = {10.1021/jacs.4c14149}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3371--3382}, shortjournal = {J. Am. Chem. Soc.}, title = {Atmospheric hydroxyl radical route revealed: Interface-mediated effects of mineral-bearing microdroplet aerosol}, volume = {147}, year = {2025}, }
• (2025). Cu-catalyzed diastereo- and enantioselective synthesis of borylated cyclopropanes with three contiguous stereocenters. JACS, 147(4), 3360--3370. (www)

  @article{ , abstract = {Direct synthesis of enantioenriched scaffolds with multiple adjacent stereocenters remains an important yet challenging task. Herein, we describe a highly diastereo- and enantioselective Cu-catalyzed alkylboration of cyclopropenes, with less reactive alkyl iodides as electrophiles, for the efficient synthesis of tetra -substituted borylated cyclopropanes bearing three consecutive stereocenters. This protocol features mild conditions, a broad substrate scope, and good functional group tolerance, affording an array of chiral borylated cyclopropanes in good to high yields with excellent diastereo- and enantioselectivities. Detailed mechanistic experiments and kinetic studies were conducted to elucidate the reaction pathway and the rate-determining step of the reaction. DFT calculations revealed that the π···π stacking interaction between the phenyl groups on the substrate and the phosphorus ligand, along with the smaller distortion in the CuL-Bpin part, contributed to the high diastereo- and enantioselectivities. The synthetic utility of the protocol was showcased by the facile synthesis of some valuable chiral cyclopropanes with multiple chiral centers.}, archive = {J_JACS}, author = {Chao Gao and Kai Tang and Xi Yang and Shen Gao and Qingshu Zheng and Xiangyang Chen and Jiawang Liu}, doi = {10.1021/jacs.4c14158}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3360--3370}, shortjournal = {J. Am. Chem. Soc.}, title = {Cu-catalyzed diastereo- and enantioselective synthesis of borylated cyclopropanes with three contiguous stereocenters}, volume = {147}, year = {2025}, }
• (2025). Peroxycarbenium-mediated asymmetric synthesis of 1,2-dioxanes and 1,2-dioxolanes. JACS, 147(4), 3353--3359. (www)

  @article{ , abstract = {The endoperoxide scaffold is found in numerous natural products and synthetic substances of pharmaceutical interest. The main challenge to their synthetic access remains the preparation of chiral compounds due to the weakness of the peroxide bond, which limits the scope of available or applicable methods. Here, we demonstrate how peroxycarbenium species can be trapped by silylated nucleophiles with high enantioselectivities and diastereoselectivities when applicable, using a chiral imidophosphorimidate (IDPi) as a catalyst. The scope of the methodology is broad, encompassing a large variety of enoxysilanes and yielding 1,2-dioxanes or 1,2-dioxolanes. Peroxides can be converted into alcohols or trans -epoxides, and the methodology was applied in a key step of the total synthesis of ethyl plakortide Z, enhancing the selectivity compared to a conventional Lewis acid-catalyzed transformation. Kinetic studies have shown that the reaction necessitates an induction period, indicating the formation of a silylium species that behaves as a true catalyst.}, archive = {J_JACS}, author = {Bastien Champciaux and Nicolas Jamey and Bruno Figadère and Laurent Ferrié}, doi = {10.1021/jacs.4c13899}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3353--3359}, shortjournal = {J. Am. Chem. Soc.}, title = {Peroxycarbenium-mediated asymmetric synthesis of 1,2-dioxanes and 1,2-dioxolanes}, volume = {147}, year = {2025}, }
• (2025). Analogue-sensitive inhibition of histone demethylases uncovers member-specific function in ribosomal protein synthesis. JACS, 147(4), 3341--3352. (www)

  @article{ , abstract = {Lysine demethylases (KDMs) catalyze the oxidative removal of the methyl group from histones using earth-abundant iron and the metabolite 2-oxoglutarate (2OG). KDMs have emerged as master regulators of eukaryotic gene expression and are novel drug targets; small-molecule inhibitors of KDMs are in the clinical pipeline for the treatment of human cancer. Yet, mechanistic insights into the functional heterogeneity of human KDMs are limited, necessitating the development of chemical probes for precision targeting. Herein, we identify analogue-sensitive ( as ) mutants of the KDM4 subfamily to elucidate member-specific biological functions in a temporally defined manner. By replacing the highly conserved phenylalanine residue in the active site of KDM4 members with alanine, we develop mutants with intact catalytic activity and substrate specificity indistinguishable from those of the wild type congener. Unlike the wild type demethylases, mutants were sensitized toward cofactor-competitive N-oxalyl glycine (NOG) analogues carrying complementary steric appendage. Particularly notable is N-oxalyl leucine (NOL) which inhibited the KDM4 mutants reversibly with submicromolar efficacy. Cell-permeable NOL prodrugs inhibited as enzymes in cultured human cells to modulate lysine methylation on nucleosomal histones. Through conditional perturbation of the orthogonal enzymes, we uncover a KDM4A-specific role in ribosomal protein synthesis and map a remarkably dynamic signaling cascade involving locus-specific histone demethylation leading to fast rRNA expression, enhanced ribosome assembly, and protein synthesis. The results provide a mechanistic clue into KDM4A’s role in cancers that rely on heightened ribosomal activity to support uncontrolled cellular proliferation.}, archive = {J_JACS}, author = {Jordan Kuwik and Valerie Scott and Sara Chedid and Stephanie Stransky and Kathryn Hinkelman and Sam Kavoosi and Michael Calderon and Simon Watkins and Simone Sidoli and Kabirul Islam}, doi = {10.1021/jacs.4c13870}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3341--3352}, shortjournal = {J. Am. Chem. Soc.}, title = {Analogue-sensitive inhibition of histone demethylases uncovers member-specific function in ribosomal protein synthesis}, volume = {147}, year = {2025}, }
• (2025). Observation of the protein-inorganic interface of ferritin by cryo-electron microscopy. JACS, 147(4), 3333--3340. (www)

  @article{ , abstract = {Visualizing the structure of the protein-inorganic interface is critically important for a more complete understanding of biomineralization. Unfortunately, there are limited approaches for the direct and detailed study of biomolecules that interact with inorganic materials. Here, we use single-particle cryo-electron microscopy (cryo-EM) to study the protein–nanoparticle (NP) interactions of human light chain ferritin and visualize the high-resolution details of the protein-inorganic interface. In this work, we determined the 2.85 Å structure of human light chain ferritin bound to its native iron oxide NP substrate. The resulting cryo-EM maps confirmed and enhanced previously proposed interactions of the protein with the material along the B-helix and revealed new interaction at the C-terminus of light chain ferritin. This work sheds new light on the mechanisms of ferritin biomineralization and further demonstrates the application of cryo-EM for the study of protein-inorganic systems.}, archive = {J_JACS}, author = {Sagnik Sen and Amar Thaker and Alison Haymaker and Dewight Williams and Po-Lin Chiu and Brent L. Nannenga}, doi = {10.1021/jacs.4c13873}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3333--3340}, shortjournal = {J. Am. Chem. Soc.}, title = {Observation of the protein-inorganic interface of ferritin by cryo-electron microscopy}, volume = {147}, year = {2025}, }
• (2025). MXenes as heterogeneous thermal catalysts: Regioselective anti-markovnikov hydroamination of terminal alkynes with 102 h–1 turnover frequencies. JACS, 147(4), 3315--3332. (www)

  @article{ , abstract = {Due to their conductive properties and optoelectronic tunability, MXenes have revolutionized the area of electrocatalysis and active materials in supercapacitors. In comparison, there are only a few reports on MXenes as thermal catalysts for general organic reactions. Herein, the unprecedented catalytic activity of Ti 3 C 2 MXene for the hydroamination of alkynes is reported, overcoming the limitations of poor activity, lack of selectivity, and stability, which are generally encountered in the solid catalysts known so far. In the case of Ti 3 C 2 , hydroamination exhibits almost complete selectivity for the anti-Markovnikov regio isomer, for both aliphatic amines and less-reactive aromatic amines. Ti 3 C 2 also efficiently catalyzes intramolecular hydroamination, leading to the formation of indol heterocycles. The catalytic hydroamination of C–C multiple bonds is a reaction with complete atom efficiency that may form C–N bonds from convenient reagents. The maximum number of hydroamination sites on the Ti 3 C 2 nanosheets is quantified by thermoprogrammed NH 3 desorption. The measured TOF values are on the order of 10 2 h –1 , with the highest TOF value being 350 h –1 for 1-hexyne hydroamination by n - butylamine. Therefore, Ti 3 C 2 is among the few heterogeneous hydroamination catalysts studied, with its activity per site being comparable to the best hydroamination catalysts reported so far. Density functional theory calculations on the models indicate the cooperation of neighboring Ti atoms in the mechanism. Considering the compositional and structural versatility of MXenes, the present findings open the door for further application of MXenes in other general organic reactions.}, archive = {J_JACS}, author = {Rubén Ramírez Grau and Pablo Garcia-Aznar and German Sastre and Sara Goberna-Ferrón and Octavian Pavel and Alina Tirsoaga and Bogdan Cojocaru and Dana Georgeta Popescu and Vasile I. Parvulescu and Ana Primo and Hermenegildo García}, doi = {10.1021/jacs.4c13481}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3315--3332}, shortjournal = {J. Am. Chem. Soc.}, title = {MXenes as heterogeneous thermal catalysts: Regioselective anti-markovnikov hydroamination of terminal alkynes with 102 h–1 turnover frequencies}, volume = {147}, year = {2025}, }
• (2025). Selective synthesis of cyclopeptides with a 2-oxindole or 3a-hydroxy-hexahydropyrrolo-[2,3-b]indole structure by cytochrome p450 enzymes. JACS, 147(4), 3304--3314. (www)

  @article{ , abstract = {The structural groups of 2-oxindole and tricyclic 3a-hydroxy-hexahydropyrrolo-[2,3- b ]indole (HO-HPI) are important pharmacophores. Chemical synthesis of complex alkaloids containing a 2-oxindole or HO-HPI moiety, especially the latter one, has been a long-standing challenge. Herein, we characterized the P450 enzyme AfnD, and its homologue proteins, HmtT, ClpD, KtzM, and LtzR, as cyclopeptide 2-oxindole and HO-HPI monooxygenases (cpOPMOs) that could introduce a 2-oxindole or HO-HPI moiety into the tryptophan-containing cyclopeptides in a pH-dependent manner. A universal catalytic mechanism was proposed for the five cpOPMOs, in which two conserved residues, Asp and Ser (Thr for LtzR), were proposed to divergently open the epoxide intermediates, thereby forming a 2-oxindole or HO-HPI moiety. Based on this, we constructed ten Asp or Ser/Thr mutants of cpOPMOs, which could synthesize cyclopeptides with an HO-HPI or 2-oxindole structure, selectively, under appropriate reaction conditions. All of the ten cpOPMO mutants exhibited high substrate promiscuities and usually performed well with cyclopeptides that are structurally similar to their native substrates. Overall, our work discovers a group of intriguing P450 enzymes, the cpOPMOs, and provides a powerful enzymatic toolkit for the selective synthesis of HO-HPI- or 2-oxindole-containing cyclopeptides.}, archive = {J_JACS}, author = {Chao Li and Junying Ma and Lu Guo and Chao Xu and Zijian Zhong and Pengwei Li and Yue Tang and Wenzhao Wang and Defeng Li and Tao Ye and Zhengyan Guo and Yihua Chen}, doi = {10.1021/jacs.4c13535}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3304--3314}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective synthesis of cyclopeptides with a 2-oxindole or 3a-hydroxy-hexahydropyrrolo-[2,3-b]indole structure by cytochrome p450 enzymes}, volume = {147}, year = {2025}, }
• (2025). OPTO: Automated optimization for solid-state NMR spectroscopy. JACS, 147(4), 3293--3303. (www)

  @article{ , abstract = {NMR spectroscopy presents boundless opportunities for understanding the structure, dynamics, and function for a broad range of scientific applications. Solid-state NMR (SSNMR), in particular, provides novel insights into biological and material systems that are not amenable to other approaches. However, a major bottleneck is the extent of user training and the difficulty of obtaining reproducible, high-quality experimental results, especially for the sophisticated multidimensional pulse sequences that are essential to provide site-resolved measurements in large biomolecules. Here, we present OPTO, a software operating environment that addresses these challenges and enhances the performance of many types of commonly utilized SSNMR experiments. OPTO is compatible with Varian OpenVnmrJ and Bruker Topspin, with a front-end graphical user interface that presents the instrument operator with access to powerful underlying optimization algorithms, including simplex and grid searches of the dozens of parameter settings required for optimal performance. Therefore, OPTO efficiently leverages instrument time and enables instrument operators to find optimal experimental conditions reliably. We demonstrate examples including improvements in (1) resolution, with an automated, global search of 21 shimming parameters to achieve a 12 parts per billion line width; (2) sensitivity, with searches and refinements of several cross-polarization conditions dependent on 16 parameters in triple resonance experiments; and (3) robustness, with results from protein samples on several spectrometers operating at different magnetic field strengths and magic-angle spinning rates.}, archive = {J_JACS}, author = {Collin G. Borcik and Barry DeZonia and Thirupathi Ravula and Benjamin D. Harding and Rajat Garg and Chad M. Rienstra}, doi = {10.1021/jacs.4c13295}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3293--3303}, shortjournal = {J. Am. Chem. Soc.}, title = {OPTO: Automated optimization for solid-state NMR spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Intercellular ion-gradient piezoheterogated biphasic gel for ultrahigh iontronic generation. JACS, 147(4), 3283--3292. (www)

  @article{ , abstract = {Piezoionic materials have attracted considerable attention for their ability to generate iontronic signals or power in response to stress stimuli. However, the limited intrinsic transport distinction between cations and anions within most ionic materials results in weakened iontronic power conversion efficiencies under stress fields. Here, we report a piezoheterogated biphasic gel for ultrahigh iontronic generation, characterized by high-internal microphase heterointerfaces that facilitate the distinct transport of various ion species. Due to the ion confinement effect of cell-like multicompartments, a stable intercellular ion gradient within biphasic gel systems can be established in situ, constructing the chemical potential to further enhance ionic transmission efficiency and obtain a high-density net ion flux in the piezoionic process. Consequently, as a reliable piezo cell, a record maximum power of 150 W/m 3 over 24 h can be realized. Meanwhile, we develop piezoionic devices that can interface with paralyzed vagus nerves and successfully regulate the blood pressure of rodents through their neuromodulation. By matching the ion species with heterointerface gating effects to regulate the ionic transmission efficiency, the piezo signal neuromodulation process can be further governed. We anticipate that the bioinspired heterointerface engineering strategy can provide new insights into designing high-performance piezoionic systems for promising abiotic–biotic applications.}, archive = {J_JACS}, author = {Weipeng Chen and Suli Zhang and Ao Zhang and Huirong Liu and Zhixin Wu and Linxin Zhai and Xiaomin Dong and Zhiping Xu and Ziguang Zhao and Liping Wen}, doi = {10.1021/jacs.4c13305}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3283--3292}, shortjournal = {J. Am. Chem. Soc.}, title = {Intercellular ion-gradient piezoheterogated biphasic gel for ultrahigh iontronic generation}, volume = {147}, year = {2025}, }
• (2025). Germanium atoms exceed the tetrahedral coordination in MFI zeolite. JACS, 147(4), 3274--3282. (www)

  @article{ , abstract = {Germanium is known to occupy tetrahedral sites by substituting silicon in germanosilicate zeolites. In this study, we present pioneering findings regarding the synthesis of zeolites with an MFI structure (GeMFI) incorporating a high germanium amount (16% Ge). Remarkably, the germanium atoms feature a slight electron deficiency with respect to GeO 2 , and the typical coordination number of 4, as usually reported for the germanosilicate zeolites, is exceeded, giving rise to Ge dimers in a double-bridge configuration. Notably, the compensation of the ammonium template is achieved not through fluorine ions in the [4 1 5 2 6 2 ] cages of the framework, as conventionally considered, but rather through oxygen. The GeMFI zeolite with the high Ge content reported in this work demonstrated exceptional thermal and hydrothermal stability, surpassing up to 1050 °C, thanks to both the double-bridge configuration and the defect-free structure. The unexpected role of germanium in MFI zeolite challenges previous assumptions, representing a paradigm shift in the understanding of porous germanosilicate structures, paving the way for a reevaluation of their synthesis, hydrolysis, and potential applications.}, archive = {J_JACS}, author = {Eddy Dib and Qiudi Yue and Giorgia Confalonieri and Davide Salusso and Georgi N. Vayssilov and Mathias Barreau and Stoyan P. Gramatikov and Rossella Arletti and Francesco Dalena and Kirill A. Lomachenko and Diogenes Honorato Piva and Valentin Valtchev and Zhengxing Qin and Zi-Feng Yan and Xionghou Gao and Franck Fayon and Spyridon Zafeiratos and Oleg I. Lebedev and Svetlana Mintova}, doi = {10.1021/jacs.4c13278}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3274--3282}, shortjournal = {J. Am. Chem. Soc.}, title = {Germanium atoms exceed the tetrahedral coordination in MFI zeolite}, volume = {147}, year = {2025}, }
• (2025). P-type BiVO4 for solar o2 reduction to H2O2. JACS, 147(4), 3261--3273. (www)

  @article{ , abstract = {Photoelectrochemical cells (PECs) can directly utilize solar energy to drive chemical reactions to produce fuels and chemicals. Oxide-based photoelectrodes in general exhibit enhanced stability against photocorrosion, which is a critical advantage for building a sustainable PEC. However, most oxide-based semiconductors are n-type, and p-type oxides that can be used as photocathodes are limited. In this study, we report the synthesis, characterization, and application of p-type BiVO 4 with a monoclinic scheelite ( ms ) structure. ms -BiVO 4 is inherently n-type, and it has been investigated only as a photoanode to date. In this study, we prepared p-type ms -BiVO 4 (bandgap of 2.4 eV) via atomic doping of Ca 2+ at the Bi 3+ site under an O 2 -rich environment and examined its performance as a photocathode. We then demonstrated that the Ca-doped ms -BiVO 4 photocathode can be used for solar O 2 reduction to H 2 O 2 when coupled with appropriate catalysts. Our computational investigation using hybrid density functional theory revealed that holes are stable as polarons in ms -BiVO 4 and have a low self-trapping energy, that may lead to free carriers in the valence band at finite temperature. Our calculations also show that Ca is an effective shallow acceptor dopant with low formation energy and thermal ionization energy leading to p-type conductivity. Our joint experimental and computational results provide critical insights into the design of p-type ms -BiVO 4 , enabling its use as a polaronic oxide photocathode.}, archive = {J_JACS}, author = {Daye Seo and Vrindaa Somjit and Dae Han Wi and Giulia Galli and Kyoung-Shin Choi}, doi = {10.1021/jacs.4c13290}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3261--3273}, shortjournal = {J. Am. Chem. Soc.}, title = {P-type BiVO4 for solar o2 reduction to H2O2}, volume = {147}, year = {2025}, }
• (2025). Substituent and heteroatom effects on π–π interactions: Evidence that parallel-displaced π-stacking is not driven by quadrupolar electrostatics. JACS, 147(4), 3243--3260. (www)

  @article{ , abstract = {Stacking interactions are a recurring motif in supramolecular chemistry and biochemistry, where a persistent theme is a preference for parallel-displaced aromatic rings rather than face-to-face π-stacking. This is typically explained in terms of quadrupole–quadrupole interactions between the arene moieties but that interpretation is inconsistent with accurate calculations, which reveal that the quadrupolar picture is qualitatively wrong. At typical π-stacking distances, quadrupolar electrostatics may differ in sign from an exact calculation based on charge densities of the interacting arenes. We apply symmetry-adapted perturbation theory to dimers composed of substituted benzene and various aromatic heterocycles, which display a wide range of electrostatic interactions, and we investigate the interplay of Pauli repulsion, dispersion, and electrostatics as it pertains to parallel-displaced π-stacking. Profiles of energy components along cofacial slip-stacking coordinates support a prominent role for the “van der Waals model” (dispersion in competition with Pauli repulsion), even for polar monomers where electrostatic interactions are significant. While electrostatic interactions are necessary to explain the optimal face-to-face π-stacking distance and to account for the relative orientation of one polar arene with respect to another, we find no evidence to support continued invocation of quadrupolar electrostatics as a basis for π-stacking. Our results suggest that a driving force for offset-stacking exists even in the absence of electrostatic interactions. Consequently, tuning electrostatics via functionalization does not guarantee that slip-stacking can be avoided. This has implications for rational design of soft materials and other supramolecular architectures.}, archive = {J_JACS}, author = {Brandon Schramm and Montgomery Gray and John M. Herbert}, doi = {10.1021/jacs.4c13291}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3243--3260}, shortjournal = {J. Am. Chem. Soc.}, title = {Substituent and heteroatom effects on π–π interactions: Evidence that parallel-displaced π-stacking is not driven by quadrupolar electrostatics}, volume = {147}, year = {2025}, }
• (2025). A hexavalent tellurium-based chalcogen bonding catalysis platform: High catalytic activity and controlling of selectivity. JACS, 147(4), 3233--3242. (www)

  @article{ , abstract = {Herein, we describe a hexavalent tellurium-based chalcogen bonding catalysis platform capable of addressing reactivity and selectivity issues. This research demonstrates that hexavalent tellurium salts can serve as a class of highly active chalcogen bonding catalysts for the first time. The tellurium centers in these hexavalent catalysts have only one exposed interaction site, thus providing a favorable condition for the controlling of reaction selectivity. The advantages of these hexavalent tellurium catalysts were demonstrated by their remarkable catalytic activity in the cyanidation of difluorocyclopropenes through C–F bond activation, which otherwise were low reactive under the catalysis of strong Lewis acids or inaccessible by representative divalent/tetravalent tellurium-based donors. The catalytic activity of the hexavalent tellurium catalyst was further highlighted by its capability to address a previously unresolved reactivity problem associated with the strong Lewis acid approach, upon using some less reactive silyl enol ethers as nucleophiles in the functionalization of difluorocyclopropenes. The generality of this catalysis platform was demonstrated by its versatile application in different reaction systems. The hexavalent tellurium catalyst can differentiate two similar free OH groups in glycosyl acceptors to achieve excellent regio- and stereoselectivity in the synthesis of disaccharides, in which the tetravalent tellurium catalyst gave low reactivity and selectivity. Mechanistic investigation suggests that a catalyst-glycosyl donor–acceptor ternary supramolecular complex is operative.}, archive = {J_JACS}, author = {Xinxin Li and Yi Liu and Wei Wang and Yao Wang}, doi = {10.1021/jacs.4c13004}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3233--3242}, shortjournal = {J. Am. Chem. Soc.}, title = {A hexavalent tellurium-based chalcogen bonding catalysis platform: High catalytic activity and controlling of selectivity}, volume = {147}, year = {2025}, }
• (2025). Modular synthesis of planar-chiral cyclononenes via trans-retentive trapping of π-allyl-pd dipoles. JACS, 147(4), 3223--3232. (www)

  @article{ , abstract = {Trans -cycloalkenes are abundant in bioactive natural products and have been used as powerful tools in chemical biology and drug discovery. However, strategies for the modular synthesis of trans -cycloalkenes, especially planar-chiral medium-sized ones, with high efficiency and selectivity, still remain elusive. Herein, we report a Pd-catalyzed asymmetric [7 + 2] cyclization strategy to address this challenge. As a result, two types of planar-chiral trans -cyclononenes bearing all-carbon chiral quaternary stereocenters are produced in up to 85% yield, >99% ee, and >19:1 dr (42 examples). The key to this success is the maintenance of the trans -2H configuration of the π-allyl-Pd species along with unusual linear selectivity during the H-bond-assisted cyclization process. In addition, the conversion of planar chirality to central chirality and its application in selective bioimaging of cancer cells via a bioorthogonal reaction were performed to demonstrate the synthetic value of this methodology.}, archive = {J_JACS}, author = {Zheng-Xin Zhou and Yue-Liu-Ting Fu and Chen Zhang and Yuan-Heng Li and Bin-Jun Zhang and Yu-Qing Xiao and Yu-Jie Li and Li-Yan Chen and Li Rao and Ying Tan and Wen-Jing Xiao and Liang-Qiu Lu}, doi = {10.1021/jacs.4c12892}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3223--3232}, shortjournal = {J. Am. Chem. Soc.}, title = {Modular synthesis of planar-chiral cyclononenes via trans-retentive trapping of π-allyl-pd dipoles}, volume = {147}, year = {2025}, }
• (2025). An icosahedral 55-atom iron hydride cluster protected by tri-tert-butylphosphines. JACS, 147(4), 3215--3222. (www)

  @article{ , abstract = {Nanoclusters are nanometer-sized molecular compounds characterized by significant metal–metal bonding and low average oxidation states, and they exhibit unique properties distinct from those of small metal complexes or nanoparticles. Unlike noble metals stable in metallic forms, the synthesis of nanometer-sized iron clusters has been precluded by the relatively weak iron–iron bonds and the high reactivity of low oxidation state iron, despite the extensive history of molecular iron compounds. Here, we report the synthesis and characterization of a cationic 55-atom iron cluster with a 1.2 nm icosahedral core. Its 12 vertices are occupied by tri -tert -butylphosphines, while multiple hydrides cover the surface. This core can be viewed as a substructure of the face-centered cubic (fcc), in contrast to the body-centered cubic (bcc) for the stable bulk phase. This work reveals a stable structure and fundamental properties of a nanometer-sized iron cluster, which have remained elusive for decades, and the simple synthetic protocol provides a route to explore molecular nanochemistry.}, archive = {J_JACS}, author = {Tatsuya Higaki and Kanata Tanaka and Hitoshi Izu and Shunya Oishi and Koki Kawamoto and Mizuki Tada and W. M. C. Sameera and Ryo Takahata and Toshiharu Teranishi and Soichi Kikkawa and Seiji Yamazoe and Takuya Shiga and Masayuki Nihei and Tatsuhisa Kato and Roger E. Cramer and Zihan Zhang and Karsten Meyer and Yasuhiro Ohki}, doi = {10.1021/jacs.4c12759}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3215--3222}, shortjournal = {J. Am. Chem. Soc.}, title = {An icosahedral 55-atom iron hydride cluster protected by tri-tert-butylphosphines}, volume = {147}, year = {2025}, }
• (2025). Emergence of chirality in an optically active two-dimensional crystal with a spiral surface pattern. JACS, 147(4), 3206--3214. (www)

  @article{ , abstract = {Some one-dimensional (1D) crystals containing a screw dislocation along their longer axis exhibit a helical twist due to lattice strain. These chiral structures have been thoroughly investigated by using transmission electron microscopy. However, whether two-dimensional (2D) crystals with a spiral surface pattern, presumably containing a screw dislocation, are structurally chiral remains unclear because their internal structures are not visible. Here, we report that a particular 2D crystal with a spiral surface pattern emits circularly polarized luminescence despite comprising achiral building blocks. Comprehensive X-ray structural analysis of this 2D crystal reveals a helical structure with an achiral space group featuring distinctive twinning. This twinned 2D crystal consists of four centrosymmetric components. Applying the twin law to these four achiral components results in a spirally arranged topology, leading to the emergence of chirality in the 2D crystals.}, archive = {J_JACS}, author = {Hubiao Huang and Gangfeng Chen and Manabu Hoshino and Kiyohiro Adachi and Daisuke Hashizume and Hiroshi Sato and Zhenghong Chen and Shaodong Zhang and Kang Wang and Xianqing Lin and Yong Sheng Zhao and Takuzo Aida}, doi = {10.1021/jacs.4c12631}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3206--3214}, shortjournal = {J. Am. Chem. Soc.}, title = {Emergence of chirality in an optically active two-dimensional crystal with a spiral surface pattern}, volume = {147}, year = {2025}, }
• (2025). Intermarrying MOF glass and lead halide perovskites for artificial photosynthesis. JACS, 147(4), 3195--3205. (www)

  @article{ , abstract = {The development of efficient artificial photosynthesis systems is crucial for sustainable chemical production, as they mimic natural processes to convert solar energy into chemical products, thereby addressing both energy and environmental challenges. The main bottlenecks in current research include fabricating highly selective, stable, and scalable catalysts, as well as effectively harnessing the full spectrum of light, particularly the low-energy, long-wavelength portion. Herein, we report a novel composite photocatalyst system based on lead halide perovskites embedded in functionalized MOF glass. The construction of a well-defined interface between the light-harvesting perovskite and stable Rh single-atom-containing MOF glass mimics the functions of photosystem I (PS I). This facilitates efficient photoinduced electron generation under visible light and subsequent electron transfer for coenzyme (NADH) regeneration with high selectivity. The regenerated NADH can then be consumed by immobilized enzymes for CO 2 reduction, realizing the artificial photosynthesis process for formic acid generation. This work also elucidates the interactions and optoelectronic responses between MOF glass and perovskites, offering insights into the design and fabrication of nanocomposite photocatalysts for other advanced chemical syntheses.}, archive = {J_JACS}, author = {Wengang Huang and Bun Chan and Yuwei Yang and Peng Chen and Jingjing Wang and Lachlan Casey and Cesare Atzori and Tobias Schulli and Olivier Mathon and Haira G. Hackbarth and Nicholas M. Bedford and Dominique Appadoo and Xuemei Li and Tongen Lin and Rijia Lin and Jaeho Lee and Zhiliang Wang and Vicki Chen and Anthony K. Cheetham and Lianzhou Wang and Jingwei Hou}, doi = {10.1021/jacs.4c12619}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3195--3205}, shortjournal = {J. Am. Chem. Soc.}, title = {Intermarrying MOF glass and lead halide perovskites for artificial photosynthesis}, volume = {147}, year = {2025}, }
• (2025). Methanol-enhanced low-cell-voltage hydrogen generation at industrial-grade current density by triadic active sites of Pt1–Pdn–(Ni,Co)(OH)x. JACS, 147(4), 3185--3194. (www)

  @article{ , abstract = {Methanol (ME) is a liquid hydrogen carrier, ideal for on-site-on-demand H 2 generation, avoiding its costly and risky distribution issues, but this “ME-to-H 2 ” electric conversion suffers from high voltage (energy consumption) and competitive oxygen evolution reaction. Herein, we demonstrate that a synergistic cofunctional Pt 1 Pd n /(Ni,Co)(OH) x catalyst with Pt single atoms (Pt 1 ) and Pd nanoclusters (Pd n ) anchored on OH-vacancy(V OH )-rich (Ni,Co)(OH) x nanoparticles create synergistic triadic active sites, allowing for methanol-enhanced low-voltage H 2 generation. For MOR, OH* is preferentially adsorbed on Pd n and then interacts with the intermediates (such as *CHO or *CHOOH) adsorbed favorably on neighboring Pt 1 with the assistance of hydrogen bonding from the surface hydrogen of (Ni,Co)(OH) x . The enhanced selectivity of the *CHOOH pathway, instead of *CO, sustains the MOR activity to a practically high current density. For HER, triadic Pt 1 , Pd n , and OH-vacancy sites on (Ni,Co)(OH) x create an “acid–base” microenvironment to facilitate water adsorption and splitting, forming H* species on Pt 1 and Pd n , and *OH at the vacancy, to promote efficient H 2 evolution from the asymmetric Pt 1 and Pd n sites via the Tafel mechanism. The triadic-site synergy opens new avenues for the design and synthesis of highly efficient and stable cofunctional catalysts for “on-site-on-demand” H 2 production, here facilitated by liquid methanol.}, archive = {J_JACS}, author = {An Pei and Ruikuan Xie and Lihua Zhu and Fengshun Wu and Zinan Huang and Yongyu Pang and Yu-Chung Chang and Guoliang Chai and Chih-Wen Pao and Qingsheng Gao and Congxiao Shang and Guang Li and Jinyu Ye and Huaze Zhu and Zhiqing Yang and Zhengxiao Guo}, doi = {10.1021/jacs.4c12665}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3185--3194}, shortjournal = {J. Am. Chem. Soc.}, title = {Methanol-enhanced low-cell-voltage hydrogen generation at industrial-grade current density by triadic active sites of Pt1–Pdn–(Ni,Co)(OH)x}, volume = {147}, year = {2025}, }
• (2025). An open-shell FeIV nitrido. JACS, 147(4), 3174--3184. (www)

  @article{ , abstract = {We report the photogeneration and characterization of an open-shell, terminal iron nitrido ( Em L)Fe(N) using a sterically encumbered dipyrrin ligand environment. The Fe–N distance in the solid-state, zero-field 57 Fe Mössbauer spectrum, and computational analysis are consistent with a triplet electronic ground state of the iron nitrido. Notably, the attenuation of Fe–N multiple bond character through occupying π* Fe–N enables (i) primary C(sp 3 )–H amination, (ii) H 2 cleavage, (iii) aromatic C–C cleavage, and (iv) photocatalytic N -atom transfer reactivity. These modes of reactivity have not previously been observed in low-spin Fe(N) analogues.}, archive = {J_JACS}, author = {Jeewhan Oh and Shao-Liang Zheng and Kurtis M. Carsch and Trevor P. Latendresse and Claire E. Casaday and Brandon M. Campbell and Theodore A. Betley}, doi = {10.1021/jacs.4c12588}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3174--3184}, shortjournal = {J. Am. Chem. Soc.}, title = {An open-shell FeIV nitrido}, volume = {147}, year = {2025}, }
• (2025). Self-cascaded pyroptosis-STING initiators for catalytic metalloimmunotherapy. JACS, 147(4), 3161--3173. (www)

  @article{ , abstract = {Gasdermin (GSDM)-mediated pyroptosis involves the induction of mitochondrial damage and the subsequent release of mitochondrial DNA (mtDNA), which is anticipated to activate the cGAS-STING pathway, thereby augmenting the antitumor immune response. However, challenges lie in effectively triggering pyroptosis in cancer cells and subsequently enhancing the cGAS-STING activation with specificity. Herein, we developed intelligent self-cascaded pyroptosis-STING initiators of cobalt fluoride (CoF 2 ) nanocatalysts for catalytic metalloimmunotherapy. CoF 2 nanocatalysts with a semiconductor structure and enzyme-like activity generated a substantial amount of reactive oxygen species (ROS) under stimulation by endogenous H 2 O 2 and exogenous ultrasound. Importantly, we discovered that Co-based nanomaterials themselves induce pyroptosis in cancer cells. Therefore, CoF 2 nanocatalysts initially acted as pyroptosis inducers, triggering caspase-1/GSDMD-dependent pyroptosis in cancer cells via Co 2+ and ROS, leading to mtDNA release. Subsequently, CoF 2 nanocatalysts were further utilized as intelligent STING agonists that were specifically capable of detecting mtDNA and augmenting the activation of the cGAS-STING pathway. These cascade events triggered a robust immune response, effectively modulating the immunosuppressive tumor microenvironment into an immune-supportive state, thereby providing favorable support for antitumor therapy. This innovative strategy not only significantly impeded the growth of the primary tumor but also elicited an immune response to further augment the efficacy of immune checkpoint inhibitors in preventing distant tumor progression. Overall, this study proposed a self-cascade strategy for activating and amplifying the cGAS-STING pathway with specificity mediated by pyroptosis, representing a valuable avenue for future cancer catalytic metalloimmunotherapy.}, archive = {J_JACS}, author = {Qiao Yu and Shumin Sun and Nailin Yang and Zifan Pei and Youdong Chen and Jihu Nie and Huali Lei and Li Wang and Fei Gong and Liang Cheng}, doi = {10.1021/jacs.4c12552}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3161--3173}, shortjournal = {J. Am. Chem. Soc.}, title = {Self-cascaded pyroptosis-STING initiators for catalytic metalloimmunotherapy}, volume = {147}, year = {2025}, }
• (2025). Controllable active intermediate in CO2 hydrogenation enabling highly selective N,N-dimethylformamide synthesis via N-formylation. JACS, 147(4), 3152--3160. (www)

  @article{ , abstract = {N , N -Dimethylformamide (DMF) is a widely used solvent, and its green and low-carbon synthesis methods are in high demand. Herein, we report a new approach for DMF synthesis using a continuous flow reaction system with a fixed-bed reactor and a ZnO-TiO 2 solid solution catalyst. This catalyst effectively utilizes CO 2 , H 2 , and dimethylamine (DMA) as feedstocks, demonstrating performance with 99% DMF selectivity and single-pass DMA conversion approaching thermodynamic equilibrium. Moreover, the catalyst demonstrates good stability, with no signs of deactivation over 1000 h of continuous operation. The key to superior activity lies in the synergetic effect of the Zn and Ti sites, which facilitates the formation of active formate species. These species act as crucial intermediates, reacting with DMA to produce DMF. Importantly, the slow hydrogenation kinetics of the formate species prevent the formation of CH 2 O* species, thereby suppressing the formation of the undesired byproduct, trimethylamine. This work underscores the potential of kinetically controlling active intermediates in CO 2 hydrogenation to prepare high-value-added chemicals by coupling them to platform molecules. It presents a promising strategy for the efficient utilization of CO 2 resources and offers a valuable solution for large-scale DMF synthesis.}, archive = {J_JACS}, author = {Jieyun Zhang and Guanna Li and Jin Xie and Yang Hai and Weiming Wan and Haotian Sun and Bin Wang and Xiaojing Wu and Jiannian Cheng and Changxin He and Wei Hu and Ying Zhang and Zelong Li and Can Li}, doi = {10.1021/jacs.4c12503}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3152--3160}, shortjournal = {J. Am. Chem. Soc.}, title = {Controllable active intermediate in CO2 hydrogenation enabling highly selective N,N-dimethylformamide synthesis via N-formylation}, volume = {147}, year = {2025}, }
• (2025). Tetra-cationic distibane stabilized by bis(α-iminopyridine) and its reactivity. JACS, 147(4), 3140--3151. (www)

  @article{ , abstract = {The work establishes the salt of a tetra-cationic distibane, [L 2 Sb 2 ][CF 3 SO 3 ] 4 = [ 1 ] 2 [OTf] 4 (CF 3 SO 3 = OTf), stabilized by a bis(α-iminopyridine) ligand L , defying the Coulombic repulsion. The synthetic approach involved a dehydrocoupling reaction when a mixture of L and Sb(OTf) 3 in a 1:1 ratio was treated with Et 3 SiH/LiBEt 3 H as the hydride source. Compound [ 1 ] 2 [OTf] 4 was also achieved from [LSbCl][OTf] 2 as a precursor and using Et 3 SiH. Dissolution of [ 1 ] 2 [OTf] 4 in polar solvents unveiled the formation of the persistent L -stabilized dicationic Sb(II) radical monomer [ 1 ][OTf] 2 , while the addition of Me 3 SiOTf regenerated the dimer in the salt [ 1 ] 2 [OTf] 4 . The homolytic cleavage of the Sb–Sb bond in [ 1 ] 2 4+ has manifested in exchange reactions between [ 1 ] 2 [OTf] 4 and Ph 2 Ch 2 (Ch = S, Se), giving [LSb(SPh)][OTf] 2 = [ 2 ][OTf] 2 and [LSb(SePh)][OTf] 2 = [ 3 ][OTf] 2 , respectively, in acetonitrile. Reaction between [ 1 ] 2 [OTf] 4 and p -benzoquinone gave [L 2 Sb 2 (C 6 H 4 O 2 )][OTf] 4 = [ 4 ][OTf] 4 . An interesting oxygen atom insertion reaction occurred when [ 1 ] 2 [OTf] 4 was treated with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) to give [L 2 Sb 2 O][ OTf] 4 = [ 5 ][OTf] 4 . The oxo-bridged compound [ 5 ][OTf] 4 was also obtained from exposure of [ 1 ] 2 [OTf] 4 in open air. The strong Mn–Mn bond in [Mn 2 (CO) 10 ] could be cleaved by reacting with [ 1 ] 2 [OTf] 4 in the presence of pyridine to form [LSbMn(CO) 5 ][ OTf] 2 = [ 6 ][OTf] 2 . On the other hand, the reaction between [Co 2 (CO) 8 ] and [ 1 ] 2 [OTf] 4 gave the oxidative addition product [L 2 Sb 2 Co(CO) 3 ][OTf] 3 = [ 7 ][OTf] 3 . The compounds were characterized both in the solid and solution states. Computational studies gave a comprehensive understanding of the experimental findings.}, archive = {J_JACS}, author = {Hritwik Haldar and Satyabrata Das and Haakon T. A. Wiedemann and Katrin Beuthert and Christopher W. M. Kay and Stefanie Dehnen and Cem B. Yildiz and Moumita Majumdar}, doi = {10.1021/jacs.4c12354}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3140--3151}, shortjournal = {J. Am. Chem. Soc.}, title = {Tetra-cationic distibane stabilized by bis(α-iminopyridine) and its reactivity}, volume = {147}, year = {2025}, }
• (2025). Proton-induced switching of paramagnetism: Reversible conversion between a low and high spin CoIII center within a heterobimetallic core. JACS, 147(4), 3129--3139. (www)

  @article{ , abstract = {The development of molecular species with switchable magnetic properties has been a long-standing challenge in chemistry. One approach involves binding an analyte, such as protons, to a compound to trigger a change in magnetism. Transition metal complexes have been targeted for this type of magnetic modulation because they can undergo changes in their spin states. However, heterobimetallic complexes have had limited utility because of a lack of ligands that create differentiated structures around each metal center that are often necessary to regulate the electronic and magnetic properties. To circumvent this problem, we have used a tripodal ligand with phosphinic amido groups to prepare a complex with a discrete [Co III (μ-OH)Fe III ] core and an overall system spin of S T = 5/2. Deprotonation readily produces a species with a unique [Co III (μ-O)Fe III ] core and an S T = 1/2 system spin. X-ray diffraction studies, electron paramagnetic resonance spectroscopy, and Mössbauer spectroscopy pinpoint the hexacoordinate Co III center as the cause of this spin change: the typical S Co = 0 spin state of the Co III center in the [Co III (μ-OH)Fe III ] complex switches to a rare S Co = 2 spin state in the [Co III (μ-O)Fe III ] analogue; this change turns on antiferromagnetic coupling between the two metal centers. Computational studies link an increase in π bonding within the Co–oxido unit to the change in the Co III spin state. The conversion is reversible and provides a blueprint for using oxido/hydroxido ligands within a heterobimetallic core to regulate the spin state of a metal site and thus modulate the paramagnetism of a system.}, archive = {J_JACS}, author = {Phan N. Phu and Justin L. Lee and Saborni Biswas and Joseph W. Ziller and Emile L. Bominaar and Michael P. Hendrich and A. S. Borovik}, doi = {10.1021/jacs.4c12327}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3129--3139}, shortjournal = {J. Am. Chem. Soc.}, title = {Proton-induced switching of paramagnetism: Reversible conversion between a low and high spin CoIII center within a heterobimetallic core}, volume = {147}, year = {2025}, }
• (2025). Improved ammonia synthesis and energy output from zinc-nitrate batteries by spin-state regulation in perovskite oxides. JACS, 147(4), 3119--3128. (www)

  @article{ , abstract = {Electrocatalytic nitrate reduction to ammonia (eNRA) is a promising route toward environmental sustainability and clean energy. However, its efficiency is often limited by the slow conversion of intermediates due to spin-forbidden processes. Here, we introduce a novel A-site high-entropy strategy to develop a new perovskite oxide (La 0.2 Pr 0.2 Nd 0.2 Ba 0.2 Sr 0.2 )CoO 3-δ (LPNBSC) for eNRA. The LPNBSC possesses a higher concentration of high-spin (HS) cobalt-active centers, resulting from an increased concentration of [CoO 5 ] structural motifs compared to conventional LaCoO 3 . Consequently, this material exhibits a significantly improved electrocatalytic performance toward ammonia (NH 3 ) production, resulting in a 3-fold increase in yield rate (129 μmol h –1 mg cat. –1 ) and a 2-fold increase in Faradaic efficiency (FE, 76%) compared to LaCoO 3 at the optimal potential. Furthermore, the LPNBSC-based Zn-nitrate battery reaches a maximum FE of 82% and an NH 3 yield rate of 57 μmol h –1 cm –2 . Density functional theory calculations reveal that A-site high-entropy management in perovskites facilitates nitrate activation and potentially optimizes the thermodynamic rate-determining step of the eNRA process, namely, *HNO 3 + H + + e – → *NO 2 + H 2 O. This work presents an efficient concept for modulating the spin state of the B-site metal in perovskites and offers valuable insights for the design of high-performance eNRA catalysts.}, archive = {J_JACS}, author = {Hele Guo and Yazhou Zhou and Kaibin Chu and Xueying Cao and Jingjing Qin and Nan Zhang and Maarten B. J. Roeffaers and Radek Zbořil and Johan Hofkens and Klaus Müllen and Feili Lai and Tianxi Liu}, doi = {10.1021/jacs.4c12240}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3119--3128}, shortjournal = {J. Am. Chem. Soc.}, title = {Improved ammonia synthesis and energy output from zinc-nitrate batteries by spin-state regulation in perovskite oxides}, volume = {147}, year = {2025}, }
• (2025). A dual-target and dual-mechanism design strategy by combining inhibition and degradation together. JACS, 147(4), 3110--3118. (www)

  @article{ , abstract = {Glioblastoma, a highly aggressive brain tumor, lacks effective treatment with low 5 year survival rates. Urgency for new therapies is evident. Mammalian targets of rapamycin (mTOR) and G1 to S phase transition 1 gene (GSPT1) are overexpressed in glioblastoma, regulating vital cellular functions. Current mTOR inhibitors face challenges in clinical efficacy and drug resistance. Similarly, GSPT1-targeting therapies have not progressed of glioblastoma in clinical trials. Research studies suggested that combining mTOR inhibition with GSPT1 degradation may overcome resistance and enhance efficacy. We propose the concept of jointly implementing inhibition and degradation on different proteins, integrating the properties of inhibitors and degraders into the same molecule. Introducing YB-3–17, a novel bifunctional molecule, robustly inhibits mTOR and selectively degrades GSPT1. As a tool compound for proof-of-concept studies, YB-3–17 sharpens selectivity, avoiding off-target effects, and selectively induces GSPT1 degradation and mTOR inhibition, showing superior efficacy in tumor cell lines compared to that of standalone therapies. RNA-seq analysis highlights the advantages of YB-3-17 over mTOR inhibitor treatment. YB-3–17 can safely and effectively inhibit tumor growth in mice, offering a promising direction for precision treatment of glioblastoma, representing the first attempt to combine mTOR inhibition with GSPT1 degradation. This work also demonstrates that it is conceptually possible to successfully combine the properties of small molecule inhibitors and degraders into a single molecule, killing two birds with one stone.}, archive = {J_JACS}, author = {Yongbo Liu and Xiuyun Sun and Qianlong Liu and Chi Han and Yu Rao}, doi = {10.1021/jacs.4c11930}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3110--3118}, shortjournal = {J. Am. Chem. Soc.}, title = {A dual-target and dual-mechanism design strategy by combining inhibition and degradation together}, volume = {147}, year = {2025}, }
• (2025). Taming highly enolizable aldehydes via enzyme catalysis for enantiocomplementary construction of β-hydroxyphosphonates. JACS, 147(4), 3102--3109. (www)

  @article{ , abstract = {Taming highly enolizable aldehydes for catalytic asymmetric C–C coupling with nucleophiles remains an elusive challenge compared to widely explored simple alkyl or aryl aldehydes. Herein, we use ThDP-dependent enzymes to realize the direct C–C coupling of highly enolizable 2-phosphonate aldehydes with in situ-generated dynamically reversible nucleophiles (acyl anions). Unlike NHC-mediated reactions that yield complex mixtures of multiple adducts, our enzymatic process selectively produces biologically active β-hydroxy phosphonates with high yields (up to 95%) and excellent enantioselectivities (up to 99% ee). The products can be obtained on gram scales and exhibit rich reactivity for downstream transformations to afford diverse molecules. Pf BAL (or its mutant A28G) and Pa BAL enzymes serve as enantiocomplementary pairs, enabling the synthesis of both product configurations. Mechanistic studies proved that the entrance directions of the active cavities of these two enzyme pairs were distinct, leading to acyl anions formed from these two enzyme pairs attacking 2-phosphonate aldehydes from different orientations.}, archive = {J_JACS}, author = {Huangong Li and Zheng Zhu and Dongqi Wu and Yongyuan Ju and Dan Li and Keke Zou and Chaonan Zhu and Jingyu Zhang and Guoliang Zhu and Lixin Zhang and Yonggui Robin Chi and Yongtao Xie}, doi = {10.1021/jacs.4c11957}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3102--3109}, shortjournal = {J. Am. Chem. Soc.}, title = {Taming highly enolizable aldehydes via enzyme catalysis for enantiocomplementary construction of β-hydroxyphosphonates}, volume = {147}, year = {2025}, }
• (2025). Spin chains with highly quantum character through strong covalency in Ca3CrN3. JACS, 147(4), 3092--3101. (www)

  @article{ , abstract = {The insulating transition metal nitride Ca 3 CrN 3 consists of sheets of triangular [CrN 3 ] 6– units with C 2 v symmetry that are connected via quasi-1D zigzag chains. Due to strong covalency between Cr and N, Cr 3+ ions are unusually low-spin, and S = 1/2. Magnetic susceptibility measurements reveal dominant quasi-1D spin correlations with very large nearest-neighbor antiferromagnetic exchange J = 340 K and yet no sign of magnetic order down to T = 0.1 K. Density functional theory calculations are used to model the local electronic structure and the magnetic interactions, supporting the low-spin assignment of Cr 3+ that is driven by strong π donation from the nitride ligands. The surprising failure of interchain exchange to drive long-range magnetic order is accounted for by the complex connectivity of the spin chain pairs that further frustrates order. Our combined results establish Ca 3 CrN 3 as a nearly ideal manifestation of a quantum spin chain whose dynamics remain unquenched down to extraordinarily low temperatures despite strong near-neighbor exchange coupling.}, archive = {J_JACS}, author = {Linus Kautzsch and Alexandru B. Georgescu and Lin-Ding Yuan and Keith M. Taddei and Aiden Reilly and Ram Seshadri and James M. Rondinelli and Stephen D. Wilson}, doi = {10.1021/jacs.4c11629}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3092--3101}, shortjournal = {J. Am. Chem. Soc.}, title = {Spin chains with highly quantum character through strong covalency in Ca3CrN3}, volume = {147}, year = {2025}, }
• (2025). A protein cleavage platform based on selective formylation at cysteine residues. JACS, 147(4), 3080--3091. (www)

  @article{ , abstract = {Site-selective cleavage of the peptide backbone in proteins is an important class of post-translational modification (PTM) in nature. However, the organic chemistry for such site-selective peptide bond cleavages has yet to be fully explored. Herein, we report cysteine S -formylation as a means of selective protein backbone cleavage. We developed N -formyl sulfonylanilide as a cysteine-selective formylation reagent for peptides and proteins. Upon S -formylation with the reagent, the amide bond adjacent to the S -formylated cysteine is cleaved by hydrolysis under neutral aqueous conditions. Formylation probes bearing a protein ligand enabled the affinity-based selective cleavage of the target proteins not only in the test tube but also under biorelevant conditions such as in crude cell lysate and on the cell surface. These results demonstrate the high biocompatibility of this protein cleavage technology. A proof-of-concept study of cleavage-induced protein activation further demonstrates its utility as a platform for the functional regulation of proteins by artificial PTM.}, archive = {J_JACS}, author = {Naoki Zenmyo and Yuya Matsumoto and Akihiro Yasuda and Shohei Uchinomiya and Naoya Shindo and Kaori Sasaki-Tabata and Emi Mishiro-Sato and Tomonori Tamura and Itaru Hamachi and Akio Ojida}, doi = {10.1021/jacs.4c10991}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3080--3091}, shortjournal = {J. Am. Chem. Soc.}, title = {A protein cleavage platform based on selective formylation at cysteine residues}, volume = {147}, year = {2025}, }
• (2025). Pseudopterosin biosynthesis: Unravelling a decades old problem in animal specialized metabolism. JACS, 147(4), 3072--3079. (www)

  @article{ , abstract = {Soft corals are prolific producers of terpenoids, such as pseudopterosins. The exact biosynthetic pathway of these anti-inflammatory diterpene glycosides has eluded the scientific community for decades. Using a forward genetic approach, we have identified, cloned, and expressed the key genes involved in pseudopterosin biosynthesis. We characterized a unique class of multifunctional cytochrome P450 enzymes that catalyze a cascade reaction that produces a nearly mature natural product using a single enzyme. This clarifies the previously proposed biosynthetic pathways to pseudopterosin A and its relatives. The mechanism of the oxidative cascade was probed using in vivo feeding studies in Saccharomyces cerevisiae expressing heterologous coral genes. The cascade produces the pseudopterosin aglycone 7,8-dihydroxyerogorgiaene via elisabethatrienol and its epimer, starting from elisabethatriene. This discovery demonstrates the potential to produce this valuable class of natural products using fermentation.}, archive = {J_JACS}, author = {Paul D. Scesa and Eric W. Schmidt}, doi = {10.1021/jacs.4c09925}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3072--3079}, shortjournal = {J. Am. Chem. Soc.}, title = {Pseudopterosin biosynthesis: Unravelling a decades old problem in animal specialized metabolism}, volume = {147}, year = {2025}, }
• (2025). Metal–Ligand spin-lock strategy for inhibiting anion dimerization in li-rich cathode materials. JACS, 147(4), 3062--3071. (www)

  @article{ , abstract = {Anion dimerization poses a significant challenge for the application of Li-rich cathode materials (LCMs) in high-energy-density Li-ion batteries because of its deleterious effects, including rapid capacity and voltage decay, sluggish reaction kinetics, and large voltage hysteresis. Herein, we propose a metal–ligand spin-lock strategy to inhibit anion dimerization, which involves introducing an Fe–Ni couple having antiferromagnetic superexchange interaction into the LCM to lock the spin orientations of the unpaired electrons in the anions in the same direction. As proof of concept, we applied this strategy to intralayer disordered Li 2 TiS 3 (ID-LTS) to inhibit S–S dimerization. Electrochemical characterization using the galvanostatic charge/discharge and intermittent titration technique demonstrated the considerably enhanced anionic redox activity, reduced voltage hysteresis, and improved kinetics of the Fe–Ni-couple-incorporated ID-LTS. Fe L 2,3 -edge X-ray absorption spectroscopy and magnetic susceptibility measurements revealed that the metal–ligand spin-lock effect and consequent suppression of anion dimerization involve ligand-to-metal charge transfer between S and Fe. Further electrochemical tests on a Fe–Ni-couple-incorporated Li-rich layered oxide (Li 0.7 Li 0.1 Fe 0.2 Ni 0.1 Mn 0.6 O 2 ) indicated the importance of the π backbond in enhancing ligand-to-metal charge transfer from S to Fe. These findings demonstrate the potential application of our metal–ligand spin-lock strategy in the development of high-performance LCMs.}, archive = {J_JACS}, author = {Zewen Jiang and Kun Zhang and Qihang Ding and Chuan Gao and Yuxuan Zuo and Hangchao Wang and Junfei Cai and Biao Li and Xinping Ai and Dingguo Xia}, doi = {10.1021/jacs.4c10815}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3062--3071}, shortjournal = {J. Am. Chem. Soc.}, title = {Metal–Ligand spin-lock strategy for inhibiting anion dimerization in li-rich cathode materials}, volume = {147}, year = {2025}, }
• (2025). Mechanically robust bismuth-embedded carbon microspheres for ultrafast charging and ultrastable sodium-ion batteries. JACS, 147(4), 3047--3061. (www)

  @article{ , abstract = {Advancements in the development of fast-charging and long-lasting microstructured alloying anodes with high volumetric capacities are essential for enhancing the operational efficiency of sodium-ion batteries (SIBs). These anodes, however, face challenges such as declined cyclability and rate capability, primarily due to mechanical degradation reduced by significant volumetric changes (over 252%) and slow kinetics of sodium-ion storage. Herein, we introduce a novel anode design featuring densely packed bismuth (Bi) embedded within highly conductive carbon microspheres to overcome the aforementioned challenges. Remarkably, the high loading Bi anode within carbon microspheres with a high tap density of 2.59 g cm –3 possesses significant mechanical strength exceeding 590 MPa and limits volume swelling of only 10.9% post-sodiation. This anode demonstrates a high volumetric capacity (908.3 mAh cm –3 ), ultrafast chargeability (200 A g –1 , full charge/discharge in just 5.5 s), and outstanding cyclability over 12,000 cycles and maintains exceptional cycling stability even at −30 °C. The full cell paired with a Na 3 V 2 (PO 4 ) 3 cathode retains over 80% capacity after 600 cycles at 36 C, demonstrating a remarkable rate capability of 126 C (full charge/discharge in 28.6 s). Our comprehensive experimental evaluations and chemo-mechanical simulations shed light on the mechanisms underpinning the anode’s superior performance. This development marks a significant advancement in the design of durable and fast-charging anodes for high-performance SIBs.}, archive = {J_JACS}, author = {Jianhai Pan and Zhefei Sun and Xiaoyu Wu and Tongchao Liu and Yurui Xing and Jiawei Chen and Zhichen Xue and Dafu Tang and Xiaoli Dong and Hongti Zhang and Haodong Liu and Qiulong Wei and Dong-Liang Peng and Khalil Amine and Qiaobao Zhang}, doi = {10.1021/jacs.4c09824}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3047--3061}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanically robust bismuth-embedded carbon microspheres for ultrafast charging and ultrastable sodium-ion batteries}, volume = {147}, year = {2025}, }
• (2025). Solvent-dependent reactivity of Fe(CO)5 under superacidic and oxidative conditions. JACS, 147(4), 3039--3046. (www)

  @article{ , abstract = {Herein, we report the solvent-dependent reactivity of Fe(CO) 5 toward AsF 5 in either anhydrous HF or liquid SO 2 . The reaction of Fe(CO) 5 with the superacid HF/AsF 5 leads to the protonation of the iron center and allows for the first-time structural characterization of [FeH(CO) 5 ] + in the solid state, representing one of the most acidic transition metal hydride complexes to ever be isolated and structurally characterized. In the aprotic but oxidation-stable solvent SO 2 , Fe(CO) 5 is oxidized and dimerized to [Fe 2 (CO) 10 ] 2+ , which is isoelectronic with well-known Mn 2 (CO) 10 . [Fe 2 (CO) 10 ] 2+ is the first structurally characterized example of a homoleptic dinuclear transition metal carbonyl cation. Together with Fe(CO) 5 and [Fe(CO) 5 ] +• , it is a rare example of an iron-centered triad from which the neutral, the radical cationic, and the dimerized dicationic species have been structurally and spectroscopically characterized. All characterizations are well supported by quantum chemical calculations. We also make the argument that the dimerization of [Fe(CO) 5 ] +• is largely dependent on the employed solvent.}, archive = {J_JACS}, author = {Willi R. Berg and Marc Reimann and Robin Sievers and Susanne M. Rupf and Johanna Schlögl and Kilian Weisser and Konstantin B. Krause and Christian Limberg and Martin Kaupp and Moritz Malischewski}, doi = {10.1021/jacs.4c09595}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3039--3046}, shortjournal = {J. Am. Chem. Soc.}, title = {Solvent-dependent reactivity of Fe(CO)5 under superacidic and oxidative conditions}, volume = {147}, year = {2025}, }
• (2025). Molecular h2 as the reducing agent in low-temperature oxide reduction using calcium hydride. JACS, 147(4), 3032--3038. (www)

  @article{ , abstract = {Low-temperature synthesis is crucial for advancing sustainable manufacturing and accessing novel metastable phases. Metal hydrides have shown great potential in facilitating the reduction of oxides at low temperatures, yet the underlying mechanism─whether driven by H – , H 2 , or atomic H─remains unclear. In this study, we employ in situ electrical transport measurements and first-principles calculations to investigate the CaH 2 -driven reduction kinetics in epitaxial α-Fe 2 O 3 thin films. Intriguingly, samples in direct contact with or separated from CaH 2 powders exhibit similar apparent activation energies for H 2 reduction, although direct contact significantly increases the reduction rate. These findings indicate that molecular H 2 is the dominant reducing species in the low-temperature reduction of oxides using CaH 2 , with a key aspect of the hydrides’ superior reducing power attributed to their ability to eliminate residual moisture. This work underscores the critical role of moisture control in enabling effective low-temperature oxide reduction for advanced material synthesis.}, archive = {J_JACS}, author = {Jiayue Wang and Yijun Yu and Ahmed Abdelkawy and Jiarui Li and Jinlei Li and Jing Yang and Eun Kyo Ko and Yonghun Lee and Vivek Thampy and Yi Cui and Mira Todorova and Jörg Neugebauer and Harold Y. Hwang}, doi = {10.1021/jacs.4c17825}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3032--3038}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular h2 as the reducing agent in low-temperature oxide reduction using calcium hydride}, volume = {147}, year = {2025}, }
• (2025). Facile access to quaternary carbon centers via ni-catalyzed arylation of alkenes with organoborons. JACS, 147(4), 3023--3031. (www)

  @article{ , abstract = {Quaternary carbon centers are widespread structural motifs, thus representing extensive interest in organic synthesis. We describe here an efficient nickel-catalyzed intermolecular, Markovnikov -selective arylation of minimally functionalized alkenes with stable organoborons, affording a broad range of cyclic or acyclic quaternary carbon centers under mild conditions. The utilization of the diimine ligand is critical for high reactivity and chemoselectivity. Furthermore, using a bulky chiral diimine as the ligand for the Ni catalyst, quaternary carbon stereocenters can be readily prepared with high levels of enantiocontrol. Mechanism studies suggest that, before protonation, a rare nickel shift from alkyl nickel to aryl nickel might occur.}, archive = {J_JACS}, author = {Zi-Chao Wang and Lei Gao and Song-Yang Liu and Peng Wang and Shi-Liang Shi}, doi = {10.1021/jacs.4c17313}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3023--3031}, shortjournal = {J. Am. Chem. Soc.}, title = {Facile access to quaternary carbon centers via ni-catalyzed arylation of alkenes with organoborons}, volume = {147}, year = {2025}, }
• (2025). C2-selective palladium-catalyzed C–S cross-coupling of 2,4-dihalopyrimidines. JACS, 147(4), 3017--3022. (www)

  @article{ , abstract = {Under most conditions, 2,4-dihalopyrimidines undergo substitution reactions at C4. Here we report that Pd(II) precatalysts supported by bulky N -heterocyclic carbene ligands uniquely effect C2-selective cross-coupling of 2,4-dichloropyrimidine with thiols. The regioselectivity of this reaction stands in stark contrast to ∼1500 previously reported Pd-catalyzed cross-couplings that favor C4 in the absence of other substituents on the pyrimidine ring. Selectivity in the catalytic system reported herein is extremely sensitive to the structure of the Pd(II) precatalyst, largely due to competing C4-selective nucleophilic aromatic substitution. C2-selectivity is high with most 1° thiols and thiophenols, and a range of substituted dichloropyrimidines can be used. The atypical selectivity of this transformation may facilitate diversity-oriented synthesis, as demonstrated for derivatives of an antiviral agent. Under these conditions, C2─Cl cleavage may not take place through a typical oxidative addition pathway.}, archive = {J_JACS}, author = {Oliver D. Jackson and Albert Reyes and Collin D. Stein and Nathaniel G. Larson and Calvin T. Andrews and Sharon R. Neufeldt}, doi = {10.1021/jacs.4c17020}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3017--3022}, shortjournal = {J. Am. Chem. Soc.}, title = {C2-selective palladium-catalyzed C–S cross-coupling of 2,4-dihalopyrimidines}, volume = {147}, year = {2025}, }
• (2025). Concise synthesis of (−)-veratramine and (−)-20-iso-veratramine via aromative Diels–Alder reaction. JACS, 147(4), 3010--3016. (www)

  @article{ , abstract = {A concise and convergent synthesis of the isosteroidal alkaloids veratramine and 20- iso -veratramine has been accomplished. A Horner–Wadsworth–Emmons olefination joins two chiral building blocks of approximately equal complexity and a transition-metal catalyzed intramolecular Diels–Alder cycloaddition-aromatization cascade constructs the tetrasubstituted arene. Other key steps include a highly diastereoselective crotylation of an N -sulfonyl iminium ion and an Eschenmoser fragmentation. The chiral building blocks developed for this synthesis could be used to access a range of additional isosteroidal alkaloids using our diversifiable strategy. Our work shows that 20- iso -veratramine is not identical with a natural product proposed to have that structure. The single crystal X-ray structures of veratramine and 20- iso -veratramine are reported.}, archive = {J_JACS}, author = {Michael D. Zott and Daniel W. Zuschlag and Dirk H. Trauner}, doi = {10.1021/jacs.4c16495}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3010--3016}, shortjournal = {J. Am. Chem. Soc.}, title = {Concise synthesis of (−)-veratramine and (−)-20-iso-veratramine via aromative Diels–Alder reaction}, volume = {147}, year = {2025}, }
• (2025). Divergent total syntheses of phragmalin and khayanolide-type limonoids: A torquoselective interrupted nazarov approach. JACS, 147(4), 3003--3009. (www)

  @article{ , abstract = {The asymmetric and divergent total syntheses of two phragmalin (moluccensins G and H) and two khayanolide-type (krishnolide F and khayseneganin F) limonoids were disclosed, which employed a torquoselective interrupted Nazarov cyclization as the key step. Taken together with a Liebeskind–Srogl coupling, a benzoin condensation, and bidirectional acyloin rearrangements, our strategy would simplify the synthetic design of both phragmalin and khayanolide-type limonoids and facilitate their modular syntheses. Moreover, the described approach also provides additional insights into the biosynthetic relationships between these two distinct skeletons.}, archive = {J_JACS}, author = {Peirong Rao and Dongmin Tang and Qidong Xia and Jialei Hu and Xufeng Lin and Jun Xuan and Hanfeng Ding}, doi = {10.1021/jacs.4c16265}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {3003--3009}, shortjournal = {J. Am. Chem. Soc.}, title = {Divergent total syntheses of phragmalin and khayanolide-type limonoids: A torquoselective interrupted nazarov approach}, volume = {147}, year = {2025}, }
• (2025). Unusual phospholipids from morganella morganii linked to depression. JACS, 147(4), 2998--3002. (www)

  @article{ , abstract = {A multifactorial association study detected a probable causal connection between the prevalence of Morganella morganii in the gut microbiome and the incidence of major depressive disorder (MDD) in the human host. A bioassay-guided fractionation approach identified bacterially produced metabolites that induced pro-inflammatory immune responses. The metabolites are unusual phospholipids that resemble conventional cardiolipins, in which diethanolamine (DEA) replaces the central glycerol. These molecular chimeras of endogenous metabolites from phospholipid biosynthetic pathways and the industrially produced micropollutant DEA activate TLR2/TLR1 receptors and induce the production of pro-inflammatory cytokines, especially IL-6. Their activity in conventional immunomodulatory assays largely parallels that of immunogenic cardiolipins with conventional structures. The molecular mechanism connecting these chimeric cardiolipins to MDD is supported by other studies and has implications for conditions other than MDD.}, archive = {J_JACS}, author = {Sunghee Bang and Yern-Hyerk Shin and Sung-Moo Park and Lei Deng and R. Thomas Williamson and Daniel B. Graham and Ramnik J. Xavier and Jon Clardy}, doi = {10.1021/jacs.4c15158}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {2998--3002}, shortjournal = {J. Am. Chem. Soc.}, title = {Unusual phospholipids from morganella morganii linked to depression}, volume = {147}, year = {2025}, }
• (2025). Fermi level equilibration and charge transfer at the exsolved metal-oxide interface. JACS, 147(4), 2991--2997. (www)

  @article{ , abstract = {Exsolution is a promising approach for fabricating oxide-supported metal nanocatalysts through redox-driven metal precipitation. A defining feature of exsolved nanocatalysts is their anchored metal-oxide interface, which exhibits exceptional structural stability in (electro)catalysis. However, the electronic interactions at this unique interface remain unclear, despite their known impact on catalytic performance. In this study, we confirm charge transfer between the host oxide and the exsolved metal by demonstrating a two-stage Fermi level ( E F ) evolution on SrTi 0.65 Fe 0.35 O 3−δ (STF) during metallic iron (Fe 0 ) exsolution. Combining ambient pressure X-ray photoelectron spectroscopy with theoretical analysis, we show that E F initially rises due to electron doping from oxygen vacancy formation in STF. Subsequently, upon Fe 0 precipitation, E F stabilizes and becomes insensitive to further oxygen release in STF, driven by E F equilibration and charge transfer between STF and the exsolved Fe 0 . These findings highlight the importance of considering electronic metal–support interactions when optimizing exsolved nanocatalysts.}, archive = {J_JACS}, author = {Jiayue Wang and Jing Yang and Jenna L. Wardini and Iradwikanari Waluyo and Adrian Hunt and Ethan J. Crumlin and Neal Fairley and William J. Bowman and Harold Y. Hwang and Bilge Yildiz}, doi = {10.1021/jacs.4c14695}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {2991--2997}, shortjournal = {J. Am. Chem. Soc.}, title = {Fermi level equilibration and charge transfer at the exsolved metal-oxide interface}, volume = {147}, year = {2025}, }
• (2025). Molecular phosphide complexes of zirconium. JACS, 147(4), 2984--2990. (www)

  @article{ , abstract = {Molecular Zr IV phosphides are extremely rare, with no examples containing a one-coordinated and terminal triple-bonded phosphorus atom. We report here an isolable and relatively stable Zr phosphide complex, [(PN) 2 Zr≡P{μ 2 -Na(OEt 2 )}] 2 ( 4 ), stemming from a cyclometalated Zr-hydride, [(PN)(PN′)Zr(H)] ( 2 ), and NaPH 2 . Complex 2 is prepared from two- or one-electron reductions of precursors [(PN) 2 ZrCl 2 ] ( 1 ) or metastable Zr III [(PN) 2 ZrCl], respectively. Oxidation of 2 with ClCPh 3 (2 equiv) or I 2 (1 equiv) resulted in re-formation of the PN ligand and isolation of the Zr IV complexes [(PN) 2 ZrX 2 ] (X = Cl, 1 ; X = I, 3 ), whereas addition of a weak acid to 2 allowed us to intercept the hydrido-halide intermediate [(PN) 2 Zr(I)(H)] (X = Cl, I) spectroscopically before conversion to 1 or 3 . Complex 2 exchanged with D 2 (1 atm) to fully deuterate the methylene all ortho -methyl groups of the PN and PN′ ligands and the hydride. Discrete salts of 4 can be readily prepared from Na + encapsulation with the crown ether 1,4,7,10,13,16-hexaoxacyclooctadecane (18-C-6) or cryptand 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (222-Kryptofix) to form [Na(18-C-6)(THF) 2 ][(PN) 2 Zr≡P] ( 5 ) and [Na(222-Kryptofix)][(PN) 2 Zr≡P] ( 6 ), respectively, which were structurally and spectroscopically characterized. Compounds 4 – 6 demonstrate exceptionally short Zr≡P bonds ( 4 , 2.3270(18) Å; 5 , 2.291(3) Å; 6 , 2.2989(17) Å) and highly downfield 31 P NMR spectral resonances ( 4 , 819 ppm; 5 and 6 , 927 and 955 ppm) in accord with a terminal phosphide ligand. The Zr≡P motif in 4 – 6 can be stabilized via coordination to a softer Tl + ion to form a nonsolvated phosphide [(PN) 2 Zr≡P{μ 2 -Tl}] 2 ( 7 ), exhibiting a phosphide resonance at ∼711 ppm.}, archive = {J_JACS}, author = {Mrinal Bhunia and Matthew R. Mena and Jacob S. Mohar and Michael R. Gau and Daniel J. Mindiola}, doi = {10.1021/jacs.4c13935}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {2984--2990}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular phosphide complexes of zirconium}, volume = {147}, year = {2025}, }
• (2025). Context-dependent heterotypic assemblies of intrinsically disordered peptides. JACS, 147(4), 2978--2983. (www)

  @article{ , abstract = {Despite their critical role in context-dependent interactions for protein functions, intrinsically disordered regions (IDRs) are often overlooked for designing peptide assemblies. Here, we exploit IDRs to enable context-dependent heterotypic assemblies of intrinsically disordered peptides, where “context-dependent” refers to assembly behavior driven by interactions with other molecules. By attaching an aromatic segment to oppositely charged intrinsically disordered peptides, we achieve a nanofiber formation. Although the same-charged peptides cannot self-assemble, oppositely charged peptides form heterotypic nanofibers. Cryo-EM analysis reveals a β-sheet arrangement within the ordered core of these nanofibers, conformational heterogeneity, and a disorder-to-order continuum and shows a high number of hydrogen bonds between tyrosine and lysine ε-amine. Additionally, this work demonstrates a post-assembly morphological change resulting from local conformational flexibility. While equal molar mixtures of the charged intrinsically disordered peptides yield nanofibers, doubling the positively charged peptides after assembly produces bundles of nanofibers. Furthermore, reducing the number of aromatic amino acid residues reduces bundle formation. Demonstrating context-dependent self-assembly of intrinsically disordered peptides and revealing atomistic insights into heterotypic assemblies of intrinsically disordered peptides for the first time, this work illustrates a straightforward approach to enable heterotypic intrinsically disordered peptides to self-assemble for the design of adaptive, multifunctional peptide nanomaterials.}, archive = {J_JACS}, author = {Yuchen Qiao and Ayisha Zia and Grace Wu and Zhiyu Liu and Jiaqi Guo and Matthew Chu and Hongjian He and Fengbin Wang and Bing Xu}, doi = {10.1021/jacs.4c12150}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {2978--2983}, shortjournal = {J. Am. Chem. Soc.}, title = {Context-dependent heterotypic assemblies of intrinsically disordered peptides}, volume = {147}, year = {2025}, }
• (2025). Toward sustainable polydienes. JACS, 147(4), 2960--2977. (www)

  @article{ , abstract = {The sustainable management of polydiene waste represents a formidable challenge in the realm of polymer chemistry, given the extensive industrial utilization of polydienes due to their superior elastomeric properties. This comprehensive Perspective addresses the multifaceted obstacles hindering efficient recycling of polydienes, encompassing environmental concerns, technical limitations, and economic disincentives. We systematically dissect the influence of polydienes’ chemical structures on their recyclability, tracing the evolution of polydiene utilization and disposal practices while assessing the current landscape of waste management strategies. Our investigation reveals the primary technical challenges associated with polydiene recycling, notably the energy-intensive nature of modification processes and the environmental detriments of prevailing disposal techniques. Furthermore, we critically evaluate existing recycling methodologies─including mechanical recycling, energy recovery, and chemical recycling─highlighting their respective merits, constraints, and environmental implications. Pioneering advancements in recycling technology, such as topochemical polymerization and computational prediction models, are spotlighted for their potential to revolutionize polydiene recycling. Looking forward, we delineate an optimistic trajectory for polydiene waste management, advocating for innovative polymerization methods, the exploration of milder recycling conditions, and the adoption of interdisciplinary approaches to bolster recycling efficiency. The Perspective culminates in a discussion on the pivotal role of policy frameworks, life cycle assessments, and economic analyses in shaping the future of polydiene recycling. Through this scholarly examination, we aim to catalyze further research and development efforts aimed at mitigating the environmental impact of polydiene waste, thereby contributing to the broader objective of sustainable chemistry.}, archive = {J_JACS}, author = {Pengfei Wu and Qixuan Hu and Lawal A. Ogunfowora and Zhixu Li and Andrew V. Marquardt and Brett M. Savoie and Letian Dou}, doi = {10.1021/jacs.4c12730}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {2960--2977}, shortjournal = {J. Am. Chem. Soc.}, title = {Toward sustainable polydienes}, volume = {147}, year = {2025}, }
• (2025). Precise synthesis of complex Si–Si molecular frameworks. JACS, 147(4), 2938--2959. (www)

  @article{ , abstract = {In this Perspective, we highlight the emergence of target-oriented syntheses of complex molecules composed of Si–Si (oligosilanes) rather than C–C bonds. Saturated oligosilanes structurally resemble alkanes with respect to a tetrahedral geometry, a preference for a staggered conformation in linear chains, the ability to form stable small rings, and tetrahedral stereochemistry at asymmetrically functionalized Si centers. There are also critical differences, for example, differences in multiple bonding and the ability to form penta- and hexacoordinated structures, that mean that chemical reactivity and, in particular, rules for stereoselective synthesis do not cleanly translate from carbon to silicon. This Perspective will discuss recent achievements in the precise, controlled synthesis of complex molecules comprised mainly of Si–Si bonds and highlight the mechanistic insights enabling increased molecular complexity. New tools, such as electrochemical and catalytic reactions, will be discussed as well as the problem of controlling relative configuration in molecules containing multiple stereogenic-at-silicon centers. These synthetic achievements facilitate the discovery of new properties, including insight into light absorption, conformation, and mechanical properties.}, archive = {J_JACS}, author = {Kelsie E. Wentz and Alexandra F. Gittens and Rebekka S. Klausen}, doi = {10.1021/jacs.4c12646}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {2938--2959}, shortjournal = {J. Am. Chem. Soc.}, title = {Precise synthesis of complex Si–Si molecular frameworks}, volume = {147}, year = {2025}, }
• (2025). Solid-state nuclear magnetic resonance spectroscopy for surface characterization of metal oxide nanoparticles: State of the art and perspectives. JACS, 147(4), 2919--2937. (www)

  @article{ , abstract = {Metal oxide materials have found wide applications across diverse fields; in most cases, their functionalities are dictated by their surface structures and properties. A comprehensive understanding of the intricate surface features is critical for their further design, optimization, and applications, necessitating multi-faceted characterizations. Recent advances in solid-state nuclear magnetic resonance (ssNMR) spectroscopy have significantly extended its applications in the detailed analysis of multiple metal oxide nanoparticles, offering unparalleled atomic-level information on the surface structures, properties, and chemistries. Herein, we present an overview of the current state of the art from an NMR perspective. We begin with a brief introduction to contemporary ssNMR methodologies. Subsequently, we introduce and provide critical reviews on the applications of different ssNMR techniques in the detailed characterizations of the surface local structures, disorders, defects, active sites, and acidity on metal oxide nanoparticles, as well as the revelation of mechanisms behind some intriguing chemistries that occur on the surfaces, referencing representative recent studies. Finally, we address the challenges beyond the current status and provide perspectives on the future development and application of advanced ssNMR methodologies in this emerging field.}, archive = {J_JACS}, author = {Pan Gao and Yi Ji and Guangjin Hou}, doi = {10.1021/jacs.4c10468}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {2919--2937}, shortjournal = {J. Am. Chem. Soc.}, title = {Solid-state nuclear magnetic resonance spectroscopy for surface characterization of metal oxide nanoparticles: State of the art and perspectives}, volume = {147}, year = {2025}, }
• (2025). Welcome, 2025. JACS, 147(4), 2917--2918. (www)

  @article{ , archive = {J_JACS}, author = {Erick M. Carreira}, doi = {10.1021/jacs.5c00776}, journal = {Journal of the American Chemical Society}, month = {1}, number = {4}, pages = {2917--2918}, shortjournal = {J. Am. Chem. Soc.}, title = {Welcome, 2025}, volume = {147}, year = {2025}, }
• (2025). Correction to “Total syntheses of scabrolide a and yonarolide”. JACS, 147(3), 2915--2916. (www)

  @article{ , archive = {J_JACS}, author = {Roberto Serrano and Yaroslav D. Boyko and Lucas W. Hernandez and Aleksandras Lotuzas and David Sarlah}, doi = {10.1021/jacs.4c18146}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2915--2916}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Total syntheses of scabrolide a and yonarolide”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Single─Not Double─3D-aromaticity in an oxidized closo icosahedral dodecaiodo-dodecaborate cluster”. JACS, 147(3), 2914. (www)

  @article{ , archive = {J_JACS}, author = {Jordi Poater and Sílvia Escayola and Albert Poater and Francesc Teixidor and Henrik Ottosson and Clara Viñas and Miquel Solà}, doi = {10.1021/jacs.4c17897}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2914}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Single─Not Double─3D-aromaticity in an oxidized closo icosahedral dodecaiodo-dodecaborate cluster”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Edge length-programmed single-stranded RNA origami for predictive innate immune activation and therapy”. JACS, 147(3), 2913. (www)

  @article{ , archive = {J_JACS}, author = {Kun Dai and Yang Xu and Yang Yang and Jianfeng Shen and Xiaoguo Liu and Xinyi Tu and Lu Yu and Xiaodong Qi and Jiang Li and Lihua Wang and Xiaolei Zuo and Yingbin Liu and Hao Yan and Chunhai Fan and Guangbao Yao}, doi = {10.1021/jacs.4c16915}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2913}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Edge length-programmed single-stranded RNA origami for predictive innate immune activation and therapy”}, volume = {147}, year = {2025}, }
• (2025). Covalent plant natural product that potentiates antitumor immunity. JACS, 147(3), 2902--2912. (www)

  @article{ , abstract = {Despite the unprecedented therapeutic potential of immune checkpoint antibody therapies, their efficacy is limited partly by the dysfunction of T cells within the cancer microenvironment. Combination therapies with small molecules have also been explored, but their clinical implementation has been met with significant challenges. To search for antitumor immunity activators, the present study developed a cell-based system that emulates cancer-attenuated T cells. The cell-based screening of 232 natural products containing electrophilic reactive functional groups led to the identification of arvenin I, also known as cucurbitacin B 2- O -β- d -glucoside (CuBg), as a plant natural product that activates T cells within the cancer-competitive environment. Chemoproteomic and mechanistic analyses indicated that arvenin I covalently reacts with and hyperactivates MKK3, thereby reviving the mitochondrial fitness of exhausted T cells through the activation of the p38MAPK pathway. In mice, administration of arvenin I enhanced the efficacy of cancer immunotherapy when used alone or in combination with an immune checkpoint inhibitor. These findings highlight the potential of arvenin I as a covalent kinase activator that potentiates antitumor immunity.}, archive = {J_JACS}, author = {Misao Takemoto and Sara Delghandi and Masahiro Abo and Keiko Yurimoto and Minami Odagi and Vaibhav Pal Singh and Jun Wang and Reiko Nakagawa and Shin-ichi Sato and Yasushi Takemoto and Asmaa M. A. S. Farrag and Yoshimasa Kawaguchi and Kazuo Nagasawa and Tasuku Honjo and Kenji Chamoto and Motonari Uesugi}, doi = {10.1021/jacs.4c17837}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2902--2912}, shortjournal = {J. Am. Chem. Soc.}, title = {Covalent plant natural product that potentiates antitumor immunity}, volume = {147}, year = {2025}, }
• (2025). Optimizing surface Maleimide/cRGD ratios enhances targeting efficiency of cRGD-functionalized nanomedicines. JACS, 147(3), 2889--2901. (www)

  @article{ , abstract = {Thiol–maleimide (MI) chemistry is a cornerstone of bioconjugation strategies, particularly in the development of drug delivery systems. The cyclic arginine–glycine–aspartic acid (cRGD) peptide, recognized for its ability to target the integrin α v β 3 , is commonly employed to functionalize maleimide-bearing nanoparticles (NPs) for fabricating cRGD-functionalized nanomedicines. However, the impact of cRGD density on tumor targeting efficiency remains poorly understood. In this study, we investigate how varying MI/cRGD ratios affect the biological fate of cRGD-functionalized nanomedicines. Using a model system of nanomedicines self-assembled from phthalocyanine derivatives and PEG–PLA block copolymers, we demonstrate that an optimized cRGD/MI ratio can markedly alter the protein corona composition, leading to increased albumin adsorption, while MI-free cRGD-functionalized nanomedicines attract immunoglobulins and complement proteins. Our findings reveal that higher cRGD densities, contrary to expectations, do not enhance tumor targeting but instead promote sequestration in the liver and spleen. However, the presence of MI moieties can significantly mitigate this sequestration of cRGD-functionalized nanomedicines by promoting the formation of an albumin-rich protein corona on nanomedicines. These insights highlight the capacity of MI moieties in improving the targeting and therapeutic effects of cRGD-functionalized nanomedicines, providing refined strategies to maximize the efficacy of nanomedicines while minimizing off-target effects.}, archive = {J_JACS}, author = {Rundi Song and Jiajia Tan and Jie Cen and Ziwei Li and Yuben Zhang and Mingxuan Hou and Runjie Li and Liqin Tang and Jinming Hu and Shiyong Liu}, doi = {10.1021/jacs.4c17178}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2889--2901}, shortjournal = {J. Am. Chem. Soc.}, title = {Optimizing surface Maleimide/cRGD ratios enhances targeting efficiency of cRGD-functionalized nanomedicines}, volume = {147}, year = {2025}, }
• (2025). Hafnium-based chiral 2D Organic–Inorganic hybrid metal halides: Engineering polarity and nonlinear optical properties via para-substituent effects. JACS, 147(3), 2880--2888. (www)

  @article{ , abstract = {Two-dimensional (2D) organic–inorganic hybrid metal halides (OIMHs), characterized by noncentrosymmetric structures arising from the incorporation of chiral organic molecules that break inversion symmetry, have attracted significant attention. Particularly, chiral-polar 2D OIMHs offer a unique platform for multifunctional applications, as the coexistence of chirality and polarity enables the simultaneous manifestation of distinct properties such as nonlinear optical (NLO) effects, circular dichroism (CD), and ferroelectricity. In this study, we report the first synthesis of hafnium (Hf)-based chiral 2D OIMHs, achieved through the strategic incorporation of para -substituents on the benzene ring of chiral organic components. By tuning the substituents, we successfully modulate the polarity of the crystal structures, resulting in both chiral-nonpolar and chiral-polar systems. Our analysis of structural and optical properties, supported by density functional theory calculations, demonstrates that the polarity of these materials can be systematically tuned, enabling adjustable band gaps and CD in the UV range (200–280 nm). Notably, halogen substitution at the para -position of the benzene ring in the organic layer produces tunable optical band gaps ranging from 4.33 to 4.48 eV, the widest reported to date for chiral-polar 2D OIMHs. Furthermore, these materials exhibit enhanced NLO properties, including a remarkable 3.3-fold increase in second-harmonic generation intensity in chiral-polar compounds compared to their chiral-nonpolar counterparts. These findings position Hf-based chiral 2D OIMHs as promising candidates for UV-region applications, such as UV NLO devices and self-driven circularly polarized light detectors, offering new opportunities for designing multifunctional optoelectronic materials by harnessing the interplay between chirality and polarity.}, archive = {J_JACS}, author = {Kyungmo Kim and Yang Li and Kang Min Ok}, doi = {10.1021/jacs.4c16985}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2880--2888}, shortjournal = {J. Am. Chem. Soc.}, title = {Hafnium-based chiral 2D Organic–Inorganic hybrid metal halides: Engineering polarity and nonlinear optical properties via para-substituent effects}, volume = {147}, year = {2025}, }
• (2025). Large polarization change induced by spin crossover-driven Fe(II) ion shuttling within a tripodal ligand. JACS, 147(3), 2871--2879. (www)

  @article{ , abstract = {The integration of spin crossover (SCO) magnetic switching and electric polarization properties can engender intriguing correlated magnetic and electric phenomena. However, achieving substantial SCO-induced polarization change through rational molecular design remains a formidable challenge. Herein, we present a polar Fe(II) compound that exhibits substantial polarization change in response to a thermally regulated low-spin ↔ high-spin transition. This large polarization change is realized by harnessing an unusual SCO-actuated large displacement of the Fe(II) ion, encapsulated within a cage-like tripodal ligand. Owing to the uniaxially aligned polar molecular structures within the lattice, alterations in the molecular dipole moment translate to notable polarization change of the single crystal with a value of 1.9 μC cm –2 . This value is 2.4 times the highest value reported for SCO compounds. The large polarization change and small dielectric constant result in an outstanding pyroelectric response in this compound, with figures of merit comparable to those of typical pyroelectric materials. The intrinsic large displacement of the Fe(II) ion provides a new strategy to effectively modulate the electric polarization via SCO magnetic switching, and the ion shuttling within a cage structure may find applications in next-generation single-molecule magnetoelectric devices.}, archive = {J_JACS}, author = {Chengdong Liu and Shu-Qi Wu and Kai-Ge Gao and Jie-Sheng Hu and Yun Li and Lu-Yao Wang and Yan Xiong and Jun Tao and Zi-Shuo Yao}, doi = {10.1021/jacs.4c16750}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2871--2879}, shortjournal = {J. Am. Chem. Soc.}, title = {Large polarization change induced by spin crossover-driven Fe(II) ion shuttling within a tripodal ligand}, volume = {147}, year = {2025}, }
• (2025). Monitoring of the local extracellular environment using chiral gold nanoparticles. JACS, 147(3), 2860--2870. (www)

  @article{ , abstract = {In three-dimensional (3D)-printed tissue models, sensitive, noninvasive techniques are required to detect in situ changes in hydrogel structure caused by cellular remodeling. We demonstrate herein that circular dichroism (CD) spectroscopy provides a reliable method for detecting hydrogel structural variations. We probe directly the plasmonic optical activity of chiral gold nanorods (c-AuNRs) embedded within the hydrogel matrix, in response to variations in the local environment. Unlike extinction spectroscopy, we found that CD features such as zero-point crossings do not get masked by the strong scattering due to the porous hydrogel structure and are therefore sensitive to changes in the refractive index of the medium, reversible swelling and deswelling of the hydrogel, and other interactions between the hydrogel and the c-AuNR surface. By culturing metastatic breast cancer cells within the 3D hydrogel nanocomposite, we demonstrate that CD can noninvasively probe the restructuring of the hydrogel. This study highlights the potential of CD spectroscopy in combination with c-AuNRs to investigate complex changes in biological or polymeric systems.}, archive = {J_JACS}, author = {Ben Tadgell and Clara García-Astrain and Malou Henriksen-Lacey and Víctor F. Martín and Manuel Obelleiro-Liz and Luis M. Liz-Marzán}, doi = {10.1021/jacs.4c16686}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2860--2870}, shortjournal = {J. Am. Chem. Soc.}, title = {Monitoring of the local extracellular environment using chiral gold nanoparticles}, volume = {147}, year = {2025}, }
• (2025). A spectrochemical series for electron spin relaxation. JACS, 147(3), 2849--2859. (www)

  @article{ , abstract = {Controlling the rate of electron spin relaxation in paramagnetic molecules is essential for contemporary applications in molecular magnetism and quantum information science. However, the physical mechanisms of spin relaxation remain incompletely understood, and new spectroscopic observables play an important role in evaluating spin dynamics mechanisms and structure–property relationships. Here, we use cryogenic magnetic circular dichroism (MCD) spectroscopy and pulse electron paramagnetic resonance (EPR) in tandem to examine the impact of ligand field (d–d) excited states on spin relaxation rates. We employ a broad scope of square-planar Cu(II) compounds with varying ligand field strength, including CuS 4 , CuN 4 , CuN 2 O 2 , and CuO 4 first coordination spheres. An unexpectedly strong correlation exists between spin relaxation rates and the average d–d excitation energy ( R 2 = 0.97). The relaxation rate trends as the inverse 11th power of the excited-state energies, whereas simplified theoretical models predict only an inverse second power dependence. These experimental results directly implicate ligand field excited states as playing a critical role in the ground-state spin relaxation mechanism. Furthermore, ligand field strength is revealed to be a particularly powerful design principle for spin dynamics, enabling formation of a spectrochemical series for spin relaxation.}, archive = {J_JACS}, author = {Nathanael P. Kazmierczak and Kay T. Xia and Erica Sutcliffe and Jonathan P. Aalto and Ryan G. Hadt}, doi = {10.1021/jacs.4c16571}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2849--2859}, shortjournal = {J. Am. Chem. Soc.}, title = {A spectrochemical series for electron spin relaxation}, volume = {147}, year = {2025}, }
• (2025). Reversible isomerization of stiff-stilbene by an oriented external electric field. JACS, 147(3), 2841--2848. (www)

  @article{ , abstract = {Understanding and effectively controlling molecular conformational changes are essential for developing responsive and dynamic molecular systems. Here, we report that an oriented external electric field (OEEF) is an effective catalyst for the cis–trans isomerization of stiff-stilbene, a key component of overcrowded alkene-based rotary motors. This reversible isomerization occurs under ambient conditions, is free from side reactions, and has been verified using ultraperformance liquid chromatography and UV–vis absorption spectroscopy. Low electric field promotes cis-to-trans conversion, and high electric field enables the reverse trans-to-cis process, demonstrating the precise reaction control through electric field manipulation. Density functional theory calculations reveal the mechanism of the electric-field-catalyzed cis–trans carbon–carbon double bond isomerization. Our findings provide a novel perspective on constructing OEEF-catalyzed, reversible molecular systems and pave the way for fully electrically driven artificial molecular machines.}, archive = {J_JACS}, author = {Rui Wang and Yingjie Li and Siyu Yan and Zekai Zhang and Cheng Lian and He Tian and Hongxiang Li}, doi = {10.1021/jacs.4c16530}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2841--2848}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible isomerization of stiff-stilbene by an oriented external electric field}, volume = {147}, year = {2025}, }
• (2025). Long, synthetic staphylococcus aureus type 8 capsular oligosaccharides reveal structural epitopes for effective immune recognition. JACS, 147(3), 2829--2840. (www)

  @article{ , abstract = {Staphylococcus aureus is a Gram-positive bacterium that is responsible for severe nosocomial infections. The rise of multidrug-resistant strains, which can pose significant health threats, prompts the development of new treatment interventions, and much attention has been directed at the development of prophylactic and therapeutic vaccination strategies. Capsular polysaccharides (CPs) are key protective elements of the S. aureus cell wall and have been proposed as promising candidate antigens. Thirteen different CP serotypes have been identified to date, of which types 5 and 8 are the most prominent. CP8 is composed of trisaccharide repeating units that are built up from an N -acetyl-4- O -acetyl -β - d -mannosaminuronic acid, that carries a C-4- O -acetyl, an N -acetyl-α- d -fucosamine, and an N -acetyl-α- l -fucosamine. Synthetic oligosaccharides are valuable tools to unravel the immunogenicity of bacterial oligosaccharides at the molecular level. However, the rare monosaccharides, cis -glycosidic linkages, and O -acetylation represent significant challenges for the synthesis of CP8 fragments. Here the stereoselective assembly of well-defined CP8 fragments, comprising a trimer, hexamer, nonamer, and dodecamer, is presented. This is the first time that fragments larger than a single repeating trisaccharide, which has been proven to be insufficient for antigenic activity, have been assembled. Structural studies have revealed a linear conformation for the oligosaccharides, with each trisaccharide repeat tilted ∼90° with respect to the flanking repeats, which is stabilized by the acetyl groups that prevent rotation around the glycosidic linkages. The N -acetyl groups in each repeating unit point in the same direction, generating a hydrophobic flank in the trisaccharide repeats. We applied the oligomers to generate model glycoconjugate vaccine modalities, which we then used to raise anti-CP8 antibodies. The antibody interaction and immunization studies have revealed a clear length dependent structure–activity relationship for the oligosaccharides, with an oligosaccharide of at least three repeating units required for an adequate immune response.}, archive = {J_JACS}, author = {Kitt Emilie Østerlid and Charlotte Sorieul and Luca Unione and Sizhe Li and Cristian García-Sepúlveda and Filippo Carboni and Linda Del Bino and Francesca Berni and Ana Arda and Herman S. Overkleeft and Gijsbert A. van der Marel and Maria Rosaria Romano and Jesús Jiménez-Barbero and Roberto Adamo and Jeroen D. C. Codée}, doi = {10.1021/jacs.4c16118}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2829--2840}, shortjournal = {J. Am. Chem. Soc.}, title = {Long, synthetic staphylococcus aureus type 8 capsular oligosaccharides reveal structural epitopes for effective immune recognition}, volume = {147}, year = {2025}, }
• (2025). Upcycling poly(vinyl chloride) and polystyrene plastics using photothermal conversion. JACS, 147(3), 2822--2828. (www)

  @article{ , abstract = {Poly(vinyl chloride) (PVC) and polystyrene (PS) are among the least recycled plastics. In this work, we developed a simple and novel strategy to valorize PVC and PS plastics via photothermal conversion to (1-chloroethyl)benzene, a commodity chemical with excellent versatility. As PVC is known to release HCl gas and decompose into conjugated polyenes, we envisioned a dual role for PVC plastics. While the in situ-generated HCl serves as a chlorine source, the resulting dehydrochlorinated-PVC (DHPVC) functions as a photothermal agent to accelerate the hydrochlorination of styrene. We converted PVC and styrene in up to 89% (1-chloroethyl)benzene in less than 1 h of white light irradiation. Subsequent nucleophilic substitution on the chloro-adduct formed 1-phenylethanol (a fragrance additive) and fendiline (a heart disease drug) in high yields. The PVC photothermal hydrochlorination system is applied to various alkenes and is compatible with post-consumer waste PVC plastics and plasticizers. Ultimately, PVC upcycling with photothermally recycled styrene achieved 84% (1-chloroethyl)benzene under white LED light in 1 h, and co-upcycling of PS and PVC achieved 42% yield under focused sunlight irradiation in just 4 min.}, archive = {J_JACS}, author = {Hanning Jiang and Erik A. Medina and Erin E. Stache}, doi = {10.1021/jacs.4c16145}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2822--2828}, shortjournal = {J. Am. Chem. Soc.}, title = {Upcycling poly(vinyl chloride) and polystyrene plastics using photothermal conversion}, volume = {147}, year = {2025}, }
• (2025). Pretargeted multimodal tumor imaging by enzymatic self-immobilization labeling and bioorthogonal reaction. JACS, 147(3), 2809--2821. (www)

  @article{ , abstract = {Covalent modification of cell membranes has shown promise for tumor imaging and therapy. However, existing membrane labeling techniques face challenges such as slow kinetics and poor selectivity for cancer cells, leading to off-target effects and suboptimal in vivo efficacy. Here, we present an enzyme-triggered self-immobilization labeling strategy, termed E-SIM, which enables rapid and selective labeling of tumor cell membranes with bioorthogonal trans-cycloctene (TCO) handles in vivo . E-SIM utilizes P-TCO, an alkaline phosphatase (ALP) responsive quinone methide (QM) precursor with a TCO group, facilitating the rapid conjugation of high-density TCO handles onto tumor cell membranes via proximity labeling. These TCO groups then react efficiently with tetrazine (Tz)-bearing reporters via a fast bioorthogonal reaction, resulting in significant enrichment of reporters of various sizes and imaging modalities on tumor cell membranes. We demonstrate the efficacy of E-SIM labeling and bioorthogonal reaction for pretargeted multimodality imaging of tumors in vivo . Notably, we achieve selective and efficient installation of Tz-modified Renilla luciferase on tumor cells in vivo , thereby offering highly sensitive bioluminescence signals for detecting and guiding the surgical removal of small human HepG2 liver tumor peritoneal metastases. E-SIM represents a robust tool for precise tumor cell labeling in complex in vivo environments, feasible for pretargeted enrichment of various reporters in tumors for multimodal imaging applications.}, archive = {J_JACS}, author = {Yinxing Miao and Yuqi Wang and Yefeng Chen and Zheng Huang and Chunmei Lu and Yili Liu and Fangfang Chen and Xidan Wen and Junya Zhang and Shiliang Zhu and Pengke Zhao and Yunhan Chen and Tian Tian and Yan Zhang and Hexin Xie and Jianguo Lin and Deju Ye}, doi = {10.1021/jacs.4c15896}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2809--2821}, shortjournal = {J. Am. Chem. Soc.}, title = {Pretargeted multimodal tumor imaging by enzymatic self-immobilization labeling and bioorthogonal reaction}, volume = {147}, year = {2025}, }
• (2025). Molecular design of hole-collecting materials for co-deposition processed perovskite solar cells: A tripodal triazatruxene derivative with carboxylic acid groups. JACS, 147(3), 2797--2808. (www)

  @article{ , abstract = {High-performance and cost-effective hole-collecting materials (HCMs) are indispensable for commercially viable perovskite solar cells (PSCs). Here, we report an anchorable HCM composed of a triazatruxene core connected with three alkyl carboxylic acid groups ( 3CATAT-C3 ). In contrast to the phosphonic acid-containing tripodal analog ( 3PATAT-C3 ), 3CATAT-C3 molecules can form a hydrophilic monolayer on a transparent conducting oxide surface, which is beneficial for subsequent perovskite film deposition in the traditional layer-by-layer fabrication process. More importantly, the larger diffusion coefficient and higher surface energy make 3CATAT-C3 suitable for the simplified, cost-effective one-step co-deposition process in which 3CATAT-C3 was directly added as part of the perovskite precursor solution. 3CATAT-C3 is predominantly located at the perovskite bottom surface after spin-coating the mixed precursor solution, facilitating charge extraction. Devices with 3CATAT-C3 fabricated by this co-deposition method exhibit superior performance with a champion power conversion efficiency of over 23%. The unencapsulated devices showed good operational stability (retaining 90% of the initial output after 100 h), thermal durability (retaining 95% of the initial value after heating at 105 °C under air), and excellent storage stability (showing no drop in performance over 8000 h). Based on the results of time-of-flight secondary-ion mass spectroscopy (ToF-SIMS) and diffusion order nuclear magnetic resonance spectroscopy (DOSY), we elucidated the effect of anchoring groups on the performance of the tripodal HCMs in PSCs as well as the mechanism of the co-deposition fabrication process. Our findings provide valuable insights for the molecular design of multifunctional hole-collecting materials, further advancing the performance of perovskite solar cells.}, archive = {J_JACS}, author = {Minh Anh Truong and Tsukasa Funasaki and Yuta Adachi and Shota Hira and Tiancheng Tan and Aruto Akatsuka and Takumi Yamada and Yasuko Iwasaki and Yuko Matsushige and Ryuji Kaneko and Chizuru Asahara and Tomoya Nakamura and Richard Murdey and Hiroyuki Yoshida and Yoshihiko Kanemitsu and Atsushi Wakamiya}, doi = {10.1021/jacs.4c15857}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2797--2808}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular design of hole-collecting materials for co-deposition processed perovskite solar cells: A tripodal triazatruxene derivative with carboxylic acid groups}, volume = {147}, year = {2025}, }
• (2025). Light-enabled reversible hydrogen storage of borohydrides activated by photogenerated vacancies. JACS, 147(3), 2786--2796. (www)

  @article{ , abstract = {Borohydrides, known for ultrahigh hydrogen density, are promising hydrogen storage materials but typically require high operating temperatures due to their strong thermodynamic stability. Here we introduce a novel light-induced destabilization mechanism for hydrogen storage reaction of borohydrides under ambient conditions via photogenerated vacancies in LiH. These vacancies thermodynamically destabilize B–H bonds through the spontaneous “strong adsorption” of BH 4 groups, which trigger an asymmetric redistribution of electrons, enabling hydrogen release at near room temperature, approximately 300 °C lower than the corresponding thermal process. By utilizing specially designed “nano-photothermal reactors”, which optimize thermodynamic destabilization effect with nanoscale dispersed LiH and create space-confined “hotspots” to enhance hydrogen storage kinetics, we achieve an ultrahigh hydrogen storage capacity of 11.02 wt % H 2 in LiBH 4 using only light irradiation. This light-induced destabilization mechanism can also be extended to other alkali metal borohydrides, offering insights for developing solid-state hydrogen storage materials under mild conditions.}, archive = {J_JACS}, author = {Xiaoyue Zhang and Chaoqun Li and Jikai Ye and Xuechun Hu and Wei Chen and Fang Fang and Dalin Sun and Yongfeng Liu and Xuebin Yu and Guanglin Xia}, doi = {10.1021/jacs.4c15744}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2786--2796}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-enabled reversible hydrogen storage of borohydrides activated by photogenerated vacancies}, volume = {147}, year = {2025}, }
• (2025). Interrupting associative π–σ–π isomerization enables Z-retentive asymmetric Tsuji–Trost reaction. JACS, 147(3), 2776--2785. (www)

  @article{ , abstract = {The asymmetric Tsuji–Trost reaction has been extensively studied due to its importance in establishing stereogenic centers, often adjacent to an E -olefin moiety in organic molecules. The generally preferential formation of chiral E -olefin products is believed to result from the thermodynamically more stable syn -π-allylpalladium intermediate. The rapid associative π–σ–π isomerization makes it challenging to synthesize chiral Z -olefin products via the transient anti -π-allylpalladium intermediate. Herein, we report a strategy for regulating associative π–σ–π isomerization by tuning the steric bulkiness of the ligands, allylic leaving groups, and counteranions. The utilization of a Pd catalyst derived from chiral phosphoramidite ligands interrupts the associative π–σ–π isomerization, enabling a highly efficient Z -retentive asymmetric Tsuji–Trost reaction toward an array of α-amino acid derivatives bearing a Z -olefin motif in high yields (up to 95%) and excellent stereoselectivity (up to 99% ee and >19:1 Z / E ) with low catalyst loading (0.1 mol %). The mechanistic insights and the design strategy reported in this work pave the way for rational developments of Z -retentive asymmetric Tsuji–Trost-type reactions.}, archive = {J_JACS}, author = {Jiandong Liu and Zhongkang Dong and Wen-Bin Cao and Chao Zheng and Shu-Li You}, doi = {10.1021/jacs.4c15635}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2776--2785}, shortjournal = {J. Am. Chem. Soc.}, title = {Interrupting associative π–σ–π isomerization enables Z-retentive asymmetric Tsuji–Trost reaction}, volume = {147}, year = {2025}, }
• (2025). Mechanical twisting-induced enhancement of second-order optical nonlinearity in a flexible molecular crystal. JACS, 147(3), 2766--2775. (www)

  @article{ , abstract = {Flexible molecular crystals are essential for advancing smart materials, providing unique functionality and adaptability for applications in next-generation electronics, pharmaceuticals, and energy storage. However, the optical applications of flexible molecular crystals have been largely restricted to linear optics, with nonlinear optical (NLO) properties rarely explored. Herein, we report on the application of mechanical twisting of flexible molecular crystals for second-order nonlinear optics. The crystal formed through the self-assembly of the model compound 9-anthraldehyde ( AA ) features an intrinsic chiral and noncentrosymmetric structure, demonstrating high efficiency second harmonic generation (SHG) and NLO circular dichroism, which could be greatly enhanced by macroscopic mechanical twisting. The anisotropic molecular stacking imparts the AA crystal with mechanical flexibility of combined elastic bending and plastic twisting. The isochiral mechanical twisting could greatly enhance the SHG intensities by an order of magnitude depending on their M - or P -configuration. Meanwhile, the SHG circular dichroism factor g SHG-CD of the isochiral twisted crystal is greatly increased, achieving the highest reported NLO anisotropy factor among organic NLO materials. These boosted NLO performances of SHG intensity and nonlinear chiroptical response are expected to greatly expand the photonic applications of flexible molecular crystals.}, archive = {J_JACS}, author = {Zhihua Wang and Wenqing Han and Bona Fu and Hanwen Kang and Puxin Cheng and Junjie Guan and Yongshen Zheng and Rongchao Shi and Jialiang Xu and Xian-He Bu}, doi = {10.1021/jacs.4c15519}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2766--2775}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanical twisting-induced enhancement of second-order optical nonlinearity in a flexible molecular crystal}, volume = {147}, year = {2025}, }
• (2025). Catalyst-free nitrogen fixation by microdroplets through a radical-mediated disproportionation mechanism under ambient conditions. JACS, 147(3), 2756--2765. (www)

  @article{ , abstract = {Nitrogen fixation is essential for the sustainable development of both human society and the environment. Due to the chemical inertness of the N≡N bond, the traditional Haber–Bosch process operates under extreme conditions, making nitrogen fixation under ambient conditions highly desirable but challenging. In this study, we present an ultrasonic atomizing microdroplet method that achieves nitrogen fixation using water and air under ambient conditions in a rationally designed sealed device, without the need for any catalyst. The total nitrogen fixation rate achieved is 6.99 μmol/h, yielding ammonium as the reduction product and nitrite and nitrate as the oxidation products, with hydrogen peroxide produced as a byproduct at a rate of 4.29 μmol/h. Using electron paramagnetic resonance (EPR) spectroscopy, we captured reactive species, including hydrogen, hydroxyl, singlet oxygen, superoxide anion, and NO radicals. In conjunction with in situ mass spectrometry (MS) and isotope labeling, we confirmed the presence of nitrogen-containing intermediates, such as HN═NOH +• , H 2 N–N(OH) 2 +• , HNO + , and NH 2 OH +• . Supported by these findings and theoretical calculations, we propose a radical-mediated nitrogen disproportionation mechanism. Simulations of naturally occurring condensed microdroplets also demonstrated nitrogen redox fixation. This microdroplet-based method not only offers a potential pathway for nitrogen fixation in practical applications and sustainable development but also deepens our understanding of the natural nitrogen cycle.}, archive = {J_JACS}, author = {Yanjie Wang and Jin Luo and Ye-Guang Fang and Zi-Ang Nan and Xi Cui and Ting Chen and Xiangbiao Zeng and Xiaofei Wang and Xianmeng Song and Jiawei Zhao and Weixin Li and Chen Zeng and Daliang Chen and Chongqin Zhu and Zhenwei Wei and Zhong-Qun Tian and Feng Ru Fan}, doi = {10.1021/jacs.4c15514}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2756--2765}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalyst-free nitrogen fixation by microdroplets through a radical-mediated disproportionation mechanism under ambient conditions}, volume = {147}, year = {2025}, }
• (2025). Biochemical and computational characterization of haloalkane dehalogenase variants designed by generative AI: Accelerating the SN2 step. JACS, 147(3), 2747--2755. (www)

  @article{ , abstract = {Generative artificial intelligence (AI) models trained on natural protein sequences have been used to design functional enzymes. However, their ability to predict individual reaction steps in enzyme catalysis remains unclear, limiting the potential use of sequence information for enzyme engineering. In this study, we demonstrated that sequence information can predict the rate of the S N 2 step of a haloalkane dehalogenase using a generative maximum-entropy (MaxEnt) model. We then designed lower-order protein variants of haloalkane dehalogenase using the model. Kinetic measurements confirmed the successful design of protein variants that enhance catalytic activity, above that of the wild type, in the overall reaction and in particular in the S N 2 step. On the simulation side, we provided molecular insights into these designs for the S N 2 step using the empirical valence bond (EVB) and metadynamics simulations. The EVB calculations showed activation barriers consistent with experimental reaction rates, while examining the effect of amino acid replacements on the electrostatic effect on the activation barrier and the consequence of water penetration, as well as the extent of ground state destabilization/stabilization. Metadynamics simulations emphasize the importance of the substrate positioning in enzyme catalysis. Overall, our AI-guided approach successfully enabled the design of a variant with a faster rate for the S N 2 step than the wild-type enzyme, despite haloalkane dehalogenase being extensively optimized through natural evolution.}, archive = {J_JACS}, author = {Natalia Gelfand and Vojtech Orel and Wenqiang Cui and Jiří Damborský and Chenglong Li and Zbyněk Prokop and Wen Jun Xie and Arieh Warshel}, doi = {10.1021/jacs.4c15551}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2747--2755}, shortjournal = {J. Am. Chem. Soc.}, title = {Biochemical and computational characterization of haloalkane dehalogenase variants designed by generative AI: Accelerating the SN2 step}, volume = {147}, year = {2025}, }
• (2025). Nitrogenative degradation of polystyrene waste. JACS, 147(3), 2737--2746. (www)

  @article{ , abstract = {Owing to massive production and poor end-of-life management, plastic waste pollution has become one of the most pressing environmental crises. In response to the mounting crisis, the past several decades have witnessed the development of numerous methods and technologies for plastic recycling. However, most of the current recycling technologies often produce low-quality or low-value products, making it difficult to recover the operating costs. To this end, we report a novel preoxygenation-induced strategy for the nitrogenative degradation of real-life polystyrene plastics into high-value aromatic nitrogen compounds in a cost-effective manner. Thus, expensive and highly demanding benzonitrile as well as benzamide were obtained in up to 74% overall isolated yield from polystyrene waste by using CuBr as the catalyst, O 2 as the oxidant, and CH 3 CN as the nitrogen source. Detailed mechanistic investigations indicate that hydroxyl radicals from O 2 activation play a role in this selective aerobic degradation process. Furthermore, multiple reaction pathways contribute to the formation of benzonitrile and benzamide.}, archive = {J_JACS}, author = {Ganfei Zeng and Yanming Su and Jianwei Jiang and Zhiliang Huang}, doi = {10.1021/jacs.4c15500}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2737--2746}, shortjournal = {J. Am. Chem. Soc.}, title = {Nitrogenative degradation of polystyrene waste}, volume = {147}, year = {2025}, }
• (2025). Structure–Reactivity relationship of zeolite-confined rh catalysts for hydroformylation of linear α-olefins. JACS, 147(3), 2726--2736. (www)

  @article{ , abstract = {Substituting the molecular metal complexes used in the industrial olefin hydroformylation process is of great significance in fundamental research and practical application. One of the major difficulties in replacing the classic molecular metal catalysts with supported metal catalysts is the low chemoselectivity and regioselectivity of the supported metal catalysts because of the lack of a well-defined coordination environment of the metal active sites. In this work, we have systematically studied the influences of key factors (crystallinity, alkali promoters, etc.) of the Rh-MFI zeolite catalysts on their performances for the hydroformylation of long-chain α-olefins (LAOs). With the help of comprehensive spectroscopy and electron microscopy characterization results, we can correlate the structural features of various Rh-MFI catalysts and their catalytic performances. The resultant structure–reactivity relationship guides us to prepare a nanosized Rh-MFI catalyst, which exhibits about a 3-fold improvement in specific activity compared to the Rh-MFI catalyst with conventional crystallite sizes and maintains very high regioselectivity for hydroformylation of LAOs.}, archive = {J_JACS}, author = {Xiaomeng Dou and Tao Yan and Wenying Li and Chaofeng Zhu and Tianxiang Chen and Benedict Tsz Woon Lo and Carlo Marini and Hai Xiao and Lichen Liu}, doi = {10.1021/jacs.4c15445}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2726--2736}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure–Reactivity relationship of zeolite-confined rh catalysts for hydroformylation of linear α-olefins}, volume = {147}, year = {2025}, }
• (2025). A self-phase separated electrolyte toward durable and rollover-stable zinc metal batteries. JACS, 147(3), 2714--2725. (www)

  @article{ , abstract = {Aqueous zinc (Zn) metal batteries (ZMBs) have received great attention due to their safety and environmental friendliness. Although aqueous electrolytes facilitate fast kinetics in metal oxide cathodes, their incompatibility with the Zn metal anodes triggers severe hydrogen evolution reaction (HER) and dendrite growth. Herein, a self-phase separated electrolyte (SPSE) is proposed to fulfill the contradictory requirements of the anode and cathode in ZMBs. Molecular modeling and experimental investigations verify that the hydrophobic fluorinated solvent with moderate dielectric constant and large Hildebrand parameter disparity relative to water contributes to a spontaneous aqueous–nonaqueous phase separation within the SPSE against stirring and aging. In the as-developed SPSE, the anode nonaqueous phase effectively inhibits the HER and dendrite formation by a synergistic effect of regulated Zn deposition and protective solid electrolyte interphase (SEI). Meanwhile, the aqueous phase in the cathode ensures fast ion insertion/extraction dynamics. Consequently, the SPSE allows for Zn||Zn symmetrical cells with 2500 h cycle life and ultralow corrosion current (0.08 mA cm –2 ). Notably, the Zn|SPSE|V 2 O 5 full cell sustains over 3000 cycles with negligible HER and corrosion, and the pouch cell demonstrates remarkable operation stability against repeated rollover. Our electrolyte design concept paves a promising path for practical ZMBs that combine long-term cyclability, enhanced safety, and durability.}, archive = {J_JACS}, author = {Xin Zhao and Jiaping Fu and Ming Chen and Yao Wang and Cong Huang and Kun Qian and Guang Feng and Baohua Li and Dong Zhou and Feiyu Kang}, doi = {10.1021/jacs.4c15132}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2714--2725}, shortjournal = {J. Am. Chem. Soc.}, title = {A self-phase separated electrolyte toward durable and rollover-stable zinc metal batteries}, volume = {147}, year = {2025}, }
• (2025). Understanding the role of potential and cation effect on electrocatalytic CO2 reduction in all-alkynyl-protected ag15 nanoclusters. JACS, 147(3), 2699--2713. (www)

  @article{ , abstract = {Atomically precise metal nanoclusters (NCs) have emerged as an intriguing class of model catalysts for electrochemical CO 2 reduction reactions (CO 2 RR). However, the interplay between the interface environment (e.g., potential, cation concentration) and electron–proton transfer (ET/PT) kinetics─particularly in alkynyl-protected metal NCs─remains poorly understood. Here, we combined first-principles simulations and electrochemical experiments to investigate the role of potential and cation effect on CO 2 RR performance in a prototype all-alkynyl-protected Ag 15 (C≡C–CH 3 ) + cluster. Our simulations revealed that the applied reduction potential triggers the elimination of the alkynyl ligand via sequentially breaking two π-type Ag–C bonds and one σ-type Ag–C bond to expose the catalytically active Ag sites, and the barrier of the Ag–C breakage monotonically decreases with the lowering in potential. Furthermore, we show that introducing the inner-sphere Na + ions greatly enhances *CO 2 activation and promotes proton transfer to generate *COOH and *CO by forming the Na + –CO 2 (*COOH) complexes, while the competitive hydrogen evolution reaction (HER) from water dissociation is greatly suppressed, thus dramatically improving the selectivity of CO 2 electroreduction. The electrochemical measurements further validated our predictions, where the CO Faradaic efficiency (FE CO ) and current density ( j CO ) show a pronounced dependence on the Na + concentration. At an optimal concentration of 0.1 M NaCl, FE CO can reach up to ∼96%, demonstrating the crucial role of cations in promoting the CO 2 RR. Our findings provide vital insights into the atomic-level reaction mechanism of the CO 2 RR on alkynyl-protected Ag 15 NCs and highlight the important role of potential and electrolyte cation in governing the electron/proton transfer kinetics.}, archive = {J_JACS}, author = {Yuping Chen and Xia Zhou and Xunying Liu and Zhenghua Tang and Likai Wang and Qing Tang}, doi = {10.1021/jacs.4c15112}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2699--2713}, shortjournal = {J. Am. Chem. Soc.}, title = {Understanding the role of potential and cation effect on electrocatalytic CO2 reduction in all-alkynyl-protected ag15 nanoclusters}, volume = {147}, year = {2025}, }
• (2025). Targeting synthesis of diatomic catalysts by selective etching and sequential adsorption of metal atom. JACS, 147(3), 2689--2698. (www)

  @article{ , abstract = {Diatomic catalysts featuring a tunable structure and synergetic effects hold great promise for various reactions. However, their precise construction with specific configurations and diverse metal combinations is still challenging. Here, a selective etching and metal ion adsorption strategy is proposed to accurately assign a second metal atom (M 2 ) geminal to the single atom site (M 1 –N x ) for constructing diatomic sites (e.g., Fe–Pd, Fe–Pt, Fe–Ru, Fe–Zn, Co–Fe, Co–Ni, and Co–Cu). In this strategy, hydrogen peroxide selectively etches the positively charged carbon atoms near the M 1 –N x moiety (denoted as α-C) and produces vacancy, which could trap the M 2 at the subsequent adsorption step. These catalysts show optimized electronic structure and enhanced oxygen reduction activity compared to single-site counterparts, and the representative Fe–Pd–NC and Co–Fe–NC catalysts stand as the most active oxygen reduction reaction catalysts (half-wave potential of 0.92 and 0.91 V, respectively). The selective etching of α-C in single-atom catalysts reported here represents a new post-treatment strategy for the targeting synthesis of diatomic sites.}, archive = {J_JACS}, author = {Xiangrong Jin and Mengyao Chang and Hao Sun and Chun-Wai Chang and Marshet Getaye Sendeku and Yajie Li and Maoyu Wang and Jinjie Fang and Yizhe Li and Qingyi Zhu and Boyuan Li and Jiage Yu and Yafei Liu and Zheng Chang and Guoxin Zhang and Zhongbin Zhuang and Lu Bai and Qing Ma and Zhenxing Feng and Wen Liu and Jiazhan Li and Xiaoming Sun}, doi = {10.1021/jacs.4c14760}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2689--2698}, shortjournal = {J. Am. Chem. Soc.}, title = {Targeting synthesis of diatomic catalysts by selective etching and sequential adsorption of metal atom}, volume = {147}, year = {2025}, }
• (2025). Dynamic kinetic activation of aziridines enables radical-polar crossover (4 + 3) cycloaddition with 1,3-dienes. JACS, 147(3), 2675--2688. (www)

  @article{ , abstract = {The cycloaddition of aziridines with unsaturated compounds is a valuable method for synthesizing nitrogen heterocycles. However, this process is predominantly substrate-controlled, posing significant challenges in regulating the regioselectivity of the C–N bond cleavage. In this study, we report a nickel-catalyzed dynamic kinetic activation strategy that enables catalyst-controlled activation of aziridines. Various types of aziridines, including 2-phenyl, 2-carbonyl, 2-alkyl, and disubstituted aziridines, consistently cleave their more sterically hindered C–N bonds to generate 1,3-radical anion intermediates. These intermediates participate in a highly regioselective 1,4-Heck/allylic substitution cascade with aromatic branched 1,3-dienes, resulting in a radical-polar crossover (4 + 3) cycloaddition that produces seven-membered azepine products. This approach not only complements traditional dipolar cycloaddition, in which aziridines typically act as zwitterionic 1,3-dipoles, but also introduces an unusual cycloaddition mode for 1,3-dienes. Experimental investigations and density functional theory (DFT) calculations provide insight into the reaction mechanism.}, archive = {J_JACS}, author = {Lei Wang and Pan-Pan Zhou and Dong Xie and Qian Yue and Hao-Zheng Sun and Shang-Dong Yang and Gang-Wei Wang}, doi = {10.1021/jacs.4c15003}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2675--2688}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic kinetic activation of aziridines enables radical-polar crossover (4 + 3) cycloaddition with 1,3-dienes}, volume = {147}, year = {2025}, }
• (2025). Deacylative homolysis of ketone C(sp3)–C(sp2) bonds: Streamlining natural product transformations. JACS, 147(3), 2664--2674. (www)

  @article{ , abstract = {The homolytic cleavage of C–C bonds adjacent to specific functional groups has lately emerged as a versatile approach for molecular diversification. Despite the ubiquity and synthetic utility of ketones, radical fragmentation of their α-C–C bonds has proven to be a formidable challenge. Here, we present a broadly applicable deacylative strategy designed to homolytically cleave aliphatic ketones of various complexities, including transformations of cycloalkanones into carboxylic acids tethered to C-centered free radicals that can be engaged in diverse radical-based processes. The method involves ketone activation through treatment with hydrogen peroxide, yielding gem -dihydroperoxides. Subsequent single-electron-transfer reduction mediated by a low-valent metal complex generates alkyl radicals that can be captured selectively with a radicophile of choice, including through catalytic cross-coupling. The logic of our deacylative functionalization is exemplified by the total synthesis of 14 natural products, one analogue, and two drugs starting from readily available natural products, showcasing its transformative power in complex settings. This approach obviates the need for complex reagents and allows the controlled conversion of ketones to reconstructed products, making the process highly applicable across a spectrum of domains.}, archive = {J_JACS}, author = {Michal Šimek and Sujit Mahato and Brady W. Dehnert and Ohyun Kwon}, doi = {10.1021/jacs.4c15045}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2664--2674}, shortjournal = {J. Am. Chem. Soc.}, title = {Deacylative homolysis of ketone C(sp3)–C(sp2) bonds: Streamlining natural product transformations}, volume = {147}, year = {2025}, }
• (2025). New molecular photoswitch based on the conformational transition of phenothiazine derivatives and corresponding triplet emission properties. JACS, 147(3), 2653--2663. (www)

  @article{ , abstract = {Molecular photoswitch research has drawn much attention in the last century owing to its great potential in the development of smart materials. However, photoswitches suitable for constructing light-responsive luminescent materials remain limited, especially those involving triplet-state phosphorescence. Herein, we designed a novel molecular photoswitch based on the conformation transition of phenothiazine derivatives, minimizing steric hindrance (−CH 3 > −Cl > −F) to regulate the conformation transition process while introducing a cyanobenzene acceptor to promote phosphorescence emission potential. When they were doped into a polymer matrix, varying photoswitch rates were achieved by incorporating different steric hindrance groups into phenothiazine or cyanobenzene groups, accompanied by photoresponsive room-temperature phosphorescence. This study is expected to greatly expand the diversity and applications of organic photoswitch molecules.}, archive = {J_JACS}, author = {Mingxue Gao and Ruimin Wu and Yawen Zhang and Yunshu Meng and Manman Fang and Jie Yang and Zhen Li}, doi = {10.1021/jacs.4c14920}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2653--2663}, shortjournal = {J. Am. Chem. Soc.}, title = {New molecular photoswitch based on the conformational transition of phenothiazine derivatives and corresponding triplet emission properties}, volume = {147}, year = {2025}, }
• (2025). A general three-component Nozaki–Hiyama–Kishi-type reaction enabled by delayed radical-polar crossover. JACS, 147(3), 2642--2652. (www)

  @article{ , abstract = {Nozaki–Hiyama–Kishi (NHK) reactions offer a mild approach for the formation of alcohol motifs through radical-polar crossover-based pathways from various radical precursors. However, the application of multicomponent NHK-type reactions, which allow the formation of multiple bonds in a single step, has been largely restricted to bulky alkyl radical precursors, thus limiting their expanded utilization. Herein, we disclose a general three-component NHK-type reaction enabled by delayed radical-polar crossover, which efficiently tolerates a plethora of radical precursors that were previously unavailable. This method enables the modular assembly of versatile homoallylic alcohols from feedstock chemicals with excellent chemo-, regio-, diastereo-, and enantioselectivities in a single step. Experimental studies and density functional theory (DFT) calculations reveal that the kinetically favored formation of an allylchromium(III) species is paramount for enforcing the delayed radical-polar crossover over direct radical addition. Finally, straightforward transformations and applications of the homoallylic alcohol products were demonstrated, showcasing the synthetic utility of this method.}, archive = {J_JACS}, author = {Yan-Bo Li and Minghao Xu and Leopold A. Kellermann and Johannes E. Erchinger and Subhabrata Dutta and Constantin G. Daniliuc and Xiaotian Qi and Frank Glorius}, doi = {10.1021/jacs.4c14913}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2642--2652}, shortjournal = {J. Am. Chem. Soc.}, title = {A general three-component Nozaki–Hiyama–Kishi-type reaction enabled by delayed radical-polar crossover}, volume = {147}, year = {2025}, }
• (2025). Origins of the superiority of oscillating electric fields for disrupting senile plaques: Insights from the 7-residue fragment and the full-length aβ-42 peptide. JACS, 147(3), 2626--2641. (www)

  @article{ , abstract = {Our recent molecular dynamics simulations of decomposing Alzheimer’s disease plaques, under oscillating- and static external electric fields (Os-EEFs and St-EEFs), revealed the superiority of Os-EEF for decomposing plaques consisting of the 7-residue peptide segment. This conclusion is now reinforced by studying the dimers of the short peptides and trimers of the full-length Aβ-42 peptide. Thus, the dispersed peptides obtained following St-EEF applications reformed the plaques once the St-EEF subsided. In contrast, plaques originating from the application of Os-EEF remained dispersed for long time scales . The present study provides insights into these results by modeling the decomposition modes that transpire under both field types. Additionally, this study provides insights into the frequency effects on the decomposition processes within the THz–MHz regions. The simulation shows that the Os-EEF in the lower frequency range (≤GHz) decomposes the plaque on a time scale of ∼50 ns, whereas the higher frequency Os-EEFs (≥THz) are less effective. As such, Os-EEFs with moderate-to-low frequencies (≤GHz) lead to an “explosion,” whereby the peptides fly distantly apart and inhibit plaque reformation. By contrast, St-EEFs form parallel peptide pairs, which are stabilized by the EEF due to the large dipole moment of the ensemble. Thus, St-EEF applications lead to sluggish and reversible plaque decomposition processes. We further conclude that the Os-EEF impact is maximal for short pulses, which prevents the EEF propensity to arrange the peptides in parallel pairs. The superiority of the Os-EEF over the St-EEF is maintained irrespective of the peptides’ length. A model is formulated that predicts the dependence of the decomposition time scale on the EEF.}, archive = {J_JACS}, author = {Surajit Kalita and David Danovich and Sason Shaik}, doi = {10.1021/jacs.4c14791}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2626--2641}, shortjournal = {J. Am. Chem. Soc.}, title = {Origins of the superiority of oscillating electric fields for disrupting senile plaques: Insights from the 7-residue fragment and the full-length aβ-42 peptide}, volume = {147}, year = {2025}, }
• (2025). Nickel-catalyzed cross-electrophile coupling of aryl triflates with alkyl halides: Mechanism-informed design of more general conditions. JACS, 147(3), 2616--2625. (www)

  @article{ , abstract = {Aryl triflates make up a class of aryl electrophiles that are available in a single step from the corresponding phenol. Despite the known reactivity of nickel complexes for aryl C–O bond activation of phenol derivatives, nickel-catalyzed cross-electrophile coupling using aryl triflates has proven challenging. Herein, we report a method to form C(sp 2 )–C(sp 3 ) bonds by coupling aryl triflates with alkyl bromides and chlorides using phenanthroline (phen) or pyridine-2,6-bis( N -cyanocarboxamidine) (PyBCam CN )-ligated nickel catalysts. The scope of the reaction is demonstrated with 38 examples (61 ± 14% average yield). Mechanistic studies provide a rationale for the conditions used and a roadmap for further applications of cross-electrophile coupling. First, the rate of alkyl radical generation is controlled by maintaining the majority of alkyl halide as the alkyl chloride, which is unreactive, and utilizing a dynamic halide exchange process to adjust the concentration of reactive alkyl bromide or iodide. Second, the challenge of using electron-rich aryl triflates appears to be due to off-cycle transmetalation to form unproductive aryl zinc reagents. The optimal PyBCam CN ligand together with LiCl avoids this deleterious transmetalation step.}, archive = {J_JACS}, author = {Seoyoung Kim and Matthew J. Goldfogel and Benjamin N. Ahern and Daniel C. Salgueiro and Ilia A. Guzei and Daniel J. Weix}, doi = {10.1021/jacs.4c14769}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2616--2625}, shortjournal = {J. Am. Chem. Soc.}, title = {Nickel-catalyzed cross-electrophile coupling of aryl triflates with alkyl halides: Mechanism-informed design of more general conditions}, volume = {147}, year = {2025}, }
• (2025). Synergistic atomic environment optimization of Nickel–Iron dual sites by co doping and cr vacancy for electrocatalytic oxygen evolution. JACS, 147(3), 2607--2615. (www)

  @article{ , abstract = {The dual-site synergistic catalytic mechanism on NiFeOOH suggests weak adsorption of Ni sites and strong adsorption of Fe sites limited its activity toward alkaline oxygen evolution reaction (OER). Large-scale density functional theory (DFT) calculations confirm that Co doping can increase Ni adsorption, while the metal vacancy can reduce Fe adsorption. The combined two factors can further modulate the atomic environment and optimize the free energy toward oxygen-containing intermediates, thus enhancing the OER activity. Accordingly, we used Co doping and Cr vacancies to fabricate an amorphous catalyst of V Cr ,Co-NiFeOOH. It provides an OER overpotential of 239 mV at 100 mA cm –2 and high stability over 500 h at 500 mA cm –2 with a ∼98% potential retention. The resulting water electrolyzer based on an anion exchange membrane (AEM) exhibits a remarkable performance of 1 A cm –2 at 1.68 V in 1 M KOH. XPS, soft-XAS, and XANES combined with Bader charge analysis results reveal that the regulation of the local microenvironment can increase the valence state of Ni by Co doping, thus improving the adsorption energy on Ni sites. The Cr vacancy can alleviate the strong adsorption on Fe sites. DFT calculations confirm that the synergistic effect of Co doping and Cr vacancies can redistribute the charge on the Ni/Fe sites, optimize the d-band center of Ni and Fe, and endow the catalyst with Ni–Fe dual sites to reduce the energy barrier of the OER rate-determining step.}, archive = {J_JACS}, author = {Hua-Jie Niu and Nian Ran and Wei Zhou and Weixuan An and Chuanxue Huang and Wenxing Chen and Min Zhou and Wen-Feng Lin and Jianjun Liu and Lin Guo}, doi = {10.1021/jacs.4c14675}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2607--2615}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic atomic environment optimization of Nickel–Iron dual sites by co doping and cr vacancy for electrocatalytic oxygen evolution}, volume = {147}, year = {2025}, }
• (2025). Highly photoreactive semiconducting polymers with cascade intramolecular singlet oxygen and energy transfer for cancer-specific afterglow theranostics. JACS, 147(3), 2597--2606. (www)

  @article{ , abstract = {Afterglow luminescence provides ultrasensitive optical detection by minimizing tissue autofluorescence and increasing the signal-to-noise ratio. However, due to the lack of suitable unimolecular afterglow scaffolds, current afterglow agents are nanocomposites containing multiple components with limited afterglow performance and have rarely been applied for cancer theranostics. Herein, we report the synthesis of a series of oxathiine-containing donor–acceptor block semiconducting polymers (PDCDs) and the observation of their high photoreactivity and strong near-infrared (NIR) afterglow luminescence. We reveal that PDCDs absorb NIR light to undergo a photodynamic process to generate singlet oxygen ( 1 O 2 ), which intramolecularly transfers to and efficiently reacts with the oxathiine block to form the afterglow oxathiine intermediates due to the low Gibbs free energy changes required for this photoreaction. Following intramolecular afterglow energy transfer from the oxathiine donor block to the acceptor block, NIR afterglow emission is produced from PDCDs. Owing to the efficient cascade intramolecular photochemical process, PDCD-based nanoparticles achieve a higher brightness and longer NIR emission compared to most reported afterglow agents, even after ultrashort photoirradiation for only 3 s. Furthermore, the cascade photochemical process within PDCD can be inhibited after bioconjugation with a quencher-linked peptide. This allows the construction of a cancer-activatable afterglow theranostic probe (CATP) that only switches on the afterglow signal and photodynamic function in the presence of a cancer-overexpressed enzyme. Thereby, CATP represents the first afterglow phototheranostic probe that permits cancer-specific detection and photodynamic cancer therapy under preclinical settings. In summary, this study provides a molecular guideline to develop afterglow probes from photoreactive polymers.}, archive = {J_JACS}, author = {Youshi Lin and Jingsheng Huang and Jing Liu and Mengke Xu and Cheng Xu and Kanyi Pu}, doi = {10.1021/jacs.4c14565}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2597--2606}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly photoreactive semiconducting polymers with cascade intramolecular singlet oxygen and energy transfer for cancer-specific afterglow theranostics}, volume = {147}, year = {2025}, }
• (2025). Structure–Optical properties relationships in cobalt-based purple pigments used by robert delaunay. JACS, 147(3), 2587--2596. (www)

  @article{ , abstract = {Following the industrial revolution and the modernization of chemistry, purple became one of the most popular colors in the palettes of late 19th- to 20th-century painters. Among them, Robert Delaunay (1885–1941) was one of the key artists of the avant-garde movement in France in the early 20th century. Although widely used in modern and contemporary paintings, inorganic purple pigments of the cobalt phosphate and cobalt arsenate families have been little studied chemically until now. The diversity of emerging chemical syntheses resulted in a wide range of products, characterized by a high diversity of hues, function of their respective composition, and crystal structures. The present work combines structural and optical analyses to probe the purple pigments used by Delaunay. Reference materials synthesized in the laboratory were characterized via synchrotron radiation-based high-angular-resolution X-ray powder diffraction and UV–vis–NIR spectroscopy. Structure–color relationships were established for the first time for several inorganic compounds of the Co–P/As family. Two of Robert Delaunay’s earliest masterpieces conserved at the Centre Pompidou in Paris were probed in situ via X-ray powder diffraction in imaging mode and fiber optic UV–vis–NIR reflectance spectroscopy. The results highlight the decisive effect of their structural chemistry on the palettes of modern and contemporary painters.}, archive = {J_JACS}, author = {Victor Gonzalez and Gilles Wallez and Didier Gourier and Camille De Caro and Steven De Meyer and Iryn Bijker and Koen Janssens and Mathieu Thoury and Francesca Gabrieli and Letizia Monico and Sara Carboni Marri and Catherine Dejoie and Véronique Sorano-Stedman and Stéphanie Elarbi and Loïc Bertrand}, doi = {10.1021/jacs.4c14523}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2587--2596}, shortjournal = {J. Am. Chem. Soc.}, title = {Structure–Optical properties relationships in cobalt-based purple pigments used by robert delaunay}, volume = {147}, year = {2025}, }
• (2025). Interlocked 2D covalent organic frameworks from overcrowded nodes. JACS, 147(3), 2579--2586. (www)

  @article{ , abstract = {A challenging aspect in the synthesis of covalent organic frameworks (COFs) that goes beyond the framework’s structure and topology is interpenetration, where two or more independent frameworks are mechanically interlocked with each other. Such interpenetrated or interlocked frameworks are commonly found in three-dimensional (3D) COFs with large pores. However, interlocked two-dimensional (2D) COFs are rarely seen in the literature, as 2D COF layers typically crystallize in stacks that maximize stabilization through π-stacking. The few interlocked 2D COFs described to date have been derived from monomers with aryl groups arranged perpendicularly. Herein, we report an interlocked 2D COF derived from a new class of monomers constituted of sterically overcrowded polycyclic aromatic hydrocarbons. The formation of such an interlocked structure is ascribed to the presence and the bulkiness of the substituents that directly interfere with interlayer π-stacking. The microscopy, gas sorption, spectroscopic, and charge transport characterization are consistent with the absence of π-stacking, as imposed by the interlocked architecture. This work evidences how the use of overcrowded aromatic systems as monomers can generate mechanically interlocked 2D COFs, offering new avenues for the design of COFs with unconventional topologies.}, archive = {J_JACS}, author = {Elisabet De Bolòs and Saibal Bera and Karol Strutyński and Andrei A. Bardin and Rhys W. Lodge and Natalia M Padial and Akinori Saeki and Carlos Martí-Gastaldo and Andrei N. Khlobystov and Brent L. Nannenga and Manuel Melle-Franco and Aurelio Mateo-Alonso}, doi = {10.1021/jacs.4c14453}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2579--2586}, shortjournal = {J. Am. Chem. Soc.}, title = {Interlocked 2D covalent organic frameworks from overcrowded nodes}, volume = {147}, year = {2025}, }
• (2025). Air and thermally stable cyclic (Alkyl)(amino)carbene ruthenium complexes for efficient ring expansion metathesis polymerization. JACS, 147(3), 2571--2578. (www)

  @article{ , abstract = {Ring expansion metathesis polymerization (REMP) has emerged as a potent strategy for obtaining cyclic polymers over the past two decades. The scope of monomers, however, remains limited due to the poor functional group tolerance and stability of the catalyst, necessitating a rational catalyst design to address this constraint. Here, we present ruthenium complexes featuring tethered cyclic (alkyl)(amino)carbene ligands for REMP, aiming to deepen our understanding of the structure–property relationship in newly designed catalysts. Notably, these ruthenium catalysts exhibit remarkable thermal stability even in air, as confirmed through monitoring the air-exposed solution at 80 °C. In addition, the initiation rate of the catalysts was effectively modulated by tuning the steric hindrance of the N -aryl substituent, adjusting tethered chain lengths, or introducing a Blechert-type ligand. Based on systematic studies of catalysts, we successfully demonstrate challenging REMP of a cyclic allene (2,8-dimethylnona-4,5-diene) for the first time, as well as methyl-5-norbornene-2-carboxylate, resulting in cyclic polymers. We also note that the exceptional stability of the catalyst enables REMP under air. This study provides valuable insights into the rational design of catalysts and introduces a novel, user-friendly platform for the synthesis of cyclic polymers.}, archive = {J_JACS}, author = {Minjae Jang and Eunsong Jung and Yongkang Yang and Jinkyung Noh and Hayoung Song and Hyunseok Kim and Hoonseok Kang and Solhye Choe and Tae-Lim Choi and Eunsung Lee}, doi = {10.1021/jacs.4c14219}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2571--2578}, shortjournal = {J. Am. Chem. Soc.}, title = {Air and thermally stable cyclic (Alkyl)(amino)carbene ruthenium complexes for efficient ring expansion metathesis polymerization}, volume = {147}, year = {2025}, }
• (2025). Impact of transition-state aromaticity on selective Radical–Radical coupling of triarylimidazolyl radicals. JACS, 147(3), 2559--2570. (www)

  @article{ , abstract = {Radical coupling reactions are generally known to have a low selectivity due to the high reactivity of radicals. In this study, high regio and substrate selectivity was discovered in the dimerization of triarylimidazolyl radicals ( TAIR ), a versatile photochromic reaction. When two different radicals, 2-(4-cyanophenyl)-4,5-diphenyl-1 H -imidazolyl radical ( CN-TAIR ) and 2-(4-methoxyphenyl)-4,5-diphenyl-1 H -imidazolyl radical ( OMe-TAIR ), were simultaneously generated in situ, a hexaarylbiimidazole, formed by selective coupling at the nitrogen atom at position 1 of CN-TAIR and the carbon atom at position 2 of OMe-TAIR , was isolated with high selectivity as the main product among 24 possible radical dimer hexaarylbiimidazole derivatives. This high regio and substrate selectivity cannot be explained solely by the stability of the product and/or the electrophilicity and nucleophilicity of the radicals but originates from the aromaticity of the transition state in the radical–radical coupling reaction. To date, the selectivity of radical coupling reactions has been thought to be controlled by steric hindrance and radical spin density, but this study revealed a new factor for controlling radical coupling, that is, transition-state aromaticity. Aromaticity has been reported to have an important effect not only in the reactivity and structure of ground-state molecules but also on the electronically excited states and transition states in pericyclic reactions such as the Diels–Alder reaction and the Cope–Claisen rearrangement. This study demonstrated for the first time that radical coupling reactions can also be controlled by transition-state aromaticity.}, archive = {J_JACS}, author = {Kazunori Okamoto and Sayaka Hatano and Manabu Abe}, doi = {10.1021/jacs.4c14095}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2559--2570}, shortjournal = {J. Am. Chem. Soc.}, title = {Impact of transition-state aromaticity on selective Radical–Radical coupling of triarylimidazolyl radicals}, volume = {147}, year = {2025}, }
• (2025). The elusive ternary intermediates of chiral phosphoric acids in ion pair Catalysis─Structures, conformations, and aggregation. JACS, 147(3), 2549--2558. (www)

  @article{ , abstract = {In ion-pair catalysis, the last intermediate structures prior to the stereoselective transition states are of special importance for predictive models due to the high isomerization barrier between E - and Z -substrate double bonds connecting ground and transition state energies. However, in prior experimental investigations of chiral phosphoric acids (CPA) solely the early intermediates could be investigated while the key intermediate remained elusive. In this study, the first experimental structural and conformational insights into ternary complexes with CPAs are presented using a special combination of low temperature and relaxation optimized 15 N HSQC-NOESY NMR spectroscopy to enhance sensitivity. Combined NMR investigations and theoretical calculations revealed three conformers of the ternary complex, of which one also closely resembles the previously calculated transition states. In addition, a 2:1:1 ternary complex as well as an unprecedent [3:3] dimeric species consisting of two ternary complexes was revealed. Given the importance of the ground state energies for the transition state interpretation in ion pair catalysis we believe that the presented experimental insight into the structural and conformational variety of the ternary complexes is a key to the future development of predictive models in ion pair catalysis.}, archive = {J_JACS}, author = {Maximilian Franta and Aryaman Pattanaik and Wagner Silva and Kumar Motiram-Corral and Julia Rehbein and Ruth M. Gschwind}, doi = {10.1021/jacs.4c14096}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2549--2558}, shortjournal = {J. Am. Chem. Soc.}, title = {The elusive ternary intermediates of chiral phosphoric acids in ion pair Catalysis─Structures, conformations, and aggregation}, volume = {147}, year = {2025}, }
• (2025). Optimally miscible polymer bulk-heterojunction-particles for nonsurfactant photocatalytic hydrogen evolution. JACS, 147(3), 2537--2548. (www)

  @article{ , abstract = {Mini-emulsion and nanoprecipitation techniques relied on large amounts of surfactants, and unresolved miscibility issues of heterojunction materials limited their efficiency and applicability in the past. Through our molecular design and developed surfactant-free precipitation method, we successfully fabricated the best miscible bulk-heterojunction-particles (BHJP) ever achieved, using donor ( PS ) and acceptor ( PSOS ) polymers. The structural similarity ensures optimal miscibility, as supported by the interaction parameter of the PS / PSOS blend is positioned very close to the binodal curve. Experimental studies and molecular dynamics simulations further revealed that surfactants hinder electron output sites and reduce the concentration of sacrificial agents at the interface, slowing polaron formation. Multiscale experiments verified that these BHJP, approximately 12 nm in diameter, further form cross-linked fractal networks of several hundred nanometers. Transient absorption spectroscopy showed that BHJP facilitates polaron formation and electron transfer. Our BHJP demonstrated a superior hydrogen evolution rate (HER) compared to traditional methods. The most active BHJP achieved an HER of 251.2 mmol h –1 g –1 and an apparent quantum yield of 26.2% at 500 nm. This work not only introduces a practical method for preparing BHJP but also offers a new direction for the development of heterojunction materials.}, archive = {J_JACS}, author = {Wei-Cheng Lin and Yu-En Sun and Ying-Rang Zhuang and Tse-Fu Huang and Kuei-Jhong Lin and Mohamed M. Elsenety and Jui-Chen Yen and Hung-Kai Hsu and Bo-Han Chen and Chen-Yu Chang and Je-Wei Chang and Hsin-Ni Huang and Bing-Heng Li and Siriporn Jungsuttiwong and Toton Haldar and Shin-Huei Wang and Wan-Chi Lin and Tien-Lin Wu and Chin-Wen Chen and Chi-Hua Yu and An-Chung Su and Kun-Han Lin and U-Ser Jeng and Shang-Da Yang and Ho-Hsiu Chou}, doi = {10.1021/jacs.4c13856}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2537--2548}, shortjournal = {J. Am. Chem. Soc.}, title = {Optimally miscible polymer bulk-heterojunction-particles for nonsurfactant photocatalytic hydrogen evolution}, volume = {147}, year = {2025}, }
• (2025). Alkoxy-directed dienamine catalysis in [4 + 2]-cycloaddition: Enantioselective synthesis of benzo-[3]-ladderanol. JACS, 147(3), 2523--2536. (www)

  @article{ , abstract = {Despite tremendous progress of dienamine catalysis along with its application in enantioselective synthesis over nearly two decades, certain limitations, especially with respect to the regioselectivity in the dienamine generation step, continue to persist. To overcome these shortcomings of classical dienamine catalysis, we now introduce the concept of alkoxy-directed dienamine catalysis and apply it to the enantioselective de novo arene construction by desymmetrizing meso -enediones through [4 + 2]-cycloaddition. Catalyzed by a diphenylprolinol silyl ether, this reaction utilizes γ-alkoxy α,β-unsaturated aldehydes as the substrate and proceeds in a highly regioselective fashion through the intermediacy of δ-alkoxy dienamine. Besides carrying out mechanistic elucidation through density functional theory (DFT) calculation, the utility of this newly developed strategy is demonstrated for the concise enantioselective synthesis of a benzo-analogue of the natural ladderane phospholipid component (+)-[3]-ladderanol. Designed as a functional analogue of natural [3]-ladderanol, this unnatural benzo-[3]-ladderanol was found to impart lower proton permeability and higher stability to the membrane compared to its natural counterpart.}, archive = {J_JACS}, author = {Sayan Ray and Deepak Behera and Mahesh Singh Harariya and Subrata Das and Pradip K. Tarafdar and Santanu Mukherjee}, doi = {10.1021/jacs.4c13713}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2523--2536}, shortjournal = {J. Am. Chem. Soc.}, title = {Alkoxy-directed dienamine catalysis in [4 + 2]-cycloaddition: Enantioselective synthesis of benzo-[3]-ladderanol}, volume = {147}, year = {2025}, }
• (2025). Pseudo-phosphorylated tau forms paired helical filaments in the presence of high-curvature cholesterol-containing lipid membranes. JACS, 147(3), 2510--2522. (www)

  @article{ , abstract = {The tau protein misfolds in neurodegenerative diseases such as Alzheimer’s disease (AD). These pathological tau aggregates are associated with neuronal membranes, but molecular structural information about how disease-like tau fibrils interact with the lipid membrane is scarce. Here, we use solid-state NMR to investigate the structure of a tau construct bearing four AD-relevant phospho-mimetic mutations (4E tau) with cholesterol-containing high-curvature lipid membranes, which mimic the membrane of synaptic vesicles in neurons. We show that 4E tau adopts the AD paired helical filament (PHF) fold in the presence of the membrane at high protein concentrations. Moreover, it inserts into the membrane–water interface with an orientation that suggests possible bridging of multiple lipid vesicles. At lower protein concentrations, moderate chemical shift changes are observed, indicating a perturbation of the PHF structure by the lipids. Removal of the phospho-mimetic mutations led to a qualitatively different β-sheet conformation. These results indicate that posttranslational modifications impact the tau fibril structure more strongly than lipid membranes, but the membrane modulates the conformational equilibria of the aggregates.}, archive = {J_JACS}, author = {Nadia El Mammeri and Pu Duan and Mei Hong}, doi = {10.1021/jacs.4c13772}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2510--2522}, shortjournal = {J. Am. Chem. Soc.}, title = {Pseudo-phosphorylated tau forms paired helical filaments in the presence of high-curvature cholesterol-containing lipid membranes}, volume = {147}, year = {2025}, }
• (2025). Advancing the mechanosensitivity of atropisomeric diarylethene mechanophores through a lever-arm effect. JACS, 147(3), 2502--2509. (www)

  @article{ , abstract = {Understanding structure–mechanical activity relationships (SMARs) in polymer mechanochemistry is essential for the rational design of mechanophores with desired properties, yet SMARs in noncovalent mechanical transformations remain relatively underexplored. In this study, we designed a subset of diarylethene mechanophores based on a lever-arm hypothesis and systematically investigated their mechanical activity toward a noncovalent-yet-chemical conversion of atropisomer stereochemistry. Results from Density functional theory (DFT) calculations, single-molecule force spectroscopy (SMFS) measurements, and ultrasonication experiments collectively support the lever-arm hypothesis and confirm the exceptional sensitivity of chemo-mechanical coupling in these atropisomers. Notably, the transition force for the diarylethene M3 featuring extended 5-phenylbenzo[ b ]thiophene aryl groups is determined to be 131 pN ± 4 pN by SMFS. This value is lower than those typically recorded for other mechanically induced chemical processes, highlighting its exceptional sensitivity to low-magnitude forces. This work contributes a fundamental understanding of chemo-mechanical coupling in atropisomeric configurational mechanophores and paves the way for designing highly sensitive mechanochemical processes that could facilitate the study of nanoscale mechanical behaviors across scientific disciplines.}, archive = {J_JACS}, author = {Cijun Zhang and Tatiana B. Kouznetsova and Boyu Zhu and Liam Sweeney and Max Lancer and Ivan Gitsov and Stephen L. Craig and Xiaoran Hu}, doi = {10.1021/jacs.4c13480}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2502--2509}, shortjournal = {J. Am. Chem. Soc.}, title = {Advancing the mechanosensitivity of atropisomeric diarylethene mechanophores through a lever-arm effect}, volume = {147}, year = {2025}, }
• (2025). Spectroscopy and bonding analysis of ArnBO+ (n = 1–3) cations that possess Argon–Boron multiple bonds. JACS, 147(3), 2491--2501. (www)

  @article{ , abstract = {Ar n BO + ( n = 1–3) complexes have been prepared and subjected to spectroscopic characterization in the gas phase. Mass-selected infrared photodissociation spectroscopy, in combination with theoretical calculations, reveals the coexistence of two nearly isoenergetic structural isomers in Ar 2 BO + . One isomer entails two equivalent Ar atoms chemically bound to BO + , while the other features an ArBO + core ion accompanied by a weakly tagging argon atom. However, only the structure with an ArBO + core ion was observed for the Ar 3 BO + complex. Quantum chemical calculations using density functional theory and ab initio methods complement the experimental work. The calculations help to identify the spectroscopically observed cations whose equilibrium structures and bond dissociation energies are given. The electronic structure and bonding situation are analyzed with a variety of theoretical methods. The ArBO + core ion is characterized as having an exceptionally strong Ar–B covalent bond with some multiple bonding character.}, archive = {J_JACS}, author = {Guanjun Wang and Qin Ma and Baichun Wang and Yang Yang and Lili Zhao and Mingfei Zhou and Gernot Frenking}, doi = {10.1021/jacs.4c13459}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2491--2501}, shortjournal = {J. Am. Chem. Soc.}, title = {Spectroscopy and bonding analysis of ArnBO+ (n = 1–3) cations that possess Argon–Boron multiple bonds}, volume = {147}, year = {2025}, }
• (2025). Mechanistic investigations of cobalt-catalyzed, aminoquinoline-directed C(sp2)–H bond functionalization. JACS, 147(3), 2476--2490. (www)

  @article{ , abstract = {Monoanionic, bidentate-auxiliary-directed, cobalt-catalyzed C–H bond functionalization has become a very useful tool in organic synthesis. A comprehensive investigation into isolated organometallic intermediates and their reactivity within the catalytic cycle is lacking. We report here mechanistic studies of cobalt-catalyzed, aminoquinoline-directed C(sp 2 )–H bond functionalization. A number of organometallic Co(III) intermediates have been isolated and structurally characterized, including, for the first time in the aminoquinoline system, complexes arising from migratory insertion into cobalt–carbon bonds. The catalytic and stoichiometric reactions of cobalt(III) aryls with alkenes, alkynes, carbon monoxide, cyclic secondary amines, and aminoquinoline benzamides have been explored. The oxidation state of cobalt intermediates in the product-forming step depends on the nature of the coupling component. Specifically, annulation with alkynes and carbonylation with CO likely proceed via a Co(I)/Co(III) catalytic cycle. Carbon–hydrogen bond functionalization with alkenes and amines, as well as benzamide homocoupling, likely proceed via a (formally) Co(IV) species and involve oxidatively induced reductive elimination.}, archive = {J_JACS}, author = {Lukass Lukasevics and George N. Oh and Xiqu Wang and Liene Grigorjeva and Olafs Daugulis}, doi = {10.1021/jacs.4c13086}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2476--2490}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic investigations of cobalt-catalyzed, aminoquinoline-directed C(sp2)–H bond functionalization}, volume = {147}, year = {2025}, }
• (2025). Removal of trace benzene from cyclohexane using a MOF molecular sieve. JACS, 147(3), 2467--2475. (www)

  @article{ , abstract = {Cyclohexane (Cy), commonly produced by the catalytic hydrogenation of benzene (Bz), is used in large quantities as a solvent or feedstock for nylon polymers. Removing trace unreacted Bz from the Cy product is technically difficult due to their similar molecular structures and physical properties. Herein, we report that a metal–organic framework (MOF) adsorbent shows a molecular sieving effect for Bz and Cy with record-high Bz/Cy adsorption selectivities (216, 723, and 1027) in their liquid mixtures (v/v = 1:1, 1:10, and 1:20), and traps Bz molecules effectively even at low partial pressure in the vapor phase (e.g., 2.49 mmol/g at 8.2 Pa) or at low content in liquid-phase Cy (e.g., 128 mg/g at 20 ppm). Over 99% removal of trace Bz (1000 ppm) from liquid Cy could be achieved in one simple stripping step at room temperature using this sorbent, producing a Cy with >99.999% purity. Single-crystal structure analyses for guest-free and Bz-loaded phases of the MOF disclosed that a narrow slit-like pore aperture and the strong uniting of multiple weak host–guest and guest–guest interactions are the co-origin of its distinct adsorption property for Bz and Cy.}, archive = {J_JACS}, author = {Rui-Chao Zhao and Lin-Hua Xie and Xiao-Min Liu and Zhe Liu and Xiang-Yu Li and Jian-Rong Li}, doi = {10.1021/jacs.4c13208}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2467--2475}, shortjournal = {J. Am. Chem. Soc.}, title = {Removal of trace benzene from cyclohexane using a MOF molecular sieve}, volume = {147}, year = {2025}, }
• (2025). Dual-mode emission and solvent-desorption dependent kinetic properties of crystalline-state chemiluminescence reaction of 9-phenyl-10-(2-phenylethynyl)anthracene endoperoxide. JACS, 147(3), 2455--2466. (www)

  @article{ , abstract = {The chemiluminescence (CL) feature and reactivity of the aromatic endoperoxide 9-phenyl-10-(2-phenylethynyl)anthracene endoperoxide (PPEA-O 2 ) were investigated in the crystalline state. For this, PPEA-O 2 crystals were prepared using dichloromethane and n -hexane. These crystals exhibited an α-phase structure containing n -hexane as a crystal solvent. The crystal structure of nonperoxidic anthracene (i.e., PPEA) was also confirmed. After optimizing heating conditions to 120 °C for the thermolytic reaction of PPEA-O 2 in crystals while maintaining the solid state, its CL characteristic and reactivity were investigated. Two key findings were derived: (1) dual-mode emission with maxima at 510 and 1275 nm and (2) distinct observation of CL emission at the first 2–3 min after the start of heating owing to the rapid thermolytic reaction coupled with n -hexane desorption. The 510 and 1275 nm emissions were attributed to the PPEA excimer and 1 O 2 ( 1 Δ g ), respectively. We proposed a mechanism involving the triplet–triplet annihilation of the excited triplet states of PPEA to explain excimer production with postulated pathways for generating these triplet states from PPEA-O 2 . The rapid thermolytic reaction of PPEA-O 2 in α-phase crystals with simultaneous n -hexane desorption was attributed to the formation of transient vacant spaces, which increased the molecular freedom necessary for the reaction (“transient vacant space effect”). Thus, the CL of PPEA-O 2 proved useful for identifying characteristic reactivity and analyzing the luminescence mechanism of aromatic endoperoxides in the crystalline state.}, archive = {J_JACS}, author = {Norihisa Yamasaki and Chihiro Matsuhashi and Hidehiro Uekusa and Naofumi Nakayama and Shigeaki Obata and Hitoshi Goto and Shojiro Maki and Takashi Hirano}, doi = {10.1021/jacs.4c12958}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2455--2466}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual-mode emission and solvent-desorption dependent kinetic properties of crystalline-state chemiluminescence reaction of 9-phenyl-10-(2-phenylethynyl)anthracene endoperoxide}, volume = {147}, year = {2025}, }
• (2025). Direct photocatalytic oxidation of methane to formic acid with high selectivity via a concerted Proton–Electron transfer process. JACS, 147(3), 2444--2454. (www)

  @article{ , abstract = {Light-driven direct conversion of methane to formic acid is a promising approach to convert methane to value-added chemicals and promote sustainability. However, this process remains challenging due to the complex requirements for multiple protons and electrons. Herein, we report the design of WO 3 -based photocatalysts modified with Pt active sites to address this challenge. We demonstrate that modulating the dimensional effect of Pt on the WO 3 support is key to enhancing the catalytic performance of selective CH 4 -to-HCOOH conversion. The Pt nanoparticles on WO 3 exhibit superior conversion rate, selectivity and durability in the production of HCOOH compared to the Pt-free sample and WO 3 decorated with Pt single atoms. The optimal Pt NPs -WO 3 catalyst achieves a HCOOH conversion rate of 17.7 mmol g –1 , with 84% selectivity and stability maintained for up to 48 h. Mechanistic studies show that the protonation of O 2 to hydroxyl radicals is the limiting step for HCOOH yield. Pt nanoparticles can facilitate electron transfer and promote O 2 dissociation, generating hydroxyl radicals via a proton-coupled electron transfer process. This process provides sufficient protons to lower the formation barrier for • OH radicals, thereby promoting the activation of CH 4 . In addition, Pt nanoparticles regulate the adsorption of oxygenated hydrocarbon intermediates, increasing the selectivity of the reaction. This work advances our understanding of catalyst design for methane conversion and the effective regulation of complex reaction pathways.}, archive = {J_JACS}, author = {Guangyao Zhai and Siyuan Yang and Yihong Chen and Junchi Xu and Shenghe Si and Honggang Zhang and Yuanyuan Liu and Jun Ma and Xiao Sun and Weixin Huang and Chao Gao and Dong Liu and Yujie Xiong}, doi = {10.1021/jacs.4c12758}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2444--2454}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct photocatalytic oxidation of methane to formic acid with high selectivity via a concerted Proton–Electron transfer process}, volume = {147}, year = {2025}, }
• (2025). No bridge between us: EXAFS and computations confirm two distant iron ions comprise the active site of alkane monooxygenase (AlkB). JACS, 147(3), 2432--2443. (www)

  @article{ , abstract = {Alkane monooxygenase (AlkB) is the dominant enzyme that catalyzes the oxidation of liquid alkanes in the environment. Two recent structural models derived from cryo-electron microscopy (cryo-EM) reveal an unusual active site: a histidine-rich center that binds two iron ions without a bridging ligand. To ensure that potential photoreduction and radiation damage are not responsible for the absence of a bridging ligand in the cryo-EM structures, spectroscopic methods are needed. We present the results of extended X-ray absorption fine structure (EXAFS) experiments collected under conditions where photodamage was avoided. Careful data analysis reveals an active site structure consistent with the cryo-EM structures in which the two iron ions are ligated by nine histidines and separated by at least 5 Å. The EXAFS data were used to inform structural models for molecular dynamics (MD) simulations. The MD simulations corroborate EXAFS observations that neither of the two conserved carboxylate-containing residues (E281 and D190) near the active site are likely candidates for metal ion bridging. Mutagenesis experiments, spectroscopy, and additional MD simulations were used to further explore the role of these carboxylate residues. A variant in which a carboxylate containing residue (E281) was changed to a methyl residue (E281A) showed little change in pre-edge features, consistent with the observation that it is not essential for activity and hence unlikely to serve as a bridging ligand at any point in the catalytic cycle. D190 variants had substantially diminished activity, suggesting an important role in catalysis not yet fully understood.}, archive = {J_JACS}, author = {Clorice R. Reinhardt and Juliet A. Lee and Lauren Hendricks and Tierani Green and Lily Kunczynski and August Jaunzarins Roberts and Naomi Miller and Noga Rafalin and Heather J. Kulik and Christopher J. Pollock and Rachel N. Austin}, doi = {10.1021/jacs.4c12633}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2432--2443}, shortjournal = {J. Am. Chem. Soc.}, title = {No bridge between us: EXAFS and computations confirm two distant iron ions comprise the active site of alkane monooxygenase (AlkB)}, volume = {147}, year = {2025}, }
• (2025). Solid-state photoswitching of hydrazones based on excited-state intramolecular proton transfer. JACS, 147(3), 2421--2431. (www)

  @article{ , abstract = {The development of new photochromic systems is motivated by the possibility of controlling the properties and functions of materials with high spatial and temporal resolution in a reversible manner. While there are several classes of photoswitches operating in solution, the design of systems efficiently operating in the solid state remains highly challenging, mainly due to limitations related to confinement effects. Triaryl-hydrazones represent a relatively new subclass of bistable hydrazone photoswitches exhibiting efficient Z / E photochromism in solution. As “large volume” photoswitches, they have been anticipated to display only limited solid-state photoswitching. Here, we show that the Z isomers of newly prepared triaryl-hydrazones containing a perfluorinated hydrazine phenyl ring (PHZs) exhibit impressive solid-state photochromism with an unexpected light-induced red-shift of the absorption maximum. Based on (time-dependent) density functional theory calculations, a photoswitching reaction mechanism involving the excited state intramolecular proton transfer has been proposed, which rationalizes the observed red-shift in absorption by the formation of a metastable proton transfer structure. Advanced experimental techniques including X-ray diffraction, solid-state NMR and EPR spectroscopy, and confocal Raman microscopy corroborated the suggested mechanism and revealed that the observed photochromism is a superficial phenomenon. This atypical photochromic behavior of PHZs can also be realized by using visible light and in the form of thin films, which manifests their potential use in optics and optoelectronics.}, archive = {J_JACS}, author = {Bernard Mravec and Šimon Budzák and Miroslav Medved’ and Lukáš F. Pašteka and Petr Lazar and Eliška Procházková and Aleš Růžička and Jozef Kožíšek and Karol Vegso and Michal Bodik and Peter Šiffalovič and Peter Švec and Juraj Filo and Marek Cigáň}, doi = {10.1021/jacs.4c12510}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2421--2431}, shortjournal = {J. Am. Chem. Soc.}, title = {Solid-state photoswitching of hydrazones based on excited-state intramolecular proton transfer}, volume = {147}, year = {2025}, }
• (2025). Suppressing polaronic Defect–Photocarrier interaction in halide perovskites by pre-distorting its lattice. JACS, 147(3), 2411--2420. (www)

  @article{ , abstract = {In halide perovskites, photocarriers can have strong polaronic interactions with point defects. For iodide-deficient MAPbI 3 , we found that the Fermi level can shift significantly by 0.6–0.7 eV upon light illumination. This energy level shift is accompanied by the formation of deep electron traps. These experimental observations are consistent with the formation of a Pb–Pb dimer when photoexcited electrons are trapped at an iodide vacancy. Interestingly, we found that this polaronic interaction is suppressed when a portion of MA + cations is replaced by smaller Cs + ions. Density functional theory calculations reveal that Cs-doping can reduce the distance between two Pb atoms across an iodide vacancy, even without electron trapping. The predistortion of the lattice induced by cation replacement resembles the Pb–Pb dimer formed by electron trapping at the defect site, which explains the suppression of light-induced effects observed in the experiment. Our finding unveils a counterintuitive strategy to enhance the photostability of halide perovskites by preintroducing distortions into its lattice.}, archive = {J_JACS}, author = {Ghadah Alkhalifah and Bipeng Wang and Oleg V. Prezhdo and Wai-Lun Chan}, doi = {10.1021/jacs.4c12322}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2411--2420}, shortjournal = {J. Am. Chem. Soc.}, title = {Suppressing polaronic Defect–Photocarrier interaction in halide perovskites by pre-distorting its lattice}, volume = {147}, year = {2025}, }
• (2025). Electrocatalytic mapping of metal fatigue with persistent slip bands. JACS, 147(3), 2403--2410. (www)

  @article{ , abstract = {Metal fatigue, characterized by the accumulation of dislocation defects, is a prevalent failure mode in structural materials. Nondestructive early-stage detection of metal fatigue is extremely important to prevent disastrous events and protect human life. However, the lack of a precise quantitative method to visualize fatigue with spatiotemporal resolution poses a significant obstacle to timely detection. Here, we demonstrate a nondestructive electrocatalytic method to visualize metal fatigue, which is promising for future fatigue early detections. The persistent slip band (PSB) is considered one of the most consequential defect structures for metal fatigue failure. The selective electrochemistry is highly dependent on the metal crystallography and the collective dislocations in the PSB structure, enabling the amplification of the electrochemical response and differentiation of the fatigue stages at a submillimeter resolution. In addition, this nondestructive electrocatalytic method is applicable to several common metals, including copper, silver, iron, and aluminum, holding great significance where metal fatigue is a critical concern.}, archive = {J_JACS}, author = {Taishi Xiao and Lixun Cheng and Zheng Chen and Yan Hu and Xiang Yao and Junxiang Shu and Sailin Yuan and Yao Ma and Can Tang and Zhewei Huang and Bin Shen and Wenzhong Bao and Xin Xu and Binghui Ge and Zhengzong Sun}, doi = {10.1021/jacs.4c12114}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2403--2410}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrocatalytic mapping of metal fatigue with persistent slip bands}, volume = {147}, year = {2025}, }
• (2025). Realizing an energy-dense potassium metal battery at −40 °C via an integrated anode-free and dual-ion strategy. JACS, 147(3), 2393--2402. (www)

  @article{ , abstract = {Potassium (K)-based batteries hold great promise for cryogenic applications owing to the small Stokes radius and weak Lewis acidity of K + . Nevertheless, energy-dense (>200 W h kg –1 cathode+anode ) K batteries under subzero conditions have seldom been reported. Here, an over 400 W h kg –1 cathode+anode K battery is realized at −40 °C via an anode-free and dual-ion strategy, surpassing these state-of-the-art K batteries and even most Li/Na batteries at low temperatures (LTs). By introduction of a strongly associating salt as an additive to this anode-free K battery, an anion-derived solid electrolyte interphase can be established for a highly reversible, zero-excess K plating/stripping behavior on a bare current collector. Meanwhile, a binary solvent is rationally designed for lowering the cation desolvation energy barrier, which ensures comparably facile cation and desolvation-free anion kinetics in this dual-ion structure even at LTs. Consequently, the K||Al half-cell delivers a high Coulombic efficiency of 99.98% at −40 °C. By pairing with a high-energy cathode, a proof-of-concept anode-free K dual-ion battery (N/P = 0) is fabricated, delivering a record-high energy density of 407 W h kg –1 cathode+anode with stable cycling of 183 cycles (80% capacity retention) at −40 °C. This work paves a way toward energy-dense batteries at extreme scenarios.}, archive = {J_JACS}, author = {Jiangchun Chen and Hao Lan and Sicong Wang and Xinyu Liu and Qiaonan Zhu and Xudong Zhang and Mengyao Tang and Shuai Dong and Jie Yang and Mirtemir Kurbanov and Lin Guo and Hua Wang}, doi = {10.1021/jacs.4c12126}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2393--2402}, shortjournal = {J. Am. Chem. Soc.}, title = {Realizing an energy-dense potassium metal battery at −40 °C via an integrated anode-free and dual-ion strategy}, volume = {147}, year = {2025}, }
• (2025). Spectroscopic and computational insights into the mechanism of cofactor Cobalt–Carbon bond homolysis by the adenosylcobalamin-dependent enzyme ethanolamine ammonia-lyase. JACS, 147(3), 2380--2392. (www)

  @article{ , abstract = {The adenosylcobalamin (AdoCbl)-dependent enzyme ethanolamine ammonia-lyase (EAL) catalyzes the conversion of ethanolamine to acetaldehyde and ammonia. As is the case for all AdoCbl-dependent isomerases, the catalytic cycle of EAL is initiated by homolytic cleavage of the cofactor’s Co–C bond, producing Co II cobalamin (Co II Cbl) and an adenosyl radical that serves to abstract a hydrogen atom from the substrate. Remarkably, in the presence of substrate, the rate of Co–C bond homolysis of enzyme-bound AdoCbl is increased by 12 orders of magnitude. For Class I AdoCbl-dependent isomerases, an important contribution to this rate acceleration stems from a stabilization of the Co II Cbl posthomolysis product by the axially coordinated histidine residue that displaces the pendant base from the Co ion upon AdoCbl binding to these enzymes. However, EAL and other Class II isomerases bind AdoCbl in the so-called “base-on” conformation and must therefore employ a different mechanism of Co–C bond activation. In the present study, we have used a combined spectroscopic and computational approach to probe the conformational changes and enzyme/cofactor/substrate interactions that contribute to the rate acceleration of Co–C bond homolysis in EAL. Spectroscopic data of AdoCbl and Co II Cbl show minimal perturbations upon cofactor binding to EAL in both the absence and presence of substrate. Structural models of free and EAL-bound AdoCbl were constructed using molecular dynamics and quantum mechanics/molecular mechanics computations. By carrying out relaxed potential energy scans for Co–C bond cleavage of free and EAL-bound AdoCbl, we identified key cofactor/enzyme interactions that contribute to the Co–C bond activation by EAL and obtained Co–C bond dissociation energies that agree well with published experimental data.}, archive = {J_JACS}, author = {Laura D. Elmendorf and Ryan L. Hall and Flavia G. Costa and Jorge C. Escalante-Semerena and Thomas C. Brunold}, doi = {10.1021/jacs.4c11488}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2380--2392}, shortjournal = {J. Am. Chem. Soc.}, title = {Spectroscopic and computational insights into the mechanism of cofactor Cobalt–Carbon bond homolysis by the adenosylcobalamin-dependent enzyme ethanolamine ammonia-lyase}, volume = {147}, year = {2025}, }
• (2025). Controlled structural activation of iridium single atom catalyst for high-performance proton exchange membrane water electrolysis. JACS, 147(3), 2369--2379. (www)

  @article{ , abstract = {Iridium single atom catalysts are promising oxygen evolution reaction (OER) electrocatalysts for proton exchange membrane water electrolysis (PEMWE), as they can reduce the reliance on costly Ir in the OER catalysts. However, their practical application is hindered by their limited stability during PEMWE operation. Herein, we report on the activation of Ir-doped CoMn 2 O 4 in acidic electrolyte that leads to enhanced activity and stability in acidic OER for long-term PEMWE operation. In-depth material characterization combined with electrochemical analysis and theoretical calculations reveal that activating Ir-doped CoMn 2 O 4 induces controlled restructuring of Ir single atoms to IrO x nanoclusters, resulting in an optimized Ir configuration with outstanding mass activity of 3562 A g Ir –1 at 1.53 V (vs RHE) and enhanced OER stability. The PEMWE using activated Ir-doped CoMn 2 O 4 exhibited a stable operation for >1000 h at 250 mA cm –2 with a low degradation rate of 0.013 mV h –1 , demonstrating its practical applicability. Furthermore, it remained stable for more than 400 h at a high current density of 1000 mA cm –2 , demonstrating long-term durability under practical operation conditions.}, archive = {J_JACS}, author = {Wonjae Ko and Jaehyuk Shim and Hyunsoo Ahn and Hee Jung Kwon and Kangjae Lee and Yoon Jung and Wytse Hooch Antink and Chan Woo Lee and Sungeun Heo and Seongbeom Lee and Junghwan Jang and Jiheon Kim and Hyeon Seok Lee and Sung-Pyo Cho and Byoung-Hoon Lee and Minho Kim and Yung-Eun Sung and Taeghwan Hyeon}, doi = {10.1021/jacs.4c11442}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2369--2379}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlled structural activation of iridium single atom catalyst for high-performance proton exchange membrane water electrolysis}, volume = {147}, year = {2025}, }
• (2025). Synergistic ultrasound-activable artificial enzyme and precision gene therapy to suppress redox homeostasis and malignant phenotypes for controllably combating hepatocellular carcinoma. JACS, 147(3), 2350--2368. (www)

  @article{ , abstract = {Hepatocellular carcinoma (HCC) remains one of the most lethal malignant tumors. Multimodal therapeutics with synergistic effects for treating HCC have attracted increasing attention, for instance, designing biocompatible porphyrin-based nanomedicines for enzyme-mimetic and ultrasound (US)-activable reactive oxygen species (ROS) generation. Despite the promise, the landscape of such advancements remains sparse. Here, we propose the de novo design of a π-conjugated, osmium (Os)-coordinated polyporphyrin (P-Por-Os) nanovesicle to serve as an ultrasound-activable artificial enzyme for synergistic therapies to suppress redox homeostasis and malignant phenotypes for controllably combating HCC. Our findings reveal that the P-Por-Os with US showed superior, multifaceted, and controllable ROS-generating activities. This system not only subverts the redox balance within HCC cells but also achieves precise and controlled tumor ablation at remarkably low concentrations, as evidenced across cellular assays and animal models. In the liver orthotopic model, US not only activates the artificial enzyme to catalyze ROS but also facilitates remote-controlled ablation of HCC through precise US positioning. Moreover, the P-Por-Os + US can assist the precision gene therapy by knocking down the ROS resistance factor, MT2A, and down-regulating its downstream oncogene IGFBP2 to attenuate ROS resistance, proliferation, and migration of HCC efficiently. We suggest that the design of this ultrasound-activable artificial enzyme presents a promising avenue for the engineering of innovative tumoricidal materials, offering a synergistic therapeutic approach with high biosecurity for HCC treatment.}, archive = {J_JACS}, author = {Yinghao Lyu and Qian Li and Sinan Xie and Zhenyang Zhao and Lang Ma and Zhe Wu and Wen Bao and Yunshi Cai and Hu Liu and Haorong He and Kunlin Xie and Fengwei Gao and Ying Yang and Pu Wu and Penghui He and Kaipeng Wang and Xinye Dai and Hong Wu and Tian Lan and Chong Cheng}, doi = {10.1021/jacs.4c10997}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2350--2368}, shortjournal = {J. Am. Chem. Soc.}, title = {Synergistic ultrasound-activable artificial enzyme and precision gene therapy to suppress redox homeostasis and malignant phenotypes for controllably combating hepatocellular carcinoma}, volume = {147}, year = {2025}, }
• (2025). Dynamic peptide nanoframework-guided protein coassembly: Advancing adhesion performance with hierarchical structures. JACS, 147(3), 2335--2349. (www)

  @article{ , abstract = {Hierarchical structures are essential in natural adhesion systems. Replicating these in synthetic adhesives is challenging due to intricate molecular mechanisms and multiscale processes. Here, we report three phosphorylated peptides featuring a hydrophobic self-assembly motif linked to a hydrophilic phosphorylated sequence (pSGSS), forming peptide fibril nanoframeworks. These nanoframeworks effectively coassemble with elastin-derived positively charged proteins (PCP), resulting in complex coacervate-based adhesives with hierarchical structures. Our method enables the controlled regulation of both cohesion and adhesion properties in the adhesives. Notably, the complex adhesives formed by the dityrosine-containing peptide and PCP demonstrate an exceptional interfacial adhesion strength of up to 30 MPa, outperforming most known supramolecular adhesives and rivaling cross-linked chemical adhesives. Additionally, these adhesives show promising biocompatibility and bioactivity, making them suitable for applications such as visceral hemostasis and tissue repair. Our findings highlight the utility of bioinspired hierarchical assembly combined with bioengineering techniques in advancing biomedical adhesives.}, archive = {J_JACS}, author = {Yusai Zhou and Rong Chang and Zhenyue Yang and Qi Guo and Mengyao Wang and Bo Jia and Bo Li and Bodan Deng and Yubin Ren and Huaxia Zhu and Xinyan Wang and Qinrui Wang and Han Wen and Hongjie Zhang and Jing Yu and Yong-Xiang Chen and Kai Liu}, doi = {10.1021/jacs.4c10882}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2335--2349}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic peptide nanoframework-guided protein coassembly: Advancing adhesion performance with hierarchical structures}, volume = {147}, year = {2025}, }
• (2025). Isolation of inner-sphere aquo complexes of Samarium(II). JACS, 147(3), 2323--2334. (www)

  @article{ , abstract = {The cis-anti-cis and cis-syn-cis isomers of [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 exhibiting trans water molecules bound to the Sm 2+ ion have been isolated and characterized. Sm 2+ possesses an electrochemical potential sufficient for water reduction, and thus these complexes add to the recent body of evidence that the oxidation of Sm 2+ by water can operate by a mechanism that is not straightforward. These complexes are obtained by the direct addition of stoichiometric amounts of water to solutions of the respective Sm(dicyclohexano-18-crown-6)I 2 isomers under an inert atmosphere. The parent complex, Sm(dicyclohexano-18-crown-6)I 2 , lacking coordinating water molecules can be obtained through rigorous exclusion of water. It was determined that the bulky cyclohexano-substituents deter intramolecular interactions between [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 complexes and slow the oxidization of the metal centers. The extent of the stability of these complexes to the presence of water has been further probed through cyclic voltammetry, where it was found that the redox potential of both isomers of [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 maintains quasi-reversible behavior with a 50,000-fold excess of water to Sm 2+ in solution with the cis-syn-cis complex being quasi-reversible at even higher concentrations of water. Solution-phase spectroscopy of these complexes in acetonitrile shows a corresponding hypsochromic shift of the Sm 2+ 4 f → 5 d transition typically observed in the visible region from Sm 2+ complexes. The crystalline compounds obtained in this study support solid-state spectroscopic trends observed from other Sm 2+ crown-ether complexes containing iodide counterions, wherein the proximity of the iodide ions to the metal center determines whether the complex can exhibit 4 f → 4 f photoluminescence.}, archive = {J_JACS}, author = {Todd N. Poe and Sarah E. Molinari and Hannah B. Wineinger and Thomas E. Albrecht}, doi = {10.1021/jacs.4c10287}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2323--2334}, shortjournal = {J. Am. Chem. Soc.}, title = {Isolation of inner-sphere aquo complexes of Samarium(II)}, volume = {147}, year = {2025}, }
• (2025). Chiral Aldehyde/Palladium catalysis enables asymmetric branched-selective ring-opening functionalization of methylenecyclopropanes with amino acid esters. JACS, 147(3), 2315--2322. (www)

  @article{ , abstract = {Achieving catalytic asymmetric functionalization of methylenecyclopropanes (MCPs) by selective C–C bond cleavage is a notable challenge due to the intricate reaction partners involved. In this work, we report that chiral aldehyde/palladium combined catalysis enables the asymmetric functionalization of MCPs with NH 2 -unprotected amino acid esters. This reaction proceeds through a regiospecific branched ring-opening mechanism, resulting in optically active α,α-disubstituted α-amino acid esters bearing nonconjugated terminal alkene units. Mechanism studies indicate that the ring-opening pathways are irreversible and the ultimate regioselectivity is governed by palladium catalysis. The products can be utilized in the construction of chiral dihydropyrazoles, α-methyl aspartic acid derivatives, and analogues of VPC01091 and BMS-986104.}, archive = {J_JACS}, author = {Fang Zhu and Hui He and Wei Wen and Hong-Lin Guan and Zhu-Lian Wu and Tian Cai and Shao-Fei Ni and Qi-Xiang Guo}, doi = {10.1021/jacs.4c16934}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2315--2322}, shortjournal = {J. Am. Chem. Soc.}, title = {Chiral Aldehyde/Palladium catalysis enables asymmetric branched-selective ring-opening functionalization of methylenecyclopropanes with amino acid esters}, volume = {147}, year = {2025}, }
• (2025). Room-temperature reversible control of fluorescently distinct polymorphs using pressure and E-field: Writing and erasing information without thermal treatment. JACS, 147(3), 2309--2314. (www)

  @article{ , abstract = {This paper presents the reversible transformation between two polymorphs of a hexacatenar liquid crystal ( 1 ) with distinct fluorescence colors at room temperature (RT). This method utilizes mechanical pressure (mechanochromism) and an electric field (E-field-chromism). The molecule ( 1 ), designed with a pyrene core and 1,2,3-triazole linkers, exhibits a blue-emissive crystalline (CRY) polymorph ( 1-B ) and a green-emissive liquid crystalline (LC) polymorph ( 1-G ) at RT, depending on the cooling rate from the liquid phase. The metastable 1-G is stabilized by hydrogen bonding (H-bonding) between 1,2,3-triazole linkers, forming a helical columnar structure. Mechanical pressure converts thermodynamically stable 1-B to 1-G , while the application of an alternating current (AC) E-field to 1-G transforms it back to 1-B . Notably, this study reports the first instance of an E-field-induced polymorphic transformation. Using mechanical pressure and E-field application at RT, patterns were successfully recorded and erased on substrates, demonstrating potential applications in data storage, anticounterfeiting, and sensor technologies.}, archive = {J_JACS}, author = {Seongwon Park and Jaeduk Byun and Ho-Joong Kim and Byoung-Ki Cho}, doi = {10.1021/jacs.4c16712}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2309--2314}, shortjournal = {J. Am. Chem. Soc.}, title = {Room-temperature reversible control of fluorescently distinct polymorphs using pressure and E-field: Writing and erasing information without thermal treatment}, volume = {147}, year = {2025}, }
• (2025). Cooperative anion−π catalysis with chiral molecular cages toward enantioselective desymmetrization of anhydrides. JACS, 147(3), 2303--2308. (www)

  @article{ , abstract = {Exploiting novel noncovalent interactions for catalysis design represents a fascinating direction. For the flexible and relatively weak anion−π interactions, manipulation of two or more π-acidic surfaces for cooperative activation is highly desirable. Here, we demonstrate the strategy of cooperative anion−π catalysis based on chiral molecular cages with V-shaped electron-deficient cavities for synergic binding and activation of dicarbonyl electrophiles toward highly enantioselective desymmetrization transformation. The chiral cages were readily synthesized by incorporation of additional chiral base sites in one step. The cages efficiently catalyzed methanolytic desymmetrization of a series of meso cyclic anhydrides in nearly quantitative yields and up to 94% ee. In contrast, the non-cage analogues and simple control catalysts showed sluggish conversion and much lower enantioselectivity. Crystal structure, substrate binding studies, and theoretical modeling consistently suggested the essential role of the cage electron-deficient cavities in harnessing cooperative anion−π interactions for efficient activation and excellent selectivity control.}, archive = {J_JACS}, author = {Ming-Sen Yue and Na Luo and Xu-Dong Wang and Yu-Fei Ao and De-Xian Wang and Qi-Qiang Wang}, doi = {10.1021/jacs.4c15978}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2303--2308}, shortjournal = {J. Am. Chem. Soc.}, title = {Cooperative anion−π catalysis with chiral molecular cages toward enantioselective desymmetrization of anhydrides}, volume = {147}, year = {2025}, }
• (2025). Aminoalkylation of alkenes enabled by triple radical sorting. JACS, 147(3), 2296--2302. (www)

  @article{ , abstract = {The direct synthesis of C(sp 3 )-rich architectures is a driving force for innovation in synthetic organic chemistry. Such scaffolds impart beneficial properties onto drug molecules that correlate with greater clinical success. Consequently, there is a strong impetus to develop new methods by which to access sp 3 -rich molecules from commercial feedstocks, such as alkenes. Herein, we report a three-component aminoalkylation reaction that utilizes the principles of triple radical sorting to regioselectively add N-centered and C-centered radicals across alkenes. This process relies upon photoredox catalysis to transform alkyl bromides and reductively activated N-centered radical precursors into high-energy radical species in a redox-neutral fashion. A broad scope of coupling partners is demonstrated, with multiple synthetic applications, including facile syntheses of pharmacophoric substituted N-heterocycles.}, archive = {J_JACS}, author = {William L. Lyon and Johnny Z. Wang and Jesús Alcázar and David W. C. MacMillan}, doi = {10.1021/jacs.4c14965}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2296--2302}, shortjournal = {J. Am. Chem. Soc.}, title = {Aminoalkylation of alkenes enabled by triple radical sorting}, volume = {147}, year = {2025}, }
• (2025). Exploring the vibrational coherences in the ultrafast electronic relaxation of pyrimidine nucleobases and nucleosides. JACS, 147(3), 2291--2295. (www)

  @article{ , abstract = {We studied the vibrational coherences during the ultrafast internal conversions (ICs) of pyrimidine nucleobases and -sides in aqueous solutions and the gas phase with an instrumental resolution of 14 fs. The coherence of the same ring-breathing vibrational mode with a frequency of 750 cm –1 was observed. In the gas phase, the vibrational coherence was transferred during IC from the 1 ππ* to the 1 nπ* state, and it survived for approximately 1 ps. In an aqueous solution, the vibrational dynamics develop in the 1 ππ* state because the 1 nπ* state is energetically upshifted via hydrogen bonding with H 2 O, and the vibrational coherence is lost on a similar time scale as that of IC to the ground electronic state.}, archive = {J_JACS}, author = {Shutaro Karashima and Toshinori Suzuki}, doi = {10.1021/jacs.4c14221}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2291--2295}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploring the vibrational coherences in the ultrafast electronic relaxation of pyrimidine nucleobases and nucleosides}, volume = {147}, year = {2025}, }
• (2025). On the tracks to “Smart” single-atom catalysts. JACS, 147(3), 2275--2290. (www)

  @article{ , abstract = {Despite their enormous impact in modern heterogeneous catalysis, single-atom catalysts (SACs) continue to puzzle the catalysis community, which often struggles to draw correct conclusions in SAC-catalyzed experiments. In many cases, the reasons for such an uncertainty originate from the lack of knowledge of the exact single-atom evolution under operative conditions and the fundamental factors controlling the fate of the single atom in relation to the catalytic mechanism. This has led to confusion also about correct definition and terminology, where the coined term single-site catalysts reflects the difficulty in defining the true active species as well as in obtaining long-range ordered homogeneous supports [Chi, S.; et al. J. Catal. 2023 , 419 , 49–57. DOI: 10.1016/j.jcat.2023.02.003 ]. Most recent studies have attempted to clarify several of the key aspects that are in play during SAC catalysis. However, one largely overlooked opportunity is to take advantage of all the dynamic phenomena occurring at the single metal site to turn the conventional catalytic sequences into a smart, stimulus-responsive, and controllable evolution of the single atom under operative conditions. Such “smartness” could potentially unleash pathways that mitigate some of the typical drawbacks of SACs, such as selectivity and stability. Here we present our vision on these yet-unexplored opportunities for exploiting the dynamicity of SACs, and we discuss various examples that could be the cornerstones for the advent of a next generation of SACs, that we term here “smart” single-atom catalysts (SSACs). Despite smart-behaving SACs still being far from realization, the clues provided here suggest pathways to achieve this goal.}, archive = {J_JACS}, author = {Michele Melchionna and Paolo Fornasiero}, doi = {10.1021/jacs.4c15803}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2275--2290}, shortjournal = {J. Am. Chem. Soc.}, title = {On the tracks to “Smart” single-atom catalysts}, volume = {147}, year = {2025}, }
• (2025). Altermagnetism: A chemical perspective. JACS, 147(3), 2257--2274. (www)

  @article{ , abstract = {Altermagnets have been recently introduced as a classification of collinear, spin compensated magnetic materials that host net-zero magnetization yet display some electronic behaviors typically associated with noncompensated magnetic materials like ferromagnets. The emergence of such properties are a consequence of spin-split bands that arise under specific symmetry conditions in the limit of zero spin–orbit coupling. In this Perspective, we summarize the fundamental criteria for realizing an altermagnetic phase and present a qualitative electronic band structure derivation and symmetry analysis through chemical principles. We then discuss the properties that make altermagnets distinctive candidates for charge-to-spin conversion elements in spintronic devices and provide a brief review of some altermagnetic candidate materials. Finally, we discuss future directions for altermagnetism and highlight opportunities for chemists to advance this emerging field.}, archive = {J_JACS}, author = {Shannon S. Fender and Oscar Gonzalez and D. Kwabena Bediako}, doi = {10.1021/jacs.4c14503}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2257--2274}, shortjournal = {J. Am. Chem. Soc.}, title = {Altermagnetism: A chemical perspective}, volume = {147}, year = {2025}, }
• (2025). High mobility emissive organic semiconductors for optoelectronic devices. JACS, 147(3), 2239--2256. (www)

  @article{ , abstract = {High mobility emissive organic semiconductors (HMEOSCs) are a kind of unique semiconducting material that simultaneously integrates high charge carrier mobility and strong emission features, which are not only crucial for overcoming the performance bottlenecks of current organic optoelectronic devices but also important for constructing high-density integrated devices/circuits for potential smart display technologies and electrically pumped organic lasers. However, the development of HMEOSCs is facing great challenges due to the mutually exclusive requirements of molecular structures and packing modes between high charge carrier mobility and strong solid-state emission. Encouragingly, considerable advances on HMEOSCs have been made with continuous efforts, and the successful integration of these two properties within individual organic semiconductors currently presents a promising research direction in organic electronics. Representative progress, including the molecular design of HMEOSCs, and the exploration of their applications in photoelectric conversion devices and electroluminescent devices, especially organic photovoltaic cells, organic light-emitting diodes, and organic light-emitting transistors, are summarized in a timely manner. The current challenges of developing HMEOSCs and their potential applications in other related devices including electrically pumped organic lasers, spin organic light-emitting transistors are also discussed. We hope that this perspective will boost the rapid development of HMEOSCs with a new mechanism understanding and their wide applications in different fields entering a new stage.}, archive = {J_JACS}, author = {Ziyi Xie and Dan Liu and Can Gao and Xiaotao Zhang and Huanli Dong and Wenping Hu}, doi = {10.1021/jacs.4c11208}, journal = {Journal of the American Chemical Society}, month = {1}, number = {3}, pages = {2239--2256}, shortjournal = {J. Am. Chem. Soc.}, title = {High mobility emissive organic semiconductors for optoelectronic devices}, volume = {147}, year = {2025}, }
• (2025). Correction to “Chemical design of spin frustration to realize topological spin glasses”. JACS, 147(2), 2238. (www)

  @article{ , archive = {J_JACS}, author = {Stephanie M. Amtry and Arthur C. Campello and Christopher L. Tong and Danilo Puggioni and James M. Rondinelli and Young S. Lee and Danna E. Freedman}, doi = {10.1021/jacs.4c18570}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2238}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Chemical design of spin frustration to realize topological spin glasses”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Peeking into the femtosecond hot-carrier dynamics reveals unexpected mechanisms in plasmonic photocatalysis”. JACS, 147(2), 2237. (www)

  @article{ , archive = {J_JACS}, author = {Giulia Dall’Osto and Margherita Marsili and Mirko Vanzan and Daniele Toffoli and Mauro Stener and Stefano Corni and Emanuele Coccia}, doi = {10.1021/jacs.4c10033}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2237}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Peeking into the femtosecond hot-carrier dynamics reveals unexpected mechanisms in plasmonic photocatalysis”}, volume = {147}, year = {2025}, }
• (2025). Uranium extraction from seawater via hydrogen bond porous organic cages. JACS, 147(2), 2228--2236. (www)

  @article{ , abstract = {Uranium (U), a high-performing, low-emission energy source, is driving sustainable economic growth. Herein, we synthesized two crystalline phases (HPOC-α and β) by an unreported amidoxime organic cage used for uranium capture. The revealed crystal structures and uranium adsorption test showed that accessible functional groups were essential to uranyl ions sorption. The amidoxime groups presented in HPOC-α gifted it an equilibrium uranium capacity of 1682 mg g –1 and could mostly maintain the performance after adsorption–desorption cycles. In natural seawater, HPOC-α exhibited an impressive uranium recovery capacity of 11.97 mg g –1 during a 30 day field testing, showing potential for economically practical uranium extraction from seawater.}, archive = {J_JACS}, author = {Wanning Wu and Dingyang Chen and Mengyuan Zhang and Xinhui Zhao and Rui Zhao and Caiyun Geng and Jiangtao Jia and Guangshan Zhu}, doi = {10.1021/jacs.4c17520}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2228--2236}, shortjournal = {J. Am. Chem. Soc.}, title = {Uranium extraction from seawater via hydrogen bond porous organic cages}, volume = {147}, year = {2025}, }
• (2025). Photochemically triggered, transient, and oscillatory transcription machineries guide temporal modulation of fibrinogenesis. JACS, 147(2), 2216--2227. (www)

  @article{ , abstract = {Photochemically triggered, transient, and temporally oscillatory-modulated transcription machineries are introduced. The resulting dynamic transcription circuits are implemented to guide photochemically triggered, transient, and oscillatory modulation of thrombin toward temporal control over fibrinogenesis. One system describes the assembly of a reaction module leading to the photochemically triggered formation of an active transcription machinery that, in the presence of RNase H, guides the transient activation of thrombin toward fibrinogenesis. A second system introduces photochemical triggering of a reaction circuit consisting of two coupled transcription machineries, leading to the temporally oscillatory formation and depletion of an intermediate reaction product. The concept is applied to develop a photochemically triggered transcription circuit that, in the presence of RNase H, leads to the oscillatory generation of an intermediate anti-thrombin aptamer-modified product. The oscillating aptamer-modified product induces the rhythmic inhibition of thrombin, accompanied by the cyclic activation and deactivation of the fibrinogenesis process. The operation of the transient and oscillatory-modulated transcription machinery reaction circuits is accompanied by computational kinetic models, allowing to predict the dynamic behaviors of the system under different auxiliary conditions. The phototriggered transient transcription machinery and oscillatory circuit-guided fibrinogenesis is examined under physiological-like conditions and within a human plasma environment.}, archive = {J_JACS}, author = {Jiantong Dong and Itamar Willner}, doi = {10.1021/jacs.4c16829}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2216--2227}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemically triggered, transient, and oscillatory transcription machineries guide temporal modulation of fibrinogenesis}, volume = {147}, year = {2025}, }
• (2025). Spontaneous catalytic reaction of a surfactant in the interfacial microenvironment of colloidal gold nanoparticles. JACS, 147(2), 2206--2215. (www)

  @article{ , abstract = {The performance of nanomaterials is significantly determined by the interfacial microenvironment, in which a surfactant plays an essential role as the adsorbent, but its involvement in the interfacial reaction is often overlooked. Here, it was discovered that citrate and ascorbic acid, the two primarily used surfactants for colloidal gold nanoparticles (Au NPs), can spontaneously undergo catalytic reaction with trace-level nitrogenous residue under ambient environment to form oxime, which is subsequently cleaved to generate CN – or a compound containing the –CN group. Such a catalytic reaction shows wide universality in both reactants, including various carbonaceous and nitrogenous sources, and metal catalysts, including Au, Ag, Fe, Cu, Ni, Pt, and Pd NPs. Furthermore, with the removal of this reaction, adsorbed CO with diverse adsorption configurations was observed via surface-enhanced Raman spectroscopy under ambient conditions without an applied potential. Our work highlights the non-negligible significance of surfactants in interfacial microenvironments and provides crucial insights into the fundamental understanding of interfacial chemical reactions.}, archive = {J_JACS}, author = {Si-Qi Pan and Ping Luo and Qiuting Huang and Jinjuan Xue and Xiang-Dong Tian and Bin Xu and Jianfeng Wu and Jia Chen and Jianwei Xie and Na Yang and Xia-Guang Zhang and Zhong-Qun Tian and Guo-Kun Liu}, doi = {10.1021/jacs.4c16796}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2206--2215}, shortjournal = {J. Am. Chem. Soc.}, title = {Spontaneous catalytic reaction of a surfactant in the interfacial microenvironment of colloidal gold nanoparticles}, volume = {147}, year = {2025}, }
• (2025). Precise preparation of size-uniform two-dimensional platelet micelles through crystallization-assisted rapid microphase separation using all-bottlebrush-type block copolymers with crystalline side chains. JACS, 147(2), 2193--2205. (www)

  @article{ , abstract = {Polymer nanoparticles with low curvature, especially two-dimensional (2D) soft materials, are rich in functions and outstanding properties and have received extensive attention. Crystallization-driven self-assembly (CDSA) of linear semicrystalline block copolymers is currently a common method of constructing 2D platelets of uniform size. Although accompanied by high controllability, this CDSA method usually and inevitably requires a longer aging time and lower assembly concentration, limiting the large-scale preparation of nanoaggregates. In this study, a series of all-bottlebrush-type block copolymers, poly(octadecyl acrylate)- block -poly(oligoethylene glycol methyl ether methacrylate)s are prepared by living polymerization. Driven by the synergistic crystallization of crystalline side chains and the rapid microphase separation of bottlebrush topology, these polymers can assemble into uniform 2D circular platelet micelles in a few minutes, without being affected by a high assembly concentration. In this process, epitaxial growth of the bottlebrush molecules proceeds with rigid cylindrical molecular conformation at the micelle crystallization sites and eventually provides a sandwich-type micelle according to a head-to-head stacking mode. This is explained as a “crystallization-assisted rapid microphase separation” mechanism. The micelle structures are affected by the assembly solvent and temperature, the size of which shows a linear dependence on the assembly temperature below the melting point of the crystalline block, which can be used to precisely control the morphology of these 2D platelets. This study establishes an efficient and rapid method to prepare 2D polymer nanosoft materials, which are promising candidates for further development, preparation, and application of various nanomaterials.}, archive = {J_JACS}, author = {Xiaoliang Yu and Yuanjian Fang and Zhiruo Luo and Xingjian Guo and Lulu Fu and Zhi Fan and Jin Zhao and Hongxiang Xie and Minjie Guo and Bowen Cheng}, doi = {10.1021/jacs.4c16546}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2193--2205}, shortjournal = {J. Am. Chem. Soc.}, title = {Precise preparation of size-uniform two-dimensional platelet micelles through crystallization-assisted rapid microphase separation using all-bottlebrush-type block copolymers with crystalline side chains}, volume = {147}, year = {2025}, }
• (2025). An emerging toolkit of ho3+ sensitized lanthanide nanocrystals with NIR-II excitation and emission for in vivo bioimaging. JACS, 147(2), 2182--2192. (www)

  @article{ , abstract = {Optical imaging in the second near-infrared window (NIR-II, 1000–1700 nm) holds great promise for biomedical detection due to reduced tissue scattering and autofluorescence. However, the rational design of NIR-II probes with superior excitation wavelengths to balance the effects of tissue scattering and water absorption remains a great challenge. To address this issue, here we developed a series of Ho 3+ -sensitized lanthanide (Ln) nanocrystals (NaYF 4 : Ho, Ln@NaYF 4 ) excited at 1143 nm, featuring tunable emissions ranging from 1000 to 2200 nm for in vivo bioimaging. Precise core–shell engineering (β-NaYF 4 : Ho@NaYF 4 : Ln@NaYF 4 and β-NaYF 4 : Ho/Yb@NaYbF 4 @NaYbF 4 : Ln@NaYF 4 ) further endows the Ho 3+ -sensitized system with the capability of energy migration within interfaces, enabling more abundant visible and NIR-II emissions that are unattainable in co-doped structures due to detrimental cross relaxation. Tissue phantom studies demonstrated the superior tissue penetration ability of 1143 photons, especially in imaging experiments through the highly photon-scattering skull, where the fluorescence transmittance of 1143 nm excited nanocrystals was 15% and 10% higher than that of the conventional 808 and 980 excitation, respectively. By leveraging these Ho 3+ -sensitized nanomaterials with multiemission characteristics and well-selected lanthanide nanomaterials with crosstalk-free excitation, we achieved six-channel NIR-II in vivo imaging, enabling the simultaneous visualization of blood vessels, liver, spleen, stomach, intestine, subcutaneous tumors, and lymph nodes in mice. Our research provides new insights into the design of lanthanide nanocrystals with NIR-II excitation and emission and highlights the potential of these materials in in vivo multichannel detection.}, archive = {J_JACS}, author = {Xusheng Wang and Wenxiao Wu and Baofeng Yun and Liwen Huang and Zi-Han Chen and Jiang Ming and Fuheng Zhai and Hongxin Zhang and Fan Zhang}, doi = {10.1021/jacs.4c16451}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2182--2192}, shortjournal = {J. Am. Chem. Soc.}, title = {An emerging toolkit of ho3+ sensitized lanthanide nanocrystals with NIR-II excitation and emission for in vivo bioimaging}, volume = {147}, year = {2025}, }
• (2025). DNA tetrahedron-driven multivalent proteolysis-targeting chimeras: Enhancing protein degradation efficiency and tumor targeting. JACS, 147(2), 2168--2181. (www)

  @article{ , abstract = {Proteolysis-targeting chimeras (PROTACs) are dual-functional molecules composed of a protein of interest (POI) ligand and an E3 ligase ligand connected by a linker, which can recruit POI and E3 ligases simultaneously, thereby inducing the degradation of POI and showing great potential in disease treatment. A challenge in developing PROTACs is the design of linkers and the modification of ligands to establish a multifunctional platform that enhances degradation efficiency and antitumor activity. As a programmable and modifiable nanomaterial, DNA tetrahedron can precisely assemble and selectively recognize molecules and flexibly adjust the distance between molecules, making them ideal linkers. Herein, we developed a multivalent PROTAC based on a DNA tetrahedron, named AS-TD2-PRO. Using DNA tetrahedron as a linker, we combined modules targeting tumor cells, recognizing E3 ligases, and multiple POI together. We took the undruggable target protein signal transducer and activator of transcription 3 (STAT3), associated with the etiology and progression in a variety of malignant tumors, as an example in this study. AS-TD2-PRO with two STAT3 recognition modules demonstrated good potential in enhancing tumor-specific targeting and degradation efficiency compared to traditional bivalent PROTACs. Furthermore, in a mouse tumor model, the superior therapeutic activity of AS-TD2-PRO was observed. Overall, DNA tetrahedron-driven multivalent PROTACs both serve as a proof of principle for multifunctional PROTAC design and introduce a promising avenue for cancer treatment strategies.}, archive = {J_JACS}, author = {Shiqing Li and Tao Zeng and Zhixing Wu and Jiabao Huang and Xiuping Cao and Yana Liu and Shiyan Bai and Qi Chen and Chunsen Li and Chunhua Lu and Huanghao Yang}, doi = {10.1021/jacs.4c16438}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2168--2181}, shortjournal = {J. Am. Chem. Soc.}, title = {DNA tetrahedron-driven multivalent proteolysis-targeting chimeras: Enhancing protein degradation efficiency and tumor targeting}, volume = {147}, year = {2025}, }
• (2025). Key for hexagonal diamond formation: Theoretical and experimental study. JACS, 147(2), 2158--2167. (www)

  @article{ , abstract = {Hexagonal diamond (HD) was reported 60 years ago and has attracted extensive attention owing to its ultrahigh theoretical hardness, 58% superior to its cubic counterpart. However, to date, synthesizing pure HD under high-pressure and high-temperature (HPHT) remains unsuccessful due to the limitations of understanding the formation mechanism. In this work, employing a systematic molecular dynamics simulation, we directly observe the graphite-to-HD transition in a nucleation-growth mechanism. Specifically, HD is formed under quasi-uniaxial compression with higher stress along the [001] direction of graphite and mild-temperature conditions for the scarce sliding of the graphite basal plane, while cubic diamond (CD) is formed when the AB-layer stacking structure of graphite is destroyed and/or freely sliding under a higher temperature. Our theoretic work is well confirmed by the controlled HPHT experiment, where HD was successfully synthesized under quasi-uniaxial conditions with high stress in the [001] g direction, while CD was synthesized when AB-layer stacking was disturbed by higher compressive stress parallel to the basal sheets. Our work not only clarifies the pressure–temperature-controlled mechanisms of graphite-to-diamond transitions but also guides a novel approach to synthesize HD by maintaining the graphite basal plane (001) in an AB-stacking configuration and precisely controlling the basal layer sliding.}, archive = {J_JACS}, author = {Sheng-Cai Zhu and Gu-Wen Chen and Xiao-Hong Yuan and Yong Cheng and Ming-Hao Wan and Baoyin Xu and Ming-sheng Wang and Hu Tang and Yanglong Hou}, doi = {10.1021/jacs.4c16312}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2158--2167}, shortjournal = {J. Am. Chem. Soc.}, title = {Key for hexagonal diamond formation: Theoretical and experimental study}, volume = {147}, year = {2025}, }
• (2025). O2 activation and enzymatic C–H bond activation mediated by a dimanganese cofactor. JACS, 147(2), 2148--2157. (www)

  @article{ , abstract = {Dioxygen (O 2 ) is a potent oxidant used by aerobic organisms for energy transduction and critical biosynthetic processes. Numerous metalloenzymes harness O 2 to mediate C–H bond hydroxylation reactions, but most commonly feature iron or copper ions in their active site cofactors. In contrast, many manganese-activated enzymes─such as glutamine synthetase and isocitrate lyase─perform redox neutral chemical transformations and very few are known to activate O 2 or C–H bonds. Here, we report that the dimanganese-metalated form of the cambialistic monooxygenase SfbO (Mn 2 –SfbO) can efficiently mediate enzymatic C–H bond hydroxylation. The activity of the dimanganese form of SfbO toward substrate hydroxylation is comparable to that of its heterobimetallic Mn/Fe form but exhibits distinct kinetic profiles. Kinetic, spectroscopic, and structural studies invoke a mixed-valent dimanganese cofactor (Mn II Mn III ) in O 2 activation and evidence a stoichiometric role for superoxide in maturing an O 2 -inert Mn II 2 cofactor. Computational studies support a hypothesis wherein superoxide addition to the Mn II 2 cofactor installs a critical bridging hydroxide ligand that stabilizes higher-valent manganese oxidation states. These findings establish the viability of proteinaceous dimanganese cofactors in mediating complex, multistep redox transformations.}, archive = {J_JACS}, author = {Chang Liu and Guodong Rao and Jessica Nguyen and R. David Britt and Jonathan Rittle}, doi = {10.1021/jacs.4c16271}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2148--2157}, shortjournal = {J. Am. Chem. Soc.}, title = {O2 activation and enzymatic C–H bond activation mediated by a dimanganese cofactor}, volume = {147}, year = {2025}, }
• (2025). Unlocking chiral sulfinimidoyl electrophiles: Asymmetric synthesis of sulfinamides catalyzed by anionic stereogenic-at-Cobalt(III) complexes. JACS, 147(2), 2137--2147. (www)

  @article{ , abstract = {Asymmetric catalysis involving a sulfoxide electrophile intermediate presents an efficient methodology for accessing stereogenic-at-sulfur compounds, such as sulfinate esters, sulfinamides, etc. , which have garnered increasing attention in modern pharmaceutical sciences. However, as the aza-analog of sulfoxide electrophiles, the asymmetric issues about electrophilic sulfinimidoyl species remain largely unexplored and represent a significant challenge in sulfur stereochemistry. Herein, we exhibit an anionic stereogenic-at-cobalt(III) complex-catalyzed asymmetric synthesis of chiral sulfinamides via chiral sulfinimidoyl iodide intermediates. Mechanistic investigations reveal that the catalytic cycle is initiated by asymmetric oxidative iodination, generating sulfinimidoyl iodides. These active intermediates subsequently undergo an enantiospecific nucleophilic substitution with water, affording a diverse array of enantioenriched sulfinamides. Notably, these sulfinamides exhibit promising antifungal activities against Sclerotinia sclerotiorum and serve as ideal platform molecules facilitating the stereospecific transformation into various stereogenic aza-sulfur compounds.}, archive = {J_JACS}, author = {Hua-Jie Jiang and Wei Fang and Xinran Chen and Xin-Ran Yu and Yan-Dong Meng and Li-Ping Fang and Meng-Lan Shen and Chuan-Zhi Yao and Qiankun Li and Xin Hong and Jie Yu}, doi = {10.1021/jacs.4c16233}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2137--2147}, shortjournal = {J. Am. Chem. Soc.}, title = {Unlocking chiral sulfinimidoyl electrophiles: Asymmetric synthesis of sulfinamides catalyzed by anionic stereogenic-at-Cobalt(III) complexes}, volume = {147}, year = {2025}, }
• (2025). DNA dendron tagging as a universal way to deliver proteins to cells. JACS, 147(2), 2129--2136. (www)

  @article{ , abstract = {The use of proteins as intracellular probes and therapeutic tools is often limited by poor intracellular delivery. One approach to enabling intracellular protein delivery is to transform proteins into spherical nucleic acid (proSNA) nanoconstructs, with surfaces chemically modified with a dense shell of radially oriented DNA that can engage with cell-surface receptors that facilitate endocytosis. However, proteins often have a limited number of available reactive surface residues for DNA conjugation such that the extent of DNA loading and cellular uptake is restricted. Indeed, DNA surface density and sequence have been correlated with scavenger-receptor engagement, the first step of cellular internalization. Here, we report how branched DNA dendrons with dibenzocyclooctyne groups and proteins genetically engineered to include the noncanonical amino acid azido-phenylalanine for click chemistry can be used to synthesize hybrid DNA dendron-protein architectures that exhibit outstanding cellular internalization properties, without the need for extensive surface modification. In a head-to-head comparison, protein–DNA dendron structures (where DNA is concentrated in a local area) are taken up by cells more rapidly and to a greater extent than proSNAs (where the DNA is evenly distributed). Also, protein-G-rich dendron structures show enhanced uptake compared to protein-T-rich dendron structures, highlighting the importance of oligonucleotide sequence on nanoconjugate uptake. Finally, a generalizable method for chemically tagging proteins with dendrons that does not require mutagenesis is described. When a range of proteins, spanning 42 to 464 kDa, were modified through surface lysines with this method, a significant increase in their cellular uptake (up to 17-fold) compared to proteins that are not coupled to a DNA dendron was observed.}, archive = {J_JACS}, author = {Kathleen H. Ngo and Max E. Distler and Michael Evangelopoulos and Tonatiuh A. Ocampo and Yinglun Ma and Andrew J. Minorik and Chad A. Mirkin}, doi = {10.1021/jacs.4c16205}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2129--2136}, shortjournal = {J. Am. Chem. Soc.}, title = {DNA dendron tagging as a universal way to deliver proteins to cells}, volume = {147}, year = {2025}, }
• (2025). Regioisomeric engineering for multicharge and spin stabilization in two-electron organic catholytes. JACS, 147(2), 2115--2128. (www)

  @article{ , abstract = {Developing multicharge and spin stabilization strategies is fundamental to enhancing the lifetime of functional organic materials, particularly for long-term energy storage in multiredox organic redox flow batteries. Current approaches are limited to the incorporation of electronic substituents to increase or decrease the overall electron density or bulky substituents to sterically shield reactive sites. With the aim to further expand the molecular toolbox for charge and spin stabilization, we introduce regioisomerism as a scaffold-diversifying design element that considers the collective and cumulative electronic and steric contributions from all of the substituents based on their relative regioisomeric arrangements. Through a systematic study of regioisomers of near-planar aromatic cyclic triindoles and nonplanar nonaromatic cyclic tetraindoles, we demonstrate that this regioisomeric engineering strategy significantly enhances the H-cell cycling stability in the above two new classes of 2e – catholytes, even when current strategies failed to stabilize the multicharged species. Density functional theory calculations reveal that the strategy operates by redistributing the charge and spin densities while highlighting the role of aromaticity in charge stabilization. The most stable 2e – catholyte candidate was paired with a viologen derivative anolyte to achieve a proof-of-concept all-organic flow battery with 1.26–1.49 V, 98% capacity retention, and only 0.0117% fade/h and 0.00563% fade/cycle over 400 cycles (192 h), which is the highest capacity retention ever reported over 400 cycles in a multielectron all-organic flow battery setup. We anticipate regioisomeric engineering to be a promising strategy complementary to conventional electronic and steric approaches for multicharge and spin stabilization in other functional organic materials.}, archive = {J_JACS}, author = {H. T. Katie Chung and Tim K. Schramm and Martin Head-Gordon and James Shee and F. Dean Toste}, doi = {10.1021/jacs.4c16027}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2115--2128}, shortjournal = {J. Am. Chem. Soc.}, title = {Regioisomeric engineering for multicharge and spin stabilization in two-electron organic catholytes}, volume = {147}, year = {2025}, }
• (2025). Investigating the molybdenum nitrogenase mechanistic cycle using spectroelectrochemistry. JACS, 147(2), 2099--2114. (www)

  @article{ , abstract = {Molybdenum nitrogenase plays a crucial role in the biological nitrogen cycle by catalyzing the reduction of dinitrogen (N 2 ) to ammonia (NH 3 ) under ambient conditions. However, the underlying mechanisms of nitrogenase catalysis, including electron and proton transfer dynamics, remain only partially understood. In this study, we covalently attached molybdenum nitrogenase (MoFe) to gold electrodes and utilized surface-enhanced infrared absorption spectroscopy (SEIRA) coupled with electrochemistry techniques to investigate its catalytic mechanism. Our biohybrid system enabled electron transfer via a mild mediator, likely mimicking the natural electron flow through the P-cluster to FeMoco, the enzyme’s active site. For the first time, we experimentally observed both terminal and bridging S–H stretching frequencies, resulting from the protonation of bridging sulfides in FeMoco during turnover conditions providing direct evidence of their role in catalysis. These experimental observations are further supported by QM/MM calculations. Additionally, we investigated CO inhibition, demonstrating both CO binding and unbinding dynamics under electrochemical conditions. These insights not only advance our understanding of the mechanistic cycle of molybdenum nitrogenase but also establish a foundation for studying alternative nitrogenases, including vanadium and iron nitrogenases.}, archive = {J_JACS}, author = {Kushal Sengupta and Justin P. Joyce and Laure Decamps and Liqun Kang and Ragnar Bjornsson and Olaf Rüdiger and Serena DeBeer}, doi = {10.1021/jacs.4c16047}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2099--2114}, shortjournal = {J. Am. Chem. Soc.}, title = {Investigating the molybdenum nitrogenase mechanistic cycle using spectroelectrochemistry}, volume = {147}, year = {2025}, }
• (2025). Tuning bro̷nsted acidity by up to 12 pKa units in a redox-active nanopore lined with multifunctional metal sites. JACS, 147(2), 2086--2098. (www)

  @article{ , abstract = {Electrostatic interactions, hydrogen bonding, and solvation effects can alter the free energies of ionizable functional groups in proteins and other nanoporous architectures, allowing such structures to tune acid–base chemistry to support specific functions. Herein, we expand on this theme to examine how metal sites ( M = H 2 , Zn II , Co II , Co I ) affect the p K a of benzoic acid guests bound in discrete porphyrin nanoprisms ( M 3 TriCage ) in CD 3 CN. These host–guest systems were chosen to model how porous metalloporphyrin electrocatalysts might influence H + transfer processes that are needed to support important electrochemical reactions (e.g., reductions of H + , O 2 , or CO 2 ). Usefully, the cavities of the host–guest complexes become hydrated at low water concentrations (10–40 mM), providing a good representation of the active sites of porous electrocatalysts in water. Under these conditions, Lewis acidic Co II and Zn II ions increase the Bro̷nsted acidities of the guests by 4 and 8 p K a units, respectively, while reduction of the Co II sites to anionic Co I sites produces an electrostatic potential that lowers acidity by ca. 4 units (8 units relative to the Co II state). Lacking functional metal sites, H 6 TriCage increases the acidity of the guests by just 2.5 p K a units despite the 12+ charge of this host and contributions from other factors (hydrogen bonding, hydration) that might stabilize the deprotonated guests. Thus, the metal sites have dominant effects on acid–base chemistry in the M 3 TriCages , providing a larger p K a range (12.75 to ≥24.5) for an encapsulated acid than attained via other confinement effects in proteins and artificial porous materials.}, archive = {J_JACS}, author = {Taro J. Jones and Kaitlyn G. Dutton and Harender S. Dhattarwal and P. Thomas Blackburn and Rupak Saha and Richard C. Remsing and Mark C. Lipke}, doi = {10.1021/jacs.4c15873}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2086--2098}, shortjournal = {J. Am. Chem. Soc.}, title = {Tuning bro̷nsted acidity by up to 12 pKa units in a redox-active nanopore lined with multifunctional metal sites}, volume = {147}, year = {2025}, }
• (2025). Chemoselectivity in pd-based dyotropic rearrangement: Development and application in total synthesis of pheromones. JACS, 147(2), 2077--2085. (www)

  @article{ , abstract = {In the dyotropic rearrangement of molecules with semiflexible structures, characterized by a freely rotating static C–C bond, the formation of a mixture of products is common due to the coexistence of several energetically comparable conformers. Herein, we report that it is possible to modulate the shifting groups by adjusting the metal’s coordination sphere in Pd-based dyotropic rearrangement. In the presence of a catalytic amount of Pd(II) salt, the reaction of γ-hydroxyalkenes or γ,δ-dihydroxyalkenes with Selectfluor affords fluorinated tetrahydropyranols or 6,8-dioxabicyclo[3.2.1]octanes (DOBCO), respectively. In this domino process, two C(sp 2 ) and one allylic C(sp 3 ) are sequentially activated and functionalized through a pivotal conformation-controlled chemoselective C(sp 3 )–C(sp 3 ) and C(sp 3 )–Pd(IV) bond metathesis reaction. Mechanistic studies suggest a reaction sequence including 5- exo -trig oxypalladation, Pd oxidation, and chemoselective ring expansion 1,2-Csp 3 /Pd(IV) dyotropic rearrangement, followed by hydroxypalladation of in situ generated dihydropyrans. These findings provide a unique retrosynthetic disconnection for the synthesis of 6,8-DOBCO. We showcase its potential by developing a concise synthesis of three important pheromones. Notably, (+)-frontalin is synthesized from a commercially available 1,5-diene in only two steps, utilizing Sharpless catalytic asymmetric dihydroxylation and Pd-catalyzed domino cyclization developed in this study.}, archive = {J_JACS}, author = {Jing Gong and Qian Wang and Jieping Zhu}, doi = {10.1021/jacs.4c15764}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2077--2085}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemoselectivity in pd-based dyotropic rearrangement: Development and application in total synthesis of pheromones}, volume = {147}, year = {2025}, }
• (2025). Mechanistic investigation of the Ce(III) chloride photoredox catalysis system: Understanding the role of alcohols as additives. JACS, 147(2), 2061--2076. (www)

  @article{ , abstract = {Photocatalytic C–H activation is an emerging area of research. While cerium chloride photocatalysts have been extensively studied, the role of alcohol additives in these systems remains a subject of ongoing discussion. It was demonstrated that the photocatalyst [NEt 4 ] 2 [Ce IV Cl 6 ] ( 1 ) produces •Cl and added alcohols exhibit zero-order kinetics. Prior studies by other researchers suggested that 1 and alcohols lead to cerium alkoxide [Ce–OR] and alkoxy radical intermediates. To understand these seemingly divergent mechanistic proposals, an expanded investigation comparing cerium(IV) catalyst 1 and cerium(III) complex [NEt 4 ] 3 [Ce III Cl 6 ] ( 2 ), which exhibit markedly different reactivity and C–H selectivity, is disclosed. Our findings reveal that alcohol additives accelerate the conversion of cerium(III) to cerium(IV) catalysts, forming key intermediates such as [NEt 4 ] 2 [Ce III Cl 5 (HOCH 3 )] ( 5 ) and [NEt 4 ] 2 [Ce IV Cl 5 (OCH 3 )] ( 6 ), driven by excited-state di- tert -butyl azodicarboxylate under blue light irradiation. The active complex 6 releases the •OCH 3 radical, in sharp contrast to •Cl radicals initiated by cerium(IV) photoredox catalyst 1 . These different reactivity and selectivity profiles can be understood in the context of complex 5 generation and in situ formation of base to afford complex 6 . Experimental validation shows enhanced selectivity toward C–H bonds with different reactivity with catalyst 1 and methanol upon the addition of base and decreased selectivity with catalyst 2 and methanol upon the addition of acid. These findings unify the previously contrasting observations of cerium halide/alkoxide photocatalytic systems and provide a comprehensive understanding on the essential role of base/acid and alcohol in selectivity and reactivity.}, archive = {J_JACS}, author = {Qiaomu Yang and Ellen Song and Yu Wu and Chenshuai Li and Michael R. Gau and Jessica M. Anna and Eric J. Schelter and Patrick J. Walsh}, doi = {10.1021/jacs.4c15627}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2061--2076}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanistic investigation of the Ce(III) chloride photoredox catalysis system: Understanding the role of alcohols as additives}, volume = {147}, year = {2025}, }
• (2025). Selective protein (Post-)modifications through dynamic covalent chemistry: Self-activated SNAr reactions. JACS, 147(2), 2049--2060. (www)

  @article{ , abstract = {S N Ar reactions were remarkably accelerated using a pretargeting and activating unit based on dynamic covalent chemistry (DCvC). A Cys attack at the C–F bond on the aromatic ring of salicylaldehyde derivatives was only observed upon iminium formation with a neighboring Lys residue of model small peptides. Such self-activation was ascribed to the stronger electron-withdrawing capability of the iminium bond with respect to that of the parent aldehyde that stabilized the transition state of the reaction, together with the higher preorganization of the reactive groups in the cationic aldiminium species. This approach was further applied for the functionalization of two antibodies. In both cases, the presence of the aldehyde group in close proximity to the reactive C–F bond resulted in a noteworthy increase in bioconjugation yields, with excellent chemo-selectivity. Whereas the modification of an IgG1 antibody led to stochastic product distributions, microenvironment selectivity was noted when employing IgG4, in line with the lower number of Lys residues in the hinge region of the latter. Additionally, the postfunctionalization of the modified antibodies was attained through the dynamic covalent exchange of the tethered iminium derivative with hydrazides, representing an unprecedented “tag and modify” selective bioconjugation strategy based on DCvC.}, archive = {J_JACS}, author = {Ferran Esteve and Jean-Louis Schmitt and Sergii Kolodych and Oleksandr Koniev and Jean-Marie Lehn}, doi = {10.1021/jacs.4c15421}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2049--2060}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective protein (Post-)modifications through dynamic covalent chemistry: Self-activated SNAr reactions}, volume = {147}, year = {2025}, }
• (2025). Light-controlled intracellular synthesis of poly(luciferin) polymers induces cell paraptosis. JACS, 147(2), 2037--2048. (www)

  @article{ , abstract = {Accumulation of misfolded proteins challenges cellular proteostasis and is implicated in aging and chronic disorders. Cancer cells, moreover, face an elevated level of basal proteotoxic stress; hence, exacerbating endoplasmic reticulum (ER) stress has been shown to induce programmed cell death while enhancing anticancer immunogenicity. We hypothesize that hydrophobic abiotic macromolecules can trigger a similar stress response. Most polymers and nanoparticles, however, are sequestered in endo/lysosomes after endocytosis, which prevents their interaction with the proteostasis machinery. We adopted an in situ polymerization approach to synthesize polymers in cells with cell-permeable monomers. Specifically, we developed a biocompatible polycondensation between l -cysteine and 2-cyanobenzothiazole (CBT) with photochemical control to form insoluble poly(luciferin) aggregates. We identified that in situ polymerization activates the BiP-PERK-CHOP pathway of the unfolded protein response and that the unresolved ER stress initiates a form of regulated cell death consistent with paraptosis. In addition, the dying cells emit damage-associated molecular patterns (DAMPs), indicating an immunogenic cell death that could potentiate antitumor immunity. Our results show that in situ polymerization mimics misfolded protein aggregates to induce proteotoxic stress and cancer cell death, offering a novel therapeutic strategy to exploit cancer vulnerability.}, archive = {J_JACS}, author = {Sheng-Yao Dai and Zhen Xiao and Fangfang Shen and Irene Lim and Jianghong Rao}, doi = {10.1021/jacs.4c15644}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2037--2048}, shortjournal = {J. Am. Chem. Soc.}, title = {Light-controlled intracellular synthesis of poly(luciferin) polymers induces cell paraptosis}, volume = {147}, year = {2025}, }
• (2025). Diatomic palladium catalyst for enhanced photocatalytic water-donating transfer hydrogenation. JACS, 147(2), 2029--2036. (www)

  @article{ , abstract = {Diatomic catalysts (DACs) present unique opportunities for harnessing ensemble effects between adjacent metal atoms, thus, expanding the properties of single-atom catalysts (SACs). However, the precise preparation and characterization of this type of catalyst remains challenging. Following a precursor-preselected strategy, here, we report the synthesis of a carbon nitride-supported Pd-DAC, which achieves an excellent yield of 92% for photocatalytic water-donating transfer hydrogenation of 4-vinylphenol to 4-ethylphenol, far exceeding that of other metal species, including Pd single atoms (47%) and nanoparticles (1%). Combining transmission electron microscopy with standardized machine learning atom-detection methods confirms the stabilization of a substantial fraction of dimeric Pd species over carbon nitride. Density functional theory (DFT) simulations associate the outstanding performance of Pd-DAC to enhanced substrate activation in the hydrogenation path compared to Pd-SAC. The work provides criteria for DACs characterization and demonstrates a transfer hydrogenation application that is sustainable and eco-friendly over conventional hydrogenation technologies.}, archive = {J_JACS}, author = {En Zhao and Jordi Morales-Vidal and Yue Yang and Sharon Mitchell and Yinlong Zhu and Zhiwei Hu and Jin-Ming Chen and Shu-Chih Haw and Ting-Shan Chan and Ziyi Fan and Zhu-Jun Wang and Núria López and Javier Pérez-Ramírez and Zupeng Chen}, doi = {10.1021/jacs.4c15235}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2029--2036}, shortjournal = {J. Am. Chem. Soc.}, title = {Diatomic palladium catalyst for enhanced photocatalytic water-donating transfer hydrogenation}, volume = {147}, year = {2025}, }
• (2025). Dearomative addition-hydrogen autotransfer for branch-selective N-heteroaryl C–H functionalization via ruthenium-catalyzed C–C couplings of diene pronucleophiles. JACS, 147(2), 2021--2028. (www)

  @article{ , abstract = {A novel mechanism for N -heteroaryl C–H functionalization via dearomative addition-hydrogen autotransfer is described. Upon exposure to the catalyst derived from RuHCl(CO)(PPh 3 ) 3 and Xantphos, dienes 1a – 1g suffer hydroruthenation to form allylruthenium nucleophiles that engage in N -heteroaryl addition-β-hydride elimination to furnish branched products of C–C coupling 3a – 3s and 4a – 4f . Oxidative cleavage of isoprene adducts 3j , 3k , 3l , and 3n followed by ruthenium-catalyzed dynamic kinetic asymmetric ketone reduction provides enantiomerically enriched N -heteroarylethyl alcohols 6a – 6d and, therefrom, N -heteroarylethyl amines 7a – 7d . Density functional theory calculations correlate experimentally observed regioselectivities with the magnitude of the N -heteroaryl LUMO coefficients and corroborate rate-determining dearomative allylruthenium addition. In the presence of 2-propanol and trifluoroethanol, dearomatized adducts derived from pyrimidine 2a and quinazoline 2n were isolated and characterized.}, archive = {J_JACS}, author = {Jonathan Z. Shezaf and Seoyoung Lee and Yhin Sarah Teoh and Zachary H. Strong and Pei-Pei Xie and Jessica Wu and Peng Liu and Michael J. Krische}, doi = {10.1021/jacs.4c15157}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2021--2028}, shortjournal = {J. Am. Chem. Soc.}, title = {Dearomative addition-hydrogen autotransfer for branch-selective N-heteroaryl C–H functionalization via ruthenium-catalyzed C–C couplings of diene pronucleophiles}, volume = {147}, year = {2025}, }
• (2025). The midas touch by iridium: A second near-infrared aggregation-induced emission-active metallo-agent for exceptional phototheranostics of breast cancer. JACS, 147(2), 2010--2020. (www)

  @article{ , abstract = {Developing small organic molecular phototheranostic agents with second near-infrared (NIR-II) aggregation-induced emission (AIE) is paramount for the phototriggered diagnostic imaging and synchronous in situ therapy of cancer via an excellent balance of the excited states energy dissipations. In this study, a multifunctional iridium(III) complex is exploited by the coordination of an AIE-active N^N ancillary ligand with a trivalent iridium ion. The resultant complex DPTPzIr significantly outperforms its parent ligand in terms of absorption/emission wavelengths, reactive oxygen species (ROS) production, and photothermal conversion, which simultaneously endow DPTPzIr nanoparticles with matched absorption peak to commercial 808 nm laser, the longest NIR-II emission peak (above 1100 nm) among those previously reported AIE iridium(III) complexes, potentiated type-I ROS generation, and as high as 60.5% of photothermal conversion efficiency. Consequently, DPTPzIr nanoparticles perform well in multimodal image-guided photodynamic therapy-photothermal therapy for breast cancer in tumor-bearing mice, enabling precise tumor diagnosis and complete ablation with high biocompatibility. Our present work provides a simple, feasible, and effective paradigm for the development of advanced phototheranostic agents.}, archive = {J_JACS}, author = {Caifa You and Leyuan Tian and Jun Zhu and Lei Wang and Ben Zhong Tang and Dong Wang}, doi = {10.1021/jacs.4c15150}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2010--2020}, shortjournal = {J. Am. Chem. Soc.}, title = {The midas touch by iridium: A second near-infrared aggregation-induced emission-active metallo-agent for exceptional phototheranostics of breast cancer}, volume = {147}, year = {2025}, }
• (2025). Dirhodium–Palladium dual-catalyzed [1 + 1 + 3] annulation to heterocycles using primary amines or H2O as the heteroatom sources. JACS, 147(2), 2000--2009. (www)

  @article{ , abstract = {The ever-increasing demand in chemical biology and medicinal research requires the development of new synthetic methods for the rapid construction of libraries of heterocycles from simple raw materials. In this context, the utilization of primary amines or H 2 O as the simple N - or O -sources in the assembly of a heterocyclic ring skeleton is highly desirable from the viewpoint of atom- and step-economy. Herein, we describe a highly efficient three-component reaction of diazo, allylic diacetates, and commercially available anilines (or H 2 O) to access structurally diverse pyrrolidine and tetrahydrofuran derivatives. This formal [1 + 1 + 3] annulation reaction features high efficiency, good yields, and broad functional group compatibility, making it a versatile and robust platform for the (formal) synthesis of several important bioactive molecules. Mechanistic studies suggested that the dirhodium–palladium bimetallic relay catalysis should play a key role in the successive steps of the current reaction, including sequential carbene insertion into the X–H bond and double allylic substitutions, thus allowing for building up molecular complexity from these simple raw materials.}, archive = {J_JACS}, author = {Jie Xu and Gaoyin Wang and Kuiling Ding and Xiaoming Wang}, doi = {10.1021/jacs.4c15161}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {2000--2009}, shortjournal = {J. Am. Chem. Soc.}, title = {Dirhodium–Palladium dual-catalyzed [1 + 1 + 3] annulation to heterocycles using primary amines or H2O as the heteroatom sources}, volume = {147}, year = {2025}, }
• (2025). Crystal lattice analysis for 2D nanomorphology prediction of phase-separated materials. JACS, 147(2), 1991--1999. (www)

  @article{ , abstract = {Spontaneous phase separation of materials is a powerful strategy to generate highly defined 2D nanomorphologies with novel properties and functions. Exemplary are such morphologies in block copolymers or amphiphilic systems, whose formation can be well predicted based on parameters such as volume fraction and shape factor. In contrast, the formation of 2D nanomorphologies is currently unpredictable in materials perfectly defined at the molecular level, in which crystallinity plays a significant role. Here, we introduce a crystal lattice analysis to predict a priori the formation of 2D nanomorphologies from the crystalline units in phase-separated soft materials. We show that the formation of lamellar morphologies, their domain spacings, and thermal transition temperatures of such materials can be predicted using a straightforward crystal lattice analysis workflow. We envision this approach to facilitate the design and discovery of new materials with 2D nanomorphologies that are essential for next-generation electronic applications.}, archive = {J_JACS}, author = {Tobias Schnitzer and Bart W. L. van den Bersselaar and Brigitte A. G. Lamers and Martin H. C. van Son and Stefan J. D. Maessen and Freek V. de Graaf and Bas F. M. de Waal and Nils Trapp and Ghislaine Vantomme and E. W. Meijer}, doi = {10.1021/jacs.4c14964}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1991--1999}, shortjournal = {J. Am. Chem. Soc.}, title = {Crystal lattice analysis for 2D nanomorphology prediction of phase-separated materials}, volume = {147}, year = {2025}, }
• (2025). An intermediate-aided perovskite phase purification for high-performance solar cells. JACS, 147(2), 1980--1990. (www)

  @article{ , abstract = {In recent years, perovskite solar cells (PSCs) have garnered considerable attention as a prime candidate for next-generation photovoltaic technology. Ensuring the structural stability of perovskites is crucial to the operational reliability of these devices. However, the nonphotoactive yellow phase (δ-FAPbI 3 ) of formamidine (FA)-based perovskites is more favorable in thermodynamics, making it challenging to achieve pure α phase in crystallization. Herein, we introduce a language machine learning approach to analyze suitable additives to achieve the desired phase purification. By fast analyzing ∼10 6 abstracts in chemistry and materials science, our approach identifies aminoguanidine (AG) hydrochloride as a promising candidate for intermediate phase formation during nucleation. The experiments confirm that AG forms a novel one-dimensional intermediate phase (AGPbI 3 ), which suppresses the solvent intermediate phase and δ-phase formation and promotes development of the α-phase. Consequently, the efficiency of the solar cells increased from 23.99 to 25.46%. The long-term thermal stability and photostability were significantly enhanced owing to the purified α-phase, maintaining 82% of the initial efficiency after 1056 h aging at 85 °C and 94.6% of the initial efficiency after 835 h of illumination in an N 2 atmosphere, respectively. This strategy also enhanced the performance of flexible solar cells, increasing their efficiency from 21.24 to 22.86%. This work is designed to fast explore new intermediate phases in improving the efficiency and operation stability of thin-film solar cells.}, archive = {J_JACS}, author = {Jinghao Ge and Yiru Huang and Xuexiao Chen and Yong Wang and Hanqing Zeng and Yiran Tao and Zixin Zeng and Lu Zhang and Lei Zhang and Xinhui Lu and Sai Wing Tsang and Jiaxue You and Alex K.Y. Jen and Shengzhong Frank Liu}, doi = {10.1021/jacs.4c14955}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1980--1990}, shortjournal = {J. Am. Chem. Soc.}, title = {An intermediate-aided perovskite phase purification for high-performance solar cells}, volume = {147}, year = {2025}, }
• (2025). Surface oxygen vacancies on copper-doped titanium dioxide for photocatalytic nitrate-to-ammonia reduction. JACS, 147(2), 1968--1979. (www)

  @article{ , abstract = {Photocatalytic transformation of nitrate (NO 3 – ) in wastewater into ammonia (NH 3 ) is a challenge in the detoxification and recycling of limited nitrogen resources. In particular, previously reported photocatalysts cannot promote the reaction using water as an electron donor. Herein, we report that copper-doped titanium dioxide (Cu-TiO 2 ) powders, prepared via the sol–gel method and subsequent calcination, promote NO 3 – -to-NH 3 reduction in water. The Cu 2+ doping into TiO 2 creates a large number of surface oxygen vacancies (OV surf ), which are stable even under aerated conditions. The Ti 3+ and Cu 2+ atoms adjacent to OV surf behave as active sites for the NO 3 – -to-NH 3 reduction. Doping with an appropriate amount of Cu 2+ and calcination at an appropriate temperature produce the catalysts with a large number of OV surf , while maintaining a high conductivity, and exhibit a high photocatalytic activity.}, archive = {J_JACS}, author = {Wataru Hiramatsu and Yasuhiro Shiraishi and Satoshi Ichikawa and Shunsuke Tanaka and Yasuo Kawada and Chihiro Hiraiwa and Takayuki Hirai}, doi = {10.1021/jacs.4c14804}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1968--1979}, shortjournal = {J. Am. Chem. Soc.}, title = {Surface oxygen vacancies on copper-doped titanium dioxide for photocatalytic nitrate-to-ammonia reduction}, volume = {147}, year = {2025}, }
• (2025). An automated workflow to discover the Structure–Stability relations for radiation hard molecular semiconductors. JACS, 147(2), 1957--1967. (www)

  @article{ , abstract = {Emerging photovoltaics for outer space applications are one of the many examples where radiation hard molecular semiconductors are essential. However, due to a lack of general design principles, their resilience against extra-terrestrial high-energy radiation can currently not be predicted. In this work, the discovery of radiation hard materials is accelerated by combining the strengths of high-throughput, lab automation and machine learning. This way, a large material library of more than 130 organic hole transport materials is automatically processed, degraded, and measured. The materials are degraded under ultraviolet-C (UVC) light in a nitrogen atmosphere, serving as the conditions for electromagnetic radiation hardness tests. A value closely related to the differential quantum yield for photodegradation is extracted from the evolution of the UV–visible (UV–vis) spectra over time and used as a stability target. Following this procedure, a stability ranking spanning over 3 orders of magnitude was obtained. Combining Gaussian Process Regression based on predictors from structural fingerprints and manual filtering of the materials by features, structure–stability relations for UVC stable materials could be found: Fused aromatic ring clusters are beneficial, whereas thiophene, methoxy and vinylene groups are detrimental. Comparing the UV–vis spectra of the degraded material in film and solution, bond cleavage could be made out as the leading degradation mechanism. Even though UVC light can in principle break most organic bonds, the stable materials are able to distribute and dissipate the energy well enough so that the chemical structures remain stable. The established predictive model quantifies the effect of specific molecular features on UVC stability, allowing chemists to consider UVC stability in their molecular design strategy. In the future, a larger data set will allow to inversely design molecular semiconductors which show high performance and radiation hardness at the same time.}, archive = {J_JACS}, author = {Andreas J. Bornschlegl and Patrick Duchstein and Jianchang Wu and Juan S. Rocha-Ortiz and Mauricio Caicedo-Reina and Alejandro Ortiz and Braulio Insuasty and Dirk Zahn and Larry Lüer and Christoph J. Brabec}, doi = {10.1021/jacs.4c14824}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1957--1967}, shortjournal = {J. Am. Chem. Soc.}, title = {An automated workflow to discover the Structure–Stability relations for radiation hard molecular semiconductors}, volume = {147}, year = {2025}, }
• (2025). Catalytic enantioselective synthesis of 1,4-(Hetero) dicarbonyl compounds through α-carbonyl umpolung. JACS, 147(2), 1948--1956. (www)

  @article{ , abstract = {The enantioselective synthesis of 1,4-dicarbonyl compounds continues to pose a significant challenge in organic synthesis, and a catalytic process which generates two adjacent stereogenic centers with full stereochemical control is lacking until now. The 1,4-relationship of the functional groups requires an Umpolung strategy as one of the α-carbonyl positions has to be inverted into an electrophilic center to react with a normal enolate. We report herein the highly enantio- and diastereoselective addition of silyl ketene acetals toward electrophilic 1-azaallyl cations to furnish chiral 4-hydrazonoesters, which are masked 1,4-dicarbonyl compounds. The products carrying up to 2 new stereogenic centers were obtained in excellent yields across a broad substrate scope. As precursors to the 1-azaallyl cations, α-acetoxy hydrazones were employed and ionized with a strongly Lewis acidic, chiral silylium imidodiphosphorimidate (IDPi). The resulting ion pair was characterized with NMR and mass spectroscopy, while DFT calculations provided further insights into the reaction mechanism. In addition, the products were successfully converted into enantiomerically highly enriched b-cyano and b-formyl esters as well as γ-lactams and γ-amino acids, as demonstrated by syntheses of the anticonvulsant agent pregabalin and a brivaracetam precursor.}, archive = {J_JACS}, author = {Till Friedmann and Karl Schuppe and Michael Laue and Ole Goldammer and Christoph Schneider}, doi = {10.1021/jacs.4c14826}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1948--1956}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic enantioselective synthesis of 1,4-(Hetero) dicarbonyl compounds through α-carbonyl umpolung}, volume = {147}, year = {2025}, }
• (2025). A cosolvent electrolyte boosting electrochemical alkynol semihydrogenation. JACS, 147(2), 1938--1947. (www)

  @article{ , abstract = {Green electricity-driven alkenol electrosynthesis via electrocatalytic alkynol semihydrogenation represents a sustainable route to conventional thermocatalysis. Both the electrocatalyst and electrolyte strongly impact the semihydrogenation performance. Despite significant progress in developing sophisticated electrocatalysts, a well-designed electrolyte in conjunction with industrial catalysts is an attractive strategy to advance the industrialization process of electrocatalytic alkynol semihydrogenation, but remains unexplored. Here, we develop a dimethyl sulfoxide (DMSO)-H 2 O cosolvent electrolyte for electrocatalytic alkynol semihydrogenation. At an alkynol conversion of about 100%, the DMSO-H 2 O electrolyte compared to the DMSO-free counterpart enables the alkenol selectivity on Cu catalysts to be promoted from 60–70% to over 90% at all measured current densities; meanwhile, the reaction rate is slightly decreased due to the inhibited water dissociation. Mechanistic studies reveal that the strong hydrogen-bond interactions between DMSO and H 2 O suppress the dissociation of interfacial H 2 O, leading to a decreased H* coverage at the electrode surface. The decreased H* coverage hinders the overhydrogenation of alkynols and favors the production of alkenols. Remarkably, the DMSO-induced enhancement of alkenol selectivity is applicable to a set of commercial catalysts and to the semihydrogenation of various alkynols. Eventually, a scaled-up 3 × 100 cm 2 electrolyzer stack is established to achieve an alkynol conversion of ∼96% and an alkenol selectivity of ∼95% in the cosolvent electrolyte. This work not only presents an electrolyte strategy for boosting alkenol electrosynthesis, but also highlights the possibility of sustainable alkenol electro-production.}, archive = {J_JACS}, author = {Yuan Zhao and Jia Wang and Xingzhou Zha and Xuedi Sheng and Lei Dong and Xin-Ping Wu and Zhen Liu and Hongliang Jiang and Chunzhong Li}, doi = {10.1021/jacs.4c14773}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1938--1947}, shortjournal = {J. Am. Chem. Soc.}, title = {A cosolvent electrolyte boosting electrochemical alkynol semihydrogenation}, volume = {147}, year = {2025}, }
• (2025). Discovery of a natural ent-kaurene diterpenoid oridonin as an e3 ligase recruiter for PROTACs. JACS, 147(2), 1920--1937. (www)

  @article{ , abstract = {PROTACs have emerged as a therapeutic modality for the targeted degradation of proteins of interest (POIs). Central to PROTAC technology are the E3 ligase recruiters, yet only a few of them have been identified due to the lack of ligandable pockets in ligases, especially among single-subunit ligases. We propose that binders of partner proteins of single-subunit ligases could be repurposed as new ligase recruiters. MDM2 is a single-subunit ligase overexpressed in tumors. Nucleolin (NCL) is an MDM2 partner protein that displays a similar tumor-specific overexpression pattern and nuclear-cytoplasmic shuttling role to MDM2. Furthermore, NCL is selectively translocated on the tumor cell surface, where it acts as an internalization receptor for its binders. We reveal that the NCL-binding Oridonin (Ori), a natural ent-kaurene diterpenoid, is capable of recruiting MDM2 by employing NCL as a molecular bridge. We design Ori-based PROTACs for modulating oncogenic POIs, including BRD4 and EGFR. These PROTACs direct the assembly of MDM2-NCL-PROTAC-POI complexes to induce proteasomal degradation of POIs and tumor shrinkage. In addition to its role as a ligase engaged by PROTACs, MDM2, along with its homologue MDMX, plays a nonredundant function in inhibiting p53 activity. Dual inhibition of MDM2/X is proposed as a promising antitumor strategy. We demonstrate that Ori also recruits MDMX in an NCL-dependent manner. Ori-based homo-PROTACs induce MDM2/X dual degradation and attenuate tumor progression. Our findings prove the feasibility of repurposing the binders of ligase partner proteins as new ligase recruiters in PROTACs and highlight the potential of Ori as an MDM2/X recruiter.}, archive = {J_JACS}, author = {Jie Huang and Xuekun Fu and Fang Qiu and Zhijian Liang and Chunhao Cao and Zhuqian Wang and Hongzhen Chen and Siran Yue and Duoli Xie and Yiying Liang and Aiping Lu and Chao Liang}, doi = {10.1021/jacs.4c14650}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1920--1937}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of a natural ent-kaurene diterpenoid oridonin as an e3 ligase recruiter for PROTACs}, volume = {147}, year = {2025}, }
• (2025). Metabotropic GABAB receptor activation induced by g protein coupling. JACS, 147(2), 1911--1919. (www)

  @article{ , abstract = {G protein-coupled receptors (GPCRs) play central roles in regulating cellular responses through heterotrimeric G proteins (GP). Extensive studies have elucidated the complex cellular signaling mediated by GPCRs that accompany dynamic conformational changes upon activation. However, there has been less focus on the role of the GP on the activation process, particularly for class C GPCRs that function as obligate dimers. Herein, we report the pivotal role of GP coupling on the dynamic activation process for the metabotropic γ-aminobutyric acid receptor (GABA B R) based on extensive atomistic simulations. We find that GP coupling triggers drastic conformational changes in the GABA B R transmembrane domain (TMD), while an agonist alone is insufficient to shift the equilibrium state from the inactive to the active states. These conformational changes induced by GP coupling destabilize the inactive TM5/TM5 interface, shifting the equilibrium toward the activated TM6/TM6 interface. This active role of the GP in activation provides fresh insights into the activation mechanism of GABA B R and perhaps other class C GPCRs. These insights should aid in the development of more potent and selective drugs.}, archive = {J_JACS}, author = {Moon Young Yang and Soo-Kyung Kim and William A. Goddard, III}, doi = {10.1021/jacs.4c14672}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1911--1919}, shortjournal = {J. Am. Chem. Soc.}, title = {Metabotropic GABAB receptor activation induced by g protein coupling}, volume = {147}, year = {2025}, }
• (2025). Dissecting the molecular structure of the Air/Ice interface from quantum simulations of the sum-frequency generation spectrum. JACS, 147(2), 1903--1910. (www)

  @article{ , abstract = {Ice interfaces are pivotal in mediating key chemical and physical processes such as heterogeneous chemical reactions in the environment, ice nucleation, and cloud microphysics. At the ice surface, water molecules form a quasi-liquid layer (QLL) with properties distinct from those of the bulk. Despite numerous experimental and theoretical studies, a molecular-level understanding of the QLL has remained elusive. In this work, we use state-of-the-art quantum dynamics simulations with a realistic data-driven many-body potential to dissect the vibrational sum-frequency generation (vSFG) spectrum of the air/ice interface in terms of contributions arising from individual molecular layers, orientations, and hydrogen-bonding topologies that determine the QLL properties. The agreement between experimental and simulated spectra provides a realistic molecular picture of the evolution of the QLL as a function of the temperature without the need for empirical adjustments. The emergence of specific features in the experimental vSFG spectrum suggests that surface restructuring may occur at lower temperatures. This work not only underscores the critical role of many-body interactions and nuclear quantum effects in understanding ice surfaces but also provides a definitive molecular-level picture of the QLL, which plays a central role in multiphase and heterogeneous processes of relevance to a range of fields, including atmospheric chemistry, cryopreservation, and materials science.}, archive = {J_JACS}, author = {Richa Rashmi and Francesco Paesani}, doi = {10.1021/jacs.4c14610}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1903--1910}, shortjournal = {J. Am. Chem. Soc.}, title = {Dissecting the molecular structure of the Air/Ice interface from quantum simulations of the sum-frequency generation spectrum}, volume = {147}, year = {2025}, }
• (2025). A borenium-borane composite for exhaustive reduction of oxo-chemicals. JACS, 147(2), 1893--1902. (www)

  @article{ , abstract = {Borenium ions have attracted significant attention in organic transformations due to their strong Lewis acidity. The reported borenium ions are often stabilized by sterically demanding substituents and strong coordination bonds. Herein, we have synthesized a small steric borenium-equivalent NH 3 BH 2 OTf and subjected it to the exhaustive reduction of a carboxylic functional group to a methyl group, which shows broad functional group tolerance. This system can also undergo a reductive deoxygenation reaction of alcohols, ethers, and other oxo-chemicals ( > 100 examples). The mechanistic studies revealed that the in situ -generated NH 3 BH 2 OTf/[NH 3 BH 2 (sol)]OTf, rendering the borenium-like properties, plays a crucial role in these transformations by interacting with the O atom of substrates to activate the carbonyl group and facilitating the cleavage of the C–O bond. This work has not only offered a system for the exhaustive reduction of oxo-chemicals but is also of great significance for providing insight into the application of the borenium ions in various reactions.}, archive = {J_JACS}, author = {Xinying Li and Kai Wang and Yi-Ge Li and Qianyi Zhao and Yan-Na Ma and Xuenian Chen}, doi = {10.1021/jacs.4c14514}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1893--1902}, shortjournal = {J. Am. Chem. Soc.}, title = {A borenium-borane composite for exhaustive reduction of oxo-chemicals}, volume = {147}, year = {2025}, }
• (2025). Modulation of the second-beyond coordination structure in single-atom electrocatalysts for confirmed promotion of ammonia synthesis. JACS, 147(2), 1884--1892. (www)

  @article{ , abstract = {Although microenvironments surrounding single-atom catalysts (SACs) have been widely demonstrated to have a remarkable effect on their catalytic performances, it remains unclear whether the local structure beyond the secondary coordination shells works as well or not. Herein, we employed a series of metal–organic frameworks (MOFs) with well-defined and tunable second-beyond coordination spheres as model SAC electrocatalysts to discuss the influence of long-distance structure on the ammonia synthesis from nitrate, which were synthesized and denoted as Cu 12 -NDI-X (X = NMe 2 , H, F). It is first experimentally confirmed that the remote substitution of function groups beyond the secondary coordination sphere can remarkably affect the activity of ammonia synthesis. Meanwhile, the -H endowed Cu 12 -NND-H exhibits a superior ammonia yield (35.1 mg·h –1 ·mg cat –1 ) and FE (98.7%) to those modified with -NMe 2 and -F, which also shows good stability at 100 mA·cm –2 . The remarkable promotion of the modulated second-beyond coordination structure is unraveled to result from the adjustable d -band center of the Cu active site leading to promoted adsorption of the NO 3 – and protonation of key intermediates. Encouraged by its extraordinary ammonia yield, we employed the Cu 12 -NND-H electrode as a cathode to assemble one rechargeable Zn-nitrate battery that exhibits an impressive power density of 34.0 mW·cm –2 , demonstrating its promising application in energy conversion and storage.}, archive = {J_JACS}, author = {Qinglin Li and Lin Luo and Xiangyang Guo and Rong Wang and Jinfeng Liu and Wenjun Fan and Zhaochi Feng and Fuxiang Zhang}, doi = {10.1021/jacs.4c14498}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1884--1892}, shortjournal = {J. Am. Chem. Soc.}, title = {Modulation of the second-beyond coordination structure in single-atom electrocatalysts for confirmed promotion of ammonia synthesis}, volume = {147}, year = {2025}, }
• (2025). Use of in situ X-ray absorption to probe reactivity: A catalysis golden rule. JACS, 147(2), 1875--1883. (www)

  @article{ , abstract = {The decomposition of ozone on supported manganese oxide catalysts, studied here, exemplifies reactions involving electron transfer. In situ extended X-ray absorption fine-structure spectra (Mn K-edge) on in situ treated samples show that the supported phase in MnO x /SiO 2 resembles Mn 3 O 4 while that in MnO x /Al 2 O 3 samples resembles MnO 2 . In situ Raman spectroscopy shows the involvement of a common peroxide surface species. Kinetic data indicate a nonuniform surface and a rate-determining step (rds) involving electron transfer from the peroxide intermediate. The activation energy for all the catalysts is the same, indicating that the pre-exponential factor controls the rate. This can be associated with the electronic partition function (unoccupied density of states (DOS)), and X-ray absorption near-edge spectroscopy duly shows that the areas of the pre-edge peaks due to 1s to 3d transitions track the reactivity trends. The relation to the unoccupied DOS is analogous to Fermi’s Golden Rule for electronic transitions, and we denote the finding here, applicable to reactions involving electron transfer, as a Catalysis Golden Rule.}, archive = {J_JACS}, author = {S. Ted Oyama and Yong-Kul Lee}, doi = {10.1021/jacs.4c14098}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1875--1883}, shortjournal = {J. Am. Chem. Soc.}, title = {Use of in situ X-ray absorption to probe reactivity: A catalysis golden rule}, volume = {147}, year = {2025}, }
• (2025). Site-selective Copper(I)-catalyzed hydrogenation of amides. JACS, 147(2), 1867--1874. (www)

  @article{ , abstract = {We present a bifunctional catalyst consisting of a copper(I)/N-heterocyclic carbene and an organocatalytic guanidine moiety that enables, for the first time, a copper(I)-catalyzed reduction of amides with H 2 as the terminal reducing agent. The guanidine allows for reactivity tuning of the originally weakly nucleophilic copper(I) hydrides – formed in situ – to be able to react with difficult-to-reduce amides. Additionally, the guanidine moiety is key for the selective recognition of “privileged” amides based on simple and readily available heterocycles in the presence of other amides within one molecule, giving rise to hitherto unknown site-selective catalytic amide hydrogenation. A substrate scope, mechanistic investigations, and a working hypothesis supported by computational analysis for site-selectivity are presented.}, archive = {J_JACS}, author = {Dimitrios-Ioannis Tzaras and Mahadeb Gorai and Thomas Jacquemin and Thiemo Arndt and Birte M. Zimmermann and Martin Breugst and Johannes F. Teichert}, doi = {10.1021/jacs.4c14174}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1867--1874}, shortjournal = {J. Am. Chem. Soc.}, title = {Site-selective Copper(I)-catalyzed hydrogenation of amides}, volume = {147}, year = {2025}, }
• (2025). Interrogation of enantioselectivity in the photomediated ring contractions of saturated heterocycles. JACS, 147(2), 1851--1866. (www)

  @article{ , abstract = {We recently reported a chiral phosphoric acid (CPA) catalyzed enantioselective photomediated ring contraction of piperidines and other saturated heterocycles. By extruding a single heteroatom from a ring, this transformation builds desirable C(sp 3 )–C(sp 3 ) bonds in the ring contracted products; however, the origins of enantioselectivity remain poorly understood. In this work, enantioselectivity of the ring contraction has been explored across an expanded structurally diverse substrate scope, revealing a wide range of enantioselectivities (0–99%) using two distinct CPA catalysts. Mechanistic investigations support rate-determining excitation that generates short-lived achiral intermediates that are intercepted by the CPA in an enantiodetermining ring closure. The effects of competitive uncatalyzed reactivity and light-driven reversibility of the enantiodetermining ring closure on enantioselectivity have been elucidated. Statistical models were built by regressing the range of enantioselectivities from the substrate scope against key structural features of the products for both CPA catalysts. The resultant models suggested distinct factors that influence the enantioselectivity response for each catalyst and enabled rational modification of a pharmaceutically relevant target molecule to improve enantioselectivity. Finally, density functional theory (DFT)-based transition state analysis identified distinct noncovalent interactions with each catalyst that correlated with the unique selectivity-relevant features uncovered through statistical modeling. Our findings not only offer comprehensive insight into the origins of enantioselectivity in this system but should also aid future development of related photomediated CPA-catalyzed reactions.}, archive = {J_JACS}, author = {Sojung F. Kim and Jordan P. Liles and Michaelyn C. Lux and Hojoon Park and Justin Jurczyk and Yasuki Soda and Charles S. Yeung and Matthew S. Sigman and Richmond Sarpong}, doi = {10.1021/jacs.4c13999}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1851--1866}, shortjournal = {J. Am. Chem. Soc.}, title = {Interrogation of enantioselectivity in the photomediated ring contractions of saturated heterocycles}, volume = {147}, year = {2025}, }
• (2025). Rapid crystallization and versatile metalation of acetylhydrazone-linked covalent organic frameworks for heterogenous catalysis. JACS, 147(2), 1840--1850. (www)

  @article{ , abstract = {Covalent organic frameworks (COFs) hold promise in heterogeneous metal catalysis benefiting from their robust, crystalline, and porous structures. However, synthetic challenges persist in prolonged crystallization times, limited metal loading, and uncertain coordination environments. Here, we present the rapid crystallization and versatile metalation of new acetylhydrazone-linked COFs (AH-COFs) by condensation of ketone and hydrazide components, featuring full conversion within 30 min under open-air and mild conditions. The obtained AH-COFs exhibit exceptional thermal and chemical stability, maintaining high crystallinity and microporosity even under harsh conditions. This method shows the versatility of in situ metalation through subcomponent assembly with a wide range of metal centers, and the delicate control of coordination geometry through isoreticular functionalization for fine-tuning of the pore environments and metal catalytic activity. The metalated AH-COFs demonstrate excellent catalytic performance: AH-COF-2-Zn achieves high efficiency in CO 2 cycloaddition, while AH-COF-1-Cu-PSM achieves near-quantitative conversion in copper-catalyzed azide–alkyne cycloaddition (CuAAC) reactions, with both catalysts retaining their activity over multiple cycles. This study offers an efficient and versatile method for the rapid crystallization of designable, stable, and functional COFs, heading to practical applications prioritized on efficiency, scalability, and sustainability.}, archive = {J_JACS}, author = {Gao-Feng Liu and Zhi-Wei Li and Zi-Jun Huang and Zhiyuan Zhou and Ying-Xian Li and Anlian Huang and Ziyang Cai and Gangfeng Ouyang and Bao-Hui Ye and Yue-Biao Zhang}, doi = {10.1021/jacs.4c13982}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1840--1850}, shortjournal = {J. Am. Chem. Soc.}, title = {Rapid crystallization and versatile metalation of acetylhydrazone-linked covalent organic frameworks for heterogenous catalysis}, volume = {147}, year = {2025}, }
• (2025). Kinetic and affinity profiling rare earth metals using a DNA aptamer. JACS, 147(2), 1831--1839. (www)

  @article{ , abstract = {Rare earth elements (REEs) are widely used in various high-tech industries. Developing affinity ligands that can detect and distinguish REEs is at the forefront of analytical chemistry. It is also interesting to understand the limits of natural biomolecules for the recognition of REEs. In this study, Sc 3+ was used as a target for the isolation of DNA aptamers, and an aptamer named Sc-1 was obtained. Using a thioflavin T (ThT) fluorescence assay, Sc-1 bound only to REEs, but not other metal ions. Additionally, the binding of Sc-1 to Sc 3+ exhibited slow kinetics, and the binding complex resisted dissociation by EDTA. Furthermore, Sc-1 displayed varying binding kinetics with trivalent lanthanide ions, allowing for the discrimination of 17 REEs into three major groups: (1) La 3+ , Ce 3+ , Pr 3+ , Nd 3+ , Sm 3+ , Eu 3+ , and Gd 3+ ; (2) Tb 3+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 3+ , Yb 3+ , Lu 3+ , and Y 3+ ; and (3) Sc 3+ . NMR spectroscopy confirmed binding-induced conformational changes in the aptamer. Using the fluorescence strand-displacement method, the true K d of the aptamer was measured to range from 0.6 to 258.5 nM for the REE ions, and it showed effective detection of Sc 3+ in real samples.}, archive = {J_JACS}, author = {Jin Wang and Yunus A. Kaiyum and Xiangmei Li and Hongtao Lei and Philip E. Johnson and Juewen Liu}, doi = {10.1021/jacs.4c13768}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1831--1839}, shortjournal = {J. Am. Chem. Soc.}, title = {Kinetic and affinity profiling rare earth metals using a DNA aptamer}, volume = {147}, year = {2025}, }
• (2025). Viridium: A stable radical and its π-dimerization. JACS, 147(2), 1823--1830. (www)

  @article{ , abstract = {The discovery of a stable organic radical formed under mild, clean, and efficient light-mediated conditions is reported. The structure of the stable acridinium-based radical photoproduct was unambiguously established by single-crystal X-ray diffraction, mass spectrometry, and in solution by EPR, UV/vis, and NMR spectroscopies. The photochemical mechanism of its formation has been elucidated by photophysical experiments coupled with EPR experiments and theoretical investigations. This unique aromatic radical is featured by amphoteric redox behavior and π-dimerization properties. Its ability to π-dimerize has been demonstrated in water and in the less studied perfluorohexane, two solvents of opposite polarity. By a simple counterion exchange, direct comparison of π-dimer thermodynamics between both antagonist solvents allowed an elucidation of the solvophobic behavior in perfluorocarbon.}, archive = {J_JACS}, author = {Henri-Pierre Jacquot de Rouville and Christophe Gourlaouen and David Bardelang and Nolwenn Le Breton and Jas S. Ward and Laurent Ruhlmann and Jean-Marc Vincent and Damien Jardel and Kari Rissanen and Jean-Louis Clément and Sylvie Choua and Valérie Heitz}, doi = {10.1021/jacs.4c13807}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1823--1830}, shortjournal = {J. Am. Chem. Soc.}, title = {Viridium: A stable radical and its π-dimerization}, volume = {147}, year = {2025}, }
• (2025). An ultramicroporous physisorbent sustained by a trifecta of directional supramolecular interactions. JACS, 147(2), 1813--1822. (www)

  @article{ , abstract = {2D and 3D porous coordination networks (PCNs) as exemplified by metal–organic frameworks, MOFs, have garnered interest for their potential utility as sorbents for molecular separations and storage. The inherent modularity of PCNs has enabled the development of crystal engineering strategies for systematic fine-tuning of pore size and chemistry in families of related PCNs. The same cannot be said about one-dimensional (1D) coordination polymers, CPs, which are understudied with respect to porosity. Here, we report that permanent porosity is exhibited by the previously reported family of linear (L) 1D porous CPs, PCPs, of formula [M(bipy)(NO 3 ) 2 (H 2 O) 2 ]n (L-chn-1-M-NO3: M = Co, Ni; bipy = 4,4′-bipyridine). Their pore structure comprises 1D channels sustained by three types of directional interaction: coordination bonds; hydrogen bonds; offset π–π interactions. Heating L-chn-1-M-NO3 in vacuo or above 383 K resulted in removal of the aqua ligands and concomitant transformation to nonporous anhydrate phases ZZ-chn-1-Co-NO3 (ZZ = zigzag) and HT-Ni. Exposure of these anhydrate phases to ambient humidity resulted in regeneration of L-chn-1-M-NO3. That L-chn-1-M-NO3 exhibits permanent porosity was supported by CO 2 and water sorption measurements, which afforded reversible type I and stepped (S-shaped) isotherm profiles, respectively, making this work the first demonstration of reversible water sorption in a 1D PCP. The water sorption properties are pertinent to atmospheric water harvesting: onset of uptake at ca. 12% relative humidity; activation required only mild heat or vacuum; relatively fast adsorption/desorption kinetics; performance retained over >100 adsorption/desorption cycles. We project water harvesting productivity of L-chn-1-M-NO3 of 3.3 L kg –1 d –1 , on par with some leading MOF desiccants. DFT and Monte Carlo simulations provide insights into the structure of water molecules in the channels, provide their influence on the host framework, and provide a plausible argument for the experimental water vapor isotherms. This work demonstrates that easily scalable 1D PCPs, a potentially vast class of materials, can exhibit porous structures sustained by three types of directional supramolecular synthons and offer desirable water sorption properties.}, archive = {J_JACS}, author = {Alan C. Eaby and Shaza Darwish and Shi-Qiang Wang and Andrey A. Bezrukov and Debobroto Sensharma and Angela Shipman and Carlos J. Solanilla and Brian Space and Soumya Mukherjee and Michael J. Zaworotko}, doi = {10.1021/jacs.4c13797}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1813--1822}, shortjournal = {J. Am. Chem. Soc.}, title = {An ultramicroporous physisorbent sustained by a trifecta of directional supramolecular interactions}, volume = {147}, year = {2025}, }
• (2025). Helical assemblies of colloidal nanocrystals with long-range order and their fusion into continuous structures. JACS, 147(2), 1803--1812. (www)

  @article{ , abstract = {Chirality epitomizes the sophistication of chemistry, representing some of its most remarkable achievements. Yet, the precise synthesis of chiral structures from achiral building blocks remains a profound and enduring challenge in synthetic chemistry and materials science. Here, we demonstrate that achiral colloidal nanocrystals, including Au and Ag nanocrystals, can assemble into long-range-ordered helical assemblies with the assistance of chiral molecules. The synchronized aggregation kinetics between colloidal silver or gold nanocrystals and π-conjugated perylene diimide molecules enables the nanocrystals to precisely follow the helical pathways of the molecular assemblies. This results in the formation of helical nanocrystal assemblies extending over tens of micrometers. These helically organized nanocrystals, exhibiting high positional precision, display linear size-dependent chiroptical properties. Furthermore, more intricate helical assemblies, featuring triple, quadruple, and quintuple nanocrystal strands, can be observed in addition to the commonly encountered double helical assemblies. Finally, these helical assemblies, composed of discrete Ag nanocrystals, can fuse into continuous Ag 2 S helical structures following a sulfidation reaction, ultimately leading to the formation of diverse metal sulfide helices through cation exchange processes.}, archive = {J_JACS}, author = {Caikun Cheng and Benyou Li and Zhenyu Feng and Rongjuan Liu and Yuting Bi and Qiang Li and Jingjing Wei and Zhijie Yang}, doi = {10.1021/jacs.4c13831}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1803--1812}, shortjournal = {J. Am. Chem. Soc.}, title = {Helical assemblies of colloidal nanocrystals with long-range order and their fusion into continuous structures}, volume = {147}, year = {2025}, }
• (2025). Colloidal germanium quantum dots with broadly tunable size and light emission. JACS, 147(2), 1792--1802. (www)

  @article{ , abstract = {Germanium (Ge) colloidal quantum dots (CQDs) were synthesized by thermal decomposition of GeI 2 using capping ligand mixtures of oleylamine (OAm), octadecene (ODE), and trioctylphosphine (TOP). Average diameters could be tuned across a wide range, from 3 to 18 nm, by adjusting reactant concentrations, heating rates, and reaction temperatures. OAm promotes decomposition of GeI 2 to Ge and serves as a weakly bound capping ligand. ODE displaces OAm during the reaction to terminate particle growth and prevent surface oxidation. TOP is necessary for obtaining nanocrystals larger than 11 nm. The Ge CQDs have relatively narrow size distributions and exhibit size-dependent, band-edge photoluminescence (PL), with peak energies from 0.8 to 1.34 eV, across a wide spectral range in the infrared (IR).}, archive = {J_JACS}, author = {Jungchul Noh and Hyun Gyung Kim and Daniel W. Houck and Tushti Shah and Yangning Zhang and Alexandra Brumberg and Richard D. Schaller and Brian A. Korgel}, doi = {10.1021/jacs.4c13692}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1792--1802}, shortjournal = {J. Am. Chem. Soc.}, title = {Colloidal germanium quantum dots with broadly tunable size and light emission}, volume = {147}, year = {2025}, }
• (2025). Dynamic features driven by stochastic collisions in a nanopore for precise single-molecule identification. JACS, 147(2), 1781--1791. (www)

  @article{ , abstract = {Nanopore technology holds great potential for single-molecule identification. However, extracting meaningful features from ionic current signals and understanding the molecular mechanisms underlying the specific features remain unresolved. In this study, we uncovered a distinctive ionic current pattern in a K238Q aerolysin nanopore, characterized by transient spikes superimposed on two stable transition states. By employing a neural network model, we demonstrated that these previously overlooked dynamic spike features exhibit superior discriminative power, improving the accuracy from 44% to 93%. We identified that the stable transition states result from simultaneous interactions of ssDNA with the two sensitive sites of the nanopore. The proposed stochastic collision model offers a mechanistic framework for interpreting the generation of the dynamic spike features. This model indicates that the continuous transitions facilitate iterative, comprehensive snapshots of molecular interactions by nanopores. Our findings introduce a new approach for optimizing nanopore technology to capture complex dynamic features and substantially improve the accuracy of single-molecule identification.}, archive = {J_JACS}, author = {Jia Wang and Shao-Chuang Liu and Zheng-Li Hu and Yi-Lun Ying and Yi-Tao Long}, doi = {10.1021/jacs.4c13664}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1781--1791}, shortjournal = {J. Am. Chem. Soc.}, title = {Dynamic features driven by stochastic collisions in a nanopore for precise single-molecule identification}, volume = {147}, year = {2025}, }
• (2025). Photoinduced regiodivergent and enantioselective cross-coupling of glycine derivatives with hydrocarbon feedstocks. JACS, 147(2), 1767--1780. (www)

  @article{ , abstract = {Regiodivergent asymmetric synthesis represents a transformative strategy for the efficient generation of structurally diverse chiral products from a single set of starting materials, significantly enriching their enantiomeric composition. However, the design of radical-mediated regiodivergent and enantioselective reactions that can accommodate a wide range of functional groups and substrates has posed significant challenges. The obstacles primarily lie in switching the regioselectivity and achieving high enantiodiscrimination, especially when dealing with high-energy intermediates. To address these issues, we have developed a new catalytic system that integrates photoinduced hydrogen atom transfer (HAT) and chiral copper catalysis, involving the fine-tuning of chiral ligands, additives, and other reaction parameters. The strategy facilitates regiodivergent and enantioselective cross-couplings between N -aryl glycine ester/amide derivatives and abundant hydrocarbon feedstocks through strong C(sp 3 )–H bond activation. This approach allows for the controlled and stereoselective formation of C(sp 3 )–C(sp 3 ) and C(sp 3 )–N bonds, yielding a rich variety of C- or N-alkylated glycine esters and amides with commendable yields (up to 92% yield), exclusive regioselectivities (typically >20:1 rr), and high enantioselectivities (up to 96% ee). Our methodology not only provides a promising avenue for the stereoselective incorporation of alkyl functionalities onto specific sites of biologically significant molecules but also offers a practical approach for regioselectivity switching while simultaneously achieving high asymmetric induction within photochemical reactions.}, archive = {J_JACS}, author = {Fuxing Yang and Longxiao Chi and Ziqi Ye and Lei Gong}, doi = {10.1021/jacs.4c13321}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1767--1780}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoinduced regiodivergent and enantioselective cross-coupling of glycine derivatives with hydrocarbon feedstocks}, volume = {147}, year = {2025}, }
• (2025). Spatiotemporal spectroscopy of fast excited-state diffusion in 2D covalent organic framework thin films. JACS, 147(2), 1758--1766. (www)

  @article{ , abstract = {Covalent organic frameworks (COFs), crystalline and porous conjugated structures, are of great interest for sustainable energy applications. Organic building blocks in COFs with suitable electronic properties can feature strong optical absorption, whereas the extended crystalline network can establish a band structure enabling long-range coherent transport. This peculiar combination of both molecular and solid-state materials properties makes COFs an interesting platform to study and ultimately utilize photoexcited charge carrier diffusion. Herein, we investigated the charge carrier diffusion in a two-dimensional COF thin film generated through condensation of the building blocks benzodithiophene-dialdehyde (BDT) and N , N , N ′, N ′-tetra(4-aminophenyl)benzene-1,4-diamine (W). We visualized the spatiotemporal evolution of photogenerated excited states in the 2D WBDT COF thin film using remote-detected time-resolved PL measurements (RDTR PL). Combined with optical pump terahertz probe (OPTP) studies, we identified two diffusive species dominating the process at different time scales. Initially, short-lived free charge carriers diffuse almost temperature-independently before relaxing into bound states at a rate of 0.7 ps –1 . Supported by theoretical simulations, these long-lived bound states were identified as excitons. We directly accessed the lateral exciton diffusion within the oriented and crystalline film, revealing remarkably high diffusion coefficients of up to 4 cm 2 s –1 (200 K) and diffusion lengths of several hundreds of nanometers and across grain boundaries. Temperature-dependent exciton transport analysis showed contributions from both incoherent hopping and coherent band-like transport. In the transport model developed based on these findings, we discuss the complex impact of order and disorder on charge carrier diffusion within the WBDT COF thin film.}, archive = {J_JACS}, author = {Laura Spies and Alexander Biewald and Laura Fuchs and Konrad Merkel and Marcello Righetto and Zehua Xu and Roman Guntermann and Rik Hooijer and Laura M. Herz and Frank Ortmann and Jenny Schneider and Thomas Bein and Achim Hartschuh}, doi = {10.1021/jacs.4c13129}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1758--1766}, shortjournal = {J. Am. Chem. Soc.}, title = {Spatiotemporal spectroscopy of fast excited-state diffusion in 2D covalent organic framework thin films}, volume = {147}, year = {2025}, }
• (2025). Smallest [5,6]Fullerene as building blocks for 2D networks with superior stability and enhanced photocatalytic performance. JACS, 147(2), 1749--1757. (www)

  @article{ , abstract = {The assembly of molecules to form covalent networks can create varied lattice structures with physical and chemical properties distinct from those of conventional atomic lattices. Using the smallest stable [5,6]fullerene units as building blocks, various 2D C 24 networks can be formed with superior stability and strength compared to the recently synthesized monolayer polymeric C 60 . Monolayer C 24 harnesses the properties of both carbon crystals and fullerene molecules, such as stable chemical bonds, suitable band gaps, and large surface area, facilitating photocatalytic water splitting. The electronic band gaps of C 24 are comparable to those of TiO 2 , providing appropriate band edges with sufficient external potential for overall water splitting over the acidic and neutral pH range. Upon photoexcitation, strong solar absorption enabled by strongly bound bright excitons can generate carriers effectively, while the type-II band alignment between C 24 and other 2D monolayers can separate electrons and holes in individual layers simultaneously. Additionally, the number of surface-active sites of C 24 monolayers are three times more than that of their C 60 counterparts in a much wider pH range, providing spontaneous reaction pathways for the hydrogen evolution reaction. Our work provides insights into materials design using tunable building blocks of fullerene units with tailored functions for energy generation, conversion, and storage.}, archive = {J_JACS}, author = {Jiaqi Wu and Bo Peng}, doi = {10.1021/jacs.4c13167}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1749--1757}, shortjournal = {J. Am. Chem. Soc.}, title = {Smallest [5,6]Fullerene as building blocks for 2D networks with superior stability and enhanced photocatalytic performance}, volume = {147}, year = {2025}, }
• (2025). Cooperative brønsted acid-single atom photocatalysis in Metal–Organic framework. JACS, 147(2), 1740--1748. (www)

  @article{ , abstract = {Enzymes, composed of earth-abundant elements, outperform conventional heterogeneous photocatalysts in hydrogen production due to the dual-site cooperation between adjacent active metal sites and proton-transferring ligands. However, the realization of such dual-site cooperation in heterogeneous catalytic systems is hindered by the challenges in the precise construction of cooperative active sites. In this study, we present the design of a structurally tuned metal–organic framework (MOF) photocatalyst that incorporates cooperative Brønsted acid-single atom catalytic sites. By grafting Co single-atom sites onto the Ti-oxo clusters and introducing Brønsted acidic P–OH moieties in tandem within the MOF-based catalyst structure, we achieved a visible-light-activated photocatalytic H 2 production rate of 6.6 mmol g –1 h –1 , which is 6.6 times higher than that of a Pt nanoparticle-based cocatalyst, emphasizing the significance of incorporating cooperative Brønsted acid-single atom catalytic sites.}, archive = {J_JACS}, author = {Yoon Jung and Chan Woo Lee and Byoung-Hoon Lee and Yunjae Yu and Jaeho Moon and Hyeon Seok Lee and Wonjae Ko and Jinsol Bok and Kangjae Lee and Jaewoo Lee and Megalamane S. Bootharaju and Jaeyune Ryu and Minho Kim and Taeghwan Hyeon}, doi = {10.1021/jacs.4c13057}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1740--1748}, shortjournal = {J. Am. Chem. Soc.}, title = {Cooperative brønsted acid-single atom photocatalysis in Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Beating the size-dependent limit with Spin–Lattice coupling in nanomagnetism. JACS, 147(2), 1732--1739. (www)

  @article{ , abstract = {Further miniaturization of magnetic nanomaterials is intrinsically accompanied by a reduction in spin ordered domains, resulting in size-dependent magnetic behaviors. Consequently, a longstanding roadblock in the advancement of nanodevices based on magnetic nanomaterials is the absence of a method to beat the size-dependent limit in nanomagnetism. Here, we discover and exploit a spin–lattice coupling effect in three-dimensional freestanding magnetic nanoparticles to beat the size-dependent limit for the first time. The so-called spin–lattice coupling involves varying spin configuration and exchange constant of spin interactions induced by lattice deformations. We correlate spin–lattice coupling to g-shift and employ two-dimensional magnetic resonance imaging to visualize g -factor. As lattice constants decrease (even ∼1%), positive offset of g-shift increases significantly, signaling stronger spin–lattice coupling, which induces a transition from paramagnetism to surperparamagnetism, thereby effectively beating the size-dependent limit.}, archive = {J_JACS}, author = {Mengmeng Li and Xiuyu Wang}, doi = {10.1021/jacs.4c12978}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1732--1739}, shortjournal = {J. Am. Chem. Soc.}, title = {Beating the size-dependent limit with Spin–Lattice coupling in nanomagnetism}, volume = {147}, year = {2025}, }
• (2025). Glycan sequencing based on glycosidase-assisted nanopore sensing. JACS, 147(2), 1721--1731. (www)

  @article{ , abstract = {Nanopores are promising sensors for glycan analysis with the accurate identification of complex glycans laying the foundation for nanopore-based sequencing. However, their applicability toward continuous glycan sequencing has not yet been demonstrated. Here, we present a proof-of-concept of glycan sequencing by combining nanopore technology with glycosidase-hydrolyzing reactions. By continuously monitoring the changes in the characteristic current generated by the translocation of glycan hydrolysis products through a nanopore, the glycan sequence can be accurately identified based on the specificity of glycosidases. With machine learning, we improved the sequencing accuracy to over 98%, allowing for the reliable determination of consecutive building blocks and glycosidic linkages of glycan chains while reducing the need for operator expertise. This approach was validated on real glycan samples, with accuracy calibrated using hydrophilic interaction chromatography-high-performance liquid chromatography (HILIC-HPLC) and mass spectrometry (MS). We achieved the sequencing of ten consecutive units in natural glycan chains, which provided the first evidence for the feasibility of a nanopore-glycosidase-compatible system in glycan sequencing. Compared to traditional methods, this strategy enhances sequencing efficiency by over 5-fold. Additionally, we introduced the concept of ‘inverse sequencing’, which focuses on electrical signal changes rather than monosaccharide identification. This eliminates the reliance on glycan fingerprint libraries typically required in putative ‘forward hydrolysis’ strategies. When the challenges in both ‘forward and inverse hydrolysis sequencing strategies’ are addressed, this approach will pave the way for establishing a glycan sequencing technology at a single-molecule level.}, archive = {J_JACS}, author = {Guangda Yao and Bingqing Xia and Fangyu Wei and Jiahong Wang and Yuting Yang and Shengzhou Ma and Wenjun Ke and Tiehai Li and Xi cheng and Liuqing Wen and Yi-tao Long and Zhaobing Gao}, doi = {10.1021/jacs.4c12940}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1721--1731}, shortjournal = {J. Am. Chem. Soc.}, title = {Glycan sequencing based on glycosidase-assisted nanopore sensing}, volume = {147}, year = {2025}, }
• (2025). Determining covalent organic framework structures using electron crystallography and computational intelligence. JACS, 147(2), 1709--1720. (www)

  @article{ , abstract = {The structural characterization of new materials often poses immense challenges, especially when obtaining single-crystal structures is difficult, which is a common difficulty with covalent organic frameworks (COFs). Despite this, understanding the atomic structure is crucial as it provides insights into the arrangement and connectivity of organic building blocks, offering the opportunity to establish the correlation of structure–function relationships and unravel material properties. In this study, we present an approach for determining the structures of COFs, an integration of electron crystallography and computational intelligence (COF+). By applying established chemistry knowledge and employing particle swarm optimization (PSO) for trial structure generation, we overcome existing limitations, thus paving the way for advancements in COF structural determination. We have successfully implemented this technique on four representative COFs, each with unique characteristics. These examples underline the accuracy and efficacy of our approach in addressing the challenges tied to COF structural determination. Furthermore, our approach has revealed new structure candidates with different topologies or interpenetrations that are chemically feasible. This discovery demonstrates the capability of our algorithm in constructing trial COF structures without being influenced by topological factors. Our new approach to COF structure determination represents a significant advancement in the field and opens new avenues for exploring the properties and applications of COF materials.}, archive = {J_JACS}, author = {Xiangyu Zhang and Junyi Hu and Huiyu Liu and Tu Sun and Zidi Wang and Yingbo Zhao and Yue-Biao Zhang and Ping Huai and Yanhang Ma and Shan Jiang}, doi = {10.1021/jacs.4c12757}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1709--1720}, shortjournal = {J. Am. Chem. Soc.}, title = {Determining covalent organic framework structures using electron crystallography and computational intelligence}, volume = {147}, year = {2025}, }
• (2025). Leveraging intramolecular π-stacking to access an exceptionally long-lived 3MC excited state in an Fe(II) carbene complex. JACS, 147(2), 1694--1708. (www)

  @article{ , abstract = {The ability to manipulate excited-state decay cascades using molecular structure is essential to the application of abundant-metal photosensitizers and chromophores. Ligand design has yielded some spectacular results elongating charge-transfer excited state lifetimes of Fe(II) coordination complexes, but triplet metal-centered ( 3 MC) excited states─recently demonstrated to be critical to the photoactivity of isoelectronic Co(III) polypyridyls─have to date remained elusive, with temporally isolable examples limited to the picosecond regime. With this report, we show how strong-field donors and intramolecular π-stacking can conspire to stabilize a long-lived 3 MC excited state for a remarkable 4.1 ± 0.3 ns in fluid solution at ambient temperature. Analysis of variable-temperature time-resolved absorption data using theoretical models ranging from Arrhenius to semiclassical Marcus theory, combined with computational modeling and X-ray crystallography, reveal a Jahn–Teller stabilized excited state with a high activation barrier for ground-state recovery. The net result is a chromophore with a 3 MC excited-state lifetime that is orders of magnitude longer than anything yet observed for an Fe(II) complex.}, archive = {J_JACS}, author = {Robert J. Ortiz and Rajarshi Mondal and James K. McCusker and David E. Herbert}, doi = {10.1021/jacs.4c12650}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1694--1708}, shortjournal = {J. Am. Chem. Soc.}, title = {Leveraging intramolecular π-stacking to access an exceptionally long-lived 3MC excited state in an Fe(II) carbene complex}, volume = {147}, year = {2025}, }
• (2025). Effects of cofeeding hydrogen on propane dehydrogenation catalyzed by isolated iron sites incorporated into dealuminated BEA. JACS, 147(2), 1677--1693. (www)

  @article{ , abstract = {Iron sites dispersed on nonacidic siliceous supports have been reported to be catalytically active for propane dehydrogenation (PDH), yet the precise relationship between site structure and catalytic activity remains elusive. This study provides a comprehensive understanding of the catalytic performance of iron supported on dealuminated BEA (DeAlBEA) zeolites for PDH. Using XAS, UV–vis, and IR spectroscopy of adsorbed pyridine and deuterated acetonitrile, it was found that, at an Fe/Al 0 of 0.04, isolated Fe sites form. These isolated sites exhibit a forward rate of PDH of 213 mol propene/mol Fe·h at 823 K and a feed containing 15 kPa propane. When 15 kPa of H 2 is added to the feed, the forward rate of PDH rises to 391 mol of propene/mol of Fe·h. In both cases, the propene selectivity is over 99%. IR spectroscopy of d 3 -acetonitrile suggests that the open Lewis acid site ((−Si–O−) 2 Fe 3+ –OH) serves as the active site responsible for PDH, while Brønsted acid sites (≡Fe 3+ –O(H)–Si≡) contribute to propane cracking with increasing Fe/Al 0 ratios. Kinetic analysis of the effects of H 2 addition to the propane feed on PDH kinetics shows that H 2 enhances the activity of 0.04FeDeAlBEA primarily by enhancing the strength of the propane adsorption.}, archive = {J_JACS}, author = {Afnan Alghannam and Alexis T. Bell}, doi = {10.1021/jacs.4c12344}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1677--1693}, shortjournal = {J. Am. Chem. Soc.}, title = {Effects of cofeeding hydrogen on propane dehydrogenation catalyzed by isolated iron sites incorporated into dealuminated BEA}, volume = {147}, year = {2025}, }
• (2025). Ni-catalyzed regioselective alkylarylation of unactivated alkenes in amines enabled by cooperative ligand effects of nitriles and electron-deficient alkenes. JACS, 147(2), 1667--1676. (www)

  @article{ , abstract = {We report a Ni-catalyzed vicinal alkylarylation of unactivated alkenes in γ,δ- and δ,ε-alkenylamines with aryl halides and alkylzinc reagents. The reaction is enabled by amine coordination and can use all primary, secondary, and tertiary amines. The reaction constructs two new C(sp 3 )–C(sp 3 ) and C(sp 3 )–C(sp 2 ) bonds and produces δ- and ε-arylamines with C(sp 3 )-branching at the γ- and δ-positions. A variety of aryl and heteroaryl iodides and both the primary and secondary alkylzinc reagents can be used as coupling carbon sources. Mechanistic studies suggest that the reaction is enabled by the cooperative effect of organic nitriles and electron-deficient alkenes (EDAs) as ligands.}, archive = {J_JACS}, author = {Vivek Aryal and Supuni I. N. Hewa Inaththappulige and Ayush Acharya and Ramesh Giri}, doi = {10.1021/jacs.4c12334}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1667--1676}, shortjournal = {J. Am. Chem. Soc.}, title = {Ni-catalyzed regioselective alkylarylation of unactivated alkenes in amines enabled by cooperative ligand effects of nitriles and electron-deficient alkenes}, volume = {147}, year = {2025}, }
• (2025). Effects of temperature fluctuations on surface mobility of atomic steps and oxidation dynamics in high-temperature alloys. JACS, 147(2), 1656--1666. (www)

  @article{ , abstract = {In contrast to the traditional perspective that thermal fluctuations are insignificant in surface dynamics, here we report their influence on surface reaction dynamics. Using real-time low-energy electron microscopy imaging of NiAl(100) under both vacuum and O 2 atmospheres, we demonstrate that transient temperature variations substantially alter the direction of atom diffusion between the surface and bulk, leading to markedly different oxidation outcomes. During heating, substantial outward diffusion of atoms from the bulk to the surface results in step growth. Conversely, cooling induces considerable inward diffusion of adatoms, producing a distinct oxide morphology. In both scenarios, initially formed oxide islands impede local atomic step mobility, thereby increasing step length due to mass transfer between the surface and bulk, with atomic steps acting as adatom sinks during heating and sources during cooling. Furthermore, we show that this pinning effect on atomic step mobility can be mitigated by applying persistent temperature fluctuations. Understanding these nuances is vital for accurately predicting and dynamically manipulating the performance of active materials in various chemical processes under transient thermal conditions.}, archive = {J_JACS}, author = {Shyam Bharatkumar Patel and Chaoran Li and Abdullah Al-Mahboob and Jerzy T. Sadowski and Guangwen Zhou}, doi = {10.1021/jacs.4c12155}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1656--1666}, shortjournal = {J. Am. Chem. Soc.}, title = {Effects of temperature fluctuations on surface mobility of atomic steps and oxidation dynamics in high-temperature alloys}, volume = {147}, year = {2025}, }
• (2025). Automated synthesis of c1-functionalized oligosaccharides. JACS, 147(2), 1649--1655. (www)

  @article{ , abstract = {Automated glycan assembly (AGA) streamlines the synthesis of complex oligosaccharides. The reducing end of the oligosaccharide serves as an attachment site to the polymer support to liberate a free reducing end or an aminopentanol for ready conjugation to carrier proteins or surfaces. The facile installation of different aglycons on oligosaccharides has not been possible via AGA until now. Here, we describe a latent-active approach enabled by a traceless photolabile linker that allows for bidirectional AGA and ready introduction of various aglycons. Oligosaccharide thioglycosides, peptidoglycans, prototypical saponins, and click-chemistry-based conjugates are synthesized to illustrate the versatility of the method.}, archive = {J_JACS}, author = {Georg B. Niggemeyer and José A. Danglad-Flores and Peter H. Seeberger}, doi = {10.1021/jacs.4c11798}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1649--1655}, shortjournal = {J. Am. Chem. Soc.}, title = {Automated synthesis of c1-functionalized oligosaccharides}, volume = {147}, year = {2025}, }
• (2025). Dual inhibitors of SARS-CoV-2 3CL protease and human cathepsin l containing glutamine isosteres are anti-CoV-2 agents. JACS, 147(2), 1631--1648. (www)

  @article{ , abstract = {SARS-CoV-2 3CL protease (Main protease) and human cathepsin L are proteases that play unique roles in the infection of human cells by SARS-CoV-2, the causative agent of COVID-19. Both proteases recognize leucine and other hydrophobic amino acids at the P 2 position of a peptidomimetic inhibitor. At the P 1 position, cathepsin L accepts many amino acid side chains, with a partial preference for phenylalanine, while 3CL-PR protease has a stringent specificity for glutamine or glutamine analogues. We have designed, synthesized, and evaluated peptidomimetic aldehyde dual-target (dual-acting) inhibitors using two peptide scaffolds based on those of two Pfizer 3CL-PR inhibitors, Nirmatrelvir , and PF-835321 . Our inhibitors contain glutamine isosteres at the P 1 position, including 2-pyridon-3-yl-alanine, 3-pyridinyl-alanine, and 1,3-oxazo-4-yl-alanine groups. Inhibition constants for these new inhibitors ranged from K i = 0.6–18 nM (cathepsin L) and K i = 2.6–124 nM (3CL-PR), for which inhibitors with the 2-pyridon-3-yl-alanal substituent were the most potent for 3CL-PR. The anti-CoV-2 activity of these inhibitors ranged from EC 50 = 0.47–15 μM. X-ray structures of the peptidomimetic aldehyde inhibitors of 3CL-PR with similar scaffolds all demonstrated the formation of thiohemiacetals with Cys 145 , and hydrogen-bonding interactions with the heteroatoms of the pyridon-3-yl-alanyl group, as well as the nitrogen of the N-terminal indole and its appended carbonyl group at the P 3 position. The absence of these hydrogen bonds for the inhibitors containing the 3-pyridinyl-alanyl and 1,3-oxazo-4-yl-alanyl groups was reflected in the less potent inhibition of the inhibitors with 3CL-PR. In summary, our studies demonstrate the value of a second generation of cysteine protease inhibitors that comprise a single agent that acts on both human cathepsin L and SARS-CoV-2 3CL protease. Such dual-target inhibitors will provide anti-COVID-19 drugs that remain active despite the development of resistance due to mutation of the viral protease. Such dual-target inhibitors are more likely to remain useful therapeutics despite the emergence of inactivating mutations in the viral protease because the human cathepsin L will not develop resistance. This particular dual-target approach is innovative since one of the targets is viral (3CL-PR) required for viral protein maturation and the other is human (hCatL) which enables viral infection.}, archive = {J_JACS}, author = {Vivek Kumar and Jiyun Zhu and Bala C. Chenna and Zoe A. Hoffpauir and Andrew Rademacher and Ashley M. Rogers and Chien-Te Tseng and Aleksandra Drelich and Sharfa Farzandh and Audrey L. Lamb and Thomas D. Meek}, doi = {10.1021/jacs.4c11620}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1631--1648}, shortjournal = {J. Am. Chem. Soc.}, title = {Dual inhibitors of SARS-CoV-2 3CL protease and human cathepsin l containing glutamine isosteres are anti-CoV-2 agents}, volume = {147}, year = {2025}, }
• (2025). PH-dependent electrocatalytic aqueous ammonia oxidation to nitrite and nitrate by a Copper(II) complex with an oxidation-resistant ligand. JACS, 147(2), 1624--1630. (www)

  @article{ , abstract = {The electrocatalytic aqueous ammonia oxidation (AO) represents a more sustainable alternative to accessing nitrite (NO 2 – ) and nitrate (NO 3 – ). We now report that Cu(pyalk) 2 {pyalk = 2-(pyridin-2-yl)propan-2-oate}, previously employed as a homogeneous water oxidation (WO) catalyst, is also active for selective AO in aqueous environments. The traditional Griess analytical test for NO 2 – /NO 3 – was modified to permit the operation in the presence of the otherwise interfering Cu 2+ ion. Choosing the right pH is crucial for achieving high AO selectivity, with optimal formation of NO 2 – occurring at pH 9 (faradaic efficiency 62%). Electrochemical analysis reveals a monometallic reaction pathway and offers a plausible explanation for the chemoselectivity: at pH 9, AO is dominant, while at elevated pH 13, WO dominates.}, archive = {J_JACS}, author = {Han-Yu Liu and Hannah M. C. Lant and Cristina Decavoli and Robert H. Crabtree and Gary W. Brudvig}, doi = {10.1021/jacs.4c11822}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1624--1630}, shortjournal = {J. Am. Chem. Soc.}, title = {PH-dependent electrocatalytic aqueous ammonia oxidation to nitrite and nitrate by a Copper(II) complex with an oxidation-resistant ligand}, volume = {147}, year = {2025}, }
• (2025). A single bioorthogonal reaction for multiplex cell surface protein labeling. JACS, 147(2), 1612--1623. (www)

  @article{ , abstract = {Small-molecule fluorophores are invaluable tools for fluorescence imaging. However, means for their covalent conjugation to the target proteins limit applications in multicolor imaging. Here, we identify 2-[(alkyl t hio)( a ryl) m ethylene] m alononitrile (TAMM) molecules reacting with 1,2-aminothiol at a labeling rate over 10 4 M –1 s –1 through detailed mechanistic investigation. The fast TAMM molecules and mild reaction conditions enable site-specific labeling of surface proteins in not only cell lines but also primary neurons and living mice. The combination of genetic code expansion and sequence-specific proteolytic cleavage enables selective modification of three different cell surface proteins through iterative TAMM condensation. TAMM condensation is also compatible with Cu-catalyzed azide–alkyne cycloaddition and tetrazine ligation for four-color fluorescent labeling, reaching the maximum available colors of conventional confocal microscopes. Thus, bioconjugation chemistry is no longer the limiting factor for multiplex cell surface protein imaging.}, archive = {J_JACS}, author = {Yang Huang and Chengyang Wu and Anjing Lu and Jingzhe Wang and Jian Liang and Han Sun and Liqing Yang and Shixiang Duan and Andrey A. Berezin and Chuanliu Wu and Bo Zhang and Yi-Lin Wu and Yu-Hsuan Tsai}, doi = {10.1021/jacs.4c11701}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1612--1623}, shortjournal = {J. Am. Chem. Soc.}, title = {A single bioorthogonal reaction for multiplex cell surface protein labeling}, volume = {147}, year = {2025}, }
• (2025). Structural basis of high-precision protein ligation and its application. JACS, 147(2), 1604--1611. (www)

  @article{ , abstract = {Enzyme-catalyzed protein modifications have become invaluable in diverse applications, outperforming chemical methods in terms of precision, conjugation efficiency, and biological compatibility. Despite significant advances in ligases, such as sortase A and OaAEP1, their use in heterogeneous biological environments remains constrained by limited target sequence specificity. In 2021, Lupas’ group introduced Connectase, a family of repurposed archaeal proteases for protein ligations, but its low processivity and lack of structural information have impeded further engineering for practical biological and biophysical applications. Here, we present the X-ray crystallographic structures of MmConnectase ( Methanococcus maripaludis , MmCET) in both apo and substrate-bound forms. Comparative analysis with its inactive paralogue, MjCET ( Methanococcus janaschi ), reveals the structural basis of MmCET’s high-precision ligation activity. We propose modifications to the N-terminal substrate recognition motifs to suppress MmCET’s reversible protease activity, enabling high-precision protein ligations in complex biological environments, such as serum-containing cell cultures. To further demonstrate the enhanced processivity and precision, single-molecule protein unfolding experiments showed that our optimized Connectase, in conjunction with OaAEP1(C247A), can perform stepwise tandem ligations of protein leading to a well-defined protein polymer.}, archive = {J_JACS}, author = {Kelvin Han Chung Chong and Lichao Liu and Rae Chua and Yoke Tin Chai and Zhuojian Lu and Renming Liu and Eddie Yong Jun Tan and Jinxi Dong and Yek How Khoh and Jianqing Lin and Franklin L. Zhong and Julien Lescar and Peng Zheng and Bin Wu}, doi = {10.1021/jacs.4c10689}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1604--1611}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural basis of high-precision protein ligation and its application}, volume = {147}, year = {2025}, }
• (2025). N-doped zigzag-type aromatic truncated cone belts. JACS, 147(2), 1595--1603. (www)

  @article{ , abstract = {Zigzag aromatic hydrocarbon belts, ultrashort segments of zigzag carbon nanotubes, have been fascinating in the chemistry community for more than a half century because of their aesthetically appealing molecular nanostructures and tantalizing applications. Precise introduction of heteroatoms of distinct electronegativity and electronic configuration can create various heterocyclic aromatic nanobelts with novel physical and chemical properties. Here, we report the synthesis of unprecedented N-doped zigzag-type aromatic belts, belt[ n ]pyrrole[ n ]pyridines ( n = 6–8), from multiple intramolecular C aryl –C aryl homocoupling reactions of readily available azacalix[ n ](3,5-dibromopyridine)s. These compounds adopt globally π-conjugated belt structures and display unique photophysical and electrochemical properties. The truncated cone cavity of belt[8]pyrrole[8]pyridine was used as the outstanding host to form very stable 2:1 encapsulation complexes with fullerenes. This work opens a new avenue to the rational design and efficient synthesis of aromatic belts of distinct topological structures and tailor-made properties, which are invaluable in applications in materials and supramolecular chemistry.}, archive = {J_JACS}, author = {Jia-Hui Chen and Teng-Yu Huang and Shuo Tong and Mei-Xiang Wang}, doi = {10.1021/jacs.4c11468}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1595--1603}, shortjournal = {J. Am. Chem. Soc.}, title = {N-doped zigzag-type aromatic truncated cone belts}, volume = {147}, year = {2025}, }
• (2025). Controlling the spatiotemporal self-organization of stimuli-responsive nanocrystals under out-of-equilibrium conditions. JACS, 147(2), 1584--1594. (www)

  @article{ , abstract = {Self-organization under out-of-equilibrium conditions is ubiquitous in natural systems for the generation of hierarchical solid-state patterns of complex structures with intricate properties. Efforts in applying this strategy to synthetic materials that mimic biological function have resulted in remarkable demonstrations of programmable self-healing and adaptive materials. However, the extension of these efforts to multifunctional stimuli-responsive solid-state materials across defined spatial distributions remains an unrealized technological opportunity. This paper describes the use of a nonequilibrium reaction–diffusion process to achieve the synthesis of a multifunctional stimuli-responsive electrically conductive metal–organic framework (cMOF) in a gelled medium with control over particle size and spatial periodicity on a macroscopic scale. Upon integration into chemiresistive devices, the resulting cMOF particles exhibit a size-dependent response toward hydrogen sulfide gas, as determined by their distinct surface-to-volume ratio, porosity, unique synthesis methodology, and unusual microcrystallite morphology compared to their counterparts obtained through bulk solution phase synthesis. Taken altogether, these achievements pave the way toward gaining access to functional nanomaterials with well-defined chemical composition, dimensions, and precisely tailored functions using far-from-equilibrium approaches.}, archive = {J_JACS}, author = {Patrick Damacet and Elissa O. Shehayeb and Katherine A. Mirica}, doi = {10.1021/jacs.4c11195}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1584--1594}, shortjournal = {J. Am. Chem. Soc.}, title = {Controlling the spatiotemporal self-organization of stimuli-responsive nanocrystals under out-of-equilibrium conditions}, volume = {147}, year = {2025}, }
• (2025). Optimal synergy between azulenes and acenes in azuacenes with 6-7-5 ring topology. JACS, 147(2), 1574--1583. (www)

  @article{ , abstract = {Azuacenes, defined as azulene fused with acenes in a 6-7-5 ring topology and spanning lengths from 3 to 6 rings, have been synthesized using a new skeleton editing and [3 + 2] annulation synthesis protocol as a distinction regarding the procedures to obtain the 6-5-7 isomers. Comprehensive studies on ground-state and excited-state spectroscopy, electrochemical properties, chemical stability, and solid-state structure have been conducted to compare these azuacenes with acenes. For the same number of rings, we found that azuacenes improve the chemical stability of acenes (i.e., smaller diradical character) and their photophysical properties (i.e., anti-Kasha emissions and modulation of the energy and strength of the visible bands) but they reduce the transport features compared to those of acenes. Compared with azulene, azuacenes improve the performance of azulene in terms of electrical properties. Overall, the fusion of known polycyclic compounds, such as acene and azulene, produces new isomeric hybrid compounds with enhanced properties. Here, the resulting compounds turn out to conserve most of the unique properties of the two building blocks that we associate with the facility of π-delocalization of the positive charge of the azulene zwitterion over the acene fragment.}, archive = {J_JACS}, author = {Fei Huang and Marcos Díaz-Fernández and José M. Marín-Beloqui and Lingyan Sun and Yong Chen and Shengpei Liu and Yuxiang Wang and Han Zheng and Silu Li and Cheng Zhang and Jingsong You and Juan Casado}, doi = {10.1021/jacs.4c11186}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1574--1583}, shortjournal = {J. Am. Chem. Soc.}, title = {Optimal synergy between azulenes and acenes in azuacenes with 6-7-5 ring topology}, volume = {147}, year = {2025}, }
• (2025). Precise synthesis of 4.75 V-tolerant LiCoO2 with homogeneous delithiation and reduced internal strain. JACS, 147(2), 1563--1573. (www)

  @article{ , abstract = {The rapid advancements in 3C electronic devices necessitate an increase in the charge cutoff voltage of LiCoO 2 to unlock a higher energy density that surpasses the currently available levels. However, the structural devastation and electrochemical decay of LiCoO 2 are significantly exacerbated, particularly at ≥4.5 V, due to the stress concentration caused by more severe lattice expansion and shrinkage, coupled with heterogeneous Li + intercalation/deintercalation reactions. Herein, employing the molten-salt synthesis technique, we propose a universal morphology-shaping strategy to attain bulk reaction homogeneity and reduce internal strains, even at extremely high charge voltages. The newly designed flattened polygon prismlike LiCoO 2 (P-LCO) particle, featuring a regular symmetrical arrangement along the c -axis, demonstrates a more homogeneous Li + extraction/insertion reaction, which results in a restrained transformation to detrimental O1 phase and reduced variation in lattice volume throughout the (de)lithiation processes. This benefits the mitigation of the local stress accumulation misfit dislocations and particle cracking, ultimately maintaining the mechanical stability of the cathode. Consequently, P-LCO is capable of breaking the voltage ceiling and exhibits exceptional long-term cycling capability at an ultrahigh voltage of 4.75 V. This work offers a brand-new perspective for the rational design of cathode morphology to address capacity deterioration caused by inhomogeneous delithiation and internal strain, thus inspiring the development of high-energy-density cathodes with improved durability.}, archive = {J_JACS}, author = {Min Zhang and Weiyuan Huang and Jiayi Tang and Zhaoguo Liu and Chuanchao Sheng and Xinyi Sun and Hanyun Zhong and Sheng Xu and Wenjie Ning and Xianghui Xiao and Tongchao Liu and Shaohua Guo and Haoshen Zhou}, doi = {10.1021/jacs.4c10976}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1563--1573}, shortjournal = {J. Am. Chem. Soc.}, title = {Precise synthesis of 4.75 V-tolerant LiCoO2 with homogeneous delithiation and reduced internal strain}, volume = {147}, year = {2025}, }
• (2025). RNA translocation through protein nanopores: Interlude of the molten RNA globule. JACS, 147(2), 1553--1562. (www)

  @article{ , abstract = {Direct translocation of RNA with secondary structures using single-molecule electrophoresis through protein nanopores shows significant fluctuations in the measured ionic current, in contrast to unstructured single-stranded RNA or DNA. We developed a multiscale model combining the oxRNA model for RNA with the 3-dimensional Poisson–Nernst–Planck formalism for electric fields within protein pores, aiming to map RNA conformations to ionic currents as RNA translocates through three protein nanopores: α-hemolysin, CsgG, and MspA. Our findings reveal three distinct stages of translocation (pseudoknot, melting, and molten globule) based on contact maps and current values. Two translocation modes emerge: fast and slow. In the fast mode, the speed is determined by the electric field, independent of pore geometry. In the slow mode, the molten globule stage is the rate-determining factor in slowing the translocation, instead of the previous paradigm of melting of the base pairs. Using these insights, we propose a neural network framework to identify and reconstruct RNA secondary structures from ionic current windows. We find that the electric field distribution, not the nanopore geometry, drives the molten globule stage. Our results explain the large current fluctuations. These results provide a fundamental understanding of the role of secondary and tertiary structures in the translocation of RNA in direct RNA translocation platforms based on single-molecule electrophoresis. This work offers design rules for new protein pores and real-time imaging of the secondary structures of RNA.}, archive = {J_JACS}, author = {Minglun Li and Murugappan Muthukumar}, doi = {10.1021/jacs.4c10640}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1553--1562}, shortjournal = {J. Am. Chem. Soc.}, title = {RNA translocation through protein nanopores: Interlude of the molten RNA globule}, volume = {147}, year = {2025}, }
• (2025). Multiarm-assisted design of dendron-like degradable ionizable lipids facilitates systemic mRNA delivery to the spleen. JACS, 147(2), 1542--1552. (www)

  @article{ , abstract = {Lipid nanoparticles (LNPs) have emerged as pivotal vehicles for messenger RNA (mRNA) delivery to hepatocytes upon systemic administration and to antigen-presenting cells following intramuscular injection. However, achieving systemic mRNA delivery to non-hepatocytes remains challenging without the incorporation of targeting ligands such as antibodies, peptides, or small molecules. Inspired by comb-like polymeric architecture, here we utilized a multiarm-assisted design to construct a library of 270 dendron-like degradable ionizable lipids by altering the structures of amine heads and multiarmed tails for optimal mRNA delivery. Following in vitro high-throughput screening, a series of top-dendron-like LNPs with high transfection efficacy were identified. These dendron-like ionizable lipids facilitated greater mRNA delivery to the spleen in vivo compared to ionizable lipid analogs lacking dendron-like structure. Proteomic analysis of corona-LNP pellets showed enhancement of key protein clusters, suggesting potential endogenous targeting to the spleen. A lead dendron-like LNP formulation, 18–2–9b2, was further used to encapsulate Cre mRNA and demonstrated excellent genome modification in splenic macrophages, outperforming a spleen-tropic MC3/18PA LNP in the Ai14 mice model. Moreover, 18–2–9b2 LNP encapsulating therapeutic BTB domain and CNC homologue 1 (BACH1) mRNA exhibited proficient BACH1 expression and subsequent Spic downregulation in splenic red pulp macrophages (RPM) in a Spic-GFP transgene model upon intravenous administration. These results underscore the potential of dendron-like LNPs to facilitate mRNA delivery to splenic macrophages, potentially opening avenues for a range of mRNA-LNP therapeutic applications, including regenerative medicine, protein replacement, and gene editing therapies.}, archive = {J_JACS}, author = {Lulu Xue and Xinhong Xiong and Gan Zhao and William Molina-Arocho and Rohan Palanki and Zebin Xiao and Xuexiang Han and Il-Chul Yoon and Christian G. Figueroa-Espada and Junchao Xu and Ningqiang Gong and Qiangqiang Shi and Qinyuan Chen and Mohamad-Gabriel Alameh and Andrew E. Vaughan and Malay Haldar and Karin Wang and Drew Weissman and Michael J. Mitchell}, doi = {10.1021/jacs.4c10265}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1542--1552}, shortjournal = {J. Am. Chem. Soc.}, title = {Multiarm-assisted design of dendron-like degradable ionizable lipids facilitates systemic mRNA delivery to the spleen}, volume = {147}, year = {2025}, }
• (2025). Genetically encoded fluorogenic DNA aptamers for imaging metabolite in living cells. JACS, 147(2), 1529--1541. (www)

  @article{ , abstract = {Genetically encoded fluorescent protein and fluorogenic RNA sensors are indispensable tools for imaging biomolecules in cells. To expand the toolboxes and improve the generalizability and stability of this type of sensor, we report herein a genetically encoded fluorogenic DNA aptamer (GEFDA) sensor by linking a fluorogenic DNA aptamer for dimethylindole red with an ATP aptamer. The design enhances red fluorescence by 4-fold at 650 nm in the presence of ATP. Additionally, upon dimerization, it improves the signal-to-noise ratio by 2–3 folds. We further integrated the design into a plasmid to create a GEFDA sensor for sensing ATP in live bacterial and mammalian cells. This work expanded genetically encoded sensors by employing fluorogenic DNA aptamers, which offer enhanced stability over fluorogenic proteins and RNAs, providing a novel tool for real-time monitoring of an even broader range of small molecular metabolites in biological systems.}, archive = {J_JACS}, author = {Yuting Wu and Wentao Kong and Jacqueline Van Stappen and Linggen Kong and Zhimei Huang and Zhenglin Yang and Yu-An Kuo and Yuan-I Chen and Yujie He and Hsin-Chih Yeh and Ting Lu and Yi Lu}, doi = {10.1021/jacs.4c09855}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1529--1541}, shortjournal = {J. Am. Chem. Soc.}, title = {Genetically encoded fluorogenic DNA aptamers for imaging metabolite in living cells}, volume = {147}, year = {2025}, }
• (2025). Chemoselective stabilized triphenylphosphonium probes for capturing reactive carbonyl species and regenerating covalent inhibitors with acrylamide warheads in cellulo. JACS, 147(2), 1518--1528. (www)

  @article{ , abstract = {Reactive carbonyl species (RCS) are important biomarkers of oxidative stress-related diseases because of their highly reactive electrophilic nature. Despite their potential as triggers for prodrug activation, selective labeling approaches for RCS remain limited. Here, we utilized triphenylphosphonium groups to chemoselectively capture RCS via an aqueous Wittig reaction, forming α,β-unsaturated carbonyls that enable further functionalization. We first designed native (light) and deuterated (heavy) probes to facilitate RCS metabolomic identification through distinct MS isotope patterns. This approach allowed us to capture and relatively quantify several endogenous RCS related to advanced lipoxidation/glycation end products (ALEs/AGEs). Second, we demonstrated that various endogenous RCS can trigger the in situ generation of acrylamide warheads of targeted covalent inhibitors (TCIs) with different substituents. These structural variations influence their protein binding profiles and consequently alter their cytotoxicity, which is beneficial for the development of inhibitor cocktails.}, archive = {J_JACS}, author = {Ai-Lin Chen and Zih-Jheng Lin and Hsiao-Yu Chang and Tsung-Shing Andrew Wang}, doi = {10.1021/jacs.4c09727}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1518--1528}, shortjournal = {J. Am. Chem. Soc.}, title = {Chemoselective stabilized triphenylphosphonium probes for capturing reactive carbonyl species and regenerating covalent inhibitors with acrylamide warheads in cellulo}, volume = {147}, year = {2025}, }
• (2025). Succinate nanomaterials boost tumor immunotherapy via activating cell pyroptosis and enhancing MHC-I expression. JACS, 147(2), 1508--1517. (www)

  @article{ , abstract = {Despite the promising clinical applications of immunotherapy, its effectiveness is often limited by low immune responses and tumor immune escape. In this study, we introduce a simple and drug-free inorganic nanomaterial, sodium succinate (C 4 H 4 Na 2 O 4 NPs), prepared using a rapid microemulsion method to enhance cancer immunotherapy. The synthesized C 4 H 4 Na 2 O 4 NPs can release high concentrations of Na + and succinate ions into tumor cells, leading to an increase in intracellular osmolarity. This triggers the pyroptosis pathway, resulting in the release of cellular contents, inflammatory factors, and damage-associated molecular patterns, which ultimately boost immune responses. Furthermore, C 4 H 4 Na 2 O 4 NPs inhibit tumor immune escape through upregulating major histocompatibility complex-I (MHC-I) expression. Collectively, C 4 H 4 Na 2 O 4 NPs significantly inhibit tumor growth and metastasis by pyroptosis-induced immune activation and MHC-I expression upregulation-remitted tumor immune escape. This research offers a novel approach to tumor treatment that leverages MHC-I expression and pyroptosis, demonstrating the potential for clinical application in cancer immunotherapy.}, archive = {J_JACS}, author = {Pan Zheng and Guanglei Wang and Bin Liu and He Ding and Binbin Ding and Jun Lin}, doi = {10.1021/jacs.4c09566}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1508--1517}, shortjournal = {J. Am. Chem. Soc.}, title = {Succinate nanomaterials boost tumor immunotherapy via activating cell pyroptosis and enhancing MHC-I expression}, volume = {147}, year = {2025}, }
• (2025). Electrochemical reduction of CO2 to CH3OH catalyzed by an iron porphyrinoid. JACS, 147(2), 1497--1507. (www)

  @article{ , abstract = {Designing catalysts for the selective reduction of CO 2 , resulting in products having commercial value, is an important area of contemporary research. Several molecular catalysts have been reported to facilitate the reduction of CO 2 (both electrochemical and photochemical) to yield 2e – /2H + electron-reduced products, CO and HCOOH, and selective reduction of CO 2 beyond 2e – /2H + is rare. This is partly because the factors that control the selectivity of CO 2 reduction beyond 2e – are not yet understood. An iron chlorin complex with a pendent amine functionality in its second sphere, known to selectively catalyze CO 2 RR to HCOOH with a very low overpotential from its formal Fe(I) state, can catalyze CO 2 RR from its formal Fe(0) state by 6e – /6H + , forming CH 3 OH as a major product with a Faradaic yield of ∼50%. Mechanistic investigations using in situ spectro-electrochemistry indicate that the reactivity of a low-spin d 7 Fe I –COOH intermediate species generated during CO 2 RR is crucial in determining the product selectivity of this reaction. In weakly acidic conditions, C-protonation of this Fe I –COOH species, which is also chemically prepared and spectroscopically characterized, leads to HCOOH. The O-protonation, leading to C–OH bond cleavage and eventually to CH 3 OH, is ∼3 kcal/mol higher in energy and can be achieved in more acidic solutions. Hydrogen bonding to the pendent amine in the catalyst stabilizes reactive intermediates formed in the CO 2 RR and enables 6e – /6H + reduction of CO 2 to CH 3 OH.}, archive = {J_JACS}, author = {Paramita Saha and Sk Amanullah and Sudip Barman and Abhishek Dey}, doi = {10.1021/jacs.4c08922}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1497--1507}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrochemical reduction of CO2 to CH3OH catalyzed by an iron porphyrinoid}, volume = {147}, year = {2025}, }
• (2025). Alkene epoxidation and oxygen evolution reactions compete for reactive surface oxygen atoms on gold anodes. JACS, 147(2), 1482--1496. (www)

  @article{ , abstract = {Rates and selectivities for the partial oxidation of organic molecules on reactive electrodes depend on the identity and prevalence of reactive and spectator species. Here, we investigate the mechanism for the epoxidation of 1-hexene (C 6 H 12 ) with reactive oxygen species formed by electrochemical oxidation of water (H 2 O) on gold (Au) in an aqueous acetonitrile (CH 3 CN) electrolyte. Cyclic voltammetry measurements demonstrate that oxygen (O 2 ) evolution competes with C 6 H 12 epoxidation, and the Au surface must oxidize before either reaction occurs. In situ Raman spectroscopy reveals reactive oxygen species and spectators (CH 3 CN) on the active anode as well as species within the electrochemical double layer. The Faradaic efficiencies toward epoxidation and the ratios of epoxide formation to O 2 evolution rates increase linearly with the concentration of C 6 H 12 and depend inversely on the concentration of H 2 O, which agree with analytical expressions that describe rates for reaction between C 6 H 12 and chemisorbed oxygen atoms (O*) and exclude proposals for other forms of reactive oxygen (e.g., O 2 *, OOH*, OH*). These findings show that the epoxidation and O 2 evolution reactions share a set of common steps that form O* through electrochemical H 2 O activation but then diverge. Subsequently, epoxides form when O* reacts with C 6 H 12 through a non-Faradaic process, whereas O 2 evolves when O* reacts with H 2 O through a Faradaic process to form OOH*, which then deprotonates. These differences lead to distinct changes in rates in response to electrode potential, and hence, disparate Tafel slopes. Collectively, these results provide a self-consistent mechanism for C 6 H 12 epoxidation that involves reactive O*.}, archive = {J_JACS}, author = {Richa Ghosh and Geoffrey M. Hopping and Jordan W. Lu and Drew W. Hollyfield and David W. Flaherty}, doi = {10.1021/jacs.4c08948}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1482--1496}, shortjournal = {J. Am. Chem. Soc.}, title = {Alkene epoxidation and oxygen evolution reactions compete for reactive surface oxygen atoms on gold anodes}, volume = {147}, year = {2025}, }
• (2025). Efficient and ultralong room temperature phosphorescence from isolated molecules under visible light excitation. JACS, 147(2), 1474--1481. (www)

  @article{ , abstract = {Visible-light-excited ultralong organic phosphorescence (UOP) materials hold significant potential for various practical applications. Red-shifted excitation wavelength can be achieved by introducing large π-conjugation structures into organic molecules, thereby increasing intermolecular interactions and coupling. However, generating visible-light-excited UOP from isolated molecules poses a great challenge. Herein, we pioneered a strategy to achieve visible-light-excited UOP by doping organic molecules into a rigid polymer. The resulting materials exhibit an ultralong lifetime of up to 2.226 s and a high phosphorescence efficiency of 42.6% under ambient conditions. Impressively, poly(vinyl alcohol) films doped with 1 wt % different guests demonstrate blue and green visible-light-excited UOP. Moreover, they show long-persistent luminescence, lasting over 30 min at room temperature. Through control experiments and theoretical calculations, we discovered that hydrogen bonding between the guests and PVA confines the molecular motion, promoting efficient UOP. The intramolecular charge transfer within the single molecular state contributes to the low energy level, thus leading to the red-shifted absorption. This work will open a new way for developing visible-light-excited UOP based on amorphous polymers, offering highly efficient UOP and long-persistent luminescence under ambient conditions.}, archive = {J_JACS}, author = {Huanyu Yang and Yuefei Wang and Xiaokang Yao and Huili Ma and Jiming Yu and Xian Li and Xing Wang and Xinyu Liang and Qiming Peng and Suzhi Cai and Zhongfu An and Wei Huang}, doi = {10.1021/jacs.4c08889}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1474--1481}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient and ultralong room temperature phosphorescence from isolated molecules under visible light excitation}, volume = {147}, year = {2025}, }
• (2025). Tetrafluoro(aryl)sulfanylated bicyclopentane crystals that self-destruct upon cooling. JACS, 147(2), 1463--1473. (www)

  @article{ , abstract = {Whereas single crystals of organic compounds that respond to heat or light have been reported and studied in detail, studies on crystalline organic compounds that elicit an extreme mechanical response upon cooling to very low temperatures are relatively rare in the chemical literature. A tetrafluoro(aryl)sulfanylated bicyclopentane synthesized in our laboratory was discovered to exhibit such behavior; i.e., the crystals jumped and forcefully disintegrated upon cooling below ∼193 K. Accordingly, the origin of this low-temperature thermosalient effect was investigated through NMR, SC-XRD, PXRD, microscopy, DSC, Raman, and Brillouin experiments. To our surprise, NMR, SC-XRD, PXRD, and DSC experiments suggest the phenomenon can neither be attributed solely to a chemical transformation nor a phase transition of the entire material. Rather, XRD, Raman, and Brillouin experiments provide evidence that built-up strain released from the crystal upon self-destruction may be associated with crystal microstructure or a phase transition that occurs in another material (i.e., an impurity) in the crystal. This study demonstrates that molecular structural changes in organic material microstructure or impurity phases (which may not necessarily be visible by X-ray diffraction) can have a significant impact on the behavior of the bulk crystalline material. Thus, the role of microstructure may be considered more heavily in future mechanistic studies on mechanically responsive crystals.}, archive = {J_JACS}, author = {Abbey N. Ragan and Yannick Kraemer and Subash K. Chaudhary and Onosai J. Fonoti and Charlotte Cook and Gang-yu Liu and Nils Trapp and Kristie J. Koski and Cody Ross Pitts}, doi = {10.1021/jacs.4c08867}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1463--1473}, shortjournal = {J. Am. Chem. Soc.}, title = {Tetrafluoro(aryl)sulfanylated bicyclopentane crystals that self-destruct upon cooling}, volume = {147}, year = {2025}, }
• (2025). Quantitative proteomics identifies profilin-1 as a pseudouridine-binding protein. JACS, 147(2), 1458--1462. (www)

  @article{ , abstract = {Pseudouridine (Ψ) is the most abundant RNA modification in nature; however, not much is known about the biological functions of this modified nucleoside. Employing an unbiased quantitative proteomics method, we identified multiple candidate reader proteins of Ψ in RNA, including a cytoskeletal protein profilin-1 (PFN1). We demonstrated that PFN1 binds directly and selectively to Ψ-containing RNA. Additionally, we discovered approximately 4000 binding sites of PFN1 in human cells, including a known dyskerin (DKC1)-installed Ψ site in TPI1 mRNA, which encodes triosephosphate isomerase. Moreover, we showed that PFN1 and DKC1 are crucial for regulating the stability and translation efficiency of TPI1 mRNA through modulating PFN1-Ψ interaction. Together, we identified PFN1 as a reader protein of Ψ in RNA and illustrated a potential role of PFN1-Ψ interaction in post-transcriptional regulation. These findings provide new insights into the functions of Ψ in RNA biology and in modulating the expression of an important metabolic enzyme.}, archive = {J_JACS}, author = {Songbo Wei and Xiaoxia Dai and Jun Yuan and Shiyang He and Kriti Shah and Shiyuan Guo and Zheng Duan and Jernej Murn and Yinsheng Wang}, doi = {10.1021/jacs.4c17659}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1458--1462}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantitative proteomics identifies profilin-1 as a pseudouridine-binding protein}, volume = {147}, year = {2025}, }
• (2025). The SUMO (Singly unoccupied molecular orbital)-LUMO (Lowest unoccupied molecular orbital) inversion radicals. JACS, 147(2), 1452--1457. (www)

  @article{ , abstract = {Herein, SUMO-LUMO inversion (SLI) radicals 2a – 2c were designed by the combination of the tris(2,4,6-trichlorophenyl)methyl (TTM) radical and pyridinium derivatives (electron-withdrawing groups) for the first time. The energy of the LUMO lies below that of the SUMO, which deviated from the Aufbau principle as an alternative electronic configuration beyond the well-established SOMO-HOMO inversed system. Thus, for SLI radicals, the injection of one extra electron preferred to occupy the LUMO rather than the SUMO, giving diradicals, one of which 3 had been fully confirmed by single crystal analysis, VT-NMR and VT-EPR experiments, as well as DFT calculations. Furthermore, SLI radicals 2a – 2c exhibit photoluminescent properties and good photostability under UV irradiation ( t 1/2 > 24 days for 2c ). This finding would open up new exploration on SLI radicals and their potential applications as photoelectromagnetic material.}, archive = {J_JACS}, author = {Zenghui Li and Xiaoyang Liu and Qidi Bao and Jing Wang and Xu Liu and Honghong Gong and Tian Han and Chao Feng and Dongmei Lu and Ling Yue and Chao Wu and Gang He and Yuanting Su and Bin Rao}, doi = {10.1021/jacs.4c16614}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1452--1457}, shortjournal = {J. Am. Chem. Soc.}, title = {The SUMO (Singly unoccupied molecular orbital)-LUMO (Lowest unoccupied molecular orbital) inversion radicals}, volume = {147}, year = {2025}, }
• (2025). Highly position- and enantioselective catalytic epoxidation of polyolefins mediated by a chiral mn complex, including a one-step conversion of squalene to the (S)-2,3-epoxide, a precursor of natural steroids and terpenoids. JACS, 147(2), 1448--1451. (www)

  @article{ , abstract = {Reported herein is the synthesis of a novel chiral dicarboxylic ligand for Mn(II) and the application of the Mn complex to the highly enantio- and position-selective epoxidation of C═C under mild conditions, even with polyolefinic substrates. A stereomechanistic basis for asymmetric induction is suggested.}, archive = {J_JACS}, author = {G. Sudhakar Reddy and E. J. Corey}, doi = {10.1021/jacs.4c16570}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1448--1451}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly position- and enantioselective catalytic epoxidation of polyolefins mediated by a chiral mn complex, including a one-step conversion of squalene to the (S)-2,3-epoxide, a precursor of natural steroids and terpenoids}, volume = {147}, year = {2025}, }
• (2025). Iron-catalyzed aerobic carbonylation of methane via ligand-to-metal charge transfer excitation. JACS, 147(2), 1440--1447. (www)

  @article{ , abstract = {The integration of ligand-to-metal charge transfer (LMCT) catalytic paradigms with radical intermediates has transformed the selective functionalization of inert C–H bonds, facilitating the use of nonprecious metal catalysts in demanding transformations. Notably, aerobic C–H carbonylation of methane to acetic acid remains formidable due to the rapid oxidation of methyl radicals, producing undesired C1 oxygenates. We present an iron terpyridine catalyst utilizing LMCT to achieve exceptional C2/C1 selectivity through synergistic photoexcitation, methyl radical generation, and carbonylation. Mechanistic studies highlight the critical roles of Fe(II) and Fe-carbonyl complexes in bypassing methyl radical oxidation via a radical rebound-like pathway, unlocking unprecedented efficiency in methane aerobic carbonylation.}, archive = {J_JACS}, author = {Hui Pan and Qing An and Binh Khanh Mai and Yuegang Chen and Peng Liu and Zhiwei Zuo}, doi = {10.1021/jacs.4c16449}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1440--1447}, shortjournal = {J. Am. Chem. Soc.}, title = {Iron-catalyzed aerobic carbonylation of methane via ligand-to-metal charge transfer excitation}, volume = {147}, year = {2025}, }
• (2025). Photochemical deracemization of 4,7-diaza-1-isoindolinones by unidirectional hydrogen atom shuttling. JACS, 147(2), 1434--1439. (www)

  @article{ , abstract = {By coupling a photochemical and a thermal step, a single chiral catalyst can establish a photostationary state in which the enantiopure form of a chiral compound is favored over its racemate. Following this strategy, 3-substituted 4,7-diaza-1-isoindolones were successfully deracemized (74–98% yield, 86–99% ee ) employing 2.5 mol % of a photocatalyst. Key to the success of the reaction is the fact that a chiral benzophenone recruits selectively one enantiomer of the substrate for a photoinduced hydrogen atom transfer. A combination of computational and experimental studies suggests that the hydrogen atom is shuttled via the oxygen atom of the catalyst to the 4-nitrogen atom of the substrate.}, archive = {J_JACS}, author = {Philip Freund and Mike Pauls and Daria Babushkina and Thomas Pickl and Christoph Bannwarth and Thorsten Bach}, doi = {10.1021/jacs.4c16053}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1434--1439}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemical deracemization of 4,7-diaza-1-isoindolinones by unidirectional hydrogen atom shuttling}, volume = {147}, year = {2025}, }
• (2025). Synthesis of chiral saturated heterocycles bearing quaternary centers via enantioselective β-C(sp3)–H activation of lactams. JACS, 147(2), 1427--1433. (www)

  @article{ , abstract = {The development of catalytic methods for the synthesis of enantiopure saturated heterocycles has been a long-standing challenge in asymmetric catalysis. We describe the first highly enantioselective palladium-catalyzed β - C(sp 3 )–H arylation and olefination of lactams for the preparation of various chiral N-heterocycles bearing quaternary carbon centers. The presence of strongly electron-withdrawing groups on the chiral bifunctional MPAThio ligand is crucial to the reactivity of weakly coordinating lactams. The resulting enantioenriched lactams are readily converted to a family of chiral piperidines and imides that are highly desirable in drug discovery.}, archive = {J_JACS}, author = {Peng Lu and William R. Burgenson and Bryan J. Simmons and Shuang Liu and Kap-Sun Yeung and Jennifer X. Qiao and Jin-Quan Yu}, doi = {10.1021/jacs.4c15834}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1427--1433}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of chiral saturated heterocycles bearing quaternary centers via enantioselective β-C(sp3)–H activation of lactams}, volume = {147}, year = {2025}, }
• (2025). Combining distibene, diazoolefins, and visible light: Synthesis and reactivity of inorganic rings. JACS, 147(2), 1421--1426. (www)

  @article{ , abstract = {The chemistry of heterocycles containing “diaza” units has been extensively studied due to their applications ranging from pharmaceuticals to advanced materials. In contrast, heterocycles incorporating heavier elements, such as Sb and Bi, remain exceedingly rare and lack straightforward synthetic methodologies. Herein, we present a comprehensive experimental and theoretical investigation of the first diazadistiboylidenes ( 1a , 1b ), synthesized via a [3 + 2]-cycloaddition between a distibene and diazoolefins. These stiboylidenes are key intermediates to promote selective nucleophilic substitution, leading to a rare example of diantimonyl anion. Furthermore, upon visible-light irradiation, we could isolate the first example of methylenedistibiranes, heavier analogs of methylenediaziridine (C 2 H 4 N 2 ). These findings offer a novel platform for heavy dipnictogen chemistry, showcasing that diazoolefins, in combination with visible light, can facilitate the formation of unprecedented heavy heterocycles and serve as a platform to promote CO 2 activation.}, archive = {J_JACS}, author = {Prasenjit Palui and Sangita Ghosh and Rosa M. Gomila and Gregor Schnakenburg and Antonio Frontera and Alessandro Bismuto}, doi = {10.1021/jacs.4c15626}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1421--1426}, shortjournal = {J. Am. Chem. Soc.}, title = {Combining distibene, diazoolefins, and visible light: Synthesis and reactivity of inorganic rings}, volume = {147}, year = {2025}, }
• (2025). Synthesis of rigid stepladder polymers via scandium-catalyzed polyspiroannulation of quinoline with alkyne. JACS, 147(2), 1416--1420. (www)

  @article{ , abstract = {Polymers with rigid three-dimensional architectures have attracted significant attention due to their high rigidity and intrinsic microporosity. Here, we report the synthesis of a new class of rigid stepladder polymers featuring unique spirodihydroquinoline skeletons. Under the catalysis of a half-sandwich scandium catalyst, quinoline compounds bearing both an aryl substituent (e.g., phenyl or naphthyl) and an alkynyl group (e.g., C≡CSiMe 3 ) selectively undergo dearomative polyspiroannulation between the quinoline skeleton and the alkyne unit via ortho -C–H activation of the aryl group. This reaction efficiently yields rigid stepladder polymers comprising a spirodihydroquinoline skeleton with a quaternary carbon stereocenter and an unprotected N–H group. Treatment of the N–H-containing polymers with an alkyl lithium reagent followed by methyl iodide leads to quantitative formation of the corresponding N -methylated polymers, which exhibit enhanced thermal stability and porosity compared to their N–H counterparts.}, archive = {J_JACS}, author = {Jingjing Shao and Lin Huang and Shao-Jie Lou and Aya Ohno and Yoichi M. A. Yamada and Masayoshi Nishiura and Tetsuro Murahashi and Zhaomin Hou}, doi = {10.1021/jacs.4c15046}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1416--1420}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of rigid stepladder polymers via scandium-catalyzed polyspiroannulation of quinoline with alkyne}, volume = {147}, year = {2025}, }
• (2025). The role of nonequilibrium solvent effects in enhancing direct CO2 capture at the Air–Aqueous amino acid interface. JACS, 147(2), 1411--1415. (www)

  @article{ , abstract = {Direct air capture (DAC) technologies are limited by the poor understanding of the dynamic role of interfaces in modulating the chemisorption of CO 2 from air into solutions. While the reactivity of aqueous amine-based solvents in the bulk environment is strongly inhibited by nonequilibrium solvent effects, promoting DAC at interfaces posits a possibility to reduce the coupling with the solvent and significantly accelerate DAC. Building on an experimentally proven concept to bring an anionic glycine absorbent to the interface through ion-pairing interactions with a positively charged surfactant, we establish the fundamental time scales for key elementary steps involved in DAC with rate theory and enhanced-sampling ab initio molecular dynamics simulations. We elucidate the mechanism by which water influences the free energy barriers and dynamical crossing-recrossing of those barriers, affecting the reaction rates. We find that water reorganizes to partially dehydrate [-NH 2 ], facilitating S N 2-based CO 2 conversion to a zwitterion, which then releases a proton via overhydration of [-NH 2 ]. The low-density interfacial water favors dehydration over overhydration, leading to a comparatively higher barrier (slower kinetics) for proton release. The barrier-recrossing events neutralize this effect, letting both steps occur at the same time scale (sub-microseconds) and making the overall DAC process faster at the interface than in the bulk water. Such an understanding of environment-sensitive solvent effects on the reaction kinetics will help design tailored interfaces for enhanced CO 2 capture kinetics via control of solvation and ion paring.}, archive = {J_JACS}, author = {Nitesh Kumar and Vyacheslav S. Bryantsev and Santanu Roy}, doi = {10.1021/jacs.4c14612}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1411--1415}, shortjournal = {J. Am. Chem. Soc.}, title = {The role of nonequilibrium solvent effects in enhancing direct CO2 capture at the Air–Aqueous amino acid interface}, volume = {147}, year = {2025}, }
• (2025). Metallo-azapeptides: Controlled metal chelation to peptide backbone nitrogen. JACS, 147(2), 1404--1410. (www)

  @article{ , abstract = {We present the first approach to controlled metal chelation of peptide backbones, where the anchoring site is an aza-amino acid nitrogen and the directionality of chelation events is dictated by the acidity of neighboring NHs. Selective backbone chelation precludes the need for metal-binding side chains and/or free N - or C -termini in peptides. We show that the presence and location of an aza-amino acid impact complex formation and report the first X-ray crystal structures of azapeptides bound to palladium and nickel. Evidence of atropisomerism in metallo-azapeptides is also presented.}, archive = {J_JACS}, author = {Maxwell O. Bowles and Evan L. Willis and Meric D. Trombley and Chun-Hsing Chen and Caroline Proulx}, doi = {10.1021/jacs.4c14536}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1404--1410}, shortjournal = {J. Am. Chem. Soc.}, title = {Metallo-azapeptides: Controlled metal chelation to peptide backbone nitrogen}, volume = {147}, year = {2025}, }
• (2025). Molecular drillers for 2 nm resolution nanochannel perforation of 2D nanoplates. JACS, 147(2), 1399--1403. (www)

  @article{ , abstract = {Perpendicular nanochannel creation of two-dimensional (2D) nanostructures requires highly controlled anisotropic drilling processes of the entire structure via void formation. However, chemical approaches for the creation of porosity and defects of 2D nanostructures have been challenging due to the strong basal plane chemical stability and the use of harsh reactants, tending to give randomly corroded 2D structures. In this study, we introduce Lewis acid–base conjugates (LABCs) as molecular drillers with attenuated chemical reactivity which results in the well-defined perpendicular nanochannel formation of 2D TiS 2 nanoplates. With the treatment of LABCs, tris(trimethylsilyl)pnictogens (TMS 3 P or TMS 3 As), high resolution perforation of TiS 2 nanoplates was achieved while maintaining their initial shape and structures. Such perforated TiS 2 nanoplates are tunable in their channel diameter between 4 and 10 nm with 2 nm resolution. With their increased surface area and enhanced adsorption of Li 2 S x , perforated TiS 2 nanoplates served as a diffusion barrier of lithium–sulfur (Li–S) cells, leading to a 2.5-fold improvement in cell performance compared to pristine TiS 2 nanoplates. Our molecular design concept for attenuated reactivity of LABCs is simple and could serve as a new approach for chemical drilling processes of 2D metal chalcogenides.}, archive = {J_JACS}, author = {Jae Hyo Han and Mansoo Park and Jung-uk Lee and Changhoon Choi and Jung Been Park and Yongjun Lim and Gooreum Kim and Jaemog Jung and Dominik Lungerich and Chul-Ho Jun and Dong-Wan Kim and Jinwoo Cheon}, doi = {10.1021/jacs.4c12803}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1399--1403}, shortjournal = {J. Am. Chem. Soc.}, title = {Molecular drillers for 2 nm resolution nanochannel perforation of 2D nanoplates}, volume = {147}, year = {2025}, }
• (2025). Synthesis of two-dimensional high-entropy transition metal dichalcogenide single crystals. JACS, 147(2), 1392--1398. (www)

  @article{ , abstract = {Two-dimensional (2D) high-entropy transition metal dichalcogenides (HETMDs) have gained significant interest due to their structural properties and correlated possibilities for high-end devices. However, the controlled synthesis of 2D HETMDs presents substantial challenges owing to the distinction in the inherent characteristics among diverse metal elements in the synthesis, such as saturated vapor pressure of precursors and formation energy of products. Here, we present the synthesis of a 2D HETMD single crystal with 0.92 nm thickness through a liquid-phase reaction system, where the metal elements are fed uniformly and simultaneously. The rapid codeposition of different precursors facilitates the formation of high-entropy products, thereby preventing phase separation. The method can be expanded to produce a variety of 2D HETMDs, such as quinary (MoNbTaV)S 2 , hexahydroxy (MoWNbTaV)S 2 , and multichalcogenide (MoWNb)SSe. The as-prepared 2D HETMD is an excellent catalyst for the hydrogen evolution reaction (HER), demonstrating the overpotential of 84 mV at 10 mA cm –2 of an individual crystal, which is much better than that of pristine MoS 2 (260 mV at 10 mA cm –2 ). The strategy offers the flexibility to artificially design the element selectivity and properties of HETMD single crystals in the 2D limit, enabling applications across a wide range of advanced fields.}, archive = {J_JACS}, author = {Zhouyang Wang and Xiaonan Chen and Yiran Ding and Xiaofei Zhu and Zihang Sun and Haitao Zhou and Xiang Li and Wenxuan Yang and Junlin Liu and Runze He and Jingrui Luo and Ting Yu and Mengqi Zeng and Lei Fu}, doi = {10.1021/jacs.4c11363}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1392--1398}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthesis of two-dimensional high-entropy transition metal dichalcogenide single crystals}, volume = {147}, year = {2025}, }
• (2025). Near-infrared magnetic circularly polarized luminescence and slow magnetic relaxation in a tetrazinyl-bridged erbium metallocene. JACS, 147(2), 1387--1391. (www)

  @article{ , abstract = {The magnetic and magneto-optical properties of a tetrazinyl radical-bridged Er III metallocene, [(Cp* 2 Er III ) 2 (bpytz •– )][BPh 4 ] ( 1 ; Cp* = pentamethylcyclopentadienyl, bpytz = 3,6-bis(3,5-dimethyl-pyrazolyl)-1,2,4,5-tetrazine), are reported. As confirmed by these studies strong Ln-rad coupling is achieved, with 1 exhibiting slow magnetic relaxation under a 1000 Oe dc field. The optical and magneto-optical profile of 1 is completed by both near-infrared (NIR) luminescence and magnetic circularly polarized luminescence (MCPL), representing the first example of NIR MCPL with Er III .}, archive = {J_JACS}, author = {Niki Mavragani and Diogo A. Gálico and Alexandros A. Kitos and Muralee Murugesu}, doi = {10.1021/jacs.4c10954}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1387--1391}, shortjournal = {J. Am. Chem. Soc.}, title = {Near-infrared magnetic circularly polarized luminescence and slow magnetic relaxation in a tetrazinyl-bridged erbium metallocene}, volume = {147}, year = {2025}, }
• (2025). Triphenylphosphine oxide-derived anolyte for application in nonaqueous redox flow battery. JACS, 147(2), 1381--1386. (www)

  @article{ , abstract = {Recent advances in redox flow batteries have made them a viable option for grid-scale energy storage, however they exhibit low energy density. One way to boost energy density is by increasing the cell potential using a nonaqueous system. Molecular engineering has proven to be an effective strategy to develop redox-active compounds with extreme potentials but these are usually challenged by resource sustainability of the newly developed redox materials. Here, we investigate the utility of phosphine oxides as anolytes with extremely negative potentials. Specifically, we found that cyclic triphenylphosphine oxide (CPO), has a highly negative potential (−2.4 V vs Fc/Fc + ). Importantly, CPO is synthesized from triphenylphosphine oxide, a common industrial chemical waste with no commercial value. Structural and electrochemical characterization of the reduced radical anion showed that enhanced stability is due to cyclization or extended pi-conjugation. Importantly, mechanistic investigation into the decomposition of CPO under various solvents and electrochemical conditions allowed us to utilize an acetonitrile/DMF binary solvent system to enable a long-lived anolyte which exhibited no fade over 350 cycles. In summary, this work led to the development of a waste-derived cyclic phosphine oxide that exhibits excellent cycling stability making it an ideal anolyte toward the development of energy-dense RFBs.}, archive = {J_JACS}, author = {Emily R. Mahoney and Maxime Boudjelel and Henry Shavel and Matthew D. Krzyaniak and Michael R. Wasielewski and Christian A. Malapit}, doi = {10.1021/jacs.4c07750}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1381--1386}, shortjournal = {J. Am. Chem. Soc.}, title = {Triphenylphosphine oxide-derived anolyte for application in nonaqueous redox flow battery}, volume = {147}, year = {2025}, }
• (2025). The importance and discovery of highly connected covalent organic framework net topologies. JACS, 147(2), 1367--1380. (www)

  @article{ , abstract = {Furthering the field of synthetic organic chemistry from the discrete molecules regime to the extended structure regime, covalent organic frameworks (COFs) represent a new genre of crystalline porous materials featuring designability with molecular-level precision, well-defined porosity, and exceptional stability imparted by the robust covalent linkages reticulating organic molecules. The topology of COFs is a principal feature that regulates their functionality and usability for emerging technologies. Profound comprehension of network topologies and maneuvering them toward targeted applications are crucial to advancing the realm of COF research and developing novel functional materials for exciting breakthroughs. In this Perspective, we discuss the recent research pursuits contributing to the discovery of highly connected COF nets having novel topologies, assess the key challenges to achieving such network topologies, and offer insights into the current scenario and future directions.}, archive = {J_JACS}, author = {Tsukasa Irie and Saikat Das and Qianrong Fang and Yuichi Negishi}, doi = {10.1021/jacs.4c14458}, journal = {Journal of the American Chemical Society}, month = {1}, number = {2}, pages = {1367--1380}, shortjournal = {J. Am. Chem. Soc.}, title = {The importance and discovery of highly connected covalent organic framework net topologies}, volume = {147}, year = {2025}, }
• (2025). Correction to “Modulated cell internalization behavior of icosahedral DNA framework with programmable surface modification”. JACS, 147(1), 1366. (www)

  @article{ , archive = {J_JACS}, author = {Kui Huang and Qiulan Yang and Min Bao and Shengwen Wang and Luming Zhao and Qian Shi and Yang Yang}, doi = {10.1021/jacs.4c16945}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1366}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Modulated cell internalization behavior of icosahedral DNA framework with programmable surface modification”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Direct measurements of covalently bonded sulfuric anhydrides from gas-phase reactions of SO3 with acids under ambient conditions”. JACS, 147(1), 1365. (www)

  @article{ , archive = {J_JACS}, author = {Avinash Kumar and Siddharth Iyer and Shawon Barua and James Brean and Emin Besic and Prasenjit Seal and Manuel Dall’Osto and David C. S. Beddows and Nina Sarnela and Tuija Jokinen and Mikko Sipilä and Roy M. Harrison and Matti Rissanen}, doi = {10.1021/jacs.4c16560}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1365}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Direct measurements of covalently bonded sulfuric anhydrides from gas-phase reactions of SO3 with acids under ambient conditions”}, volume = {147}, year = {2025}, }
• (2025). Correction to “Programming sp3 quantum defects along carbon nanotubes with halogenated DNA”. JACS, 147(1), 1364. (www)

  @article{ , archive = {J_JACS}, author = {Xiaojian Wu and Mijin Kim and Lucy J. Wang and Abhindev Kizhakke Veetil and YuHuang Wang}, doi = {10.1021/jacs.4c16192}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1364}, shortjournal = {J. Am. Chem. Soc.}, title = {Correction to “Programming sp3 quantum defects along carbon nanotubes with halogenated DNA”}, volume = {147}, year = {2025}, }
• (2025). Hydroxyl spillover in Fe–Se dual-site catalysts for mixed plastics assay. JACS, 147(1), 1356--1363. (www)

  @article{ , abstract = {The complex composition of real plastic wastes poses a significant challenge for their large-scale disposal. A responsive on-site compositional analysis of plastics is informative in choosing downstream processing methods. Nanocatalyst-based assay kit is highly qualified for this scene; however, there remain no efficient nanocatalysts for plastics due to their highly inert chemistry. Herein, we first unveiled the hydroxyl spillover effect in an Fe–Se dual-site catalyst (FeSe/NC) and devised a prototype colorimetric assay kit for mixed plastics. Experimental and theoretical results unveiled that Fe sites acted as the main active sites for H 2 O 2 activation to produce adsorbed hydroxyl (*OH) intermediates, which subsequently desorb as hydroxyl radicals ( • OH) and transfer to Se sites, supports, and even plastics for further catalysis. Specifically, • OH transferred to different plastics shows varying activities, where signal outputs were hereby used as the fingerprint for plastic identification. Moreover, the remaining *OH could respond to redox interferences in the samples for enhanced accuracy. In contrast to traditional techniques involving precise apparatus and complex pretreatments, our approach enables a rapid assay (∼10 min) of raw powdery mixed plastic wastes with an ultralow cost (0.0012 $). This discovery fills a crucial gap in the plastic assay, offering new technical guidance for diverse upcycling and recycling strategies to tackle the global plastic waste crisis.}, archive = {J_JACS}, author = {Yu Wu and Wenxuan Jiang and Weiqing Xu and Fan Lv and Shaojia Song and Liuyong Hu and Canglong Wang and Lirong Zheng and Wenling Gu and Riguang Zhang and Shaojun Guo and Chengzhou Zhu}, doi = {10.1021/jacs.4c16655}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1356--1363}, shortjournal = {J. Am. Chem. Soc.}, title = {Hydroxyl spillover in Fe–Se dual-site catalysts for mixed plastics assay}, volume = {147}, year = {2025}, }
• (2025). Merging and clipping nets for the synthesis of three- and two-merged net Metal–Organic frameworks. JACS, 147(1), 1344--1355. (www)

  @article{ , abstract = {Herein, we report how merging and clipping nets in metal–organic frameworks (MOFs) can be controlled in a single-crystal-to-single-crystal fashion using three different approaches─the merged net, clip-off chemistry, and linker reinstallation─to design and synthesize three- and two-merged net MOFs. Initially, we show the formation of three isoreticular three-merged net MOFs by linking a trimeric Sc 3+ cluster, Sc 3 (μ 3 -Ο)(−COO) 6 , with ditopic zigzag and tritopic linkers. The resulting MOFs exhibit three-merged edge-transitive nets─ kgd + hxl + pcu ─for the first time. Then, using these three-merged net MOFs as precursors, we selectively remove one of these subnets, the hxl net, via clip-off chemistry to form two-merged net MOFs. This process involves the cleavage of olefinic groups via ozonolysis, providing the resulting two-merged net MOFs with free carboxylic acid groups that can be used to tune their sorption properties such as the removal of cationic organic pollutants. Finally, we use the linker reinstallation approach to convert the two-merged net MOFs back to the three-merged net MOFs. This approach allows for the postsynthetic addition of the previously removed hxl merged net, enabling recovery of the initial three-merged net MOFs or synthesis of new ones using novel ditopic zigzag linkers.}, archive = {J_JACS}, author = {Yunhui Yang and Pilar Fernández-Seriñán and Borja Ortín-Rubio and Partha Samanta and Felipe Gándara and Davide M. Proserpio and Dongsik Nam and Judith Juanhuix and Inhar Imaz and Daniel Maspoch}, doi = {10.1021/jacs.4c15936}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1344--1355}, shortjournal = {J. Am. Chem. Soc.}, title = {Merging and clipping nets for the synthesis of three- and two-merged net Metal–Organic frameworks}, volume = {147}, year = {2025}, }
• (2025). Phase engineering facilitates O–O coupling via lattice oxygen mechanism for enhanced oxygen evolution on Nickel–Iron phosphide. JACS, 147(1), 1334--1343. (www)

  @article{ , abstract = {Nickel–iron-based catalysts are recognized for their high efficiency in the oxygen evolution reaction (OER) under alkaline conditions, yet the underlying mechanisms that drive their superior performance remain unclear. Herein, we revealed the molecular OER mechanism and the structure-intermediate-performance relationship of OER on a phosphorus-doped nickel–iron nanocatalyst (NiFeP). NiFeP exhibited exceptional activity and stability with an overpotential of only 210 mV at 10 mA cm –2 in 1 M KOH and a cell voltage of 1.68 V at 1 A cm –2 in anion exchange membrane water electrolyzers. The evolution of active sites and intermediates during OER on NiFeP was in situ probed and correlated using shell-isolated nanoparticle-enhanced Raman spectroscopy, complemented by differential electrochemical mass spectrometry and density functional theory. These results provide direct evidence that OER proceeds via the lattice oxygen-mediated mechanism. Remarkably, phosphorus doping plays a critical role in stabilizing the active β-Ni(Fe)OOH phase, which facilitates the *OH deprotonation and the subsequent O–O coupling to form *OO intermediates. Our findings offer a deeper understanding of the OER mechanism, providing a clear pathway for designing next-generation OER catalysts with improved efficiency and durability.}, archive = {J_JACS}, author = {Zheng-Xin Qian and Ge-Hao Liang and Liang-Fei Shen and Ge Zhang and Shisheng Zheng and Jing-Hua Tian and Jian-Feng Li and Hua Zhang}, doi = {10.1021/jacs.4c15847}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1334--1343}, shortjournal = {J. Am. Chem. Soc.}, title = {Phase engineering facilitates O–O coupling via lattice oxygen mechanism for enhanced oxygen evolution on Nickel–Iron phosphide}, volume = {147}, year = {2025}, }
• (2025). Contrasteric glycosylations of cotylenol and 1,2-diols by virtual linker selection. JACS, 147(1), 1327--1333. (www)

  @article{ , abstract = {Many terpene glycosides exhibit contrasteric patterns of 1,2-diol glycosylation in which the more hindered alcohol bears a sugar; protection of the less hindered alcohol only increases steric repulsion. Here, we report a method for contrasteric glycosylation using a new sugar-linker that forms a cleavable, 10-membered ring with high efficiency, leading to syntheses of cotylenin E, J, and ISIR-050. Linker selection was aided by DFT calculations of side reactions and stereoselectivity, as well as conformational analyses using autoDFT, a Python script that converts SMILES strings to DFT-optimized conformational ensembles.}, archive = {J_JACS}, author = {Dylan W. Snelson and Stephen I. Ting and Ryan A. Shenvi}, doi = {10.1021/jacs.4c15719}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1327--1333}, shortjournal = {J. Am. Chem. Soc.}, title = {Contrasteric glycosylations of cotylenol and 1,2-diols by virtual linker selection}, volume = {147}, year = {2025}, }
• (2025). Substituent effects on cooperativity in three-component H-bond networks involving Phenol–Phenol interactions. JACS, 147(1), 1319--1326. (www)

  @article{ , abstract = {Cooperativity between H-bonding interactions in networks is a fundamental aspect of solvation and self-assembly in molecular systems. The interaction of a series of bisphenols, which make an intramolecular H-bond between the two hydroxyl groups, and quinuclidine was used to quantify cooperativity in three-component networks. The presence of the intramolecular H-bond in the bisphenols was established by using 1 H NMR spectroscopy in solution and X-ray crystallography in the solid state. The interactions with quinuclidine were investigated using UV–vis and 1 H NMR titrations, which show that the intramolecular hydrogen bonds persist in the 1:1 complexes. By varying substituents on one of the phenol groups, it was possible to measure the effect of changing the strength of the intramolecular H-bond between the hydroxyl groups on the strength of the intermolecular H-bond with quinuclidine. Strong positive cooperativity was observed between the two interactions, with increases in binding free energy of up to 16 kJ mol –1 . By varying substituents on the other phenol group, which makes both an intramolecular H-bond and an intermolecular H-bond in the complex, it was possible to measure how the properties of this central hydroxyl group modulate cooperativity between the interactions with the other two functional groups. Changing the polarity of this phenol had no effect on the measured cooperativity. The results indicate that cooperativity in H-bond networks can be understood as a polar interaction between two remote functional groups that is damped by a central functional group. The extent of damping is quantified by cooperativity parameter κ, which is 0.33 for the hydroxyl group and appears to be an intrinsic property of the geometry or polarizability of the functional group rather than polarity.}, archive = {J_JACS}, author = {Lucia Trevisan and Andrew D. Bond and Christopher A. Hunter}, doi = {10.1021/jacs.4c15767}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1319--1326}, shortjournal = {J. Am. Chem. Soc.}, title = {Substituent effects on cooperativity in three-component H-bond networks involving Phenol–Phenol interactions}, volume = {147}, year = {2025}, }
• (2025). Galloyl dialkyl lipids drive encapsulation of peptides into lipid nanoparticles by hydrogen bonding. JACS, 147(1), 1307--1318. (www)

  @article{ , abstract = {The intracellular delivery of peptides and proteins is crucial for various biomedical applications. Lipid nanoparticles (LNPs) have emerged as a promising strategy for delivering peptides to phagocytic cells. However, the diverse physicochemical properties of peptides necessitate tailored formulations. This study introduces a generic approach using galloyl (GA)-functionalized lipids for the encapsulation of peptides in LNPs via hydrogen bonding between the ubiquitously present amides in peptides and the multivalently displayed galloyl phenol groups in GA-LNPs. In vitro studies showed that GA-LNPs significantly improved the cellular uptake of peptides and activated immune responses when combined with Toll-like receptor (TLR) agonists MPLA and IMDQ. In vivo, GA-LNPs accumulated in the spleen and enhanced peptide delivery to antigen-presenting cells. GA-LNPs coencapsulating peptide antigens and TLR agonists elicited robust antigen-specific CD8+ T-cell responses in mice.}, archive = {J_JACS}, author = {Tingting Ye and Yong Chen and Zifu Zhong and Yi Huang and Jamie De Baere and Mark Gontsarik and Kim Deswarte and Bianka Golba and Martijn Risseeuw and Serge Van Calenbergh and Bart N. Lambrecht and Bruno G. De Geest}, doi = {10.1021/jacs.4c15688}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1307--1318}, shortjournal = {J. Am. Chem. Soc.}, title = {Galloyl dialkyl lipids drive encapsulation of peptides into lipid nanoparticles by hydrogen bonding}, volume = {147}, year = {2025}, }
• (2025). Rare-earth metal-enabled ring-opening metathesis of benzene. JACS, 147(1), 1300--1306. (www)

  @article{ , abstract = {Activation and transformation of inert C–C bonds within arenes are challenging and important topics in synthetic chemistry. While there have been some reports on the activation of C–C bonds in arene rings, the realm of metathesis reactions involving arene C–C bonds remains unexplored. Here, we report a rare-earth metal-enabled intramolecular metathesis reaction of one benzene C–C bond and another C–C single bond, assisted by the high reactivity and unique synergistic effect of rare-earth metallacycles. Mechanistic studies disclose an intriguing pathway that forms a fused tricyclic intermediate bearing a 4-membered ring through stepwise [2 + 2] cycloaddition, followed by stepwise [2 + 2] cycloreversion. The distinct reaction discovered here extends the reactivity of arenes and is expected to inspire the development of aromatic ring-opening metathesis reactions.}, archive = {J_JACS}, author = {Wei Liu and Ping Wu and Yibo Liang and Junnian Wei and Gen Luo and Wen-Xiong Zhang}, doi = {10.1021/jacs.4c15650}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1300--1306}, shortjournal = {J. Am. Chem. Soc.}, title = {Rare-earth metal-enabled ring-opening metathesis of benzene}, volume = {147}, year = {2025}, }
• (2025). Cooperative regulation of ns2 lone-pair expression realizes distinct excitonic emissions in hybrid germanium, tin, and lead halides. JACS, 147(1), 1291--1299. (www)

  @article{ , abstract = {Lone-pair expression is significantly influenced by geometric constraints in hybrid metal halides (HMHs). Two-dimensional (2D) HMHs possess reduced structural dimensionality, allowing for a wide range of off-center displacement of the metal center. However, the effect of lone-pair-induced off-center distortion on the geometric configuration of inorganic units, electronic properties, and exciton emissions in 2D HMHs remains unclear. In this study, 2D DMPMBr 4 (DMP = N , N ′-dimethylpiperazine) HMHs of group 14 elements (M = Ge, Sn, and Pb) are developed, exhibiting pronounced stereochemical activity of n s 2 lone-pair electrons. Such 2D HMHs are chosen as a model system to demonstrate the influence of the stereochemical activity of n s 2 lone-pair electrons on the geometric configuration of inorganic units, electronic properties, and exciton emissions. The off-center distortion D is introduced to describe the degree of lone-pair expression in these HMHs, and a quantitative relationship between the D and FE/STE emissions is established. When the D is reduced to less than 0.24, the off-center distortion of the units is sufficiently suppressed to limit the lone-pair expression, facilitating the excitonic transition from the STE state to the FE state upon compression. Substituting metal cations with those having more inactive n s 2 lone-pair electrons exerts a similar effect to pressure in promoting the excitonic transitions in the DMPMBr 4 series. This study uncovers the relationship between the stereochemical activity of n s 2 lone-pair electrons and excitonic emissions, which could accelerate the development of HMHs with the desired optical properties.}, archive = {J_JACS}, author = {Jiang Han and Yawen Li and Peijie Zhang and Bin Xu and Xiaofan Xu and Zewei Quan}, doi = {10.1021/jacs.4c15554}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1291--1299}, shortjournal = {J. Am. Chem. Soc.}, title = {Cooperative regulation of ns2 lone-pair expression realizes distinct excitonic emissions in hybrid germanium, tin, and lead halides}, volume = {147}, year = {2025}, }
• (2025). Structural insights into the opening mechanism of C1C2 channelrhodopsin. JACS, 147(1), 1282--1290. (www)

  @article{ , abstract = {Channelrhodopsins, light-gated cation channels, enable precise control of neural cell depolarization or hyperpolarization with light in the field of optogenetics. This study integrates time-resolved serial crystallography and atomistic molecular dynamics (MD) simulations to resolve the structural changes during C1C2 channelrhodopsin activation. Our observations reveal that within the crystal environment, C1C2 predominantly remains in a light-activated state with characteristics of the M 390 intermediate. Here, rearrangement of retinal within its binding pocket partially opens the central gate toward the extracellular vestibule. These structural changes initiate channel opening but were insufficient to allow K + flow. Adjusting protonation states to represent the subsequent N 520 intermediate in our MD simulations induced further conformational changes, including rearrangements of transmembrane helices 2 and 7, that opened the inner gate and the putative ion-translocation pathway. This allowed spontaneous cation conduction with low conductance, aligning with experimental findings. Our findings provide critical structural insights into key intermediates of the channel opening mechanism, enhancing our understanding of ion conduction and selectivity in channelrhodopsins at an atomistic level.}, archive = {J_JACS}, author = {Matthias Mulder and Songhwan Hwang and Matthias Broser and Steffen Brünle and Petr Skopintsev and Caspar Schattenberg and Christina Schnick and Sina Hartmann and Jonathan Church and Igor Schapiro and Florian Dworkowski and Tobias Weinert and Peter Hegemann and Han Sun and Jörg Standfuss}, doi = {10.1021/jacs.4c15402}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1282--1290}, shortjournal = {J. Am. Chem. Soc.}, title = {Structural insights into the opening mechanism of C1C2 channelrhodopsin}, volume = {147}, year = {2025}, }
• (2025). Reversible bimetallic inhibition to modulate selectivity during catalysis. JACS, 147(1), 1271--1281. (www)

  @article{ , abstract = {Bimetallic complexes have demonstrated a great ability to enhance the activity of monometallic systems for bond activation and catalysis. In this work, we explore the opposite approach: using a second metal to passivate the activity of another by reversible bimetallic inhibition. To do so we have synthesized a family of nine electrophilic gold complexes of formula Au(PR 3 )(NTf 2 ) ([NTf 2 ] − = [N(SO 2 CF 3 ) 2 ] − ) that can act as inhibitors in the semihydrogenation of terminal and internal alkynes catalyzed by the iconic iridium Vaska complex IrCl(CO)(PPh 3 ) 2 . This behavior parallels the well-known passivation effect of lead over palladium in the heterogeneous Lindlard catalyst. Most gold fragments, except for the most hindered, form metal-only Lewis pairs upon combination with iridium, which have been fully characterized and exhibit distinct dative Ir → Au bonds. When applied to alkyne hydrogenation, these bimetallic structures have a clear tendency toward olefin formation, while the monometallic catalyst unselectively leads to overreduction products. Our computational studies not only provide a feasible mechanism for the Ir-only system, but also evince the active role of gold in passivating iridium by reversibly forming heterobimetallic structures that lead to enhanced selectivity.}, archive = {J_JACS}, author = {Emmanuel Serrano-Díez and Alejandra Pita-Milleiro and Jesús Rangel-García and Juan J. Moreno and Marta Roselló-Merino and Jesús Campos}, doi = {10.1021/jacs.4c15359}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1271--1281}, shortjournal = {J. Am. Chem. Soc.}, title = {Reversible bimetallic inhibition to modulate selectivity during catalysis}, volume = {147}, year = {2025}, }
• (2025). Pt2Gd alloy nanoparticles from organometallic pt and gd complexes and hollow mesoporous carbon spheres: Enhanced oxygen reduction reaction activity and durability. JACS, 147(1), 1262--1270. (www)

  @article{ , abstract = {Pt 2 Gd alloy nanoparticles supported in hollow mesoporous carbon spheres (HMCS; Pt 2 Gd/HMCS ) were successfully prepared by the thermal reduction of organometallic Pt and Gd complexes without oxygen atoms supported in the pores of HMCS. The structures of Pt 2 Gd alloy nanoparticles were fully characterized by TEM, HAADF-STEM-EDS, XRD, XAFS, and XPS, suggesting the formation of uniform Pt 2 Gd alloy nanoparticles with an average particle size of 5.9 nm. Pt 2 Gd/HMCS showed superior oxygen reduction reaction activity (2.4 times higher mass-specific activity to Pt nanoparticles on HMCS ( Pt/HMCS )) and remarkable durability even after the 100,000 cycles of accelerated degradation tests compared to Pt/HMCS and a commercial Pt/C catalyst. The structure of the Pt 2 Gd alloy nanoparticles after initial aging and the durability tests suggested that the Pt 2 Gd core–Pt shell structure with a particle size similar to the pore size of HMCS was stably formed inside the porous structure of HMCS and maintained under the oxygen-reduction working conditions.}, archive = {J_JACS}, author = {Takumi Moriyama and Satoshi Muratsugu and Mitsuhiko Sato and Kimitaka Higuchi and Yasumasa Takagi and Mizuki Tada}, doi = {10.1021/jacs.4c15181}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1262--1270}, shortjournal = {J. Am. Chem. Soc.}, title = {Pt2Gd alloy nanoparticles from organometallic pt and gd complexes and hollow mesoporous carbon spheres: Enhanced oxygen reduction reaction activity and durability}, volume = {147}, year = {2025}, }
• (2025). Unveiling the centrosymmetric effect in the design of narrowband fluorescent emitters: From single to double difluoroboron cores. JACS, 147(1), 1251--1261. (www)

  @article{ , abstract = {Narrowband fluorescent emitters are receiving significant attention due to the great potential for creating ultrahigh-definition organic light-emitting diode displays (UHD-OLED). Unveiling innovative mechanisms to design new high-performance narrowband fluorescent emitters is a concerted endeavor in both academic and industrial circles. Theoretical calculations reveal that the centrosymmetric dianilido-bipyridine boron difluoride framework ( cs -DAPBF 2 ) exhibits significantly reduced structural relaxation compared to previously reported asymmetric structures with monofluoroboron cores, creating new opportunities for the development of narrowband fluorescent emitters. In this work, we present a dual chelation-assisted C–H/C–H homocoupling strategy to efficiently synthesize the 3,3′-amino-2,2′-bipyridine skeleton, enabling the straightforward construction of a series of symmetric cs -DAPBF 2 -based fluorescent emitters. Through molecular optimization, we have developed a high-performance narrowband green fluorescent emitter, cs -DMeAPBF 2 -MP, which demonstrates a narrow full width at half-maximum (fwhm) of 20 nm, a high photoluminescence quantum yield (Φ PL ) of 98%, a large molar absorptivity (ε) of 2.10 × 10 4 M –1 cm –1 , and a high horizontal dipole ratio (Θ // ) of 77%. These properties make cs -DMeAPBF 2 -MP a promising candidate for fabricating high-efficiency, narrowband green organic light-emitting diodes (OLEDs) with minimal efficiency roll-off. This study represents the first successful application of the DAPBF 2 architecture in the design of narrowband fluorescent emitters for high-performance OLEDs.}, archive = {J_JACS}, author = {Ge Yang and Junjie Liu and Yudong Yang and Zhengyang Bin and Jingsong You}, doi = {10.1021/jacs.4c15233}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1251--1261}, shortjournal = {J. Am. Chem. Soc.}, title = {Unveiling the centrosymmetric effect in the design of narrowband fluorescent emitters: From single to double difluoroboron cores}, volume = {147}, year = {2025}, }
• (2025). Precise large-scale chemical transformations on surfaces: Deep learning meets scanning probe microscopy with interpretability. JACS, 147(1), 1240--1250. (www)

  @article{ , abstract = {Scanning probe microscopy (SPM) techniques have shown great potential in fabricating nanoscale structures endowed with exotic quantum properties achieved through various manipulations of atoms and molecules. However, precise control requires extensive domain knowledge, which is not necessarily transferable to new systems and cannot be readily extended to large-scale operations. Therefore, efficient and autonomous SPM techniques are needed to learn optimal strategies for new systems, in particular for the challenge of controlling chemical reactions and hence offering a route to precise atomic and molecular construction. In this paper, we developed a software infrastructure named AutoOSS ( Auto nomous O n- S urface S ynthesis) to automate bromine removal from hundreds of Zn(II)-5,15-bis(4-bromo-2,6-dimethylphenyl)porphyrin (ZnBr 2 Me 4 DPP) on Au(111), using neural network models to interpret STM outputs and deep reinforcement learning models to optimize manipulation parameters. This is further supported by Bayesian optimization structure search (BOSS) and density functional theory (DFT) computations to explore 3D structures and reaction mechanisms based on STM images.}, archive = {J_JACS}, author = {Nian Wu and Markus Aapro and Joakim S. Jestilä and Robert Drost and Miguel Martínez García and Tomás Torres and Feifei Xiang and Nan Cao and Zhijie He and Giovanni Bottari and Peter Liljeroth and Adam S. Foster}, doi = {10.1021/jacs.4c14757}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1240--1250}, shortjournal = {J. Am. Chem. Soc.}, title = {Precise large-scale chemical transformations on surfaces: Deep learning meets scanning probe microscopy with interpretability}, volume = {147}, year = {2025}, }
• (2025). A crystalline unsupported phosphagallene and phosphaindene. JACS, 147(1), 1231--1239. (www)

  @article{ , abstract = {The synthesis and isolation of TerP═GaTer and TerP═InTer (Ter = 2,6-Dipp 2 -C 6 H 3 ; Dipp = 2,6-diisopropylphenyl) is reported. These compounds feature unsupported P═Ga and P═In double bonds and two-coordinate triel element centers. Key to the stabilization of such compounds is the steric bulk of the terphenyl substituents, which serve to shield the highly reactive P═E bonds (E = Ga, In) and prevent further aggregation. When smaller aromatic substituents are employed on the phosphorus-containing precursor, the cyclic compounds Mes*P(ETer) 2 (Mes* = 2,4,6- t Bu 3 -C 6 H 2 ) are isolated instead. These species contain weakly aromatic three-membered rings. The presence of an external base (PMe 3 ) is required in order to stabilize a phosphagallene when the smaller Mes* substituent is used, allowing for the isolation of Mes*P═GaTer(PMe 3 ).}, archive = {J_JACS}, author = {Álvaro García-Romero and Chenyang Hu and Maren Pink and Jose M. Goicoechea}, doi = {10.1021/jacs.4c15041}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1231--1239}, shortjournal = {J. Am. Chem. Soc.}, title = {A crystalline unsupported phosphagallene and phosphaindene}, volume = {147}, year = {2025}, }
• (2025). Migratory aryl cross-coupling. JACS, 147(1), 1224--1230. (www)

  @article{ , abstract = {A fundamental property of cross-coupling reactions is regiospecificity, meaning that the site of bond formation is determined by the leaving group’s location on the electrophile. Typically, achieving a different substitution pattern requires the synthesis of a new, corresponding starting-material isomer. As an alternative, we proposed the development of cross-coupling variants that would afford access to multiple structural isomers from the same coupling partners. Here, we first demonstrate that a bulky palladium catalyst can facilitate the efficient, reversible transposition of aryl halides by temporarily forming metal aryne species. Despite the nearly thermoneutral equilibrium governing this process, combining it with the gradual addition of a suitable nucleophile results in dynamic kinetic resolution of the isomeric intermediates and high yields of unconventional product isomers. The method accommodates a range of oxygen- and nitrogen-centered nucleophiles and tolerates numerous common functional groups. A Curtin–Hammett kinetic scheme is supported by computational and experimental data, providing a general mechanistic framework for extending this migratory cross-coupling concept.}, archive = {J_JACS}, author = {Yoshiya Sekiguchi and Polpum Onnuch and Yuli Li and Richard Y. Liu}, doi = {10.1021/jacs.4c15086}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1224--1230}, shortjournal = {J. Am. Chem. Soc.}, title = {Migratory aryl cross-coupling}, volume = {147}, year = {2025}, }
• (2025). Architecting ultra-robust Zr(IV) Metal–Organic framework for energy-efficient desiccant air conditioning. JACS, 147(1), 1214--1223. (www)

  @article{ , abstract = {Air-conditioning systems, composed mainly of humidity control and heat reallocation units, play a pivotal role in upholding superior air quality and human well-being across diverse environments ranging from international space stations and pharmacies to granaries and cultural relic preservation sites, and to commercial and residential buildings. The adoption of sorbent water as the working pair and low-grade renewable or waste heat in adsorption-driven air-conditioning presents a state-of-the-art solution, notably for its energy efficiency and eco-friendliness vis-à-vis conventional electricity-driven vapor compression cycles. Here, we introduce a rational π-extension strategy to engineer an ultrarobust and highly porous zirconium metal–organic framework (Zr-MOF). This MOF sorbent showcases hysteresis-free S-shaped water sorption isotherms, characterized by a rapid ascent within the 40–60% relative humidity range with a working capacity of 0.63 g g –1 , thus facilitating intelligent indoor humidity regulation. Moreover, we demonstrate, for the first time, that this material with such distinctive isotherms can yield a 10 °C temperature lift between ambient and chiller output with a high cooling capacity of 336 kW h m –3 per cycle, even at exceptionally low driving temperatures (below 50 °C), while also delivering a substantial coefficient of performance of 0.96. This material is amenable to scale-up and is chemically ultrastable that can endure strong acids and be cycled for at least 200 runs without compromising any of its capacity. These exceptional attributes signify the viability of this material as a pragmatic alternative for deployment in energy-efficient desiccant air-conditioning systems, particularly in hot and humid climatic regions.}, archive = {J_JACS}, author = {Wei Gong and Haomiao Xie and Kyung Ho Cho and Xianhui Tang and Jaedeuk Park and Zhijie Chen and Jinqiao Dong and Omar K. Farha and Yong Cui}, doi = {10.1021/jacs.4c15087}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1214--1223}, shortjournal = {J. Am. Chem. Soc.}, title = {Architecting ultra-robust Zr(IV) Metal–Organic framework for energy-efficient desiccant air conditioning}, volume = {147}, year = {2025}, }
• (2025). Crystalline silylene-stabilized diboryne and siladiborirene. JACS, 147(1), 1207--1213. (www)

  @article{ , abstract = {The exploration of main group compounds with multiple bonds has significantly enhanced our understanding of chemical bonding and expanded transition-metal-free bond activation and catalysis. Diborynes, characterized by a boron–boron triple bond (B≡B), represent a particularly challenging area due to boron’s limited valence electrons. Here, we report the synthesis and characterization of a silylene-stabilized diboryne ( 7 ), expanding the frontier of diboryne stabilization. X-ray diffraction analysis and density functional theory calculations confirm the presence of a B≡B bond in the diboryne. Remarkably, this diboryne undergoes [1 + 2] cycloaddition reactions with dichlorosilylene and terphenyl isocyanide, producing unprecedented siladiborirene (8) and diborirenimine ( 9 ), respectively. X-ray diffraction studies show that 8 and 9 bear a three-membered boron-containing heterocycle with a B═B bond, and computational studies reveal their distinct aromatic character.}, archive = {J_JACS}, author = {Chuangchuang Xu and Fanshu Cao and Xingge Chen and Ming Chen and Zhenbo Mo}, doi = {10.1021/jacs.4c14991}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1207--1213}, shortjournal = {J. Am. Chem. Soc.}, title = {Crystalline silylene-stabilized diboryne and siladiborirene}, volume = {147}, year = {2025}, }
• (2025). Total syntheses of diepoxy-ent-kaurane diterpenoids enabled by a bridgehead-enone-initiated intramolecular cycloaddition. JACS, 147(1), 1197--1206. (www)

  @article{ , abstract = {Here, we report the enantioselective total syntheses of four diepoxy- ent -kaurane diterpenoids including (−)-Macrocalin B, (−)-Acetyl-macrocalin B, and (−)-Isoadenolin A and the revised structure of (−)-Phyllostacin I, which hinges on the strategic design of a regioselective and stereospecific trapping of a highly reactive [3.2.1]-bridgehead enone intermediate via a tethered intramolecular Diels–Alder reaction. Combined experimental and computational studies demonstrated that the novel bridgehead-enone-initiated intramolecular cycloaddition could proceed in a stepwise diradical mechanism. Although the key step partially led to unexpected [2 + 2]-cycloaddition outcomes, we ultimately implemented an unprecedented Ti III -catalyzed cyclobutane ring-opening-annulation radical cascade to reassemble a keystone pentacyclic core. Coupled with a sequence of organized oxidation-state manipulations and an efficient late-stage assembly of the C-7,20 hemiketal bridge, our strategy would streamline the synthetic design of diepoxy- ent -kaurane diterpenoids and pave the way for their modular syntheses as well as highlight the powerful utility of [3.2.1]-bridgehead enone intermediates in the construction of structural complexity.}, archive = {J_JACS}, author = {Yin Li and Qilin Xue and Xiangbo Zhao and Dawei Ma}, doi = {10.1021/jacs.4c15004}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1197--1206}, shortjournal = {J. Am. Chem. Soc.}, title = {Total syntheses of diepoxy-ent-kaurane diterpenoids enabled by a bridgehead-enone-initiated intramolecular cycloaddition}, volume = {147}, year = {2025}, }
• (2025). Photochemical deracemization of lactams with deuteration enabled by dual hydrogen atom transfer. JACS, 147(1), 1186--1196. (www)

  @article{ , abstract = {Photochemical deracemization has emerged as one of the most straightforward approaches to access highly enantioenriched compounds in recent years. While excited-state events such as energy transfer, single electron transfer, and ligand-to-metal charge transfer have been leveraged to promote stereoablation, approaches relying on hydrogen atom transfer, which circumvent the limitations imposed by the triplet energy and redox potential of racemic substrates, remain underexplored. Conceptually, the most attractive method for tertiary stereocenter deracemization might be hydrogen atom abstraction followed by hydrogen atom donation. However, implementing such a strategy poses significant challenges, primarily because the enantioenriched products are also reactive if the chiral catalyst is unable to differentiate between the two enantiomers. Herein we report a distinct dual hydrogen atom transfer strategy for photochemical deracemization of δ- and γ-lactams, achieving high enantioenrichment and deuterium incorporation despite the inherent reactivity of the products. Mechanistic studies reveal that benzophenone enables nonselective hydrogen atom abstraction while a tetrapeptide-derived thiol dictates the enantioselectivity of the hydrogen atom donation step. More importantly, a pyridine-based alcohol was found to play crucial roles in facilitating the hydrogen atom abstraction as well as enhancing the enantioselectivity of the hydrogen atom donation step.}, archive = {J_JACS}, author = {Xiaoyu Yan and Yubing Pang and Yutong Zhou and Rui Chang and Juntao Ye}, doi = {10.1021/jacs.4c14934}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1186--1196}, shortjournal = {J. Am. Chem. Soc.}, title = {Photochemical deracemization of lactams with deuteration enabled by dual hydrogen atom transfer}, volume = {147}, year = {2025}, }
• (2025). Copper-catalyzed asymmetric nucleophilic opening of 1,1,2,2-tetrasubstituted Donor–Acceptor cyclopropanes for the synthesis of α-tertiary amines. JACS, 147(1), 1172--1185. (www)

  @article{ , abstract = {Catalytic asymmetric transformation of donor–acceptor cyclopropanes (DACs) has been proven to be a highly valuable and robust strategy to construct diverse types of enantioenriched molecules. However, the use of 1,1,2,2-tetrasubstituted DACs to form products bearing quaternary stereocenters remains a long-term unsolved challenge. Here, we report the copper-catalyzed asymmetric aminative ring opening of tetrasubstituted alkynyl DACs that delivers a myriad of α-tertiary amines with high levels of enantioselectivities. The alkyne, amine, and ester moieties within the products enable diverse further applications, including the asymmetric synthesis of bioactive molecules. Mechanistic studies indicate that the zwitterionic intermediate bearing a copper-acetylide unit plays a key role in the process, which represents a new mode for achieving catalytic asymmetric transformation of DACs.}, archive = {J_JACS}, author = {Shouang Lan and Qinqin Cui and Defu Luo and Siyu Shi and Chengyang He and Shengyu Huang and Chao Xu and Lili Zhao and Jinggong Liu and Cheng-Zhi Gu and Shuang Yang and Xinqiang Fang}, doi = {10.1021/jacs.4c14944}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1172--1185}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper-catalyzed asymmetric nucleophilic opening of 1,1,2,2-tetrasubstituted Donor–Acceptor cyclopropanes for the synthesis of α-tertiary amines}, volume = {147}, year = {2025}, }
• (2025). Multielectron redox chemistry of ytterbium complexes reaching the +1 and zero formal oxidation states. JACS, 147(1), 1162--1171. (www)

  @article{ , abstract = {Lanthanide redox reactivity remains limited to one-electron transfer reactions due to their inability to access a broad range of oxidation states. Here, we show that multielectron reductive chemistry is achieved for ytterbium by using the tripodal tris(siloxide)arene redox-active ligand, which can store two electrons in the arene anchor. Reduction of the Yb(III) complex of the tris(siloxide)arene tripodal ligand affords the Yb(II) analogue by metal-centered reduction. Two subsequent reduction events occur mainly at the ligand with retention of the ligand framework and formation of analogous complexes of Yb in the formal +1 and zero oxidation states. Four complexes of Yb in four different oxidation states were isolated, crystallographically and spectroscopically characterized, and their electronic structure was confirmed by DFT studies. Reactivity studies show that the “Yb(I)” complex can transfer two electrons to organic azides, with retention of its molecular structure, to form highly reactive imido intermediates, providing a rare example of a two-electron transfer at a single lanthanide center that does not involve accessing the +4 oxidation state.}, archive = {J_JACS}, author = {Maxime Tricoire and Weronika Sroka and Thayalan Rajeshkumar and Rosario Scopelliti and Andrzej Sienkiewicz and Laurent Maron and Marinella Mazzanti}, doi = {10.1021/jacs.4c14904}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1162--1171}, shortjournal = {J. Am. Chem. Soc.}, title = {Multielectron redox chemistry of ytterbium complexes reaching the +1 and zero formal oxidation states}, volume = {147}, year = {2025}, }
• (2025). Aerobic ammoxidation of cyclic ketones to dinitrile products with copper-based catalysts. JACS, 147(1), 1155--1161. (www)

  @article{ , abstract = {Adiponitrile (ADN) has wide applications, especially in the polymer industry. With the substantial and increasing global demand for ADN, effective production of ADN using safe and abundant starting materials is highly desirable but very challenging. Herein, we discovered that CuBr, combined with 1,10-phenanthroline (phen), could effectively promote the ammoxidation reaction of cyclohexanone to ADN with a yield of >99% using aqueous ammonia as the nitrogen source and O 2 as the terminal oxidant under mild reaction conditions (80 °C, 5 atm O 2 ). Moreover, cyclic ketones with various carbon numbers and substituent groups could also be converted into the corresponding dinitrile products with high yields. A detailed mechanistic study revealed that the reaction proceeded through a radical-mediated pathway, and the reason for the high selectivity to ADN was discussed. This study offers a new, simple, and cost-effective route to produce ADN and other dinitrile products.}, archive = {J_JACS}, author = {Ziwei Zhao and Zhanrong Zhang and Qingling Xu and Shunhan Jia and Ying Wang and Wenli Yuan and Mingyang Liu and Huizhen Liu and Qinglei Meng and Pei Zhang and Bingfeng Chen and Haijun Yang and Buxing Han}, doi = {10.1021/jacs.4c14875}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1155--1161}, shortjournal = {J. Am. Chem. Soc.}, title = {Aerobic ammoxidation of cyclic ketones to dinitrile products with copper-based catalysts}, volume = {147}, year = {2025}, }
• (2025). Solubility-equilibrium-assisted kinetic resolution polymerization toward isotactic polyesters containing axial chirality. JACS, 147(1), 1147--1154. (www)

  @article{ , abstract = {High-level control over polymer stereochemistry leverages the fine-tuning of material properties, but it is still a formidable challenge in synthetic polymer chemistry. Herein we prepared a new class of salph yttrium catalysts bearing axially chiral binaphthyl moieties for axially stereocontrolled polymerization of rac -Me-DBO. ( S )- Y3- bearing bulkier binaphthyl units accomplished moderate isoselectivity via kinetic resolution polymerization, affording P(Me-BDO) with a P m of up to 0.80. Remarkably, exploiting the solubility equilibrium to maintain a constant for the concentration of two enantiopure monomer pairs in the solution state contributed to a boost in polymerization isoselectivity and furnished isotactic P(Me-DBO) products with a P m of up to 0.93. Detailed mechanistic investigations supported our solubility-equilibrium shifting hypothesis. This solubility-equilibrium-assisted kinetic resolution polymerization strategy was expected to become a versatile platform to improve stereocontrol without de novo catalyst design.}, archive = {J_JACS}, author = {Qing Cao and Hua-Zhong Fan and Min Xie and Zhongzheng Cai and Jian-Bo Zhu}, doi = {10.1021/jacs.4c14778}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1147--1154}, shortjournal = {J. Am. Chem. Soc.}, title = {Solubility-equilibrium-assisted kinetic resolution polymerization toward isotactic polyesters containing axial chirality}, volume = {147}, year = {2025}, }
• (2025). Facile synthesis of functional polytrithiocarbonates from multicomponent tandem polymerizations of CS2, thiols, and alkyl halides. JACS, 147(1), 1134--1146. (www)

  @article{ , abstract = {Polytrithiocarbonates have attracted significant attention recently because of their good thermal stability, light refractivity, crystallinity, and mechanical properties; however, the exploration of their structures and functionalities has been limited by their synthetic approaches. Multicomponent polymerization featuring simple monomers, mild conditions, diversified product structures, and high efficiency could provide a powerful and versatile tool to synthesize various polytrithiocarbonates from commercially available monomers. Herein, a robust and efficient multicomponent tandem polymerization (MCTP) of CS 2 , dithiols, and alkyl halides was developed in DMF with K 2 CO 3 at room temperature in air to synthesize 12 polytrithiocarbonates with diversified and systematically tuned structures, high molecular weights ( M n s up to 37900 g/mol), and high yields (up to 93%). Depending on the different polymer backbone structures, amorphous polytrithiocarbonates showed excellent breaking elongations, and crystallinic polytrithiocarbonates possessed a large process temperature window (about 200 °C) and good mechanical performance (σ B of 23.6 MPa and ε B of 858%), whose tensile strength could be dramatically enhanced to 87.5 MPa after uniaxial extension deformation. The upper critical solution temperature (UCST) in organic solvents, together with nonconventional luminescence, were observed for the crystallinic polytrithiocarbonates, even without any aromatic ring. This efficient, robust, mild, and economic MCTP of CS 2 thus opened up an avenue for the facile construction of polytrithiocarbonates with structural diversity, bringing modulable mechanical, thermal, luminescent, and thermal-responsive properties, which would greatly broaden the scope of structures and applications of sulfur-containing polymers.}, archive = {J_JACS}, author = {Longbin Chen and Rongrong Hu and Ben Zhong Tang}, doi = {10.1021/jacs.4c14708}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1134--1146}, shortjournal = {J. Am. Chem. Soc.}, title = {Facile synthesis of functional polytrithiocarbonates from multicomponent tandem polymerizations of CS2, thiols, and alkyl halides}, volume = {147}, year = {2025}, }
• (2025). Lanthanum-promoted electrocatalyst for the oxygen evolution reaction: Unique catalyst or oxide deconstruction?. JACS, 147(1), 1123--1133. (www)

  @article{ , abstract = {A conventional performance metric for electrocatalysts that promote the oxygen evolution reaction (OER) is the current density at a given overpotential. However, the assumption that increased current density at lower overpotentials indicates superior catalyst design is precarious for OER catalysts in the working environment, as the crystalline lattice is prone to deconstruction and amorphization, thus greatly increasing the concentration of catalytic active sites. We show this to be the case for La 3+ incorporation into Co 3 O 4 . Powder X-ray diffraction (PXRD), Raman spectroscopy and extended X-ray absorption fine structure (EXAFS) reveal smaller domain sizes with decreased long-range order and increased amorphization for La-modified Co 3 O 4 . This lattice deconstruction is exacerbated under the conditions of OER as indicated by operando spectroscopies. The overpotential for OER decreases with increasing La 3+ concentration, with maximum activity achieved at 17% La incorporation. HRTEM images and electron diffraction patterns clearly show the formation of an amorphous overlayer during OER catalysis that is accelerated with La 3+ addition. O 1s XPS spectra after OER show the loss of lattice-oxide and an increase in peak intensities associated with hydroxylated or defective O-atom environments, consistent with Co(O) x (OH) y species in an amorphous overlayer. Our results suggest that improved catalytic activity of oxides incorporated with La 3+ ions (and likely other metal ions) is due to an increase in the number of terminal octahedral Co(O) x (OH) y edge sites upon Co 3 O 4 lattice deconstruction, rather than enhanced intrinsic catalysis.}, archive = {J_JACS}, author = {Alaina C. Hartnett and Ryan J. Evenson and Agnes E. Thorarinsdottir and Samuel S. Veroneau and Daniel G. Nocera}, doi = {10.1021/jacs.4c14696}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1123--1133}, shortjournal = {J. Am. Chem. Soc.}, title = {Lanthanum-promoted electrocatalyst for the oxygen evolution reaction: Unique catalyst or oxide deconstruction?}, volume = {147}, year = {2025}, }
• (2025). Selective reduction of esters to access aldehydes using fiddler crab-type boranes. JACS, 147(1), 1112--1122. (www)

  @article{ , abstract = {The partial reduction of esters to aldehydes is a fundamentally important transformation for the synthesis of numerous fine chemicals and consumer goods. However, despite the many efforts, limitations have persisted, such as competing overreduction, low reproducibility, use of exigent reaction conditions and hazardous chemicals. Here, we report a novel catalyst family with a unique steric design which promotes the catalytic partial reduction of esters with unprecedented, near-perfect selectivity and efficiency. This metal-free catalytic method is ready to be placed at the disposal of chemists to provide valuable aldehyde intermediates and products and shows promise for streamlining synthetic methods in academic and industrial settings.}, archive = {J_JACS}, author = {Ádám Dudás and Ádám Gyömöre and Bence Balázs Mészáros and Stefánia Gondár and Renáta Adamik and Dániel Fegyverneki and Dávid Papp and Konrad Bernhard Otte and Sergio Ayala, Jr. and János Daru and József Répási and Tibor Soós}, doi = {10.1021/jacs.4c14596}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1112--1122}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective reduction of esters to access aldehydes using fiddler crab-type boranes}, volume = {147}, year = {2025}, }
• (2025). In-cage recombination facilitates the enantioselective organocatalytic [1,2]-rearrangement of allylic ammonium ylides. JACS, 147(1), 1101--1111. (www)

  @article{ , abstract = {The [1,2]-rearrangement of allylic ammonium ylides is traditionally observed as a competitive minor pathway alongside the thermally allowed [2,3]-sigmatropic rearrangement. Concerted [1,2]-rearrangements are formally forbidden, with these processes believed to proceed through homolytic C–N bond fission of the ylide, followed by radical–radical recombination. The challenges associated with developing a catalytic enantioselective [1,2]-rearrangement of allylic ammonium ylides therefore lie in biasing the reaction pathway to favor the [1,2]-reaction product, alongside controlling a stereoselective radical–radical recombination event. Herein, a Lewis basic chiral isothiourea facilitates catalytic [1,2]-rearrangement of prochiral aryl ester ammonium salts to generate unnatural α-amino acid derivatives with up to complete selectivity over the [2,3]-rearrangement and with good to excellent enantiocontrol. Key factors in favoring the [1,2]-rearrangement include exploitation of disubstituted terminal allylic substituents, cyclic N-substituted ammonium salts, and elevated reaction temperatures. Mechanistic studies involving 13 C-labeling and crossover reactions, combined with radical trapping experiments and observed changes in product enantioselectivity, are consistent with a radical solvent cage effect, with maximum product enantioselectivity observed through promotion of “in-cage” radical–radical recombination. Computational analysis indicates that the distribution between [1,2]- and [2,3]-rearrangement products arises predominantly from C–N bond homolysis of an intermediate ammonium ylide, followed by recombination of the α-amino radical at either the primary or tertiary site of an intermediate allylic radical. Electrostatic interactions involving the bromide counterion control the facial selectivity of the [1,2]- and [2,3]-rearrangements, while the sterically hindered tertiary position of the allylic substituent disfavors the formation of the [2,3]-product. These results will impact further investigations and understanding of enantioselective radical–radical reactions.}, archive = {J_JACS}, author = {Will C. Hartley and Kevin Kasten and Mark D. Greenhalgh and Taisiia Feoktistova and Henry R. Wise and Jacqueline M. Laddusaw and Aileen B. Frost and Sean Ng and Alexandra M. Z. Slawin and Bela E. Bode and Paul Ha-Yeon Cheong and Andrew D. Smith}, doi = {10.1021/jacs.4c14516}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1101--1111}, shortjournal = {J. Am. Chem. Soc.}, title = {In-cage recombination facilitates the enantioselective organocatalytic [1,2]-rearrangement of allylic ammonium ylides}, volume = {147}, year = {2025}, }
• (2025). Unraveling the bonding and aromaticity of pentazole, pentaphosphole, and cyclopentadiene anions: A comprehensive study. JACS, 147(1), 1092--1100. (www)

  @article{ , abstract = {This study investigates π-delocalization, π-bonding situations, and aromaticity of the pentazolate anion ([cyclo-N 5 – ], ( a )), which was detected by Christe et al. in 2002. To gain a broader perspective, we investigated the iso-π-electronic species [cyclo-P 5 – ] ( b ) and [cyclo-(CH) 5 – ] ( c ). VB analyses reveal that the three studied molecules display significant resonance stabilization, as indicated by their high resonance energy values. A comprehensive analysis of aromaticity was conducted using electronic and magnetic aromaticity indices, revealing that all three anions exhibit strong π-aromaticity and relatively weak σ-aromaticity.}, archive = {J_JACS}, author = {Shailja Jain and David Danovich and Slavko Radenković and Sason Shaik}, doi = {10.1021/jacs.4c14515}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1092--1100}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling the bonding and aromaticity of pentazole, pentaphosphole, and cyclopentadiene anions: A comprehensive study}, volume = {147}, year = {2025}, }
• (2025). Assembly of pyrenes through a quadruple photochemical cascade: Blocking groups allow diversion from the double mallory path to photocyclization at the bay region. JACS, 147(1), 1074--1091. (www)

  @article{ , abstract = {We present a six-step cascade that converts 1,3-distyrylbenzenes ( bis -stilbenes) into nonsymmetric pyrenes in 40–60% yields. This sequence merges photochemical steps, E , Z -alkene isomerization, a 6π photochemical electrocyclization (Mallory photocyclization); the new bay region cyclization, with two radical iodine-mediated aromatization steps; and an optional aryl migration. This work illustrates how the inherent challenges of engineering excited state reactivity can be addressed by logical design. An unusual aspect of this cascade is that the same photochemical process (the Mallory reaction) is first promoted and then blocked in different stages within a photochemical cascade. The use of blocking groups is the key feature that makes simple bis -stilbenes suitable substrates for directed double cyclization. While the first stilbene subunit undergoes a classic Mallory photocyclization to form a phenanthrene intermediate, the next ring-forming step is diverted from the conventional Mallory path into a photocyclization of the remaining alkene at the phenanthrene’s bay region. Although earlier literature suggested that this reaction is unfavorable, we achieved this diversion via incorporation of blocking groups to prevent the Mallory photocyclization. The two photocyclizations are assisted by the relief of the excited state antiaromaticity. Reaction selectivity is controlled by substituent effects and the interplay between photochemical and radical reactivity. Furthermore, the introduction of donor substituents at the pendant styrene group can further extend this photochemical cascade through a radical 1,2-aryl migration. Rich photophysical and supramolecular properties of the newly substituted pyrenes illustrate the role of systematic variations in the structure of this classic chromophore for excited state engineering.}, archive = {J_JACS}, author = {Nikolas R. Dos Santos and João Vitor Schober and Croix J. Laconsay and Alexandria M. Palazzo and Leah Kuhn and Angel Chu and Benjamin Hanks and Kenneth Hanson and Judy Wu and Igor V. Alabugin}, doi = {10.1021/jacs.4c14486}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1074--1091}, shortjournal = {J. Am. Chem. Soc.}, title = {Assembly of pyrenes through a quadruple photochemical cascade: Blocking groups allow diversion from the double mallory path to photocyclization at the bay region}, volume = {147}, year = {2025}, }
• (2025). Power strokes in molecular motors: Predictive, irrelevant, or somewhere in between?. JACS, 147(1), 1063--1073. (www)

  @article{ , abstract = {For several decades, molecular motor directionality has been rationalized in terms of the free energy of molecular conformations visited before and after the motor takes a step, a so-called power stroke mechanism with analogues in macroscopic engines. Despite theoretical and experimental demonstrations of its flaws, the power stroke language is quite ingrained, and some communities still value power stroke intuition. By building a catalysis-driven motor into simulated numerical experiments, we here systematically report on how directionality responds when the motor is modified accordingly to power stroke intuition. We confirm that the power stroke mechanism generally does not predict motor directionality. Nevertheless, the simulations illustrate that the relative stability of molecular conformations should be included as a potential design element to adjust the motor directional bias. Though power strokes are formally unimportant for determining directionality, we show that practical attempts to alter a power stroke have side effects that can in fact alter the bias. The change in the bias can align with what power stroke intuition would have suggested, offering a potential explanation for why the flawed power stroke mechanism can retain apparent utility when engineering specific systems.}, archive = {J_JACS}, author = {Emanuele Penocchio and Geyao Gu and Alex Albaugh and Todd R. Gingrich}, doi = {10.1021/jacs.4c14481}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1063--1073}, shortjournal = {J. Am. Chem. Soc.}, title = {Power strokes in molecular motors: Predictive, irrelevant, or somewhere in between?}, volume = {147}, year = {2025}, }
• (2025). Ligand-mediated surface reaction for achieving pure 2D phase passivation in high-efficiency perovskite solar cells. JACS, 147(1), 1055--1062. (www)

  @article{ , abstract = {The surface passivation with the heterostructure of the 2D/3D stack has been widely used for boosting the efficiency of n-i-p perovskite solar cells (PSCs). However, the disordered quantum well width distribution of 2D perovskites leads to energy landscape inhomogeneity and crystalline instability, which limits the further development of n-i-p PSCs. Here, a versatile approach, ligand-mediated surface passivation, was developed to produce a phase-pure 2D perovskite passivation layer with a homogeneous energy landscape by dual-ligand codeposition. The preferential adsorption of 3,6-dimethyl-carbazole-9-ethylammonium iodide with a large molecular size and lower adsorption energy could regulate the surface reaction between the m -fluorophenylethylammonium iodide and perovskite surface, resulting in a 2D perovskite with a narrow quantum well distribution and a uniform surface potential distribution. Beyond this, the preservation of the surface-confined 2D passivation layer retained a higher electric field at the interface of perovskite and the hole transport layer. As a result, the champion device reached an efficiency of 25.86% for the 0.05 cm 2 device and 25.08% for the 1 cm 2 device, with enhanced operational stability (T 90 > 1000 h) and much better thermal stability. Our work provides deeper insights into efficient and stable 2D passivation for PSCs.}, archive = {J_JACS}, author = {Zhuojie Shi and Shunchang Liu and Ran Luo and Jianpeng Ma and Hao Tian and Xi Wang and Zijing Dong and Xiao Guo and Jinxi Chen and Jiangang Feng and Chuanxiao Xiao and Yuchen Wu and Wenping Hu and Yi Hou}, doi = {10.1021/jacs.4c14473}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1055--1062}, shortjournal = {J. Am. Chem. Soc.}, title = {Ligand-mediated surface reaction for achieving pure 2D phase passivation in high-efficiency perovskite solar cells}, volume = {147}, year = {2025}, }
• (2025). Data-efficient multifidelity training for high-fidelity machine learning interatomic potentials. JACS, 147(1), 1042--1054. (www)

  @article{ , abstract = {Machine learning interatomic potentials (MLIPs) are used to estimate potential energy surfaces (PES) from ab initio calculations, providing near-quantum-level accuracy with reduced computational costs. However, the high cost of assembling high-fidelity databases hampers the application of MLIPs to systems that require high chemical accuracy. Utilizing an equivariant graph neural network, we present an MLIP framework that trains on multifidelity databases simultaneously. This approach enables the accurate learning of high-fidelity PES with minimal high-fidelity data. Employing the generalized gradient approximation (GGA) and meta-GGA as low- and high-fidelity approaches, respectively, we tested this framework on the Li 6 PS 5 Cl and In x Ga 1– x N systems. The results show that using a high-fidelity training set with a size approximately 10% of the low-fidelity set, the multifidelity training framework achieves excellent accuracy, with Li-ion conductivity predictions within 10% error and In x Ga 1– x N mixing energy showing an R 2 of 0.98 compared to the reference high-fidelity MLIP results. It indicates that geometric and compositional spaces not covered by the high-fidelity meta-GGA database can be effectively inferred from low-fidelity GGA data, thus enhancing accuracy and molecular dynamics stability. We also developed a general-purpose MLIP that utilizes both GGA and meta-GGA data from the Materials Project, significantly enhancing MLIP performance for high-accuracy tasks such as predicting energies above hull for crystals in general. Furthermore, we demonstrate that the present multifidelity learning is more effective than transfer learning or Δ-learning and that it can also be applied to learn higher-fidelity up to the coupled-cluster level. We believe this methodology holds promise for creating highly accurate bespoke or universal MLIPs by effectively expanding the high-fidelity data set.}, archive = {J_JACS}, author = {Jaesun Kim and Jisu Kim and Jaehoon Kim and Jiho Lee and Yutack Park and Youngho Kang and Seungwu Han}, doi = {10.1021/jacs.4c14455}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1042--1054}, shortjournal = {J. Am. Chem. Soc.}, title = {Data-efficient multifidelity training for high-fidelity machine learning interatomic potentials}, volume = {147}, year = {2025}, }
• (2025). Copper-catalyzed cyclization and alkene transposition cascade enables a modular synthesis of complex spirocyclic ethers. JACS, 147(1), 1034--1041. (www)

  @article{ , abstract = {Complexity-generating reactions that access three-dimensional products from simple starting materials offer substantial value for drug discovery. While oxygen-containing heterocycles frequently feature unique, nonaromatic architectures such as spirocyclic rings, exploration of these chemical spaces is limited by conventional synthetic approaches. Herein, we report a copper-catalyzed annulation and alkene transposition cascade reaction that enables a modular preparation of complex, spirocyclic ethers from readily available alkenol substrates via a copper-catalyzed annulation and transannular 1,5-hydrogen atom transfer-mediated C–H functionalization. Our transformation displays a broad substrate scope, shows excellent heteroatom compatibility, and readily constructs spirocycles of varying ring sizes. The wider synthetic utility of this method is highlighted by numerous product diversifications and a short synthesis of the all-carbon framework of spirotenuipesine A. We anticipate that this transformation can significantly streamline access to a privileged class of three-dimensional oxygen-containing heterocycles and will find broad application in natural product synthesis.}, archive = {J_JACS}, author = {Wan-Xu Wei and Yangjin Kuang and Martin Tomanik}, doi = {10.1021/jacs.4c14418}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1034--1041}, shortjournal = {J. Am. Chem. Soc.}, title = {Copper-catalyzed cyclization and alkene transposition cascade enables a modular synthesis of complex spirocyclic ethers}, volume = {147}, year = {2025}, }
• (2025). Exploiting 19F NMR in a multiplexed assay for small GTPase activity. JACS, 147(1), 1028--1033. (www)

  @article{ , abstract = {Small GTPases (smG) are a 150-member family of proteins, comprising five subfamilies: Ras, Rho, Arf, Rab, and Ran-GTPases. These proteins function as molecular switches, toggling between two distinct nucleotide-bound states. Using traditional multidimensional heteronuclear NMR, even for single smGs, numerous experiments, high protein concentrations, expensive isotope labeling, and long analysis times are necessary. 19 F NMR of fluorinated proteins or ligands can overcome these drawbacks. Using indole position-specific 19 F labeling of the proteins, the activities of several smGs were measured in a multiplexed fashion. We investigated 4-, 5-, 6-, and 7-fluoro tryptophan containing smGs to study nucleotide binding. Distinct resonances for GDP- or GTP-bound states of three different 19 F-labeled smGs, RhoA, K-Ras, and Rac1, were observed, and the kinetics of exchange and hydrolysis were measured. This multiplexed system will permit screening of nucleotide-specific ligands of smGs under true physiological conditions.}, archive = {J_JACS}, author = {Fatema Bhinderwala and Angela M. Gronenborn}, doi = {10.1021/jacs.4c14294}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1028--1033}, shortjournal = {J. Am. Chem. Soc.}, title = {Exploiting 19F NMR in a multiplexed assay for small GTPase activity}, volume = {147}, year = {2025}, }
• (2025). Doublet spin state mediated photoluminescence upconversion in organic radical donor-triplet acceptor dyads. JACS, 147(1), 1017--1027. (www)

  @article{ , abstract = {Donor–acceptor dyads are promising materials for improving triplet-sensitized photon upconversion due to faster intramolecular energy transfer (ET), which unfortunately competes with charge transfer (CT) dynamics. To circumvent the issue associated with CT, we propose a novel purely organic donor–acceptor dyad, where the CT character is confined within the donor moiety. In this work, we report the synthesis and characterization of a stable organic radical donor-triplet acceptor dyad ( TTM–Cz–Per ) consisting of the acceptor perylene ( Per ) linked to the donor (4- N -carbazolyl-2,6-dichlorophenyl)-bis(2,4,6-trichlorophenyl)methyl radical ( TTM–Cz ). Upon red-excitation of TTM–Cz–Per , the doublet emission of the donor ( TTM–Cz ) is significantly quenched, and a recorded delayed emission centered at ca. 490 nm was attributed to the fluorescence emission from the Per acceptor. Time-resolved transient absorption spectroscopy suggests doublet-to-triplet energy transfer (DTET) dynamics from the donor to the acceptor as the time constant τ for the donor transient species decreases from 21.47 ns for the TTM–Cz sensitizer to 8.73 ns for TTM–Cz–Per dyad. This process is accompanied by the appearance of a long-lived component with τ = 97.06 ns, which we ascribe to the triplet transient of the acceptor Per . Furthermore, computational results indicate that the DTET is intramolecular as computed spin densities of the quartet state show unpaired electrons of ρ ≈ 1 on the TTM-Cz donor and of ρ ≈ 2 on the acceptor Per . The present study highlights the possibility to employ doublet chromophoric systems for light-harvesting and energy upconversion, which can be further tailored for several optoelectronic applications.}, archive = {J_JACS}, author = {Joseph M. O’Shea and Young Ju Yun and Abdelqader M. Jamhawi and Francesca Peccati and Gonzalo Jiménez-Osés and Anoklase Jean-Luc Ayitou}, doi = {10.1021/jacs.4c14303}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1017--1027}, shortjournal = {J. Am. Chem. Soc.}, title = {Doublet spin state mediated photoluminescence upconversion in organic radical donor-triplet acceptor dyads}, volume = {147}, year = {2025}, }
• (2025). PH-ultrasensitive membranolytic polyesters with alternating sequence of ionizable and hydrophobic groups for selective oncolytic therapy. JACS, 147(1), 1008--1016. (www)

  @article{ , abstract = {Oncolytic therapy, inducing cell death via cell membrane lysis, holds considerable promise in cancer treatment. However, achieving precise control over the structure and function of oncolytic materials for highly selective oncolytic therapy is a key challenge in the context of the subtle differences between tumor and normal tissues/cells. Herein, we report the development of pH-ultrasensitive oncolytic polyesters (pOPs) with an alternating sequence of ionizable and hydrophobic groups. This design enables a refined “OFF” to “ON” switch within 0.2 pH units, ensuring high selectivity in membranolytic activity and cytotoxicity of pOPs between the pH levels of normal tissues and tumor acidity. The top-performing pOP, P(P-AC7), demonstrated a maximum tolerated dose of >100 mg kg –1 after intravenous administration and potent cytotoxicity at pH 6.8. Notably, the molecular weight of P(P-AC7) had a minimal effect on its pH-dependent cytotoxicity once the degree of polymerization was ≥49, ensuring consistency in properties across batches. P(P-AC7) exerts membranolytic activity by interacting with phosphatidylserine at pH 6.8 and shows high antitumor efficacy in various tumor models. Overall, we developed a strategy to develop oncolytic polymers with a precise structure for selective oncolytic therapy.}, archive = {J_JACS}, author = {Jihong Wang and Yueling Yuan and Chanjuan Su and Yan Bao and Weide Xu and Yandan Yao and Lifang Liang and Yuxuan Zeng and Menghua Xiong}, doi = {10.1021/jacs.4c14199}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1008--1016}, shortjournal = {J. Am. Chem. Soc.}, title = {PH-ultrasensitive membranolytic polyesters with alternating sequence of ionizable and hydrophobic groups for selective oncolytic therapy}, volume = {147}, year = {2025}, }
• (2025). Efficient cytosolic delivery of single-chain polymeric artificial enzymes for intracellular catalysis and chemo-dynamic therapy. JACS, 147(1), 998--1007. (www)

  @article{ , abstract = {Designing artificial enzymes for in vivo catalysis presents a great challenge due to biomacromolecule contamination, poor biodistribution, and insufficient substrate interaction. Herein, we developed single-chain polymeric nanoparticles with Cu/N-heterocyclic carbene active sites (SCNP-Cu) to function as peroxidase mimics for in vivo catalysis and chemo-dynamic therapy (CDT). Compared with the enzyme mimics based on unfolded linear polymer scaffold and multichain cross-linked scaffold, SCNP-Cu exhibits improved tumor accumulation and CDT efficiency both in vitro and in vivo. Protein-like size of the SCNP scaffold promotes passive diffusion, whereas positive surface charge allows its active transcytosis for deep tumor penetration and hence accumulation in the tumor site. The submolecular compartments of the SCNP scaffold effectively protect the active sites from protein bindings, thereby providing a “cleaner” microenvironment for catalysis within a living system. The folded structure of SCNP-Cu facilitates their cytosolic delivery of and free diffusion within cytosol, ensuring efficient contact with endogenous H 2 O 2 , in situ generation of toxic hydroxyl radicals (·OH), and effective damage of intracellular targets (i.e., lipids, nucleic acids). This work establishes versatile SCNP-based nanoplatforms for developing artificial enzymes for in vivo catalysis.}, archive = {J_JACS}, author = {Di Zheng and Jing Tao and Liping Jiang and Xinyue Zhang and Huibin He and Xiaoxue Shen and Yutao Sang and Yunen Liu and Zhenzhong Yang and Zhihong Nie}, doi = {10.1021/jacs.4c14264}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {998--1007}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient cytosolic delivery of single-chain polymeric artificial enzymes for intracellular catalysis and chemo-dynamic therapy}, volume = {147}, year = {2025}, }
• (2025). Critical role of tetrahedral coordination in determining the polysulfide conversion efficiency on spinel oxides. JACS, 147(1), 988--997. (www)

  @article{ , abstract = {Understanding the structure–property relationship and the way in which catalysts facilitate polysulfide conversion is crucial for the rational design of lithium–sulfur (Li–S) battery catalysts. Herein, a series of NiAl 2 O 4 , CoAl 2 O 4 , and CuAl 2 O 4 spinel oxides with varying Ni 2+ , Co 2+ , or Cu 2+ tetrahedral and octahedral site occupancy are studied as Li–S battery catalysts. Combined with experimental and theoretical analysis, the tetrahedral site is identified as the most active site for enhancing polysulfide adsorption and charge transfer. This work demonstrates the geometric configuration dependence of spinel oxides for polysulfide conversion and highlights the role of the molecular orbital in determining the activity of cations in different geometries, thereby providing new insights into the rational design of Li–S battery catalysts.}, archive = {J_JACS}, author = {Wen Xie and Samuel Jun Hoong Ong and Zihan Shen and Liying Tian and Kai Tang and Shibo Xi and Zhichuan J. Xu}, doi = {10.1021/jacs.4c14263}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {988--997}, shortjournal = {J. Am. Chem. Soc.}, title = {Critical role of tetrahedral coordination in determining the polysulfide conversion efficiency on spinel oxides}, volume = {147}, year = {2025}, }
• (2025). Radical anions of porphyrin molecular wires: Delocalization and dynamics. JACS, 147(1), 978--987. (www)

  @article{ , abstract = {The delocalization length of charge carriers in organic semiconductors influences their mobility and is an important factor in the design of functional materials. Here, we have studied the radical anions of a series of linear and cyclic butadiyne-linked porphyrin oligomers using CW-EPR, 1 H Mims ENDOR and NIR/MIR spectroelectrochemistry together with DFT calculations and multiscale molecular modeling. Low-temperature hyperfine EPR spectroscopy and optical data show that polarons are delocalized nonuniformly over about four porphyrins with most of the spin density on just two units even in the cyclic structures, in which all porphyrin sites are identical. Room temperature CW-EPR spectra indicate a larger spatial distribution of spin density on the EPR time scale. We introduce a combined molecular dynamics simulations and DFT approach to demonstrate that dynamic migration of delocalized polarons can occur in porphyrin oligomers and that this fully accounts for the apparent spin density distribution at room temperature. This method is a powerful tool in both the study and development of molecular wires and molecular electronics.}, archive = {J_JACS}, author = {Janko Hergenhahn and Jake M. Holmes and Jie-Ren Deng and Henrik Gotfredsen and Robert M. J. Jacobs and Sebastian M. Kopp and Christiane R. Timmel and Harry L. Anderson}, doi = {10.1021/jacs.4c14161}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {978--987}, shortjournal = {J. Am. Chem. Soc.}, title = {Radical anions of porphyrin molecular wires: Delocalization and dynamics}, volume = {147}, year = {2025}, }
• (2025). FeCl2-mediated rearrangement of aminoperoxides into functionalized tetrahydrofurans: Dynamic non-innocence of O-ligands at an fe center coordinates a radical cascade. JACS, 147(1), 965--977. (www)

  @article{ , abstract = {The selective reaction of cyclic aminoperoxides with FeCl 2 proceeds through a sequence of O–O and C–C bond cleavages, followed by intramolecular cyclization, yielding functionalized tetrahydrofurans in 44–82% yields. Replacing the peroxyacetal group in the peroxide structure with a peroxyaminal fragment fundamentally alters the reaction pathway. Instead of producing linear functionalized ketones, this modification leads to the formation of hard-to-access substituted tetrahydrofurans. Although the aminoperoxide cores undergo multiple bond scissions, this cascade is atom-economical. Computational analysis shows that the O-ligands at the Fe center have enough radical character to promote C–C bond fragmentation and subsequent cyclization. The stereoelectronic flexibility of oxygen, combined with iron’s capacity to stabilize multiple reactive intermediates during the multistep cascade, explains the efficiency of this new atom-economic peroxide rearrangement.}, archive = {J_JACS}, author = {Yulia Yu. Belyakova and Peter S. Radulov and Roman A. Novikov and Ilya V. Prolomov and Nikolai V. Krivoshchapov and Michael G. Medvedev and Ivan A. Yaremenko and Igor V. Alabugin and Alexander O. Terent’ev}, doi = {10.1021/jacs.4c14062}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {965--977}, shortjournal = {J. Am. Chem. Soc.}, title = {FeCl2-mediated rearrangement of aminoperoxides into functionalized tetrahydrofurans: Dynamic non-innocence of O-ligands at an fe center coordinates a radical cascade}, volume = {147}, year = {2025}, }
• (2025). High molecular conductance and inverted conductance decay over 3 nm in aminium-terminated carbon-bridged oligophenylene-vinylenes. JACS, 147(1), 957--964. (www)

  @article{ , abstract = {With the progressing miniaturization of electronic device components to improve circuit density while retaining or even reducing spatial requirements, single molecules employed as electric components define the lower limit of accessible structural width. To circumvent the typical exponential conductance decay for increasing length in molecule-based wires, topological states, which describe the occurrence of discontinuities of a bulk material’s electronic structure confined to its surface, can be realized for molecules by the introduction of unpaired spins at the molecular termini. The resulting high conductance and reversed conductance decay are typically only observed for shorter molecules, as the terminal spins must be within the electronic coupling range to produce the desired effects. We expand the realm of long and exceptionally conductive molecular wires by employing highly conjugated, planarized carbon-bridged oligo(phenylene-vinylene)s as conduits between readily oxidizable diarylamine termini. This yields molecular wires of already decent conductance values and small conductance decay in the neutral state. Upon the introduction of topological states, the conductance can be increased by a factor of up to 1800 for a 3 nm long molecule, and the conductance decay becomes inverted, together with an excellent signal intensity at concentrations as low as 0.01 mM.}, archive = {J_JACS}, author = {Luisa K. I. Rieger and Susanne Leitherer and William Bro-Jørgensen and Gemma C. Solomon and Rainer F. Winter}, doi = {10.1021/jacs.4c13901}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {957--964}, shortjournal = {J. Am. Chem. Soc.}, title = {High molecular conductance and inverted conductance decay over 3 nm in aminium-terminated carbon-bridged oligophenylene-vinylenes}, volume = {147}, year = {2025}, }
• (2025). Regioselective copolymerization of glucose-derived allopyranoside epoxide with cyclic anhydrides: Developing precise sugar-functionalized polyesters with unique altrose linkages. JACS, 147(1), 945--956. (www)

  @article{ , abstract = {Uniform sugar-functionalized polyesters combine the benefits of sugar’s structural diversity, biocompatibility, and biodegradability with precise postfunctionalization capabilities, making them a highly valuable class of materials with extensive application potential. However, the irregular placement of hydroxyl groups has limited the synthesis of these polyesters. Here, we present the first platform for uniform sugar-functionalized polyesters via regioselective ring-opening copolymerizations (ROCOPs) of allopyranoside anhydrosugar epoxide ( 1 , derived from d -glucose) with cyclic anhydrides, followed by complete selective deprotection. This method yields polyesters with controlled molecular weights, narrow molecular weight distributions ( D̵ < 1.19), high glass transition temperatures (up to 188 °C), and uniform hydroxyl functionality. Furthermore, the degradation of the polyesters offers an efficient route for producing the highly valuable d -altrose. Mechanistic insights, supported by DFT calculations, as well as NMR and HPLC analyses, confirm the regioselective nucleophilic attack at the C2 position of the pyranose ring. Kinetic studies reveal a first-order dependence on 1 and a zero-order dependence on the cyclic anhydrides. Additionally, these uniform sugar-functionalized polyesters can be incorporated into triblock terpolymers through one-pot/one-step or one-pot/two-step procedures, forming uniform sugar-functionalized multiblock copolymers.}, archive = {J_JACS}, author = {Jiaxi Xu and Jingjing Liu and Nikos Hadjichristidis}, doi = {10.1021/jacs.4c13984}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {945--956}, shortjournal = {J. Am. Chem. Soc.}, title = {Regioselective copolymerization of glucose-derived allopyranoside epoxide with cyclic anhydrides: Developing precise sugar-functionalized polyesters with unique altrose linkages}, volume = {147}, year = {2025}, }
• (2025). Mechanism of C-3 acyl neighboring group participation in mannuronic acid glycosyl donors. JACS, 147(1), 932--944. (www)

  @article{ , abstract = {One of the main challenges in oligosaccharide synthesis is the stereoselective introduction of the glycosidic bond. In order to understand and control glycosylation reactions, thorough mechanistic studies are required. Reaction intermediates found by NMR spectroscopy often cannot explain the glycosylation’s stereochemical outcome. Hence, reactions may proceed through low-abundance reaction intermediates that are difficult to detect, according to a Curtin–Hammett scenario. We have previously observed that manno-type sugars can engage in C-3 acyl neighboring group participation. Herein, we report the detection of glycosyl dioxanium ions that result from C-3 neighboring group participation in mannuronic acid donors. Using a suite of exchange NMR techniques, we were able to dissect the kinetics of the conformational ring-flip that precedes C-3 acyl participation and the participation event itself in various manno-type sugars. Hence, this study provides a complete picture of mannosyl dioxanium ion formation.}, archive = {J_JACS}, author = {Frank F. J. de Kleijne and Peter H. Moons and Floor ter Braak and Hero R. Almizori and Luuk J. H. Jakobs and Kas J. Houthuijs and Giel Berden and Jonathan Martens and Jos Oomens and Floris P. J. T. Rutjes and Paul B. White and Thomas J. Boltje}, doi = {10.1021/jacs.4c13910}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {932--944}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanism of C-3 acyl neighboring group participation in mannuronic acid glycosyl donors}, volume = {147}, year = {2025}, }
• (2025). Highly rigid, yet conformationally adaptable, bisporphyrin sp2-cage receptors afford outstanding binding affinities, chelate cooperativities, and substrate selectivities. JACS, 147(1), 918--931. (www)

  @article{ , abstract = {If we aim to develop efficient synthetic models of protein receptors and enzymes, we must understand the relationships of intra- and intermolecular interactions between hosts and guests and how they mutually influence their conformational energy landscape so as to adapt to each other to maximize binding energies and enhance substrate selectivities. Here, we introduce a novel design of cofacial (Zn II )bisporphyrin cages based on dynamic imine bonding, which is synthetically simple, but at the same time highly robust and versatile, affording receptors composed of only sp 2 -hybridized C and N atoms. The high structural rigidity of these cages renders them ideal hosts for ditopic molecules that can fit into the cavity and bind to both metal centers, leading to association constants as high as 10 9 M –1 in chloroform. These strong binding affinities are a consequence of the remarkable chelate cooperativities attained, with effective molarity ( EM ) values reaching record values over 10 3 M. However, we discovered that the cages can still adapt their structure to a more compact version, able to host slightly smaller guests. Such a conformational transition has an energy cost, which can be very different depending on the direction of the imine linkages in the cage skeleton and which results in EM values 2–3 orders of magnitude lower. This interplay between cooperativity and conformational adaptability leads to strong and unusual selectivities. Not only these metalloporphyrin receptors can choose to bind preferably to a particular guest, as a function of its size, but also the guest can select which host to bind, as a function now of the host’s conformational rigidity. Such highly cooperative and selective associations are lost, however, in related flexible receptors where the imine bonds are reduced.}, archive = {J_JACS}, author = {A. Priscila Gia and Alberto de Juan and Daniel Aranda and Fernando G. Guijarro and Juan Aragó and Enrique Ortí and Miguel García-Iglesias and David González-Rodríguez}, doi = {10.1021/jacs.4c13756}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {918--931}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly rigid, yet conformationally adaptable, bisporphyrin sp2-cage receptors afford outstanding binding affinities, chelate cooperativities, and substrate selectivities}, volume = {147}, year = {2025}, }
• (2025). Real-time elemental and isotopic measurements of molten salt systems through laser-induced breakdown spectroscopy. JACS, 147(1), 910--917. (www)

  @article{ , abstract = {Molten salt reactors are an emerging advanced nuclear reactor concept in which the fuel is dissolved into the working fluid in the form of a high-temperature molten salt. The complex, mobile, and corrosive nature of this fluid presents a fundamental challenge for analytical measurements. Tracking species throughout the reactor is important for ensuring proper operation. This article presents laser-induced breakdown spectroscopy (LIBS) used to monitor the elemental composition of a molten salt and corresponding hydrogen isotopic shifts in real-time. A NaNO 3 –KNO 3 eutectic salt was saturated with protium and deuterium gases, then the effluent aerosol stream formed using an argon sparging vessel was monitored with LIBS. This modular LIBS system permitted several spectrometers to be used simultaneously to capture high-resolution isotopic shifts and provide broadband elemental coverage. The results exhibit how LIBS can be used to understand salt–gas chemical and physical interactions such as diffusion. Furthermore, LIBS’ broad elemental coverage can provide greater insight into the chemical reactions within the salt vessel such as the formation of water vapor by monitoring hydrogen and oxygen signatures simultaneously. Ultimately, this study demonstrates the analytical possibilities of LIBS for real-time monitoring of isotopes and elemental composition in molten salt systems.}, archive = {J_JACS}, author = {Hunter B. Andrews and Zechariah B. Kitzhaber and Daniel Orea and Joanna McFarlane}, doi = {10.1021/jacs.4c13684}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {910--917}, shortjournal = {J. Am. Chem. Soc.}, title = {Real-time elemental and isotopic measurements of molten salt systems through laser-induced breakdown spectroscopy}, volume = {147}, year = {2025}, }
• (2025). Visible light photolysis at single atom sites in semiconductor perovskite oxides. JACS, 147(1), 898--909. (www)

  @article{ , abstract = {Designing catalysts with well-defined active sites with chemical functionality responsive to visible light has significant potential for overcoming scaling relations limiting chemical reactions over heterogeneous catalyst surfaces. Visible light can be leveraged to facilitate the removal of strongly bound species from well-defined single cationic sites (Rh) under mild conditions (323 K) when they are incorporated within a photoactive perovskite oxide (Rh-doped SrTiO 3 ). CO, a key intermediate in many chemistries, forms stable geminal dicarbonyl Rh complexes (Rh + (CO) 2 ), that could act as site blockers or poisons during a catalytic cycle. For the first time, we demonstrate that CO removal can occur at mild temperatures (323 K) under low-energy red light (635 nm) irradiation, which is not possible for supported isolated-site Rh catalysts (0.2 wt % Rh/γ-Al 2 O 3 ). Photolysis of supported Rh + (CO) 2 complexes (e.g., 0.2 wt % Rh/γ-Al 2 O 3 ) has been demonstrated but is limited to high energy UV photons. Rigorous kinetic experiments elucidate disparate mechanisms for CO photodepletion from Rh-doped SrTiO 3 and supported isolated site Rh/γ-Al 2 O 3 . CO photodepletion from supported isolated site Rh/γ-Al 2 O 3 involves a direct metal to ligand charge transfer mechanism, whereas Rh-doped SrTiO 3 is governed by electron–hole pair formation in the perovskite. We show that under visible, low-energy red light, surface Rh species in Rh-doped SrTiO 3 introduce midgap energy states above the valence band that facilitate electronic excitations leading to surface CO removal. Isolated Rh sites in Rh-doped SrTiO 3 also exhibit exceptional stability under multiple CO photodepletion cycles. Overall, incorporating single sites into photoactive perovskite oxides is an effective strategy to influence surface chemistries with visible light.}, archive = {J_JACS}, author = {Michael G. Allan and Rachel A. Yang and Silvia Marino and Michael J. Gordon and Phillip Christopher and Eranda Nikolla}, doi = {10.1021/jacs.4c13821}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {898--909}, shortjournal = {J. Am. Chem. Soc.}, title = {Visible light photolysis at single atom sites in semiconductor perovskite oxides}, volume = {147}, year = {2025}, }
• (2025). The precise synthesis of ultradense bottlebrush polymers unearths unique trends in lyotropic ordering. JACS, 147(1), 889--897. (www)

  @article{ , abstract = {Biomacromolecular networks with multiscale fibrillar structures are characterized by exceptional mechanical properties, making them attractive architectures for synthetic materials. However, there is a dearth of synthetic polymeric building blocks capable of forming similarly structured networks. Bottlebrush polymers (BBPs) are anisotropic graft polymers with the potential to mimic and replace biomacromolecules such as tropocollagen for the fabrication of synthetic fibrillar networks; however, a longstanding limitation of BBPs has been the lack of rigidity necessary to access the lyotropic ordering that underpins the formation of collagenous networks. While the correlation between BBP rigidity and grafting density is well established, synthetic approaches to rigidify BBPs by increased grafting density are underdeveloped. To address this gap in synthetic capability, we report the synthesis of novel macroinitiators that provide well-defined BBPs with an unprecedentedly high grafting density. A suite of light scattering techniques are used to correlate macromolecular rigidity with grafting architecture and density and demonstrate for the first time that poly(norbornene) BBPs exhibit long-range lyotropic ordering as a result of their rodlike character. Specifically, the newly reported ultradensely grafted structures, preparable on multigram scale, form hexagonal arrays while conventional BBPs do not, despite showing long-range spatial correlations. These results implicate the central role of density and entanglement in the solution phase assembly of BBPs and provide new fundamental insight that is broadly relevant to the fabrication and performance of BBP-derived materials, spanning biomedical research to photonic materials and thermal management technologies. Furthermore, these newly reported liquid crystalline BBPs provide a structural template to explore the untapped potential of the bottom-up assembly of semiflexible networks and are ultimately intended to provide a modular route to hierarchically structured biomimetic materials.}, archive = {J_JACS}, author = {Timea Kolozsvary and Phillip Kohl and Tianyu Li and David Gillespie and Youli Li and Benjamin R. McDonald}, doi = {10.1021/jacs.4c13759}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {889--897}, shortjournal = {J. Am. Chem. Soc.}, title = {The precise synthesis of ultradense bottlebrush polymers unearths unique trends in lyotropic ordering}, volume = {147}, year = {2025}, }
• (2025). Borenium-catalyzed “Boron walking” for remote site-selective hydroboration. JACS, 147(1), 880--888. (www)

  @article{ , abstract = {Remote functionalization through progressive olefin isomerization enables site-selective modification at a distal position, diversifying the synthetic approaches. However, the developed protocols have long relied on transition metal catalysis. Transition metal catalysts are deemed irreplaceable, albeit facing challenges in metal residue and catalyst poisoning. In this work, we present a pioneering approach that employs a borenium ion as a catalyst for site-selective, remote borylation, eliminating the need for metal catalysts. As the reaction progresses, borylation isomers at different positions emerge, gradually and ultimately converging into the predominant α-borylation product. This process is akin to a “walking” of a boron moiety along a carbon skeleton toward an aryl terminus. Detailed mechanistic studies and DFT calculations substantiate the borenium-catalyzed, stepwise migration via a reversible B–H insertion/elimination sequence. This remote borylation exhibits good functional group compatibility, complementing those methods reliant on transition metals. Furthermore, this metal-free protocol permits the convenient synthesis of silyl-remote-boryl compounds, demonstrating an opposite regioselectivity to that observed in transition-metal-catalyzed tandem silylation-borylation reactions. This discovery therefore contributes to site-selective, remote difunctionalization via sequential C–B and C–Si derivatizations, exemplified by the synthesis of amino-remote-alcohol bioactive molecules.}, archive = {J_JACS}, author = {Zheng Zhu and Wing Chun Chan and Bin Gao and Guanwen Hu and Peiqi Zhang and Yiyi Fu and Kit San Ly and Zhenyang Lin and Yangjian Quan}, doi = {10.1021/jacs.4c13726}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {880--888}, shortjournal = {J. Am. Chem. Soc.}, title = {Borenium-catalyzed “Boron walking” for remote site-selective hydroboration}, volume = {147}, year = {2025}, }
• (2025). Photoswitchable diazocine derivative for adenosine a3 receptor activation in psoriasis. JACS, 147(1), 874--879. (www)

  @article{ , abstract = {Incorporating photoisomerizable moieties within drugs offers the possibility of rapid and reversible light-dependent switching between active and inactive configurations. Here, we developed a photoswitchable adenosine A 3 receptor (A 3 R) agonist that confers optical control on this G protein-coupled receptor through noninvasive topical skin irradiation in an animal model of psoriasis. This was achieved by covalently bonding an adenosine-5′-methyluronamide moiety to a diazocine photochrome, whose singular photoswitching properties facilitated repeated interconversion between a thermally stable, biologically inactive Z agonist form and a photoinduced, pharmacologically active E configuration. As a result, our photoswitchable agonist allowed the precise modulation of A 3 R function both in vitro and in vivo , which led to a clear light-controlled pharmacotherapeutic effect on mouse skin lesions. This breakthrough not only demonstrates the potential of diazocine photoswitches for in vivo photopharmacology but also paves the way for the development of new strategies for skin-related diseases that require localized and temporally controlled drug action.}, archive = {J_JACS}, author = {Marc López-Cano and Mirko Scortichini and Dilip K. Tosh and Veronica Salmaso and Tongil Ko and Glòria Salort and Ingrid Filgaira and Concepció Soler and Dirk Trauner and Jordi Hernando and Kenneth A. Jacobson and Francisco Ciruela}, doi = {10.1021/jacs.4c13558}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {874--879}, shortjournal = {J. Am. Chem. Soc.}, title = {Photoswitchable diazocine derivative for adenosine a3 receptor activation in psoriasis}, volume = {147}, year = {2025}, }
• (2025). Bidentate lewis base ligand-mediated surface stabilization and modulation of the electronic structure of CsPbBr3 perovskite nanocrystals. JACS, 147(1), 862--873. (www)

  @article{ , abstract = {The desorption of conventional ligands from the surface of halide perovskite nanocrystals (NCs) often causes their structural instability and deterioration of the optoelectronic properties. To address this challenge, we present an approach of using a bidentate Lewis base ligand, namely, 1,4-bis(diphenylphosphino)butane (DBPP), for the synthesis of CsPbBr 3 NCs. The phosphine group of DBPP has a strong interaction with the PbBr 2 precursor, forming a highly crystalline intermediate complex during the reaction. In the presence of oleic acid, the uncoordinated phosphine group of DBPP is converted into the phosphonium cation, which strongly binds to the surface bromide of the formed CsPbBr 3 NCs through hydrogen bonding. Density functional theory calculations suggest that DBPP can strongly bind to the undercoordinated lead and surface bromide ions of CsPbBr 3 NCs through its unprotonated and protonated phosphine groups, respectively. The robust binding of DBPP to the surface of perovskite NCs helps to preserve their structural integrity under various environmental stresses. Moreover, the electron density and energy levels are regulated in DBPP-capped CsPbBr 3 NCs by the donation of electrons from the ligands to the NCs, resulting in their improved photocatalytic CO 2 reduction performance. Our study highlights the potential of using bidentate ligands to stabilize the surface of perovskite NCs and modulate their optical and electronic properties.}, archive = {J_JACS}, author = {Md. Samim Hassan and Pooja Basera and Bilawal Khan and Arsenii S. Portniagin and Kunnathodi Vighnesh and Ye Wu and Daniil A. Rusanov and Maria Babak and Jr-Hau He and Michal Bajdich and Andrey L. Rogach}, doi = {10.1021/jacs.4c13724}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {862--873}, shortjournal = {J. Am. Chem. Soc.}, title = {Bidentate lewis base ligand-mediated surface stabilization and modulation of the electronic structure of CsPbBr3 perovskite nanocrystals}, volume = {147}, year = {2025}, }
• (2025). Effect of strain on the photocatalytic reaction of graphitic carbon nitride: Insight from single-molecule localization microscopy. JACS, 147(1), 851--861. (www)

  @article{ , abstract = {Strain engineering in two-dimensional nanomaterials holds significant potential for modulating the lattice and band structure, particularly through localized strain, which enables modulation at specific regions. Despite the remarkable effects of local strain, the relationships among local strain, spatial correlation of photogenerated charge carriers, and photocatalytic performance remain elusive. The current study coupled single-molecule localization microscopy with coordinate-based colocalization (CBC) analysis to explain these relationships. The methodology involved mapping the spatial distributions of photoinduced oxidation and reduction reaction sites across graphitic carbon nitride (g-C 3 N 4 ) nanosheets, quantifying and spatially resolving their spatial correlation, and also evaluating their photocatalytic activity. The study examined 65 individual g-C 3 N 4 nanosheets, revealing interparticle and intraparticle heterogeneity, which was classified based on their CBC score distributions. Among the 65 g-C 3 N 4 nanosheets, type A nanosheets predominated (45 out of 65) and demonstrated both correlated and noncorrelated subregions along some wrinkles. In contrast, type B nanosheets (20 out of 65) were primarily characterized by noncorrelated subregions with minimal correlated localizations. The coexistence of both noncorrelated and correlated subregions inferred the structure of the wrinkles as folding wrinkles, which have larger tensile-strained areas than rippling wrinkles. Folding wrinkles promote colocalization through the formation of type I band alignment at tensile-strained subregions. This band alignment also enhances photocatalytic activity through a funneling effect and improved light absorption, leading to higher specific activity in correlated subregions compared to noncorrelated ones. The role of strain-induced band alignment in modulating the spatial correlation of the photoredox reaction and the photocatalytic performance at the subregion level is highlighted.}, archive = {J_JACS}, author = {Jia Xin Chan and Shuyang Wu and Jinn-Kye Lee and Mingyu Ma and Zhengyang Zhang}, doi = {10.1021/jacs.4c13707}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {851--861}, shortjournal = {J. Am. Chem. Soc.}, title = {Effect of strain on the photocatalytic reaction of graphitic carbon nitride: Insight from single-molecule localization microscopy}, volume = {147}, year = {2025}, }
• (2025). Supramolecular Host:Guest arrays site-selectively recognize peptide phosphorylation and kinase activity. JACS, 147(1), 841--850. (www)

  @article{ , abstract = {A synergistic combination of cationic styrylpyridinium dyes and water-soluble deep cavitand hosts can recognize phosphorylated peptides with both site- and state-selectivity. Two mechanisms of interaction are dominant: either the cationic dye interacts with Trp residues in the peptide or the host:dye pair forms a heteroternary complex with the peptide, driven by both strong dye–peptide and cavitand–peptide binding ( K d values up to 4 μM). The presence of multiple recognition mechanisms results in varying fluorescence responses dependent on the phosphorylation state and position, eliminating the need for covalent modification of the peptide target. Differential sensing aided by machine learning algorithms permits full discrimination between differently positioned serine phosphorylations with a minimal 3-component array. The array is fully functional in the presence of protein kinase A (PKA) and its required cofactors and capable of site-selective monitoring of serine phosphorylation at the privileged PKA motif, in the presence of serine residues that do not undergo reaction, illustrating the potential of the system in kinase-based drug screening.}, archive = {J_JACS}, author = {Junyi Chen and Parisa Fasihianifard and Ria Lian and Lucas J. Gibson-Elias and Jose L. Moreno, Jr. and Chia-En A. Chang and Wenwan Zhong and Richard J. Hooley}, doi = {10.1021/jacs.4c13757}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {841--850}, shortjournal = {J. Am. Chem. Soc.}, title = {Supramolecular Host:Guest arrays site-selectively recognize peptide phosphorylation and kinase activity}, volume = {147}, year = {2025}, }
• (2025). Mapping the extended ground state reactivity landscape of a photoswitchable molecule at a single molecular level. JACS, 147(1), 830--840. (www)

  @article{ , abstract = {Photoswitchable molecules with structural flexibility can exhibit a complex ground state potential energy landscape due to the accessibility of multiple metastable states at merely low energy barriers. However, conventional bulk analytical techniques are limited in their ability to probe these metastable ground states and their relative energies. This is partially due to the difficulty of inducing changes in small molecules in their ground state, as they do not respond to external stimuli, such as mechanical force, unless they are incorporated into larger polymer networks. This hinders the understanding of ground-state reactivity and the associated dynamics. In this study, we leverage the “perturb-probe” capability of the single molecular break junction technique to explore the ground state 6π electrocyclization of a dithienylethene (DTE) derivative, a process traditionally achieved through electro- or photochromism. Our findings reveal that this reaction can also be triggered by mechanical force and an oriented electric field at the single-molecule level via ground state dynamics. We demonstrated that external perturbations could control the ground state reaction dynamics and steer the reaction trajectories away from constraints imposed by typical excited state dynamics. This strategy will thus offer access to a whole new dimension of single molecular electromechanical conversions and extend our knowledge of the ground state potential energy surface available to molecules under external force fields.}, archive = {J_JACS}, author = {Umar Rashid and Leonardo Medrano Sandonas and Elarbi Chatir and Zakaria Ziani and PA Sreelakshmi and Saioa Cobo and Rafael Gutierrez and Gianaurelio Cuniberti and Veerabhadrarao Kaliginedi}, doi = {10.1021/jacs.4c13531}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {830--840}, shortjournal = {J. Am. Chem. Soc.}, title = {Mapping the extended ground state reactivity landscape of a photoswitchable molecule at a single molecular level}, volume = {147}, year = {2025}, }
• (2025). Electrostatic control of electronic structure in modular inorganic crystals. JACS, 147(1), 821--829. (www)

  @article{ , abstract = {The rules that govern structure and bonding, established for elemental solids and simple compounds, are challenging to apply to more complex crystals formed of polyatomic building blocks, such as layered or framework materials. Whether these modular building blocks are electrically neutral or charged influences the physical properties of the resulting crystal. Despite the prevalence of alternating charged units, their effects on the electronic structure remain unclear. We demonstrate how the distribution of charged building blocks, driven by differences in the electrostatic potential, governs the electronic band energies formed in layered crystals. This coarse-grained model predicts the spatially separated valence and conduction band edges observed in the metal-oxyhalide Ba 2 Bi 3 Nb 2 O 11 Cl and explains observed property trends in the Sillén–Aurivillius crystal system. Moreover, the general nature of the model allows for extension to other modular structure types, illustrated for Sillén and Ruddlesden–Popper layered compounds, and can support the rational design of electronic properties in diverse materials.}, archive = {J_JACS}, author = {Kanta Ogawa and Aron Walsh}, doi = {10.1021/jacs.4c13637}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {821--829}, shortjournal = {J. Am. Chem. Soc.}, title = {Electrostatic control of electronic structure in modular inorganic crystals}, volume = {147}, year = {2025}, }
• (2025). Dion–Jacobson perovskites with a ferroelectrically switchable chiral nonlinear optical response. JACS, 147(1), 811--820. (www)

  @article{ , abstract = {Electrically switchable second harmonic generation (SHG) is highly valuable in electro-optic modulators, which can be deployed in data communication and quantum optics. Coupling circular dichroism (CD) with an electrically controlled SHG process is advantageous because it enhances the signal transmission bandwidth and security while enabling multiple modulation modes for optical logic. However, ferroelectrically switchable chiral second-order nonlinearity is rarely reported. Here, we demonstrate the electro-optic modulation of SHG based on the multipolar effect in a chiral ferroelectric two-dimensional hybrid perovskite s -(FBDA)CdCl 4 ( s -FBDA = (2 s )-2-fluorobutane-1,4-diamine). s -(FBDA)CdCl 4 ( s -FCC) crystals are highly stable in air, and its SHG response exhibits circular dichroism (i.e., SHG-CD) that can be ferroelectrically switched. The ferroelectrically switchable SHG-CD arises from the reconfiguration of distinct chirality-induced multipolar moments during the ferroelectric switching process. This reconfiguration induces a π/2 circular difference in SHG, leading to a reversal of circularly polarized light sensitivity. As a proof of concept, we demonstrate that the electrically controlled SHG-CD of s -FCC can be used in the transmission of encrypted optical communications.}, archive = {J_JACS}, author = {Weixin He and Changjiang Chen and Shiyao Wu and Walter P. D. Wong and Zhenyue Wu and Kai Chang and Jiesu Wang and Heng Gao and Kian Ping Loh}, doi = {10.1021/jacs.4c13604}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {811--820}, shortjournal = {J. Am. Chem. Soc.}, title = {Dion–Jacobson perovskites with a ferroelectrically switchable chiral nonlinear optical response}, volume = {147}, year = {2025}, }
• (2025). Mechanism-inspired synthesis of poly(alkyl malonates) via alternating copolymerization of epoxides and meldrum’s acid derivatives. JACS, 147(1), 801--810. (www)

  @article{ , abstract = {Direct incorporation of malonate units into polymer backbones is a synthetic challenge. Herein, we report the alternating and controlled anionic copolymerization of epoxides and Meldrum’s acid (MA) derivatives to access poly(alkyl malonates) using ( N,N’ -bis(salicylidene)phenylenediamine)AlCl and a tris(dialkylamino)cyclopropenium chloride cocatalyst. This unique copolymerization yields a malonate-containing repeat unit while releasing a small molecule upon MA-derivative ring-opening. Mechanistic and computational studies reveal that the nature of the small molecule released influences overall polymerization kinetics, side reaction behavior, and molecular weight control. Controlled copolymerization of MA derivatives with a range of epoxides ultimately yields a library of new poly(alkyl malonates) with diverse and tunable thermal properties.}, archive = {J_JACS}, author = {Sarah M. Severson and Bai-Hao Ren and May Cayzer and Ivan Keresztes and Mary L. Johnson and Xiao-Bing Lu and Geoffrey W. Coates}, doi = {10.1021/jacs.4c13550}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {801--810}, shortjournal = {J. Am. Chem. Soc.}, title = {Mechanism-inspired synthesis of poly(alkyl malonates) via alternating copolymerization of epoxides and meldrum’s acid derivatives}, volume = {147}, year = {2025}, }
• (2025). Late-stage reshaping of phage-displayed libraries to macrocyclic and bicyclic landscapes using a multipurpose linchpin. JACS, 147(1), 789--800. (www)

  @article{ , abstract = {Genetically encoded libraries (GEL) are increasingly being used for the discovery of ligands for “undruggable” targets that cannot be addressed with small molecules. Foundational GEL platforms like phage-, yeast-, ribosome-, and mRNA-display have enabled the display of libraries composed of 20 natural amino acids (20AA). Unnatural amino acids (UAA) and chemical post-translational modification (cPTM) expanded GEL beyond the 20AA space to yield unnatural linear, cyclic, and bicyclic peptides. The standard operating procedure incorporates UAA and cPTM into a “naive” library with 10 8 –10 12 compounds and uses a chemically upgraded library in multiple rounds of selection to discover target-binding hits. However, such an approach uses zero knowledge of natural peptide-receptor interactions that might have been discovered in selections performed with 20AA libraries. There is currently no consensus regarding whether “zero-knowledge” naive libraries or libraries with pre-existing knowledge can offer a more effective path to discovery of molecular interactions. In this manuscript, we evaluated the feasibility of discovery of macrocyclic and bicyclic peptides from “nonzero-knowledge” libraries. We approach this problem by late-stage chemical reshaping of a preselected phage-displayed landscape of 20AA binders to NS3aH1 protease. The reshaping is performed using a novel multifunctional C 2 -symmetric linchpin, 3,5-bis(bromomethyl)benzaldehyde (termed KYL), that combines two electrophiles that react with thiols and an aldehyde group that reacts with N-terminal amine. KYL diversified phage-displayed peptides into bicyclic architectures and delineated 2 distinct sequence populations: (i) peptides with the HXDMT motif that retained binding upon bicyclization and (ii) peptides without the HXDMT motif that lost binding once chemically modified. The same HXDMT family can be found in traditional selections starting from the naive KYL-modified library. Our report provides a case study for discovering advanced, chemically upgraded macrocycles and bicycles from libraries with pre-existing knowledge. The results imply that other selection campaigns completed in 20AA space, potentially, can serve for late-stage reshaping and as a starting point for the discovery of advanced peptide-derived ligands.}, archive = {J_JACS}, author = {Kejia Yan and Mark Miskolzie and Fernando Banales Mejia and Chuanhao Peng and Arunika I. Ekanayake and Alexey Atrazhev and Jessica Cao and Dustin J. Maly and Ratmir Derda}, doi = {10.1021/jacs.4c13561}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {789--800}, shortjournal = {J. Am. Chem. Soc.}, title = {Late-stage reshaping of phage-displayed libraries to macrocyclic and bicyclic landscapes using a multipurpose linchpin}, volume = {147}, year = {2025}, }
• (2025). High molecular weight uniform polymers encoding octal sequences by passerini iterative exponential growth. JACS, 147(1), 780--788. (www)

  @article{ , abstract = {Sequence-defined polymers composed of a large pool of chemically distinct monomers (SDPs) have been pursued to achieve the structural and functional precisions exhibited by biopolymers in nonbiological environments. In contrast to the incremental growth of SDPs by sequential addition of individual monomers, the iterative exponential growth (IEG) method allows the synthesis of high molecular-weight SDPs, but their sequences have been composed mostly of binary monomers. Consequently, achieving high molecular-weight SDPs built with a large pool of monomers remains a challenge. Here we report the Passerini iterative exponential growth (P-IEG) approach that enables efficient synthesis of 128-mer uniform poly(hydroxybutyrate) (PHB), possessing 127 γ-acylamino cyclohexyl side groups (27 kDa, Đ = 1) and a 31-mer SDP, encoding an octal sequence composed of eight chemically distinct repeating units. Taking advantage of the combinatorial character of the Passerini three-component reaction involving an aldehyde, a carboxylic acid, and an isocyanide to form an acyloxy amide linkage, we simultaneously achieved the exponential chain growth through the convergence of bifunctional building blocks and side-chain implementation by selecting appropriate isocyanides as a third component. The P-IEG approach enabled the synthetic encoding of complex information, an octal sequence equivalent to a 93-bit binary code, into a 31-mer SDP. Our proposed P-IEG method could contribute to the synthesis of synthetic macromolecules with absolutely defined sequences of functionalities. These polymers could be used for the development of functional materials with properties not achievable by conventional polymers, including polymers storing digital information at higher density.}, archive = {J_JACS}, author = {Valene Wang and Su Bin Park and Soo Jeong Lee and Mo Beom Koo and Kyoung Taek Kim}, doi = {10.1021/jacs.4c13528}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {780--788}, shortjournal = {J. Am. Chem. Soc.}, title = {High molecular weight uniform polymers encoding octal sequences by passerini iterative exponential growth}, volume = {147}, year = {2025}, }
• (2025). In crystallo o2 cleavage at a preorganized triiron cluster. JACS, 147(1), 770--779. (www)

  @article{ , abstract = {In Nature, the four-electron reduction of O 2 is catalyzed at preorganized multimetallic active sites. These complex active sites often feature low-coordinate, redox-active metal centers precisely positioned to facilitate rapid O 2 activation processes that obviate the generation of toxic, partially reduced oxygen species. Very few biomimetic constructs simultaneously recapitulate the complexity and reactivity of these biological cofactors. Herein, we report solid-state O 2 activation at a triiron(II) active site templated by phosphinimide ligands. Insight into the structure of the O 2 reduction intermediates was obtained via in crystallo O 2 dosing experiments in conjunction with spectroscopic, structural, magnetic, and computational studies. These data support the in situ formation of an Fe 2 III Fe IV -dioxo intermediate upon exposure to O 2 that participates in oxygen atom and hydrogen atom transfer reactivity with exogenous substrates to furnish a stable Fe II Fe 2 III -oxo species. Combined, these studies provide an extraordinary level of detail into the dynamics of bond-forming and -breaking processes operative at complex multimetallic active sites.}, archive = {J_JACS}, author = {Heui Beom Lee and Nicholas Ciolkowski and Mackenzie Field and David A. Marchiori and R. David Britt and Michael T. Green and Jonathan Rittle}, doi = {10.1021/jacs.4c13492}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {770--779}, shortjournal = {J. Am. Chem. Soc.}, title = {In crystallo o2 cleavage at a preorganized triiron cluster}, volume = {147}, year = {2025}, }
• (2025). CF3-functionalized side chains in nonfullerene acceptors promote electrostatic interactions for highly efficient organic solar cells. JACS, 147(1), 758--769. (www)

  @article{ , abstract = {The advent of next-generation nonfullerene acceptors (NFAs) has propelled major advances in organic solar cells (OSCs). Here we report an NFA design incorporating CF 3 -terminated side chains having varying N -(CH 2 ) n -CF 3 linker lengths ( n = 1, 2, and 3) which introduce new intermolecular interactions, hence strong modulation of the photovoltaic response. We report a systematic comparison and contrast characterization of this NFA series with a comprehensive set of chemical/physical techniques versus the heavily studied third-generation NFA, Y6, revealing distinctive and beneficial properties of this new NFA series. Single-crystal diffraction analyses reveal unusual two-dimensional mesh-like crystal structures, featuring strong interactions between the side chain CF 3 -terminal and NFA core F substituents. These atomistic and morphological features contribute to enhanced charge mobility and significantly enhanced photovoltaic performance. We show that varying the CF 3 -terminated side chain linker length strongly modulates light harvesting efficiency as well as charge recombination and the photovoltaic bandgap. The CF 3 -(CH 2 ) 2 -based OSC demonstrates the most balanced performance metrics, achieving a remarkable 19.08% power conversion efficiency and an exceptional 80.09% fill-factor. These results imply that introducing CF 3 -terminated side chains into other OSC conjugated constituents may accelerate next-generation solar cell development.}, archive = {J_JACS}, author = {Yongjoon Cho and Zhe Sun and Guoping Li and Dayong Zhang and Sangjin Yang and Tobin J. Marks and Changduk Yang and Antonio Facchetti}, doi = {10.1021/jacs.4c13471}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {758--769}, shortjournal = {J. Am. Chem. Soc.}, title = {CF3-functionalized side chains in nonfullerene acceptors promote electrostatic interactions for highly efficient organic solar cells}, volume = {147}, year = {2025}, }
• (2025). Polar networks mediate ion conduction of the SARS-CoV-2 envelope protein. JACS, 147(1), 746--757. (www)

  @article{ , abstract = {The SARS-CoV-2 E protein conducts cations across the cell membrane to cause pathogenicity to infected cells. The high-resolution structures of the E transmembrane domain (ETM) in the closed state at neutral pH and in the open state at acidic pH have been determined. However, the ion conduction mechanism remains elusive. Here, we use solid-state NMR spectroscopy to investigate the side chain structure, dynamics, and interactions of five polar residues at the N-terminal entrance of the channel and three polar residues at the C-terminal end. The chemical shifts of the N-terminal Glu8 reveal that the Glu side chain interacts with protons, Ca 2+ and two neighboring Thr residues, and adopts distinct motionally averaged conformational ensembles. These polar interactions are sensitive to the presence of negatively charged lipids in the membrane. A T9I mutation, prevalent in the Omicron variants of SARS-CoV-2 E, perturbs these interactions and partially immobilizes the N-terminal segment. Deeper into the channel, two polar residues, Asn15 and Ser16, form interhelical hydrogen bonds in the closed state but become separated by water molecules in the open state. This is manifested by Asn15-Ser16 correlation signals at neutral pH and the loss of these correlations and the appearance of water cross peaks with Ser16 at acidic pH in the presence of Ca 2+ . Finally, the guanidinium side chain of the C-terminal Arg38 undergoes fast reorientations in the closed state but becomes more restricted in the open state. These results provide evidence for a dynamic and hydrogen-bonded N-terminal polar network that recruits and relays protons and Ca 2+ in a lipid-dependent manner. Once inside, the ions permeate past the hydrophobic middle of the transmembrane domain with the help of enhanced hydrophilicity of the C-terminal channel lumen due to the insertion of the Arg38 side chain into the pore.}, archive = {J_JACS}, author = {João Medeiros-Silva and Yanina Pankratova and Iva Sučec and Aurelio J. Dregni and Mei Hong}, doi = {10.1021/jacs.4c13229}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {746--757}, shortjournal = {J. Am. Chem. Soc.}, title = {Polar networks mediate ion conduction of the SARS-CoV-2 envelope protein}, volume = {147}, year = {2025}, }
• (2025). Diazocines as guests of cucurbituril macrocycles: Light-responsive binding and supramolecular catalysis of thermal isomerization. JACS, 147(1), 734--745. (www)

  @article{ , abstract = {The photoswitching of supramolecular host–guest complexes is the basis of numerous molecularly controlled macroscopic functions, such as sol–gel transition, photopharmacology, the active transport of ions or molecules, light-powered molecular machines, and much more. The most commonly used systems employ photoactive azobenzene guests and synthetic host molecules, which bind as the stable E isomers and dissociate as the Z forms after exposure to UV light. We present a new, extraordinarily efficient cucurbit[7]uril (CB7)/diazocine host/guest complex with inverted stability that self-assembles under UV irradiation and dissociates in the dark. The association constants of the Z and E isomers in water differ by more than 10 4 -fold. We also show that the thermally activated E → Z isomerization is significantly accelerated by CB7, which is a rare case of enzyme-like catalysis by transition state stabilization without product inhibition. In contrast to CB7, cucurbit[8]uril (CB8) binds both isomers with high affinity, showing good selectivity (∼1000-fold) toward the Z isomer. Notably, this isomer preferentially binds CB8 relative to CB7 by a factor greater than 1 × 10 6 . We also use the system to introduce a supramolecular photoacid that builds on the increased basicity of a guest bound to CB7 and on the extremely high affinity of the E isomer, which is utilized to displace the acid from CB7, thereby switching the pH of the solution.}, archive = {J_JACS}, author = {Miriam Colaço and Julia Ewert and Jan-Simon von Glasenapp and Uwe Pischel and Rainer Herges and Nuno Basílio}, doi = {10.1021/jacs.4c13353}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {734--745}, shortjournal = {J. Am. Chem. Soc.}, title = {Diazocines as guests of cucurbituril macrocycles: Light-responsive binding and supramolecular catalysis of thermal isomerization}, volume = {147}, year = {2025}, }
• (2025). Small-molecule hole transport materials for >26% efficient inverted perovskite solar cells. JACS, 147(1), 725--733. (www)

  @article{ , abstract = {Chemically modifiable small-molecule hole transport materials (HTMs) hold promise for achieving efficient and scalable perovskite solar cells (PSCs). Compared to emerging self-assembled monolayers, small-molecule HTMs are more reliable in terms of large-area deposition and long-term operational stability. However, current small-molecule HTMs in inverted PSCs lack efficient molecular designs that balance both the charge transport capability and interface compatibility, resulting in a long-standing stagnation of power conversion efficiency (PCE) below 24.5%. Here, we report the comprehensive design of HTMs’ backbone and functional groups, which optimizes a simple planar linear molecular backbone with a high mobility exceeding 7.1 × 10 –4 cm 2 V –1 S –1 and enhances its interface anchoring capability. Owing to the improved surface properties and anchoring effects, the tailored HTMs enhance the interface contact at the HTM/perovskite heterojunction, minimizing nonradiative recombination and transport loss and leading to a high fill factor of 86.1%. Our work has overcome the persistent efficiency bottleneck for small-molecule HTMs, particularly for large-area devices. Consequently, the resultant PSCs exhibit PCEs of 26.1% (25.7% certified) for a 0.068 cm 2 device and 24.7% (24.4% certified) for a 1.008 cm 2 device, representing the highest PCE for small-molecule HTMs in inverted PSCs.}, archive = {J_JACS}, author = {Jie Zeng and Zhixin Liu and Deng Wang and Jiawen Wu and Peide Zhu and Yuqi Bao and Xiaoyu Guo and Geping Qu and Bihua Hu and Xingzhu Wang and Yong Zhang and Lei Yan and Alex K.-Y. Jen and Baomin Xu}, doi = {10.1021/jacs.4c13356}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {725--733}, shortjournal = {J. Am. Chem. Soc.}, title = {Small-molecule hole transport materials for >26% efficient inverted perovskite solar cells}, volume = {147}, year = {2025}, }
• (2025). Switching CO-to-acetate electroreduction on cu atomic ensembles. JACS, 147(1), 713--724. (www)

  @article{ , abstract = {The electrocatalytic reaction pathway is highly dependent on the intrinsic structure of the catalyst. CO 2 /CO electroreduction has recently emerged as a potential approach for obtaining C 2+ products, but it is challenging to achieve high selectivity for a single C 2+ product. Herein, we develop a Cu atomic ensemble that satisfies the appropriate site distance and coordination environment required for electrocatalytic CO-to-acetate conversion, which shows outstanding overall performance with an acetate Faradaic efficiency of 70.2% with a partial current density of 225 mA cm –2 and a formation rate of 2.1 mmol h –1 cm –2 . Moreover, a single-pass CO conversion rate of 91% and remarkable stability can be also obtained. Detailed experimental and theoretical investigations confirm the significant advantages of the Cu atomic ensembles in optimizing C–C coupling, stabilizing key ketene intermediate (*CCO), and inhibiting the *HOCCOH intermediate, which can switch the CO reduction pathway from the ethanol/ethylene on the conventional metallic Cu site to the acetate on the Cu atomic ensembles.}, archive = {J_JACS}, author = {Libing Zhang and Jiaqi Feng and Ruhan Wang and Limin Wu and Xinning Song and Xiangyuan Jin and Xingxing Tan and Shunhan Jia and Xiaodong Ma and Lihong Jing and Qinggong Zhu and Xinchen Kang and Jianling Zhang and Xiaofu Sun and Buxing Han}, doi = {10.1021/jacs.4c13197}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {713--724}, shortjournal = {J. Am. Chem. Soc.}, title = {Switching CO-to-acetate electroreduction on cu atomic ensembles}, volume = {147}, year = {2025}, }
• (2025). Bioorthogonal activation of deep red photoredox catalysis inducing pyroptosis. JACS, 147(1), 701--712. (www)

  @article{ , abstract = {The revolutionary impact of photoredox catalytic processes has ignited novel avenues for exploration, empowering us to delve into nature in unprecedented ways and to pioneer innovative biotechnologies for therapy and diagnosis. However, integrating artificial photoredox catalysis into living systems presents significant challenges, primarily due to concerns over low targetability, low compatibility with complex biological environments, and the safety risks associated with photocatalyst toxicity. To address these challenges, herein, we present a novel bioorthogonally activatable photoredox catalysis approach. In this approach, potent photocatalyst selection via atom replacement of the rhodamine core yielded the bioorthogonally activatable photocatalyst ( PC-Tz ). The introduction of 1,2,4,5-tetrazine quenched its photocatalytic properties, which were restored upon an intracellular inverse electron-demand Diels–Alder (iEDDA) reaction with trans -cyclooctene (TCO) localized in mitochondria. This reaction led to remarkable photocatalytic oxidation of nicotinamide adenine dinucleotide (NADH), effectively manipulating the mitochondrial electron transport chain (ETC) under hypoxic conditions in cancer cells. Additionally, photocatalytic pyroptotic cell death was observed through a caspase-3/gasdermin E (GSDME) pathway, achieving notable antitumor efficacy and adenosine triphosphate (ATP) reduction in tumor cells. To the best of our knowledge, this represents the first example of bioorthogonally activatable photoredox catalysis, opening new avenues for chemists to spatiotemporally control activity in specific cell organelles without disrupting other native biological processes.}, archive = {J_JACS}, author = {Jungryun Kim and Yunjie Xu and Jong Hyeon Lim and Jin Yong Lee and Mingle Li and Joseph M. Fox and Marc Vendrell and Jong Seung Kim}, doi = {10.1021/jacs.4c13131}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {701--712}, shortjournal = {J. Am. Chem. Soc.}, title = {Bioorthogonal activation of deep red photoredox catalysis inducing pyroptosis}, volume = {147}, year = {2025}, }
• (2025). Activity-drop of hydrogen evolution reaction in LiNO3 based “Hydronium-in-salt” acidic electrolytes on platinum enables electrochemical nitrate reduction. JACS, 147(1), 687--700. (www)

  @article{ , abstract = {The electrochemical nitrate reduction reaction (NO 3 – RR) involves multiple hydrogenation and deoxygenation steps, which compete with the hydrogen evolution reaction (HER). Therefore, NO 3 – RR driven in acidic media is challenging in spite of advantageous fast hydrogen transfers in its elementary steps. The findings presented in this article first demonstrate that the NO 3 – RR is significantly activated even in acidic lithium nitrate solutions at LiNO 3 concentrations exceeding 6 m on a Pt electrode (the highly effective catalyst for HER) by the formation of a “hydronium-in-salt” electrolyte (HISE), a new type of aqueous high concentration salt electrolyte. The observed enhancement of NO 3 – RR while the suppression of HER-activity in the LiNO 3 based HISE was verified by scanning electrochemical microscopy, electrochemical impedance spectroscopy, UV–vis/IR spectroscopy, and molecular dynamics simulations. The formation of a HISE in acidic LiNO 3 solutions contrasts with that of a “water-in-salt” electrolyte in LiTFSI with the same concentration. The mechanism of NO 3 – RR activation in a HISE suggests facilitated proton-coupled electron transfers (PCETs) from H 3 O + to NO 3 – and subsequent reactive intermediates owing to the proximity between the two ions induced by the unique solvation structure blended with all ions together (Li + + NO 3 – + H 3 O + ). In contrast, all the ions are separately hydrated at low concentrations of LiNO 3 electrolytes. On the other hand, PCET from H 2 O to NO 3 – in a high concentration LiNO 3 electrolyte (e.g., 9 m) is not kinetically preferred, probably owing to the slow dissociation kinetics of H 2 O, and therefore, H 2 O reduction is not suppressed by the NO 3 – RR.}, archive = {J_JACS}, author = {Cheolmin Park and Min Young Seo and Taesung Kwon and Jiyoon Kim and Ki Min Nam and YongJoo Kim and Jinho Chang}, doi = {10.1021/jacs.4c13117}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {687--700}, shortjournal = {J. Am. Chem. Soc.}, title = {Activity-drop of hydrogen evolution reaction in LiNO3 based “Hydronium-in-salt” acidic electrolytes on platinum enables electrochemical nitrate reduction}, volume = {147}, year = {2025}, }
• (2025). Water-pore flow permeation through multivalent H-bonding pyridine-2,6-dicarboxamide-histamine/Histidine water channels. JACS, 147(1), 678--686. (www)

  @article{ , abstract = {Aquaporins (AQPs) are natural proteins that can selectively transport water across cell membranes. Heterogeneous H-bonding of water with the inner wall of the pores of AQPs is of maximal importance regarding the optimal stabilization of water clusters within channels, leading to selective pore flow water transport against ions. To gain deeper insight into the water permeation mechanisms, simpler artificial water channels (AWCs) have been developed. Several H-bonding motifs (i.e., imidazole, polyhydroxy, etc.) have been reported as distinct and efficient for water-cluster stabilization within AWCs. Herein we combine two pyridine-2,6 dicarboxamide and imidazole to conceive multivalent U-shaped AWCs able to stabilize, like in AQP water clusters via different H-bonding groups. The crystal structures reveal that stable water superstructures are formed in the solid state, one with hydrophilic pores of ∼9 Å diameter, accommodating water clusters, and one with sterically hindered hydrophobic channels of ∼3 Å diameter, stabilizing water wires. As a result, a single-channel permeability of 1.2 × 10 7 H 2 O/s/channel has been achieved by the U-channels, which is only 1 order of magnitude lower than that of AQPs. Moreover, U-channels perform proton transport and completely reject anions and potentially can be applied in desalination membranes. Molecular simulation confirmed that U-channels can generate stable supramolecular porous sponges when they are decorated with hydrophobic alkyl chains featuring multivalent water H-bonding units that serve as water-cluster relays within the channel. To the best of our knowledge, this work is a rare biomimetic example of the importance of water-cluster stabilization via multivalent H-bonding and toward selective transport through water channels.}, archive = {J_JACS}, author = {Li-Bo Huang and Dan-Dan Su and Arthur Hardiagon and Istvan Kocsis and Arie van der Lee and Fabio Sterpone and Marc Baaden and Mihail Barboiu}, doi = {10.1021/jacs.4c13072}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {678--686}, shortjournal = {J. Am. Chem. Soc.}, title = {Water-pore flow permeation through multivalent H-bonding pyridine-2,6-dicarboxamide-histamine/Histidine water channels}, volume = {147}, year = {2025}, }
• (2025). Robust I···H–O intramolecular halogen bond boosts reversible I3–/I– redox behavior for sustainable Potassium–Iodine batteries. JACS, 147(1), 669--677. (www)

  @article{ , abstract = {Potassium–iodine batteries show great promise as alternatives for next-generation battery technology, owing to their high power density and environmental sustainability. Nevertheless, they suffer from polyiodide dissolution and the multistep electrode fabrication process, which leads to severe performance degradation and limitations in mass-market adoption. Herein, we report a simple “solution–adsorption” strategy for scale-up production of Ti 3 C 2 (OH) x -wrapped carbon nanotube paper (CNP), as an economic host for strengthening the iodine encapsulation. The cutting-edge characterizations and theoretical calculation results reveal that CNP exhibits great affinity to the electrochemically active I 3 – /I – redox couple, while the Ti–OH functional groups on MXene restrict the dissolution of polyiodides through forming the stable I···H–O intramolecular halogen bond. Benefiting from such a synergistic effect, the free-standing electrode ensures the reversible redox chemistry for developing high-performing potassium–iodine batteries. The fabricated pouch cell (100 mAh) shows a high energy density (130 Wh kg –1 ) with a full charge/discharge of 10 min, outperforming state-of-the-art new battery systems that require both high energy/power density. Such a potassium–iodine battery reduces the cost to 255 US$ kW h –1 , which is much lower than that of the cathode materials in lithium-ion batteries and offers a sustainable option for grid-scale energy storage.}, archive = {J_JACS}, author = {Shuoqing Zhao and Bohan Zhang and Lu Li and Peng Zhang and Guohao Li and Zhenyu Zhu and YoonJeong Choi and Liubing Dong and Mingchuan Luo and Shaojun Guo}, doi = {10.1021/jacs.4c12960}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {669--677}, shortjournal = {J. Am. Chem. Soc.}, title = {Robust I···H–O intramolecular halogen bond boosts reversible I3–/I– redox behavior for sustainable Potassium–Iodine batteries}, volume = {147}, year = {2025}, }
• (2025). Conjugation length dependence of intramolecular singlet fission in a series of regioregular oligo 3-alkyl(thienylene-vinylene)s. JACS, 147(1), 662--668. (www)

  @article{ , abstract = {Activated intramolecular singlet fission is known to occur in the conjugated polymer polythienylene-vinylene (P3TV). Instead, efficient intersystem crossing has been observed in a short 3-alkyl(thienylene-vinylene) dimer. Here, we investigate a series of oligomers covering the conjugation length gap between the dimer and polymer. We confirm that the polymer and longer oligomers undergo activated intramolecular singlet fission, while the shorter oligomers with less than 3 units predominantly undergo efficient intersystem crossing. For the longer oligomers, the intermediate state of singlet fission is assigned to the 3A g – covalent state of triplet pair character, as predicted by several computational studies. Our results point to potential pitfalls when assigning triplet production pathways solely with transient absorption spectroscopy.}, archive = {J_JACS}, author = {Daniel W. Polak and Iain Andrews and Enrico Salvadori and Andrew J. Musser and Alexander Auty and Dimitri Chekulaev and Julia A. Weinstein and Martin Heeney and Jenny Clark}, doi = {10.1021/jacs.4c12877}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {662--668}, shortjournal = {J. Am. Chem. Soc.}, title = {Conjugation length dependence of intramolecular singlet fission in a series of regioregular oligo 3-alkyl(thienylene-vinylene)s}, volume = {147}, year = {2025}, }
• (2025). Machine learning accelerated discovery of entropy-stabilized oxide catalysts for catalytic oxidation. JACS, 147(1), 651--661. (www)

  @article{ , abstract = {The catalytic properties of unary to ternary metal oxides were already well experimentally explored, and the left space seems like only high entropy metal oxides (HEOs, element types ≥5). However, the countless element compositions make the trial-and-error method of discovering HEO catalysts impossible. Herein, based on the study of the crystal phase and catalytic performance of the ACr 2 O x catalyst system, the strong correlation between the single spinel phase and good catalytic activity of CH 4 oxidation was inferred owing to the similar element importance sequences, which were acquired by the corresponding high accuracy machine learning models (cross-validation score >0.7). Furthermore, searching for negative data and choosing the proper training data resulted in high-quality regression models to search for better catalysts. Finally, the screened irregular catalyst Ni 0.04 Co 0.48 Zn 0.36 V 0.12 Cr 2 O x with outstanding sulfur and moisture resistance and long-term stability (>7000 h, T 90 = 345 °C) envisions the potential of applying the machine learning method to discover HEOs for target processes.}, archive = {J_JACS}, author = {Xiaolan Duan and Yang Li and Jiahua Zhao and Mengyuan Zhang and Xiaopeng Wang and Li Zhang and Xiaoxuan Ma and Ying Qu and Pengfei Zhang}, doi = {10.1021/jacs.4c12838}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {651--661}, shortjournal = {J. Am. Chem. Soc.}, title = {Machine learning accelerated discovery of entropy-stabilized oxide catalysts for catalytic oxidation}, volume = {147}, year = {2025}, }
• (2025). Hyperpolarized 13C NMR metabolomics of urine samples at natural abundance applied to chronic kidney disease. JACS, 147(1), 644--650. (www)

  @article{ , abstract = {NMR is a central tool in the field of metabolomics, thanks to its ability to provide valuable structural and quantitative information with high precision. Most NMR-based metabolomics studies rely on 1D 1 H detection, which is heavily limited by strong peak overlap. 13 C NMR benefits from a wider spectral dispersion and narrower signal line width but is barely used in metabolomics due to its low sensitivity. Dissolution dynamic nuclear polarization (d-DNP) offers an opportunity to improve 13 C NMR sensitivity by several orders of magnitude. Here, we show that this emerging hyperpolarized metabolomics approach can provide meaningful information about clinical samples. Achieving sub-mM limits of detection with 13 C at natural abundance in urine samples was made possible by a meticulous design of the experimental workflow. The analysis of human urine samples from patients with different stages of chronic kidney disease (CKD) was performed using 13 C d-DNP NMR and benchmarked to conventional 1 H NMR metabolomics at a high magnetic field to explore the complementarity between the two methods. Multivariate analysis of the d-DNP 13 C NMR dataset provided a statistical model able to distinguish patients with CKD from control patients. Moreover, 13 C d-DNP NMR spectra highlighted several biomarkers known to be biologically relevant. Some of them were in agreement with those obtained with conventional 1 H NMR, and the results also highlighted the complementarity of biomarker coverage between hyperpolarized and conventional NMR metabolomics. In particular, 13 C hyperpolarized NMR allowed the annotation of two biomarkers that could not be detected by 1 H NMR because of peak overlap (i.e., guanine and guanidoacetate).}, archive = {J_JACS}, author = {Victor Ribay and Benoît Charrier and Mikaël Croyal and Bertrand Cariou and Samy Hadjadj and Julien Boccard and Claire Cannet and Jean-Nicolas Dumez and Marine P. M. Letertre and Patrick Giraudeau}, doi = {10.1021/jacs.4c12607}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {644--650}, shortjournal = {J. Am. Chem. Soc.}, title = {Hyperpolarized 13C NMR metabolomics of urine samples at natural abundance applied to chronic kidney disease}, volume = {147}, year = {2025}, }
• (2025). Total synthesis of (+)-mannolide b. JACS, 147(1), 636--643. (www)

  @article{ , abstract = {(+)-Mannolide B possesses an intriguing and complex 5/7/5/6/6/6-fused hexacyclic scaffold including two bridged-lactone moieties and nine contiguous stereocenters, and thus represents a formidable challenge for total synthesis. Herein, the evolution of a successful strategy for the synthesis of mannolide B is described. The 7/5 ring system of the 7/5/6/6 tetracyclic carbon skeleton was efficiently constructed by a ring-closing metathesis starting from commercially available (−)-methyl jasmonate. Attempts to access the 6/6 ring system were unexpectedly challenging. Initially, an intramolecular Diels–Alder reaction was designed; however, the desired cyclization precursor could not be obtained. Furthermore, a radical cascade cyclization was investigated and produced only one six-membered ring with poor stereoselectivity at C5. Finally, the 6/6 ring system was successfully generated through a Pauson–Khand reaction, followed by a highly regioselective Büchner–Curtius–Schlotterbeck reaction, enabling us to achieve the first total synthesis of (+)-mannolide B in 24 steps.}, archive = {J_JACS}, author = {Peng Chen and Lijun Chen and Hongpeng Lin and Yanxing Jia}, doi = {10.1021/jacs.4c12767}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {636--643}, shortjournal = {J. Am. Chem. Soc.}, title = {Total synthesis of (+)-mannolide b}, volume = {147}, year = {2025}, }
• (2025). Catalytic asymmetric oxidative coupling between C(sp3)–H bonds and carboxylic acids. JACS, 147(1), 627--635. (www)

  @article{ , abstract = {The direct enantioselective functionalization of C(sp 3 )–H bonds in organic molecules could fundamentally transform the synthesis of chiral molecules. In particular, the enantioselective oxidation of these bonds would dramatically change the production methods of chiral alcohols and esters, which are prevalent in natural products, pharmaceuticals, and fine chemicals. Remarkable advances have been made in the enantioselective construction of carbon–carbon and carbon–nitrogen bonds through the C(sp 3 )–H bond functionalization. However, the direct enantioselective formation of carbon–oxygen bonds from C(sp 3 )–H bonds remains a considerable challenge. We herein report a highly enantioselective C(sp 3 )–H bond oxidative coupling with carboxylic acids. The method applies to allylic and propargylic C–H bonds and employs various carboxylic acids as oxygenating agents. The method successfully synthesized a range of chiral esters directly from readily available alkenes and alkynes, greatly simplifying the synthesis of chiral esters and related alcohols.}, archive = {J_JACS}, author = {Xian-Ming Liu and Fu Li and Tongkun Wang and Ling Dai and Yin Yang and Neng-Quan Jiang and Li-Yuan Xue and Jing-Yuan Liu and Xiao-Song Xue and Li-Jun Xiao and Qi-Lin Zhou}, doi = {10.1021/jacs.4c12544}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {627--635}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic asymmetric oxidative coupling between C(sp3)–H bonds and carboxylic acids}, volume = {147}, year = {2025}, }
• (2025). Formation and reactivity of a MnIV(O)(μ-O)CeIV species: A closest mimic of photosystem II. JACS, 147(1), 619--626. (www)

  @article{ , abstract = {Understanding the basic structure of the oxygen-evolving complex (OEC) in photosystem II (PS-II) and the water oxidation mechanism can aid in the discovery of more efficient and sustainable catalysts for water oxidation. In this context, we present evidence of the formation of a [(TPA)Mn IV (O)(μ-O)Ce IV (NO 3 ) 3 ] + ( 2 ) complex (TPA = tris(pyridyl-2-methyl)amine) by adding aqueous ceric ammonium nitrate to an acetonitrile solution of the [(TPA)Mn II ] 2+ ( 1 ) complex. This unique intermediate ( 2 ) was analyzed by using various spectroscopic techniques and electrospray ionization mass spectrometry. Remarkably, 2 closely mimics the structure of Mn V (O)(μ-O)Ca II (OH 2 ) proposed in the OEC of PS-II. Notably, 2 reacts effectively with ferrocene derivatives, indicating that redox-active Ce IV binding enhances the electron transfer efficiency. Additionally, 2 demonstrated the ability to perform oxygen atom transfer and hydrogen atom abstraction reactions. The discovery of this reactive [(TPA)Mn IV (O)(μ-O)Ce IV (NO 3 ) 3 ] + species provides exciting opportunities for investigating the structure of the Mn V (O)(μ-O)Ca II (OH 2 ) unit in the OEC.}, archive = {J_JACS}, author = {Sikha Gupta and Pragya Arora and Zahra Aghaei and Baghendra Singh and Timothy A. Jackson and Apparao Draksharapu}, doi = {10.1021/jacs.4c12523}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {619--626}, shortjournal = {J. Am. Chem. Soc.}, title = {Formation and reactivity of a MnIV(O)(μ-O)CeIV species: A closest mimic of photosystem II}, volume = {147}, year = {2025}, }
• (2025). Iridium-catalyzed enantioconvergent construction of piperidines and tetrahydroisoquinolines from racemic 1,5-diols. JACS, 147(1), 610--618. (www)

  @article{ , abstract = {We report herein a one-step synthesis of valuable enantioenriched piperidines and tetrahydroisoquinolines from readily available racemic 1,5-diols. Key to the success is the development of new iridacycle catalysts that enable efficient redox-neutral construction of two C–N bonds between diols and amines in an enantioconvergent fashion. Mechanistic studies identified an intriguing preferential oxidation of secondary versus primary alcohol in the diol substrate by the iridacycle catalyst, which set a challenging intermolecular amination of aryl–alkyl-substituted alcohol as the enantiodetermining step for this catalytic N -heterocycle synthesis. Application of this catalytic method to the preparation of important drugs and bioactive compounds is also demonstrated.}, archive = {J_JACS}, author = {Huanlin Diao and Kexin Liu and Rong Yu and Jilin Chen and Yongbing Liu and Bin-Miao Yang and Yu Zhao}, doi = {10.1021/jacs.4c12466}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {610--618}, shortjournal = {J. Am. Chem. Soc.}, title = {Iridium-catalyzed enantioconvergent construction of piperidines and tetrahydroisoquinolines from racemic 1,5-diols}, volume = {147}, year = {2025}, }
• (2025). What is the “Other” site in M–N–C?. JACS, 147(1), 603--609. (www)

  @article{ , abstract = {Single metal atoms embedded in nitrogen-doped graphene (M–N–C) have emerged as a promising catalyst for a wide variety of reactions. In addition to the pyridinic site, there is another site responsible for the catalytic activity, but its structure is under debate. Here, we resolve its structure using first-principles calculations. Using Fe–N–C as a representative example, we systematically explore numerous possible structures and discover a new moiety with comparable energy to the pyridinic. This moiety features a hybrid coordination environment between pyridinic and porphyrinic and is located at the edge of graphene sheets or pores. We further calculate its X-ray absorption spectrum, catalytic thermodynamics for oxygen reduction reaction (ORR), and stability under ORR conditions, all of which support its existence. Lastly, we show that this site also exists in other M–N–C with different M elements. This study uncovers a new and important structure in M–N–C and paves a critical step toward site engineering for improved catalytic performance.}, archive = {J_JACS}, author = {Zachary Levell and Saerom Yu and Ruoyu Wang and Yuanyue Liu}, doi = {10.1021/jacs.4c12479}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {603--609}, shortjournal = {J. Am. Chem. Soc.}, title = {What is the “Other” site in M–N–C?}, volume = {147}, year = {2025}, }
• (2025). Accelerated continuous flow depolymerization of Poly(Methyl methacrylate). JACS, 147(1), 594--602. (www)

  @article{ , abstract = {A continuous flow setup comprising an inline dialysis unit for immediate monomer removal is used for the depolymerization of poly(methyl methacrylate) (pMMA), synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization. The approach used allows one to carry out solution depolymerizations at much higher polymer content compared to batch processes while maintaining high depolymerization conversions. pMMA is efficiently depolymerized in the flow reactor, yielding up to 68% monomer recovery under catalyst-free reaction conditions at 160 °C, starting from a 1 molar repeat unit concentration, which is a 20-fold improvement compared to previous batch studies. This was achieved by using the inline dialysis to continuously remove monomer from the depolymerization solution and hence continuously shifting of the depolymerization equilibrium to the recycling side. Depolymerizations at various temperatures, starting polymer concentrations, and reactor setup modifications are investigated, clearly showing the highly advantageous effect of the monomer removal on the reaction. The employed approach represents a significant advancement toward the industrial feasibility of depolymerization of methacrylates by lowering the solvent use, expanding its temperature operation window, and bringing polymer contents to a practically relevant level.}, archive = {J_JACS}, author = {Katharina S. C. Jäger and Gayathri Dev Ammini and Pieter-Jan Voorter and Priya Subramanian and Anil Kumar and Athina Anastasaki and Tanja Junkers}, doi = {10.1021/jacs.4c12455}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {594--602}, shortjournal = {J. Am. Chem. Soc.}, title = {Accelerated continuous flow depolymerization of Poly(Methyl methacrylate)}, volume = {147}, year = {2025}, }
• (2025). Plasma-catalyst dynamics: Nonthermal activation of strong Metal–Support interactions. JACS, 147(1), 585--593. (www)

  @article{ , abstract = {Nonthermal plasma-surface interactions enable transformative advancements in green chemistry, healthcare, materials processing, pollution abatement, and the ever-growing area of plasma catalysis. In the context of plasma catalysis, the fate of the active sites during plasma treatment has remained enigmatic, and observation of low-temperature plasma-catalyst events has been challenging. The induction of strong metal–support interactions (SMSI) through high-temperature hydrogen treatment is a well-documented and established, yet limited, method to impact selectivity and stability of noble metal catalysts on reducible supports. Thermally driven SMSI occurs through reduction and subsequent migration of the support to the surface of exposed metal sites, thus affecting the catalyst both electronically and geometrically and serving as an ideal system to evaluate dynamic plasma-catalyst interactions. In this study, a dielectric barrier discharge of hydrogen was used to successfully induce a plasma-SMSI state (P-SMSI) in niobia-supported platinum particles at bulk-gas temperatures as low as −30 °C, which enhances the selectivity for propane dehydrogenation and offers conclusive evidence of plasma-catalyst interactions. Time-resolved spectroscopic evidence of this phenomenon was obtained in situ using a cryogenically cooled plasma IR transmission cell, which provided evidence of diffusion-controlled surface migration. Collectively, P-SMSI constitutes a promising, low-impact technology for synthesizing SMSI-enhanced catalysts with controllable active sites, and knowledge of the nonthermal plasma-catalyst dynamics is critical in designing materials for specific applications or selecting conditions of operation.}, archive = {J_JACS}, author = {Russell J. Clarke and Isaac J. Nice and Jason C. Hicks}, doi = {10.1021/jacs.4c12388}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {585--593}, shortjournal = {J. Am. Chem. Soc.}, title = {Plasma-catalyst dynamics: Nonthermal activation of strong Metal–Support interactions}, volume = {147}, year = {2025}, }
• (2025). Catalytic enantioselective nucleophilic amination of α-halo carbonyl compounds with free amines. JACS, 147(1), 576--584. (www)

  @article{ , abstract = {Catalytic enantioselective substitution of the readily available racemic α-halo carbonyl compounds by nitrogen nucleophiles represents one of the most convenient and direct approaches to access enantioenriched α-amino carbonyl compounds. Distinct from the two available strategies involving radicals and enolate ions, herein we have developed a new protocol featuring an electronically opposite way to weaken/cleave the carbon–halogen bond. A suitable chiral anion-based catalyst enables effective asymmetric control over the key positively charged intermediates. This protocol not only allows free amines to serve as nucleophiles but also permits different types of carbonyl compounds (ketones, esters, and amides) to participate in the enantioselective C–N bond formation, thereby providing a valuable complement to the known strategies that are limited to certain carbonyl substrates and/or nitrogen nucleophiles. Preliminary studies indicated that an S N 2 pathway is operational and kinetic resolution is involved.}, archive = {J_JACS}, author = {Zhiyang Li and Baocheng Wang and Shuaixin Fan and Chaoshen Zhang and Jianwei Sun}, doi = {10.1021/jacs.4c12069}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {576--584}, shortjournal = {J. Am. Chem. Soc.}, title = {Catalytic enantioselective nucleophilic amination of α-halo carbonyl compounds with free amines}, volume = {147}, year = {2025}, }
• (2025). Stable Na/K–S batteries with conductive organosulfur polymer microcages as cathodes. JACS, 147(1), 566--575. (www)

  @article{ , abstract = {Na–S and K–S batteries, with high-energy density, using naturally more abundant and affordable metals compared with rare resources like Li, Co, and Ni elements, have inspired intense research interest. However, the sulfur cathodes for Na/K storage are plagued by soluble polysulfide shuttling, larger volumetric deformation, and sluggish redox kinetics. Here, we report that a conductive organosulfur polymer microcage, fabricated facilely with the microbe and elemental sulfur as precursors, can effectively address these issues for stable high-capacity Na–S and K–S batteries. The covalently bonded short-chain sulfur species enable superior reaction kinetics and avoid soluble polysulfide formation. The microcage architecture with built-in cavities buffers the volume deformation to ensure a resilient electrode. The resultant conductive organosulfur polymer can promise a combination of high capacity and extraordinary cyclability with a promising rate and Coulombic efficiency. Especially, as a K–S battery cathode, it could deliver a high capacity of 1206.5 mAh g –1 together with an extraordinary cyclability (>99% capacity retention over 1100 cycles), which is much better than that of state-of-the-art sulfur cathodes. This work envisions new perspectives on building conductive organosulfur cathode materials with high performance via a simple and feasible protocol.}, archive = {J_JACS}, author = {Xian Zeng and Zi-Jian Yi and Guo-Yu Zhu and Ning-Ning Zhu and Yan-Fei Chen and Ji-Miao Xiao and Run-Hang Chen and Menghua Yang and Hongchang Jin and De-Shan Bin and Dan Li}, doi = {10.1021/jacs.4c11845}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {566--575}, shortjournal = {J. Am. Chem. Soc.}, title = {Stable Na/K–S batteries with conductive organosulfur polymer microcages as cathodes}, volume = {147}, year = {2025}, }
• (2025). Highly efficient transpeptidase-catalyzed isopeptide ligation. JACS, 147(1), 557--565. (www)

  @article{ , abstract = {Transpeptidases are specialized enzymes that have evolved for site-selective modification of peptides and proteins at their backbone termini. Approaches for adapting transpeptidases to catalyze side chain modifications are substantially more restricted, and typically rely on large recognition tags or require specific reaction conditions that are not easily compatible with broader applications. Here we show that the engineered asparaginyl ligase Oa AEP1 catalyzes direct isopeptide ligation by accepting an internal 2,3-diaminopropionic acid (Dap) residue adjacent to Leu, a motif that mimics the canonical N-terminal Gly-Leu substrate. These reactions proceed efficiently at near-neutral pH without any required additives, enabling straightforward formation of diverse isopeptide-linked products under simple reaction conditions. We demonstrate that Oa AEP1-catalyzed isopeptide ligation can be utilized for site-selective side chain labeling at an introduced Dap residue with minimal off-target labeling of Lys residues. Additionally, we generate engineered peptide topologies via intramolecular side chain-to-tail cross-links and produce direct protein–cyclic peptide fusions via efficient intermolecular ligation. We also show that Oa AEP1-catalyzed isopeptide ligation extends to d -peptide acceptors containing a retro-inverso d -Leu- d -Dap motif. This capability further expands the range and complexity of isopeptide-linked products that can be accessed with Oa AEP1, which we exemplify by forming a hybrid d -/ l - bicyclic peptide topology where both termini are linked to internal side chains.}, archive = {J_JACS}, author = {Simon J. de Veer and David J. Craik and Fabian B. H. Rehm}, doi = {10.1021/jacs.4c11964}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {557--565}, shortjournal = {J. Am. Chem. Soc.}, title = {Highly efficient transpeptidase-catalyzed isopeptide ligation}, volume = {147}, year = {2025}, }
• (2025). Enzymatic ring contraction for the biosynthesis of sulfur-containing cyclopentachromone. JACS, 147(1), 548--556. (www)

  @article{ , abstract = {Cyclopentachromone, distinguished by its 6/6/5 heterotricyclic ring structure, is a key building block in many bioactive natural products, yet its enzymatic origin remains unclear. We identified a new class of cyclopentachromone-containing compounds, termed isochromosulfines, characterized by unique C–S bonds. A distinct FAD-dependent monooxygenase, IscL, was identified to catalyze the formation of the 6/6/5 cyclopentadiene intermediate, 2 S -remisporine A, from a 6/6/6 xanthone precursor via benzene ring contraction. The high reactivity of 2 S -remisporine A further promotes a spontaneous thiol-Michael addition reaction with thiol-containing compounds, forming the C–S bond in isochromosulfines. Additionally, we demonstrate that IscL homologues mediate a bifurcated pathway of benzene ring modification in the xanthone intermediate, leading to either ring contraction or cleavage, which is determined by a critical residue at position 230 to be phenylalanine or tyrosine. Our findings highlight the pivotal role of IscL in forming the 6/6/5 cyclopentachromone scaffold and offer deep insights into its catalytic mechanism. Our work lays the foundation for genome mining of cyclopentachromone-containing compounds and shows the potential application of IscL in biocatalysis.}, archive = {J_JACS}, author = {Qiuyue Nie and Chunxiao Sun and Shuai Liu and Qiang Li and Maria Zotova and Tong Zhu and Xue Gao}, doi = {10.1021/jacs.4c11906}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {548--556}, shortjournal = {J. Am. Chem. Soc.}, title = {Enzymatic ring contraction for the biosynthesis of sulfur-containing cyclopentachromone}, volume = {147}, year = {2025}, }
• (2025). Microtubule-targeting NAP peptide-Ru(II)-polypyridyl conjugate as a bimodal therapeutic agent for triple negative breast carcinoma. JACS, 147(1), 532--547. (www)

  @article{ , abstract = {Triple-negative breast cancer (TNBC) poses significant treatment challenges due to its high metastasis, heterogeneity, and poor biomarker expression. The N-terminus of an octapeptide NAPVSIPQ ( NAP ) was covalently coupled to a carboxylic acid derivative of Ru(2,2′-bipy) 3 2+ ( Rubpy ) to synthesize an N-stapled short peptide-Rubpy conjugate ( Ru-NAP ). This photosensitizer (PS) was utilized to treat TNBC through microtubule (MT) targeted chemotherapy and photodynamic therapy (PDT). Ru-NAP formed more elaborate molecular aggregates with fibrillar morphology as compared to NAP . A much higher binding affinity of Ru-NAP over NAP toward β-tubulin ( K Ru-NAP : (6.8 ± 0.55) × 10 6 M –1 ; K NAP : (8.2 ± 1.1) × 10 4 M –1 ) was observed due to stronger electrostatic interactions between the MT with an average linear charge density of ∼85 e/nm and the cationic Rubpy part of Ru-NAP . This was also supported by docking, simulation, and appropriate imaging studies. Ru-NAP promoted serum stability, specific binding of NAP to the E-site of the β III -tubulin followed by the disruption of the MT network, and effective singlet oxygen generation in TNBC cells (MDA-MB-231), causing cell cycle arrest in the G2/M phase and triggering apoptosis. Remarkably, MDA-MB-231 cells were more sensitive to Ru-NAP compared to noncancerous human embryonic kidney (HEK293 cells) when exposed to light ( Light IC 50 Ru-NAP [HEK293]: 17.2 ± 2.5 μM, compared to Light IC 50 Ru-NAP [MDA-MB-231]: 32.5 ± 7.8 nM, Dark IC 50 Ru-NAP [HEK293]: > 80 μM, compared to Dark IC 50 Ru-NAP [MDA-MB-231]: 2.9 ± 0.5 μM). Ru-NAP also effectively inhibited tumor growth in MDA-MB-231 xenograft models in nude mice. Our findings provide strong evidence that Ru-NAP has a potential therapeutic role in TNBC treatment.}, archive = {J_JACS}, author = {Atin Chatterjee and Sandip Sarkar and Sangheeta Bhattacharjee and Arpan Bhattacharyya and Surajit Barman and Uttam Pal and Raviranjan Pandey and Anitha Ethirajan and Batakrishna Jana and Benu Brata Das and Amitava Das}, doi = {10.1021/jacs.4c11820}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {532--547}, shortjournal = {J. Am. Chem. Soc.}, title = {Microtubule-targeting NAP peptide-Ru(II)-polypyridyl conjugate as a bimodal therapeutic agent for triple negative breast carcinoma}, volume = {147}, year = {2025}, }
• (2025). Enriched molecular-level view of saline wetland soil carbon by sensitivity-enhanced solid-state NMR. JACS, 147(1), 519--531. (www)

  @article{ , abstract = {Soil organic matter (SOM) plays a major role in mitigating greenhouse gas emission and regulating earth’s climate, carbon cycle, and biodiversity. Wetland soils account for one-third of all SOM; however, globally, coastal wetland soils are eroding faster due to increasing sea-level rise. Our understanding of carbon sequestration dynamics in wetlands lags behind that of upland soils. Here, we employ solid-state nuclear magnetic resonance (ssNMR) to investigate the molecular-level structure of biopolymers in wetland soils spanning 11 centuries. High-resolution multidimensional spectra, enabled by dynamic nuclear polarization (DNP), demonstrate enduring preservation of molecular structures within herbaceous plant cores, notably condensing aromatic motifs and carbohydrates, even over a millennium, with the preserved cores constituting a decreasing minority among molecules from decomposition and repolymerization with depth and age. Such preserved cores occur alongside molecules from the decomposition of loosely packed parent biopolymers. These findings emphasize the relative vulnerability of coastal wetland SOM when exposed to oxygenated water due to geological and anthropogenic changes.}, archive = {J_JACS}, author = {Wancheng Zhao and Elizabeth C. Thomas and Debkumar Debnath and Faith J. Scott and Frederic Mentink-Vigier and John R. White and Robert L. Cook and Tuo Wang}, doi = {10.1021/jacs.4c11830}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {519--531}, shortjournal = {J. Am. Chem. Soc.}, title = {Enriched molecular-level view of saline wetland soil carbon by sensitivity-enhanced solid-state NMR}, volume = {147}, year = {2025}, }
• (2025). Atomic ordering-induced ensemble variation in alloys governs electrocatalyst On/Off states. JACS, 147(1), 510--518. (www)

  @article{ , abstract = {The catalytic behavior of a material is influenced by ensembles─the geometric configuration of atoms on the surface. In conventional material systems, ensemble effects and the electronic structure are coupled because these strategies focus on varying the material composition, making it difficult to understand the role of ensembles in isolation. This study introduces a methodology that separates geometric effects from the electronic structure. To tune the Pd ensemble size on the catalyst surface, we compared the reactivity of structurally different but compositionally identical Pd 3 Bi intermetallic and solid solution alloys. Pd 3 Bi intermetallics display no reactivity for methanol oxidation (MOR), while their solid solution counterparts show significant reactivity (0.5 mA cm Pd –2 ). Intermetallics form smaller ensembles (1, 3, 4, and 5 atoms across all low-energy facets), whereas solid solution Pd 3 Bi has several facets that support larger Pd ensembles, with an average size of 5.25 atoms and up to 6 atoms. A partially ordered Pd 3 Bi (a mixed phase of intermetallic and solid solution) alloy shows intermediate MOR activity (0.1 mA cm Pd –2 ), confirming that methanol oxidation activity tracks with the average ensemble size. All Pd 3 Bi alloys maintained similar electronic structures, as confirmed by X-ray photoelectron spectroscopy (XPS) valence band spectroscopy and X-ray absorption near edge structure (XANES) measurements, indicating that reactivity differences arise from variations in the ensemble size induced by differences in the atomic ordering. Our findings offer an approach for designing materials with controllable active site configurations while maintaining the catalyst’s electronic structure, thereby enabling more efficient catalyst design.}, archive = {J_JACS}, author = {Tianyao Gong and Guotao Qiu and Mo-Rigen He and Olga V. Safonova and Wei-Chang Yang and David Raciti and Corey Oses and Anthony Shoji Hall}, doi = {10.1021/jacs.4c11753}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {510--518}, shortjournal = {J. Am. Chem. Soc.}, title = {Atomic ordering-induced ensemble variation in alloys governs electrocatalyst On/Off states}, volume = {147}, year = {2025}, }
• (2025). Stereo-differentiating asymmetric Rh(I)-catalyzed Pauson–Khand reaction: A DFT-informed approach to thapsigargin stereoisomers. JACS, 147(1), 498--509. (www)

  @article{ , abstract = {We report a stereo-differentiating dynamic kinetic asymmetric Rh(I)-catalyzed Pauson–Khand reaction, which provides access to an array of thapsigargin stereoisomers. Using catalyst-control, a consistent stereochemical outcome is achieved at C2─for both matched and mismatched cases─regardless of the allene-yne C8 stereochemistry. The stereochemical configuration for all stereoisomers was assigned by comparing experimental vibrational circular dichroism (VCD) and 13 C NMR to DFT-computed spectra. DFT calculations of the transition-state structures corroborate experimentally observed stereoselectivity and identify key stabilizing and destabilizing interactions between the chiral ligand and allene-yne PKR substrates. The robust nature of our catalyst-ligand system places the total synthesis of thapsigargin and its stereoisomeric analogues within reach.}, archive = {J_JACS}, author = {Fatemeh Haghighi and Luke T. Jesikiewicz and Corrinne E. Stahl and Jordan Nafie and Amanda Ortega-Vega and Peng Liu and Kay M. Brummond}, doi = {10.1021/jacs.4c11661}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {498--509}, shortjournal = {J. Am. Chem. Soc.}, title = {Stereo-differentiating asymmetric Rh(I)-catalyzed Pauson–Khand reaction: A DFT-informed approach to thapsigargin stereoisomers}, volume = {147}, year = {2025}, }
• (2025). Parallel proteomic and transcriptomic microenvironment mapping (μMap) of nuclear condensates in living cells. JACS, 147(1), 488--497. (www)

  @article{ , abstract = {Cellular activity is spatially organized across different organelles. While several structures are well-characterized, many organelles have unknown roles. Profiling biomolecular composition is key to understanding function but is difficult to achieve in the context of small, dynamic structures. Photoproximity labeling has emerged as a powerful tool for mapping these interaction networks, yet maximizing catalyst localization and reducing toxicity remains challenging in live cell applications. Here, we disclose a new intracellular photocatalyst with minimal cytotoxicity and off-target binding, and we utilize this catalyst for HaloTag-based microenvironment-mapping (μMap) to spatially catalog subnuclear condensates in living cells. We also specifically develop a novel RNA-focused workflow (μMap-seq) to enable parallel transcriptomic and proteomic profiling of these structures. After validating the accuracy of our approach, we generate a spatial map across the nucleolus, nuclear lamina, Cajal bodies, paraspeckles, and PML bodies. These results provide potential new insights into RNA metabolism and gene regulation while significantly expanding the μMap platform for improved live-cell proximity labeling in biological systems.}, archive = {J_JACS}, author = {Steve D. Knutson and Chenmengxiao Roderick Pan and Niels Bisballe and Brandon J. Bloomer and Philip Raftopolous and Iakovos Saridakis and David W. C. MacMillan}, doi = {10.1021/jacs.4c11612}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {488--497}, shortjournal = {J. Am. Chem. Soc.}, title = {Parallel proteomic and transcriptomic microenvironment mapping (μMap) of nuclear condensates in living cells}, volume = {147}, year = {2025}, }
• (2025). Two different clar’s sextets: Clar’s rule does not necessarily contradict the global pathway of conjugated macrocycles. JACS, 147(1), 480--487. (www)

  @article{ , abstract = {Two contradictory theories, Clar’s sextet and resonance theory, explain the stability of conjugated macrocycles using localized and delocalized models, respectively. To reconcile these theories and gain better insights, PAH-containing porphyrinoids were chosen as a representative class of conjugated macrocycles. Two types of Clar’s sextets were identified and proposed for the first time based on their interaction with global conjugated pathways: (i) shared sextets that integrate with and perturb the global resonance pathway, and (ii) independent sextets that are separate from the pathway and potentially stabilize or do not perturb it. To test our hypothesis, we synthesized precise regioisomers with and without an independent sextet to exclude variables such as steric hindrance, different PAH characteristics, and other elements. This task is challenging due to the extensive synthetic efforts needed for regioisomeric PAH-containing porphyrinoids. We focused on 2,3-vinylnaphthiporphyrin, which features shared sextets, because its o -regioisomers are readily accessible. Two distinct regioisomers (1,2-vinylnaphthiporphyrins) with an independent sextet were synthesized along with unexpected nonaromatic N-fused porphyrinoids. Our analysis shows that 1,2-vinylnaphthiporphyrins with an independent sextet are more aromatic than 2,3-vinylnaphthiporphyrin (nonaromatic). This sextet analysis was also applied to other reported and yet-to-be-synthesized PAH-containing porphyrinoids, and these results are consistent with our current study.}, archive = {J_JACS}, author = {Pradeep P. Desale and Min-Sung Ko and Tae-Ho Roh and Jeong-Im Ham and Dong-Gyu Cho}, doi = {10.1021/jacs.4c11437}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {480--487}, shortjournal = {J. Am. Chem. Soc.}, title = {Two different clar’s sextets: Clar’s rule does not necessarily contradict the global pathway of conjugated macrocycles}, volume = {147}, year = {2025}, }
• (2025). Stacking engineering toward giant second harmonic generation in twisted graphene superstructures. JACS, 147(1), 473--479. (www)

  @article{ , abstract = {The nonlinear optical response in graphene is finding increasing applications in nanophotonic devices. The activation and enhancement of second harmonic generation (SHG) in graphene, which is generally forbidden in monolayer and AB-stacked bilayer graphene due to their centrosymmetry, is of urgent need for nanophotonic applications. Here, we present a comprehensive study of SHG performance of twisted multilayer graphene structures based on stacking engineering. It is found that the modulation of in-plane and out-of-plane SHG susceptibility components by stacking few-layer graphene is essential in producing giant SHG response in twisted multilayer graphene. Giant SHG intensity in twisted multilayer graphene is observed, reaching nearly 10 times that of monolayer MoS 2 under 1064 nm excitation, which significantly outperformed graphene structures reported to date. Our findings present a facile and effective approach to enhance SHG in graphene structures, showing promise for future application of graphene in second harmonic nanophotonic devices as well as prospects for the study of SHG among two-dimensional (2D) structures in general.}, archive = {J_JACS}, author = {Ge Song and Hao Hong and Chaojie Ma and He Hao and Shuowen Yan and Yanfeng Zhang and Kaihui Liu and Lianming Tong and Jin Zhang}, doi = {10.1021/jacs.4c11429}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {473--479}, shortjournal = {J. Am. Chem. Soc.}, title = {Stacking engineering toward giant second harmonic generation in twisted graphene superstructures}, volume = {147}, year = {2025}, }
• (2025). Quantitative unraveling of exsolved heteroboundaries for high-temperature electrocatalysis. JACS, 147(1), 462--472. (www)

  @article{ , abstract = {The application of perovskite oxide for high-temperature electrocatalysis is hindered by its limited activity. Exsolution is a smart strategy that allows the enrichment of the perovskite’s surface with highly reactive phases, yielding heteroboundaries. However, the identification of the exact catalytic role of this complex architecture is still elusive. Here we presented a quantitative analysis of the CO 2 electroreduction reactivity of a series of perovskite thin film platforms (La 0.4 Ca 0.4 Ti 0.94 Ni 0.06 O 3 , LCTN) boosted by exsolved heteropical nanoparticles (particularly for Ni and NiO). The cross-scale electrochemical characterizations, together with density functional theory (DFT) modelings, have shown clear evidence that the boundary length of the NP/perovskite interface is strictly correlated with the CO 2 RR activity. The intrinsic reaction rate per active site at the NiO/LCTN boundary demonstrates a highest turnover frequency (TOF) of 7.05 ± 0.75 × 104 s –1 at 800 °C, which is 2.5 times and 4 orders of magnitude better than that of Ni/LCTN and LCTN, respectively. The ab initio molecular dynamics (AIMD) proves that the CO 2 absorption at the NiO/LCTN boundary leverages a bidentate carbonate modality with a reduced dissociation energy barrier. Moreover, a multifold enhancement in oxygen exchange rate was confirmed, which correlated to the facilitated oxygen ion hopping between adjacent TiO 6 octahedrons. Further near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) during CO 2 electrolysis on model electrolyzers reveals the crucial role of the NiO/LCTN boundary in stabilizing oxidized carbon intermediates, raising the onset potential threshold of adventitious carbon as well as preventing its build-up.}, archive = {J_JACS}, author = {Xiaoxin Zhang and Xiao Xiao and Qiuyue Zhang and Zhou Chen and Chang Jiang and Mingshu Chen and Ning Yan and Shidi Mo and Meng Wu and Jianhui Li and Jijie Huang and Abdullah N. Alodhayb and Xianzhu Fu and Min Chen and Xinchun Lv and Yifei Sun}, doi = {10.1021/jacs.4c11274}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {462--472}, shortjournal = {J. Am. Chem. Soc.}, title = {Quantitative unraveling of exsolved heteroboundaries for high-temperature electrocatalysis}, volume = {147}, year = {2025}, }
• (2025). G3BP1/2-targeting PROTAC disrupts stress granules dependent ATF4 migracytosis as cancer therapy. JACS, 147(1), 446--461. (www)

  @article{ , abstract = {Stress granules (SGs) are membraneless cytoplasmic compartments that form in response to stress stimuli. In these compartments, most translation factors stall, except for activating transcription factor 4 (ATF4), which is preferentially translated to ensure cell survival under stressful conditions. Cancer cells encounter various stress conditions in the tumor microenvironment during tumorigenesis; however, how they exploit the pro-survival effects of ATF4 in SGs remains unclear. G3BP1/2 are central nodes of the SG network, regulating SG dynamics. In this study, we designed two small molecules, #129 and PROTAC (Proteolysis Targeting Chimera) degrader 129 (PT-129), which specifically target the NTF2L domain of G3BP1/2, a crucial hub for protein and RNA interactions. These compounds inhibit the formation of stress granules in stressed cells and disassemble pre-existing stress granules. Furthermore, pharmacological inhibition by PT-129 suppressed fibroblast-mediated cancer cell growth in vitro and reduced tumor growth in vivo. Mechanistically, SG facilitates the delivery of ATF4 from fibroblasts to tumor cells via migracytosis, a primary mediator of fibroblast-associated tumor growth. PT-129-mediated disassembly of stress granules disrupts ATF4 delivery, thereby preventing cancer cell proliferation. These compounds, therefore, represent powerful tools for gaining molecular insights into SGs and hold promise for cancer therapeutic interventions by modulating stress granule dynamics.}, archive = {J_JACS}, author = {Ting Dong and Fabao Zhao and Mengmeng Wang and Kaige Lyu and Jiayu Zhu and Wenru Zhang and Wenzhe Li and Yixuan An and Na Liu and Akhand Pratap Singh and Yue Yang and Dongwei Kang and Xiaohui Liu}, doi = {10.1021/jacs.4c11146}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {446--461}, shortjournal = {J. Am. Chem. Soc.}, title = {G3BP1/2-targeting PROTAC disrupts stress granules dependent ATF4 migracytosis as cancer therapy}, volume = {147}, year = {2025}, }
• (2025). The interfacial interpenetration effect for controlled reaction stability of palladium catalysts. JACS, 147(1), 436--445. (www)

  @article{ , abstract = {Tailoring well-defined interfacial structures of heterogeneous metal catalysts has become an effective strategy for identifying the interface relationships and facilitating the reactions involving multiple intermediates. Here, a particle–particle heterostructure catalyst consisting of Pd and copper oxide nanoparticles is designed to achieve high-performance alkaline methanol oxidation electrocatalysis. The strong coupling particle–particle heterostructure catalyst induced a unique interfacial interpenetration effect to improve the interfacial charge redistribution and regulate the d -band structure for optimizing the adsorption of CO intermediates on the catalyst. The resulting catalyst shows impressive mass activity (4.0 A mg Pd –1 ) and current density (215.8 mA cm –2 ) for the methanol oxidation reaction (MOR) in alkaline media, which is 80.0 and 154.1 times higher than 10% Pd/C. The catalyst also exhibited outstanding stability for the MOR without obvious mass activity decay after 30,000 cycles. Experimental results and theoretical simulation (DFT) studies show that the chemical bond of the Cu–O–Pd interface can be regulated by the Pd penetration effect, greatly improving the activity and stability of the MOR. The present work exhibits the superiority of the metal particle–metal oxide heterostructure interface toward the rational design of advanced electrocatalysts.}, archive = {J_JACS}, author = {Xueting Zhang and Lan Hui and Feng He and Yuliang Li}, doi = {10.1021/jacs.4c11234}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {436--445}, shortjournal = {J. Am. Chem. Soc.}, title = {The interfacial interpenetration effect for controlled reaction stability of palladium catalysts}, volume = {147}, year = {2025}, }
• (2025). Roles of the polymer backbone for sulfurized polyacrylonitrile cathodes in rechargeable lithium batteries. JACS, 147(1), 426--435. (www)

  @article{ , abstract = {Sulfurized polyacrylonitrile (SPAN) has emerged as a highly promising cathode material for next-generation lithium–sulfur (Li–S) batteries primarily due to its non-polysulfide dissolution and excellent cycle stability. Nevertheless, the specific roles and impacts of the pyrolyzed polyacrylonitrile, which constitutes the polymer backbone of SPAN, remain inadequately understood. In this study, comprehensive investigations from multiple aspects, including electrochemistry, spectroscopy, electron microscopy, and theoretical calculations, were conducted on a series of SPAN materials with various sulfur contents. The results reveal that the polymer backbone serves at least four critical functions. First, during the synthesis of SPAN, the polymer backbone provides reactive sites for the incorporation of sulfur through chemical bonding. Second, it establishes an extensive π-conjugated network via a dehydrogenation reaction by sulfur and serves as a conductive framework for SPAN. The chemically bonded sulfur atoms dope the polymer backbone, which narrows the highest occupied molecular orbitals–lowest unoccupied molecular orbitals (HOMO–LUMO) energy gap. Third, the polymer backbone plays an essential role in determining the first Coulombic efficiency, and the irreversibly inserted Li atoms further dope the polymer backbone and reduce the HOMO–LUMO energy gap. Lastly, the pyridine nitrogen within the polymer backbone exhibits an adsorption effect on lithium sulfide (Li 2 S) species, which stabilizes the cycling performances of the SPAN cathode. It is worth noting that the polymer backbone hardly contributes reversible capacity for the SPAN cathode in carbonate electrolytes within the 1 to 3 V operating voltage range. This study enhances our understanding of SPAN and may provide valuable guidance for the development of better SPAN materials and rechargeable batteries.}, archive = {J_JACS}, author = {Jiqiong Liu and Huichao Lu and Qihang Wang and Xirui Kong and Chenran Hao and Jun Yang and Yanna NuLi and Huanan Duan and Jiulin Wang}, doi = {10.1021/jacs.4c11216}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {426--435}, shortjournal = {J. Am. Chem. Soc.}, title = {Roles of the polymer backbone for sulfurized polyacrylonitrile cathodes in rechargeable lithium batteries}, volume = {147}, year = {2025}, }
• (2025). Palladium bisphosphine monoxide complexes: Synthesis, scope, mechanism, and catalytic relevance. JACS, 147(1), 409--425. (www)

  @article{ , abstract = {Recent studies in transition metal catalysis employing chelating phosphines have suggested a role for partial ligand oxidation in formation of the catalytically active species, with potentially widespread relevance in a number of catalytic systems. We examine the internal redox reaction of Pd II (bisphosphine)X 2 (X = Cl, OAc, etc. ) complexes to reveal previously underexplored aspects of bisphosphine monoxides (BPMOs), including evaluation of ligand structure and development of general reaction conditions to access a collection of structurally diverse BPMO precatalysts based on organopalladium oxidative addition complexes. In particular, a series of Pd II (BPMO)(R)(X) (R = aryl, alkyl; X = I, Br) oxidative addition complexes bearing 24 different BPMO ligands were characterized by NMR and X-ray crystallography. Comparison of the catalytic performance of the oxidative addition complexes of bisphosphine versus bisphosphine monoxides as precatalysts is demonstrated to be an enabling diagnostic tool in Pd catalytic reaction development. Finally, the differences in catalytic behavior between bisphosphine and bisphosphine monoxide complexes were rationalized through solid-state parametrization and stoichiometric experiments.}, archive = {J_JACS}, author = {Shenghua Yang and Min Deng and Ryan A. Daley and Andrea Darù and William J. Wolf and David T. George and Senjie Ma and Bryn K. Werley and Erika Samolova and Jake B. Bailey and Milan Gembicky and Jonathan Marshall and Steven R. Wisniewski and Donna G. Blackmond and Keary M. Engle}, doi = {10.1021/jacs.4c10718}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {409--425}, shortjournal = {J. Am. Chem. Soc.}, title = {Palladium bisphosphine monoxide complexes: Synthesis, scope, mechanism, and catalytic relevance}, volume = {147}, year = {2025}, }
• (2025). AC plasmas directly excited in liquid-phase hydrocarbons for h2 and unsaturated c2 hydrocarbon production. JACS, 147(1), 397--408. (www)

  @article{ , abstract = {AC plasmas directly excited within liquid hydrocarbons were investigated for the production of hydrogen and unsaturated C 2 hydrocarbon in a recirculating liquid “jet” flow configuration. Arc discharges were excited at two different frequencies (60 Hz and 17.3 kHz) in C 6 –C 8 hydrocarbons (hexane, cyclohexane, benzene, toluene, and xylene) to produce H 2 , C 2 H 4 , C 2 H 2 , and CH 4 , along with liquid and solid carbon byproducts. AC frequency was seen to modify the plasma properties and gas bubble formation dynamics, significantly influencing the efficiency and reaction pathway. Higher discharge frequency increased energy efficiency more than 2-fold by minimizing thermal losses and favored the production of hydrogenated compounds due to shorter reactant–plasma contact times. Further optimization of hexane conversion was achieved by introducing fluid flow around the plasma electrodes, which led to competitively low specific energy requirements (SERs) of 3.2 kWh/kg C 2 H 4 , 4.9 kWh/kg C 2 H 2 , and 24.3 kWh/kg H 2 . The effect of hydrocarbon feed chemistry was analyzed, showing that hexane and cyclohexane are preferable for C 2 hydrocarbon syntheses, whereas aromatic hydrocarbons produce more H 2 . Gas bubble dynamics and liquid/solid products were analyzed using high-speed imaging, optical emission spectroscopy (OES), gas chromatography–mass spectrometry (GC-MS), scanning electron microscopy/transmission electron microscopy (SEM/TEM), and Raman spectroscopy. This work contributes to the understanding of plasma conversion mechanisms within liquids and demonstrates the potential for the energy-efficient transformation of hydrocarbons with plasma in unique reaction environments.}, archive = {J_JACS}, author = {Norleakvisoth Lim and Eric McFarland and Michael J. Gordon}, doi = {10.1021/jacs.4c11174}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {397--408}, shortjournal = {J. Am. Chem. Soc.}, title = {AC plasmas directly excited in liquid-phase hydrocarbons for h2 and unsaturated c2 hydrocarbon production}, volume = {147}, year = {2025}, }
• (2025). Sequence-specific minor groove binders in labeling and single-molecule analysis of DNA. JACS, 147(1), 384--396. (www)

  @article{ , abstract = {The ability to address specific sequences within DNA is of tremendous interest in biotechnology and biomedicine. Various technologies have been established over the past few decades, such as nicking enzymes and methyltransferase-directed sequence-specific labeling, transcription activator-like effector nucleases (TALENs), the CRISPR-Cas9 system, and polyamides of heterocycles as sequence-specific DNA minor groove binders. Pyrrole-imidazole polyamides have been reported to recognize predetermined DNA sequences, and some successful attempts have demonstrated their potential in regulating gene expression. However, few studies on single-molecule labeling and analysis of DNA have been explored, particularly at single-targeting sites. In this study, we rationally designed and synthesized a set of functional minor groove binders, varying in structures, sequence information addressed, and methods of dye introduction. Their potential for sequence-specific labeling and single-molecule DNA analysis was evaluated through chromatographic and on-surface optical assays. First results indicated that, while they yielded excellent imaging output, the labeling specificity of the hairpin polyamides for single-molecule use was hindered by single-mismatch sites. To address this issue, and in an unprecedented approach, we devised a competitive binding strategy that utilizes ethidium bromide as a nonspecific binder to competitively block the mismatches, significantly enhancing the labeling specificity. These findings provide valuable insights into the use of hairpin polyamides as sequence-programmable and enzyme-free DNA labelers in the field of sequence-specific DNA recognition and modification.}, archive = {J_JACS}, author = {Xiong Chen and Sergey Abakumov and Moa Sandberg Wranne and Vince Goyvaerts and Milena Helmer Lauer and Jana Rubberecht and Taoufik Rohand and Volker Leen and Fredrik Westerlund and Johan Hofkens}, doi = {10.1021/jacs.4c11028}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {384--396}, shortjournal = {J. Am. Chem. Soc.}, title = {Sequence-specific minor groove binders in labeling and single-molecule analysis of DNA}, volume = {147}, year = {2025}, }
• (2025). A self-assembled nano-molecular glue (Nano-mGlu) enables GSH/H2O2-triggered targeted protein degradation in cancer therapy. JACS, 147(1), 372--383. (www)

  @article{ , abstract = {Molecular glues are promising protein-degrading agents that hold great therapeutic potential but face significant challenges in rational design, effective synthesis, and precise targeting of tumor sites. In this study, we first overcame some of these limitations by introducing a fumarate-based molecular glue handle onto specific ligands of therapeutic kinases (TBK1, FGFR, and Bcr-Abl), resulting in the effective degradation of these important cancer targets. Despite the broad applicability of the strategy, we unexpectedly discovered potent and widespread cytotoxicity across various cell lines, including noncancerous ones, rendering it less effective in cancer therapy. To address this critical issue, we next developed a self-assembled nanoparticle-based molecular glue (nano-mGlu) based on one of the newly discovered Bcr-Abl-degrading molecular glues ( H1-mGlu ). We showed that the resulting nano-mGlu (named Cle-NP ) was able to release H1-mGlu in vitro in the presence of a high concentration of GSH or H 2 O 2 (commonly found in the tumor microenvironment). Subsequent in vivo antitumor studies with a K562-xenografted mouse model indicated that Cle-NP was highly effective in tumor-specific degradation of endogenous Bcr-Abl expressed in K562 cells, leading to eventual tumor regression while maintaining good biosafety profiles. With key advantages of generality in molecular glue design, targeted delivery (e.g., H1-mGlu ), potent antitumor activity partially induced by target-specific degradation, and minimized collateral damage to healthy tissues, our self-assembled nano-mGlu strategy thus provides a novel approach that might hold a significant promise for effective and personalized cancer therapy.}, archive = {J_JACS}, author = {Jie Sun and Mingxi Gu and Lvyang Peng and Jing Guo and Peng Chen and Yalei Wen and Fang Feng and Xiaojuan Chen and Tongzheng Liu and Yongheng Chen and Xiaoyun Lu and Liqian Gao and Shao Q. Yao and Peiyan Yuan}, doi = {10.1021/jacs.4c11003}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {372--383}, shortjournal = {J. Am. Chem. Soc.}, title = {A self-assembled nano-molecular glue (Nano-mGlu) enables GSH/H2O2-triggered targeted protein degradation in cancer therapy}, volume = {147}, year = {2025}, }
• (2025). Consecutive C–C coupling of CH4 and CO2 mediated by heteronuclear metal cations CuTa+. JACS, 147(1), 362--371. (www)

  @article{ , abstract = {The conversion of methane and carbon dioxide to form C 2 products is of great interest but presents a long-standing grand challenge due to the significant obstacle of activating the inert C–H and C═O bonds as well as forming the C–C bonds. Herein, the consecutive C–C coupling of CH 4 and CO 2 was realized by using heteronuclear metal cations CuTa + , and the desorption of H 2 C═C═O molecules was evidenced by state-of-the-art mass spectrometry. The CuTa + reaction system is significantly different from the homonuclear metal systems of Cu 2 + and Ta 2 + . On the basis of density functional theory calculations, we identified that Cu can modulate the charge distribution and reduce the energy difference of crucial orbitals for the C–C coupling of CH 2 and CO units that are from the activation of CH 4 and CO 2 , respectively. The crucial role of the Cu atom is of substantial importance to understand the process of the C–C coupling reaction in Cu-based heterogeneous catalytic systems. This study not only provides a promising paradigm for the design of non-noble metal species in direct conversion of CH 4 and CO 2 under mild conditions but also reveals a new molecular-level mechanism of consecutive C–C coupling for the production of H 2 C═C═O, a crucial intermediate during carbonylation reactions.}, archive = {J_JACS}, author = {Yuan Yang and Li-Jiao Zhang and Xiao-Li Wang and Rui Wang and Yan-Xia Zhao and Sheng-Gui He and Shuang-Quan Zang}, doi = {10.1021/jacs.4c10819}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {362--371}, shortjournal = {J. Am. Chem. Soc.}, title = {Consecutive C–C coupling of CH4 and CO2 mediated by heteronuclear metal cations CuTa+}, volume = {147}, year = {2025}, }
• (2025). Selective ni-catalyzed cross-electrophile coupling of heteroaryl chlorides and aryl bromides at 1:1 substrate ratio. JACS, 147(1), 353--361. (www)

  @article{ , abstract = {Nickel-catalyzed cross-electrophile coupling (XEC) reactions of (hetero)aryl electrophiles represent appealing alternatives to palladium-catalyzed methods for biaryl synthesis, but they often generate significant quantities of homocoupling and/or proto-dehalogenation side products. In this study, an informer library of heteroaryl chloride and aryl bromide coupling partners is used to identify Ni-catalyzed XEC conditions that access high selectivity for the cross-product when using equimolar quantities of the two substrates. Two different catalyst systems are identified that show complementary scope and broad functional-group tolerance, and time-course data suggest that the two methods follow different mechanisms. A NiBr 2 /terpyridine catalyst system with Zn as the reductant converts the aryl bromide into an arylzinc intermediate that undergoes in situ coupling with 2-chloropyridines, while a NiBr 2 /bipyridine catalyst system with tetrakis(dimethylamino)ethylene as the reductant uses FeBr 2 and NaI as additives to achieve selective cross-coupling.}, archive = {J_JACS}, author = {Zhi-Ming Su and Jieru Zhu and Darren L. Poole and Mohammad Rafiee and Robert S. Paton and Daniel J. Weix and Shannon S. Stahl}, doi = {10.1021/jacs.4c10776}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {353--361}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective ni-catalyzed cross-electrophile coupling of heteroaryl chlorides and aryl bromides at 1:1 substrate ratio}, volume = {147}, year = {2025}, }
• (2025). Enantioselective synthesis of chiral β2-amino phosphorus derivatives via nickel-catalyzed asymmetric hydrogenation. JACS, 147(1), 342--352. (www)

  @article{ , abstract = {Compared with chiral β 3 -amino phosphorus compounds, which can be easily derived from natural optically pure α-amino acids, obtaining chiral β 2 -amino phosphorus derivatives remains a challenge. These derivatives, which cannot be derived from chiral natural amino acids, possess unique biological activities or potential catalytic activities. Herein, highly enantioselective hydrogenation for the preparation of chiral β 2 -amino phosphorus derivatives from E -β-enamido phosphorus compounds is reported by using a green and low-cost earth-abundant metal nickel catalyst (13 examples of 99% ee). In particular, this catalytic system provides the same enantiomer product from the E - and Z -alkene substrates, and the E / Z -substrate mixtures provide good results (up to 96% ee). The products can be diversely derivatized, and the derivatives exhibit good catalytic activities as novel chiral β 2 -aminophosphine ligands. Density functional theory calculations reveal that the weak attractive interactions between the nickel catalyst and the substrate are crucial for achieving perfect enantioselectivities. In addition, the different coordination modes between the E - or Z -substrates and the catalyst may result in the formation of the same enantiomer product.}, archive = {J_JACS}, author = {Hanlin Wei and Yicong Luo and Jinhui Li and Jianzhong Chen and Ilya D. Gridnev and Wanbin Zhang}, doi = {10.1021/jacs.4c10623}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {342--352}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective synthesis of chiral β2-amino phosphorus derivatives via nickel-catalyzed asymmetric hydrogenation}, volume = {147}, year = {2025}, }
• (2025). Room-temperature optical spin polarization of an electron spin qudit in a vanadyl-free base porphyrin dimer. JACS, 147(1), 331--341. (www)

  @article{ , abstract = {Photoexcited organic chromophores appended to molecular qubits can serve as a source of spin initialization or multilevel qudit generation for quantum information applications. So far, this approach has been primarily investigated in chromophore–stable radical systems. Here, we extend this concept to a meso-meso linked oxovanadium(IV) porphyrin–free-base porphyrin dimer. Femtosecond transient absorption experiments reveal that photoexcitation of the free-base porphyrin leads to picosecond triplet state formation via enhanced intersystem crossing. Time-resolved electron paramagnetic resonance (TREPR) experiments carried out at both 85 K and room temperature reveal the formation of a long-lived spin-polarized quartet state through triplet–doublet spin mixing. Notably, a distinct hyperfine structure arising from the interaction between the electron spin quartet state and the vanadyl nucleus ( 51 V, I = 7/2) is evident, with the quartet state showing long-lived spin polarization even at room temperature. Theoretical simulations of the TREPR spectra confirm the photogenerated quartet state and provide insights into the non-Boltzmann spin populations. Exploiting this phenomenon affords the possibility of using photoinduced triplet states in porphyrins for quantum information as a resource to polarize and magnetically couple molecular electronic or nuclear spin qubits and qudits.}, archive = {J_JACS}, author = {Alberto Privitera and Alessandro Chiesa and Fabio Santanni and Angelo Carella and Davide Ranieri and Andrea Caneschi and Matthew D. Krzyaniak and Ryan M. Young and Michael R. Wasielewski and Stefano Carretta and Roberta Sessoli}, doi = {10.1021/jacs.4c10632}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {331--341}, shortjournal = {J. Am. Chem. Soc.}, title = {Room-temperature optical spin polarization of an electron spin qudit in a vanadyl-free base porphyrin dimer}, volume = {147}, year = {2025}, }
• (2025). Elucidating the mechanism of electrooxidative allene dioxygenation: Dual role of tetramethylpiperidine N-oxyl (TEMPO). JACS, 147(1), 318--330. (www)

  @article{ , abstract = {The cumulated π system of a nonsymmetric allene contains three distinct unsaturated carbons that imbue it with unique reactivity toward radicals as compared to its alkene and alkyne counterparts. Despite the synthetic potential of these versatile building blocks, electrochemical transformations of allenes have been historically underexplored. Myriad strategies for easy access to allenes, coupled with the resurgence of interest in sustainable oxidative transformations of hydrocarbons, prompted our efforts to conduct an in-depth investigation of a rare example of an electrochemical TEMPO-mediated allene dioxygenation. The resultant vinyl-TEMPO motif is readily postfunctionalized to install a heteroatom at each allene carbon. Mechanistic investigations, including cyclic voltammetry (CV) studies, computations, and monitoring by operando NMR (ReactNMR) were performed to lay the groundwork for future electrochemical allene functionalizations that deliver unique synthetic building blocks.}, archive = {J_JACS}, author = {Ken S. Lee and Federico Barbieri and Emanuele Casali and Elijah T. Marris and Giuseppe Zanoni and Jennifer M. Schomaker}, doi = {10.1021/jacs.4c10431}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {318--330}, shortjournal = {J. Am. Chem. Soc.}, title = {Elucidating the mechanism of electrooxidative allene dioxygenation: Dual role of tetramethylpiperidine N-oxyl (TEMPO)}, volume = {147}, year = {2025}, }
• (2025). Indirect formation of peptide bonds as a prelude to ribosomal transpeptidation. JACS, 147(1), 305--317. (www)

  @article{ , abstract = {The catalytic competency of the ribosome in extant protein biosynthesis is thought to arise primarily from two sources: an ability to precisely juxtapose the termini of two key substrates─3′-aminoacyl and N -acyl-aminoacyl tRNAs─and an ability to ease direct transpeptidation by their desolvation and encapsulation. In the absence of ribosomal, or enzymatic, protection, however, these activated alkyl esters undergo efficient hydrolysis, while significant entropic barriers serve to hamper their intermolecular cross-aminolysis in bulk water. Given that the spontaneous emergence of a catalyst of comparable size and sophistication to the ribosome in a prebiotic RNA world would appear implausible, it is thus natural to ask how appreciable peptide formation could have occurred with such substrates in bulk water without the aid of advanced ribozymatic catalysis. Using a combination of fluorine-tagged aminoacyl adenylate esters, in situ monitoring by 19 F{ 1 H} NMR spectroscopy, analytical deconvolution of kinetics, pH–rate profile analysis, and temperature-dependence studies, we here explore the mechanistic landscape of indirect amidation, via transesterification and O-to-N rearrangement, as a highly efficient, alternative manifold for transpeptidation that may have served as a prelude to ribosomal peptide synthesis. Our results suggest a potentially overlooked role for those amino acids implicated by the cyanosulfidic reaction network with hydroxyl side chains (Ser and Thr), and they also help to resolve some outstanding ambiguities in the broader literature regarding studies of similar systems (e.g., aminolyzes with Tris buffer). The evolutionary implications of this mode of peptide synthesis and the involvement of a very specific subset of amino acids are discussed.}, archive = {J_JACS}, author = {Harvey J. A. Dale and John D. Sutherland}, doi = {10.1021/jacs.4c10326}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {305--317}, shortjournal = {J. Am. Chem. Soc.}, title = {Indirect formation of peptide bonds as a prelude to ribosomal transpeptidation}, volume = {147}, year = {2025}, }
• (2025). 10-fold increase in hydrogen atom transfer reactivity for a series of s = 1 FeIV═O complexes over the s = 2 [(TQA)FeIV═O]2+ complex via entropic lowering of reaction barriers by secondary sphere cycloalkyl substitution. JACS, 147(1), 292--304. (www)

  @article{ , abstract = {Nonheme iron enzymes utilize S = 2 iron(IV)-oxo intermediates as oxidants in biological oxygenations. In contrast, corresponding synthetic nonheme Fe IV ═O complexes characterized to date favor the S = 1 ground state that generally shows much poorer oxidative reactivity than their S = 2 counterparts. However, one intriguing exception found by Nam a decade ago is the S = 1 [Fe IV (O)(Me 3 NTB)] 2+ complex (Me 3 NTB = [tris(( N -methyl-benzimidazol-2-yl)methyl)amine], 1O ) with a hydrogen atom transfer (HAT) reactivity that is 70% that of the S = 2 [Fe IV (O)(TQA)] 2+ complex (TQA = tris(2-quinolylmethyl)amine, 3O ). In our efforts to further explore this direction, we have unexpectedly uncovered a family of new S = 1 complexes with HAT reaction rates beyond the currently reported limits in the tripodal ligand family, surpassing oxidation rates found for the S = 2 [Fe IV (O)(TQA)] 2+ complex by as much as an order of magnitude. This is achieved simply by replacing the secondary sphere methyl groups of the Me 3 NTB ligand with larger cycloalkyl-CH 2 (R groups in 2O R ) moieties ranging from c -propylmethyl to c -hexylmethyl. These 2O R complexes show Mössbauer data at 4 K and 1 H NMR spectra at 193 and 233 K that reveal S = 1 ground states, in line with DFT calculations. Nevertheless, they give rise to the most reactive synthetic nonheme oxoiron(IV) complexes found to date within the tripodal ligand family. Our DFT study indicates transition state stabilization through entropy effects, similar to enzymatic catalysis.}, archive = {J_JACS}, author = {Abhishek Das and Nabhendu Pal and Jin Xiong and Victor G. Young, Jr. and Yisong Guo and Marcel Swart and Lawrence Que, Jr.}, doi = {10.1021/jacs.4c10120}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {292--304}, shortjournal = {J. Am. Chem. Soc.}, title = {10-fold increase in hydrogen atom transfer reactivity for a series of s = 1 FeIV═O complexes over the s = 2 [(TQA)FeIV═O]2+ complex via entropic lowering of reaction barriers by secondary sphere cycloalkyl substitution}, volume = {147}, year = {2025}, }
• (2025). Nuclear quadrupolar resonance structural characterization of halide perovskites and perovskitoids: A roadmap from electronic structure calculations for Lead–Iodide-based compounds. JACS, 147(1), 278--291. (www)

  @article{ , abstract = {Metal halide perovskites, including some of their related perovskitoid structures, form a semiconductor class of their own, which is arousing ever-growing interest from the scientific community. With halides being involved in the various structural arrangements, namely, pure corner-sharing MX 6 (M is metal and X is halide) octahedra, for perovskite networks, or alternatively a combination of corner-, edge-, and/or face-sharing for related perovskitoids, they represent the ideal probe for characterizing the way octahedra are linked together. Well known for their inherently large quadrupolar constants, which is detrimental to the resolution of nuclear magnetic resonance spectroscopy, most abundant halide isotopes ( 35/37 Cl, 79/81 Br, 127 I) are in turn attractive for magnetic field-free nuclear quadrupolar resonance (NQR) spectroscopy. Here, we investigate the possibility of exploiting NQR spectroscopy of halides to distinctively characterize the various metal halide structural arrangements, using density functional theory simulations. Our calculations nicely match the available experimental results. Furthermore, they demonstrate that compounds with different connectivities of their MX 6 building blocks, including lower dimensionalities such as 2D networks, show distinct NQR signals in a broad spectral window. They finally provide a roadmap of the characteristic NQR frequency ranges for each octahedral connectivity, which may be a useful guide to experimentalists, considering the long acquisition procedures typical of NQR. We hope this work will encourage the incorporation of NQR spectroscopy to further our knowledge of the structural diversity of metal halides.}, archive = {J_JACS}, author = {Claudio Quarti and Régis Gautier and Marios Zacharias and Axel Gansmuller and Claudine Katan}, doi = {10.1021/jacs.4c09877}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {278--291}, shortjournal = {J. Am. Chem. Soc.}, title = {Nuclear quadrupolar resonance structural characterization of halide perovskites and perovskitoids: A roadmap from electronic structure calculations for Lead–Iodide-based compounds}, volume = {147}, year = {2025}, }
• (2025). Discovery of a chimeric polyketide family as cancer immunogenic chemotherapeutic leads. JACS, 147(1), 265--277. (www)

  @article{ , abstract = {Discovery of cancer immunogenic chemotherapeutics represents an emerging, highly promising direction for cancer treatment that uses a chemical drug to achieve the efficacy of both chemotherapy and immunotherapy. Herein, we report a high-throughput screening platform and the subsequent discovery of a new class of cancer immunogenic chemotherapeutic leads. Our platform integrates informatics-based activity metabolomics for the rapid identification of microbial natural products with both novel structures and potent activities. Additionally, we demonstrate the use of microcrystal electron diffraction (MicroED) for direct structure elucidation of lead compounds from partially purified mixtures. Using this strategy to screen geographically and phylogenetically diverse microbial metabolites against pseudomyxoma peritonei, a rare and severe cancer, we discovered a new class of leads, aspercyclicins. The aspercyclicins feature an unprecedented tightly packed polycyclic polyketide scaffold that comprises continuous fused, bridged, and spiro rings. The biogenesis of aspercyclicins involves two distinct biosynthetic pathways, leading to formation of chimeric compounds that cannot be predicted by bottom-up approaches mining natural product biosynthetic genes. With comparable potency to some clinically used anticancer drugs, aspercyclicins are active against multiple cancer cell types by inducing immunogenic cell death (ICD), including the release of damage-associated molecular patterns and subsequent phagocytosis of cancer cells. The broad-spectrum ICD-inducing activity of aspercyclicins, combined with their low toxicity to normal cells, represents a new class of potential cancer immunogenic chemotherapeutics and, particularly, the first drug lead for pseudomyxoma peritonei treatment.}, archive = {J_JACS}, author = {Dan Xue and Mingming Xu and Michael D. Madden and Xiaoying Lian and Ethan A. Older and Conor Pulliam and Yvonne Hui and Zhuo Shang and Gourab Gupta and Manikanda K. Raja and Yuzhen Wang and Armando Sardi and Yaoling Long and Hexin Chen and Daping Fan and Tim S. Bugni and Traci L. Testerman and Qihao Wu and Jie Li}, doi = {10.1021/jacs.4c09582}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {265--277}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of a chimeric polyketide family as cancer immunogenic chemotherapeutic leads}, volume = {147}, year = {2025}, }
• (2025). Discovery of a gut bacterial pathway for ergothioneine catabolism. JACS, 147(1), 257--264. (www)

  @article{ , abstract = {Ergothioneine is a diet-derived micronutrient for humans. However, enzymes involved in the catabolism of ergothioneine in human gut bacteria have not yet been identified. Herein, we characterize a sulfidogenic pathway for gut bacterial catabolism of this micronutrient, which involves an unprecedented reductive desulfurization reaction catalyzed by members of the xanthine oxidoreductase family (XOR), a class of molybdenum-containing flavoproteins. Notably, this is the first C–S bond cleavage reaction known to be catalyzed by XORs. Evidence for operation of this pathway was gained through in vitro reconstruction using heterologously produced enzymes derived from the human gut bacterium Blautia producta ATCC 27340. This catabolic activity enables B. producta ATCC 27340 to use ergothioneine as an alternative electron acceptor source. Homologues of the pathway enzymes are shown to be present not only in human gut bacteria but also in many environmental bacteria, suggesting the wide distribution of this catabolic strategy. In relation to the sulfur-containing metabolite, this discovery provides significant insight into biogeochemical sulfur cycling in diverse anoxic habitats beyond the human gut and, moreover, the design of new approaches for controlling intestinal hydrogen sulfide (H 2 S) production.}, archive = {J_JACS}, author = {Chenxi Feng and Qiongxiang Yan and Xianyi Li and Hong Zhao and Hua Huang and Xinshuai Zhang}, doi = {10.1021/jacs.4c09350}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {257--264}, shortjournal = {J. Am. Chem. Soc.}, title = {Discovery of a gut bacterial pathway for ergothioneine catabolism}, volume = {147}, year = {2025}, }
• (2025). Synthetic T-cell receptor-like protein behaves as a janus particle in solution. JACS, 147(1), 247--256. (www)

  @article{ , abstract = {Protein engineering enables the creation of tailor-made proteins for a variety of applications. ImmTACs stand out as promising therapeutics for cancer and other treatments while also presenting unique challenges for stability, formulation, and delivery. We have shown that ImmTACs behave as Janus particles in solution, leading to self-association at low concentrations, even when the average protein–protein interactions suggest that the molecule should be stable. The formation of small but stable oligomers was confirmed by static and dynamic light scattering and analytical ultracentrifugation. Modeling of the structure using AlphaFold leads to a rational explanation for this behavior, consistent with the Janus particle assembly observed for inverse patchy particles.}, archive = {J_JACS}, author = {Emily Sakamoto-Rablah and Jordan Bye and Arghya Modak and Andrew Hooker and Shahid Uddin and Jennifer J. McManus}, doi = {10.1021/jacs.4c08932}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {247--256}, shortjournal = {J. Am. Chem. Soc.}, title = {Synthetic T-cell receptor-like protein behaves as a janus particle in solution}, volume = {147}, year = {2025}, }
• (2025). Efficient orthogonal spin labeling of proteins via aldehyde cyclization for pulsed dipolar EPR distance measurements. JACS, 147(1), 234--246. (www)

  @article{ , abstract = {Pulsed dipolar electron paramagnetic resonance (PD-EPR) measurement is a powerful technique for characterizing the interactions and conformational changes of biomolecules. The extraction of these distance restraints from PD-EPR experiments relies on manipulation of spin–spin pairs. The orthogonal spin labeling approach offers unique advantages by providing multiple distances between different spin–spin pairs. Here, we report an efficient orthogonal labeling approach based on exploiting the cyclization between the 1,2-aminothiol moiety in a protein (e.g., the N-terminal cysteine) with the aldehyde group in a spin label and a thiol substitution (or addition) reaction with a different spin label. We demonstrated that this orthogonal spin labeling method enables high accuracy and precision of multiple protein distance constraints through the PD-EPR measurement from a single sample. This spin labeling approach was applied to characterize the oligomeric state of the trigger factor (TF) protein of Escherichia coli , an important protein chaperone, in solution and cell lysates by distance measurements between different spin–spin pairs. Contrary to popular belief, TF exists mainly in the monomeric state and not as a dimer in the cell lysate.}, archive = {J_JACS}, author = {Wei-Han Meng and Xing Zhang and Bin-Bin Pan and Xiaoli Tan and Jia-Long Zhao and Yangping Liu and Yin Yang and Daniella Goldfarb and Xun-Cheng Su}, doi = {10.1021/jacs.4c09139}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {234--246}, shortjournal = {J. Am. Chem. Soc.}, title = {Efficient orthogonal spin labeling of proteins via aldehyde cyclization for pulsed dipolar EPR distance measurements}, volume = {147}, year = {2025}, }
• (2025). Oxygen dimerization-driven cation migration induces voltage hysteresis in disordered rocksalt cathodes. JACS, 147(1), 223--233. (www)

  @article{ , abstract = {Despite the potential to increase the energy limit of Li-rich cathodes by using oxygen redox, its practicality has been limited by the accompanying structural changes and voltage hysteresis. While voltage hysteresis is commonly associated with transition metal (TM) migration and oxygen dimerization, the specific contribution of each is unclear. We provide a mechanistic insight into how each of these changes induces hysteresis in a representative Li-rich disordered rocksalt cathode, Li 1.2 Mn 0.4 Ti 0.4 O 2 . We reveal that the formation and cleavage of oxygen dimers can occur exceptionally rapidly during the electrochemical process, suggesting that the dimerization process is not directly the cause of voltage hysteresis, contrary to prevailing arguments. Instead, oxygen dimers are found to indirectly exacerbate hysteresis by instigating TM migration, which leads to the evolution of dimer-rich and TM-rich regions within the structure. We demonstrate that TM migration is relatively slower than dimerization and as such contributes to hysteresis by dissipating internal energy during the relaxation of charged electrodes and by inducing cation rearrangement with each cycle.}, archive = {J_JACS}, author = {Byunghoon Kim and Peichen Zhong and Yunyeong Choi and Shashwat Anand and Han-Ming Hau and Bowen Deng and Gerbrand Ceder}, doi = {10.1021/jacs.4c09070}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {223--233}, shortjournal = {J. Am. Chem. Soc.}, title = {Oxygen dimerization-driven cation migration induces voltage hysteresis in disordered rocksalt cathodes}, volume = {147}, year = {2025}, }
• (2025). Tropospheric fate of methylhydroxycarbene and the ability of a single water molecule to efficiently promote its isomerization into acetaldehyde. JACS, 147(1), 211--222. (www)

  @article{ , abstract = {The ultraviolet (UV) photodissociation of pyruvic acid through the absorption of solar actinic flux generates methylhydroxycarbene (MHC) in the atmosphere. It is recognized that isolated MHC can undergo unimolecular isomerization to form acetaldehyde and vinyl alcohol. However, the rates and mechanism for its possible bimolecular reactions with atmospheric constituents, which can occur in parallel with its unimolecular reaction, is not well understood. Here we investigate the energetics, kinetics, and mechanism of the reaction of MHC with three ubiquitous atmospheric molecules N 2 , O 2 , and H 2 O over the 160 K-380 K temperature range. Our study, at the CCSD(T)/6-311++G(3df,3pd)//M06-2 X /6-311++G(3df,3pd) level, reveals that the MHC + N 2 encounter is nonreactive, while the MHC + O 2 reaction, which leads to CH 3 CO + HO 2 formation, has a rate that is significantly different from previous estimates. For the MHC + H 2 O reaction, we find that a single H 2 O molecule is very effective in catalyzing the isomerization of MHC to form predominantly acetaldehyde. An analysis of the computed rate for this reaction indicates that it will be an important source of tropospheric acetaldehyde ̵ a major pollutant and precursor for atmospheric reactive intermediates. Our findings are in sharp contrast to current assessments in the literature that the MHC + H 2 O reaction is minor. Furthermore, in the MHC + H 2 O reaction system, we find that due to the presence of the OH group on MHC, the concerted insertion mechanism, which is typically dominant in reactions involving singlet carbenes, is suppressed relative to a hydrogen bond mediated double hydrogen atom transfer mechanism.}, archive = {J_JACS}, author = {Soumen Mondal and Saikat Sadhukhan and Amitabha Sinha and Montu K. Hazra}, doi = {10.1021/jacs.4c08903}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {211--222}, shortjournal = {J. Am. Chem. Soc.}, title = {Tropospheric fate of methylhydroxycarbene and the ability of a single water molecule to efficiently promote its isomerization into acetaldehyde}, volume = {147}, year = {2025}, }
• (2025). Constructing atomic tungsten-based solid frustrated-lewis-pair sites with d-p interactions for selective CO2 photoreduction. JACS, 147(1), 200--210. (www)

  @article{ , abstract = {Solid frustrated Lewis pair (FLP) shows remarkable advantages in the activation of small molecules such as CO 2 , owing to the strong orbital interactions between FLP sites and reactant molecules. However, most of the currently constructed FLP sites are randomly distributed and easily reunited on the surface of catalysts, resulting in a low utilization rate of FLP sites. Herein, atomic tungsten-based FLP (N···W SA FLP) sites are constructed for photocatalytic CO 2 conversion through introducing W single-atoms into polymeric carbon nitride. In the atomically dispersed N···W SA FLP, the electron-deficient W single-atom acts as the Lewis acid (LA), and the adjacent electron-rich N atom acts as the Lewis base. Through the combination of various characterizations, including pyridine-IR, in situ diffuse reflectance infrared Fourier transform spectroscopy, CO 2 -temperature programmed desorption, and theoretical calculations, the positive effects of N···W SA FLP on photocatalytic CO 2 reduction are well revealed. The N···W SA FLP can effectively adsorb CO 2 to form an unusual W–O–C–N structure with significant d-p orbital interactions, which leads to an interesting “push–push” electron transfer effect. The π back-donation from W 5d to the antibonding orbital (2π) of CO 2 realizes reverse electron transfer from the W single-atom to the O site, while the electrons are transferred from the electron-rich N site to the electropositive C site via Lewis acid–base interactions, therefore effectively breaking the C═O bond to activate CO 2 molecules and boost CO 2 -to-CO performance. This work provides a brand new route for the research on high-efficiency activation of small molecules based on single-atom-based FLP catalysts.}, archive = {J_JACS}, author = {Baorong Xu and Shicheng Luo and Weibo Hua and Hang Xiao and Ben Chong and Guocheng Yan and He Li and Honghui Ou and Bo Lin and Guidong Yang}, doi = {10.1021/jacs.4c08953}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {200--210}, shortjournal = {J. Am. Chem. Soc.}, title = {Constructing atomic tungsten-based solid frustrated-lewis-pair sites with d-p interactions for selective CO2 photoreduction}, volume = {147}, year = {2025}, }
• (2025). Programming the kinetics of chemical communication: Induced fit vs conformational selection. JACS, 147(1), 192--199. (www)

  @article{ , abstract = {Life on Earth depends on chemical communication and the ability of biomolecular switches to integrate various chemical signals that trigger their activation or deactivation over time scales ranging from microseconds to days. The ability to similarly program and control the kinetics of artificial switches would greatly assist the design and optimization of future chemical and nanotechnological systems. Two distinct structure-switching mechanisms are typically employed by biomolecular switches: induced fit (IF) and conformational selection (CS). Despite 60 years of experimental and theoretical investigations, the kinetic and evolutive advantages of these two mechanisms remain unclear. Here, we have created a simple modular DNA switch that can operate through both mechanisms and be easily tuned and adapted to characterize its thermodynamic and kinetic parameters. We show that the fastest activation rate of a switch occurs when the ligand is able to bind its inactive conformation (IF). In contrast, we show that when the ligand can only bind the active conformation of the switch (CS), its activation rate can be easily programmed over many orders of magnitude by a simple tuning of its conformational equilibrium. We demonstrate the programming ability of both these mechanisms by designing a drug delivery vessel that can be programmed to release a drug over different time scales (>1000-fold). Overall, these findings provide a programmable strategy to optimize the kinetics of molecular systems and nanomachines while also illustrating how evolution may have taken advantage of IF and CS mechanisms to optimize the kinetics of biomolecular switches.}, archive = {J_JACS}, author = {Carl Prévost-Tremblay and Achille Vigneault and Dominic Lauzon and Alexis Vallée-Bélisle}, doi = {10.1021/jacs.4c08597}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {192--199}, shortjournal = {J. Am. Chem. Soc.}, title = {Programming the kinetics of chemical communication: Induced fit vs conformational selection}, volume = {147}, year = {2025}, }
• (2025). Unraveling serial degradation pathways of supported catalysts through reliable electrochemical liquid-cell TEM analysis. JACS, 147(1), 181--191. (www)

  @article{ , abstract = {Electrochemical liquid-cell transmission electron microscopy (e-LCTEM) offers great potential for investigating the structural dynamics of nanomaterials during electrochemical reactions. However, challenges arise from the difficulty in achieving the optimal electrolyte thickness, leading to inconsistent electrochemical responses and limited spatial resolution. In this study, we present advanced e-LCTEM techniques tailored for tracking Pt/C degradation under electrochemical polarization at short intervals with high spatial resolution. Our innovative approach combines microfabrication-based sample preparation with in situ control of electrolyte thickness, ensuring reliable electrochemical signal acquisition and direct observation of sequential catalyst degradation. Quantitative imaging analyses conducted at both global areas and single-particle levels unveil a distinctive degradation mechanism primarily driven by nanoparticle migrations. Smaller nanoparticles exhibit a higher susceptibility to migration, leading to coalescence and final detachment in series. This migration-gated degradation mechanism provides a new perspective on the size-dependent durability of supported nanoparticles, complementing the prevailing explanation centered on the size-dependent dissolution kinetics of nanoparticles.}, archive = {J_JACS}, author = {Sungin Kim and Jimin Kwag and Minyoung Lee and Sungsu Kang and Dongjun Kim and Jong-Gil Oh and Young-Jung Heo and Jaeyune Ryu and Jungwon Park}, doi = {10.1021/jacs.4c08825}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {181--191}, shortjournal = {J. Am. Chem. Soc.}, title = {Unraveling serial degradation pathways of supported catalysts through reliable electrochemical liquid-cell TEM analysis}, volume = {147}, year = {2025}, }
• (2025). CRISPR/RNA aptamer system activated by an AND logic gate for biomarker-driven theranostics. JACS, 147(1), 169--180. (www)

  @article{ , abstract = {The development of an engineered RNA device capable of detecting multiple biomarkers to evaluate pathological states and autonomously implement responsive therapies is urgently needed. Here, we report InCasApt, an integrated nano CRISPR Cas13a/RNA aptamer theranostic platform capable of achieving both biomarker detection and biomarker-driven therapy. Within this system, a Cas13a/crRNA complex, a hairpin reporter (HR), a dinitroaniline caged Ce6 photosensitizer (Ce6-DN), and a DN-binding RNA aptamer precursor (DNBApt) are coloaded onto dendritic mesoporous silicon nanoparticles (DMSN) in a controlled manner. While InCasApt remains inert in normal cells, its programmable theranostic capabilities are activated in tumor cells that have elevated expression of carcinogenic miRNA-155 and miRNA-21. These miRNAs act as an AND logic gate, generating fluorescence for disease condition evaluation and ROS for photodynamic therapy. This process also upregulates antioncogene BRG1 and suppresses tumor migration by inhibiting the function of miRNA-155 and miRNA-21. These effects underscore the versatility of InCasApt as an miRNA-targeting strategy for bridging the gap between diagnosis and therapy.}, archive = {J_JACS}, author = {Qiqi Yang and Ming-Jie Dong and Jianglian Xu and Yi Xing and Yue Wang and Jinlong Yang and Xiangdan Meng and Tianzhen Xie and Yingfu Li and Haifeng Dong}, doi = {10.1021/jacs.4c08719}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {169--180}, shortjournal = {J. Am. Chem. Soc.}, title = {CRISPR/RNA aptamer system activated by an AND logic gate for biomarker-driven theranostics}, volume = {147}, year = {2025}, }
• (2025). MXenes spontaneously form active and selective single-atom centers under anodic polarization conditions. JACS, 147(1), 161--168. (www)

  @article{ , abstract = {Single-atom catalysts (SACs) have emerged as a new class of materials for the development of active and selective catalysts. These materials are commonly based on anchoring a noble transition metal to some kind of carrier. In the present work, we demonstrate that MXenes─two-dimensional materials with application in energy storage and conversion─spontaneously form SAC-like sites under anodic polarization conditions, using the applied electrode potential as a probe to form catalytically active surface sites reminiscent of a SAC-like structure. Combining ab initio molecular dynamics simulations and electronic structure calculations in the density functional theory framework, we demonstrate that only the SAC-like sites rather than the basal planes of MXenes are highly active and selective for the oxygen evolution or chlorine evolution reactions, respectively. Our findings may simplify synthetic routes toward the formation of active and selective SAC-like sites and could pave the way for the development of smart materials by incorporating fundamental principles from nature into material discovery: while the pristine form of the material is inactive, the application of an electrode potential activates the material by the formation of active and selective single-atom centers.}, archive = {J_JACS}, author = {Samad Razzaq and Shohreh Faridi and Stephane Kenmoe and Muhammad Usama and Diwakar Singh and Ling Meng and Francesc Vines and Francesc Illas and Kai S. Exner}, doi = {10.1021/jacs.4c08518}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {161--168}, shortjournal = {J. Am. Chem. Soc.}, title = {MXenes spontaneously form active and selective single-atom centers under anodic polarization conditions}, volume = {147}, year = {2025}, }
• (2025). Single-vesicle electrochemistry in fresh brain slices enables in situ quantification of vesicular monoamine. JACS, 147(1), 149--160. (www)

  @article{ , abstract = {The quantitative analysis of vesicular neurotransmitters in neurons in situ is paramount for investigating neurodegenerative disorders, such as Alzheimer’s disease and Parkinson’s disease (PD). Unfortunately, a direct approach for monitoring neurotransmitter chemistry in single vesicles in fresh brain tissue has remained inaccessible so far. Here, we introduce an innovative platform of single-vesicle electrochemistry (SVE) in fresh brain tissue, enabling the quantification of neurotransmitters at the single-vesicle level for both soma and varicosity. Utilizing this methodology, we investigated a PD animal model, which demonstrated a significant reduction in both vesicular dopamine (DA) storage and exocytotic release in DA neurons in the substantia nigra. Furthermore, SVE unveiled the heterogeneous nature of chemical neurotransmission among DA neurons across different brain regions. Importantly, this tissue-based SVE approach can be extended to quantify other monoamine neurotransmitters, such as norepinephrine and serotonin, at the single-vesicle level. The introduction of this methodology marks a significant advancement, offering a novel avenue to explore neurological and psychiatric disorders through the lens of neurotransmitter signaling in the mammalian brain. This breakthrough has the potential to deepen our understanding of the underlying mechanisms of these complex disorders and may pave the way for the development of targeted therapeutic interventions.}, archive = {J_JACS}, author = {Yuying Liu and Lijiao Cao and Junlan Zhou and Chuqi Li and Jinchang Du and Yifei Xue and Xianchan Li and Lanqun Mao}, doi = {10.1021/jacs.4c06572}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {149--160}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-vesicle electrochemistry in fresh brain slices enables in situ quantification of vesicular monoamine}, volume = {147}, year = {2025}, }
• (2025). High entropy 2D layered double hydroxide nanosheet toward cascaded nanozyme-initiated chemodynamic and immune synergistic therapy. JACS, 147(1), 136--148. (www)

  @article{ , abstract = {High-entropy nanomaterials (HEMs) are a hot topic in the fields of energy and catalysis. However, in terms of promising biomedical applications, potential therapeutic studies involving HEMs are unprecedented. Herein, we demonstrated high entropy two-dimensional layered double hydroxide ( HE-LDH ) nanoplatforms with versatile physicochemical advantages that reprogram the tumor microenvironment (TME) and provide antitumor treatment via cascaded nanoenzyme-initiated chemodynamic and immune synergistic therapy. In response to the TME, the multifunctional HE-LDHs sequentially release metal ions, such as Co 2+ , Fe 3+ , and Cu 2+ , exhibiting exquisite superoxide dismutase (SOD), peroxidase (POD), and glutathione peroxidase (GPX) activities. The multiple enzymatic activities convert specific tumor metabolites into a continuous supply of cytotoxic reactive oxygen species (ROS) to relieve hypoxia under a TME. Thus, HE-LDHs facilitate robust nanozyme-initiated chemodynamic therapy (NCDT), achieving high therapeutic efficacy without obvious side effects. In addition, the release of Zn 2+ from the HE-LDH matrix triggers the cyclic GMP-AMP synthase/stimulator of interferon gene (cGAS/STING) signaling pathway, boosting the innate immunotherapeutic efficacy. The intratumoral applications of the nanocomposite in tumor-bearing mice models indicate that HE-LDH -mediated NCDT and immune synergistic therapy effectively upregulated the expression of relevant antitumor cytokines and induced cytotoxic T lymphocyte infiltration, showing superior efficacy in inhibiting tumor growth. Therefore, this work opens a new research direction toward synchronized NCDT and immunotherapy of tumors using HEMs for advanced healthcare.}, archive = {J_JACS}, author = {Chen Wang and Fengying Yuan and Zichao Yan and Tianqi Zhang and Chenchen Fu and Ya Li and Guidong Dai and Hyeong Seok Kim and Shuwei Xia and Liangmin Yu and Snehasish Debnath and Wen Xiu Ren and Jian Shu and Meng Qiu and Jong Seung Kim}, doi = {10.1021/jacs.4c04523}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {136--148}, shortjournal = {J. Am. Chem. Soc.}, title = {High entropy 2D layered double hydroxide nanosheet toward cascaded nanozyme-initiated chemodynamic and immune synergistic therapy}, volume = {147}, year = {2025}, }
• (2025). Total syntheses of scabrolide b, ineleganolide, and related norcembranoids. JACS, 147(1), 130--135. (www)

  @article{ , abstract = {Concise total syntheses of several 5/7/6 norcembranoids, including ineleganolide, scabrolide B, sinuscalide C, and fragilolide A have been achieved through a fragment coupling/ring closure approach. The central seven-membered ring was forged through sequential Mukaiyama–Michael/aldol reactions using norcarvone and a decorated bicyclic lactone incorporating a latent electrophile. Subsequent manipulations installed the reactive enedione motif and delivered scabrolide B in 11 steps from a chiral pool-derived enone. Finally, ineleganolide, sinuscalide C, and fragilolide A were each accessed in one additional step.}, archive = {J_JACS}, author = {Emma J. Simmons and David B. Ryffel and Diego A. Lopez and Yaroslav D. Boyko and David Sarlah}, doi = {10.1021/jacs.4c16629}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {130--135}, shortjournal = {J. Am. Chem. Soc.}, title = {Total syntheses of scabrolide b, ineleganolide, and related norcembranoids}, volume = {147}, year = {2025}, }
• (2025). Two blatter radicals face-to-face: A constrained diradical architecture. JACS, 147(1), 125--129. (www)

  @article{ , abstract = {Cofacial arrangement of two Blatter radicals enforced by the peri -naphthalene scaffold represents a new approach to stable diradicals with strong through-space interactions. Two stereoisomers of the naphthalene-diradicals, anti and syn , are investigated by XRD, VT-EPR, UV–vis, electrochemical, kinetic, and DFT methods. In solutions, both stereoisomers exist as open-shell singlets with Δ E S-T = −3.1 and −3.8 kcal mol –1 , respectively. The anti isomer was resolved into enantiomers and converts to syn with Δ G ‡ 298 = 23.6(8) kcal mol –1 .}, archive = {J_JACS}, author = {Paulina Bartos and Dominika Pomikło and Kadin B. Sorenson and Oleksandr Hietsoi and Andrienne C. Friedli and Piotr Kaszyński}, doi = {10.1021/jacs.4c16500}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {125--129}, shortjournal = {J. Am. Chem. Soc.}, title = {Two blatter radicals face-to-face: A constrained diradical architecture}, volume = {147}, year = {2025}, }
• (2025). Heteroaryl-directed iridium-catalyzed enantioselective C–H alkenylations of secondary alcohols. JACS, 147(1), 118--124. (www)

  @article{ , abstract = {Under iridium-catalyzed conditions, 2-aza-aryl-substituted secondary alcohols undergo C(sp 3 )–H addition reactions to alkynes to provide alkenylated tertiary alcohols. The processes occur with very high regio- and enantioselectivity. An analogous addition to styrene is shown to provide a prototype C(sp 3 )–H alkylation process. A mechanism based on directed aza-enolization of the reactant alcohol is proposed.}, archive = {J_JACS}, author = {Wenbin Mao and Craig M. Robertson and John F. Bower}, doi = {10.1021/jacs.4c16414}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {118--124}, shortjournal = {J. Am. Chem. Soc.}, title = {Heteroaryl-directed iridium-catalyzed enantioselective C–H alkenylations of secondary alcohols}, volume = {147}, year = {2025}, }
• (2025). Molten metal synthesis of nanographenes. JACS, 147(1), 111--117. (www)

  @article{ , abstract = {This manuscript describes a simple and effective method to cyclodehydrogenate arenes using liquid alkali metals. Direct reaction between molten potassium and arenes forms 6-membered rings and zigzag edged structures within polyarenes. The approach is extended to integration of pyridinic nitrogen and 5-membered rings to arene structures and synthesis of larger, open-shell nanographenes.}, archive = {J_JACS}, author = {Jacklin H. Smith and Daniel Čavlović and Luke T. Lackovic and Miguel Medina Lopez and Elena Meirzadeh and Michael L. Steigerwald and Xavier Roy and Colin P. Nuckolls and Scott R. Docherty}, doi = {10.1021/jacs.4c16328}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {111--117}, shortjournal = {J. Am. Chem. Soc.}, title = {Molten metal synthesis of nanographenes}, volume = {147}, year = {2025}, }
• (2025). Enantioselective vinylogous addition of enones to allenes enabled by synergistic Borane/Palladium catalysis. JACS, 147(1), 104--110. (www)

  @article{ , abstract = {Herein, we report a method for enantioselective vinylogous addition of enones to alkoxyallenes enabled by synergistic borane/palladium catalysis. The inductive effect provided by borane coordination to the ketone was essential for closing the gap between the conditions needed for the generation of a dienolate and those needed for initiation of the palladium catalytic cycle by protonation of the metal catalyst. Furthermore, we accomplished the first example of stereodivergent synthesis with chiral borane/transition-metal catalysts.}, archive = {J_JACS}, author = {Heng Luo and Ming Zhang and Ze-Qun Xing and Xiao-Chen Wang}, doi = {10.1021/jacs.4c16214}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {104--110}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective vinylogous addition of enones to allenes enabled by synergistic Borane/Palladium catalysis}, volume = {147}, year = {2025}, }
• (2025). Enantioselective carbonylative cyclization of alkenes with C–H bonds for synthesis of γ-lactams bearing an α-quaternary carbon. JACS, 147(1), 96--103. (www)

  @article{ , abstract = {The development of effective synthetic methods to construct γ-lactams bearing a chiral α-quaternary carbon from relatively inert C(O)–H bonds with alkenes has been an elusive challenge. Herein, we used a naphthylamine-derived phosphine oxide ligating Ni and Al bimetallic catalyst to realize a carbonylative cyclization of formyl C–H bonds with alkenes, highly regio- and enantioselectively constructing γ-lactams bearing a chiral α-quaternary carbon in up to 99% yield and 98% ee. These γ-lactams proved to be versatile synthetic precursors for many biologically active molecules.}, archive = {J_JACS}, author = {Weiwei Xu and Yanan Sun and Yuqing Jiang and Xueyuan Yan and Zhixuan Gao and Haorui Wang and Genping Huang and Qi-Lin Zhou and Mengchun Ye}, doi = {10.1021/jacs.4c15875}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {96--103}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective carbonylative cyclization of alkenes with C–H bonds for synthesis of γ-lactams bearing an α-quaternary carbon}, volume = {147}, year = {2025}, }
• (2025). Enantioselective α-C(sp3)–H borylation of masked primary alcohols enabled by iridium catalysis. JACS, 147(1), 88--95. (www)

  @article{ , abstract = {Functional group-directed site- and enantioselective C(sp 3 )–H functionalization of alcohols or masked alcohols represents a formidable challenge. We herein report the first example of iridium-catalyzed asymmetric α-C(sp 3 )–H borylation of primary alcohol-derived carbamates by the judicious choice of directing groups. A variety of chiral borylated carbamates were obtained with good to high enantioselectivities. We also demonstrated the synthetic utility by taking advantage of the highly transformable feature of C–B bonds and the leaving ability of carbamates.}, archive = {J_JACS}, author = {Qian Gao and Yinwu Li and Lili Chen and Liang-Jun Xie and Xiangfeng Shao and Zhuofeng Ke and Senmiao Xu}, doi = {10.1021/jacs.4c14890}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {88--95}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective α-C(sp3)–H borylation of masked primary alcohols enabled by iridium catalysis}, volume = {147}, year = {2025}, }
• (2025). Direct determination of a giant zero-field splitting of 5422 cm–1 in a triplet organobismuthinidene by infrared electron paramagnetic resonance. JACS, 147(1), 84--87. (www)

  @article{ , abstract = {Stable monocoordinated organobismuthinidenes were only recently isolated and analyzed toward their chemical and electronic structure. Quantum chemical calculations on t Bu-M S Fluind-Bi(I) ( 2 ) predicted an unusual electronic structure dominated by a triplet ground state and a spectacular zero-field splitting (ZFS) > 4500 cm –1 . However, experimental evidence for these predictions remained elusive due to limitations in the available magnetic characterization techniques. Herein, we determine an axial ZFS of D = 5422 cm –1 for 2 , by direct detection of triplet electron paramagnetic resonance using magneto-optical infrared spectroscopy. To date, this represents the largest ZFS experimentally measured.}, archive = {J_JACS}, author = {Tarek Al Said and Davide Spinnato and Karsten Holldack and Frank Neese and Josep Cornella and Alexander Schnegg}, doi = {10.1021/jacs.4c14795}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {84--87}, shortjournal = {J. Am. Chem. Soc.}, title = {Direct determination of a giant zero-field splitting of 5422 cm–1 in a triplet organobismuthinidene by infrared electron paramagnetic resonance}, volume = {147}, year = {2025}, }
• (2025). Biomimetic synthesis of azorellolide via cyclopropylcarbinyl cation chemistry. JACS, 147(1), 78--83. (www)

  @article{ , abstract = {A concise synthesis of the complex diterpene azorellolide, inspired by speculations on biosynthetic cationic cascades, is presented. The approach, guided by computation, relies on the intramolecular interception of a cyclopropylcarbinyl cation by an appended carboxylate. The successful execution of this strategy was achieved through acid-catalyzed isomerization of a β-lactone in competition with a type I dyotropic rearrangement.}, archive = {J_JACS}, author = {Jordan Y. Artzy and Dean J. Tantillo and Dirk H. Trauner}, doi = {10.1021/jacs.4c14664}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {78--83}, shortjournal = {J. Am. Chem. Soc.}, title = {Biomimetic synthesis of azorellolide via cyclopropylcarbinyl cation chemistry}, volume = {147}, year = {2025}, }
• (2025). Pd-catalyzed migratory 1,1-cycloannulation reaction of alkenes. JACS, 147(1), 69--77. (www)

  @article{ , abstract = {Here, we report a novel strategy for the preparation of diverse heterocycles via a Pd-catalyzed migratory 1,1-cycloannulation reaction (MCAR) of alkenes. Starting from readily available alkenyl amines and alkenyl alcohols, this approach allows the formation of a wide range of five- to seven-membered azaheterocycles and oxaheterocycles with high efficiency and good functional group tolerance. The key to the realization of this reaction is the use of 4-iodophenol or 2-iodophenol derivatives where the phenolic hydroxyl group plays a critical role in controlling the direction of migration and the ring-size of the heterocycles through the formation of a quinone methide intermediate.}, archive = {J_JACS}, author = {Jin-Ping Wang and Tao Liu and Yichen Wu and Peng Wang}, doi = {10.1021/jacs.4c14153}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {69--77}, shortjournal = {J. Am. Chem. Soc.}, title = {Pd-catalyzed migratory 1,1-cycloannulation reaction of alkenes}, volume = {147}, year = {2025}, }
• (2025). Mixed ionic and electronic conductivity in a tetrathiafulvalene-phosphonate Metal–Organic framework. JACS, 147(1), 63--68. (www)

  @article{ , abstract = {Mixed ionic-electronic conductors have great potential as materials for energy storage applications. However, despite their promising properties, only a handful of metal–organic frameworks (MOFs) provide efficient pathways for both ion and electron transport. This work reports a proton–electron dual-conductive MOF based on tetrathiafulvalene(TTF)-phosphonate linkers and lanthanum ions. The formation of regular, partially oxidized TTF stacks with short S···S interactions facilitates electron transport via a hopping mechanism, reporting a room-temperature conductivity of 7.2 × 10 –6 S cm –1 . Additionally, the material exhibits a proton conductivity of 4.9 × 10 –5 S cm –1 at 95% relative humidity conditions due to the presence of free −POH groups, enabling efficient proton transport pathways. These results demonstrate the potential of integrating electroactive building blocks along with phosphonate groups toward the development of mixed ionic-electronic conductors.}, archive = {J_JACS}, author = {Catarina Ribeiro and Bowen Tan and Flávio Figueira and Ricardo F. Mendes and Joaquín Calbo and Gonçalo Valente and Paula Escamilla and Filipe A. Almeida Paz and João Rocha and Mircea Dincă and Manuel Souto}, doi = {10.1021/jacs.4c13792}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {63--68}, shortjournal = {J. Am. Chem. Soc.}, title = {Mixed ionic and electronic conductivity in a tetrathiafulvalene-phosphonate Metal–Organic framework}, volume = {147}, year = {2025}, }
• (2025). Single-carbon insertion into single C–C bonds with diazirines. JACS, 147(1), 57--62. (www)

  @article{ , abstract = {A novel platform for the skeletal editing of single C–C bonds via a single-carbon insertion has been developed using diazirines. This strategy involves the photogeneration of arylchlorocarbenes as carbynoid species that undergo site-selective carbene insertion into tertiary C–H bonds and a subsequent Wagner–Meerwein rearrangement promoted by a silver salt. Our skeletal editing strategy based on a formal selective carbyne C–C bond insertion has been demonstrated in six core-to-core conversions, including linear and cyclic benzylic substrates, alkanes and late-stage functionalizations.}, archive = {J_JACS}, author = {Valero G. Alfonso and Karen de la Vega-Hernández and Marcos G. Suero}, doi = {10.1021/jacs.4c12632}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {57--62}, shortjournal = {J. Am. Chem. Soc.}, title = {Single-carbon insertion into single C–C bonds with diazirines}, volume = {147}, year = {2025}, }
• (2025). Enantioselective alkylation of primary C(sp3)–H bonds in N-methyl tertiary amine enabled by iridium complex of axially chiral β-aryl porphyrins. JACS, 147(1), 51--56. (www)

  @article{ , abstract = {A fine-tuning of enantioselective carbene insertion into primary C( sp 3 )–H bonds has been realized in challenging substrates, such as N -methyl unblocked aromatic and non-deactivated aliphatic tertiary amines, in which sterically demanding β-axially chiral iridium porphyrin catalysts play a crucial role. This primary C( sp 3 )–H alkylation with diazo compounds affords a series of β-chiral tertiary amines in high yields with excellent enantioselectivities. Notably, the protocol was successfully applied to the postmodification of chiral bicuculline, yielding the desired derivative with high diastereoselectivity. This approach paves a facile way for the stereodivergent derivation of chiral alkaloid natural products featuring an N -methyl handle. In addition, a mechanism for the reaction was proposed based on deuterium experiments and an identified cationic iridium species via HRMS analysis.}, archive = {J_JACS}, author = {Shanshan Yuan and Sheng-Yu Li and Xiao-Ming Zhao and Ya-Zhou Lin and Sheng-Cai Zheng}, doi = {10.1021/jacs.4c12449}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {51--56}, shortjournal = {J. Am. Chem. Soc.}, title = {Enantioselective alkylation of primary C(sp3)–H bonds in N-methyl tertiary amine enabled by iridium complex of axially chiral β-aryl porphyrins}, volume = {147}, year = {2025}, }
• (2025). Unbuckling the 18-crown-6 ether belt around metal ions: Forging the connection to the condensed phase. JACS, 147(1), 45--50. (www)

  @article{ , abstract = {Crown ethers are central to supramolecular chemistry, recognizing and binding specific ions in solution. The most well-known, 18-Crown-6 (18C6), preferentially captures K + in an aqueous solution, while gas phase binding of 18C6 with alkali metal ions decreases linearly with an increasing ionic radius. Why the high affinity for Li + and Na + in the gas phase is dramatically reduced with hydration remains an open question in understanding the K + selectivity in the aqueous phase. A combined spectroscopic and computational study of M + 18C6(H 2 O) n =0–3 (M = Li, Na, and K) in the CH stretch region has revealed how stepwise hydration unbuckles the crown ether belt from Li + and Na + , substantially changing the backbone structure of 18C6. In contrast, the structure of the K + 18C6 complex is unbuckled and is unaffected by hydration. Combined with new measurements of the OH stretch, a direct connection is provided between the stepwise hydration of M + 18C6 and the selectivity for K + in an aqueous solution. It demonstrates and validates at the molecular level the application of gas-phase measurements to condensed-phase studies.}, archive = {J_JACS}, author = {Ryu Sakuma and Keisuke Hirata and James M. Lisy and Masaaki Fujii and Shun-ichi Ishiuchi}, doi = {10.1021/jacs.4c12036}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {45--50}, shortjournal = {J. Am. Chem. Soc.}, title = {Unbuckling the 18-crown-6 ether belt around metal ions: Forging the connection to the condensed phase}, volume = {147}, year = {2025}, }
• (2025). Enhancing proton-coupled electron transfer in blue light using FAD photoreceptor AppABLUF. JACS, 147(1), 39--44. (www)

  @article{ , abstract = {The Blue Light Using FAD (BLUF) photoreceptor utilizes a noncovalently bound FAD to absorb light and trigger the initial ultrafast events in receptor activation. FAD undergoes 1 and 2 electron reduction as an enzyme redox cofactor, and studies on the BLUF photoreceptor PixD revealed the formation of flavin radicals (FAD •– and FADH • ) during the photocycle, supporting a general mechanism for BLUF operation that involves PCET from a conserved Tyr to the oxidized FAD. However, no radical intermediates are observed in the closely related BLUF proteins AppA BLUF and BlsA, and replacing the conserved Tyr with fluoro-Tyr analogs that increase the acidity of the phenol OH has a minor effect on AppA BLUF photoactivation in contrast to PixD where the photocycle is halted at FAD •– . The hydrogen bonding network in BLUF proteins contains several strictly conserved residues but differs in the identity of amino acids that interact with the flavin C2═O. In PixD there are two hydrogen bonds to the C2═O, whereas there is only one in AppA BLUF . Using TRIR we show that the introduction of a second hydrogen bond to the C2═O in AppA BLUF results in the formation of flavin radicals (FAD •– and FADH • ) during the photocycle. Subsequent replacement of the conserved Tyr (Y21) in the double mutant with 2,3,5-trifluoroTyr prevents radical formation and generation of the light state, indicating that the AppA BLUF photocycle is now similar to that of PixD. The ability to trigger PCET provides fundamental insight into the role of electron transfer in the mechanism of BLUF photoactivation.}, archive = {J_JACS}, author = {YongLe He and Agnieszka A. Gil and Sergey P. Laptenok and Anam Fatima and Jinnette Tolentino Collado and James N. Iuliano and Helena A. Woroniecka and Richard Brust and Aya Sabbah and Michael Towrie and Gregory M. Greetham and Igor V. Sazanovich and Jarrod B. French and Andras Lukacs and Stephen R. Meech and Peter J. Tonge}, doi = {10.1021/jacs.4c11817}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {39--44}, shortjournal = {J. Am. Chem. Soc.}, title = {Enhancing proton-coupled electron transfer in blue light using FAD photoreceptor AppABLUF}, volume = {147}, year = {2025}, }
• (2025). Fluoroform (CHF3) production from CF3CHO photolysis and implications for the decomposition of hydrofluoroolefins and hydrochlorofluoroolefins in the atmosphere. JACS, 147(1), 33--38. (www)

  @article{ , abstract = {Hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs) are the leading synthetic replacements for compounds successively banned by the Montreal Protocol and amendments. HFOs and HCFOs readily decompose in the atmosphere to form fluorinated carbonyls, including CF 3 CHO in yields of up to 100%, which are then photolyzed. A long-standing issue, critical for the transition to safe industrial gases, is whether atmospheric decomposition of CF 3 CHO yields any quantity of CHF 3 (HFC-23), which is one of the most environmentally hazardous greenhouse gases. This comprehensive experimental investigation employs purpose-built photoionization mass spectrometry, Fourier-transform infrared, and microwave spectroscopy techniques and confirms production of CHF 3 following excitation at a tropospherically relevant wavelength (λ = 308 nm) and under atmospheric pressure conditions. Pressure-dependent CHF 3 quantum (Φ) and molar ( Y ) yields are reported from Φ = Y = 0.16 ± 0.03 under collision-free conditions to Φ = (2.3 ± 0.3) × 10 –4 , Y = (1.17 ± 0.27) × 10 –3 at 1 bar N 2 .}, archive = {J_JACS}, author = {Joshua D. Thomson and Jyoti S. Campbell and Ethan B. Edwards and Christopher Medcraft and Klaas Nauta and Maria Paula Pérez-Peña and Jenny A. Fisher and David L. Osborn and Scott H. Kable and Christopher S. Hansen}, doi = {10.1021/jacs.4c11776}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {33--38}, shortjournal = {J. Am. Chem. Soc.}, title = {Fluoroform (CHF3) production from CF3CHO photolysis and implications for the decomposition of hydrofluoroolefins and hydrochlorofluoroolefins in the atmosphere}, volume = {147}, year = {2025}, }
• (2025). Selective synthesis of Z-michael acceptors via hydroalkylation of conjugated alkynes. JACS, 147(1), 27--32. (www)

  @article{ , abstract = {Hydroalkylation of terminal alkynes is a powerful approach to the synthesis of disubstituted alkenes. However, its application is largely unexplored in the synthesis of α,β-unsaturated carbonyls, which are common among synthetic intermediates and biologically active molecules. The thermodynamically less stable Z -isomers of activated alkenes have been particularly challenging to access because of their propensity for isomerization and the paucity of reliable Z -selective hydroalkylation methods. We developed a highly Z -selective silver-catalyzed hydroalkylation of terminal conjugated alkynes using alkyl boranes as coupling partners. The reaction allows access to ( Z )-α,β-unsaturated esters, secondary and tertiary alkyl amides, aryl amides, and alkyl and aryl ketones and tolerates a wide range of functional groups. The reaction can be performed successfully in the presence of alkyl and aryl halides, esters, protected alcohols, and amines. The hydroalkylation involves the formation of an alkynylboronate complex followed by a 1,2-metalate shift. This sequence of steps mechanistically constrains the stereochemical outcome, which, together with mild reaction conditions, ensures high Z -selectivity.}, archive = {J_JACS}, author = {Austin B. Shaff and Avijit Hazra and Bradley W. Gardner and Gojko Lalic}, doi = {10.1021/jacs.4c09755}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {27--32}, shortjournal = {J. Am. Chem. Soc.}, title = {Selective synthesis of Z-michael acceptors via hydroalkylation of conjugated alkynes}, volume = {147}, year = {2025}, }
• (2025). Compartmentalizing Donor–Acceptor stenhouse adducts for Structure–Property relationship analysis. JACS, 147(1), 10--26. (www)

  @article{ , abstract = {The development of photoswitches that absorb low energy light is of notable interest due to the growing demand for smart materials and therapeutics necessitating benign stimuli. Donor–acceptor Stenhouse adducts (DASAs) are molecular photoswitches that respond to light in the visible to near-infrared spectrum. As a result of their modular assembly, DASAs can be modified at the donor, acceptor, triene, and backbone heteroatom molecular compartments for the tuning of optical and photoswitching properties. This Perspective focuses on the electronic and steric contributions at each compartment and how they influence photophysical properties through the adjustment of the isomerization energetic landscape. An emphasis on current synthetic strategies and their limitations highlights opportunities for DASA architecture, and thus photophysical property expansion.}, archive = {J_JACS}, author = {Cesar A. Reyes and Alexander Karr and Chloe A. Ramsperger and A. Talim G. K and Hye Joon Lee and Elias Picazo}, doi = {10.1021/jacs.4c14198}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {10--26}, shortjournal = {J. Am. Chem. Soc.}, title = {Compartmentalizing Donor–Acceptor stenhouse adducts for Structure–Property relationship analysis}, volume = {147}, year = {2025}, }
• (2025). Classical view on nonclassical crystal growth in a biological setting. JACS, 147(1), 1--9. (www)

  @article{ , abstract = {Crystallization by amorphous particle attachment, a nonclassical crystal growth mode, is prevalent in minerals formed by living tissues. It allows the organism to intervene at every step of crystal growth, i.e., particle formation, stabilization, accretion, and crystallization, and thus to orchestrate biomineral morphogenesis and crystallographic texturing; all toward achieving a required functionality for the organism. Therefore, significant effort is aimed at achieving similar control and crystal growth tunability through bioinspired and biomimetic synthetic means. This Perspective examines the driving forces and the kinetics of crystallization by amorphous particle attachment in a biological setting, and through an analogy to classical molecule-by-molecule crystallization, it establishes distinct crystal growth mechanisms. It underlines the role of physics and chemistry of materials in the “Growth and Form” of biogenic minerals.}, archive = {J_JACS}, author = {Richard Johannes Best and Deborah Stier and Lucas Kuhrts and Igor Zlotnikov}, doi = {10.1021/jacs.4c11940}, journal = {Journal of the American Chemical Society}, month = {1}, number = {1}, pages = {1--9}, shortjournal = {J. Am. Chem. Soc.}, title = {Classical view on nonclassical crystal growth in a biological setting}, volume = {147}, year = {2025}, }